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POLYMER HANDBOOK
J . BRANDRUP, E. H. IMMERGUT, and E. A. GRULKE
Associate Editors
A. ABE
D. R. BLOCH
Abe, A.
Tokyo Institute of Polytechnics, Atsugi, Japan
Allegra, G.
Dipartimento di Chimica de1 Politecnico, Milano, Italy
Andreeva, L. N.
Institute of High Molecular Weight Compounds, Russian
Academy of Sciences, St. Petersburg, Russian Federation
Andrews, R. J.
Chemical and Materials Engineering Department, University of
Kentucky, Lexington, Kentucky, USA
Bai, F.
The Maurice Morton Institute of Polymer Science, Univeristy
of Akron, Akron, USA
Bareiss, R. E.
Editorial Office, Macromolecular Chemistry and Physics,
Mainz, FR Germany
Barrales-Rienda, J. M.
Instituto de Ciencia y Tecnologia de Polimeros, Madrid, Spain
Bello, A.
Instituto de Ciencia y Tecnologia de Polimeros, Madrid, Spain
Bello, P.
Instituto de Ciencia y Tecnologia de Polimeros, Madrid, Spain
Bloch, D. R.
Lakeshore Research, Racine, Wisconsin, USA
Brandrup, J.
Wiesbaden, FR Germany
Calhoun, B. H.
The Maurice Morton Institute of Polymers Science, University
of Akron, Akron USA
Casassa, E. F.
Department of Chemistry, Cameagie-Mellon University, Pitts-
burgh, Pennsylvania, USA
Cheng, S. Z. D.
The Maurice Morton Institute of Polymer Science, University
of Akron, Akron, Ohio, USA
Chiu, F.-C.
The Maurice Morton Institute of Polymer Science, University
of Akron, Akron, Ohio, USA
Cho, J.
Polymer Science and Engineering Department: Dankook
University, Seoul, South Korea
Collins, E. A.
Avon Lake, Ohio, USA
Daniels, C. A.
The Geon Company, Avon Lake, Ohio, USA
DeLassus, P. T.
The Dow Chemical Company, Freeport, Texas, USA
Dixon, K. W.
Akzo Nobel Chemicals, Inc., Dobbs Ferry, New York, USA
Elias, H.-G. >.?
Michigan Molecular Institute, Midland, Michigan, USA
Fink, G.
Max-Planck-Institut fur Kohlenforschung, Mtilheim an der
Ruhr, FR Germany
Fink, H.-P.
Fraunhofer Institut fur angewandte .Polymerforschung, Teltow-
Seehof, FR Germany
Fouassier, J. P.
Laboratoire de Photochimie G&&ale, Ecole Nationale
Superieure de Chimie, Mulhouse, France
Fu, Q.
The Maurice Morton Institute and Department of Polymer
Science, University of Akron, Akron, Ohio, USA
Furuta, I.
Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie,
Ganster, J.
Fraunhofer Institute for Applied Polymer Research, Teltow-
Seehof, Germany
Greenley, R. Z.
Monsanto Corporation (retired), St. Louis, Missouri, USA
Grulke, E. A.
Chemical and Materials Engineering, University of Kentucky,
Lexington, Kentucky, USA
Goh, S. H.
Department of Chemistry, National University of Singapore,
Singapore
Guzmin G. M.
Instituto de Ciencia y Tecnologia de Polimeros, Madrid,
Spain
Hill, D. J. T.
Department of Chemistry, University of Queensland, St. Lucia,
Australia
Hiltner, A.
Department of Macromolecular Science, School of Engineering
Case Western University, Cleveland, Ohio, USA
Inomata, K.
Department of Polymer Chemistry, Tokyo Institute of Technol-
ogy, Ookayama, Meguro-ku, Tokyo, Japan
Iwama, M.
Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie,
Japan
Jenkins, A. D.
School of Chemistry, Physics and Environmental Science,
University of Sussex, Brighton, Sussex, UK
Jenkins, J.
School of Chemistry, Physics and Environmental Science,
University of Sussex, Brighton, Sussex, UK
V
vi CONTRIBUTORS
Johnson, M. Muck, K.-F.
Chemistry/Physics Library, University of Kentucky, Lexington,
Kentucky, USA
Ticona GmbH, Kelsterbach, FR Germany
Nagai, S.
Kamachi, M. Plastics Technical Association, Osaka, Japan
Department of Applied Physics and Chemistry, Fukui Uni-
versity of Technology, Gakuen, Fukui, Japan
Nordmeier, E.
Kerbow, D. L.
Physikalische Chemie, Universitat Osnabriick, Osnabrtick
FR Germany
DuPont Fluoroproducts, Wilmington, Delaware, USA
ogo, Y.
Kimura, S.-I.
Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie,
Japan
Research Institute for Solvothermal Technology, Hayashi,
Takamatsu, Kagawa, Japan
Orwoll, R. A.
Korte, S. College of William and Mary, Williamsburg, Virginia, USA
Zentrale Ferschung, Bayer AG, Leverkunsen, FR Germany
Pauly, S.
Krause, S.
Department of Chemistry, Rensselaer Polytechnic Institute,
Troy, New York, USA
Fachlaboratorium fur Permeationspriifung, Wiesbaden,
FR Germany
Kurata, M.
Institute for Chemical Research, Kyoto University, Uji, Kyoto,
Japan
Peebles, L. H., Jr.
Chemistry Division, Naval Research Laboratory, Washington,
DC, USA
Perera, M. C. S.
Lechner, M. D.
Physikalische Chemie, Universitat Osnabriick, Osnabrtick, FR
Germany
Magnetic Resonance Facility, School of Science, Griffith
University, Nathan, Australia
Leonard, J.
Porzio, W.
Department de Chimie and CERSIM, Universite Laval,
Quebec, Canada
Instituto di Chimica delle Macromolecole de1 C.N.R., Milano,
Italy
Li, F.
Pyda, M.
The Maurice Morton Institute of Polymer Science, University
of Akron, Akron, Ohio, USA
Liggat, J.
Department of Chemistry, University of Tennessee, Knoxville,
Tennessee: USA
Quirk, R. P.
Department of Pure and Applied Chemistry, University of
Strathclyde, Glasgow, Scotland
The Maurice Morton Institute of Polymer Science, University
of Akron, Akron, Ohio, USA
Lindemann, M.
Riande, E.
Greenville, South Carolina, USA
Instituto de Ciencia y Tecnologia de Polimeros, Madrid,
Spain
Luft, G.
Institut fur Chemische Technologie, Technische Hochschule,
Darmstadt, FR Germany
Richter, W. J.
Max-Planck-Institut fur Kohlenforschung, Miilheim an der
Magill, J. H.
School of Engineering, University of Pittsburgh, Pittsburgh,
Pennsylvania, USA
Ruhr, FR Germany
Rothe, M.
McKenna, T. F.
University of Ulm, Ulm, FR Germany
Rule, M.
Centre Nationale de la Recherche Scientifique, Laboratoire de
Chimie et Pro&d& de Polymerisation/Departement Genie des
Pro&d&, Villeurbanne, France
Mehta, R. H.
DuPont Nylon, Chattanooga, Tennessee, USA
Coca Cola Company, Atlanta, Georgia,
Salort, J. F.
Madrid, Spain
Salom, C.
Meille, S. V.
Dipartimento di Chimica de1 Politecnico, Milano, Italy
Metanomski, W. V.
Chemical Abstracts Service, Columbus, Ohio, USA
Escuela TCcnica Superior de Ingenieros Aeronauticos, Uni-
versidad Politecnica, Madrid, Spain
Sanchez, I. C.
Chemical Engineering Department, University of Texas at
Austin, Austin, Texas, USA
Michielsen, S. Santos, A. M.
School of Textile and Fiber Engineering, Georgia Institute of
Technology, Atlanta, Georgia, USA
Faculdade de Engenharia Quimica de Lorena - FAENQUIL,
Lorena, Sao Paulo, Brazil
Miller, R. L. Schoff, C. K.
Michigan Molecular Institute, Midland, Michigan, USA PPG Industries, Allison Park, Pennsylvania, USA
Morita, Y. Schuld, N.
Japan Atomic Energy Research Institute, Takasaki,
Gunma-ken, Japan
Institut fur Physikalische Chemie, Universitat Mainz, Mainz,
FR Germany
USA
Seferis, J. C.
Chemical Engineering Department, University of Washington,
Seattle, Washington, USA
Seguchi, T.
Japan Atomic Energy Research Institute, Takasaki, Gunma-ken,
Japan
Schrader, D.
The Dow Chemical Company, Midland, Michigan, USA
Sperati, C. A.
Chemical Engineering Department, Ohio University, Athens,
Ohio, USA
Steinmeier, D. G.
Physikalische Chemie, UniversitHt Osnabtick, Osnabriick,
FR Germany
Tsunashima, Y.
Institute for Chemical Research, Kyoto University, Uji, Kyoto,
Japan
Tsvetkov, N. V.
Institute of High Molecular Weight Compounds, Russian
Academy of Science, St. Petersburg, Russian Federation
Tsvetkov, V. N.
Institute of High Molecular Weight Compounds, Russian
Academy of Science, St. Petersburg, Russian Federation
Ueda, A.
Osaka Municipal Technical Research Institute, Morinomiya,
Joto-ku, Osaka, Japan
Cont ri but ors vii
Wagener, K. B.
Department of Chemistry and Center for Macromolecular
Science and Engineering, University of Florida, Gainesville,
Florida, USA
Whiteman, N. F.
The Dow Chemical Company, Freeport, Texas, USA
Witenhafer, D. E.
Dublin, Ohio, USA
Wolf, B. A.
Institut fiir Physikalische Chemie, UniversitPt Mainz, Mainz,
FR Germany
wu, s.
E. I. DuPont de Nemours, Central Research and Development
Department, Experimental Station, Wilmington, Delaware
Wunderlich, B.
Department of Chemistry, University of Tennessee, Knoxville,
Tennessee, USA
Wunderlich, W.
ROHM GmbH, Darmstadt, FR Germany
Yamada, B.
Department of Applied Chemistry, Faculty of Technology,
Osaka City University, Sumiyoshi, Osaka, Japan
Zhu, L.
The Maurice Morton Institute of Polymer Science, University
of Akron, Akron, Ohio, USA
Preface
The purpose of the Polymer Handbook is to bring together
the data and constants needed in theoretical and experi-
mental polymer research. All polymer researchers have
experienced the frustration of searching for data in the ever-
expanding polymer literature and know the difficulties
involved in trying to locate a particular constant that is
buried in a long journal article. The contributors to this
Handbook have taken on the arduous task of searching the
literature and compiling the data and constants that polymer
chemists, polymer physicists, and polymer engineers are
likely to need.
I
The 520 and odd tables in this Handbook are divided into
eight sections. The first lists the IUPAC nomenclature rules
for polymers and the International System of Units.
Although several naming conventions exist in the technical
literature, IUPAC names permit a consistent listing of all
polymers. Section II contains data and constants needed for
polymer synthesis, kinetic mechanisms, and thermody-
namic studies of polymerization and depolymerization
reactions. Sections III and IV contain physical constants
of monomers, solvents, and oligomers. Section V lists the
I
physical constants of many important commercial poly-
mers. Section VI and VII cover the solid state properties of
polymers and the properties of polymer solutions. Section
VIII of the Handbook lists the commonly used abbrevia-
tions or acronyms for polymers and Chemical Abstract
Registry Numbers, and gives suggestions for electronic data
searching for polymer information. This section should also
be consulted in the few cases where contributors have not
used IUPAC nomenclature.
As in the previous editions, the Polymer Handbook
concentrates on synthetic polymers, poly(saccharides) and
derivatives, and oligomers. Few data on biopolymers are
included. Spectroscopic data as well as data needed by
engineers and designers, such as mechanical and rheologi-
cal data, are minimized, since many excellent compilations
exist elsewhere. Only fundamental constants and para-
meters that refer to the polymer molecule, that describe the
I solid state of polymer molecules, or that describe polymer
1
solutions, were compiled. Constants that depend on
processing conditions or on sample history were not
emphasized, as they can be found in existing plastics
I
handbooks and encyclopedias.
A critical evaluation of the values published in the
literature was not attempted, since such a task would have
required an inordinate amount of time and a sizable staff.
Therefore, the users of this Handbook should consult the
original literature for details when in doubt about the
validity of any data. (The authors of the individual tables
were nevertheless requested to eliminate obviously erro-
neous data from otherwise complete compilations.)
The Fourth Edition revisions have focused on data
generated in the ten years since the publication of the Third
Edition. Therefore, a completely revised Polymer Hund-
book has been prepared. We have added new tables and
incorporated a large amount of new data into existing
tables. As a result, the Fourth Edition contains approxi-
mately twenty-five percent more data, and the number of
pages has increased from about 1850 in the Third Edition to
about 2250.
We hope that this new edition will be as useful to the
polymer research community as the three earlier editions
and that many of the Polymer Handbooks previous users
will also obtain the Fourth Edition for their laboratory and
library.
The publisher plans a CD-ROM for the Polymer
Handbook in the near future. We would be grateful if our
contributors and users send us any new data they
accumulate in the course of their research, and any errors,
misprints, omissions and other flaws. We will pass on such
data to the publisher, for the polymer database, and for
.future editions of this Handbook.
We would like to thank all of the contributors to the
Polymer Handbook for their help and continued patience.
The staff at John Wiley, especially Carla Fjerstad, Shirley
Thomas, and Jacqueline Kroschwitz, have provided excel-
lent help and support in getting all the work done. We hope
that the outstanding efforts of all these people will find due
appreciation among the users of this Handbook.
July, 1998 J. Brandrup
E. H. Immergut
E. A. Grulke
A. Abe
D. R. Bloch
i x
Contents
I. NOMENCLATURE RULES - UNITS
Nomenclature, I/l
W K Metanomski
Units, I/13
J. Brandrup
II. POLYMERIZATION AND DEPOLYMERIZATION
Decomposition Rates of Organic Free Radical
Initiators, II/l
K. W! Dixon
Propagation and Termination Constants in Free
Radical Polymerization II/77
M. Kamachi and B. Yamada
Transfer Constants to Monomers, Polymers,
Catalysts and Initiators, Solvents and Additives,
and Sulfur Compounds in Free Radical
Polymerization, II/97
A. Uedu and S. Nagai
Photopolymerization Reactions, II/169
J. P Fouassier
Free Radical Copolymerization Reactivity Ratios,
II/181
R. Z. Greenley
Q and e Values for Free Radical Copolymerizations
of Vinyl Monomers and Telogens, II/309
R. Z. Greenley
Patterns of Reactivity (U,V) Parameters for the
Prediction of Monomer Reactivity Ratios and
Transfer Constants in Radical Polymerization,
II/321
A. D. Jenkins and J. Jenkins
Copolymerization Parameters of Metallocene-
Catalyzed Copolymerizations, II/329
G. Fink and W J. Richter
Rates of Polymerization and Depolymerization,
Average Molecular Weights, and Molecular Weight
Distribution of Polymers, II/339
L. H. Peebles, Jr:
Heats and Entropies of Polymerization, Ceiling
Temperatures, Equilibrium Monomer
Concentrations, and Polymerizability of
Heterocyclic Compounds, II/363
J. Leonard
Activation Energies of Propagation and Termination
in Free Radical Polymerization, II/415
T F McKenna and A. M. Santos
Activation Volumes of Polymerization Reactions,
II/429
G. Luft and Y Ogo
Activation Enthalpies and Entropies of Stereocontrol
in Free Radical Polymerizations, II/445
H. -G. Elias
Products of Thermal Degradation of Polymers,
II/451
J. J. Liggat
Radiation Chemical Yields: G Values, II/481
M. C. S. Perera and D. J. I? Hill
Ill. PHYSICAL PROPERTIES OF MONOMERS
AND SOLVENTS
Physical Properties of Monomers, III/l
D. R. Bloch
Isorefractive and Isopycnic Solvent Pairs, III/43
H. -G. Elias
Refractive Indices of Common Solvents, III/55
H. -G. Elias
Physical Constants of the Most Common Solvents
for Polymers, III/59
D. R. Bloch
IV. PHYSICAL DATA OF OLICOMERS
Physical Data of Oligomers, IV/l
M. Rothe
V. PHYSICAL CONSTANTS OF SOME IMPORTANT
POLYMERS
Physical Constants of Rubbery Polymers, V/l
I. Furuta, S.-I. Kimura, and M. Iwama
Physical Constants of Poly(ethylene), V/9
L. Zhu, F-C. Chiu, Q. Fu, R. P Quirk, and
S. Z. D. Cheng
Physical Constants of Poly(propylene), V/21
F Bai, R Li, B. H. Calhoun, R. l? Quirk, and
S. Z. D. Cheng
Physical Constants of Fluoropolymers, V/31
D. L. Kerbow and C. A. Sperati
Physical Constants of Poly(acrylonitrile), V/59
S. Korte
Physical Constants of Poly(vinyl chloride), V/67
E. A. Collins, C. A. Daniels, and D. E. Witenhafer
xi
xii CONTENTS
Physical Constants of Poly(vinyl acetate), V/77
M. K. Lindemann
Physical Constants of Poly(methy1 methacrylate),
V/S7
W Wunderlich
Physical Constants of Poly(styrene), V/91
D. Schrader
Physical Constants of Poly(oxymethylene), V/97
K.-F Muck
Physical Constants of Poly(oxyethylene-
oxyterephthaloyl), (Poly(ethylene terephthalate)),
V/l13
M. Rule
Physical Constants of Poly(oxytetramethylene-
oxyterephthaloyl) and Copolymers with
Tetramethylene Oxide Thermoplastic Elastomers,
V/l19
K. B. Wagener
Physical Constants of Various Polyamides:
Poly[imino(l-oxohexamethylene)], (Polyamide 6)
Poly(iminoadipoyl-iminohexamethylene),
(Polyamide 66), Poly(iminohexamethylene-
iminosebacoyl), (Polyamide 610),
Poly[imino(l-oxododecamethylene)],
Poly(amide 12), V/l21
R. H. Mehta
Physical Constants of Cellulose, V/l35
J . Ganster and H.-R Fink
Physical and Mechanical Properties of Some
Important Polymers, V/l59
R T DeLassus and N. E Whiteman
VI. SOLID STATE PROPERTIES
Crystallographic Data and Melting Points for
Various Polymers, VI/l
R. L. Miller
Glass Transition Temperatures of Polymers, VI/193
R. J . Andrews and E. A. Grulke
Rates of Crystallization of Polymers, VI/279
J . H. Magi11
Isomorphous Polymers Pairs, VI/399
G. Allegra, S. V Meille, and W? Porzio
Miscible Polymers, VI/409
S. Krause, S. H. Goh
Heat Capacities of High Polymers, VI/483
M. Pyda and B. Wunderlich
Surface and Interfacial Tensions of Polymers,
Oligomers, Plasticizers, and Organic Pigments, VI/521
s. wu
Permeability and Diffusion Data, VI/543
S. Paul y
Refractive Indices of Polymers, VI/571
J . C. Seferis
Radiation Resistance of Plastics and Elastomers,
VI/583
T Seguchi and Y Morita
PVT Relationships and Equations of State of
Polymers VI/591
J . Cho and I . C. Sanchez
VII. SOLUTION PROPERTIES
Viscosity - Molecular Weight Relationships and
Unperturbed Dimensions of Linear Chain
Molecules, VII/l
M. Kurata and X Tsunashima
Sedimentation Coefficients, Diffusion Coefficients,
Partial Specific Volumes, Frictional Ratios, and
Second Virial Coefficients of Polymers in Solution,
VII/85
M. D. Lechnei; L. Nordmeier and D. G. Steinmeier
Polymolecularity Correction Factors, VII/215
R. E. Bareiss
Polymer-Solvent Interaction Parameters, VII/247
N. Schuld and B. A. Wolf .
Concentration Dependence of the Viscosity of Dilute
Polymer Solutions: Huggins and Schulz-Blaschke
Constants, VII/265
C. K. Schoff
Theta Solvents, VII/291
H. -G. Elias
Fractionation of Polymers, VII/327
J . M. Barrales-Rienda, A. Bello, R Bello, and
G. M. Guzman
Solvents and NonSolvents for Polymers, VII/497
D. R. Bloch
Specific Refractive Index Increments of Polymers in
Dilute Solution, VII/547
S. Michielsen
Particle Scattering Factors in Rayleigh Scattering,
VII/629
E. F Casassa
Dipole Moments of Polymers in Solution, VII/637
J . E Salort, C. Salom, and E. Riande
Heat, Entropy and Volume Changes for Polymer-
Liquid Mixtures, VII/649
R. A. Orwol l
Heats of Solution of Some Common Polymers,
VII/671
R. A. Onvol l
Solubility Parameter Values, VII/675
E. A. Grulke
Optically Active Polymers, VII/715
K. I nomata and A. Abe
Anisotropy of Segments and Monomer Units of
Polymer Molecules, VII/745
V N. Tsvetkov, L. N. Andreeva, and N. I ? Tsvetkov
Contents ** Xl11
Gelation Properties of Polymer Solutions, VII/765
A. Hiltner
Chemical Abstract Registry Numbers and Online
Database Searching for Polymer Literature, VIII/25
M. Johnson and E. A. Grulke
VIII. ABBREVIATIONS OF POLYMER NAMES AND
CHEMICAL ABSTRACT NUMBERS IX. Index, IX/l
Abbreviations for Thermoplastics, Thermosets,
Fibers, Elastomers and Additives, VIII/l
H.-G. Elias
c
SECTION I
NOMENCLATURE RULES-UNITS
Nomenclature
W. V. Metanomski
Chemical Abstracts Service, Columbus, Ohio, USA
A. Introduction
B. IUPAC Recommendations
1. Source-Based Nomenclature
1.1. Homopolymers
1.2. Copolymers
1.3. Nonlinear Macromolecules &
Macromolecular Assemblies
2. Structure-Based Nomenclature
2.1. Regular Single-Strand Organic Polymers
2.2. Regular Double-Strand Organic Polymers
2.3. Regular Single-Strand Inorganic and
Coordination Polymers
2.4. Regular Quasi-Single-Strand Coordination
Pol ymer s
2.5. Irregular Single-Strand Organic Polymers
C. Use of Commonand Semisystematic Names
D. Chemical Abstracts (CA) Index Names
E. Polymer Class Names
F. References
l-l
I - 1
I-2
I-2
I-2
I-3
I-3
I-6
I-6
I-7
I-7
I-8
I-8
l -l 1
I-1 2
A. INTRODUCTION
Macromolecular (polymer) nomenclature has an almost
50-year history. As early as 1949 there existed a
Subcommission on Nomenclature within the International
Union of Pure and Applied Chemistry (IUPAC) under the
chairmanship of Maurice L. Huggins. The Subcommission
was part of the IUPAC Commission on Macromolecules,
chaired then by Herman F. Mark. Other notable pioneers in
polymer science, Jan Joseph Hermans, Otto Kratky, Harry
W. Melville, and George J. Smets, were members of the
/
Commission.
The Subcommission produced its first official report in
1952. It recognized then, what is just as true today, that the
practice in the field of small molecules of providing
-rigdrous definitions is impractical for polymers. The latter
consist of molecules not necessarily exactly of the same
size, chemical composition, or structure. The differences
result from the presence of end groups, branches, variation
in orientation of monomeric units, and irregularity in the
sequence of different types of units.
The American Chemical Society (ACS) Division of
Polymer Chemistry established its Nomenclature Commit-
tee in 1963 to try to unify earlier attempts to name polymers
in some coherent way. Their first major project resulted in a
structure-based nomenclature for regular linear polymers,
first published in ACS Polymer Preprints in 1967, adopted
by Chemical Abstracts in 1968, and incorporated in IUPAC
recommendations in 1975 [ 11.
When the IUPAC Commission on Macromolecules was
elevated to become the IUPAC Division of Macromolecular
Chemistry, the latter in turn established its Commission on
Macromolecular Nomenclature in 1968.
The Commission in the course of its nearly 30 years of
existence produced a series of major documents that have
shaped modern nomenclature and terminology of polymer
science. The recommendations are being published in the
IUPAC official journal, Pure and Applied Chemistry, and
occasionally are republished in the form of a Compen-
dium which groups all the currently valid documents in a
single volume. The Commission published its Compen-
dium of Macromolecular Nomenclature in 1991 [2]. The
book, which IUPAC has designated the Purple Book, in
analogy to other IUPAC books (Blue - organic, Red
- inorganic, Orange - analytical, Green- physical,
and Gold - overall chemistry), has the two most basic
macromolecular nomenclature recommendations: nomen-
clature of regular single-strand organic polymers and
source-based nomenclature for copolymers. In more
recent years, the Commission extended that basic nomen-
clature to double-strand (ladder and Spiro) organic poly-
mers, irregular and crosslinked polymers, and polymer
blends and interpenetrating networks.
In this article, the basic structure-based and source-based
nomenclature of polymers is explained and illustrated in
some detail. The continuing use of common and
semisystematic nomenclature with reference to specific
tables in this Handbook is highlighted. The current
Chemical Abstracts (CA) index names [3] are compared
and contrasted with the IUPAC practice and typical names
employed in the polymer journals and textbooks.
6. IUPAC RECOMMENDATIONS
Since polymers, unlike low-molecular-weight compounds,
have no uniform structure and are mixtures of macro-
molecules of different length and different structural
I/l
I/2
NOMENCLATURE
arrangement, their graphical representation and their names
require a special approach.,
Often enough, the structure of the polymer has not been
sufficiently characterized and the researcher cannot draw its
chemical structure. Consequently, no name of the polymer
reflecting its structure is possible.
A polymerization reaction for a polymer formed from
a monomer such as vinyl chloride can schematically be
represented by
nCH2=CHCl + +CH2-CHCl j,,
That shows an idealized product. In fact, however, the
polymer consists of long-chains of various lengths. The
repeating units, -CHz-CHCl-, are not necessarily all
uniquely oriented and joined in a regular fashion as shown
in the idealized structure above. In addition to head-to-
tail links
-CH2-CHCl-CH2-CHCl-
other links such as head-to-head
-CHCl-CH2-CH2-CHCl-
and tail-to-tail
-CH2-CHCl-CHCl-CH2-
can occur, and the exact sequence of all these repeating
units usually is not known.
This becomes even more complicated when a copolymer
is derived from more than one monomer, such as styrene
and methyl acrylate, which contribute two constitutional or
monomeric units:
- YH- CH2-
-YH-cH2-
$=o
b-CH,
They can combine into a polymeric chain, resulting in
many types such as unspecified, statistical, random,
alternating, periodic, block, or graft copolymers.
Because the exact structure of the polymer is not always
known, two systems of naming polymers exist:
source-based nomenclature,
structure-based nomenclature.
1. Source-Based Nomenclature
1.7. Homopolymers Homopolymers are derived froin
only one species of monomer, which may be the actual
starting reactant (or source), or be a hypothetical monomer
if the homopolymer is formed by a modification of another
homopolymer.
The name of the polymer is formed by attaching the
prefix poly to the name of the actual or assumed
monomer, or the starting reactant (source), from which the
polymer is derived.
Examples: poly(acrylic acid)
polyacrylonitrile
polybutadiene
polyethylene
poly(methy1 methacrylate)
poly(methy1 vinyl ether)
polystyrene
poly(tetrafluoroethylene)
poly(viny1 alcohol)
poly(viny1 acetate)
poly(viny1 chloride)
poly(vinylidene dichloride)
Parentheses are used when the name of the monomer
consists of two or more words, and when the monomer has
substituents.
These are all olefinic type reactants, from which two
carbon atoms originally linked by a double bond form a
bivalent group:
R-CH=CH-R1 + -CHR-CHR I-
where R and R represent a hydrogen atom or a substituent
group. Many of these are joined, in turn, to each other but
their exact orientation or sequence is seldom known.
On the other hand, different polymers derived from a
single monomer and having identical constitutional units
can still be differentiated by additional information, such as
average molecular weight and other chemical and physical
characteristics.
7.2. Copo/ymers For copolymers, the names of mono-
mers are cited after the prefix poly. In addition, an
italicized connective (infix) is placed between the names of
monomers to denote the kind of sequential arrangement by
which the constitutional (monomeric) units, derived from
each monomer, are related in the structure [4].
Seven types of sequence arrangements are listed with
their corresponding connectives:
Type
Connective
unknown or unspecified -co-
statistical (obeying known statistical laws) -stat-
random (obeying Bernoullian distribution) -ran-
alternating (for two monomeric units) -ah-
periodic (ordered sequence of more than two) -per-
block (linear arrangement of blocks) -block-
graft (side blocks chains connected to -graft-
main chain)
Examples: poly[styrene-co-(methyl methacrylate)]
poly(styrene-stat-acrylonitrile-stat-butadiene)
poly[ethylene-ran-(vinyl acetate)]
poly[(ethylene glycol)-alt-(terephthalic acid)]
poly[formaldehyde-per-(ethylene oxide)-per-
(ethylene oxide)]
polystyrene-block-polybutadiene
polybutadiene-graft-polystyrene
Structure-Based Nomenclature
I/3
The names of the monomers are those common or
semisystematic names that are encountered most often in
the literature of polymer science. The order of citation of
monomers in copolymer names is arbitrary.
An equally acceptable alternative scheme for naming
copolymers utilizes the prefix copoly, followed by
citation of the names of the monomers, separated by an
oblique stroke (a solidus). Parentheses are not needed to
enclose monomer names consisting of two or more words.
Examples: copoly(styrene/methyl methacrylate)
stat-copoly(styrene/acrylonitrile/butadiene)
run-copoly(ethylenelviny1 acetate)
alt-copoly(ethylene glycol/terephthalic acid)
per-copoly(formaldehyde/ethylene oxide/ethy-
lene oxide)
block-copoly(styrene-butadiene)
graft-copoly(butadiene-styrene)
1.3. Nonlinear Macromolecules and Macromolecular
Assemblies Most recently, the source-based nomenclature
has been extended for non-linear macromolecules and
macromolecular assemblies [5]. The non-linear macromo-
lecules comprise branched, graft, comb, star, cyclic, and
network macromolecules. The macromolecular assemblies
comprise polymer blends, interpenetrating polymer net-
works, and polymer-polymer complexes.
The following italicized qualifiers can be used as both
prefixes (e.g., blend-, net-) and infixes (connectives) (e.g.,
-blend-, -net-) to designate the skeletal structure of non-
linear macromolecules or macromolecular assemblies:
Type Connective
cyclic
branched, unspecified
short-chain-branched
long-chain-branched
branched with branch point
of functionality f
comb
star
star with f arms
network
crosslink
polymer blend
interpenetrating polymer network
semi-interpenetrating polymer network
polymer-polymer complex
cycle
branch
sh-branch
l -branch
f-branch
comb
star
f-star
net
L (Greek iota)
blend
ipn
si pn
compl
In naming non-linear homopolymer molecules, the
italicized prefix for the skeletal structure of the macro-
molecule is placed before the source-based name of the
constituent linear chain.
Assemblies of macromolecules held together by non-
covalent bonds are named by a combination of the names of
the constituent macromolecules with an italicized con-
nective between them.
Examples: polystyrene-comb-polyacrylonitrile
comb-poly(styrene-stat-acrylonitrile)
polystyrene-comb-[polyacrylonitrile;
poly(methy1 methacrylate)]
4-star-polystyrene
star-(polyA-block-polyB-block-polyC)
star-(polyA; polyB; polyC)
star-(polyacrylonitrile; polystyrene)
(Ad, 100000 : 20000)
net-polystyrene+divinylbenzene
net-poly[styrene-alt-(maleic anhydride)]-
L-(ethylene glycol)
polystyrene-blend-poly(2,6-dimethylphenol)
poly(methy1 methacrylate)-blend-poly(n-butyl
acrylate)
(net-polystyrene)-sipn-poly(viny1 chloride)
[net-poly(styrene-stat-butadiene]-ipn-[net-
poly(ethy1 acrylate)
2. Structure-Based Nomenclature
2.1. Regular Single-Strand Organic Polymers For
regular organic polymers which have only one species of
constitutional repeating unit (CRU) in a single sequential
arrangement and consist of single strands only, the name is
poly(constitutional repeating unit),
wherein the repeating group is named as a bivalent organic
group according to the IUPAC nomenclature rules for
organic compounds [l]. Each such repeating group can
consists of simple or substituted subunits such as:
-CH2-
-CH2CH2-
-CH=CH-
-CH2CH2CH2CH2CH2CH2-
-CHCl-CH2-
-COCH2-CH2-
-COCH2CH2CH2CH2CO-
/-\
--ilk
-o-
OXY
-s- thio
-so2- sulfonyl
-NH- i mi no
-N(CH3)- met hyl i mi no
-NHNH- hydrazo
- N
3
-SiH2-
-Si(CHa)a-
methylene
ethylene
vinylene
hexane- 1,6-diyl
-1 -chloroethylene
1 -oxopropane- 1,3-diyl
adipoyl
1,4-phenylene
cyclohexane- 1,6diyl
piperidine- 1 ,Cdiyl
silanediyl
di met hyl si l anedi yl
Before the total constitutional repeating unit (CRU) can
be given a unique name, a single preferred CRU must be
selected.
References page I - 12
I/4
NOMENCLATURE
For instance, in a polymer such as
-00CH-CHz-0-CH-CH2-OCH-CH2-O-
C l C l C l
it is immediately evident that a three-atom group (oxygen,
chlorine-substituted methylene group, and methylene
group) are being regularly repeated. Yet, the CRU can be
identified in at least three ways
-0-CH-CH2- -00CH2-CH- -CH2-O-CH-
I
C l
or
Cl Or C l
To obtain a unique name based on a preferred CRU, several
rules have to be applied. Rules have been developed to
specify both seniority among subunits, that is, the point at
which to begin writing the CRU, and also the direction in
which to move along the chain from left to right to reach
the end of the chain.
The order of seniority among the types of bivalent
groups that are parts of the chain of a single-strand polymer
is
a . heterocycles, e.g., piperidine- 1,6diyl: -N
3-
thiophene-2,5-diyl: e
b. heteroatomic acyclic groups, e.g., oxy: -0-,
sulfonyl: -SOz-, imino: -NH-
C. carbocycles, e.g., 1,4-phenylene:
a-
cyclobutane-1,3-diyl: u
d. carbon-containing acyclic groups,
e.g., I-chloroethylene: -CHCl-CHz-
propane-1,3-diyl: -CHz-CH2-CHz-
Within each structural type, the seniority is established by
further criteria:
a . for heterocycles, a ring system containing nitrogen is
senior to a system containing a hetero atom other
than nitrogen, with further descending order of
seniority governed by the greatest number of rings in
the ring system, the largest individual ring in the ring
system, the largest number of hetero atoms, and the
greatest variety of hetero atoms;
b . for heteroatomic acyclic chains, oxygen is senior to
sulfur, sulfur to nitrogen, nitrogen to phosphorus,
phosphorus to silicon, silicon to germanium, etc.;
c. for carbocycles, a three-ring system is senior to a
two-ring system, a two-ring system containing two
6-membered rings is senior to one containing a 5-
and a 6-membered rings, a fused two-ring system
(two atoms common to both rings) is senior to a
Spiro two-ring system (one atom in common), and an
unsaturated ring is senior to a saturated ring of the
same size;
d. for carbon-only acyclic chains, seniority is deter-
mined first by length, then by the number of
substituents, by the ascending order of locants,
and, finally, by the alphabetical order of the names of
the substituent groups.
In all cases, the basic seniority rules apply only to those
atoms or groups of atoms that are in the main chain. The
kinds of substituents on the main chain (whether acyclic
carbon-only groups, or hetero-atom-containing groups, or
any ring systems) do not affect the selection of the CRU,
unless identical basic subunits in the chain have to be
further differentiated by the number of substituents and
their alphabetical order, but not by the type of the
substituent.
If completely identical subunits are separated by other
subunits, the direction of citation is determined by the
shorter part between them.
The preferred CRU is the one beginning with the subunit
of highest seniority. To establish direction, one proceeds
from this subunit to the neighboring subunit of the same
or next in seniority. In the example of a poly(chloro-
ethylene oxide), shown above, where a regularly repeating
structure has been assumed, the subunit of the highest
seniority is the oxygen atom and the subunit next in
seniority is a substituted -CHz-CH2-. The substituted
subunit, -CHCl-CH2-, is oriented in such a way that the
substituent, chlorine atom, is assigned the lowest locant (1
rather than 2). The CRU is written to read from left to right.
Thus, the preferred CRU is
-00CH-CH2-
and the polymer
+O-TCH2f;;
C l
is named
poly[oxy( 1-chloroethylene)]
The second example:
fN-F-NH
C l
poly[(methylimino)methyleneimino- 1,3-phenylene]
illustrates a polymer whose CRU starts with a substituted
nitrogen atom and proceeds through the shortest path to
the unsubstituted nitrogen atom and then through a
carbocycle.
The chemical structure of the CRU is enclosed in
parentheses or brackets. While dashes representing chemi-
cal bonds may be omitted within the formula unless
necessary for clarity, at the ends of the CRU, dashes must
be shown. They are drawn across the enclosing marks.
St r uc t ur e-Based Nomenc l at ur e
115
The third example: symbol CY denoting the left-hand end group and the symbol
o denoting the other end group.
poly(pyridine-3,5diylcarbonyloxymethylene)
Example:
I--\
shows a polymer, whose CRU starts with a heterocycle and
then proceeds through a substituted carbon atom toa hetero
atom.
If the end groups of the chain are known, they may be
specified by adding prefixes to the polymer name, with the
a-(trichloromethyl)-o-chloropoly( 1 ,Cphenylene-
methylene)
The following table compares and contrasts structure-
based and source-based names of some common polymers.
Structure Structure-based name Source-based or trivial name
fCH2CH2fn
t$CH,-),
+C%Mbjn
+C=CHCH2CH2&
Poly(methylene)
Poly(propylene)
Poly(l,l-dimethylethylene)
Poly( l-methyl- 1-butenylene)
f ;zH21;; Poly( 1-phenyletbylene)
bN
ti:"""2j;;
OCOCH3
fCWH2fn
fCWFz+n
+9CH2+,
OY
C3H7
t CPWHdi
COOCH3
f0CHzCH2fn
0
I I
f NH- C- (CWs-2;;
0
Poly(l-chloroethylene)
Poly( 1-cyanoethylene)
Poly( 1 -acetoxyethylene)
Poly( 1,l -difluoroethylene)
Poly(difluoromethylene)
Poly[(2-propyl-1,3-dioxane-4,6-diyl)methylene]
Poly[l-(methoxycarbonyl)-1-methylethylene]
Poly(oxyethylene)
Poly(oxy-1,4-phenylene)
Poly [imino( 1-oxohexane-1,6-diyl)]
?
Poly(E-caprolactam)
+OCH2CH2&
-
-0
\ , k-);; Poly(oxyethyleneoxyterephtbaloy1) Poly(ethylene terephthalate)
0 0
--(NH- &CH2)&NH(CH2)& Poly(iminoadipoyliminohexamethylene) Poly(hexamethylenediamine-alt-adipic acid)
or poly(hexamethylene adipamide)
- CH- CH- CHCH,?
O=L\ , C = O &Hs
Poly[(2,5-dioxotetrahydrofuran-3,4-diyl)( 1-phenylethylene)] Poly(maleic anhydride-alt-styrene)
Polyethylene
Polypropene
Polyisobutylene
Polyisoprene
Polystyrene
Poly(viny1 chloride)
Polyacrylonitrile
Poly(viny1 acetate)
Poly(vinylidene fluoride)
Polytetrafluoroethylene
Poly(viny1 butyral)
Poly(methy1 metbacrylate)
Poly(ethylene oxi de)
Poly(phenylene oxide)
0
References page I - 12
116
NOMENCLATURE
2.2. Regular Double-Strand Organic Polymers In a
double-strand polymer, the macromolecules consist of an
uninterrupted sequence of rings with adjacent rings having
two or more atoms in common (a ladder polymer) or one
atom in common (a Spiro polymer).
As for a single-strand polymer, a single preferred
constitutional repeating unit (CRU) must be selected in
order to obtain a unique name [6]. The CRU is usually a
tetravalent group denoting attachment to four atoms and is
named according to the usual rules of organic nomen-
clature. Again, the name of the polymer is in the form of
poly(constitutiona1 repeating unit)
Since the polymer has a sequence of rings, in order to
identify a preferred CRU, the rings must be broken by
observing the following criteria in decreasing order of
priority:
a . minimize the number of free valences in the CRU,
b . maximize the number of most preferred hetero atoms
in the ring system,
c . retain the most preferred ring system, and
d . choose the longest chain for acyclic CRU.
Further decisions are based on the seniority of ring
systems (indicated in the preceding section), on the
orientation of the CRU to give the lowest free valence
locant at the lower left of the structural diagram, and on
placing the acyclic subunits, if any, on the right side of the
ring system within the CRU.
For a polymer consisting of adjacent 6-membered
saturated carbon rings:
the name of the preferred CRU, which in this case is an
acyclic chain of four carbon atoms with four free valences
at each atom (the lowest at the lower left), is
\ /n
poly(butane-1,4 : 3,2-tetrayl)
The free valence locants are always placed just in front of
the corresponding ending of the tetravalent unit and are
cited in the order
lower-left, upper-left : upper-right, lower-right
that is, in a clockwise direction, the left locants being
separated from the right locants by a colon.
For a more complex ladder polymer consisting of an
alternating sequence of 6-membered sulfur-containing rings
and keto-group containing carbocycles, with two atoms in
common at each junction:
J+jpfJ~:-~
0
the name based on the preferred CRU is
b v
poly(l,4-dithiin-2,3 : 5,6-tetrayl-5,6-dicarbonyl)
Here, by applying the seniority of the rings system, the
heterocycle was left intact, but the carbocycle was broken.
That left two bivalent acyclic subunits (car-bony1 groups),
which according to the rule, have been placed on the right
side of the cyclic subunit, with attachments as in the
original polymer.
Another, still more complex ladder polymer, derived
from the polycondensation of 1,4,5&naphthalenetetra-
carboxylic dianhydride with 1,2,4,5-benzenetetramine:
poly[(7-oxo-7H,lOKbenz[de]imidazo[4,5 : 5,6]benzimi-
dazo [2,1-alisoquinoline-3,4: lO,l l-tetrayl)-lo-carbonyl]
illustrates a six-ring system with four free valences oriented
in such a way that the lowest free valence locant is at lower
left. It is followed within the total CRU by an acyclic group
at the upper right side of the diagram.
For a polymer consisting of regularly repeating adjacent
cyclohexane and 1,3-dioxane rings in a Spiro sequence (one
atom in common at each junction):
the preferred CRU and the name are:
, 0 - CH2
c\
C/
/\
0-CH2
poly(2,4,8,lO-tetraoxaspiro[5.5]undecane-3,3:9,9-tetrayl-9,9-diethylene)
2.3. Regular Single-Strand Inorganic and Coordina-
tion Polymers The names of inorganic and coordination
polymers are based on the fundamentals developed for
organic polymers [7]. As in the nomenclature of organic
polymers, these rules apply to structural representations
Structure-Based Nomenclature
I/7
which may at times be idealized and do not take into
account irregularities, chain imperfections, or random
branching.
A constitutional repeating unit (CRU) is selected and
named. However, because of the basic difference between
the organic and inorganic nomenclature, the subunits of the
CRU are not named as bivalent groups, but as inorganic or
coordination groups indicating covalent and/or coordinate
bonding.
The name of the polymer is the name of the CRU
prefixed by the term poly, cute&, or other structural
indicator. In order to arrive at the preferred CRU, seniorities
of the constitutent subunits are considered as well as the
preferred direction for the sequential citation.
The constituent subunit of the highest seniority must
contain one or more central atoms; bridging groups
between central atoms in the backbone of the polymer are
of lower seniority. This is consistent with the principle of
coordination nomenclature which puts the emphasis on the
coordination center.
Examples of homoatomic backbones are
73
F CH3
fyj;;
--f Ai- AiJ,
C3
A &H
3
catena-poly[dimethyltin] catenu-poly[(difluorosilicon)
(dimethylsilicon)]
More common coordination polymers consist of a
mononuclear central atom with a bridging ligand. The
CRU of such a polymer cites the central atom first, which is
prefixed by its associated non-bridging ligands, followed in
turn by the name of the bridging ligand prefixed by the
Greek letter p:
rH3
fzn-Cl-fii-
Cl
cutenu-poly[(ammine-
chlorozinc)-p-chloro]
7 7H3
e--N%
iI A
3
cutenu-poly[(dihydro-
boron)-p-(dimethylamido)]
Multiple bridging ligands between the pair of central
atoms are cited in alphabetic order. Italicized element
symbols indicating the coordinating atoms in bridging
ligands are cited in the order of direction of the CRU and
are separated by a colon:
cutena-poly[copper-[CL-chloro-bis-p-(diethyl disulfide-S:
S)]-copper-p-chloro]
2.4. Regular Quasi-Single-Strand Coordination
Polymers In a regular quasi-single-strand coordination
polymer, the preferred CRU has one terminal constituent
subunit connected through a single atom to the next CRU
[7]. Such polymers are named as single-strand coordination
polymers:
catenu-poly[palladium-
di-p-chloro]
cutenu-poly[silicon-
di-p-thio]
i >
dBT
\
Cl n
catenu-poly[platinum(~-
bromo-p-chloro)]
cutenu-poly[titanium-
tri-y-chloro]
2.5. h-regular Sing/e-Strand Organic Polymers Irregu-
lar polymers are named by placing the prefix poly before
the structure-based names of the constitutional units,
collectively enclosed in parentheses or brackets, with the
individual constitutional units separated by an oblique
stroke (a solidus) [8]. The stroke indicates the irregular or
unknown sequential arrangement of these units. The dashes
at each end of the formula are drawn fully inside the
enclosing marks to denote that these are not necessarily
terminal bonds of the macromolecule.
For instance, a partially
containing units:
hydrolyzed poly(viny1 acetate)
- CH- CH2- - CH- CH2-
0-CO--H3
and
bH
is represented graphically and named:
t y- CH2- / - y- CH2+
0-CCPCH3 O H
poly( 1-acetoxyethylene/l-hydroxyethylene)
A copolymer of vinyl chloride and styrene joined head-to-
tail is
t CH- CH2- / - CH- CH2f,
Cl
C65
poly( 1 -chloroethylene/l -phenylethylene)
A chlorinated polyethylene consisting of units
- C H - - C - -CH2-
Cl Cl
References page I - 12
118
NOMENCLATURE
is shown and named as
+CHCl-/-CC12-/-CH2- j,
poly(chloromethylene/dichloromethylene/methylene)
C . USE OF COMMON AND SEMISYSTEMATIC NAMES
The main purpose of chemical nomenclature is to identify a
chemical species by means of written or spoken words for a
useful communication among chemists. A systematic
nomenclature arose from the need to provide a relationship
between the structure and the name. In other words, the
reader should be able to deduce and identify the structure
from the name.
Traditional names, however, not necessarily based on
structures, have been widely used for many common
compounds. These are the so-called common, trivial, or
semisystematic names, which are satisfactory for commu-
nication within a given special chemical field.
It was earlier stated that in the macromolecular
nomenclature IUPAC is recommending the use of common
and semisystematic names for monomers in the source-
based polymer names. The structure-based names, on the
other hand, are more related to the structural characteristic
of the polymers. But even there, IUPAC allows for a limited
number of common names for such substituent groups as
allyl and vinyl, and for bivalent groups such as
adipoyl and terephthaloyl.
The authors in this Handbook for the most part are using
the IUPAC-recommended names, or very close variants
thereof. On the other hand, in some compilations such as
Crystallographic Data for Various Polymers (in Section
VI), the author provides an excellent introduction and
explanation of the names used. For some structure-based
names, reflecting constitutional repeating units (CRU),
especially for those with a center of symmetry, the naming
of linking bivalent groups begins with the central subunit
and proceeds in both directions. The IUPAC method selects
the most senior bivalent group and proceeds naming from
left to right.
Examples:
+0-c-0-p-c6~4-S02-p-c6~4*
6
Handbook name: poly(4,4-sulfonyldiphenylene car-
bonate)
IUPAC name: poly(oxycarbonyloxy- 1,4-phenylene-
sulfonyl- 1,4-phenylene)
Handbook name: poly(oxydiethylene succinate)
IUPAC name: poly(oxyethyleneoxyethyleneoxysuc-
cinyl)
In no case, there is any misunderstanding in either case as
to which structure is associated with each name.
Abbreviations and acronyms are also extensively used in
the chemical literature for monomers, polymers, as well as
for additives, modifiers, and fillers. Their extensive list is
provided in Section VIII of this Handbook.
As is clearly stated there, the same abbreviation is often
used for different monomers and polymers, and the same
polymer may have different abbreviations or acronyms.
Examples:
1. DPP
2. PVA
3. trioctyl phosphate
4. polyacrylonitrile
diphenyl phthalate
dipropyl phthalate
poly(viny1 alcohol)
poly(viny1 acetate)
TOF
TOP
PAC
PAN
The IUPAC policy [9] on the use of abbreviations in the
chemical literature states that there are great advantages in
defining all abbreviations in a single conspicuous place in
each paper, preferably near the beginning of the paper in a
single list. An alternative is to define each abbreviation
fully the first time it appears in the text. No abbreviations
should be used in the titles of publications. A chapter of this
Handbook contains a set of abbreviations recognized by
international organizations.
D. CHEMICAL ABSTRACTS (CA) INDEX NAMES
Chemical Abstracts Service (CAS), the publisher of printed
Chemical Abstracts (CA) and corresponding products and
services in microform, online databases, CD-ROM, and
World Wide Web also names the polymers, selected for
inclusion in the CAS Chemical Registry System and in the
CA Chemical Substance Indexes, in two ways:
a . in terms of the component monomer(s) from which
they are prepared
b. in terms of the final structure of the resulting
polymer.
There are definitive rules that govern when each type of
structure is recorded and named [3]. The primary,
comprehensive representation of polymers by CAS is by
citation of the component monomer(s) because, in many
cases, the structure of the final polymer is either not known
or is not described in sufficient detail by the author.
When the polymer structure is well documented by the
author or can be confidently assumed, because one and only
one structure is chemically possible, then a supplementary
representation with a corresponding systematic name is
added to the CAS Registry System and included in the
printed indexes and online files.
The chemical nomenclature used by CAS has developed
in parallel, and generally in accordance, with the rules and
recommendations published by IUPAC. However, their
rules of systematic nomenclature do not necessarily lead to
a unique name for each compound, but do lead to an
unambiguous one. This causes no difficulty in normal
scientific communication, but is unacceptable in a formal,
rigidly controlled, alphabetic listing such as the CA
Chemical Substance Index.
The CA index names must not only be unambiguous,
unique, and totally reproducible, but also selected so as to
bring the names of structurally related substances into
juxtaposition in the alphabetic index. CAS has always
recognized that, while a unique name is needed for an index
and for substance identification, the use of such invariant
name in scientific papers is neither practicable nor
desirable.
In this section, it is intended to highlight the character-
istics of the CA index names for polymers and compare
them with some of the typical names used in the scientific
community.
a .
b .
C.
d .
e .
IUPAC rules have been adapted to the specific needs
of a highly ordered alphabetical index.
Most common names were eliminated and excep-
tional treatment for various classes of substances
was discontinued.
A single preferred name is determined for each
identifiable substance.
A strict order of precedence of chemical functions
and compound classes is followed to determine the
preferred index heading parent.
A total name is inverted by citing first the index
heading parent (usually, basic skeleton name with a
locant and suffix denoting the principal function),
followed by the comma of inversion, the substituents,
and the mod@cation (derivative of the principal
function), e.g., 2-propenoic acid, a-methyl-, methyl
est er
As mentioned above, most common names, including
those still sanctioned by IUPAC, have been replaced by
fully systematic names. The following is a short list of most
common monomers with both common names and CA
Index names:
Common CA Index names (inverted form)
acrylamide 2-propenamide
acrylic acid 2-propenoic acid
acrylonitrile 2-propenamide
adipic acid hexanedioic acid
c-caprolactam 2H-azepin-2-one, hexahydro-
s-caprolactone 2-oxepanone
ethylene glycol 1,2-ethanediol
ethylene oxide oxirane
fumaric acid 2-butenedioic acid, (E>-
glycolic acid
hydroquinone
isophthalic acid
lactic acid
maleic acid
maleic anhydride
melamine
methacrylic acid
methyl acrylate
phthalic anhydride
propylene oxide
styrene
terephthalic acid
vinyl alcohol
vinyl chloride
vinylidene chloride
Chemi cal Abstracts I ndex Names
119
acetic acid, hydroxy-
1,4-benzenediol
1,3-benzenedicarboxylic acid
propanoic acid, 2-hydroxy-
2-butenedioic acid, (Z)-
2,5-furandione
1,3,5-triazine-2,4,6-triamine
2-propenoic acid, 2-methyl-
2-propenoic acid, methyl ester
1,3-isobenzofurandione
oxirane, methyl-
benzene, ethenyl-
1,4-benzenedicarboxylic acid
ethenql
ethene, chloro-
ethene, 1,l -dichloro-
Similarly, commonly named substituent and multiplying
groups have their systematic equivalents in CA Indexes:
adipoyl
ally1
tert-butyl
ethylene
hexamethylene
isopropyl
succinyl
vinyl
vinylene
1,6-dioxo- 1,6-hexanediyl
2-propenyl
1,l -dimethylethyl
1,2-ethanediyl
1,6-hexanediyl
1-methylethyl
1,4-dioxo-1,4-butanediyl
ethenyl
1,2-ethenediyl
Homopolymers are described by the term homopoly-
mer cited in the modiJication under the monomer name in
the index. In the structural diagram derived from the CAS
Registry System records, the structure of the monomer is
enclosed in parentheses followed by a subscript x. The
corresponding empirical formula is also expressed in a
similar way.
Examples:
1. Poly(methacrylic acid):
(CH2= y- COOHX
GKj:::
CA name: 2-Propenoic acid, 2-methyl-, homopoly-
mer
2. Polystyrene:
(CH2= 7%
C6%
GHs>x
CA name: Benzene, ethenyl-, homopolymer
3 . Poly( 11 -aminoundecanoic acid):
(H2WCHdlo-COOHL
(CllH23NOdx
CA name: Undecanoic acid, 1 l-amino-, homopoly-
mer
References page I - 12
c
,
I/10 NOMENCLATURE
4. Poly(lactic acid):
(CH3- y- COOH),
KY-k~~~r
CA name: Propanoic acid, 2-hydroxy-, homopolymer
Copolymers formed from two or more monomers are
described by the term polymer with (followed by the
other monomers in alphabetical order) cited in the
mod$cation under each monomer name. In the structural
diagram derived from the CAS Registry System records, the
structures of monomers, separated by a period or periods,
are enclosed in parentheses followed by a subscript x.
The corresponding empirical formulas are similarly ex-
pressed. The descriptors alternating, block, and graft are
cited whenever applicable.
Examples:
1. Butadiene-vinyl ethyl ether copolymer:
(CH2=CH-CH=CH2CH2=CH-0-CH2CH3>,
(C4Hs0C4H6)x (in Formula Index order)
CA names: 1,3-Butadiene, polymer with ethoxy-
ethene
Ethene, ethoxy-, polymer with 1,3-
butadiene
2. Isophthalic acid-terephthalic acid-ethylene glycol
polyester:
(HOOC-m-CgHq-COOH.HOOC-p-CgHq--COOH.
OH-(CH2)2-OH),
(CgH604.C8H604.C2H602)x
CA names: 1,3-Benzenedicarboxylic acid, polymer
with 1,4-benzenedicarboxylic acid and
1,2-ethanediol
1,4-Benzenedicarboxylic acid, polymer
with 1,3-benzenedicarboxylic acid and
1 ,Zethanediol
1,2-Ethanediol, polymer with 1,3-benze-
nedicarboxylic acid and 1,4-benzenedi-
carboxylic acid
Telomers are named as copolymers with the term
telomer with cited in the modification under both the
monomer (taxogen) and the chain-transfer agent (telogen).
In the structural representation, the monomer is enclosed in
parentheses with a subscript x, followed by the telogen
structure. The corresponding empirical formula is
expressed in the same way.
Examples:
1. Vinylpyrrolidone homopolymer terminated with
mercaptopropionic acid:
CH= CH2
t i
A
c-l==
0
- SH-CH2- CH2- COOH
x
(C&NO)n.C3%02S
CA names: 2-Pyrrolidinone, 1-ethenyl-,
with 3-mercaptopropanoic acid
Propanoic acid, 3-mercapto-,
with 1-ethenyl-2-pyrrolidinone
telomer
telomer
2. Acrylic acid-vinyl choride copolymer terminated
with carbon tetrachloride:
(CH2=CH-COOHC1-CH=CH2)x.CC14
(C3H402C2H3C1),CC14
CA names: 2-Propenoic acid, telomer with chloro-
ethene and tetrachloromethane
Ethene, chloro-, telomer with 2-propenoic acid and
tetrachloromethane
Methane, tetrachloro-, telomer with chloroethene
and 2-propenoic acid
Structural repeating units (SRU), equivalent to IUPAC
constitutional repeating units (CRU), are selected and
named for polymers that have well documented regular
structure, or can confidently be assumed. Assumptions are
made for
a. polyamides formed from a dibasic acid (ester or
halide) and a diamine; from an amino acid (ester or
halide); from a lactam;
b. polyesters formed from a dibasic acid (anhydride,
ester, or halide) and a dihydric alcohol (phenol);
from a hydroxy acid (ester, halide); from a lactone;
c. polycarbonates formed from carbonic acid (ester,
dihalide) and a dihydric alcohol (phenol);
d. polyurethanes formed from a diisocyanate and a
dihydric alcohol (phenol).
The structural repeating unit is named by citation of one
or more multivalent radicals of regular substitutive
nomenclature. The selection of the preferred SRU, its
orientation, and the construction of the name, proceeding
from left to right, follows the same rules as those in the
IUPAC recommendations for the CRU. In CA names,
however, the names of the radicals are fully systematic, as
explained and contrasted above. The empirical formula is
enclosed in parentheses followed by a subscript n.
Examples:
1. Nylon 11:
0
fNH&W,,)-,
(CllfhNO)n
CA name: Poly [imino( 1 -oxo- 1,ll -undecanediyl)]
2. Poly(ethylene adipate):
0 0
fO-CH,-CH2-O-!-(CH2)4-&
(Cd1204)n
CA name: Poly[oxy-1,2-ethanediyloxy(l,6-dioxo-
1,6-hexanediyl)]
Pol ymer Cl ass Names I/11
I
3. Poly(ether ether ketone) (PEEK):
0
SO--p-C~H~-O-p-Cfj*&p-cfjH&
(C19H1203)n
CA name: Poly(oxy-1,4-phenyleneoxy- 1,6pheny-
lenecarbonyl- 1,4-phenylene)
Poly(alkylene glycols) and their ethers and esters are
indexed in CA as structural repeating units with the
specified end groups, if aplicable.
Examples:
1. Poly(ethylene glycol):
H +O-CH2-CH2 jnOH
CA name: Poly(oxy-l,Zethanediyl), a-hydro-
o-hydroxy-
2. Poly(trimethylene glycol) dimethyl ether:
CH3fO-CH2-CH2-CH&O-CH3
CA name: Poly(oxy-1, 3-propanediyl), a-methyl-
o-methoxy-
3. Poly(tetramethylene glycol) diacrylate:
CH2=CH-C(O) GO-CH2-CH2-CH2-CH2+,
0-C(O)-CH=CH2
CA name: Poly(oxy-1, 4-butanediyl), rx-( l-oxo-
2-propenyl)-o-[(1-oxo-2-propenyl)oxy]-
E. POLYMER CLASS NAMES
In most textbooks, handbooks, encyclopedias, and indexes
to polymer nomenclature, information on polymer is
grouped under polymer class names. The following is a
list of such terms extracted from these sources.
Acrylic Polymers
Alkyd resins
Aminoplasts
Coumarone-indene-resins
Epoxy resins
Pluoropolymers
Phenolic resins
Polyacetals
Polyacetylenes
Polyacrylics
Polyalkylenes
Polyalkenylenes
Polyalkynylenes
Polyamic acids
Polyamides
Polyamines
Polyanhydrides
Polyarylenealkenylenes
Polyarylenealkylenes
Polyarylenes
Polyazomethines
Polybenzimidazoles
Polybenzothiazoles
Polybenzoxazinones
Polybenzoxazoles
Polybenzyls
Polycarbodiimides
Polycarbonates
Polycarboranes
Polycarbosilanes
Polycyanurates
Polydienes
Polyester-polyurethanes
Polyesters
Polyetheretherketones ,
Polyether-polyurethanes
Polyethers
Polyhydrazides
Polyimidazoles
Polyimides
Polyimines
Polyisocyanurates
Polyketones
Polyolefins
Polyoxadiazoles
Polyoxides
Polyoxyalkylenes
Polyoxyarylenes
Polyoxymethylenes
Polyoxyphenylenes
Polyphenyls
Polyphosphazenes
Polypyrroles
Polypyrrones
Polyquinolines
Polyquinoxalines
Polysilanes
Polysilazanes
Polysiloxanes
Polysilsesquioxanes
Polysulfides
Polysulfonamides
Polysulfones
Polythiazoles
Polythioalkylenes
Polythioarylenes
Polythioethers
Polythiomethylenes
Polythiophenylenes
Polyureas
Polyurethanes
Polyvinyl acetals
Polyvinyl butyrals
Polyvinyl formals
Vinyl polymers
These classes are not mutually exclusive, some are
relatively generic and some more specific. Some of them
References page I - 12
I/ 12 NOMENCLATURE
could be grouped and arranged in a hierarchy, e.g., 3. Chemical Abstracts Service, CA Index Guide 1997,
I
Polyacetals Polyethers
Polyvinyl acetals epoxy resins
polyvinyl butyrals polyetheretherketones
polyvinyl formals polyoxyalkylenes
polyoxymethylenes
Polyesters polyoxyarylenes
polycarbonates polyoxyphenylenes
Some are synonymous or near synonymous, e.g.,
polyalkenylenes and polydienes, polyalkynylenes and
polyacetylenes, polyethers and polyoxides, polythioethers
and polysulfides.
Appendix IV, Chemical Substance Index Names,
Chemical Abstracts Service, Columbus, Ohio, 1997.
i
/
4. IUPAC, Source-Based Nomenclature for Copolymers
(Recommendations 1985), Pure Appl. Chem. 57, 1427
(1985). Reprinted as Chapter 7 in Ref. 2.
I
5. IUPAC, Source-Based Nomenclature for Non-Linear
Macromolecules and Macromolecular Assemblies (Recom-
i
mendations 1997), Pure Appl. Chem. 69, 2511 (1997).
6. IUPAC, Nomenclature of Regular Double-Strand (Ladder
and Spiro) Organic Polymers (Recommendations 1993),
I
Pure Appl. Chem. 65, 1561 (1993).
c
7. IUPAC, Nomenclature for Regular Single-Strand and
Quasi-Single-Strand Inorganic and Coordination Polymers
(Recommendations 1984), Pure Appl. Chem. 57, 149
(1985). Reprinted as Chapter 6 in Ref. 2.
(, /
8. IUPAC, Structure-Based Nomenclature for Irregular
Single-Strand Polymers (Recommendations 1994), Pure
Appl. Chem. 66, 873 (1994).
F. REFERENCES
1. IUPAC, Nomenclature of Regular Single-Strand Organic
Polymers (Recommendations 1975), Pure Appl. Chem. 48,
373 (1976). Reprinted as Chapter 5 in Ref. 2.
2. IUPAC, Compendium of Macromolecular Nomenclature.
W. V. Metanomski, (Ed.), Blackwell Scientific, Oxford,
1991.
9. IUPAC, Use of Abbreviations in the Chemical Literature
(Recommendations 1979), Pure Appl. Chem. 52, 2229
(1980).
Units
J. Brandrup
Wiesbaden, FR Germany
A. Introduction
B. International Units
C. SI-Prefixes
D. Conversion Factors
E. Conversion Table for SI vs. English-American
Uni t s
l-l 3
l-l 3
l-l 4
I-1 4
l-l 7
A. INTRODUCTION
The International System of Units (1) is used in this
Handbook as far as possible, since this system has become
obligatory in many European countries and since it is
supported by the National Bureau of Standards (2) and the
American Society for Testing and Materials (3). Only
6. INTERNATIONAL UNITS
cursory information is given here for units needed in this
Handbook. Detailed information may be found in the
following References:
1. SI-units and recommendations for the use of their
multiples and of certain other units, IS0 1000-1973.
2. The International System of Units (SI), Eds. C. H.
Page, P. Vigoreux, Natl. Bur. Std. Spec. Publ., 1981,330.
3. Standard Metric Practice Guide, ASTM E-380-85.
4. Manual of Symbols and Terminology for Physicochem-
ical Quantities and Units; Pergamon Press, Oxford 1979
(Pure Appl. Chem., 51, 1 (1979).
5. F. S. Conant, using the SI units, Polym. Eng. Sci., 17,
222 (1977) (further references).
Quantity H-unit
Selection of multiples
of the SI-unit
Accepted units
used with SI
Units accepted
temporarily
Non SI units
that should not be used
Length
Area
Volume
Time
Frequency
M a s s
De n s i t y
Force
Pr es s ur e
Stress Pa or N/m*
Viscosity (dynamic) Pas
Viscosity (kinematic) m2/s
Surface tension N/ m
Energy, work, heat J (joule)
Power
Temperature
Thermal conductivity
Heat capacity
Specific heat
Entropy
Amount of substance
Electrical resistance
Electrical conductivity
W (watt)
K (kelvin), C
WlmK
J/ K
J&g K)
J/ K
mol (mole)
R
s (l/R)
m (metre)
,:
s (second)
Hz (hertz)
kg (kilogram)
kg/m 3
N (newton)
Pa (Pascal)
or N/m*
km, cm, mm, pm, nm
km*, dm*, cm*, mm*
dm3, cm3, mm3
ks, ms, us, ns
THz, GHz, MHz, kHz
Mg, g9 mg, lg
mg/m3; kg/dm3; g/cm3
MN W mN PN
lA= lo-torn
litre (1, L) (1 1 = 1 dm3)
d, h, min
t
t/m3; kg/l
GPa, MPa, kPa,
mPa, pPa
lbar=105Pa
latm=101325Pa
GPa; MPa or N/mm2; kPa
mPas
mm*/s
mN/m
TJ, GJ, MJ,
kJ, mJ
GW, MW, kW, mW, uW
Electronvolt (eV)
1eV=1.602x10-19J
1p=10-6m
ly=10-9kg
1 dyn = 10m5 N;
pond, kilopond
1 Torr=-
101325 Pa
760
= 133.32 Pa
poise; lP=O.lPas
stokes; 1 St = 1 cm*/s
dynlcm
1erg=10m7J
lcal=4.1868J
lK= 1K
0.86 kcal/(m h grd)
kJ/K
Wkg K)
kJ/K
I/13
I/14 UNI TS
C. SI-PREFIXES
Factor Prefix Symbol Factor Prefix Symbol
108
105
102
109
106
103
IO2
10
exa
peta
tera
gka
mega
kilo
hecto
deca
E
P
T
G
M
k
h
d a
lo-
10-2
10-3
10-6
10-9
10-12
;;I::
deci
centi
milli
micro
nano
pica
f emt o
atto
D. CONVERSION FACTORS
Length m i n ft
Yd
thou or ml1
Im 1 3. 937xl O' 3. 281 1. 094 3. 937x 104
in 2. 540 x 1O-2 1 8. 333 xlO- 2. 778 x lo- 1. 0 x 103
ft 3. 048 x lo- 1 2 1 3. 333 x lo- 1. 2 x 104
yd 9.144 x lo- 36 3 1 3. 6 x lo4
thou or mil 2. 540~ lo- 1.0 x 10-3 8. 334 x 10-5 2. 778 x lO-5 1
Area mz sq. in sq. ft ar
lm2 1 1.550 x 103 1. 076 x 10 1.196 1. 0 x 10-2
sq. in 6. 452 x 1O-4 1 6. 994 x lO-3 7. 716 x lO-4 6. 452~ 1O- 6
sq. ft 9. 290 x lo- 1.440 x 102 1 1.111 x 10-1 9. 290 x lO-4
sq. yd 8. 361 x lo- 1.296 x lo3 9 1 8. 361 x lO-3
ar 1. 0 x 102 1.550 A 105 1. 076 x lo3 1.196 x 10 1
Volume m3 1 (lit) cu. in cu. ft cu. yd
gal (US) @(UK)
lm3 1 103 6. 102 x IO4 3.531 x 10 1. 308 2. 642 x 10 2. 20 x 102
1 (lit) 10-3 1 6. 102 x 10 3.531 x 10-2 1.308 x 1O-3 2. 642 x lo- 2. 20 x lo-
cu. in 1.639 x lO-s 1.639 x lo-* 1 5. 787 x lO-4 2.143 x lO-5 4. 329 x 1O-3 3. 605 x 1O-3
cu. ft 2. 832 x 1O-2 2. 832~ 10 1. 728 x lo3 1 3. 703 x 10-2 7.481 6. 229
cu. yd 7. 646 x lo- 7. 645 x lo2 4. 666 x lo4 2. 7 x 10 1 2. 02ox 102 1.682 x IO*
gal (US) 3. 785 x 1O-3 3. 785 2. 310~ lo2 1.337 x IO- 4.951 x 10-3 1 8. 327 x i O- '
gal ( UK) 4. 546 x lO-3 4. 546 2. 714 x lo2 1.605 x lo- 5. 946 x lO-3 1.201 1
Mass
kg
l bm
ton (UK)
(long ton)
cwt (UK)
(long cwt)
ton (US)
(short ton) ounce grain
1 kg 1 2. 205 9. 842 x 1O-4 1.968 x 1O-2 1.102 x 10-3 3. 527 x 10 1. 543 x 104
l bm 4. 536~ lo- 1 4. 464 x 10-4 8. 929 x lO-3 5. 0 x 10-4 1.6 x 10 7. 0 x 103
ton (metric) 1 x 103 2. 205 x lo3 9. 842 x lo- 19.68 1.102 3. 527 x104 1. 543 x 10
ton (UK) 1. 016 x lo3 2. 240 x 10 1 2. 0 x 10 1.120 3. 584~ lo4 1. 568 x 10
cwt (UK) 5. 080~ 10 1.120 x 102 5. 0 x 10-2 1 5. 600 x lo-* 1.792 x lo3 7. 840 x 10
ton (US) 9. 072~ 10 2. 0 x 103 8. 929 x lo- 1.786 x 10 1 3. 2 x lo4 1. 4 x 10
ounce 2. 835 x lO-z 6. 250 x lO-2 2. 190 x lO-s 5. 580 x 1O-4 3.125 x lo- 1 4. 375x 102
grain 6. 480 x 1O-5 1.429 x lo-* 6. 378 x 1O-8 1.276 x 1O-6 7.143 x 10-8 2. 286~ 1O-3 1
Densi ty
1 kg/m3
Mg/m3 =g/cm3
lbm/cu. ft
lbm/cu. in
lbm/gal (UK)
lbm/gal (US)
kg/m3
1
1. 0 x 103
1. 602 x 10
2. 768~ lo4
9. 978~ 10'
1. 198 x lo2
Mg/m3 = g/cm3 lbmfcu.ft lbm/cu.in lbndgal (UK) lbndgal (US)
1.0 x 10-3 6. 243 x lO-2 3.613 x 1O-5 1.002 x 10-2 8. 345 x 1O-3
1 6. 243 x 10 3.613 x lO-2 1.002 x 10 8. 345
1.602 x lO-2 1 5. 789 x lO-4 1.605 x lo- 1.337 x lo-
2. 768~ 10 1.728 x lo3 1 2. 774~ lo2 2.310 x lo2
9. 978 x lO-2 6. 229 3. 605 x lO-3 1 8. 327 x lo-
1.198 x lo- 7. 480 4. 329 x 1O-3 1.201 1
Conversion Factors I/15
Force N ( kg m/ s )
k& kp
Ibf tonf (UK) (long ton) tonf (US) (short ton)
1N 1 1.020 x 10-1 2.248 x lo- 1. 0 x 105 1.004 x 10-4 1.124 x 1O-4
kp 9.807 1 2.205 9.807 x lo5 9.842 x 1O-4 1.102 x 10-3
lbf 4.448 4.536 x 10 - 1 4.448 x IO5 4.464 x 10 -4 5.0 x 10-4
d
yn
1.0 x 10-5 1.020 x 10-6 2.248 x 1O-6 1 1.004 x 10-9 1.124 x 1O-9
tonf (UK) 9.964 x lo3 1.016 x lo3 2.240 x lo3 9.964 x 10 1 1.120
tonf (US) 8.896 x lo3 9.072 x IO* 2.0 x 103 8. 896 x 10 8.929 x 10 - 1
Pa kPa MPa (N/mm 2, b a r p/cm z kplm at+ stmt Tcwr + Psi (IbUsq. in) +
1Pa(=lN/m2)
lkpa
1 MPa(=l N/mm
1 bar ( = 0.1 MPa)
lphn
lkp/m2+
lat(=lkp/cm*)+
1 atm ( = 76OTotr) +
lTotr(=l/76Oatm)+
Psi (lbfhq. in)
1
10
106
105
9.81 x 10
9.81
9.81 x 104
1.01325 x lo5
1.33 x 102
6.895 x 10
10 -3
1
10
102
9.81 x lo-*
9.81 x lo-3
9.81 x 10
1.01325 x lo2
1.33 x 10-1
6.895
10-6
lo-
lo-
9.81 x 10-5
9.81 x lO-6
9.81 x lo-*
1.01325 x lo-
1.33 x 10-4
6.895 x lo-
10-5
10-2
10
9.81 x lO-4
9.81 x 10-5
9.81 x lo-
1.013
1.33 x lo-
6.895 x lo-*
1.02 x 10-2 1.02 x lo- 1.02 x 10-5
1.02x 10 1.02x 102 1.02 x 10-2
1.02 x 104 1.02 x 105 1.02 x 10
1.02 x 103 1.02 x 104 1.02
1 10 10-3
lo- 1 10-4
103 104 1
1.033 x 10 1.033 x 104 1.033
1.36 1.36 x 10 1.36 x lo-
7.031 x 10-5 7.031 x 10-6 7.031 x 10-2
9.87 x 10-6
9.87 x 10 -3
9.87
9.87 x lo-
9.68; lO-4
9.68 x 10 -
9.68 x lo-
1.32 x lO-3
6.805 x 10 -2
7.50 x 10-6
7.50
7.50 x 103
7.50 x 102
7.36 x 10 -I
7.36 x lo-
7.36 x 10
7.60 x lo*
5.171 x 10-1
1.450 x 10 -4
1.450 x 10-1
1.450 x 102
1.450 x 10
1.422 x 10 -*
1.422 x 10 -)
1.422 x 10
1.470 x 10
1.934 x 10-2
t Non SI units.
Stress Pa N/llUll* kp/cm 2 i kp/mm * i Psi (Ibf/sq. in)i
lPa(=lN/m*) 1 10-6 1.02 x 10-5 1.02 x 10-7 1.450 x 10-4
1 N/mm*( = 1 MPa) 106 1 1.02 x 10 1.02 x lo- 1.450 x 102
1 kp/cm* (= 1 at)+ lo4 9. 81 x 9.81 x lo-* 1 10-2 1.422 x 10
1 kp/mm* + 9. 81 x lo6 9.81 102 1 1.422 x lo3
Psi lbflsq. in 6.895 x IO3 6.895 x 1O-3 7.031 x 10-2 7.031 x 10-4 1
t Non SI units.
Viscosity (dynamic)
Pas
(N s/rem*)
WCs m))
mPa s
(mNs/m2) CP kps/m* kph/m* Ibm/(ft s) lbm/(ft h) Ibfs/sq. ft
1Pas
mPa s
gs/m2
kph/m*
lbd(ft s)
lbm/(ft h)
lbf slsq. ft
1 1.0 x 103 1.0 x 103 1.020 x lo- 2.833 x 1O-5 6.720 x lo- 2. 419 x lo3 2.089 x lo-*
1.0 x 10-3 1 1 1.020 x 10-4 2.833 x 1O-8 6.720 x 1O-4 2.419 2.089 x 1O-5
1.0 x 10-3 1 1 1.020 x 10-4 2.833 x 1O-8 6.720 x 1O-4 2.419 2.089 x 1O-5
9.807 9.807 x lo3 9.807 x lo3 1 2.778 x 1O-4 6.590 2. 372 x lo4 2.048 x lo-
3.530 x 104 3.530 x 107 3.530 x 107 3.60 x lo3 1 .2.372 x lo4 8. 540 x lo7 7.373 x lo*
1.488 1.488 x lo3 1.488 x lo3 1.518 x lo- 4.215 x 1O-5 1 3. 60 x lo3 3.103 x lo-*
4.134 x 10-4 4.134 x lo- 4.134 x lo- 4.215 x 1O-5 1.171 x 10-8 2.778 x 1O-4 1 8.634 x 10m6
4.788 x 10 4.788 x lo4 4.788 x lo4 4.882 1.356 x lo-j 3.217 x 10 1. 158 x 10 1
Viscosity (kinematic) m*/s mm*/s m*fh cst sq. ft/s sq. ft/h
1 m*/s 1 1.0 x 106 3.60 x lo3 1.0 x 106 1.076 x 10 3.875 x lo4
mm*/s 1.0 x 10-6 1 3.60 x 1O-3 1.0 1.076 x lo- 3.875 x 1O-2
mZih 2.778 x 1O-4 2.778 x lo* 1 2.778 x lo* 2.990 x 1O-3 1.076 x 10
cst 1.0 x 10-6 1.0 3.60 x 1O-3 1 1.076 x 1O-5 3.875 x lo-*
sq. ws 9.290 x 10 -* 9.290 x lo4 3.345 x 102 9.290 x lo4 1 3.60 x IO3
sq. fvh 2.581 x lo- 2.581 x lo- 9.290 x 10 -* 2.581 x 10 2.778 x 1O-4 1
I/16 UNI TS
Surface tension N/ m (kg/sz) mN/m
kgYm (kp/m) dyn/cm
1 N/m 1 1.0 x 103 1.020 x 10-1 1.0 x 103
mN/m 1.0 x 10-3 1 1.020 x 10-4 1.0
kp/m 9.807 9.807 x lo3 1 9.807 x lo3
dyn/cm 1.0 x 10-3 1.0 1.020 x 10-4 1
J (NM kgfm
Energy (kgm%*) kWh
kpm
Psh lbfft
erg
HPh kcai BTU
1J 1 2. 778 x lo- 1.020 x 10 -1 3. 777 x 10-7 7. 376 x l o- ' 1. 0 x 10' 3. 725 x I O- ' 2. 388 x 1O-4 9. 478 x 1O- 4
kWh 3. 6Ox 106 1 3.671 x lo5 1.360 2. 655 x I O6 3. 60 x lOI 1.341 8. 598 x lo2 3.412 x lo3
bm 9. 807 2. 724 x 1O-6 1 3. 704x 10-6 7. 233 9. 807~ 10 3. 653 x lO-6 2. 342 x 1O-3 9. 295 x lo-
PSh 2. 648~lo6 7. 355 x 10-1 2. 70 x lo5 1 1.953 x 106 2. 648 x 10 I3 9.863 x lo-1 6. 324 x lo2 2.510 x lo3
lbf ft 1.356 3. 766 x lo- 1.363 x lo- 5.120 x lo- 1.356 x 10 5.051 x 10-7 3: 238x lO-4 1.285 x lo-
erg
1.0 x 10-7 2. 778 x lo-l4 1.020 x IO- 3.777 x lo-l4 7.375 1, 1O-8 3. 725 x lo-l4 2.388 x lo- 9.478 x lo-
HPh 2. 685 x lo6 7. 457 x lo- 2. 737 x lo5 1.014 1.980 x lo6 2. 685 : lOI 6. 412 x lo2 2. 544x 103
kcal 4.187 x lo3 1.163 x 1O-3 4. 269 ti lo! 1.581 x 1O-3 3. 088~ lo3 4.187 x 1OO 1.560: lO-3 1 3. 968
BTU 1.055 x 103 2. 931 x lO-4 1.076 x lo2 3. 985 x 1O-4 7. 782 x lo2 1.055 x 100 3.930 x 10-4 2. 520 x lo- 1
a British thermal unit.
Heat J (Nm) (kgm2/s2) kcal BTU CHU
1J 1 2.388 x 1O-4 9.478 x 1O-4 5.262 x 10-4
kcal 4.187 x lo3 1 3.968 2.203
BTU 1.055 x 103 2.520 x 10 - 1 5.552 x lo-
CHU 1.900 x 103 4.539 x lo- 1.80 1
Wh 3.60 x IO3 8.598 x lo- 3.412 1.894
a Centigrade heat unit.
W (J/s) kgfm/s PS
Power (kgm2/s3) kp m/s HP (metr) H P erg/s ft lbf/s kcaUh BTU/ h
1w 1 1.020 x lo- 1.360 x 1O-3 1.341 x 10-3 1.0 x 107 7.376 x lo- 8.598 x lo- 3.412
kp m/s 9. 807 1 1.333 x 10-2 1.315 x 10-2 9.807 x 10 7.233 8.432 3.346 x 10
PS 7.355 x 102 7.5 x 10 1 9.863 x lo- 7.355 x 109 5.425 x lo2 6.324 x lo2 2.510 x lo3
H P 7.457 x to2 7.604 x 10 1.014 7.457 x 109 5.50 x 102 6.412 x lo* 2.544 x lo3
erg/s 1.0 x 10-7 1.020 x 10-8 1.360 x lo- 1.341 L 10-10 1 x lo-s 7.375 8.598 x lO-8 3.412 x lo-
ft Ibf/s 1.356 1.383 x lo- 1.843 x 1O-3 1.818 x 10-3 1.356 x lo7 1 1.166 4.626
kcallh 1.163 1.186 x 10-1 1.581 x lO-3 1.560 x 10-3 1.163 x lo7 8.578 x lo- 1 3.968
BTU/h 2.931 x lo- 2.988 x lO-2 3.985 x lO-4 3.930 x 10 -4 2.931 x lo6 2.162 x lo- 2.520 x lo- 1
W/ m K BTU in/
Thermal conductivity (kg Ws 3 K)) kcal/(m h C) BTU/(ft b F) BTU/(in h F) (sq. ft h F)
1 W/(m K) 1 8.598 x lo- 5.778 x lo- 4.815 x 1O-2 6.933
kcaY(m hC) 1.163 1 6.720 x lo- 5.60 x lO-2 8.064
BTU/(ft h F) 1.731 1.488 1 8.333 x lO-2 1.2 x 10
BTU/@ h F) 2.077 x 10 1.786 x 10 1.2 x 10 1 1.44 x 102
BTU in&. ft h F) 1.442 x lo- 1.24 x lo- 8.333 x lO-2 6.944 x lO-3 1
Specific heat, J/kg K
heat capacity (m2/(s2 K))
W&it K)
kcal/(kg C) BTU/(lbm F)
1 J/(kg K) 1 1.0 x 10-3 2.389 x lO-4 2.389 x 10 -4
kJ@g K)
1.0 x 103 1 2.389 x lo- 2.389 x 10 -
kcal/(kg C) 4.187 x 103 4.187 I 1.0
BTU/(lbm F) 4.187 x lo3 4.187 1.0 1
WWkg K) 3.60 x lo3 3.60 8.598 x lo- 0.8598
Conversion Table for SI vs. English-American units I/17
E. CONVERSION TABLE FOR SI vs. ENGLISH-AMERICAN UNITS
SI to English-American unit Engl i sh-Ameri can uni t to SI
Length
1 m = 1.0936yd = 3.28ft
= 39.37 in
1 mm = 0.03937 in
lyd=3ft=0,9144m
lft = 12in = 0.3048m
1 in = 25.4 mm
Mass, weight
Force
1 kg = 2.2046 lb 1 lb = 0.45359 kg
1 N = l(kgm)/s* = 2.248 x lo- lbf 1 lbf = 4.448 N
Pressure
1Pa=1N/m2=1.450x10~41bf/in2
= 2.953 x 10m4in Hg
= 4.015 x 1O-3 in Hz0
1 bar = lOsPa = 1.450 x 10 lbf/in*
= 2.953 x 10 in Hg
= 4.015 x lo* in Hz0
1 lbf/in* = 1 psi = 6.89475 x lo3 Pa
= 6.89475 x lo-* bar
1 inHg = 3.38638 x lo3 Pa
= 3.38638 x lo-* bar
1 inH20 = 2.49089 x lo* Pa
= 2.49089 x 10m3 bar
Tension, stress
1 N/mm* = 1.450 x lo* lbf/in* 1 lbf/in* = 6.89475 x 10e3 N/mm*
Dynamic viscosity
1Pas = (Ns)/m* = 2.089 x IO-* (Ibfs)/ft*
= 1 kg/(ms) = 6.72 x lO~lbf/(fts)
1 (lbfs)/ft* =4.78802 x 1OPas
1 lb/(ft s) = 1.488 Pas
Kinematic viscosity
1 m*/s = 1.076 x 10 ft*/s 1 ft*/s = 9.29 x lo-* m*/s
Energy, quantity of heat
1 J = 1 Ws = 1 Nm = 7.376 x lo- ftlbf
1 kJ = 9.478 x lo- BTU
1 ft lbf = 1.35582 J
1 BTU = 1.05506 kJ
Power, heat flow rate
1 W = 1 Nm/s = 7.367 x lo-* (ftlbf)/s
= 1 J/s = 4.425 x 10 (ftlbf)/min
= 3.412BTU/h
1 (ft lbf)/s = 1.35582 W
1 (ftlbf)/min = 2.25969 x lo-* W
1 BTU/ h = 2.93072 x lo- W
Specific heat capacity
1 J/(kg K) = 2.388 x 1O-4 BTU/(lb/ OF)
1 J/(m3 K) = 1.491 x 10m5BTU/(ft3 OF)
1 BTU/(lb OF) = 4.1868 x lo3 J/(kgK)
1 BTU/(ft3 OF) = 6.71 x lo4 J/(m3 K)
Thermal conductivity
1 W/(mK) = 6.933 (BTUin)/(ft* h OF)
= 5.778 x lo- BTU/(fth OF)
= 4.815 x lo-* BTU/(in h F)
1 (BTUin)/(ft*hF) = 1.442 x lo-W/(mK)
1 BTU/ (ft h OF) = 1.7307 W/(mK)
1 BTU/(in h OF) = 2.07689 x 10 W/(m K)
I/l8 UNITS
SI to English-American unit Engl i sh-Ameri can uni t to SI
Heat flux density
1 W/m* = 3.17 x lo- BTU/(ft* h)
= 2.201 x 10e3 BTU/(in* h)
1 BTU/(ft* h) = 3.1546W/m2
1 BTU/(in* h) = 4.54263 x lo* W/m*
Heat transfer coefficient
Thermal resistance
1 W/(m* K) = 1.761 x lo-BTU/(ft* h OF) 1 BTU/(ft* h OF) = 5.678 W/(m* K)
Temperature
1 (m* K)/W = 5.678 (ft* h F)/BTU
1 K = 1 C = 1.8 F
1 (ft* h F)/BTU = 1.761 x IO- (m*/K)/ W
1 F = 5.555 x lo- K = 5.553 x lo- C
Conversion:
Tc=+32) T~=;T~f32
TK =; T~+255.372 TF = g (TK - 255.372)
Tc - Temperature in celsius (C); Tr - Temperature in fahrenheit (F); TK - Temperature in kelvin (IQ.
SECTION II
POLYMERIZATION AND
DEPOLYMERIZATION
Decomposition Rates of Organic
Free Radical Initiators
K. W. Dixon
Akzo Nobel Chemicals Inc., Dobbs Ferry, NY, USA
A. Introduction
B. Tables of Decomposition Rates of Organic
Free Radical Initiators
Table 1. Azonitriles
Table 2. Miscellaneous Azo-Derivatives
Table 3. Alkyl Peroxides
Table 4. Acyl Peroxides
Table 5. Hydroperoxides and Ketone Peroxides
Table 6. Peresters and Peroxy Carbonates
Table 7. Miscellaneous Initiators
C. Notes
D. References
II-1
II-2
II-2
II-9
II-23
II-29
II-43
II-48
II-68
II-69
II-70
A. INTRODUCTION
The decomposition of most organic free radical initiators
follows first order kinetics. With certain peroxides, how-
ever, higher order decompositions are observed. Generally,
the higher order reaction is caused by a reaction of radicals
with the initiator (induced decomposition). The value of the
rate for unimolecular decomposition may be determined
either by extrapolation of the rate back to zero initiator
concentration or by use of a monomer or other radical
trap. Some of the peroxides may also decompose by
non-radical routes. Acids, bases, and polar solvents favor
ionic intermediates. Koenig (296) presents an excellent
discussion of azo and peroxide decomposition pathways.
Decomposition rate (kd) data in these tables are reported
for first order kinetics:
dL/dt = kdL
where I is the initiator concentration (mol/l) and t is the
time (s). The decomposition rate constant kd is related to
half-life (t i/z) by the following equation:
t 1/2 = 0.693/kd
Fig. 1 relates kd in s-l to half-life for the range of kd found
in the tables.
For some of the initiators listed, the enthalpy (AH*) is
given (Note h) rather than the Arrhenius activation energy
(E,). The two quantities are related by the equation
E, = AH* + RT, where R is the gas constant (in kJ/mol-
deg.) and Tis the absolute temperature (94). Assuming that
kd is linear with respect to l/T and that the activation
energy, Ea, and the decomposition rate constant, kd, for one
temperature are known, kd for any temperature can be
calculated from the following expression:
logk2 = logkt -
Ea(T2 - TI)
2.303R(T2T1)
Where given by the author, the overall equation for kd in
terms of the frequency factor (A) and activation energy (E,)
has been included. Thus for any temperature (converted to
K) the kd may be calculated:
kd = A exp(-E,/RT)
Although a wide range of initiators is reported in the tables,
the author admits that the compilation is far from complete.
There are several purposeful omissions: (a) azo compounds,
where the azo group is part of a ring structure - these
recombine almost exclusively; (b) compounds that decom-
pose at appreciable rates only above 200 degrees. Neither
class would be expected to be useful initiators. The data
have been arranged into seven tables. Within each table the
individual initiators are listed according to the following
criteria:
1. Initiators:
(a) according to increasing number of carbon atoms;
(b) alphabetically (neglecting trivial prefixes), for
compounds containing equal number of carbons;
(c) miscellaneous initiators are listed alphabetically in
Table 7.
2. For each initiator, solvents are listed alphabetically.
3. For a given solvent, all measurements reported by one
investigator are listed in a series, with the activation
energy listed opposite the lowest temperature.
Abbreviations: DMSO - dimethyl sulfoxide; DMAC -
dimethylacetamide; DMF - dimethylformamide; THF -
tetrahydrofuran; DCB - 1,2-dichlorobenzene.
II / 1
II/2 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
50 days s-loo hrs.
- - l Ohrs. , , 4osf%.
, , 5sec. 0. 5 sec.
- - l o mi n.
l . E+oB l . E+07 1. tz+O6 l . E+OS l . E+04 l . E+03 l . E+OZ l . E+Ol l . E+OO
Rdcconstmtkj l
Figure 1. Relationship of half life to rate constant (kd) (half lives are to the right of each vertical line)
B. TABLES OF DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 1. AZONITRILES
Number of
C atoms Initiator Solvent TN3 ka (S-l) E. (kJ/mol) Notes Refs.
5 N-Acetyl N-wcyanoethyl diimide Toluene
2-Cyano-2-propyl-azo-formamide Chlorobenzene
Toluene
Xylene
2-(Carbamoylazo)isobutyronitrile
N-Acetyl N-a-cyanocyclopentyl-
diimide
Toluene
Toluene
2,2-Azo-bis-isobutyronitrile
(2,2-azo-bis-2-methylpropionitrile)
Acetic acid
Acetonitrile
kwAmy1 alcohol
Aniline
Benzene
60. 8 2. 46 x lo-
68. 6 5. 45 x 10-5
82. 0 2 . 4 9 x 10-4
1 0 0 1.5 x 10-5
1 0 0 2.1 x 10-5
1 1 0 6. 8 x 10-5
1 0 4 1.9 x 10-5
1 0 0 2.1 x 10-5
1 2 0 2. 4 x 1O-4
1 0 4 1.93 x 10-5
65. 7 1.82 x 1O-5
76. 8 7 . 2 9 x 10-5
9 1 . 5 3. 65 x 1O-4
7 9 . 9 1.43 x 10-4
7 9 . 9 1.48 x 1O-4
7 9 . 9 1.62 x 1O-4
80 1.52 x 1O-4
82 1.50 x 10-4
82 1.49 x 10-4
19. 9 1.25 x 1O-4
79. 9 1.24 x 1O-4
80. 2 1.40 x 10-4
80. 2 1.68 x 10-4
40. 0 5. 44 x 10-7
45. 2 1.12 x 10-6
50. 0 2. 64 x 10-6
55. 0 5 . 1 9 x 10-6
60. 5 1.16 x 1O-5
69. 5 3. 78 x 1O- 5
1 1 0 . 2
144.3
a
144.3
a
120.3
v2
3
a
a
a
v2
128. 4 a, tz
apt2
a, t 2
a,t 2
as2
a,tz
322
322
322
93
93
93
339
93
93
340
322
322
322
146
146
146
62
2
175
146
146
61
61
69
69
69
69
69
69
TABLE 1. contd
Azonitriles II / 3
Number of
C atoms Initiator Solvent T (C) ka (S-l) E, Wmol) Notes Refs.
8 (conrd) 2,2-Azo-bis-isobutyronitrile Benzene
Benzene or Toluene
n-Butanol
Isobutanol
Di-n-butyl phthalate
Carbon tetrachloride
Chlorobenzene
Cyclohexanone
Dichloroethane
Dichloroethane:
propionitrile (1 : I)
Diethylene glycol
monobutylether
DMF
DMF
DMF/methyl
methacrylate (9/1)
@/3
(713)
(6/4)
(515)
(4/6)
(317)
CV)
(1/9)
NJV-Dimethylaniline
DioxanefWater (80/20)
pH 7.0
Dioxane/Water (80/20)
pH 10.7
4 0
5 0
6 0
7 0
7 8
3 7
4 3
5 0
6 0
1 0 0
T W
8 2
8 2
8 2
80.2
8 0
9 0
1 0 0
1 1 0
1 2 0
1 2 7
1 3 7
1 4 5
8 0
9 0
1 0 0
1 1 0
1 2 0
4 0
6 0
7 7
6 4
8 2
1 0 1
T (K)
8 2
7 0
4.83 x lo-
2.085 x 1O-6
8.45 x 10 -6
3.166 x 1O-5
8.023 x lo-
2.83 x lo-
7.35 x lo-
2.16 x 1O-6
9.15 x 10-6
1.52 x 1O-3
1.58 x lOI5
1.54 x 10-4
1.55 X 10-4
1.66 x 10-4
(1.67-1.76) x 1O-4
2.64 x 1O-4
6.47 x 1O-4
1.78 x 1O-3
4.88 x 1O-3
1.43 x 10-2
2.48 x 1O-2
5.43 x 10-2
1.24 x lo-
2.22 x 10-4
4.23 x 1O-4
1.99 x 10-3
5.3 x 10-3
1.48 x 10-2
2.15 x lo-
4.00 x 10-6
1.21 x 10-4
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
2.89 x lOI
1.43 x 10-4
2.01 x 10-5
1.64 x 10-5
123. 4
128.9
exp[- 128.9/RT]
a
a
a
122.2
Y4
Y4
Y4
Y4
Y4
Yl6
Y16
Y32
128.4 a,t 2
as2
a
exp[- 130.23/RT]
a
m8
6 6
6 6
6 6
6 6
6 6
3 9
3 9
3 9
1 9
3 9
3 9
1 7 5
2
2,175
6 1
236
236
236
236
236
236
236
236
3 7 5
3 7 5
3 7 5
3 7 5
375
6 9
6 9
6 2
344
344
344
344
2,175
293
293
7 0
66.82
1.94 x 10-5
2.442 x 10-5
293
2 6
71.2 6.2096 x 10 -5 294
6 0 6.45 x 1O-4 3 5 5
6 0 5.55 x 10-4
6 0 5.10 x 10-4
6 0 5.10 x 1o-4
6 0 5.30 x 10-4
6 0 5.65 x 1O-4
6 0 5.35 x 10-4
6 0 5.65 x 1O-4
6 0 6.25 x 1O-4
6 0 6.50 x 1O-4
66.82 3.483 x 1O-5
72.27 6.914 x 1O-5
8 0 1. 83 x 1O-4
65.3 2.53 x 1O-5
70.0 3.20 x 1O-5
75.0 8.5 x 1O-5
80.0 1. 62 x 1O-4
a
141.0
3 5 5
3 5 5
3 5 5
3 5 5
3 5 5
3 5 5
3 5 5
3 5 5
3 5 5
2 6
2 6
6 2
1 8 6
1 8 6
1 8 6
1 8 6
75.0 1.72 x 1O-4
8 0 1.46 x 1O-4 a
1 8 6
6 2
Notes page II - 69; References page II - 70
II / 4 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 1. contd
Number of
C atoms Initiator Solvent
T(C) kd (S-) E. Wmol) Notes Refs.
8 (contd) 2,2-Azo-bis-isobutyronitrile Ethyl acetate
Ethyl acetate/
SnC14 (1: 1)
GlycerolIDMF 95/5, (v/v)
Maleimide (solid state)
Methyl methacrylate
Nitrobenzene
I-Nitrobutane
Propionitrile/SnC14 (1 : 1)
Propylene carbonate
Styrene
Toluene
Toluene/SnCl 4 (1 : 1)
Xylene
o-Xylene
3,6-Dicyano-3,6-dimethyl-
1,2-diazacyclohexene- 1
Water
Dichloromethane
2,2-Azo-bis[2-(hydroxymethyl)
propionitrile
Methyl cellosolve
9 N-Acetyl N-u-cyanocyclohexyl-
diimide
Toluene
1 0 N-Acetyl N-a-cyanocycloheptyl-
diimide
Toluene
4,4-Azo-bis-(4-cyanopentanol) Acetone
4,4-Azo-bis-(4-cyanovaleric acid) Acetone
1,l -Azo-bis-1-cyclobutanenitrile Mesitylene
2,2-Azo-bis-2-methylbutyronitrile
Xylene
Toluene
Xylene
40 4.7 x 10-7
6 0 9.36 x 1O-6
T W)
8.56 x lOI
128.5
exp[- 127.4/RT]
7 1 . 2 2.6054 x 10 -s
6 5 4.97 x 10-5
72 2.07 x 1O-4
50 9.7 x 10-7
50 7.5 x 10-6
60 7.20 x 1O-4
70 3.1 x 10-5
70 1.27 x 1O-4
8 0 1.98 x 10-4
1 0 0 2.24 x 1O-3
8 2 1.45 x 10-4
T 6) 9.10 x 105
7 2 . 2 7 5.821 x lo-s
5 0 2.97 x 1Om6
7 0 4.72 x 1O-5
T 6) 1.29 x 10
6 8 . 4 3.8 x 10-5
60.00 9.03 x 1Om6
6 0 9.8 x 10-6
6 5 1.9 x 10-5
7 0 4.0 x 10-5
8 0 . 4 1.55 x 10-4
9 0 . 0 4.86 x 10m4
1 0 0 . 0 1.60 x 1O-3
105.0 2.61 x 1O-3
6 9 . 8 3.8 x 10-5
8 0 . 2 (1.72-1.60) x 1O-4
8 0 . 3 1.30 x 10-4
6 0 4.0 x 10-5
5 0 2.0 x 10-6
7 7 9.46 x 1O-5
8 2 1.44 x 10-4
8 0 1.53 x 10-4
8 0 1.50 x 1o-4
8 2 1.45 x 10-5
8 5 2.751 x 1O-4
9 5 9.581 x 1O-4
105 2.782 x 1O-3
T 6) 3.16 x lOI
5 0 1.56 x 1O-6
- 6.06 4.60 x 10m4
0 . 0 3 1.14 x 10-3
2 . 5 2 1.64 x 1O-3
7 7 1.93 x 10-5
8 2 . 0 5.21 x 1O-5
9 2 . 8 1.70 x 1om4
1 0 0 . 6 3 . 7 4 x 1om4
5 9 . 4 4.44 x lo-s
66.1 9 . 8 2 x 1O-5
7 9 . 6 4 . 5 1 x 10-4
7 0 4.26 x lo-
7 0 4 . 5 8 x lo-
1 3 0 . 4 5 . 2 0 x 1O-5
1 4 1 . 6 1.60 x 1O-4
1 2 0 . 4 2 . 0 5 x lo-
6 9 . 8 2 . 3 x lo-
8 0 . 2 8.4-9.0 x 10 -5
8 0 9 . 9 7 x 10-5
1 3 2 . 2
exp[- 127.O/RT]
1 2 7 . 6
exp[- 127.6/RT]
121.3
142.3
1 3 1 . 0
131.8
exp[- 131.8/RT]
8 8 . 8
114.8
1 1 2 . 0
134.3
1 2 9 . 7
1 2 3 . 0 a
as2
as2
a
a
a
a,v 20
v4
a
a
a
a
a
cm3
a
m2
a
a
a
a
as4
a
h
a
m7
m7
6 9
6 9
290
294
1 8 5
1 8 5
289
289
3 5 5
216
216
226
226
2 , 1 7 5
290
26
1 3 2
1 3 2
1 3 2
234
2 9 1
290
339
4 7
47
47
4 7
4 7
61
6 1
234
290
1 7 5
1 7 5
175
6 2
62
2
332
332
332
332
2 8 5
252
252
252
339
322
322
322
322
322
322
3 0 5
3 0 5
101
101
101
61
61
6 2
TABLE 1. conrd
Azoni t ri l es II/5
Number o f
C atoms Initiator Solvent T (C) kd (S-l) E. Wmol) Notes Refs.
10 (co&d) 2,2-Azo-bis-2-ethylpropionitrile
2,2-Azo-bis-2-methylbutyronitrile
N-benzoyl N-a-cyanoethyldiimide
4-Bromophenyl-azo-2-methyl-
2-propionitrile
4-Bromophenyl-azo-(methyl-
propanedinitrile)
4-Nitrophenyl-azo-2-methyl-
2-propionitrile
4-Nitrophenyl-azo-2-(methyl-
propanedinitrile)
Phenyl-azo-2-methyl-2-
propionitrile
Phenyl-azo-2-(methyl-
propanedinitrile)
Phenyl-azo-2-(methyl-
propanedinitrile)
1 1 4-Bromophenyl-azo-2-(ethyl-
propanedinitrile)
4-Methoxyphenylazo-2-
(methylpropanedinitrile)
4-Methoxyphenyl-azo-
2-(methylpropanedinitrile)
Ni t r o b e n z e n e
Cyclohexanone
Ch l o r o b e n z e n e
Ethanol
Ethylbenzene
To l u e n e
To l u e n e
DCB
DCB
DCB
DCB
DCB
DMF
1,2,4-Trimethylbenzene
DCB
DCB
DCB
Butanol
Ch l o r o b e n z e n e
DCB
Decane
DMSO
He p t a n e
Hexanol
Oc t a n e
Oc t a nol
Pr o p a n o l
To l u e n e
Ch l o r o b e n z e n e
DCB
8 0 8.3 x 1O-5
1 0 0 1.08 x 1O-3
79.9 1.06~ 1O-4
90.0 3.71 x 10-4
100.1 1.27 x 1O-3
66 1.93 x 10-5
8 4 1.93 x 1o-4
1 0 4 1.93 x 10-3
T (W 1.38 x 1015
80.0 1.05 x 1o-4
90.0 3.23 x 1O-4
100.0 9.87 x 1O-4
80.0 8.22 x 1O-5
90.0 2.94 x 1O-4
100.0 1.02 x 10-3
6 7 1.9 x 10-5
69.2 1.31 x 10-5
83.2 7.96 x 1O-5
90.0 1.744 x 10 -4
1 6 0 2.85 x 1O-5
8 0 2.4 x 10 -
8 5 4.8 x 1O-5
90 9.4 x 10-5
T 6) 7.23 x lOI
1 6 0 2.3 x lo-
8 0 3.1 x 10-5
8 5 6.0 x 1O-J
90 1.14 x 10-4
T (K)
1.35 x 106
1 6 0 5.65 x 1O-5
1 6 0 6.9 x 1O-5
1 6 0 5.35 x 1o-5
80 4.45 x 10-5
8 5 8.0 x 1O-5
90 1.42 x 1O-4
T W
8.48 x lOI
80 2.4 x 1O-5
8 5 4.8 x 1O-5
90 9.4 x 10 -5
T (K) 7.23 x 1016
8 0 1.85 x 1O-5
8 5 3.65 x 1O-5
90 7.05 x 10-5
T W) 3.00 x 106
8 5 2.9 x 1O-4
8 5 9.5 x 10 -5
8 5 8.35 x 1O-5
8 5 3.8 x 1O-5
8 5 4.87 x 1O-4
8 5 5.15 x 10-5
8 5 1.6 x 1O-4
8 5 4.4 x 10-5
8 5 1.5 x 10-4
8 5 3.1 x 1o-4
8 5 6.75 x lo-s
78.1 5.74 x 10-5
85.3 9.52 x lo-
90.2 1.307 x 1o-4
75.0 2.73 x lo-
85.1 8.35 x lo-
95.1 2.236 x 1O-4
104.9 6.397 x 1O-4
143.1
131.6
exp[- 129.93/RTj
119.8
134.9
127.9
145.0
exp[- 145.O/RTJ
139.1
exp[- 139.1/RT]
123.2
exp[- 123.2/RT]
145.0
exp[- 145.O/RTj
142.9
exp[- 142.9/RT]
1 1 0
71
1 1 5
1 4 2
1 1 4
1 3 6
1 0 2
1 4 0
1 1 2
1 0 3
1 3 7
71.5
1 1 6
a 226
a 226
h 336
336
336
344
344
344
344
h 336
336
336
h 336
336
336
a 339
322
322
322
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
3 2 9
329
329
329
329
329
3 3 1
3 3 1
3 3 1
3 3 1
3 3 1
3 3 1
3 3 1
3 3 1
3 3 1
3 3 1
331
330
330
330
330
330
330
330
Not es page I I - 69; References page II - 70
II/6 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 1. contd
Number of
C atoms Initiator Solvent
T W) kd (S-) E. Wmol) Notes Refs.
11 (cant d) 4-Methoxyphenyl-azo-
2-(methylpropanedinitrile)
Phenyl-azo-2-(2-methyl-
butyronitrile)
4-Tolyl-azo-2-(methyl-
propanedinitrile)
12 4,4-Azo-bis-(l-bromo-
4-cyanopentane)
4,4-Azo-bis-4-cyano-
pentanoic acid
4,4-Azo-bis-(4-cyanopentanol)
1,l -Azo-bis- 1 -cycle-
pe nt a ne ni t r i l e
2,2-Azo-bis-2-cyclopropyl-
propionitrile (mp 64-65)
2,2-Azo-bis-2-cyclopropyl-
propionitdle (mp 76-77)
2,2-Azo-bis-2,3-
dimethylbutyronitrile
2,2-Azo-bis-2-methyl-
valeronitrile
4-Bromophenyl-azo-2-
(isopropylpropanedinitrile)
2,6-Dimethylphenyl-azo-
2-methylpropanedinitrile
13 N-Benzoyl N-u-cyanocyclo-
pentyl diimide
4-Bromophenyl-azo-
isobutylpropanedinitrile
4-Bromophenyl-azo-Z
(2-reti-butylpropionitrile)
4-Nitrophenyl-azo-2-
(2-terr-butylpropionitrile)
Phenyl-azo-2-(2-rert-butyl-
propionitrile)
1 4 2,2-Azo-bis-2-cyclobutyl-
propionitrile (mp 38-42)
2,2-Azo-bis-2-cyclobutyl-
propionitrile (mp 81.5-82.5)
DCB
DCB
DMP
1,2,4-Trimethylbenzene
DCB
To l u e n e
Wat er
Di-n-butyl phthalate
To l u e n e
To l u e n e
To l u e n e
To l u e n e
To l u e n e
DCB
DCB
To l u e n e
DCB
DCB
DCB 1 6 0 1.8 x 1O-5 329
DCB
1,2,4-Trimethylbenzene
Hexamethyl-
phosphoramide
To l u e n e
To l u e n e 80.5 1.51 x 10-4 w 1 0 4
exp[-116/RTJ
114.8
exp[- 114.8/RT]
T 6) 5.67 x 10
8 0 4.7 x 10-5
85 8.1 x 1O-5
90 1.38 x 10-4
T (W 2.94 x 102
1 6 0 5.0 x 10-5
1 6 0 5.2 x 1O-5
1 6 0 5.05 x 10-5
80 4.5 x lo-s
8 5 7.9 x 10-5
90 1.365 x 10 -
T W 1.21 x 103
T (K)
1.0 x 10
117.7
exp[- 117.7yRT]
exp[- 104.7/RT]
330
329
329
329
329
329
329
329
329
329
329
329
307
69 1.9 x 10-5
80 8.97 x 1O-5
80 2.55 x 1O-4
90 7.99 x 1o-4
1 0 0 2.81 x 10-3
1 1 0 8.99 x 1o-3
1 2 0 2.6 x 1O-2
1 3 0 5.2 x 1O-2
80.3 7.45 x 10-5
89.2 2.43 x 1O-4
95.1 5.18 x 10-4
44.2 3.50 x 10-5
49.5 7.53 x 10-5
59.2 2.68 x lo-
44.2 3.90 x 10-5
49.5 8.17 x 1O-5
59.3 2.46 x 1O-4
69.8 2.6 x lo-
80.2 1.02 x 10-4
69.8 4.2 x 1O-5
80.2 (1.65-1.74) x 1O-4
8 0 1.4 x 10-5
8 5 2.80 x lo-
90 5.4 x 10 -s
T (K)
1.73 x 106
60.1 3.06 x 1O-5
70.0 1.177 x 10-4
80.6 4.594 x 10-4
84.5 7.320 x 10 -4
T (W
2.06 x 10
76.7 1.62 x 1O-5
82.0 3.17 x 10-5
98.4 2.252 x 10-4
80 1.12 x 10-4
8 5 2.21 x 10-4
90 4.26 x 1O-4
T W
1.19 x 107
1 6 0 4.85 x 10-5
142.3
141.4
117.2
108.8
133.9
138.1
142.0
exp[- 142.O/RT]
130.5
exp[- 130.5/Rfl
131.9
141.6
exp[- 141.6kJ/RT]
a 339
a 6 2
375
3 7 5
3 7 5
3 7 5
3 7 5
375
101
101
101
W 57
W 5 7
w 5 7
W 5 7
W 5 7
W 5 7
6 1
61
61
61
329
3 2 9
329
329
330
330
330
330
330
322
322
322
329
329
329
329
329
1 6 0 9.35 x 1o-5 329
1 6 0 9.65 x 1O-5 329
1 6 0 9.5 x 10-5 329
80.5 1.51 x 10-4 W 1 0 4
.
Azonitriles II / 7
TABLE 1. contd
Number of
c atoms Initiator Solvent T(C) kd (s-) E, Wmol) Notes Refs.
14 (contd) 1,l -Azo-bis- 1 -cyclohexane nitrile Chlorobenzene
DMSO
Nitrobenzene
Toluene
2,2-Azo-bis-2,4-dimethyl-
valemnitrile
Dimethyl-4,4-azo-bis-cyano-
pentanoate (meso)
(not)
bD-)
4,4-Azo-bis-4-cyano-l-methyl-
piperidine
2,2-Azo-bis-2-propylbutyronitrile Nitrobenzene
2,2-Azo-bis-2,3,3-trimethylbutyro-
nitrile (mp 114-116)
2,2-Azo-bis-2,3,3-trimethylbutyro-
nitrile (mp 116-118)
2,2-Azo-bis-2-methylhexylnitrile
2,2-Azo-bis-2,4-dimethylvaleronitrile
2,2-Azo-bis-2,4-dimethylvaleronitrile
(mp 56-57)
2,2-Azo-bis-2,4dimethylvaleronitrile
(mp 74-76)
2,2-Azo-bis-2-isopropylbutyronitrile
N-(4Chlorobenzoyl) W-u-
cyanocyclohexyl diimide
N-(l-Cyanocyclohexyl)-
pentamethyleneketenimine
15
2-Phenyl-azo-2,4-dimethyl-
4-methoxyvaleronittile
IV-Benzoyl N-a-cyanocyclo-
heptyl diimide
Xylene
Toluene
Xylene
DMAC
DMSO
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Chlombenzene
Cumene
Toluene
rerr-Butylbenzene
Xylene
79. 97 8. 42 x 1O-6
100. 12 1.107 x 10-4
80 1.01 x 10-5
85 2.01 x 10-5
9 0 3. 89 x 1O-5
95 6. 83 x 1O-5
1 0 0 1.14 x 1o-4
80. 3 6. 5 x 1O-6
95. 2 5. 44 x 10-5
102. 4 1.26 x 1O-4
88 1.9 x 10-5
77 5.31 x 10-6
51 1.9 x 10-5
68 1.9 x 10-4
T (K)
6. 98 x 1014
77 5. 77 x 10-4
17. 9 1.43 x 10-4
85. 0 3. 76 x 1O-4
90. 2 6. 80 x 1O-4
99. 1 2. 05 x lO-3
77. 6 1.46 x 1O-4
85. 9 4. 03 x 10 -4
90. 0 6. 90 x 1O-4
99. 2 2. 04 x 10-3
11. 9 1.49 x 10-4
85. 4 3. 90 x 10-4
90. 2 6. 95 x 1O-4
99. 0 1. 91 x 10-3
80 9. 7 x 10-6
85 1.75 x 10-5
90 3. 64 x 10-5
95 6. 47 x 1O-5
80 2. 55 x lO-4
1 0 0 2. 72 x 1O-5
79. 9 7. 42~ 1O-5
89. 0 2.59 x 10-4
79. 9 1.05 x 10-4
88. 9 3. 09 x 10-4
80. 2 1.58 x lO-4
69. 8 1.98 x 10-4
80. 2 7.1 x 10-4
59. 7 8. 05 x 1O-5
69. 9 2. 89 x 1O-4
69. 8 1.98 x 1O-4
80. 2 7.1 x 10-4
80. 5 1.01 x 10-4
79. 1 8. 6 x 1O-6
86. 4 2.01 x 10-5
99. 1 1.044 x 10-4
l o o 3. 85 x 10-5
1 0 0 2. 07 x 1O-5
1 0 0 3. 93 x 1o-5
1 0 0 1. 42 x 1O-5
1 0 0 3. 1ox 10-5
1 0 0 1.83 x 1O-5
1 0 0 2.39 x 10-5
1 0 0 1.22 x 10-5
1 2 2 1.9 x 10-5
14. 6 6. 49 x 1O-5
82. 8 1.781 x 1O-4
89. 2 3.519 x 1o-4
1 4 0 . 2
1 3 5 . 6
1 2 1 . 3
121
exp[- 121/RT]
1 3 3 . 9
1 3 6 . 4
1 2 8 . 9
1 4 6 . 4
125.5
121.3
121.3
121.3
1 3 2 . 7
122.8
h
a
a
a
a
a
a
a
a
a
a
a
a
L
W
W
W
w
PYz (1)
p,z ( 3950)
PJ (1)
p,z (3950)
p.= (1)
p,z ( 3950)
PJ (1)
p,z ( 3950)
1 7 9
119
135
135
135
135
226
101
101
101
339
1 1 5
343
343
343
115
205
205
205
205
205
205
205
205
205
205
205
205
135
135
135
135
226
226
57
51
57
57
61
61
61
51
57
51
57
50
322
322
322
299
299
299
299
299
299
299
299
339
322
322
322
Notes page II - 69; References page II - 70
II/8 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 1. contd
Number of
C atoms _ Ini ti ator Solvent
T (C) kd (S-l) E. Wmol) Notes Ref s.
15 (conrd) N-(4-Methoxybenzoyl) N/-a-
cyanocyclohexyldiimide
N-(4-Methylbenzoyl) N-a-
cyanocyclohexyl diimide
N-Phenylacetyl N-cl-cyano-
cyclohexyl diimide
4-Cyano-1-methylpiperidine-4,4-azo-
4.cyano-l,l-dimethylpiperidinium
nitrate
16 4,4-Azo-bis-4-cyano-1,l -dimethyl-
piperidinium nitrate
4,4-Azo-bis(4cyanopentanoyl)bis
2-aminoethanol
1,l -Azo-bis- 1 -cycloheptane-nitrile
2,2-Azo-bis-(4-methoxy-2,4-
di met hyl val eroni t ri l e)
2,2-Azo-bis-2-methylheptylonitrile
18
1.1 -Azo-bis-1-(2-methylcyclohexane)-
nitrile
1,l -Azo-bis- 1 -cyclohexane-
carbonitrile
2,2-Azo-bis-cyclopentylpropio-
nitrile (mp 72.2-74.5)
2,2-Azo-bis-2-cyclopentyl-
propionitrile (mp 96.3-97.6)
2,2-Azo-bis-2,4,4-trimethyl-
valeronitrile (mp 67.5-69)
2,2-Azo-bis-2,4,4-trimethylvalero-
nitrile (mp 94.5-95.5)
2,2-Azo-bis-2-isopropyl-3-methyl-
butyronitrile
1,l -Azo-bis- 1 -cyano-4,4 -
dimethyl cyclohexane
2,2-Azo-bis-2cyclohexylL
propionitrile
1,l -Azo-bis-1-cyclooctanenitrile
20 4,4-Azo-bis(4-cyanopentanoyl)bis-
2-(2-aminoethoxy)ethanol
2,2-Azo-bis-2-benzylpropionitrile Toluene
Toluene
Toluene
Toluene
DMSO
DMSO
DMF
DMAC
Acetic acid
Toluene
Toluene
Toluene
Xylene
Toluene
8 0 . 8
8 7 . 9
1 0 1 . 2
8 1 . 4
8 7 . 3
1 0 1 . 9
7 4 . 3
8 2 . 9
9 1 . 2
8 0
8 5
9 0
9 5
8 0
8 5
9 0
9 5
6 5
6 9
7 4
6 5
6 9
74
6 9 . 5
4 8 . 9
5 8 . 9
6 7 . 3
3 0
4 7
T 6)
8 0 . 0
8 0 . 0
8 0 . 2
Xylene
Toluene
8 0
7.1 x 10-6
1.71 x 10-5
9 . 7 3 x 10-5
1.06 x 1O-5
2 . 2 0 x 10-5
1.255 x 1O-4
3 . 0 8 x 1O-5
9 . 7 6 x 1O-5
2 . 7 7 x 1O-4
1.76 x 1O-5
3.31 x 10-5
6 . 2 3 x 1O-5
1 . 1 5 6 x 1O-4
2 . 8 4 x 1O-5
5.11 x 10-5
9 . 8 7 x lo-
1 . 6 2 6 x 1O-4
1.76 x 1O-5
2 . 8 5 x 1O-5
4 . 6 6 x 1O-5
1.73 x 10-5
2 . 7 3 x 1O-5
4 . 5 3 x 10-5
3 . 2 8 x 1O-4
2 . 6 9 x 1O-5
9 . 7 2 x 1O-5
2 . 6 9 x 1O-4
1.9 x 10-5
1.9 x 10-4
1.03 x 105
1.63 x 1O-4
1.78 x 1O-4
7 . 4 3 x 10-6
4 . 7 x 10-6
80.5
Toluene 80.5
Toluene
Toluene
40
50
40
5 0
1.31 x 1om4
1.30 x 10-4
1.175 x 10-4
4 . 4 5 x 1o-4
6 . 9 5 x lo-
2.89 x 1O-4
Toluene 80.5 (1.325i0.35) x 10m4
DMSO
Toluene
Toluene
DMF
DMAC
8 0 1.51 x 10-5
8 5 2 . 7 9 x lo-
90 5 . 4 0 x 10-5
9 5 9 . 7 7 x 10-5
80.3 8.3 x 1O-6
8 0 . 5 2 . 2 7 x 1O-4
3 6 . 6 5 . 3 5 x 10-5
4 5 . 4 1.45 x 1o-4
4 9 . 7 2 . 6 0 x 1O-4
6 5 1.77 x 1o-5
6 9 2 . 9 0 x 10m5
7 4 4.90 x 10-5
6 5 1.74 x 10-5
6 9 2 . 8 3 x 1O-5 3 5 7
7 4 4 . 6 5 x 1O-5 3 5 7
8 0 1 . 1 6 x 1O-4 5 4
1 4 2 . 8
134.1
1 3 3 . 9
1 3 2 . 6 h
124.7 h
115.1
a
a
exp[- 115/RT]
1 2 6 . 4 a
322
322
322
322
322
322
322
322
322
1 3 5
1 3 5
135
135
135
1 3 5
1 3 5
135
3 5 7
3 5 7
357
357
357
357
101
101
101
101
3 4 3
3 4 3
343
5 0
6 2
101
1 6 6 . 9 a 6 2
w 1 0 4
w 1 0 4
113.5
121.3
w
w
w
w
50
50
50
50
5 0
132.2 h
1 0 8 . 4
1 3 5
1 3 5
1 3 5
1 3 5
61
1 0 4
101
101
101
357
3 5 7
351
3 5 7
TABLE 1. contcf
Mi scel l aneous Azo- Deri vat i ves II/9
Number of
c atoms Initiator Solvent
TCC) kd (s-l)
E, (kJ/mol) Notes Refs.
2 0 (contd) 2,2-Azo-bis-2-isobutyl-4-methyl- Toluene 6 0 . 1 3 . 7 8 x 1O-4 50
valeronitrile 8 0 . 5 5 . 2 8 x 1O-3 50
2,2-Azo-bis-2-(4-chIorobenzyl)- Toluene 8 0 8 . 8 x 10-5 54
propionitrile
2,2-Azo-bis-2-(4-nitrohenzyI)- Toluene 8 0 1.00 x 10-4 54
propionitrile
2 2 I,1 -Azo-bis- 1 -cyclodecanenitriIe Toluene 5 0 . 8 5 . 4 0 x 10-5 101
6 0 . 2 1 . 7 0 x 10-4 101
6 9 . 5 5 . 6 9 x 10 -4 101
3 4 4,4-Azo-bis-(4-cyanopentanyl)- Di-n-butyl phthalate 90 9.86 x 1O-4 3 7 5
bis(heptadecatluorododecanoate) 1 0 0 2.11 x 10-3 3 7 5
1 1 0 4 . 4 x 10-3 3 7 5
1 2 0 1.1 x 10-2 375
1 3 0 1.42 x 1O-2 3 7 5
TABLE 2. MISCELLANEOUS AZO-DERIVATIVES
Number of
c atoms Initiator Sol vent T(C) kd (S-l) E, Wmol) Notes Refs.
2 1,l -Azo-bis-formamide DMF
DMSO
Formamide
4 Methyl-azo-3-propene
Hexamethyl-
phosphoramide
Vapor
5 2,3-Diazobicyclo[2,2,l]hept-Zene Isooctane
6 2,2-Azo-bis-propane
Toluene
Vapor
3,3-Azo-bis-1-propene Vapor
2,2-Dichloro-2,2-azo-bis-propane Diphenyl ether
Silicone oil
Methyl-azo- 1 ,I -dimethyl-2-propene
(cis)
Acetone
(tram) p-Diisopropyl-
Benzene
Pertluoroazo-2-propane Vapor
8 6 . 0
1 0 0 . 3
115.3
8 6 . 0
100.3
1 1 5 . 3
8 6 . 0
1 1 5 . 3
115.3
163.3 5.88 x 1O-4
1 6 9 . 8 1.110 x 10-3
1 8 2 . 8 3.36 x 1O-3
T 6)
3.2 x 10 I4
131.5 5.44 x 10-6
142.3 1.82 x 1O-5
164.1 1.66 x 10-4
1 8 0 . 8 8.35 x lO-4
164.1 1.64 x 10 -4
250 7.67 x 1O-3
260 1.67 x 10 -2
270 3.35 x 10 -2
280 6.52 x 1O-2
290 1.28 x lo-
1 4 2 . 6 5 3.88 x 1O-4
1 5 2 . 6 8 1.10 x 10-3
1 6 7 . 1 2 4.45 x 10-3
1 5 8 . 5 1.03 x 10-4
1 6 7 . 9 4.54 x 10-4
178.5 8.08 x 10-4
185 4.8 x 1O-4
1 9 9 2.1 x 10-3
2 2 1 1.6 x 1O-2
- 13.89 3.62 x lo-
- 5.04 1.70 x 10-4
4.00 6.82 x 10 -4
1 1 4 . 5 5 1.02 x 10-4
1 2 3 . 8 3 2.68 x 1O-4
1 3 3 . 3 3 8.44 x 1O-4
T (K) 5.01 x 106
1.56 x 1O-5
5.73 x 10-5
1.14 x 10-4
5.48 x 1O-6
2.72 x 1O-5
1.01 x 10-4
9.25 x 10-5
-2.0 x 10-3
3.83 x lo-
1 4 8
exp[- 148/RT]
1 5 7 . 7
171.1
1 5 1 . 3
1 3 8 . 3
9 6 . 8
1 4 7 . 9
exp[- 189.O/RT]
c2
c2
CZ
C
C
C
h
hru4
u4
u4
h
h
268
268
268
268
268
268
268
268
268
298
298
298
298
1 8 0
1 8 0
1 8 0
1 8 0
1 8 0
110
1 1 0
1 1 0
1 1 0
110
3 1 9
319
3 1 9
297
297
297
240
240
240
252
252
252
252
252
252
360
Notes page II - 69; References page II - 70
II/l0 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. contcf
Number of
C atoms Initiator Sol vent
T (C) kd (S-l) E, Wmol) Notes Refs.
6 (contd) I-Propyl-azo-3.propene
Triazobenzene
ferr-Butyl-azo-3-propene
2,2-Azo-isobutyramide
Azo-bis-isobutyramidine
Azo-bis-isobukyramidine
2HCl (AIBA)
AIBA
AIBA-kaolin adduct
AIBA-bentonite adduct
Azo-bis(2amidinopropane) 2HCl
2,2-Azo-bis(2-amidinopropane) 2HCl
Azo-bis-isobutyramidine 2HNOs
Methanol
Water
Water
DMSO-cumene
2.2-Azo-bis-isobutane Vapor
2,2-Azo-bis-isobutane
Vapor
Nitrobenzene
Tetralin
Water
Water
Chloroform
DMSO
Methanol
Water (pH 1.9)
Water (pH 5.8)
Water (pH 9.5)
Water
Water
Water
Water
Diphenyl ether/iso-
quinoline (90/ 10)
1 0 1 . 3 2 1.10 x 10-6
1 1 4 . 1 0 5 . 6 0 x 1O-6
1 2 6 . 0 2 2.11 x 10-5
T (K) 6 . 3 x 10 l4
1 0 5 3 . 5 x 10-7
115 1.20 x 10-6
1 3 0 6 . 2 5 x 1O-6
145 2.50 x 10m5
105 4 . 0 x 10-7
115 1.34 x 10-6
1 3 0 6.01 x 1O-6
1 4 5 2 . 4 7 x lo-
8 0 . 8 8 2 . 1 3 x 1O-6
90.90 7 . 2 7 x 1O-6
106.81 3 . 8 9 x 1O-5
T W
5 . 4 x 102
8 8 1.9 x lo-s
60 3 . 1 5 x lo-s
6 0 2 . 8 0 x 1O-5
6 0 7.1 x 10-6
70 3 . 6 8 x 1O-6
60 1.45 x 10-6
50 8 . 3 x lo+
6 0 3 . 4 2 x 1O-5
5 0 8 . 0 x 1O-6
60 3 . 2 2 x 1O-5
50 4 . 7 x 10-6
60 2 . 5 3 x 10 -5
6 0 . 0 3 . 7 0 x 10-5
7 0 . 0 1.33 x 10-4
7 5 . 0 2 . 5 8 x 1O-4
8 0 . 0 5 . 1 3 x 1o-4
40.15 2 . 4 9 x 10 -6
50.05 9 . 7 9 x 10-6
60.20 4 . 0 3 x 10-5
70.10 1.52 x 1O-4
1 0 0 . 1 0 4.96 x 1O-3
7 0 1.52 x 1O-4
5 0 . 0 1.37 x 10-5
6 0 . 0 6 . 1 6 x 10-5
7 0 . 0 2 . 2 8 x 1O-4
8 0 . 0 9 . 5 3 x 10-4
5 0 . 0 1.80 x 1O-5
5 5 . 0 3 . 9 7 x 10-5
6 5 . 0 1.53 x 1o-4
7 0 . 0 3.21 x 1O-4
8 0 . 0 1.04 x 10-3
50 1.45 x 10-5
50 8.1 x 1O-6
5 6 1.93 x 10-5
6 0 4.86 x 1O-5
70 1.53 x 10-4
1 6 0 1.9 x 10-5
1 8 0 5.01 x 10-5
1 9 0 1.53 x 10-4
210 1.05 x 10-3
1 7 4 . 8 6 . 8 x 10-5
188.3 1.75 x 10-4
188.8 1 . 1 4 x 10-4
165 2.782 x lo-
175 8 . 7 4 x 1O-5
1 8 5 2 . 5 1 3 x 1O-4
1 9 0 4.143 x 10-4
1 4 9 . 2
exp[- 149.2/RT]
1 4 0 . 2
1 3 6 . 0
1 2 4 . 9
exp[- 124.9/RT]
1 2 6 . 5
1 2 4 . 4
1 5 1 . 7
1 2 8 . 9
1 2 2 . 6
133.9
1 2 6 . 4
1 7 6 . 6
v21
v21
v21
v21
v21
v21
v21
a
q2
q3
h
h
h
h
a
a
m4
m4
m4
m4
h
2 9 8
2 9 8
2 9 8
298
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 5
298
2 9 8
2 9 8
298
/
342 :
288
288
1 8 4
21
1 8 4
3 4 1
3 4 1
3 4 1
341 )
3 4 1
3 4 1
2 3 3
2 3 3
2 3 3
2 3 3
237
237
237
237
2 3 7
2 1
233
233
233
233
233
2 3 3
2 3 3
2 3 3
2 3 3
356
356
340
21
21
339
2 2 1
2 2 1
221
2 4 3
?
243
243
171
171
171
171
TABLE 2. contd
Miscellaneous Azo-Derivatives II/11
Number of
C atoms Initiator Solvent
T ((3 kd (S-l)
-
E. Wmol) Notes Refs.
8 (contd) 2,2-Azo-bis-isobutane
2,2-Dimethoxy-2,2- azopropane
2,2-Dimethylmercapto-2,2-
azopropane
Isopropyl-azo-1, I-dimethyl-2-
propene (cis)
(trans)
9
2,2-Azo-bis(2-methylpropane)
2-(4-Bromophenyl-azo)-2-
nitropropane
tert-Butyl-azo-l,l-dimethyl-
2-propene (trans)
2-(4-Nitrophenylazo)-2-nitro-
propane
a-Phenylethyl-azo-methane Diphenyl ether
10 2,2-Diacetylthio-2,2-azopropane
2,2-Diacetoxy-2,2-azopropane Diphenyl ether
Azo-bis( 1.1 -dimethyl-2-propene)
(tram)
Azo-bis-( 1,l -dimethyl)-2-propyne
(tram)
Xylene
2,2-Azo-bis-2-methylbutane Ethylbenzene
2,2-Azo-bis-2-methylbut-3-ene n-Demure
2,2-Azo-bis-2-(methylcarboxy)-
propane
2,2-Azo-bis-methyl-2-methyl-
propionate
2,2-Azo-bis-methyl-2-methyl- Undecane
propionate Xylene
Diphenyl ether/iso-
quinoline (90/ 10)
Diphenyl ether
Diphenyl ether
Acetone
Diisopropylbenzene
Vapor
D C B
Diisopropylbenzene
D C B
Hexadecane
Diphenyl ether
Silicone oil
Xylene
Isoamyl alcohol
Water
Collidine
1,2-Dichlorobenzene
Diethyl oxalate
Ethylene glycol
Nitrobenzene
195 6 . 7 3 1 x lo-
200 1.093 x 10-3
150.1 4 . 0 2 x 1O-5
1 5 9 . 9 1.50 x 10-4
1 7 4 . 6 6 . 6 7 x 10 -4
1 2 5 . 0 3 . 4 0 x 10-4
1 3 5 . 0 7.10 x 10-4
1 4 5 . 0 1.15 x 10-3
- 25.09 6.30 x 1O-5
- 16.65 2 . 8 7 x 1O-4
- 8.20 1 . 1 0 x 1o-3
9 7 . 4 1 1.15 x 10-4
1 0 6 . 0 6 3 . 1 9 x 10-4
1 1 5 . 0 6 9 . 2 2 x 1o-4
1 6 0 1.93 x 10-5
1 3 0 1.62 x 10m4
135 2 . 5 9 x 1O-4
1 4 0 4.30 x 1o-4
T W 1.1 x 103
73.72 8 . 6 9 x 1O-5
8 0 . 3 1 1.83 x 1O-4
8 7 . 0 8 3 . 8 0 x 1O-4
1 3 0 1.00 x 10-4
1 4 0 2 . 4 4 x 1O-4
145 4.06 x 1O-4
T (K) 1.1 x 103
151 4 . 3 5 x 10 -5
161 1 . 1 6 x 1O-4
171 3 . 4 8 x 1O-4
161 1.20 x 1o-4
1 3 0 . 0 1.33 x 10-4
1 4 0 . 0 4.40 x 10-4
1 4 9 . 4 1.19 x 10-5
1 9 0 . 0 8 . 2 3 x 1O-5
2 0 0 . 1 2.61 x 1O-4
2 1 0 . 3 6 . 3 8 x 1O-4
258 1 . 4 6 x lo-
42.03 5 . 9 5 x 10-5
49.98 1.73 x 10-4
51.39 4 . 5 4 x 10-4
41.32 5 . 3 7 x 10-5
48.20 1.30 x 1o-4
57.19 4.39 x 10 -4
1 8 0 . 0 1.36 x 1O-4
1 9 0 . 0 3 . 8 9 x 1O-4
200.0 1.03 x 10-3
1 8 0 . 0 1.14 x 1o-4
1 9 0 . 0 3.51 x 1o-4
200.0 9 . 2 6 x 1O-4
44.90 6 . 7 3 x lo-
55.44 2 . 6 3 1 x 1O-4
63.74 7.045 x 10 -4
5 0 3.51 x 10-6
8 0 1.67 x 1O-4
8 0 1.44 x 1o-4
8 0 1.52 x 1O-4
8 0 1 . 2 4 x 1O-4
8 0 1.61 x 1O-4
1 0 0 1.73 x 10-3
80 1.04 x 10-4
8 0 1.09 x 10-4
1 7 1 . 8
8 4 . 6
9 1 . 3
137.8
1 3 0
exp[- 130/RT]
1 1 2 . 3
1 3 4
exp[- 134/RT]
1 6 1 . 5
1 5 1 . 3
1 7 1 . 4
1 0 9 . 4
1 1 1 . 9
1 7 6 . 4
1 7 6 . 0
107.3
129.3
149.8
b5
U5
U5
h
h
a
h
h
h
171
171
291
297
297
291
2 9 7
297
252
252
252
252
252
252
340
3 2 5
3 2 5
325
3 2 5
252
252
252
3 2 5
3 2 5
3 2 5
3 2 5
1 4 9
1 4 9
1 4 9
1 4 9
297
297
297
2 9 7
297
297
240
h
h
h
h
h
252
252
252
252
252
252
336
336
336
336
336
336
278
278
278
2 8 5
a 226
a 226
a 226
a 226
a 226
a 226
a 226
a 6 2
Notes page 11-69; References page II- 70
II/12 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. contd
Number of
C atoms Initiator Solvent
T(Cl ka (S-l) E. Wmol) Notes Refs.
IO (contd) N,N-Azo-piperidine
2-(4-Methoxyphenylazo)-
2-nitropropane
Silicone oil
D C B
Dimethyl 2,2-azo-isobutyrate Acetic acid
Dimethyl-2,2-azo-isobutyrate Methanol
11
2,3,7,8-Tetraazahexacyclo-
[7.4.1.04~2.06~1.00~3]tetradeca-
2,7-diene
2-(2,6-Dimethylphenylazo)-
2nitropropane
cc-Phenylethyl-azo-2-propane
12 Azo-bis-isobutanoldiacetate Cyclohexane
Azo-bis-(I-carbomethoxy-3-methyl-
prowe)
4,4-Azo-bis-(4-cyanopentanoic acid)
(meso)
Acetonitrile
Benzene
Cyclohexane
Methanol/SnCl4
Methanol/ZnCl 2
Paraffm
Toluene
Toluene/SnCl 4
Acetonitrile-d 3
D C B
Diphenyl ether/
benzoquinone
Diphenyl ether
Benzene
Carbon tetrachloride
DMAC
181 1.7 x 10-3
228 4.3 x 10-2
1 3 5 7.4 x 10-5
1 4 0 1.30 x 10-4
1 5 0 3.67 x 1O-4
T 6)
2.5 x lOIs
40 8.61 x 10-7
50 3.16 x 1O-6
60 1.56 x 1O-5
70 5.49 x 10-5
40 5.44 x 10-7
50 2.68 x 1O-6
60 1.01 x 10-5
70 3.57 x lo-s
50 2.22 x 10-6
60 8.85 x 1O-6
70 3.27 x 1O-s
40 2.89 x lo-
50 1.38 x 1O-6
60 5.85 x 1O-6
8 0 2.22 x 1o-s
40 6.86 x 10-7
50 3.12 x 1O-6
60 1.44 x 10-5
40 1.20 x 10-6
50 4.46 x 1O-6
60 1.98 x 1O-s
60 1.51 x 10-5
9 9 . 2 1.02 x 10-3
60 8.9 x 10-6
60 8.11 x 10-6
66 1.93 x 10-5
70 3.17 x 10-5
8 0 1.19 x 10-4
60 1.63 x 1O-4
2 1 5 1.18 x 1O-s
230 6.65 x 1O-s
250 3.40 x 10-4
1 3 5 9.0 x lo-s
1 4 0 1.44 x 10-4
1 5 0 3.86 x 1O-4
T 6) 4.8 x lOI3
1 4 3 . 2 1.50 x 10-4
1 4 3 . 0 1.54 x 10-4
1 5 2 . 0 4.24 x 1O-4
165.5 1.570 x 10-3
1 7 0 . 0 4.86 x 1O-s
1 8 0 . 0 1.27 x 1O-4
1 8 9 . 0 3.47 x 10-4
1 9 9 . 0 1.01 x 10-3
3 6 3.05 x 10-7
4 5 1.31 x 10-6
55 4.54 x lo-6
6 5 1.82 x 10-5
4 5 7.18 x lo-
5 5 3.79 x 10-6
6 5 1.02 x 10-5
7 7 . 6 1.33 x 10-4
8 5 . 3 3.70 x 10-4
90.9 7.17 x 10-4
99.8 2.02 x 10-3
1 5 3
exp[- 153/RT]
1 3 1 . 6
1 8 8 . 7
exp[- 138/RZj
133.5
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
Xl
Xl
Xl
t13
t13
t13
240
240
3 2 5
3 2 5
3 2 5
3 2 5
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
240
290
340
340
340
340
290
1 7 4
1 7 4
1 7 4
325
325
325
325
220
310
310
310
1 8 9
1 8 9
1 8 9
1 8 9
6 8
6 8
6 8
6 8
6 8
6 8
6 8
2 0 5
2 0 5
2 0 5
205
TABLE 2. contd
Miscellaneous Azo- Deri vat i ves II/13
Number of
C at oms Initiator Sol vent T (Cl kd (S-l) E. Wmol) Notes Refs.
12 (contd) 4,4-Azo-bis-(4-cyanopentanoic acid)
(Doi)
@D+)
(Do-)
2,2-Azo-bis-(ethyl-2methyl- Chlorobenzene
2,2-Azo-bis-[2-methyl+
(2-hydroxyethyl) propionamide]
Azo-bis-(PI&-dimethyleneisobutyr-
amidine) 2HNOs
Azo-bis-(N,N-dimethylene
isobutyramidine) 2HCl
Azo-bis-(N,N-dimethyleneisobutyr-
amidine)
terr-Butyl(2,2,4-trimethyl-
2-pentyl)diazene
DMSO-tetralin
Methanol
Diphenyl ether
wCumyl-azo-isopropane Diphenyl ether
2,2-Dicyclopropyl-2,2-azopropane
Di-(2-hydroxyethyl)-2,2-azo-
bis-isobutyrate
14
2,2-Azo-bis[N-(2-hydroxyethyl)-
2-methylpropionamidine] 2HCl
2,2-Azo-bis[2-(imidazoline-2-yl)-
propane 2HCl
2,2-Azo-bis[2-(imidazoline-2-yl)-
propane
2,2-Azo-bis-(2-cyclobut-
I-enylpropane)
Nitrobenzene
Water
DMSO
DMSO-cumene
DMSO-tetralin
Water
DMSO
DMSO-cumene
Diphenyl ether/
isoquinoline (90/ 10)
Dioxane
DMF
Toluene
Water
8 0 1.79 x 10-4
7 5 8.04 x 1O-5
8 0 1.39 x 1o-4
8 5 2.6 x 1O-4
60 1.09 x 10-5
61 1.9 x 10-5
1 5 5 1.61 x 1O-4
165.7 4.15 x 10-4
1 8 0 . 0 1.98 x 1O-3
1 2 0 . 0 1.06 x 1O-4
1 3 5 . 0 5.94 x 10-4
1 4 3 . 0 1.421 x 1O-3
1 4 5 . 0 7.56 x 1O-5
1 5 0 . 0 1.273 x 1O-4
1 5 5 . 0 2.147 x 1O-4
1 6 0 . 0 3.771 x 10-4
1 6 5 . 0 6.07 x 1O-4
1 7 0 . 0 1.033 x 1o-3
60 1.61 x 1O-5
70 5.88 x 1O-5
8 0 2.02 x 10-4
6 0 1.53 x 10-5
70 5.62 x 1O-5
8 0 2.0 x 1o-4
60 1.62 x 1O-5
70 5.83 x 1O-5
8 0 2.066 x 10 -4
5 8 1.93 x 10-5 a
21
21
21
21
21
339
314
314
314
310
310
310
171
171
171
171
171
171
292
292
292
292
292
292
292
292
292
339
Methanol 50 4.83 x 1o-5 356
Water 50 4.02 x 1O-5 356
Methanol
n-Decane
5 0 4.7 x 10-6
3 9 . 2 1 1.286 x 1O-4
50. 7 1 5.678 x 1O-4
5 8 . 9 5 1.762 x 1O-3
112.3 h
356
278
278
278
1 7 . 9 1.53 x 10-4
8 5 . 8 4.11 x 10-4
90.1 7.00 x 1o-4
9 9 . 1 2.09 x 1O-3
78.0 1.55 x 10-4
8 5 . 4 4.05 x 10-4
90.0 6.98 x 1O-4
99.0 2.00 x 10-3
7 7 . 7 1.51 x 10-4
8 6 . 0 4.34 x 1o-4
9 0 . 5 7.33 x 10-4
9 9 . 7 2.24 x 1O-3
70 4.13 x 10-5
9 2 . 6 5.93 x 1o-4
8 0 1.56 x 1O-4
8 6 1.9 x 1o-5
60 2.06 x 1O-4
70 6.64 x 1O-4
15 1.08 x 10-3
70 6.97 x 1O-4
6 0 2.13 x 1O-4
44 1.9 x 1o-5
1 2 3 . 0
1 5 9 . 6
1 5 8 . 2
1 2 5 . 7
1 2 9 . 9
1 2 9 . 9
a 2 0 5
a 2 0 5
a 2 0 5
a 2 0 5
a 2 0 5
a 2 0 5
a 205
a 205
a 2 0 5
a 205
a 205
a 2 0 5
a 1 3 9
a 1 3 9
a 226
a 342
a
21
2 1
21
21
21
339
a
h
h
Notes page II - 69; References page II - 70
II/14 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. contd
Number of
C atoms Initiator Sol vent
T (0 ka (S-l) E. Wmol) Notes Refs.
14 (cornd) 2,2-Azo-bis-(2-methylhex-3-ene) n-Decane
Di-(2-chloroethyl)-2,2-azo-bis-
isobutyrate
Di-(2-chloroethyl)-2,2-azo-bis-
isobutyrate
1 ,l -bis-(4-Chlorophenyl)
azomethane
Di-(2-hydroxypropyl)-
2,2-azo-bis-isobutyrate
2,2,3,3,3,3-Hexamethyl.
2,2-azo-butane
1,l -Diphenyl-azo-methane Diphenyl ether
15
2,2-Azo-bis[2-methyl-N-(phenyl-
methyl)propionamidine] 2HCl
2,2-Azo-bis[2-(4-methyl-
imidazoline-2-yl)-propane
2,2-Azo-bis[2-(4-methylimidazoline-
2-yl)-propane 2HC1
2,2-Azo-bis[2-(3,4,5trihydro-
pyrimidine-2-yl)propane
2,2-Azo-bis[2-(3,4,%rihydro-
pyrimidine-2-yl)propane 2HCl
1-Methylcyclopentyl-azo-
cc-cumene
16 1,l -Azo-bis-l-chloro-
I-phenylethane
1.1 -Azo-bis-l-chloro-l-
(3-bromophenyl)ethane
l,l-Azo-bis-l-chloro-l-
(4-bromophenyl)ethane
Dioxane
DMF
Toluene
Diphenyl ether
Dioxane
DMF
Diphenyl ether
Water
Methanol 50 1.23 x 1O-5 356
Methanol 50 7 . 4 8 x 1O-5 356
Water 50 6 . 7 3 x 1O-5 356
Methanol 50 1.1 x 10-6 356
Methanol
Water
rert-Butyl benzene
50 7 . 8 x 1O-6
50 5 . 9 x 10 -6
8 8 . 3 5 . 0 0 x 10-5
107.3 4 . 9 5 x 10-4
1 1 7 . 6 1.43 x 10-3
7 4 . 8 8 . 6 x 1o-4
8 3 1.95 x 10-3
6 7 . 8 2 . 8 x 1O-4
8 6 . 2 3 . 3 x 10-3
9 8 . 2 1 . 4 0 x 10-2
9 4 . 5 2 . 4 x 1O-3
112.3 5 . 2 x 1O-2
120.5 1.03 x lo-r
129.3 1.6 x lo-
1 3 7 5 . 0 x 10-1
64 1.8 x 1O-4
74 7 . 2 x 1O-4
64 1.79 x 10-4
74 7 . 2 0 x 1O-4
59 1 . 6 4 x 10-4
69 6.64 x 1O-4
59 1.77 x 10-4
6 9 6 . 7 5 x 1O-4
1 3 2 . 0
356
356
h 3 2 7
327
327
240
240
240
240
240
240
240
240
240
240
240
240
a 239
a 239
a 239
a 239
a 239
a 239
Acetophenone
Benzophenone
Pa&in
Toluene
Toluene
Toluene
3 9 . 2 5 5 . 3 3 x 10-5
49.52 2.256 x 10 -4
5 8 . 9 5 7.584 x 10 -4
6 0 1.56 x lo-s
7 0 5 . 5 5 x 10-5
8 0 1 . 9 6 7 2 x 10 -4
6 0 1.25 x 1O-5
70 4.902 x 1O-5
8 0 1.9125 x 1O-4
60 1 . 6 6 6 x 10-5
70 5.018 x 1O-5
8 0 1.99 x 1o-4
1 4 5 . 5 6 2.30 x 1O-4
155>56 7.60 x 1O-4
1 6 5 . 5 6 1.49 x 10-3
1 7 5 . 5 6 4.40 x 10-3
60 1.80 x 1O-5
70 7 . 6 x 1O-5
80 2 . 2 2 x 10-4
60 1.97 x 10-5
70 6 . 5 5 x 1O-5
80 2 . 3 0 x 1O-4
60 1.90 x 10-5
70 7 . 7 2 x 1O-5
8 0 2 . 3 6 5 x 1O-4
1 7 0 . 0 2 . 3 7 x 1O-4
1 8 0 . 0 5 . 2 9 x 1O-4
1 9 0 . 0 1.00 x 10-3
1 4 5 . 0 1.72 x 1O-4
1 5 5 . 0 4 . 9 3 x 10-4
1 6 5 . 0 1.12 x 10-3
1 7 5 . 0 2 . 3 4 x 1O-3
5 3 1.93 x 10-5
1 1 5 . 2
1 2 9 . 9
134.1
1 2 9 . 9
1 4 6 . 6
121.5
1 2 1 . 5
121.5
1 5 6 . 7
1 1 9 . 0
135.1
1 3 1 . 8
1 2 7 . 2
h 278
278
278
292
292
292
292
292
292
292
292
292
h 297
297
297
297
292
292
292
292
292
292
292
292
292
h 297
297
297
h 297
297
297
297
a 339
TABLE 2. contd
Miscellaneous Azo- Deri vat i ves II/W
Number of
C atoms Initiator Solvent
T 03 kd (S-l) E. Wmol) Notes Refs.
16 (conrd) 1,l -Azo-bis-l-chloro-l-
(4-chlorophenyl)ethane
2,2-Azo-bis-(2-cyclopent-l-
e n y l p r o p a n e )
To l u e n e
n-Decane
1,l -Azo-bis-l,l-dicyclo- Diphenyl ether/
p r o p y l e t h a n e isoquinoline (90/ 10)
2,2-Azo-bis-(2-methyl-N-[l,l-
(bis-hydroxymethyl)-2-hydroxyethyl]
propionamide)
2,2-Azo-bis-[2-methyl-N-[l,l-
(bis-hydroxymethyl)ethyll
pr opi ona mi de )
2,2-Azo-bis[2-(4,
4-dimethylimidazoline-2-yl)
ewme
2,2-Azo-bis[2-(4,4-dimethyl-
imidazoline-2-yl)propane 2HCl
2,2-Azo-bis[2-(4,5dimethyl-
imidazoline-2-yl)propane 2HCl
2,2-Azo-bis[2-(4,5,6,7-tetrahydro-
lH-1,3-diazepine-2-yl)propane
2HCl
2,2-Azo-bis-(2,2,4-trimetbyl-
pe nt a ne )
1,l -Azo-bis-1-phenylethane
1,l -Azo-bis-1-phenylethane
(l,l-dd
(l,l,l,l,l,l-de)
rert-Butyl-(2,2,4,6,6-penta-
methyl-4-heptyl)-diazine
1,l -Di-(3-chlorophenyl)-l,l-
a z o - e t h a n e
1,l -Di-(4-chlorophenyl)-l,l-
a z o - e t h a n e
u,cr-Diethylbenzyl-azo-3-pentane
l,l-Di-(3-fluorophenyl)-
1,l -azo-ethane
1.1 -Di-(4-fluorophenyl)-
1,l -azo-ethane
Di-(3-hydroxybutyl)-2,2-azo-bis-
i s o b u t y r a t e
59 1.97 x 1o-4
69 6.93 x 1O-4
39.21 9.98 x 1O-5
49.52 4.593 x 10-4
58.95 1.528 x 1O-3
1 2 0 6.33 x lo-*
1 3 0 2.03 x 1O-4
1 4 0 6.07 x 1O-4
1 5 0 1.695 x 1O-3
8 0 1.9 x 10-5
118.8
116.9
a
a
h
149.0 h
Wat er a
239
239
278
278
278
171
171
171
171
342
Water 8 2 1.9 x 10-5 a 342
Me t ha nol 50 9.3 x 10-6 356
Me t ha nol
Water
50
50
9.55 x 10-5
9.30 x 10-5
356
356
Me t ha nol 50 9.21 x 1O-5 356
Water 50 8.94 x lo- 356
Me t ha nol 5 0 1.23 x 1O-5 356
Water 50 1.04 x 10-5 356
Diphenyl ether
Do d e c a n e
Et h y l b e n z e n e
To l u e n e
Et h y l b e n z e n e
1 1 0 1.9 x 10-5 a 339
97.3
100.4
110.3
105.02
105.28
105.28
105.02
97.3
97.3
97.3
97.3
140.0
150.1
164.8
9 5
105
8 5
9 5
105
120.05
130.0
139.0
147.0
105
3.175 x 10-5
(5.45 f 0.05) x 1o-5
(1.6950.01) x 1O-4
8.473 x 10 -
9.02 x 1O-5
7.62 x 1O-5
7.623 x 1O-5
4.135 x 10-5
3.688 x lo-s
3.995 x 10-5
3.294 x 10 -5
1.93 x 1o-4
5.29 x 1O-4
2.18 x 1O-3
4.13 x 10-5
1.218 x 1O-4
1.45 x 10-5
4.82 x 1O-5
1.650 x 1O-4
7.8 x 1O-5
2.63 x 1O-4
7.38 x 1O-4
1.906 x 1O-3
1.121 x 10-4
5.5 x 10-6
2.35 x 1O-5
7.85 x 1O-5
2.22 x 10-5
7.84 x 1O-5
2.413 x 1O-4
1.83 x 1O-5
7.69 x 1O-5
2.424 x 10 -4
136.4
N-Methyl-N-benzyl aniline
N-Methyl propionamide
Diphenylmethane
Pr opyl e ne c a r bona t e
Diphenyl ether 141.6 h
p-Cymene
p-Cymene
122.3 h
h
Diphenyl ether
p-Cymene
p-Cymene
2 6
107,98
107,98
1 5 2
1 8 3
1 8 3
1 5 2
2 6
2 6
2 6
2 6
314
314
314
266,313
266,3 13
266.313
266,313
266,313
310
310
310
310
266,313
Dioxane
D M F
8 5
9 5
105
60
70
8 0
6 0
70
8 0
147.0 h
117.3
121.5
266,3 13
266,313
266,313
292
292
292
292
292
292
Notes page II - 69; References page II - 70
II/16 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. contd
Number of
C atoms Initiator Sol vent T (3 kd (s-l) E, Wmol) Notes Refs.
16 (contd) Di-(3-hydroxybutyl)-2,2-azo-bis-
isobutyrate
Di-(4-hydroxybutyl)-azo-bis-
isobutyrate
1 ,l -Bis-(4-methoxyphenyl)-
azo-methane
Diphenyl ether
2,2,4,4,4,4-Hexamethyl-
2,2-azo-pentane
Diphenyl ether
1 -Methylcyclohexyl-azo-a-cumene rerr-Butylbenzene
1 ,l -Diphenyl- 1,l -azo-ethane
2-(Phenylazo)-2-propyl perbenzoate
(I-Phenylethyl)-azo-diphenylmethane
1,l -Bis(p-tolyl)-azo-methane
1 7 3,7-Diphenyl-1,2-diaza-l-cyclo-
heptene
1 8 1,l -Azo-bis-cumene
Toluene
Dioxane
DMF
p-Cymene
Chlorobenzene
Chloroform-d
Chlorotoluene
Ethylbenzene
Diphenyl ether
Benzene
rerr-Butylbenzene
Chlorobenzene
Cumene
Dodecane
n-Octane
Toluene
6 0 2.43 x 10 -
IO 8.18 x 10-5
8 0 2.461 x 1O-4
6 0 2.12 x lo-s
7 0 6.57 x 1O-5
8 0 2.539 x 10 -4
6 0 1. 97 x 1om5
7 0 6.19 x 1O-5
8 0 2.50 x 1O-4
6 0 2.59 x 1O-5
7 0 6.66 x 10-5
8 0 2.628 x 1O-4
145.0 2.23 x 1O-4
155.0 5.67 x 1O-4
165.0 1. 61 x 1O-3
175.0 3.79 x 1o-3
130. 2 1. 82 x 1O-4
140.0 4. 51 x 10-4
150.0 1. 28 x 1O-3
102.2 2.58 x 1O-4
113. 1 9. 81 x 10-4
122.0 2.20 x 10-3
9 5 2.74 x lo-
1 0 5 8. 21 x lo-
1 0 4.5 x 10-4
3 5 1 . 9 x 10-3
1 0 5 . 1 x 10-4
1 0 6.4 x 1O-4
5 8 1 . 9 x 10-5
145.0 2.00 x 10-4
155.0 4.69 x 1O-4
165.0 1. 22 x 10-3
175.0 3.45 x 10-3
61.0 3.80 x 10-5
70.0 1. 34 x 1o-4
80.0 4.21 x 1O-4
89.3 1. 59 x 10-3
100.2 4.04 x 10-3
8 0 4.26 x 1O-4
100.2 3.94 x 1o-3
58.91 1. 94 x 1o-4
6 0 1. 03 x 1o-4
6 0 4.03 x 10-5
6 0 4.44 x 10-6
5 5 8.50 x 1O-5
5 5 6.88 x 1O-5
5 5 4.42 x 1O-5
5 5 8.10 x 10-5
5 5 6.75 x 1O-5
5 5 3.83 x 10 -5
6 0 1. 16 x 1O-4
6 0 4.73 x 1o-5
6 0 7.23 x 1O-6
60.23 1. 47 x 1o-4
6 0 1.14 x 10-4
6 0 4.44 x 10-5
6 0 8.32 x lO-j
40.04 9.46 x 1O-6
49.52 4.33 x 10-5
59.42 1. 62 x 1O-4
69.23 5.80 x 10-4
41.0 9.6 x 1O-6
44.8 1. 98 x 10-5
58.5 1.280 x 1O-4
117. 3
125.7
125.7
121. 5
145.0 h
132.8 h
131. 1 h
124.0 h
a
145.4 h
a
a
vs
z (1256)
z (3890)
z (1013)
z (4154)
z (1013)
z (4154)
z (1256)
z (3890)
z (1256)
z (3890)
h
122.8
292
292
292
292
292
292
292
292
292
292
292
292
291
297
297
297
297
297
297
327
327
327
266,313
266,313
372
3 7 2
372
3 7 2
339
291
297
297
297
1 3 8
1 3 8
1 3 8
1 3 8
1 3 8
4 4
4 4
217
3 3 3
3 3 3
333
280
280
280
280
280
280
3 3 3
3 3 3
3 3 3
217
3 3 3
3 3 3
3 3 3
217
217
217
217
309
309
309
TABLE 2. contd
Miscellaneous Azo- Deri vat i ves II/17
Number of
C atoms Initiator Solvent
T (0 kd (S-l) E. Wmol) Notes Refs.
18 (contd) 1,l -Azo-bis-4-bromocumene Toluene
1.1 -Azo-bis-3-chlorocumene Toluene
1,l -Azo-bis-4-chlorocumene Toluene
1,l -Azo-bis-l-chloro-l-(Ctolyl)-
ethane
Acetophenone
2,2-Azo-bis[2-(4-ethyl-4-methyl-
imidazoline-2-yl)propane 2HCl
2,2-Azo-bis[2-(4-ethyl-5-methyl-
imidazoline-2-yl)propane 2HCl
2,2-Azo-bis[2-(5,5-dimethyl-3,4,5-tri-
hydropyrimidine-2-yl)propane
2,2-Azo-bis[2-(5,5-dimethyl-3,4,5-tri-
hydropyrimidine-2-yl)propane 2HCl
1,l -Azo-bis-4-fluorocumene
1 ,l -Di-3-ttifluoromethyl-
phenyl)- 1 ,l -azo-ethane
1 ,l -Azo-bis-(2-methoxyphenyl).
ethane
1 ,l -Azo-bis-(2-methoxyphenyl)-
ethane
1,1 -Azo-bis-(3-methoxyphenyl)-
ethane
1 ,l -Azo-bis-(4-methoxyphenyl)-
ethane
1,l -Azo-bis- 1-(6methoxyphenyl)-
ethane
1,l -Azo-bis- 1 -phenylpropane
2,2-Azo-bis-2-phenyl-hexafluoro-
propane
1,l -Dimethyl-azo-cyclooctane
1.1 -Diphenyl-azo-cyclopropane
Paraffin
Toluene
Methanol
Water
Methanol
Water
Methanol
Methanol
Water
Toluene
p-Cymene
p-Cymene
Ethylbenzene
p-Cymene
p-Cymene
Ethylbenzene
Toluene
Benzene
Benzene
Ethylbenzene
4 2 . 8
48.6
5 8 . 0
3 6 . 0
4 2 . 8
48.2
61.1
36.0
4 2 . 8
4 8 . 2
7 4 . 8
7 9 . 5
8 6
1 0 5
109.5
1 2 6
135.5
5 9
6 9
59
6 9
50
50
50
50
50
5 0
50
3 6 . 0
4 2 . 8
48.2
61.1
9 5
105
8 4 . 6
9 5
1 0 5
1 0 6 . 0 6
113.81
1 3 3 . 6 6
9 5
105
9 5
105
1 0 0 . 4
110.3 (2.48 f 0.02) x 1O-4
1 0 0 . 4 (2.35 fO.l) x 1O-5
110.3 (7.2f0.2) x 1O-5
45.0 8 . 3 6 x lo+
5 0 . 0 2 . 1 6 x 1O-5
5 5 . 0 4.92 x 1O-5
6 0 . 0 8.81 x 10-5
6 7 . 0 2 . 4 6 x 1O-4
4 3 . 8 6 . 3 x 1O-5
5 3 . 8 2 . 4 x 1O-4
1 3 0 . 0 1.09 x 10-4
1 4 0 . 0 3 . 0 5 x 10-4
1 5 0 . 0 8 . 9 6 x 1O-4
1 6 5 . 0 9 . 6 x lo-
1 7 5 . 0 2.21 x 10-4
1 8 5 . 0 5 . 0 9 x 1o-4
1 7 0 . 0 1.67 x 1O-4
1 8 0 . 0 3 . 4 8 x 1O-4
2 . 7 2 x 1O-5
6 . 2 8 x 1O-5
2.189 x 1O-4
8 . 8 x 10-6
2 . 4 6 x 1O-5
5 . 5 5 x 10-5
2.796 x 10 -4
1.11 x 10-5
2 . 9 0 x 1O-5
6 . 5 2 x lo-
2.1 x 10-3
3 . 0 x 10-3
7 . 4 x 10-3
1.66 x 10-3
2 . 5 x lo-
6 . 4 x lo-
1.7 x lo-
1.03 x 10-4
4 . 0 x 10-4
1.03 x 1o-4
3 . 9 3 x 10-4
6.80 x 10-5
7 . 3 8 x 1O-5
9 . 4 8 x 1O-5
1.1 x 10-4
9 x 10-7
8 . 0 x 1O-6
7 . 9 x 10-6
5 . 7 x 10-6
1.31 x 10-5
2.94 x lo-
1 . 8 8 0 x 10-4
4 . 1 3 x 10-5
1.357 x 10-4
1.69 x 1O-5
6.11 x 1O-5
1.975 x 10-4
2 . 2 9 x 1O-5
5 . 5 2 x 1O-5
4 . 8 7 x 1O-4
1.53 x 10-5
6.91 x 1O-5
3.56 x 1O-5
1 . 0 9 0 x 1o-4
(7.15 *o.l) x 10-5
117.7
1 1 5 . 9
1 1 2 . 5
1 2 6 . 8 a
1 1 5 . 9
1 3 4 . 9 h
1 3 5 . 6 h
1 7 1 . 8
1 2 6 . 5 h
1 4 9 . 8
135.1
1 3 7 . 2 h
115.5
145.8 h
135.3 h
309
309
309
200
200
200
200
200
200
200
240
240
240
240
240
240
240
240
240
239
239
356
356
356
356
356
356
356
200
200
200
200
266,313
266,313
266
266,3 13
266,313
300
300
300
266,313
266,313
266,313
266,313
9 8
9 8
9 8
9 8
1 7 3
173
173
173
173
4 2
4 2
3 2 7
3 2 7
3 2 7
3 2 3
3 2 3
3 2 3
3 2 3
3 2 3
Notes page II - 69; References page II - 70
II/l8 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. cont d
Number of
C atoms Initiator Sol vent
T ((3 ka (S-l) E. Wmol) Notes Refs.
18 (contd) 3,8-Diphenyl-1,2-diaza-l-
cyclooctene
I,1 -Di-(3-tolyl)-1,l -azo-ethane p-Cymene
1.1 -Di-(Ctolyl)-1,l -azo-ethane pCymene
19 Phenyl-azo-diphenylmethane
2-(2-Phenyl-4-methylpentyl)-
azo-2-(4-methylpentane)
Decalin
Diphenyl ether
20 1,l -Azo-bis-l-acetoxy-
I-phenylethane
Paraffin
1,l -Azo-bis- 1, I-dicyclopropyl- Diphenyl ether/
butane isoquinoline (90/ 10)
9-Azo-bis-decalin (cis) Ethylbenzene
(rruns)
~,a-Azo-bis(a-methylbenzyl) diacetate Dichlorobenzene
Azo-bis-4-methylcumene Cumene
2,2-Azo-bis[2-(4-ethyl-5-isopropyl- Methanol
imidazoline-2-yl)propane 2HCl Water
2,2-Azo-bis-2-(4-tolyl)-propane Toluene
l,l-Azo-bis-l,l,l-tricyclopropyl- Diphenyl ether/
methane isoquinoline (90/ 10)
1 ,l -Di-(4-ethylphenyl)-
1, 1-azo-ethane
1,l -Diphenyl-azo-butane
1,l -Diphenyl-azo-cyclobutane Ethylbenzene
Tetralin
Toluene
Decalin/
isoquinoline (90/10)
Isoquinoline
Cumenel
isoquinoline (90/ 10)
pCymene
Ethylbenzene
1 4 3 9 . 5 2 x 1O-5
151 2 . 0 9 x 1O-4
1 6 5 8 . 7 7 x 1O-4
1 7 3 1.82 x 1O-3
1 0 5 8 . 1 7 x 1O-5
9 5 3 . 0 6 x lo-*
1 0 5 9 . 3 5 x 1o-5
124.5 3 . 4 4 x 10-5
144.5 2 . 6 9 x 1O-4
1 0 3 . 0 1.17 x 1o-4
1 1 0 . 0 2 . 5 2 x 1O-4
1 2 0 . 0 8.51 x 1O-4
1 3 0 . 0 2 . 6 1 1 x 1O-3
131 3 . 2 x lo-*
1 4 2 4 . 3 x 10-2
149.5 8 . 0 x IO-*
1 2 0 . 0 4.26 x 1O-5
1 2 5 . 0 7 . 9 4 x lo-s
1 3 0 . 0 1.49 x 10-4
1 3 5 . 0 2.697 x 1O-4
1 4 0 . 0 4.774 x 10 -4
1 4 7 . 0 1.055 x 10-3
1 8 0 . 0 1.41 x 10-4
1 9 0 . 0 3 . 9 5 x 10-4
200.0 1.05 x 10-3
1 8 0 . 0 1.90 x 1o-4
1 9 0 . 0 5 . 3 5 x 10-4
200.0 1.41 x 10-3
6 5 1.86 x 10-5
70 4.00 x 10-5
80 1 . 5 9 2 x 1O-4
90 5 . 5 2 5 x 1O-4
5 5 8 . 8 6 x lo-s
5 5 7 . 5 4 x 10-5
5 5 4 . 4 7 x lo-s
41.0 1.33 x lo-s
4 9 . 5 5 . 0 2 x 1O-5
5 8 . 5 1 . 6 9 0 x 1O-4
50 7 . 7 2 x 1O-5
50 1.01 x 1o-4
3 6 . 0 8 . 4 x 1O-6
4 2 . 8 1.62 x 1O-5
61.1 2 . 0 8 x 1O-4
1 0 5 . 0 7.89 x lo-s
1 1 0 . 0 1 . 3 7 4 x 1o-4
1 1 5 . 0 2.36 x 1O-4
1 2 0 . 0 4 . 5 8 x 1O-4
1 2 5 . 0 7.76 x 10-4
1 3 0 . 0 1.38 x 1O-3
1 3 5 . 0 2 . 3 9 x 1O-3
118.5
118.5
118.5
9 5
105
93.88
1 0 5 . 6 8
1 1 9 . 5 5
6 3 . 2
7 3 . 8
79.1
8 7 . 7
3 . 6 0 x 1O-4
3 . 3 0 x 10-4
445 x 10-4
3 . 0 2 x 1O-5
9.14 x 10-5
1.67 x 1O-5
6 . 9 6 x 1O-5
3 . 3 9 x 10-4
8 . 2 x 1O-6
3 . 5 x 10-5
6 . 9 x 1O-5
1.69 x 1O-4
1 5 3 . 6
126.5
1 4 2 . 3
1 5 9 . 0
175.1
175.1
1 2 0 . 7
1 1 0 . 0
1 4 3 . 5
125.3
122.3
1 3 7
1 3 7
1 3 7
1 3 7
266,313
h 266,313
266,313
46
46
310
310
310
310
240
240
240
h 171
171
171
171
171
171
h 3 3 5
335
3 3 5
h 335
3 3 5
3 3 5
366
366
366
366
280,333
z (1013) 280,333
z (4154) 280,333
309
309
309
356
356
200
200
200
h 171
171
171
171
171
171
171
171
171
h 171
266,313
a 266,313
a 300
;: 3 0 0 3 0 0
3 2 3
3 2 3
3 2 3
b,h 3 2 3
TABLE 2. contd
Miscellaneous Azo-Derivatives II/19
Number of
C atoms Initiator Solvent T (C) ka (S-l) E. Wmol) Notes Refs.
20 (mlfd)
2 2
(-)-(s)-l,l-Diphenyl-l-
methyl-azo-methane
2,2-Azo-bis(2-methyl-fV-phenyl-
propionamidine) 2HCl
2,2-Azo-bis[N-(4-chlorophenyl)-
2-methylpropionamidine] 2HCl
2,2-Azo-bis[N-(4-hydroxyphenyl)-
2-methylpropionamidine] 2HCl
1,l -Azo-bis-1-phenyl-3-
methylbutane
1,l -Azo-bis-4-ethylcumene
1,l -Azo-bis-4-isopropylcumene Toluene
1,l -Diisopropyl- l,l-
diphenyl-azo-ethane
1,l -Diphenyl-azo-
cyclopentane
2 4
2,2-Azo-bis[2-methyl-fV-(phenyl-
methyl)propionamidine] 2HCl
2,2-Azo-bis[2-(4-methyl-4-isobutyl-
imidazoline-2-yl)propane 2HCl
2,2-Azo-bis[2-(4-methyl-Sisobutyl-
imidazoline-2-yl)propane 2HCl
2,2-Azo-bis[2-(4-ethyl-S-propyl-
imidazoline-2-yl)propane 2HCl
1,l -Azo-bis-4-rerr-butylcumene
~,a-Azo-bis(a-methylbenzyl)-
dimethacrylate
Bis(2,2,4,6,6-pentamethyl-
4-heptyl)diazine
1,l -Diphenyl-azo-cyclohexane Benzene
2 5 3-Bromophenyl-azo-triphenyl-
methane
4-Bromophenyl-azo-triphenyl-
methane
4-Hydroxyphenyl-azo-triphenyl-
methane
2-Nitrophenyl-azo-9-phenylfluorene Toluene
4-Nitrophenyl-azo-9-phenylfluorene
2,4-Dinitrophenyl-azo-9-phenyl-
fluorene
2-Nitrophenyl-azo-triphenylmethane
3-Nitrophenyl-azo-triphenylmethane
Cumene
Water
Water
Water
Ethylbenzene
Toluene
Ethylbenzene
Benzene
Water
Methanol
Water
Methanol
Water
Methanol
Water
Toluene
Dichlorobenzene
Diphenyl ether
Toluene
Toluene
Acetic acid
Pyridine
Toluene
Toluene
Toluene
Toluene
Toluene
Benzene
ferr-Butylbenzene
1 0 6 . 0 8 . 2 6 x 1O-6
1 2 7 . 9 1.18 x 1O-4
4 5 1.93 x lo-s
4 5 . 5 1.93 x 10-5
4 7 . 5 1.93 x 1o-5
1 0 0 . 4 7 . 6 x 1O-5
110.3 2 . 4 2 x 1O-4
4 2 . 8 1.29 x IO-
4 8 . 6 3 . 2 9 x 1O-5
58.0 1 . 2 4 0 x 10-4
42.8 1.13 x lo-s
5 1 . 2 4.26 x 1O-5
5 8 . 0 1 . 0 7 8 x 1O-4
50 3 . 5 2 x 1O-5
2 9 . 5 3 . 1 6 x 1O-4
40.0 1.24 x 1O-3
5 0 . 0 4.68 x 1O-3
5 2 1.93 x 10-5
50 5 . 5 4 x 10-5
50 7 . 0 8 x 1O-5
50 7.72 x lo-
50 9 . 7 8 x lo-
50 1.06 x 1O-4
50 1.41 x 10-4
4 2 . 8 1.16 x 1O-5
48.6 2 . 5 8 x 1O-5
5 8 . 0 1 . 0 8 0 x 10 -4
6 5 3 . 6 5 x 1O-5
70 7 . 9 8 x 10 -5
80 2.313 x 1O-4
90 1 . 3 4 4 x 10-3
100.1 3 . 0 3 x 10 -4
1 0 9 . 2 7.62 x 10 -4
1 2 5 . 0 3 . 9 0 x 10-3
4 5 . 5 2 . 5 2 x 1O-5
54.0 8 . 7 4 x 1O-5
6 9 . 7 7 . 1 2 x 1O-4
5 3 . 8 1 . 1 4 x 10-4
64.0 4 . 5 8 x 1O-4
53.35 1.05 x 10-4
64.30 4 . 2 8 x 1O-4
54.00 1.42 x 1O-4
64.00 6 . 2 x 1O-4
54.00 1.52 x 1O-4
64.00 6 . 7 x 1O-4
54.00 1 . 7 0 x 1o-4
64.00 6 . 4 x lO-4
45.45 1.01 x 10-4
55.55 3.71 x 10-4
45.45 2.06 x 1O-4
55.55 7 . 5 3 x 10-4
55.55 2 . 0 6 x 1O-4
64.94 6 . 9 2 x 1O-4
64.94 1 . 4 6 x 1O-4
75.06 5 . 2 6 x 1O-4
5 3 . 8 5 . 8 x 1O-5
64.0 1.99 x 10-4
60 9 . 9 2 x 1O-5
60 9 . 1 8 x 1O-5
1 4 9 . 2
1 0 8 . 9
1 2 4 . 4
1 1 3 . 6
1 2 3 . 6
1 2 5 . 7
1 2 5 . 7
125.1
1 1 7 . 2
1 3 3 . 9
1 3 3 . 9
121.3
119.7
111.7
1 1 9 . 2
123.8
1 1 0 . 9
318
318
339
339
339
9 8
9 8
309
309
309
309
309
309
324
323
3 2 3
3 2 3
339
356
356
356
356
356
356
309
309
309
366
366
366
366
314
314
314
323
3 2 3
3 2 3
42
42
5 2
52
5 2
5 2
5 2
5 2
52
5 2
7 5
7 5
7 5
7 5
7 5
7 5
7 5
7 5
4 2
4 2
2 6 3
2 6 3
Notes page II - 69; References page II - 70
II/20 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. contd
Number of
C atoms Initiator Sol vent
T (Cl kd (S-l) E, Wmol) Notes Refs.
2 5 (co&d) 3-Nitrophenyl-azo-triphenylmethane Cumene
Ethylbenzene
Octane
Toluene
4-Nitrophenyl-azo-triphenylmethane Benzene
reti-Butylbenzene
Chlorobenzene
Cumene
1 -Decene
Dodecane
1-Eicosene
Heptane
Hexadecane
LHexadecene
Hexane
1-Hexene
Nonane
Octadecane
1-Octadecene
Octane
1-Octene
Pentane
Tetradecane
4-Nitrophenyl-azo-triphenylmethane 1-Tetradecene
Toluene
2,4-Dinitrophenyl-azo-triphenyl-
methane
Phenyl-azo-triphenylmethane
Toluene
Acetic acid
Anisole
6 0 1.04 x 1o-4
6 0 1. 10 x 10-4
6 0 1. 01 x 10-4
4 5 1. 25 x 1O-5
6 0 1. 22 x 10-4
6 0 1. 09 x 10-4
6 0 9.7 x 10-5
6 0 4.03 x 10-5
6 0 4.44 x 10-6
5 5 8.50 x lO-5
5 5 6.88 x 10-5
5 5 4.42 x 1O-5
5 5 8.10 x 10-5
5 5 6.75 x 1O-5
5 5 2.62 x 1O-5
6 0 1. 15 x 10-4
6 0 4.73 x 10-5
6 0 7.23 x 1O-6
5 0 2.017 x 10 -5
6 0 9.988 x 1O-4
7 0 3.350 x 10-4
77.5 1. 16 x 1O-3
6 0 1. 038 x 1o-4
5 0 1. 933 x 10-5
6 0 9.166 x 1O-5
7 0 3.250 x 1O-4
6 0 7.60 x 1O-5
5 0 2.716 x 1O-5
6 0 1. 043 x 10-4
7 0 3.900 x 10-4
5 0 1.716 x 1O-5
6 0 8.133 x 1O-5
7 0 2.966 x 10 -4
77.5 1. 09 x 10-3
6 0 8.25 x 10 -5
50 2.750 x 1O-5
6 0 1.195 x 1o-4
6 0 1.143 x 1o-4
5 0 2.200 x 1o-5
6 0 9.900 x 10-5
7 0 3.710 x 1o-4
6 0 7.780 x 10-5
7 0 2.783 x 1O-4
6 0 7.58 x 1O-5
6 0 1. 015 x 10-4
7 0 3.650 x 10 -4
77.5 1. 78 x 10-3
6 0 1.123 x 1O-4
5 0 3.600 x 1O-5
6 0 1.280 x 10 -4
5 0 1.866 x 10-5
6 0 8.800 x 10 -5
7 0 3.116 x 1O-4
6 0 9.02 x lo-
64.94 2.58 x 1O-4
75.06 9.19 x 1o-4
53.35 5.7 x 1o-5
64.30 2.25 x 1O-4
75.06 1. 90 x 1o-4
84.98 6.13 x 1O-4
43.30 5.7 x 10-5
64.00 8.4 x 10-4
25.0 2.58 x 1O-6
123.0
113.0
122.6
117.2
120. 5
z (1256)
z (3890)
z (1013)
z (4154)
z (1013)
z (6180)
z (1256)
z (3890)
b,h
263
2 6 3
2 6 3
2 6 3
263
2 6 3
263
2 6 3
263
333
333
3 3 3
3 3 3
3 3 3
333
263
263
263
168,263
168,263
1 6 8
1 6 8
1 6 8
168,263
168,263
1 6 8
1 6 8
1 6 8
168,263
1 6 8
168,263
168,263
1 6 8
1 6 8
1 6 8
168,263
168,263
1 6 8
168,263
168,263
1 6 8
168,263
1 6 8
1 6 8
168,263
1 6 8
1 6 8
1 6 8
168,263
168,263
168,263
168,263
1 6 8
1 6 8
7 5
7 5
5 2
5 2
7 5
7 5
5 2
5 2
1 0 3
TABLE 2. contd
Miscellaneous Azo- Deri vat i ves II/21
Number of
C atoms Initiator Sol vent
T (Cl ka (S-l) E, Wmol) Notes Refs.
25 (conrd) Phenyl-azo-triphenylmethane Anisole 50.2
74.7
25.0
74.5
8 0 . 1
85.9
Benzene 25.0
49.6
74.7
5 0
Benzonitrile 25.0
50.3
74.7
rut-Butylbenzene 5 0
5 0
5 0
Chlorobenzene 25.0
49.6
74.7
5 0
5 0
5 0
Cyclohexane 25.0
49.6
74.7
Decane 6 0
Dodecane 6 0
Diethyl malonate 2 5 . 1
74.5
8 0 . 1
85.9
Ethylbenzene 5 0
Heptane 6 0
Hexadecane 6 0
Hexane 6 0
Nitrobenzene 25.0
74.5
8 0 . 1
85.9
Octane 5 0
5 0
5 0
6 0
Pyridine 53.35
64.00
Tetradecane 6 0
Toluene 43.8
53.8
4 5
5 0
45.45
55.55
43.30
53.35
53.3
2 6 2,2-Azo-bis[2-(4-ethyl-5-propyl- Methanol 5 0
imidazoline-2-yl)propane 2HCl Water 5 0
Azo-bis-diphenylmethane Toluene 54.0
64.0
1,l -Bis-biphenyl-azo-methane Diphenyl ether 135.0
145.0
155.0
165.0
1,l -Azo-bis-1-(4-tolyl)-cyclohexae Toluene 36.0
1. 31 X 10-4
3.03 x 10-3
3.0 x 10-6
2.9 x 1O-3
6.8 x 10-3
1 . 1 x 10-2
4.29 x 1O-6
1. 24 x 1O-4
3.12 x 1O-3
1. 37 x 10-4
2.62 x 1O-6
1. 56 x 1O-4
3.14 x 10-3
1. 33 X 10-4
3.83 x 1O-5
9.53 x 10-6
3.77 x 10-6
1. 67 x 1O-4
3.93 x 10-3
1.50 x 10-4
6.82 x 1O-5
7.65 x 1O-6
4.22 x 1O-6
9.90 x 10-5
1. 75 x 1o-3
5.72 x 10m4
5.35 x 1o-4
3 . 1 x 10-6
2.8 x 1O-3
5.9 x 10-3
1 . 0 x 10-2
1. 58 x 1O-4
6.60 x 1o-4
4.76 x 1O-4
7.60 x 1O-4
2.6 x 1O-6
3.0 x 10-3
5.8 x 1O-3
9.8 x 1O-3
1. 59 x 10-4
7.53 x 10-5
1. 17 x 10-5
6. 41 x 1O-4
1. 74 x 10-4
8.0 x 1O-4
4.99 x 10-4
6.3 x 1O-5
2.4 x 1O-4
9.23 x lo-
1. 73 x 10-4
8.48 x 1O-5
3. 51 x 10-4
6.0 x 1O-5
2.25 x 1O-4
2.25 x 1O-4
9.75 x 10-5
1. 33 x 10-4
1. 01 x 10-4
3.40 x 1o-4
1. 23 x 1O-4
3.58 x 1O-4
7.76 x 1O-4
2.09 x 1O-3
8.7 x 1O-6
118.3
121. 3
118.4
102. 5
118.7
129. 7
122.6
z (1140)
z (4265)
bh
b
b
z (1140)
z (4265)
h
b
b
b 1 0 3
b 1 0 3
1 1 4
1 1 4
1 1 4
1 1 4
b,h 1 0 3
1 0 3
b 1 0 3
2 6 3
b,h 1 0 3
b 1 0 3
1 0 3
2 6 3
2 6 3
263
1 0 3
1 0 3
1 0 3
2 6 3
2 6 3
2 6 3
1 0 3
1 0 3
1 0 3
263
263
1 1 4
1 1 4
1 1 4
1 1 4
263
2 6 3
2 6 3
2 6 3
1 1 4
1 1 4
1 1 4
1 1 4
2 6 3
2 6 3
2 6 3
2 6 3
5 2
5 2
2 6 3
4 2
4 2
2 6 3
2 6 3
15
15
5 2
5 2
4 6
356
356
107,312
46,107,312
h 297
297
2 9 7
2 9 7
200
z (1140)
z (4265)
Notes page II - 69; References page II - 70
II/22 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. contd
Number of
C atoms Initiator Sol vent
T (0 kd (s-l) E, Wmol) Notes Refs.
26 (conrd) 1,l -Azo-bis-1-(4-tolyl)-cyclohexanne
I.1 -Diisopropyl-2,2-dimethyl-
1.1 -Diphenyl-azo-propane
4-Methoxyphenyl-azo-triphenyl-
methane
1.1 -Diphenyl-azo-cycloheptane
3-Tolyl-azo-triphenylmethane
4-Tolyl-azo-triphenylmethane
2 7
2 8
4-Acetaminophenyl-azo-triphenyl-
methane
1,l -Azo-bis-1,2-diphenyl-
ethane (meso)
(QL)
3 0 1,l -Dibutyl- 1, I -diphenyl-
azo-pentane
3 4
40
1, I -Azo-bis-( 1,3-diphenyl-
pentane)
3,10,13,20-Tetraphenyl-1,2,11,12-tetra-
aza-1,l 1-cycloeicosadiene
44 3,12,15,24-Tetraphenyl-1,2,13,14-tetra- Ethylbenzene
aza-1,13-cyclotetracosadiene Xylene
Poly[oxyethylenexoxy-
(1-oxo-2,2-dimethylethylene)
azo-(2-oxo- 1,l -dimethyl-
ethylene)
Toluene
Ethylbenzene
Toluene
Benzene
Benzene
terz-Butylbenzene
Cumene
Ethylbenzene
Octane
Toluene
Benzene
rerfButylbenzene
Cumene
Ethylbenzene
Octane
Toluene
Toluene
Ethylbenzene
Ethylbenzene
Bromobenzene
Xylene
Xylene
o-Xylene
4 2 . 8 2.01 x 10-5
61.1 2.009 x 10 -4
50.0 6 . 2 4 x 1O-5
60.0 2 . 4 9 x 1O-4
70.0 7 . 7 7 x 10-4
54.00 2 . 1 3 x 1O-4
64.00 7 . 6 x 1O-4
16.2 1.65 x 1O-4
2 4 . 8 5 . 5 2 x 1O-4
3 3 . 4 1.66 x 10-3
41.1 4 . 5 2 x 1O-3
5 0 1 . 3 0 x 10-4
5 0 1 . 3 0 x 10-4
50 I.51 x 10-4
50 1.72 x 1O-4
4 5 8 . 9 x lo-s
4 3 . 8 7 . 4 x 10-5
5 3 . 8 2 . 7 7 x 1O-4
4 5 9 . 7 4 x lo-s
50 1.81 x 1o-4
50 1 . 2 6 x 1O-4
5 0 1.35 x 1o-4
50 1 . 4 0 x 10-4
50 1.62 x 1O-4
4 5 8 . 6 x 10-5
43.30 6 . 9 x 1O-5
5 3 . 3 5 2 . 2 5 x 1O-4
4 5 9 . 3 x 10-5
5 0 1.52 x lO-4
54.00 1.46 x 1O-4
64.00 5 . 9 x 10-4
96.56 2 . 7 5 x 1O-5
1 0 6 . 4 7 9 . 0 3 x 10 -5
1 1 5 . 2 8 2 . 4 2 x 1O-4
96.56 3 . 2 2 x 1O-s
1 0 6 . 4 7 1.04 x 1o-4
1 1 5 . 2 8 2 . 8 4 x 1O-4
50.0 5 . 0 5 x 10-5
6 0 . 0 2 . 0 3 x 1O-4
7 0 . 0 6 . 2 4 x 1O-4
8 9 . 7 1.5 x lo-s
1 1 8 . 8 5 . 6 x 1O-4
1 1 0 7 . 2 0 x 1O-5
1 2 0 2 . 3 0 x 1O-4
1 3 0 6 . 9 0 x 1O-4
112.95 8 . 7 6 1 x 1O-5
1 1 0 . 8 8 . 9 x 1O-5
1 1 9 . 8 2 . 2 x 1o-4
1 1 0 7 . 6 3 x 1O-5
1 2 0 2 . 4 6 x 1O-4
1 3 0 7.12 x 1O-4
8 5 2.106 x 1O-4
9 5 7.312 x 1O-4
1 0 5 1.995 x 10-3
r (K) 1.99 x 104
1 1 7 . 2
1 1 3 . 8
1 0 0 . 4
125.5
138.5
1 3 8 . 9
1 0 8 . 9
145.6
1 2 6 . 4
1 4 3 . 9
1 2 4 . 0
exp[ - 124.O/RT]
200
200
324
324
324
52
52
3 2 3
3 2 3
323
3 2 3
2 6 3
2 6 3
2 6 3
263
263
42
42
263
2 6 3
2 6 3
263
263
263 (
263
52
5 2
263
263
52
5 2
ah 1 6 2
a 1 6 2
a 1 6 2
ah 1 6 2
a 1 6 2
a 1 6 2
h 324
324
324
3 1 1
3 1 1
3 8
3 8
3 8
1 5 8
48
48
3 8
3 8
3 8
332
332
332
332
TABLE 3. ALKVL PEROXIDES
Alkyl Peroxides II/23
Number of
C atoms Initiator Solvent
TO3 ka (S-l) E. (kJ/mol) Notes Ref s.
2 Methyl peroxide
4 Ethyl peroxide
Vapor
Methanol
Styrene
Vapor
Vapor (toluene)
5 2,CPentanedione peroxide Triethyl phosphate
6 Propyl peroxide Vapor
7
Isopropyl peroxide Styrene
Ally1 fert-butylperoxide Toluene
Dimethylaminomethyl terr-butyl
peroxide
8 rerf-Butyl peroxide Acetic acid
Acetonitrile
Benzene
Benzhydrol
tea-Butanol
2-Butanol
n-Butyl mercaptan
Tri-n-butylamine
T W 1.6 x 10 l5
T (K)
4.1 x 105
6 0 1.2 x 10-9
140.2 1.75 x 10-4
147.8 3.60 x 1O-4
160.0 1.08 x 1O-3
176. 5 3.78 x 1O-3
184. 5 7.16 x 1O-3
145.9 6.69 x 1O-4
145.9 5.02 x 1O-4
200 3.58 x lo-*
210 6.76 x 1O-2
218 1.47 x lo-
226 2.23 x lo-
234 3.86 x lo-
2 4 5 6.43 x lo-
1 0 0 1.9 x 10-6
1 1 5 6.1 x 1O-6
1 2 5 1.4 x 10-5
146. 5 2.50 x 1O-4
155. 3 6.00 x 1O-4
166.8 1.95 x 10-3
175.4 4.10 x 10-3
6 0 6. x lo-I0
1 3 0 5.76 x 1O-5
1 4 0 1.785 x 1O-4
1 5 0 4.800 x 1O-4
1 6 0 1.270 x 1O-3
1 1 0 5.5 x 10-5
1 2 0 1.9 x 1o-4
1 3 0 4.76 x 1O-4
1 1 5 1.2 x 10-5
1 2 0 2.19 x 1O-5
1 2 5 2.98 x 1O-5
1 3 0 6.29 x 1O-5
9.5 9.53 x lo-
1 2 5 3.89 x 1O-5
1 1 5 1.19 x 10-5
1 2 0 2.21 x 10-5
1 2 5 3.47 x 10-5
1 3 0 5.63 x 1O-5
8 0 7.81 x 1O-8
1 3 0 (2. 48-3. 04) x 10 -5
1 0 0 8.8 x 10-7
1 0 0 8.75 x lo-
1 1 5 5.66 x 1O-6
1 3 0 3.00 x 10-5
1 2 0 1.39 x 10-5
1 2 0 7.6 x 1O-6
1 2 0 7.5 x 10-6
1 2 0 3.7 x 10-6
1 2 0 1.10 x 10-5
1 2 5 1.99 x 10-5
1 3 0 3.22 x 1O-5
1 3 5 6.19 x 1O-5
1 2 5 8.7 x 10-5
1 2 0 1.41 x 10-5
1 2 5 2.49 x 1O-5
1 3 0 4.30 x 10-5
1 3 5 7.32 x 1O-5
1 2 5 4.8 x 1O-5
1 2 5 1.5 x 10-5
1 2 5 (1.7f0.3) x 10-5
1 3 5 (4.2 f 0.4) x 1O-5
exp[- 147.7/RT]
exp[- 153.9/Rfl
147. 3
131.8
t8
132.6
9 2
132.2
154.8
139. 1 h,ms
134. 5
139.7 h
129.7
d
h
142. 3
146.9
m2,u2
m242
a
147. 7
143. 5
a
a
z (0.98)
z (864)
z (1620)
~(3480)
h
h
7 2
225
92 .
1 2 7
1 2 7
1 2 7
1 2 7
1 2 7
1 8 7
1 8 7
8 7
8 7
8 7
8 7
8 7
8 7
337
337
337
1 2 8
1 2 8
1 2 8
1 2 8
9 2
3 2 1
3 2 1
3 2 1
3 2 1
3 0 3
3 0 3
3 0 3
1 9 2
1 9 2
1 9 2
1 9 2
208
208
1 9 2
1 9 2
1 9 2
1 9 2
1 2 9
1 2 9
126,337
1 9 7
126,337
126,337
3 3
3 3
3 3
3 3
1 9 2
1 9 2
1 9 2
1 9 2
1 4 0
1 9 2
1 9 2
1 9 2
1 9 2
1 4 0
1 4 0
6 4
6 4
Notes page II - 69; References page II - 70
II / 24 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 3. contd
Number of
C atoms Initiator Sol vent
T (C) kd (S-l) E, Wmol) Notes Refs.
8 (conrd) rerr-Butyl peroxide Tri-n-butylamine
tert-Butylbenzene
Carbon tetrachloride
Chlorobenzene
Cumene
Cyclohexane
Cyclohexanol
Cyclohexene
Cyclohexylamine
Decane
Dodecane
Dimethylaniline
Ethyl benzoate
N-Ethylcyclohexyl amine
Heptane
Hexadecane
1 4 . 5 (1.60f0.21) x 1O-4
T 09 2.8 x lOI
1 2 5 (1.5 kO.2) x 10-5
1 3 5 (5.0 f 0.3) x 10 -5
1 4 5 (1.51 iO.22) x 10-4
T W
2.8 x 10
1 2 5 2.10 x 10-6
1 2 5 2.49 x 1O-6
1 2 5 2.03 x 1O-6
1 2 0 9 x lo-6
1 2 0 2.4 x 1O-6
1 2 0 2.3 x 1O-6
1 2 0 8.6 x 10-7
1 2 5 1.40 x 10-6
1 5 0 4.45 x 104
1 2 1 1.93 x 10-5
1 4 1 1.93 x 10-4
1 6 4 1.93 x 10-3
T (K) 4.20 x 1015
1 2 5 (1.6kO.l) x 1O-5
1 3 5 (5210.3) x 10-5
1 4 5 (1.5650.13) x 1O-4
T 09 2.8 x 10 I4
9 5 2.48 x lo-
1 2 0 6.3 x 10m6
1 2 5 1.52 x 10m5
1 3 0 2.59 x 10m5
1 3 5 4.64 x 1O-5
1 2 5 2.4 x 1O-5
1 2 0 7.6 x 1O-6
1 2 5 1.38 x 1O-5
1 3 0 2.81 x 1O-5
1 3 5 4.41 x 10-5
1 2 0 8.3 x 1O-6
1 2 0 6.2 x 1O-6
1 2 0 3.77 x 10-6
1 2 0 2.65 x 1O-6
1 2 5 5.50 x 10-5
8 0 1.39 x 10-8
1 1 0 2.01 X 10-6
1 3 0 2.48 x 1O-5
1 1 5 3.00 x 10-6
1 3 0 2.16 x 1O-5
1 4 0 6.66 x 10-5
8 0 1.29 x lo-*
1 1 0 1.87 x 1O-6
1 3 0 2.44 x 1O-5
1 2 0 9.6 x 1O-6
1 2 5 1.89 x 1O-s
1 3 0 3.41 x 10-5
1 3 5 5.84 x 1O-5
1 2 0 1.07 x 10-5
1 2 5 1.92 x 1O-5
1 3 0 3.39 x 10-5
1 3 5 5.90 x 10-5
1 2 5 4.01 x 10-5
8 0 1.44 x 10-8
1 1 0 2.19 x 1O-6
8 0 1.07 x lo-8
1 1 0 1.82 x 1O-6
1 3 0 2.33 x 10m5
8 0 1.64 x 1O-8
1 1 0 2.17 x 1O-6
exp[- 146.4/RTj
exp[- 146.4/RT]
Ul
s
%t6
z (0.98)
z (1930)
z (2890)
z (5525)
Ul>t6
exp[- 153.46/R~]
exp[- 146.4/RT]
170. 7 h
156. 1 h
157. 3
z (0.98)
z (1275)
z (2890)
z (5725)
h
1 6 3 a
a
a
148. 5 h
6 4
1 2 3
6 4
6 4
6 4
1 2 3
3 0 1
3 0 1
3 0 1
3 3
3 3
3 3
3 3
3 0 1
346
344
344
344
344
6 4
6 4
6 4
1 2 3
208
1 9 2
1 9 2
1 9 2
1 9 2
1 4 0
1 9 2
1 9 2
1 9 2
1 9 2
3 3
3 3
3 3
3 3
1 4 3
270
270
270
337
3 3 7
3 3 7
270
270
270
1 9 2
1 9 2
1 9 2
1 9 2
1 9 2
1 9 2
1 9 2
1 9 2
1 4 3
270
270
270
270
270
270
270
TABLE 3. contd
Alkyl Peroxi des II/25
Number of
c at oms Initiator Sol vent
T(C) ka (S-l) E. Wmol) Notes Refs.
8 (contd) [err-Butyl peroxide 2-Methyl-2-butanol
Methyl methacrylate
N-Methylpipendine
Mineral oil
Nonane
Norbomanol
Nujol
Octane
2-Octanol
Piperidine
1 Propanol
Styrene
Tetradecane
Tetrahydrofuran
Triethylamine
Vapor (acetone)
Vapor (carbon
tetrachloride)
Vapor (chloroform)
Vapor (dichloro-
difluoromethane)
Vapor (trichloro
ethylene)
Vapor (methylene
chloride)
Vapor (3-pentanone)
Vapor (silicon
tetrafluoride)
Vapor (toluene)
1 2 0
1 2 5
1 3 0
1 3 5
T 6)
1 2 5
T 09
8 0
1 1 0
1 3 0
1 2 5
1 2 5
8 0
1 1 0
1 2 5
1 2 5
1 2 5
T (K)
8 0
1 1 0
1 3 0
1 2 0
1 2 5
1 3 0
1 3 5
1 2 5
1 0 0
1 2 0
1 2 0
1 2 0
1 2 0
1 2 5
1 2 5
T (K)
1 2 0
1 2 5
1 3 0
1 3 5
127. 5
1 3 1
1 4 6
151. 5
1 6 2
1 6 7
1 4 5
T 6)
1 5 0
1. 26 x 1O-5
2.34 x 1O-5
4.47 x 10-5
6.80 x lo-s
2.8 x lOI
1. 54 x 10-5
1. 31 x 105
1. 36 x lo-*
2. 01 x 10-6
2.54 x 1O-5
4.4 x lo-
7.8 x lo-
1. 48 x lo-*
2.19 x 1O-6
5.5 x 10-5
3.49 x 10-5
2.8 x 1O-5
2.8 x 1014
1. 12 x 10-8
1. 82 x 1O-6
2.38 x 1O-5
9.7 x 10-6
1. 84 x 1O-5
3.39 x 10-5
5.76 x 1O-5
1 . 5 x 10-5
6.82 x lo-
1. 34 x 10-5
9.5 x 10-6
8.0 x 1O-6
5.7 x 10-6
1 . 6 x 1O-5
1. 62 x 1O-5
1.30 x 106 exp[- 158.3/RT]
7.9 x 10-6 169.9
1. 69 x 1O-5
3.15 x 10-5
5.55 x 10-5
7.4 x 10-6
1. 13 x 10-5
6.0 x 1O-5
1. 03 x 10-4
3.6 x 1O-4
5.2 x 1O-4
1 . 3 x 10-4 165. 3
5.9 x 106 exp[- 165.3/RT]
8.58 x 1O-4
1 5 0 1.167 x 1O-3
1 5 0 >(2.00 x 10 -4)
1 5 0
1. 50
1 4 5
T WI
1 6 0
1 6 0
1 6 0
1 4 8
1 5 8
103.2
111.9
2.35 x 1O-3
1.017 x 10-3
1 . 5 x 10-4 165. 3
6.8 x 10 6 exp[- 165.3/RZJ
1. 05 x lo-
1.25 x 1O-3
1.27 x 1O-3
9.0 x 10-5
2.5 x 1O-4
5.6 x lo-
2.03 x 1O-6
149.4 h
exp[- 146.4/RT]
exp[- 154.6/RT]
U
exp[- 146.4/RT]
155.2 h
z (0.98)
z mw
z (2850)
z (5170)
113.0 a,i(2.6)
a,i(33)
a,i( 100)
1 9 2
1 9 2
1 9 2
1 9 2
1 2 3
1 4 3
376
270
270
270
1 4 0
3 0 1
270
270
1 4 0
1 4 3
1 4 0
1 2 3
270
270
270
1 9 2
1 9 2
1 9 2
1 9 2
1 4 0
1 9 7
3 3
3 3
3 3
3 3
1 4 0
1 4 3
376
1 9 2
1 9 2
1 9 2
1 9 2
238
238
238
238
238
238
1 2 5
1 2 5
1 3 0
1 3 0
1 3 0
1 3 0
1 3 0
125
1 2 5
1 1 7
1 1 7
1 1 7
8 8
8 8
227
227
Notes page II - 69; References page II - 70
II/26 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 3. co&c/
Number of
C atoms Initiator Solvent
T(C) kd (S-l) E, GJ/mol) Notes Refs.
8 (contd) tert-Butyl peroxide Vapor 120.2
129. 5
138. 5
145.4
1 2 5
1 3 5
1 4 5
129.6
141.0
152. 5
166.8
1 3 0
1 4 0
1 5 0
1 6 0
1 7 0
1 2 9
1 3 8
1 4 9
1 5 2
139. 7
147. 2
154.6
159. 8
T (K)
1 4 5
T (K)
149. 5
1 6 0
1 6 0
1 6 0
1 3 0
1 4 0
1 5 0
1 6 0
Vapor (He) 280
290
300
310
320
330
340
350
KBr pellets 1 0 9
1 2 7
1 4 9
rert-Butyl Z-chloro-l,l-dimethylethyl- Cumene 1 2 0
peroxide 1 3 0
1 4 0
1 5 0
1 0 0
1 0 0
8 0
8 0
8 0
8 0
8 0
6 0
8 0
1 5 0
1 5 0
1 5 0
1 5 0
set-Butyl peroxide
Butyl peroxide
Bromo-w-r-butyl peroxide
Chloro-tert-butyl peroxide
Bis(chloro-tert-butyl) peroxide
2-rert-Butyl peroxy-2-methyl-
I-propanol
Toluene
Vapor
Decane
Dodecane
Heptane
Hexadecane
Octane
Styrene
Tetradecane
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
6.39 x 1O-6
1.98 x 1O-5
6.00 x 1O-5
1.24 x 1O-4
1.1 x 10-5
3.6 x 1O-5
1.15 x 10-4
1.64 x 1O-5
6.28 x 1O-5
2.25 x 1O-4
8.92 x 10 -4
1.82 x 1O-5
5.75 x 10-5
1.75 x 10-4
4.88 x 1O-4
1.35 x 10-3
1.97 x 10-5
4.3 x 10-5
1.30 x 10-4
1.62 x 1O-4
6.0 x 1O-5
1.43 x 10-4
3.22 x 1O-4
5.53 x 10-4
3.2 x 1016
1.3 x 10-4
1.9 x 106
1.79 x 10-4
4.00 x 10-4
4.53 x 1o-4
4.83 x 1O-4
1.91 x 10-5
5.95 x 10-5
1.78 x 1O-4
4.96 x 1O-4
7.7
1.51 x 10
2.77 x 10
4.87 x 10
8.34 x 10
1.38 x lo*
2.13 x 10
3.22 x lo*
3.8 x lo-
2.96 x 1O-5
4.4 x 10-4
8.82 x 1O-6
2.80 x 1O-5
9.26 x 1O-5
2.78 x 1O-4
2.7 x 1O-6
1.5 X 10-6
1.43 x lo-s
1.17 x 10-8
2.04 x lo-
8.8 x 10-9
1.58 x lo-*
3.3 x 10-9
9.6 x 1O-9
3.63 x 1O-4
4.15 X 10-4
3.11 x 10-4
1.16 x 1O-3
159,0 a
a
a
a
a
163.6
exp[- 163.6/RT]
161. 5
exp[- 161S/RT] 1
156. 5 i(37-132)
154. 8 aj(2.6)
a,i(33)
a,i( 100)
156.7
u3
u3
u3
u3
154. 8 i(10)
i(10)
$10)
i(10)
$10)
$10)
i(10)
i(10)
159.0 h
t6
t6
t6
t6
t6
142. 3
t6
2 2 7
227
227
227
6 4
6 4
6 4
8 6
8 6
8 6
8 6
9 6
9 6
9 6
9 6
9 6
8 8
8 8
8 8
8 8
6 3
6 3
6 3
6 3
6 3
1 2 5
75,125
8 3
1 1 7
1 1 7
1 1 7
277
2 7 7
277
277
1 1 1
1 1 1
1 1 1
1 1 1
1 1 1
1 1 1
1 1 1
1 1 1
2 4 1
2 4 1
2 4 1
363
3 6 3
3 6 3
3 6 3
1 9 7
1 9 7
270
270
270
270
270
9 2
270
346
346
3 4 6
346
TABLE 3. contcl
Alkyl Peroxides II/27
Number of
C atoms Initiator Sol vent
T (Cl kd (S-l) E, Wmol) Notes Refs.
8 (contd) 2-tert-Butyl peroxy-2-methyl-
I-propanol-d t
1-Hydroxybutyl-n-butyl peroxide
Chlorobenzene
a-Methylstyrene
1-Hydroxyisobutyl-isobutyl peroxide cc-Methylstyrene
1-Hydroxyisobutyl-l-di-isobutyl-
1,l -dz peroxide
cc-Methylstyrene
Dimethylaminomethyl-
rerr-amyl peroxide
Styrene
Diethylaminomethyl-
rerf-butyl peroxide
Styrene
N-Biperidinomethyl-
rert-butyl peroxide
Styrene
9 rerr-Butyl rerr-amyl peroxide Cumene
10 tert-Amy1 peroxide Bulk
Chlorobenzene
Decalin
Octane
Triethylamine
Vapor
tert-Butyl 1, 1-dimethylbutyl
peroxide
Cumene
rert-Butyl 1,1,2-trimethylpropyl
peroxide
Cumene
2-Methyl-2-rerr-butyl-peroxyacetate
Ethyl 2-rert-butylperoxymethyl-
propenoate
Chlorobenzene
Triisopropylbenzene
11
12
Apocamphane- 1 - formyl peroxide
2,2-Bis(terr-butylperoxybutane)
Benzene
Benzene
1 5 0 1.23 x 1O-3 346
79.4 1.7 X 10-5
99.4 1.06 x 1O-4
1 0 9 . 9 2 . 9 x 10-4
7 9 . 4 3 . 7 x 10-5
99.4 2 . 0 x 10-4
1 0 9 . 9 4 . 8 x 10-4
9 9 . 5 6 . 9 x 1O-5
1 0 9 . 8 1.8 x 1o-4
1 2 2 . 0 4 . 2 x 1O-4
1 1 0 4 . 9 x 10-5
1 2 0 1.19 x 10-4
1 3 0 3 . 7 6 x 1O-4
1 1 0 4.1 x 10-5
1 2 0 1.35 x 1o-4
1 3 0 3 . 2 5 x 1O-4
1 1 0 5 . 5 x 10-5
1 2 0 2 . 6 6 x 1O-4
1 3 0 4.16 x 1O-4
1 1 0 3 . 8 6 x 1O-6
1 2 0 1 . 2 8 7 x 10 -5
1 3 0 4.30 x 10-5
1 4 0 1 . 4 0 6 x 10 -4
1 2 5 5 . 7 x 10-5
1 3 2 . 2 1.15 x 10-4
1 0 8 1.93 x 10-5
1 2 8 1.93 x 10-4
1 5 0 1.93 x 10-3
T W
4 . 0 2 x 10 l5
1 2 5 2 . 8 x 1O-5
1 2 5 3 . 0 x lo-s
1 2 5 3.5 x 10-5
1 3 2 . 2 7 . 2 x 1O-5
1 3 6 . 7 1.15 x 1o-4
1 4 2 . 2 2 . 1 6 x 1O-4
1 4 9 . 2 4 . 8 x 1O-4
136.7 1.34 x 10-4
1 4 2 . 2 2.41 x 1O-4
149.7 5.61 x 1O-4
1 1 0 4 . 3 8 x 1O-6
1 2 0 1.537 x 10-5
1 3 0 4.99 x 10-5
1 4 0 1 . 5 4 4 x 10-4
1 1 0 7 . 0 7 x 10-6
1 2 0 2.374 x 1O-5
1 3 0 7 . 6 2 x 1O-5
1 4 0 2.308 x 1O-4
1 5 0 4 . 1 2 x 1O-4
127.5 1.63 x 1O-4
1 3 0 1.95 x 10-4
132.5 2 . 1 6 x 1O-4
1 3 5 2 . 5 6 x 1O-4
137.5 3 . 4 7 x 10-4
1 4 0 3 . 9 2 x 10-4
142.5 4 . 6 8 x 1O-4
1 4 5 5 . 3 7 x 10-4
147.5 6 . 3 0 x 10 -4
1 5 0 7 . 7 6 x 1O-4
8 0 2 . 3 x 1O-4
8 5 3 . 0 x 10-6
1 0 0 1.9 x 10-5
115 9 . 3 6 x 1O-5
1 0 2 . 9
8 3 . 7 C
C
C
8 9 . 5
* 130.7
tll
tll
t11
1 3 2 . 4
t11
t11
tll
1 3 0 . 7
tll
tll
tll
exp[- 148.35/RT]
154.8-171.5 i(200-225)
i(200-225)
i(200-225)
i(lOO-200)
i(440-610)
i(440-610)
i(440-610)
c2
c2
c2
c2
c2
c2
c2
c2
c2
c2
151 a
a
a
3 2
3 2
3 2
3 2
3 2
3 2
2 5
2 5
2 5
3 0 3
3 0 3
3 0 3
3 0 3
3 0 3
303
3 0 3
3 0 3
303
3 6 3
3 6 3
3 6 3
3 6 3
202
202
344
344
344
344
202
202
202
6 3
6 3
6 3
6 3
6 3
6 3
6 3
3 6 3
3 6 3
3 6 3
363
3 6 3
3 6 3
3 6 3
3 6 3
346
3 5 3
3 5 3
3 5 3
3 5 3
3 5 3
3 5 3
3 5 3
3 5 3
3 5 3
3 5 3
244
3 3 7
3 3 7
3 3 7
Notes page II - 69; References page II - 70
II/28 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 3. contd
Number of
C atoms Initiator Sol vent
-
T(C) kd (S-l) E. WhoI) Notes Refs.
12 (cm&d) rerr-Butyl 1,1,3,3-tetramethylbutyl
peroxide
1-Hydroxy-l-hydroperoxy-
dicyclohexyl peroxide
Di -( l-hydroxycyclohexyl)-
peroxide
Diisopropylaminomethyl-
rerr-amyl peroxide
13
I-Phenylethyl ret?-butyl peroxide
rerr-Butylcc-cumyl peroxide
1 4
reti-Butyl p-chlorocumyl peroxide
terr-Butyl p-nitrocumyl peroxide
terr-Butyl l, l-dimethyl-2-phenyl-
ethyl peroxide
1,l -Di-(rert-butylperoxy)-
cyclohexane
Ethyl-3,3-di-terr-butylperoxy)-butyrate
I-[4-(Dimethylamino)phenyl]-
ethyl tert-butyl peroxide
15
16
tert-Butyl p-methoxycumyl peroxide
rerr-Butyl p-methylcumyl peroxide
reti-Butyl m-methoxycumyl peroxide
Bis( 1,1,2,2-ktramethylpropyl) peroxide
2-[4-(Dimethylamino)phenyl]-
propyl rerr-butyl peroxide
1 ,l-Di-(terr-amylperoxy)-
cyclohexane
reti-Butyl 3-isopropenyl-
cumyl peroxide
2,5-Dimethyl-2,5-di(rer?-butyl-
peroxy)-hexane
2,5-Dimethyl-2,5-di(rert-butyl-
peroxy)-3-hexyne
Cumene
Benzene
Chlorobenzene
Styrene
Chlombenzene
rer&Butylbenzene
Chlorobenzene
Cumene
Dodecane
Cumene
Cumene
Cumene
Benzene
Benzene
Chlorobenzene
Cumene
Cumene
Cumene
Cumene
Chlorobenzene
Benzene
Chlorobenzene
Benzene
Chlorobenzene
Benzene
1 1 0 1.085 x lo-*
1 2 0 3.13 x 10-5
1 3 0 1.141 x 10-4
140 3.40 x 10-4
8 5 9.6 x 1O-6
1 0 0 5.1 x 10-5
115 1.9 x 10-4
1 3 0 5.2 x 10 -4
1 0 5 N1.9X 10-5
1 2 0 -1.9x 10-4
1 1 0 3.9 x 10-5
120 1.21 x 10-4
1 3 0 3.0 x 10-4
1 2 9 . 2 3.09 x 10-5
1 3 8 1.48 x 1O-4
1 5 8 9.62 x 1O-4
1 1 5 1.93 x 10-5
1 3 6 1.93 x 10-4
1 5 9 1.93 x 10-3
T 6) 1.17 x 105
1 3 8 1.44 x 10-4
1 5 8 8.88 x 10-4
125 3.04 x 10-5
1 2 8 4.44 x 10-5
1 3 8 1.39 x 10-4
1 4 8 3.21 x 1O-4
1 5 8 8.88 x 10-4
1 2 5 2.42 x 1O-5
125 2.20 x 10-5
1 1 0 4.35 x 10-6
1 2 0 1.458 x 1O-5
1 3 0 4.70 x 10 -5
1 4 0 1.463 x 1O-4
9 3 1.9 x 10-5
111 1.9 x 10-5
1 0 0 . 4 1.82 x 1O-6
1 1 0 . 8 6.97 x 1O-6
1 2 0 . 9 2.18 x 1O-5
1 2 9 . 2 6.18 x 10-5
1 2 9 . 2 . 5.22 x 1O-5
1 2 5 3.72 x 1O-5
125 3.22 x 1O-5
1 2 5 2.84 x 1O-5
1 2 5 4.84 x 1O-4
1 2 9 . 2 1.51 x 1o-4
90
1 0 4
1 2 6
1 5 2
T 03
115
1 3 0
1 4 5
115
1 3 4
1 5 6
T (K)
1 1 5
1 3 0
1 4 5
1 6 0
1.9 x 10-5
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
1.161 x lOI
1.15 x 10-5
6.86 x 10 -5
4.75 x 1o-4
1.93 x 10-5
1.93 x 1o-4
1.93 x 10 -3
1.68 x 106
3.91 x 1o-6
2.35 x 1O-5
1.14 x 1o-4
6.17 x 1O-4 a
a,c 2
a,c 2
a,c 2
a,c 2
1 3 2 . 4 t11
t11
tll
a
a
exp[- 146.98/RT]
a
a
1 4 6 . 4 a
a
a
a
a
a
1 5 1 . 7
m2
m2
a
exp[- 128.33/RT]
1 6 6 . 9 a
a
a
exp[- 155.49/RT]
1 5 6 . 9 a
a
a
3 6 3
363
363
363
337
337
337
337
344
344
303
303
303
282
8 0
8 0
344
344
344
344
80
80
352
80
80
8 0
80
352
352
3 6 3
3 6 3
3 6 3
363
338
338
282
282
282
282
282
352
352
352
352
282
338
344
344
344
344
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
344
344
344
344
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
TABLE 3. cont d
Acyl Peroxides II/29
Number of
C atoms Initiator Solvent T (Cl kd (S-l) E, Wmol) Notes Refs.
16 (contd) 2,5-Dimethyl-2,5-di(ferr-butyl- Chlorobenzene
peroxy)-3-hexyne
17 n-Butyl-4,4-bis(rerbutylperoxy)-
valerate
Dodecane
l,l-Bis-(ren-butylperoxy)-
3,3,5&methylcyclohexane Benzene
18 Cumyl peroxide Benzene
terf-Butylbenzene
Chlorobenzene
Cumene
Dodecane
Diisopropylcarbinol
Neat
Bicyclo[2.2.2]octane-
1-formyl peroxide
Carbon tetrachloride
2 0 cc,cc-Bis(teti-butylperoxy)-
diisopropyl benzene
Chlorobenzene
Cyclohexane
Isooctane
Toluene
Benzene
Chlorobenzene
Neat
2 4 2,5-Dimethyl-2,5-di-(2-ethyl-
hexanoylperoxy) hexane
Benzene
1 2 0 1.93 x 10-5
141 1.93 x 10-4
1 6 4 1.93 x 1o-3
T (K) 1.90 x 10 l5
1 0 0 5 . 8 3 x 1O-6
115 3 . 5 3 x 10-5
1 3 0 2 . 9 1 x 1O-4
8 5
1 0 0
115
1 1 5
1 3 0
1 4 5
158
1 1 2
1 3 2
1 5 4
T 09
T (K)
1 3 8
1 5 8
1 2 8
1 3 8
1 4 8
1 5 8
138
1 5 0
155
1 6 0
165
30
3 0
3 0
3 0
3 0
1 1 5
125
1 3 0
1 1 4
1 3 4
1 5 6
T (K)
1 5 5
1 6 0
165
6 8
6.9 x 1O-6
5.05 x 10-5
2.71 x 1O-4
2.05 x lo-
1.05 x 10-4
6.86 x 10-4
1.72 x 1O-3
1.93 x 10-5
1.93 x 1o-4
1.93 x 10-3
9.24 x 10
4.31 x lOi
2.57 x 1O-4
1.52 x 1O-3
8.75 x 1O-5
2.31 x 1O-4
5.37 x 1o-4
1.83 x 1O-3
3.16 x 1O-4
3.98 x 1O-3
4.81 x 1O-3
9.63 x 1O-3
1.16 x lo-
1.71 x 10-4
1.73 x 10-3
1.68 X 10-4
6.20 x 1O-4
6.1 x 1O-5
5.0 x lo-5
3.66 x 1O-4
1.9 x 10-5
4.91 x 10-5
9.61 x 1O-5
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
7.65 x 10
3.61 x 1O-3
4.44 x 10-3
4.62 x 1O-3
1.9 x 10-5
exp]- 150.67/RT]
a
a
a
1 3 8 a
a
a
1 5 9 a
a
a
a
exp[- 152.67/RT]
exp[- 144.3/RT]
a
a
a
a
a
a
a
a
a
a
a
n
VI
1 4 7 a
a
a
exp[- 152.69 kJ/RT]
a
a
a
a
344
344
344
344
8
8
8
337
337
337
3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
8 0
344
344
344
344
6 7
8 0
8 0
8 0
8 0
80
8 0
8 0
3 7 1
3 7 1
3 7 1
3 7 1
244
244
244
244
244
244
244
3 3 7
3 3 7
3 3 7
344
344
344
344
3 7 1
3 7 1
3 7 1
3 3 8
TABLE 4. ACYL PEROXI DES
Number of
C atoms Initiator Solvent
T(C) kd (S-l) E. Wmol) Notes Ref s.
4 Acetyl peroxide Acetic acid 5 5 . 2 2 . 8 x 1O-6 126.4 d,e 1 0 6 , 1 7 6
6 4 . 9 9 . 9 x 10-6 d,e 1 0 6 , 1 7 6
7 5 . 2 3 . 7 5 x 10-5 d,e 1 0 6 , 1 7 6
8 5 . 2 1 . 3 0 x 1o-4 d,e 1 0 6 , 1 7 6
7 3 . 2 2 . 6 2 x lo- a 1 0 0
Notes page II - 69; References page II - 70
I i / 30 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Table 4. contd
Number of
C atoms Initiator Solvent
T ((3 kd (S-l) E, (kJhol) Notes Ref s.
4 (contd) Acetyl peroxide Benzene
n-Butanol
set-Butanol
terr-Butanol
Carbon tetrachloride
Chloroform
Cyclohexane
Cyclohexene
Cyclopentene
Cumene
Decane
n-Dodecane
Ethanol
Heptane
Hexadecane
n-Hexane
1 -Hexene
2-Methyl-I-pentene
n-Octadecane
n-Octane
Isooctane
1-Pentene
Propionic acid
3 5 9.5 x lo-
5 5 3.14 x 10-6
6 5 1.27 x 1O-5
5 0 1.1 x 10-6
7 0 2.39 x 1O-5
8 5 1.73 x 10 -4
7 0 2.38 x lo-
60.3 5.0 x 1o-6
8 0 8.7 x lo-
55.2 2.6 x 1O-6
64.9 1.07 x 10-5
75.2 4.65 x lo-
85.2 1.62 x 1O-4
60.3 3.4 x 10-5
60.3 3 x 10-5
60.3 3.1 x 10-6
80.3 4.9 x 10-5
2 6 1.08 x IO-
4 6 4.84 x lo-
6 5 2.11 x 10-6
8 0 5.5 x 10-5
80.3 - 5
55.2 2.1 x 10-6
64.9 8.3 x 1O-6
75.2 3.60 x 1O-5
85.2 1.27 x 1O-4
6 0 4.5 x 10-6
7 0 1.77 x 10-5
8 0 7.0 x lo-
9 0 2.28 x 10-4
1 0 0 7.61 x 1O-4
7 0 1.60 x 1O-5
8 0 7.0 x 10-5
9 0 2.55 x 1O-4
1 0 0 7.25 x 1O-4
8 0 7.6 x 1O-5
8 0 6.85 x 1O-5
6 0 2.3 x 1O-6
8 0 6.15 x 1O-5
60.3 1.01 x 1o-4
80.3 1.40 x 10-3
8 0 7.72 x 1O-5
8 0 5.39 x 10-5
6 0 3.4 x 10-6
7 0 2.35 x 1O-5
8 0 8.7 x 1O-5
9 0 3.05 x 10-4
1 0 0 9.83 x 1O-4
8 0 9.0 x 10-5
9 0 3.12 x 1O-4
1 0 0 9.81 x 1O-4
6 0 1.9 x 10-6
6 0 2.9 x 10 -
8 0 7.34 x 10-5
6 0 2.9 x 1O-6
55.2 2.35 x 1O-6
64.9 9.4 x 10-6
75.2 4.03 x 10-5
85.2 1.49 x 1o-4
7 0 2.45 x 1O-5
8 0 9.4 x 10-5
9 0 3.22 x 1O-4
64.9 1.4 x 10-5
85.2 1.66 x 1o-4
1 3 4
135. 1
133.9
131.4
133. 5
137.2
129.7
132.6
126.8
134.7
c,e
c,e
c,e
c,e
c,e
c,e
c,e
c,e
c,e
c,e
c,e
c,e
d,e
6 8
6 8
6 8
3 3 7
126,337
126,337
1 6
4
2 0
106,176
106,176
106,176
106,176
4
4
4
4
6 8
6 8
6 8
2 0
4
106,176
106,176
106,176
106,176
2 0
2 0
2 0
2 0
2 0
2 0
2 0
2 0
2 0
2 0
1 6 8
7 0
1 6 8
4
4
1 6 8
1 6 8
7 0
2 0
2 0
2 0
2 0
2 0
2 0
2 0
7 0
7 0
1 6 8
7 0
106,176
106,176
106,176
106,176
2 0
2 0
2 0
106,176
106,176
i
Table 4. contd
Acyl Peroxides II/31
Number of
C atoms IilitiZItor Solvent T (Cl ka (S-l) E. Wmol) Notes Refs.
4 (contd) Acetyl peroxide n- Te t r a de c a ne 60
8 0
To l u e n e 60. 3
55. 2
64. 9
15. 2
85. 2
13. 2
85. 5
90
Vapor (toluene) 88. 0
134. 7
150. 7
161. 7
170. 7
184. 2
6 Pr o p i o n y l p e r o x i d e Acetic acid 65. 0
85. 0
Acetic anhydride 65. 0
85. 0
Be n z e n e 65. 0
85. 0
50
70
85
65. 0
85. 0
Dioxane 65. 0
85. 0
n-Hexane 65. 0
85. 0
Isooctaue 65. 0
86. 5
Ni t r o b e n z e n e 65. 0
85. 0
To l u e n e 65. 0
85. 0
Va p o r 65. 0
85. 0
99. 4
134. 4
152. 2
176. 4
190. 9
T W
2-Iodopropionyl peroxide Ac e t o n e 56
Be n z e n e 62. 5
62. 5
62. 5
n-Butyl vinyl ether 62. 5
Cyclohexene 62. 5
95% Ethanol 62. 5
Perfluoropropionyl peroxide Freon 113 20
30
40
T (W
Isooctane
T W
2,2,3,3-Tetrafluoropropionyl Freon 113 25
peroxide 35
8 rert-Butyl perrnaleic acid Ac e t o n e 81
Butyryl peroxide Acetic acid 65. 0
85. 0
Acetic anhydride 65. 0
85. 0
2. 0 x 10-6
5. 90 x 10-5
5x10- 6
2. 7 x 10-6
1.14 x 10-5
4. 70 x 1o-5
1.59 x 10-4
3. 06 x lO-5
1. 72 x 1O-4
7. 33 x 10-5
3. 12 x 1O-4
3. 1 x 10-2
1.18 x lo-
2. 77 x lo-
6.10 x lo-
1. 76
3. 8 x 10 -5
4. 3 x 10 -4
3. 5 x 10-5
4. 5 x 1o-4
1. 88 x 10-5
2. 40 x 1O-4
2. 12 x 10-6
4. 30 x 10-5
2. 89 x 1O-4
3. 9 x 10-5
5. 1 x 1o-4
4. 5 x 10-5
4. 5 x 10-4
1. 50 x 10-5
1. 72 x 1O-4
9.8 x 1O-6
1.44 x 10-4
3. 7 x 10-5
4.1 x 1o-4
1. 87 x 1O-5
2. 54 x 1O-4
1.0 x 10-5
1.6 x 1O-4
8 x 1O-4
2. 6 x 1O-2
1.22 x 10-1
8. 0 x lo-
2. 33
2. 5 x 1O-4
2.19 x 10-4
( 2. 40- 2. 81) ~ 1O-4
7.12 x 1O-4
( 2. 36f 0. 07) x 1O-4
2. 47 x 1O-4
2. 1 x 1o-4
4. 0 x 10-4
2.19 x 10-5
8. 50 x 1O-s
3. 26 x 1O-4
1. 8 x log
1. 5 x 10
2. 26 x 1O-4
7. 17 x 10-4
1. 9 x 10-5
4. 7 x 10-5
5. 6 x 1O-4
4. 3 x 1o-s
5. 5 x 10-4
129.7
133. 9
138. 1
129. 7
123. 4
123. 0
128. 9
129.3
127.6
130.5
116.7
123.8
130.5
120.9
130.1
125. 5
125. 5
exp[- 125.5/RT]
108. 8
100.1
exp[- 83.8/RT]
exp[- 121.5/RT]
86. 3
125. 1
c,e
c,e
c,e
c,e
a
a
a
c,e
c,e
d,e
c,e
c,e
c,e
a
a
a
d,e
d,e
c,e
c,e
c,e
c,e
c,e
S
S
n,s
P
S
S
s,
h
a
c,e
c,e
c,e
70
168
4
106, 176
106, 176
106, 176
106, 176
1 0 0
100
1 1 3
1 0 5
105
105
105
105
105
51
51
51
51
51
51
126, 337
126, 337
126, 337
51
51
51
51
51
51
51
51
51
51
51
51
51
51
85
85
85
85
85
85
71
17
17
17
17
77
71
283
283
283
304
304
283
283
338
51
5 1
5 1
51
Notes page II - 69; References page II - 70
II/32 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Table 4. contd
Number of
C atoms Initiator Solvent
T (C) kd (S-l) E, Wmol) Notes Ref s.
8 (contd) Butyryl peroxide Benzene
Benzonitrile
Dioxane
Hexane
Isooctane
Toluene
Vapor
Isobutyryl peroxide Acetonitrile
Benzene
Benzonitrile
terr-Butanol
Carbon tetrachloride
Chlorobenzene
Chloroform
Cyclohexane
Fluorobenzene
Cyclopropane formyl peroxide
Isopropanol
Nitrobenzene
Nujol
Tetralin
Toluene
Vapor
p-Xylene
Carbon tetrachloride
Diacetyl succinoyl diperoxide Styrene
Succinoyl peroxide Acetone
65. 0 2. 24 x 1O-5
85. 0 3. 02 x 1O-4
65. 0 4. 3 x 10-5
85. 0 5. 8 x 1O-4
65. 0 4. 6 x 1O-5
85. 0 4. 6 x 1O-4
65. 0 1.14 x 10-5
85. 0 1.53 x 1o-4
65. 0 1.11 x 1o-5
85. 0 1.56 x 1O-4
65. 0 2.14 x 1O-5
85. 0 2. 87 x 1O-4
65. 0 1.6 x 1O-5
85. 0 2. 0 x 10-4
96. 1 8. 6 x 1o-4
127. 4 1.5 x 10-2
158. 9 3. 0 x lo-
178. 9 1.27
T WI
1.9 x 1o-4
40 6.81 x 1o-4
20 1.6 x 1O-5
30 6. 75 x 1O-5
40 2. 59 x 1O-4
40 2. 38 x 1O-4
40 2. 40 x 1O-4
40 4. 2 x 1O-4
40 2.51 x 1O-4
40 7. 8 x 10-5
45 1.58 x 1O-4
50 3. 05 x 1o-4
55 5.61 x 1O-4
60 7. 67 x 1O-4
40 1.73 x 1o-4
23 1.93 x 10-5
39 1.93 x 10-4
57 1.93 x 10-3
T W)
3. 37 x 104
40 7. 5 x 10-5
40 4. 5 x 1o-5
40 4. 70 x 10-5
40 1.23 x 1O-4
25 3. 35 x 10-6
35 1.54 x 10-5
45 6.14 x 1O-5
55 2. 26 x 10 -4
T W)
2. 8 x lOI
40 3. 2 x 1O-5
40 3. 05 x 1o-4
40 5. 80 x 1O-4
40 4. 63 x 1O-5
40 1.75 x 10 -4
40 1.43 x 10-4
40 -1 x 10-5
40 1.40 x 10-4
64. 5 4. 4 x 10-6
10. 4 9. 3 x 10-6
11. 8 2.31 x 1O-5
60 5. 2 x lO-j
13. 5 2. 3 x 1O-5
85 9. 3 x 10-5
70 2. 80 x 1O-5
85 1.21 x 1o-4
1 0 0 4. 36 x 1O-4
1 3 1 . 4
1 3 1 . 4
116.3
1 3 1 . 4
133.5
130.5
123.i
1 2 3 . 8
exp[- 123.8/RT]
1 0 9
exp[- 109.06/RT]
1 1 4 . 2
exp[- 114.2/RT]
125. 5
99. 6
d,e
c,e
d,e
c,e
c,e
v
c,e
c,e
c,e
d,e
c,e
m3
a
a
a
m3
a
a
a
51
51
51
51
51
51
51
51
51
51
51
51
51
51
85
85
85
85
85
167
337
337
337
167
148, 244
148
148
148
148
148
148
148
148
344
344
344
344
148
148
167
148
84
84
84
84
84
148
148
148
167
148
148
167
148
34
34
34
215
215
215
126, 337
126, 337
126. 337
Table 4. contd
Acyl Peroxides II/33
Number of
C atoms Initiator Solvent T (0 ka (S-) E. WhoI) Notes Refs.
9 Acetyl benzoyl peroxide
10 5.Bromo-2-thenoyl peroxide Carbon tetrachloride
4-Bromo-2-thenoyl peroxide Carbon tetrachloride
5-Chloro-2-thenoyl peroxide Carbon tetrachloride
a-Chloropropionyl m-chlorobenzoyl- Acetonitrile
peroxide Cyclohexane
Cyclobutane formyl peroxide Carbon tetrachloride
Cyclopropane acetyl peroxide Carbon tetrachloride
Diacetyladipoyl diperoxide Styrene
Difuroyl peroxide styrene
2 2 3 3 4 4 5 ,1,,,7. 5-Octafluoropentanoyl
peroxide
1 1
Perfluoro-2-(2-ethoxysulfinic
acid) propionyl peroxide
Pivaloyl peroxide
2-Thenoyl peroxide
3-Thenoyl peroxide
Benzoyl isobutyryl peroxide
mChlorobenzoy1 isobutyryl peroxide
p-Chlorobenzoyl isobutyryl peroxide Cyclohexane
p-Fluorobenzoyl isobutyryl peroxide Cyclohexane
5-Methyl-bis-2-thenoyl peroxide Carbon tetrachlotide
p-Nitrobenzoyl isobutyryl peroxide Cyclohexane
12 P-Allyloxypropionyl peroxide
mChlorobenzoy1 2-methyl- Acetic acid
butanoyl peroxide Acetonitrile
Freon 113
Freon 113
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
Acetonitrile
Cyclohexane
Acetonitrile
Cyclohexane
p-Xylene
70 2 x 10-5
96 5.12 x 1O-4
96 4.08 x 1O-4
7 5 1.53 x 10-5
7 5 1.14 x 10-5
15 1.58 x 1O-5
4 1 3.05 x 10-5
4 1 1.51 x 10-5
6 5 5.15 x 10-5
70 8.95,6.63 x 1O-5
7 5 1.41 x 10-4
1 4 9.45 x 1o-5
2 5 9.75.10.57 x 10-4
44.5 5.01 x 10-5
5 6 . 5 2.64 x 10-4
4 4 . 5 6.5-8.0 x 1O-4
60 6.6 x 10-6
7 3 . 5 4.73 x 10-5
8 5 1.84 x 1O-4
50 7.0 x 10-7
60 2.9 x 1O-6
70 1.03 x 10-5
20 3.29 x 1O-5
3 0 1.27 x 1O-4
40 5.01 x 10-4
T 6) 2.8 x lOI
1 0 1.9 x 10-4
15 2.21 x 10-5
7 5 2.14 x 1O-5
4 1 4.06 x 1O-4
4 1 1.63 x 1O-5
70 3.05 x 1o-4
40 1.45 x 10-5
50 5.398 x 1O-5
60 1.924 x 1O-4
70 6.872 x 1O-4
4 1 1.03 x 10-3
40 3.486 x 1O-5
50 1.362 x 1O-4
4 1 4.40 x 10-5
50 1.029 x 1O-4
5 5 1.651 x 1O-4
60 3.21 x 1O-4
6 5 5.638 x 1O-4
5 5 1.117 x 10-4
60 2.038 x 1O-4
6 5 4.893 x 1O-4
70 9.603 x 10 -4
7 5 2.92 x 1O-5
40 8.1 x 1O-5
4 5 1.336 x 1O-4
50 2.889 x 1O-4
5 5 4.725 x 10 -4
60 8.921 x 1O-4
70 2.01 x 10-5
8 0 8.62 x 1O-5
90 2.53 x 1O-4
70 2.32 x 1O-5
8 0 8.88 x 10 -5
90 2.95 x 1O-4
40 1.60 x lo-
40 1.72 x 1O-3
~(25)~~ l3
z(l9),v 13
a,m 1
a,m L
a,m L
m3
m3
1 0 1 . 7
n
1 2 5 . 7 h
1 0 0 . 6 h
exp[- 95.1/RT]
am I
a,m 1
1 1 2 . 5 hj
1 1 1 . 3
hj
j
a
155
284
284
232
232
232
1 6 7
1 6 7
3 4
3 4
3 4
3 4
3 4
24
2 4
2 4
215
2 1 5
2 1 5
287
287
287
283
283
283
304
244
232
232
1 6 7
1 6 7
1 6 7
1 6 4
1 6 4
1 6 4
1 6 4
1 6 7
1 6 4
1 6 4
1 6 7
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
232
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
191
191
191
191
191
191
256
256
Notes page II - 69; References page II - 70
II/34 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Table 4. contd
Number o f
C atoms Initiator Solvent
TV3 kd (S-l) E. Wmol) Notes Refs.
12 (co&d) mXhlorobenzoy1 2-methyl-
butanoyl peroxide
Cyclobutane acetyl peroxide
Cyclopentane formyl peroxide
Hexanoyl peroxide
5-Hexenoyl peroxide
4-Methoxybenzoyl isobutyryl-
peroxide
4-Methylbenzoyl isobutyryl-
peroxide
4-Methyl-2-thenoyl peroxide
5-Methyl-Zthenoyl peroxide
Perlluoro-2-fumanacetyl peroxide
Perlluoro-2-propoxypropionyl-
peroxide
Perfluoro-2+propoxypropionyl-
peroxide
Perlluoro-2-iso-propoxypropionyl-
peroxide
1 4 2-Azidobenzoyl peroxide
Benzoyl peroxide
2-Butanol
Carbon tetrachloride
Cyclohexane
Carbon tetrachloride
Carbon tetrachloride
Toluene
Toluene
Cyclohexane
Cyclohexane
Carbon tetrachloride
Carbon tetrachloride
Freon 113
Freon 113
perF-ether mix.
Freon 113
Freon 113
Benzene
Acetic acid
Acetone
Acetonitrile
Acetophenone
Ally1 alcohol
Anisole
Benzaldehyde
Benzene
40 9.0 x 10-4
40 1.32 x 1O-4
40 6.0 x 1O-5
6 5 1.37 x 10-5
70 2.13,3.08 x 1O-5
7 5 3.83 x lo-
40 1.50 x 10-5
4 5 2.55 x 1O-s
50 4.96 x 1O-5
5 5 8.17,7.85 x 1O-5
7 7 1.186 x 10-4
60.1 1.06 x 1O-5
7 0 . 4 4.15 x 1o-5
7 6 . 4 8.59 x 1O-5
8 5 . 0 2.668 x 1O-4
5 5 5.465 x 1O-5
6 0 1.024 x 1O-4
6 5 1.876 x 1O-4
70 3.208 x 1O-4
40 9.61 x 1O-6
50 3.619 x 1O-5
60 1.305 x 10-4
7 0 4.772 x 10 -4
7 5 2.92 x lo-
7 5 4.21 x lo-5
T 6)
1.2 x 10
T W
4.4 x 104
T W) 8.9 x 1016
20 4.81 x 1O-5
30 1.96 x 1O-4
40 7.16 x 1O-4
2 0 8.32 x 10 -5
3 0 3.43 x 10-4
40 1.34 x 10-3
50 2.5 x 1O-5
8 0 9.4 x 1o-4
7 5 7.53 x 10-5
50 2.25 x 1O-6
70 2.63 x 1O-5
8 5 1.34 x 10-4
1 0 0 5.83 x 1O-4
7 0 1.76 x lo-
70 1.15 x 10-5
8 0 4.32 x 1O-5
9 4 . 5 2.30 x 1O-4
80 3.80 x 1O-4
3 0 1.42 x lo-
8 0 5.50 x 10-5
90 1.71 x 10-4
2 5 6.4 x 1O-5
3 0 4.80 x lo-*
5 5 1.14 x 10-6
6 0 2.76 x 1O-6
60 2.0 x 10-6
8 0 2.5 x 1O-5
70 1.38 x 1O-5
7 8 2.30 x 1O-5
7 8 1.67 x 1O-5
7 9 . 8 3.48 x 1O-5
8 0 4.8 x 1O-5
66 7.72 x 1O-6
7 2 . 5 1.87 x 1O-5
7 8 3.77 x 10-5
70 1.17 x 10-5
129.3
j
j
j
j
am 1
am I
exp[-77.1/RT]
exp[- 98.5/RT]
exp[- 110,2/RT]
100.1 h
1 0 2 . 7 h
1 1 1 . 3
1 2 6 . 4
116.3
1 2 4 . 3
dz
d2
a,r
a
a
a
a
t1
a
a
a
a,r
a
a,r
a,r
P2
a
a,r
a,r
m2
m2
a
C
t9
1 2 9 . 7
1 3 3 . 9
256
256
256
34
34
3 4
3 4
34
34
34
209
209
209
209
209
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
232
232
304
304
304
283
283
2 8 3
2 8 3
283
283
161
161
74
1 2 6
1 2 6
1 2 6
1 2 6
1 2 4
5
5
5
74
1 0 9
74
74
279
1 0 9
74
74
1 4
1 4
2 1 3
230
230
1 7 0
2 0
131
131
131
7 3
Table 4. contd
Acyl Peroxi des II/35
Number of
C atoms Initiator Solvent
T(C) kd (S-I) E. Wmol) Notes Ref s.
14 (contd) Benzoyl peroxide Benzene
Benzyl alcohol
Bromohenzene
Butanol
Butanone
Di-n-butyl phthalate
Carbon tetrachloride
Chlorohenzene
Chloroform
C u m e n e
Cyclohexane
Decane
Decalin
Dioxane
15
8 0
8 0
50.8
54.9
60.9
65.6
71.0
75.8
7 0
8 5
1 0 0
7 0
7 0
7 5
7 5
8 5
8 5
1 0 0
100
7 9
8 0
8 0
80.2
8 0
8 0
1 1 7
1 2 7
1 3 7
1 4 7
7 5
7 9
7 0
8 0
80.2
80.2
80.2
80.2
7 1
9 1
1 1 3
T (K)
3 0
8 0
8 5
9 0
3 0
4 5
6 0
8 0
T WI
1 0 0
8 0
8 0
8 0
7 0
8 0
8 0
8 0
2.62 x 1O-5
4.39 x 10-5
3.27 x 1O-5
4.28 x lo-
8.53 x lo-
1.66 x 10-6
3.22 x 1O-6
5.94 x 10-6
1.19 x 10-5
1.27 x lo-
8.94 x 10-5
4.96 x 10 -4
1.03 x 10-5
1.18 x 10-5
1.48 x 1O-5
1.66 x 10-5
4.7 x lo-J
5.5 x 10-5
2.28 x 10-4
2.56 x 1O-4
2.58 x 1O-5
3.35 x 10-5
4.44 x 10-4
8.15 x 1O-5
2.19 x 1O-5
3.84 x 1O-5
3.55 x 10-5
4.34 x 10-5
6.06 x 10-4
4.64 x 1O-5
2.78 x 1O-3
7.44 x 10-3
1.72 x lo-
3.89 x 1O-2
1.07 x 10-5
1.69 x 1O-5
1.35 x 10-5
4.64 x 1O-5
2.85 x 1O-5
2.36 x 1O-5
3.52 x 1O-5
2.62 x 1O-5
1.93 x 10-5
1.93 x 10-4
1.93 x 10 -3
6.94 x lOI
5.47 x 10-8
3.69 x 1O-5
6.39 x 1O-5
1.19 x 10-4
7.30 x 10-8
1.85 x 10
1.45 x 10-6
1.70 x 10-5
1.20 x 103
2.5 x 1O-4
1.12 x 10-5
2.53 x 1O-5
2.26 x 1O-4
1.30 x 10-5
6.72 x 1O-4
4.20 x 1O-4
4.18 x 10-5
123. 8
1 3 0
128.0
124. 3
ml
m3
m5
120. 1
exp[- 122.35/RT]
120.5
exp[- 120.5/RT]
a
a
a,b 2
as2
02
as 2
as2
a,t2
a,t 2
a
a
a
am2
tl
m3
m3
m3
apt 6
a
a,r
t9
a,r
a,r
Y 16
a,r
t6.a
t1
a,r
t9
cm 1
cm3
a
a,r
a,r
a,r
a
a,t 7
a,r
a,r
t1
a,r
a,r
am I
7 3
7 3
347
6 9
6 9
6 9
6 9
6 9
6 9
3 3 7
126,337
126,337
1 6
1 2 4
1 2
1 2
1 2
1 2
1 2
1 2
1 2 0
7
7 4
2 3 1
2 3 1
2 3 1
2 3 1
2 3 1
7 4
7 4
236
236
236
236
14
1 2 1
1 2 4
7 4
2 3 1
2 3 1
2 3 1
2 3 1
344
344
344
344
1 0 9
14
7 4
7 4
1 0 9
6 7
6 7
6 7
6 7
1 2 2
7 4
270
7 4
7 4
7 4
6
232
Notes page II - 69; References page II - 70
II/36 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Table 4. contcf
Number of
C atoms Initiator Solvent
T((2 kd (S-l) E, Wmol) Notes Refs.
14 (contd) Benzoyl peroxide Ethanol
Et h y l b e n z e n e
90% Formic acid
n - He p t a n e
He x a d e c a n e
He x a n e
I s o o c t a n e
I s o p r o p y l b e n z e n e
Met hyl acet at e
Me t h y l c y c l o h e x a n e
4 - Me t h y l - 2 p e n t a n o n e
a - Me t hyl s t yr e ne
Mineral oil
N e a t
Ni t r o b e n z e n e
PEG 400
90% aq. PEG 400
80% aq. PEG 400
70% aq. PEG 400
n - Pe n t a n o l
Ph e n o l
Propionic acid
Pr o p y l e n e g l y c o l
St y r e n e
25 3. 02 x lo-*
40 2. 77 x lo-7
50 4. 72 x lo-
30 3.61 x lo-*
75 1.81 x 1O-5
80 3. 33 x 10-5
85 5. 56 x 1O-5
90 1.01 x 10-4
80 3.15 x 10-5
80 6. 94 x 1O-4
80 3.11 x 10-5
80 2.71 x 1O-5
130 5. 73 x 10-3
135 1.02 x 10-2
140 1.54 x 10-2
145 2. 25 x lo-*
145 2. 22 x 10-2
145 2.21 x 10-2
145 2.12 x 10-2
150 3. 47 x 10-2
155 5.21 x lo-*
160 7. 87 x 10-2
80 2.51 x 1O-5
80 2. 85 x 1O-5
80 2. 79 x 1O-5
80 2. 70 x 1O-5
80 3. 34 x 10-5
49. 2 6. 28 x lo-
53. 9 1.0 x 10-6
80 5. 25 x 1O-5
80 4. 28 x 1O-5
70 3. 02 x 1O-5
80 2. 89 x 1O-s
105 7. 22 x 1O-3
80 4. 58 x 10-5
30 6.61 x 10-8
25 5.01 x 10-7
40 5. 73 x 10-6
50 1.15 x 10-5
70 1.15 x 10-4
25 3. 65 x lo-
40 5. 35 x 10-6
50 1.15 x 10-5
70 1.15 x 10-4
25 2. 77 x lo-
40 3. 09 x 10-6
50 7. 29 x 1O-6
70 1.15 x 10-4
25 1.71 x 10-7
40 2.11 x 10-6
50 5.01 x 10-6
70 1.15 x 1o-4
80 1.48 x 1O-4
80 6. 25 x 1O-4
80 3.19 x 10-5
25 3. 25 x 1O-8
40 1.51 x 10-7
50 3.16 x lo-
34. 8 3. 89 x lo-
49. 4 5. 28 x lo-
61. 0 2. 58 x 1O-6
74. 8 1.83 x 1O-5
100.0 4. 58 x 10-4
a
a
a
a
a,r
a,r
a,r
a,r
C
a,r
a,r
2 ( 1500)
z( 1500)
z( 1500)
z ( 500)
z (1000)
z (1500)
z ( 2000)
z( 1500)
z ( 1500)
z ( 1500)
m2
C
123. 8 as2
as2
a, r
a, r
a
m2
a
a,r
117.6 a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a,r
a,r
a,r
a
a
a
a
a
a
a
a
351
351
351
109
74
74
74
74
239
74
74
270
377
377
377
377
377
377
377
377
377
377
270
270
270
308
229
69
69
74
74
213
308
371
74
109
351
351
351
351
351
351
351
351
351
351
351
352
351
351
351
351
74
74
74
351
351
351
1 0
1 0
1 0
1 0
1 0
T a
Nl
c?
Table 4. contd
Acyl Peroxi des II/37
Number of
C atoms Initiator Solvent
T (Cl kd (S-l) E, Wmol) Notes Refs.
14 (contd) Benzoyl peroxide Poly(styrene)
Tetradecane
Tetralin
Toluene
Poly(vinylchloride)
Styrene
3-Bromobenzoyl peroxide
p-Xylene
Benzene
4-Bromobenzoyl peroxide
4-fer&Butylbenzoyl peroxide
2Chlorobenzoyl peroxide
3-Chlorobenzoyl peroxide
4-Chlorobenzoyl peroxide
Dioxane
Dioxane
Dioxane
Acetophenone
Benzene
Acetophenone
Dioxane
Acetophenone
Benzene
Dioxane
Styrene
Cyclohexane formyl peroxide
Carbon tetrachloride
Cyclopentane acetyl peroxide Carbon tetrachloride
Diacetylsebacoyl diperoxide Carbon tetrachloride
56. 4 3. 8 x 1O-7
64. 6 1.47 x 10-6
16. 1 9. 27 x 1O-6
83. 4 2. 50 x 1O-5
98. 5 1.41 x 10-4
70. 9 2. 86 x 1O-6
80. 1 1.11 x 10-5
89. 5 3. 33 x 10-5
80 2. 64 x 1O-5
80 3. 72 x 1O-5
30 4. 94 x lo-s
49. 0 6. 0~ 1O-7
55. 1 1. 31 x 10-6
60. 2 2. 83 x 1O-6
65. 1 5.69 x 1O-6
70. 3 1.10 x 10-5
60. 00 2. 24 x 1O-6
64. 6 6. 3 x 1O-7
16. 1 5.11 x 10-6
83. 4 1.44 x 10-5
98. 5 9. 33 x 10-5
50 7 x 1o-7
60 7. 7 x 10-6
70 9.9 x 1o-6
80 3.10 x 10-5
60 1.1 x 10-6
80 1.22 x 10-5
80 2. 60 x 1O-5
80 2. 57 x 1O-5
80 3. 23 x 1O-5
80 6. 06 x 10-5
80 3. 88 x 1O-4
80 3.12 x 1O-4
80 2. 85 x 1O-5
80 2. 63 x 1O-5
80 3. 83 x 10m5
80 2.17 x 1O-5
50 6. 2 x 1O-7
85 6. 64 x 1O-5
1 0 0 3. 86 x 1O-4
80 3. 62 x 1O-5
34. 8 8. 3 x 1O-8
49. 4 8. 3 x 1O-7
61. 0 3. 33 x 1o-6
74. 8 2. 22 x 10-5
1 0 0 . 0 4.17 x 10-4
30 9. 64 x 1O-5
35 1.46 x 1O-4
40 3.10 x 10-4
45 5.11 x 1o-4
50 7.17 x 1o-4
35 6. 6 x 10-5
45 2.11 x 10-4
50 4. 45 x 10-4
60 1.30 x 10-3
35 2. 87 x 1O-5
40 5. 22, 5. 29 x 1O-5
45 9.67 x 1O-5
65 1.48 x 10-5
70 3. 20 x 1O-5
75 4. 91 x 10-5
60 1.04 x 10-5
73. 5 5. 20 x 1O-5
85 2. 30 x 1O-4
120. 5
123. 8
125. 7
123. 0
128. 4
127. 2
1 2 8 . 9
84. 5
a,r
a
a,t2
as2
as2
a,t 2
a,t2
em 3
a
a
a
a
C
a
am L
a,m 1
am
a
a
a
am 1
a
a
a
a
a
a,m 1
a
a
a
a
a
a,h
Xl
Xl
Xl
17
17
17
17
1 7
15
15
15
270
74
109
69
69
69
69
69
291
17
17
17
17
287
287
287
229
116
116
7
6, 232
6, 232
232
5
7
5
6
5
7
126
126
126
6
1 0
1 0
10
10
1 0
219
219
219
219
219
1 4 8
1 4 8
1 4 8
1 4 8
34
34
34
34
34
34
215
215
215
Not es page I I - 69; References page II - 70
I I / 38 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Tabl e 4. contd
Number of
C atoms Initiator Solvent
T(C) kd (S-l) E. Wmol) Notes Refs.
14 (contd) 2,4-Dichlorobenzoyl peroxide Be n z e n e
223344556677Dodeca-
17719,,0,,
fluoroheptanoyl peroxide
Heptanoyl peroxide
6-Heptenoyl peroxide
2-Iodobenzoyl peroxide
2-Iodobenzoyl 4-nitrobenzoyl
peroxide
3-Methylbenzoyl peroxide
4-Methylbenzoyl peroxide
2-Nitrobenzoyl peroxide
3-Nitrobenzoyl peroxide Ac e t o p h e n o n e
4-Nitrobenzoyl peroxide Ac e t o p h e n o n e
3,SDinitrobenzoyl peroxide Ac e t o p h e n o n e
Perlluoroheptanoyl peroxide Freon 113
15 Benzoyl phenylacetyl peroxide Be n z e n e
4-rerr-Butylbenzoyl isobutyryl
peroxide
3-Cyanobenzoyl benzoyl peroxide
3-Methoxybenzoyl benzoyl peroxide
4-Methoxybenzoyl benzoyl peroxide
4-Methoxybenzoyl 3-bromobenzoyl
peroxide
4-Methoxybenzoyl-3,5-dinitro-
benzoyl peroxide
4-Methoxybenzoyl 4nitrobenzoyl
peroxide
16 3,5-Dibromo-4-methoxybenzoyl
peroxide
Caprylyl peroxide Be n z e n e
Freon 113
To l u e n e
To l u e n e
Chloroform
Ac e t o n e
Acetonittile
Be n z e n e
Carbon tetrachloride
Chloroform
Ni t r o b e n z e n e
Dioxane
Dioxane
Ac e t o p h e n o n e
Methyl iodide
Cyclohexane
Dioxane
Dioxane
Dioxane
Dioxane
Ni t r o b e n z e n e
Be n z e n e
Be n z e n e
70 9.70 x 10 -5
70 1.24 x 1O-4
50 1.08 x 1O-5
70 1.37 x 10-4
8 5 7.69 x 1O-4
34.8 3.88 x 1O-6
49.4 2.39 x 10-5
61.0 7.78 x 10-5
74.8 2.78 x 10 -4
100.0 4.17 x 10-3
30 1.14 x 10-4
40 4.06 x 1O-4
7 7 1.24 x 1O-4
70 5.33 x 1o-s
70 5.01 x 10-5
7 7 1.07 x 10-4
8 5 2.88 x 1O-4
2 2 1.86 x 1O-3
2 5 3.0 x 1o-4
2 5 2.1 x 10-4
2 5 5.7 x 10-5
2 5 3.4 x 10-5
2 5 2.8 x 1O-4
2 5 6.2 x 1O-4
80 4.38 x 1O-5
80 6.11 x 1O-5
59.3 5.80 x 1O-5
80 1.34 x 10-3
24.95 1.78 x 1O-5
45.05 1.50 x 10-4
80 3.80 x lo-s
80 4.33 x 10-5
80 1.87 x 10-5
2 0 3.01 x 10-5
3 0 1.11 x 10-4
40 4.20 x 10 -4
20 1.10 x 1o-4
2 5 2.05 x 1O-4
2 5 3.15 x 10-4
2 5 6.38 x 1O-4
3 0 3.88 x 1O-4
3 5 6.67 x 1O-4
5 5 6.543 x 1O-5
60 1.171 x 10-4
6 5 2.663 x 1O-4
70 5.016 x 1O-4
8 0 2.73 x lo-*
8 0 4.82 x lo-*
8 0 7.57 x 10-5
8 0 4.43 x 10-2
aj
a,k
117.6 a
a
a
a
a
a
a
a
100.6 h
a
a,k
aj
ai
a,k
119.7
81.2
am 1
am 1
a
a
h
126.4 a
126.8 a
130.5 a
98.0
90. 8
Vl
n
t10
110
t10
t10
am I
am I
am I
am 1
16
16
126,337
126,337
126,337
10
10
1 0
1 0
1 0
2 8 3
283
19
1 9
1 9
19
19
8 2
78
7 8
7 8
7 8
7 8
7 8
232
232
5
5
8 2
8 2
5
5
5
2 8 3
2 8 3
2 8 3
222
222
222
222
222
222
1 6 4
1 6 4
1 6 4
1 6 4
6
6
6
6
5 1 1.02 x 10-5
5 1 9.61 x 1O-4
51 1.67 x 1O-3
t5
1 0 8
1 0 8
1 0 8
70 2.08 x 1O-5 a 8 9
70 8.03 x 10-5 a 8 9
60 9.5 x lo-
60 6.1 x 1O-7
8 0 9.4 x 10-6
50 3.44 x 10-6
70 5.78 x 10-5
8 5 3.78 x 1O-4
128.9 a
a
a
9 5
1 1 6
1 1 6
1 2 6
1 2 6
1 2 6
Table 4. contd
Acyl Peroxides II/39
Number of
C atoms Initiator Solvent
T(C) kd (s-l) E. Wmol) Notes Refs.
16 (contd) Caprylyl peroxide Mineral oil
p-(Chloromethyl)benzoyl peroxide Ac e t o n e
3-Cyanobenzoyl peroxide
4-Cyanobenzoyl peroxide
Cycloheptane formyl peroxide
Cyclohexane acetyl peroxide Carbon tetrachloride
2-Ethyl-4-methyl-2-pentenoyl
p e r o x i d e
2-Ethylhexanoyl peroxide
2-Ethyl-2-hexenoyl peroxide
2-Iodophenylacetyl peroxide
2-Methoxybenzoyl peroxide
3-Methoxybenzoyl peroxide
4-Methoxybenzoyl peroxide
2-Methylbenzoyl peroxide
3-Methylbenzoyl peroxide
4-Methylbenzoyl peroxide
Endo-norbomane-2-carbonyl-
peroxide
Exo-norbomane-2-carbonyl-
peroxide
Endo-norbomene-Scarbonyl-
peroxide
Exo-norbomene-karbonyl-
peroxide
Dioctanoyl peroxide n - He p t a n e
T H F
To l u e n e
Dioxane
Ac e t o p h e n o n e
Dioxane
Carbon tetrachloride
Mineral oil
Mineral oil
Mineral oil
Ac e t o n e
Chloroform
To l u e n e
Ac e t o p h e n o n e
Ac e t o p h e n o n e
Dioxane
Ac e t o p h e n o n e
Dioxane
Ac e t o p h e n o n e
Ac e t o p h e n o n e
Dioxane
Ac e t o p h e n o n e
Dioxane
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
T (K)
9.8 x 1015
7 0 2.07 x 1O-5
7 0 1.82 x 10-5
7 0 1.15 x 10-5
7 0 8.8 x 1o-6
8 0 1.70 x 10-2
8 0 2.43 x 1O-5
8 0 2.03 x 1O-5
3 5 7.85 x 10 -5
4 0 1.63,1.34x 1O-5
4 5 2.02 x 10-4
6 5 1.27 x 1O-5
7 0 2.76 x 1O-5
7 5 3.61 x 1O-5
54.4 3.1 x 10-6
64.3 1.19 x 10-5
71.8 2.95 x 1O-5
exp[- 140.1/RT)
m7
am I
a
am L
1
307
3 0 7
3 0 7
307
6
5
6
3 4
3 4
3 4
3 4
3 4
3 4
2 4
2 4
2 4
T 6)
7.1 x 106
T 6) 1.2 x 104
T (K)
1.6 x 1016
0 2.60 x 1O-5
0 3.98 x 10 -5
0 1.3 x 1o-5
5 0 6.0 x 1O-5
8 0 2.15 x 1O-3
8 0 6.42 x lo-
8 0 5.75 x 10-5
8 0 1.56 x 1O-4
8 0 1.18 x 1O-4
7 0 9.02 x 1O-5
8 0 4.70 x 10-5
8 0 4.40 x 10 -5
8 0 5.92 x 1O-5
8 0 6.13 x 1O-5
exp[- 138.4/RT]
exp[- 106.4/RT]
exp[- 136.3/RT]
113.8
120.9
120.1
126.4
126.4
125.1
c ,e,q
4
a
a
a
a,m 1
a
a,m L
a
a
am 1
a
am I
1
1
1
7 9
7 9
7 9
5
5
5
6
5
6
5
5
6
5
6
44.5 6.1 x lo+
j
2 3
53.9 2.83 x 1O-5
j
2 3
65.9 1.25 x 1O-4
j
2 3
44.5 9.1 x 10-6 j m2 2 3
53.9 4.33 x 10-5 j, m2 2 3
65.9 1.28 x 10-4
j m2
2 3
44.5 4.68 x 1O-5
j
2 3
53.9 2.05 x 10 -4
j
2 3
65.9 8.18 x 10-4
j
2 3
44.5 7.2 x 1O-5 j. m2 2 3
53.9 1.60 x 1O-4 jm2 2 3
65.9 8.48 x 1O-4
i m2
2 3
44.5 6.30 x lo- j
2 3
53.9 1.21 x 10-4
j
2 3
65.9 7.18 x 10-4
j
2 3
445 2.22 x lo- j,m2 2 3
53.9 4.52 x 1O-5
i m2
2 3
65.9 2.37 x 1O-4 i m2 2 3
44.5 6.58 x 1O-5
j
2 3
53.9 1.21 x 10-4
j
2 3
65.9 8.42 x 1O-4
j
2 3
44.5 2.58 x 1O-5 km2 2 3
53.9 1.20 x 10-4
i m2
2 3
65.9 7.10 x 1o-4 j m2
2 3
7 0 1.70 x 10-5 z (1500) 377
8 0 7.01 x 10-5
z (500)
377
8 0 6.80 x 10-5
z (low
3 7 7
Notes page II - 69; References page II - 70
II/40 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Table 4. contd
Number of
C atoms Initiator Solvent T ((-2 kd (S-l) E. Wmol) Notes Refs.
16 (contii) Dioctanoyl peroxide n-Heptane
Dioctanoyl peroxydicarbonate Chlorobenzene
Phenylacetyl peroxide
Triptoyl peroxide Benzene
18 Apocamphoyl peroxide
cis-5-fert-Butylcyclohexylformyl-
m-chlorobenzoyl peroxide
frans-4-ferr-Butylcyclohexylformyl-
m-chlorobenzoyl peroxide
5-terr-Butylthenoyl peroxide
Cinnamoyl peroxide
Acetonitrile
2-Butanol
Carbon tetrachloride
Cyclohexane
Carbon tetrachloride
Styrene
Dibenzoyl succinoyl diperoxide Unknown
Nonanoyl peroxide
Isononanoyl peroxide (3,5,5-
trimethylhexanoyl peroxide)
2-Nonenoyl peroxide
exp[- 129,05/RT]
Acetonitrile
Benzene
Carbon tetrachloride
Cyclohexane
Styrene
Toluene 9 6 . 2 f,u 1
f,u 1
Benzene
8 0 6 . 2 7 x 1O-5
8 0 6.01 x 1O-5
8 0 5 . 7 7 x 10-5
90 2 . 1 3 x 1O-4
9 5 3 . 8 0 x 1O-4
1 0 0 6 . 7 9 x 1O-4
6 3 1.93 x 10-5
8 0 1.93 x 10-4
1 0 0 1.93 x 10-3
T W
2 . 3 0 x lOI5
2 0 1.02 x 10-3
2 0 4 . 7 6 x 1O-4
2 0 1.86 x 10-4
2 0 1.60 x 1O-4
0 7 . 8 x 10m5
0 2 . 5 0 x lo-
18 3 . 3 4 x 10-4
8 0 1.42 x 1O-4
8 0 1.4 X 10-4
8 0 2 . 3 x 1O-4
3 7 7
3 7 7
3 7 7
377
377
3 7 7
344
344
344
344
1 6 7
1 6 7
1 6 7
1
I
1 6 7
316
5 9
5 9
1 0 2
244
102
Acetonitrile 40 5 . 9 x 10-3 256
2-Butanol 40 4 . 4 x 10-3 256
Carbon tetrachloride 40 6 . 7 x 1O-4 256
Cyclohexane 40 4 . 4 x 10-4 256
40 4 . 2 x 1O-3
40 2 . 8 x 1O-3
40 6 . 5 x 1O-4
40 3 . 9 x 1om4
75 4 . 0 3 x 10-5
5 0 1 . 2 0 x 10-5
7 0 1.67 x 1O-4
7 0 7 . 7 x 10-6
7 5 1.42 x 1O-5
8 5 5 . 4 x 10-5
T (K)
8 . 4 x lOI
am I
1 2 5 . 5 Xl
Xl
X l
exp[- 127.1/RT]
256
256
1
256
256
232
316
316
214
214
214
1 Mineral oil
Benzene
Chlorobenzene
n-Heptane
Mineral oil
5 0 6.1 x 1O-6
7 0 8 . 0 2 x 1O-5
8 5 5 . 3 0 x 1o-4
60 1.9 x 10-5
5 9 1.93 x 10-5
7 7 1.93 x 1o-4
9 6 1.93 x 10-3
T (K)
2 . 8 4 x lOI5
6 0 5 . 2 8 x 1O-6
7 0 2 . 0 6 x lo-s
8 0 9 . 5 3 x 10-5
8 0 9 . 1 0 x 10-5
8 0 8 . 6 2 x 10m5
8 0 8 . 2 4 x 1O-5
8 0 7 . 8 6 x 1O-5
8 0 7 . 4 6 x 1O-5
9 0 2 . 5 2 x 1O-4
1 0 0 8.81 x 1o-4
1 2 0 6 . 9 8 x 1O-3
125 1.27 x 10m2
1 3 0 2 . 1 5 x lo-*
135 2.60 x 1O-2
1 4 0 5.71 x 10-2
145 8 . 6 2 x 1O-2
1 5 0 1.17 x lo-
T 09
1.6 x lOI
z (1500)
z (2000)
z (2500)
z (1500)
z (1500)
z (1500)
1 2 6 a
a
a
exp[- 128.34/RT]
z (1500)
z (1500)
z (1)
z (500)
z (1000)
z (1500)
z (2000)
z (2500)
z (1500)
z (1500)
z (1500)
z (1500)
z (1500)
z (1500)
z (1500)
i (1500)
z (1500)
exp[- 128.8/RT]
337
337
3 3 7
3 3 8
344
344
3 4 4
344
3 7 7
3 7 7
3 7 7
3 7 7
3 7 7
3 7 7
3 7 7
3 7 7
377
377
377
377
377
377
377
3 7 7
3 7 7
1
Table 4. contd
Acyl Peroxides II/41
Number of
C atoms Initiator Solvent T (0 kd (S-I) E. Wmol) Notes Refs.
18 (conrd) 3-Nonenoyl peroxide
2-Phenylpropionyl peroxide
19 Dibenzoyl itaconyl diperoxide
Dibenzoyl a-methylsuccinoyl-
diperoxide
2 0 De c a n o y l p e r o x i d e Be n z e n e
Dioctanoyl a-bromosuccinoyl-
diperoxide
Dioctanoyl a-chlorosuccinoyl-
diperoxide
21
Dioctanoyl a-chlorosuccinoyl-
diperoxide
4-Ethyl-2-octenoyl peroxide
Dioctanoyl itaconoyl diperoxide
Dioctanoyl a-methyl succinoyl-
diperoxide
2 2 Benzoyl 2-[nuns-2-(3-nitrophenyl)-
vinyllbenzoyl peroxide
Benzoyl 2-[rrans-2-(4nitrophenyl)-
vinyllbenzoyl peroxide
Benzoyl 2-[truns-2-(4nitrophenyl)-
vinyl]-4-nitrobenzoyl peroxide
Benzoyl 2-[rrans-2-(phenyl)vinyl]-
benzoyl peroxide
4-Benzylidenebutyryl peroxide
Mineral oil T 6)
Cyclohexane 55.8
On silica 49.4
St y r e n e IO
Un k n o wn 70
exp[- lOS.O/RZJ
83.7
115.1
15
8 5
Un k n o wn 70 82.8
116.3
7 5
8 5
127.2
XZ
x2
x2
x2
x2
x2
x2
x2
x2
x2
x2
x2
a
a
a
Ch l o r o b e n z e n e
Mineral oil
Un k n o wn
60
IO
8 5
6 3
8 0
1 0 0
T 6)
T 6)
70
exp[- 130.48/RT]
exp[- 131.9/Rfl
96.2
126.4
15
8 5
Un k n o wn 70 95.4
126.4
15
8 5
3.1 x 104
6.8 x 10-6
7.5 x 10 -5
5.5 x 10-5
5.63 x 1O-4
1.87 x 10-5
8.63 x 1O-4
3.62 x lo--
1.69 x 1O-3
1.00 x 10-4
2.74 x 1O-4
1.26 x 1O-5
4.26 x 1O-4
2.40 x 1O-5
9.60 x 1O-4
8.7 x 1O-5
1.53 x 10-5
5.67 x 1O-5
3.80 x 1O-4
1.93 x 10-5
1.93 x 10-4
1.93 x 10-9
3.64 x lOI
2.7 x lOI
1.52 x 1O-4
1.82 x 1O-5
2.74 x 1O-4
3.83 x 1O-5
6.91 x 1O-4
1.15 x 10-4
2.02 x 1o-4
2.42 x 1O-5
3.23 x 1O-4
4.83 x 10-5
8.50 x 10-4
x2
x2
x2
x2
x2
x2
x2
x2
x2
x2
x2
Un k n o wn 8 5
Mineral oil
T 6)
Un k n o wn 70
x2
expI- 127.41~~~
92.9
127.6
15
8 5
Un k n o wn 70 96.2
131.0
75
8 5
Ch l o r o b e n z e n e 70
1.58 x 10-4
8.2 x 104
3.23 x 1O-4
2.80 x 10-5
5.47 x 1o-4
5.60 x 10 -5
1.28 x lo-
1.92 x 1O-4
5.48 x 10-4
5.88 x lO-5
9.58 x 1O-4
1.06 x 10 -4
2.61 x 1O-3
3.84 x 10-4
1.87 x 1O-4
x2
x2
x2
x2
x2
x2
x2
x2
x2
XZ
x2
x2
t9
Ch l o r o b e n z e n e 70 1.18 x 10-4 t9
T H F 70 6.2 x 10 -5 t9
Ch l o r o b e n z e n e IO 1.54 x 10-5
t9
Ch l o r o b e n z e n e 3 5 9.42 x 1O-5
IO 3.02 x 1O-3
3 5 9.77 x 10-4
50 7.92 x 10 -5
5 5 1.45 x 10-4
6 5 4.13 x 10-4
T 6)
1.07 x 102
5 5 1.38 x 10-4
84.5
Me t ha nol
Ac e t o p h e n o n e 99.6
h,b
t9
t9
exp[- 99.6/RT]
98.7 m2
1
258
258
316
214
214
214
214
214
214
214
214
214
214
214
214
126,337
126,337
126,337
344
344
344
344
1
214
214
214
214
214
214
214
214
214
214
214
214
1
214
214
214
214
214
214
214
214
214
214
214
214
1 7 5
1 7 5
1 7 5
175
1 7 5
175
175
133
133
1 3 3
1 3 3
133
Not es page I I - 69; References page II - 70
I I / 42 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Table 4. contd
Number OP
Catoms Initiator Solvent T (C) kd (S-l) E, Wmol) Notes Ref s.
22 (conrd) 4-Benzylidenebutytyl peroxide Acetophenone
4-ferr-Butylbenzoyl peroxide
cis-4-rert-Butylcyclobexane formyl-
peroxide
mans-4-reti-Butylcyclobexane formyl-
peroxide
frans-4-(4-Chlorobenzylidene)-
butyryl peroxide
Benzene
Carbon tetrachloride
Nitrobenzene
Propylene carbonate
Toluene
Dioxane
Butane
Carbon tetrachloride
Carbon tetrachloride
Benzene
Propylene carbonate
rrans-4-(4-Fluorobenzylidene)-
butyryl peroxide
Propylene carbonate
I-Naphthoyl peroxide
4-Nitrobenzoyl-2-[trans-2-(4-nitro-
phenyl)vinyl] benzoyl peroxide
2-Phenylisovaleryl peroxide
5-Phenylpenta-2,4-dienoyl-peroxide
SPhenylpentanoyl peroxide
2 4 Dibenzoyl 2-bromosebacoyl-
diperoxide
Dioctanoyl 2-bromosebacoyl-
diperoxide
Chlorobenzene
Acetonitrile
Cyclohexane
On silica
Styrene
Acetophenone
Benzene
Carbon tetrachloride
Propylene carbonate
Unknown
Unknown
6 5 4.02 x 1O-4
T 6) 7.14 x 10
50 2.40 x 1O-5
6 0 6.80 x 10-5
70 1.845 x 1O-4
6 0 3.47 x 10 -5
70 1.06 x 1O-4
T 09 1.42 x lOI3
60 3.38 x 1O-4
40 7.36 x 1O-5
50 2.13 x 1O-4
T W 5.93 x loto
5 0 2.08 x 1O-4
40 7.23 x 1O-5
5 0 2.093 x 1O-4
60 5.117 x 1o-4
70 1.64 x 1O-4
8 0 6.08 x 10-2
40 1.25 x 10-5
40 1.69 x lo-s
4 0 . 0 (8.65 f0.35) x 1O-5
4 5 . 4 5 (1.32 hO.04) x 1O-4
5 0 . 7 (2.35 f 0.05) x 10 -4
4 0 . 0 (4.25 k 0.23) x 1O-5
4 4 . 7 (7.10i0.38) x 1O-5
4 8 . 9 (1.14ik0.04) x 10-4
50 2.10 x 10-5
6 0 6.56 x 1O-5
70 1.75 x 10-4
40 5.33 x 10-5
5 0 1.448 x 1O-4
60 2.791 x 1O-4
5 0 2.67 x 1O-5
60 8.44 x 1O-5
70 2.119 x 1O-4
40 6.53 x 1O-5
50 1.685 x 1O-4
60 4.540 x 10 -4
5 4 . 6 1.01 x 1o-4
5 9 . 9 1.86 x 10-4
6 4 . 5 3.0 x 1o-4
70 6.06 x 10-5
5 5 . 0
55.0
50
7 0
7 7
7 7
7 0
7 7
8 5
T 6)
60
60
7 0
7 5
8 5
7 0
7 5
2.27 x 10 -5
6.4 x lO-j
2.56 x 1O-4
2.18 x 1O-4
2.37 x 1O-4
1.054 x 10 -5
2.76 x 1O-5
7.19 x 10-5
1.87 x 1O-4
1.76 x 1015
4.41 x 10-5
2.80 x 1O-5
4.80 x 1O-4
3.87 x lo-
7.64 x 1O-4
7.22 x lo-
2.00 x 10-3
2.02 x 1o-4
6.46 x 1O-4
5.23 x 1O-5
1.171 x 10-5
7-2
m2
e x p [ - 98.7/RT] rn2
91.2 h
112.5
m2
m2
exp[- 112.5/RT] rn2
8 9 . 5
exp[- 89.5/R7J
8 2 . 0
mz
h
76.1
am 1
z (0.98)
z (1010)
h
8 1 . 6 h
95.0 h
94.1 h
t9
n2
1 2 7 . 6
130.1
hm
m2
m2
m2
e x p [ - 130.1/RT] mz
m2
8 7 . 9
x2
110.8
XZ
x2
x2
x2
x2
9 9 . 6 x2
1 2 9 . 7
x2
133
133
1 9 4
1 9 4
1 9 4
133
133
133
133
133
133
133
133
1 9 4
1 9 4
1 9 4
1 3 3
6
1 4 5
145
3 5
3 5
3 5
3 5
3 5
3 5
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 7 0
1 7 0
1 7 0
175
258
258
258
316
1 3 3
1 9 4
1 3 3
1 3 3
133
133
1 3 3
133
214
214
214
214
214
214
214
214
214
i
:
Table 4. contd
Hydroperoxides and Ketone Peroxides II/43
Number o f
C atoms Initiator Solvent TV3 kd (s-l) E, W/mol) Notes Ref s.
24 (conrd) Dioctanoyl 2-bromosebacoyl- Unknown
diperoxide 8 5
Lauroyl peroxide Benzene 3 0
40
5 0
60
70
60
70
8 5
70
Carbon tetrachloride 40
5 0
60
70
Chlorobenzene 6 1
79
9 9
T 6)
Ethyl acetate 40
50
61
70
Ethyl ether 3 0
Mineral oil
T 6)
3 4 . 8
49.4
6 1 . 0
7 4 . 8
1 0 0 . 0
5 0
60
6 5
70
trans-4-(4-Methoxybenzylidene)- Benzene 50
butyryl peroxide
rrans-4-(4-Methylbenzylidene)- Benzene 5 0
butyryl peroxide 60
70
26 2-Phenoxybenzoyl peroxide Acetophenone 6 5
28 Myristoyl peroxide Benzene 7 0
36 Menthylphthaloyl peroxide D i o x a n e 5 5
x Aliphatic polymeric Chlorobenzene 7 5
diacyl peroxide 7 5
8 0
1.08 x 1O-4
3 . 0 0 x 1o-3
3 . 7 2 x 1O-4
2 . 5 6 x 1O-7
4 . 9 1 x 10-7
2 . 1 9 x 10-6
9 . 1 7 x 10-6
2 . 8 6 x 1O-5
1.51 x 10-5
5 . 5 8 x 1O-5
3 . 7 5 x 10-4
4 . 3 3 x 10-5
2.91 x lo-
1.15 x 10-6
4 . 7 5 x 10-6
1.87 x lo-
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
3 . 9 2 x 1o14
6 . 0 3 x lo-
2.70 x lO-6
1.05 x 10-5
3 . 9 9 x 10-5
1.97 x 10-6
2 . 2 x 106
2 . 0 6 x lo-
2 . 2 5 x 1O-6
1.42 x lO-5
1.00 x 10-4
2 . 3 9 x 10-3
3.1 x 10-6
1.20 x 10-5
2 . 2 2 x 10-5
4 . 3 2 x 1O-5
2 . 0 3 x 1O-4
6 . 5 8 x 1O-5
1 . 8 1 5 x 1O-4
4.729 x 10 -4
8 . 1 8 X 10-5
3 . 3 8 x 1O-5
1.15 x 10-4
9 . 0 4 x 10-5
9.00 x 10-5
1 . 7 2 0 x 10 -4
x2
x2
x2
a
1 2 7 . 2 a
a
a
aj
exp[- 123.37/RT]
a
exp[- 137.9/RTj
a
a
a
a
a
121.1
90.4
c,h
C
C
121.3 a
a
v 14
v 15
VI5
214
214
214
9 9
6 8
6 8
6 8
6 8
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
16
6 8
6 8
6 8
6 8
344
344
344
344
6 8
6 8
6 8
6 8
9 9
1
10
10
1 0
1 0
1 0
287
2 8 7
2 8 7
287
1 9 4
1 9 4
1 9 4
1 9 4
5
16
6 5
3 0 2
302
302
TABLE 5. HYDROPEROXIDES AND KETONE PEROXIDES
Number of
C at oms Initiator Solvent
T ((3 kd (S-l) E. Wmol) Notes Ref s.
4 set-Butyl hydroperoxide Toluene
terr-Butyl hydroperoxide Benzene
1 7 2 . 0 2 . 6 5 x 1O-5
182.3 4 . 9 x 10-5
1 3 0 3 x 10-7
145 1.6 x 10-6
1 6 0 6 . 6 x 10-6
154.5 4.29 x 10-6
161.7 9 . 2 7 x 10-6
169.3 2 . 0 x 10 -5
1 7 4 . 6 4 . 0 x 10-5
1 3 8
1 7 0 . 7
1 9 9
1 9 9
3 3 7
3 3 7
337
7 6
7 6
7 6
7 6
Notes page II - 69; References page II - 70
II / 44 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 5. contd
1
Number of
c atoms Initiator Solvent
T (C) ka (S-1 E, Wmol) Notes Refs.
1
t
4 (contd) tert-Butyl hydroperoxide Be n z e n e
Ch l o r o b e n z e n e
C u m e n e
Cyclohexane
Do d e c a n e
He p t a n e
n- Oc t a ne
To l u e n e
Va p o r
tert-Butyl hydroperoxidelcobalt
Z-Ethyl hexanoate
rerr-Butyl hydroperoxide/cobalt
s t ear at e
Methyl ethyl ketone peroxides
rert-Amy1 hydroperoxide
Acetone cyclic diperoxide
3,3,6,6-Tetramethyl- 1,2,4,5-
t e t r o x a n e
Ch l o r o h e n z e n e
Be n z e n e
Ethyl acetate
Ch l o r o b e n z e n e
To l u e n e
Be n z e n e
To l u e n e
Va p o r
Cyclohexyl hydroperoxide Be n z e n e
Benzenelstyrene (50/50)
172.3 1. 09 x 10-5
182.6 3.1 x 10-5
171 1.93 x 10-5
1 9 9 1.93 x 10-4
2 3 1 1.93 x 10-3
182.6 8.1 x 1O-5
1 0 0 1.2 x 10-7
1 7 2 1.41 x 10-4
86.1 1.32 x 1O-6
98. 5 5. 55 x 10-6
172 1.41 x 10-4
149. 8 8 x 1O-6
159. 9 2. 5 x 1O-5
169. 6 6. 9 x 1O-5
179. 6 1.82 x 1O-5
1 0 0 5. 7 x lo-s
172.5 9. 2 x lo+
181.5 2. 69 x 1O-5
192.6 8. 3 x 1O-5
204. 5 1.52 x 1O-4
214. 9 3. 24 x 1O-4
570 3. 4 x 10
670 4. 95
773 8. 4 x 10
873 5. 66 x lo*
973 2. 58 x lo3
0 1.01 x 10-3
0 8. 29 x 1O-5
0 5. 40 x 10-4
25 2. 3 x 1O-3
25 1.1 x 10-3
45 1.4 x 10-3
45 1.0 x 10-3
1 0 0 1.3 x 10-5
115 4. 80 x 1O-5
1 3 0 1.60 x 10-4
70 1.28 x 1O-6
153 1.93 x 10-5
190 1.93 x 10-4
228 1.93 x 10-3
135. 5 6. 25 x lo-
145. 5 2. 09 x lo+
165. 0 1.41 x 10-5
165. 0 1.37 x 10-5
135. 5 6. 25 x lo-
140. 5 1.19 x 10-6
145. 5 2. 09 x 10-6
150. 5 2. 83 x 1O-6
165. 0 1.41 x 10-5
165. 0 1.37 x 10-5
130. 1 1.8 x 1O-6
150. 1 3. 4 x 10-6
170. 1 3. 5 x 10-6
177. 1 4. 6 x 1O-6
185. 1 1.3 x 10-5
194. 1 2. 4 x 1O-5
207. 1 8. 5 x 1O-s
215. 1 1.66 x 10-4
250. 1 4. 88 x 1O-4
70 0
70 1.27 x 1O-3
130 2. 38 x 1O-3
140 1.16 x 1O-2
150 3. 20 x lo-*
C
C
128.4 b
b
163. 2 f
C
VI0
Vl
VI
101
Vl
a
a
a
147. 1 b
1 9 9
1 9 9
t
i
54
344
344
344
199
199
199
41
41
199
118
118
118
118
199
199
I
71
1 9 9
1
1 9 9
81
199
I
199
,
188
188
188
188
188
190
190
190
198
198
198
198
337
337
(1
337
13
344
9
344
344
286
286
286
286
373
373
373
373
373
373
365
365
365
365
365
365
365
365
365
91
91
1
9 1
9 1
91
TABLE 5. contd
Hydroperoxides and Ketone Peroxides II/45
Number of
C atoms Initiator Solvent
T(C) kd (S-l) E, Wmol) Notes Ref s.
Benzyl hydroperoxide
1,4-Dimethylcyclohexane-
hydroperoxide
1,1,3,3-Tetramethylbutyl-
hydroperoxide
Cumyl hydroperoxide
6 (co&d) Cyclohexyl hydroperoxide Benzene
Cyclohexane
8 0
80
Cyclohexene 8 0
Dimethylheptadiene 8 0
1-Octene 8 0
Styrene
1,4-Dimethylcyclohexane
Benzene
Chlorobenzene
60
60
1 2 0
1 3 0 1.7 x 1o-s
145 7.41 x 10-5
1 6 0 2.83 x lO-4
135 1.93 x lo-s
1 5 3 1.93 x 10-4
1 7 3 1.93 x 10-3
@)x
9
2,5-Dimethyl-2,5-di(hydro-
peroxy)hexane
n-Octyl hydroperoxide
2,4,4-Trimethylpentyl-
2-hydroperoxide
Poly(phenyleneethy1 hydro-
peroxide)/manganese resinate
Cumene hydroperoxide
Benzene
White oil
White oil
Chlorobenzene
Benzene
Chlorobenzene
1 3 0 2.7 x 1O-6
1 4 5 1.0 x lo-s
1 6 0 3.16 x lO-5
1 5 0 9.29 x lo-
1 5 0 9.29 x lO-5
Cumene
2 6 2.00 x 10-4
30 2.75 x lO-4
3 5 3.67 x 1O-4
1 1 5 4 x 10-7
1 3 0 1.7 x 10-6
1 4 5 6.6 x 10-6
1 5 9 1.93 x 10-5
1 9 3 1.93 x 10-4
2 5 3 1.93 x 10-3
1 1 0 2.742 x 1O-6
1 2 0 5.194 x 10-6
1 3 2 9.305 x 10-6
T 6) 2.10 x 10
Mesitylene
Styrene
Toluene
White oil
Acetone-d6
125 9 x 10-6
1 3 9 3 x lo-5
1 8 2 . 3 6.45 x 1O-5
1.50 1.34 x 10-4
- 33.0 7.0 x 10 -s
- 23.0 2.28 x 1O-4
- 12.0 1.21 x 10-3
- 18.0 8.3 x 1O-5
- 8.0 4.23 x 1O-4
1 0 p-Cymene hydroperoxide p-Cymene
Reaction order
varies from
1.5 to 2.0
Reaction order
varies from
1.5 to 2.0
Reaction order
varies from
1.5 to 2.0
Reaction order
varies from
1.5 to 2.0
Reaction order
varies from
1.5 to 2.0
9 x 10-6
1.8 x 1O-5
1.4 x lo-s
- 3.0 1.65 x lO-3
1 1 0 5.500 x 10 -e
1 2 0 1.200 x 10-5
1 3 2 2.089 x 10 -
T W
1.23 x lo*
1 3 7 . 2
1 3 4
1 1 3
112.5
112.5
46.0
1 2 2
exp[- 80.O/RT]
9 8 . 7
101.3
1 2 1 . 3
6 2 . 0
110.2
exp[- 85.48/RT]
c3 276
c4
276
c 224
a
a
a
3 3 7
337
3 3 7
344
344
344
a
a
a
a
a
t3
t3
t3
a
a
a
337
337
3 3 7
1 7 7
1 7 7
a
t 14
t14
t14
212
212
212
3 3 7
337
3 3 7
344
344
344
3 6 7
3 6 7
3 6 7
3 6 7
5 8
5 8
1 9 9
1 9 9
1 9 9
177
264
264
264
264
264
264
367
367
367
3 6 7
1 1 9
1 1 9
1 1 9
1 1 9
1 1 9
Notes page II - 69; References page II - 70
II/46 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 5. contd
Number of
C atoms Initiator Solvent T (C) ka (S-l) E. Wmol) Notes Refs.
10 (contd) Decalin hydroperoxide
Pinane hydroperoxide
2-Phenylbutyl 2-hydroperoxide set-Butylbenzene
1-Phenyl-2-methylpropyl-
hydroperoxide
I-Phenyl-2-methylpropyl-2-
hydroperoxide
Tetralin hydroperoxide
(10) Poly(cumyleneethylhydroperoxide)
(Mw 1100)
11 2,2-Bis(fert-butyldioxy)propane
1-Methoxy-1-(rerr-butylperoxy)
cyclohexane
set-Butyltoluene hydroperoxide set-Butyl toluene
12 2,2-Di-(ferf-butylperoxy)butane Chlorobenzene
2,2-Bis(terf-butyldioxy)butane
Diisopropylbenzene
monohydroperoxide
I-Methoxy-1-(rerr-amylperoxy)
cyclohexane
Acetic acid
Chlorobenzene
Decalin
1,2-Dichlorobenzene
Ethylene glycol
Nitrobenzene
Pyr i di ne
Benzene
Benzene
Poly(butene)
n-Butyl stearate
2-Ethyl-1-hexene
1-Hexadecene
Mineral oil
n-Octadecane
Isooctane
Octyl ether
Poly(propylene)
n-Tetradecane
Tetralin
2,2,4-Trimethyl-l-pentene
white oil
Cumene
Chlorobenzene
Cumene
1 3 0 5 . 5 x 10-4
1 3 0 10% in 3 h
1 3 0 1.41 x 10-5
1 3 0 4 . 4 8 x 1O-5
1 3 0 1.65 x 1O-4
1 3 0 4 . 7 3 x 10-5
1 3 0 (2.31-2.89) x 1O-4
1 3 0 7 . 0 8 x 1O-6
1 4 5 2 . 7 2 x 1O-5
1 6 0 9 . 1 7 x 10-5
1 1 0 2.944 x 1O-6
1 2 0 6 . 6 1 1 x 10-6
1 3 2 1 . 0 8 9 x 1O-5
T (K)
4.06 x 10 I2
133.8 3 . 1 8 x 1O-6
143.9 8 . 9 5 x 1O-6
1 5 3 . 9 2 . 0 x 10-5
1 6 3 . 7 4 . 0 3 x 10-5
1 7 4 9 . 7 7 x 10-5
1 4 4 . 2 5 . 0 4 x 10-6
154.5 1.21 x 10-5
1 6 5 . 6 2 . 9 2 x 1O-5
1 7 6 . 0 6 . 9 7 x 1O-5
1 7 0 2 . 1 7 x 1O-3
1 7 0 1.47 x 10-4
1 3 0 1.08 x 1O-4
1 7 0 1.26 x 1O-3
1 7 0 7 . 9 2 x 1O-4
1 3 5 . 6 4 . 2 x 1O-5
1 5 0 . 6 1.00 x 10-4
1 7 0 4.82 x 1O-4
1 7 0 2 . 5 4 x 1O-4
1 7 0 131 x 10-4
1 7 0 1.45 x 10-3
1 7 0 2 . 5 0 x 1O-3
1 7 0 2 . 3 2 x 1O-4
T W
2.27 x lo9
1 7 0 1.67 x 1O-3
1 5 0 1.34 x 10-4
1 3 0 2 . 7 9 x 1O-5
1 4 0 4 . 0 x 10-5
1 5 0 5 . 7 8 x 1O-5
90 2 . 1 6 x 1O-6
1 0 0 9 . 1 4 x 10-6
1 1 0 2 . 9 7 x 1O-5
1 2 0 9 . 5 6 x 1O-5
8 0 4.79 x 10-6
90 1 . 8 9 8 x 1O-5
1 0 0 6 . 5 7 x 1O-5
1 1 0 2.139 x 1O-4
1 0 0 4 . 1 1 1 x 10-6
1 1 0 8.194 x 1O-6
1 2 0 1 . 9 5 5 5 x lo-
T 6)
1.02 x 106
9 8 1.93 x 10-5
1 1 6 1.93 x 10-4
1 3 6 1.93 x 10-3
T W
9 . 3 0 x 106
1 0 0 1 . 8 4 x 1O-5
1 5 0 1.93 x 10-5
1 8 2 1.93 x 10-4
218 1.93 x 10-3
8 0 7 . 8 2 x 1O-6
90 3 . 0 7 x 10-5
124.3
1 7 6 . 4
1 1 7 . 2
123.8
exp[- 87.15/RT]
1 2 2 . 2
125.5 h
7 8 . 2
125.5
8 2 . 8
1 1 7 . 2
1 3 1 . 4
1 1 9 . 2
1 2 1 . 3
exp[- 102.1/RT]
121.3
exp[- 110.2/RT]
exp[- 154.08/RT]
a
a
a
h
t3
t3
e,t 3
t3
t3
t3
e,t 3
t3
t3
t3
t3
t3
t3
t3
2 2 8
2 2 8
2 2 8
2 2 8
2 2 8
2 2 8
2 2 8
18
18
18
3 6 7
3 6 7
3 6 7
3 6 7
7 6
7 6
7 6
7 6
76
76
76
7 6
7 6
7 1
7 1
7 1
7 1
71
71
71
71
71
7 1
71
7 1
7 1
1 1 2
7 1
1 7 7
210
210
210
3 6 1
3 6 1
3 6 1
3 6 1
348
348
348
348
367
367
367
367
344
344
344
344
3 6 1
344
344
344
348
3 4 8
TABLE 5. contd
Hydroperoxides and Ketone Peroxides II/47
Number of
C atoms Initiator Solvent
TV3 kd (S-l) E, Wmol) Notes Refs.
12 (contcq
13
1 -Methoxy- 1 -@err-amylperoxy)
cyclohexane
1-Methoxy-1-(ten-hexylperoxy)
cyclohexane
l,l-Bis(terr-butylperoxy)-
c y c l o p e n t a n e
2,2-Bis(?ert-butyldioxy)-3-methyl-
b u t a n e
14 l,l-Bis(rert-butylperoxy)-
cyclohexane
C u m e n e
C u m e n e
C u m e n e
Diphenylmethane
C u m e n e
C u m e n e
Ch l o r o b e n z e n e
n - Do d e c a n e
n- He xa de c a ne
n-Hexane
n - No n a n e
C u m e n e
Ch l o r o b e n z e n e
Cumene
C u m e n e
C u m e n e
Cumene
C u m e n e
C u m e n e
C u m e n e
l,l-Bis(fert-butylperoxy)-2-methyl-
c y c l o p e n t a n e
1,l -Diphenylethyl hydroperoxide
1 5 I-Methoxy-l-(terr-octylperoxy)-
cyclohexane
1,1-Bis(rert-butylperoxy)-2-methyl-
cyclohexane
16 l,l-Bis(tert-amylperoxy)-
cyclohexane
l,l-Bis(tert-butylperoxy)-
c y c l o o c t a n e
17 l,l-Bis(rerr-butylperoxy)-2-n-propyl-
c y c l o h e x a n e
l,l-Bis(terr-butylperoxy)-
2 - i s o p r o p y l c y c l o h e x a n e
l,l-Bis(tert-butylperoxy)-
3,3,5-trimethylcyclohexane
1 0 0
1 1 0
8 0
90
1 0 0
1 1 0
8 0
90
1 0 0
1 1 0
90
1 0 0
1 1 0
1 2 0
1 0 0
8 0
90
1 0 0
1 1 0
94
113
1 3 4
T 6)
1 0 0
1 0 0
1 0 0
loo
8 0
90
1 0 0
1 1 0
90
1 1 0
1 3 0
1 5 0
T W)
70
8 0
90
1 0 0
80
90
1 0 0
1 1 0
8 0
90
1 0 0
1 1 0
90
1 0 0
1 1 0
1 2 0
8 0
90
1 0 0
70
8 0
90
1 0 0
8 0
90
1 0 0
1 1 0
1.058 x 1O-4
3.450 x 10-4
8.34 x lo-
3.17 x 10-5
1.120 x 10-4
3.653 x 1O-4
4.98 x 10 -6
1.80 x lo-
6.67 x 1O-5
2.17 x 1O-4
1.08 x 1O-5 ,
3.75 x 10-5
1.29 x 1O-4
4.11 x 10-4
3.17 x 10-5
3.47 x 10-6
1.45 x 10-5
5.06 x 1O-5
1.62 x 1O-4
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
3.47 x 10 I5 exp[- 142.4/RIJ
3.51 x 10-5
3.15 x 10-5
3.82 x 1O-5
3.62 x 1O-5
1.55 x 10-5
5.82 x 1O-5
1.85 x 1O-4
6.00 x 1O-4
2.0 x 10-9
1.007 x 10 -6
1.034 x 1o-6
1.223 x 1O-6
1.38 x lo8 exp[- 105.4/RT]
5.9 x 10-6
2.30 x lo-
8.18 x 10-5
2.840 x 1O-4
1.29 x 1O-5
4.51 x 10-5
1.43 x 10-4
4.58 x 10 -4
5.34 x 10-6
2.02 x 10-5
7.32 x 1O-5
2.44 x 1O-4
1.11 x 10-5
4.15 x 10-5
1.36 x 1O-4
4.24 x 1O-4
1.20 x 10-5
4.19 x 10-5
1.38 x 1O-4
2.59 x 1O-5
4.86 x 1O-s
1.98 x 1O-4
7.46 x lo4
3.82 x 1O-6
1.50 x 10-5
5.31 x 10-5
1.75 x 10-4
348
348
348
348
3 4 8
3 4 8
349,364
349,364
349,364
349,364
3 5 8
358
358
358
3 6 1
349,350
349,350
349,350
348,349,350
344
344
344
344
364
364
364
364
349
349
349
349
374
374
374
374
374
348
3 4 8
348
3 4 8
3 4 9
349
3 4 9
349
3 4 8
3 4 8
3 4 8
3 4 8
364
364
364
364
349
349
349
349
349
349
349
349,364
349,364
349,364
349,364
Notes page II - 69; References page II - 70
II/48 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 5. contd
Number of
C atoms Initiator Solvent
T (Cl kd (S-) E. (kJ /mol) Notes Ref s.
17 (conrd) l,l-Bis(terf-butylperoxy)- Chlorobenzene 8 5 1.93 x 10-5 3 4 4
3,3,5-trimethylcyclohexane 105 1.93 x 10-4 3 4 4
1 2 8 1.93 x 10-3 3 4 4
T WI 7 . 5 9 x 10 l3 exp[- 127.52/RT] 3 4 4
n-Butyl 4,4-di-(tert-butylperoxy) Chlorobenzene 1 0 2 1.93 X 10-5 344
valerate 121 1.93 x 10-4 3 4 4
1 4 3 1.93 x 10-3 3 4 4
T 6) 1.91 x 105 exp[- 143.51/R71 344
18 l,l-Bis(tert-hexylperoxy)- Cumene 8 0 5 . 3 8 x 1O-6 3 4 8
cyclohexane 9 0 2 . 0 6 x 1O-5 3 4 8
1 0 0 7 . 4 8 x 1O-5 3 4 8
1 1 0 2 . 4 8 x 1O-4 348
20 1,l -Bis(rert-butylperoxy)- Cumene 90 8 . 1 4 x 1O-6 364
cyclododecane 1 0 0 3 . 2 2 x 1O-5 364
1 1 0 9 . 9 3 x 10-5 364
2 2 l,l-Bis(rerr-octylperoxy)- Cumene 8 0 1.513 x 10-5 3 4 8
cyclohexane 9 0 5 . 6 2 x 1O-5 348
1 0 0 1.983 x 1O-4 348
1 1 0 6 . 2 6 x 1O-4 3 4 8
31 2,2-Bis[4,4-di-(terr-butyl- Chlorobenzene 8 7 1.93 x 10-5 344
peroxycyclohexyl)propane 1 0 6 1.93 x 10-4 344
1 2 8 1.93 x 10-3 344
T W) 8 . 7 9 x 1014 exp[- 135.56/RT] 344
TABLE 6. PERESTERS AND PEROXYCARBONATES
Number of
C atoms Initiator Solvent TV3 kd (S-) E. Wmol) Notes Ref s.
Dimethyl peroxalate
rert-Butyl percarbamate
rerr-Butyl performate
Isobutyl peracetate
n-Butyl peracetate
set-Butyl peracetate
fert-Butyl peracetate
4
5
Pentane
Chlorobenzene
Chlorobenzene
4-Chlorotoluene
Cumene
a-Methylstyrene
a-Methylstyrene
c+Methylstyrene
ferr-Amy1 alcohol
n-Butanol
2 5 1.7 x 10-5
9 0 6 . 6 x 10-6
1 3 0 . 8 5 . 4 3 x 10-5 1 5 9 . 0
1 4 0 . 8 1 . 7 0 x 10-4
1 4 0 . 6 1.80 x 1O-4
1 4 0 2 . 1 2 x 10-3 6 4 . 0
1 4 0 5 . 0 6 x 1O-4
1 4 0 . 6 1.61 x 1O-4
1 4 0 1.62 x 1O-3
1 4 0 . 6 1.77 x 10-4
1 4 0 1.02 x 10-3
7 9 . 5 1 . 3 6 x 1O-5 1 1 5 . 2
8 8 . 4 3.61 x 1O-5
9 2 . 8 5 . 5 8 x 1O-5
64 - 9.6 x 1O-3
64 8 . 2 x 1O-3
64 6 . 5 x 1O-4
6 4 1.2 x 10-3
7 9 . 6 1.57 x 10-5 1 0 1 . 0
8 7 . 8 3 . 2 7 x 1O-5
9 2 . 6 5 . 3 8 x 1O-5
8 8 . 2 1.79 x 10-5 104.3
9 2 . 8 3 . 1 9 x 10-5
9 9 . 4 5 . 3 7 x 10-5
7 5 2 . 8 x 1O-6
8 5 1.2 x 10-6
8 5 2 . 1 8 x lo+ 1 5 1 . 9
1 0 0 1.54 x 10-5
115 1.02 x 10-4
1 3 0 5 . 6 9 x 1O-4
7 5 2 . 6 5 x 1O-5
h
m2
v8
VI
v8
b
b,v 6
g2,f16
g2.v 17
g2.v18
g2.v 19
2 0 3
141
218
218
218
218
218
218
218
218
218
253
2 5 3
253
253
253
2 5 3
2 5 3
2 5 3
253
2 5 3
2 5 3
2 5 3
2 5 3
193
1 9 3
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
193
TABLE 6. contd
Peresters ad Peroxycarbonates II/49
Number of
C at oms Initiator Solvent
T ((3 kd (S-l) E. Wmol) Notes Refs.
6 (conrd) rerr-Butyl peracetate 2-Butanol 75 1.13 x 10-4
7 5 5 . 3 x 10-5
7 5 4 x lo-
60 2 . 3 1 x lo-*
1 0 0 1.93 x 10-5
1 1 9 1.93 x 10-4
1 3 9 1.93 x 10-3
T 6)
1.57 x 106
1 0 0 1.5 x 10-5
115 7.91 x 10-5
125 2 . 4 5 x 1O-4
1 0 0 1.95 x 10-5
1 0 0 1.78 x lo-
1 0 0 1.55 x 10-5
130.1 5 . 0 8 x 1O-4
1 0 0 2 . 0 7 x 1O-5
130.1 3 . 1 3 x 10-4
1 0 0 1.55 x 10-5
60 1.19 x 10-5
6 6 . 8 2 . 7 5 x 1O-5
71.0 1 . 0 0 x 1o-4
4 5 1.25 x 10-5
55 5 . 7 x 10-5
40 6.94 x 1O-6
50 2 . 8 6 x lo-
60 1.28 x 1O-4
2 5 2 . 6 x 1O-5
90 1.93 x 10-5
1 0 8 1.93 x 10-4
1 2 9 1.93 x 1o-3
T W) 4 . 1 3 x 101s
40.0 2 . 2 x 1o-4
3 9 . 6 1 . 9 4 x 1o-4
5 0 . 2 8 . 2 4 x 1O-4
60.1 2 . 3 5 x 1O-3
90 1 . 1 2 x 10-5
1 0 0 1.51 x 10-5
1 1 0 4 . 8 5 x 1O-5
9 8 1.93 x 10-5
1 1 7 1.93 x 10-4
1 3 7 1.93 x 10-3
T 6)
2 . 4 9 x 1Or6
8 0 1.53 x 10-6
90 6.04 x 1O-6
1 0 0 1.82 x 1O-5
1 0 0 1.78 x 1O-5
1 0 0 1.58 x 1O-5
70 3 . 0 2 x lo-
90 4 . 8 5 x 1O-6
1 0 0 2 . 0 3 x 1O-5
1 0 0 1.68 x 1O-5
9 1 . 8 2 . 7 3 x 1O-5
1 1 3 . 0 5 . 4 8 x 1O-5
1 0 2 . 6 1.28 x 1O-5
1 1 3 . 0 4 . 9 2 x 1O-5
1 0 2 . 6 1.71 x 10-5
1 1 3 . 0 6 . 1 9 x 1O-5
1 2 0 . 4 1.505 x 10-4
40.0 2.96 x 1O-4
40.6 2 . 8 9 x 1O-4
46.0 5 . 5 8 x 1O-4
5 5 . 6 1.94 x 10-3
C 1 9 3
1 9 3
193
81
344
344
344
344
331
337
337
270
270
270
1 6 9
270
1 6 9
270
81
2 8
2 8
18
18
90
90
90
203
344
344
344
344
3 1 5
3 2 8
328
3 2 8
2 1 1
2 1 1
2 1 1
344
344
344
344
213
213
270
270
270
213
2 1 3
270
270
328
2 5 5
2 5 5
2 5 5
2 5 5
2 5 5
2 5 5
315
3 2 8
3 2 8
3 2 8
1 5 9 . 0
t7
m3
a.h Chlorohenzene
exp[- 149.36/RT]
1 3 4 Decane
Dodecane
Hexadecane
Hexane
Octane
Paraffin
Tetradecane
Chlorobenzene rerr-Butyl trichloroperacetate
Diethyl peroxydicarbonate rerr-Butanol
1 2 5 . 9 ah
1 2 6 . 8 h
2,2-Oxydiethylene
bis(ally1 carbonate)
Diethyl peroxalate Pentane
terr-Amy1 peracetate Chlorobenzene
133.9-138.1 C
1 2 7 . 2 a
a
a
7
exp[- 141.1/RT]
104.7
ah
1 0 3 . 9 h
rerr-Butyl methoxyperacetate Ethylbenzene
rerr-Butyl peracrylate Benzene
rerr-Butylperoxy isopropyl Chlorobenzene
8 6 . 2 a
a
a
exp[- 150.15/RT]
a
a
rerr-Butyl perpropionate
carborate
Benzene
Decane
Dodecane
Hexadecane
a-Methylstyrene
ren-Butyl 2-acetoxyperacetate
rerr-Butyl cyclopropane-
percarboxylate
Octane
Tetradecane
Ethylbenzene
n-Dodecane
n-Hexadecane
2,2,4-Trimethyl-
pentane
rerr-Butyl ethoxyperacetate Ethylbenzene
a
a
8
b
1 5 3 . 8 h
1 4 6 . 2 h
1 0 5 a
102.7 mz,h
Not es page I I - 69; References page II - 70
I I / 5 0 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T(C) kd (S-l) E. (kI/mol) Notes Ref s.
Benzene
Methanol
Methoxybenzene
Nitrobenzene
Octane
Fyridine
Toluene
Ethylbenzene
Benzene
Bulk
Chlorobenzene
Cumene
Decane
Dodecane
Hexadecane
Iso-octane
Nujol
Octane
Benzene
rerr-Butyl heptafluoroperoxy-
butyrate
rert-Butyl methoxypetpropionate
felt-Butyl perisobutyrate
[err-Butyl percrotonate
8 (contd) 65.0 1.56 x 1O-5
70.0 3.09 x 10-5
75.0 5.27 x 1O-5
80.0 9.08 x lo-
60.0 9.5 x 10-6
65.0 1. 61 x lo-
70.0 2.70 x 1O-5
75.0 5.23 x 1O-5
80.0 9.18 x 1O-5
60.0 9.6 x 1O-6
65.0 1. 93 x 1o-5
70.0 3.57 x 10-5
75.0 6.35 x 1O-J
1 0 . 0 7.19 x 10-5
1 5 . 0 9.37 x 10-5
1 9 . 6 1.304 x 1o-4
30.0 2.604 x 1O-4
55.0 5. 01 x 10-5
60.2 8.56 x 1O-5
65.0 1.378 x 1O-4
70.0 2.444 x 1O-4
40.0 3.26 x 1O-5
45.0 6.36 x 1O-5
50.0 9.31 x 10-5
85.0 5 . 1 x 10-6
90.0 9.5 x 10-6
95.0 1. 75 x 10-5
100.0 3. 41 x 10-5
30.0 2.74 x 1O-5
40.0 7.66 x 1O-5
50.0 1. 868 x 10-4
65.0 1. 88 x 10-5
75.0 4.66 x 1O-5
80.0 7.06 x 1O-5
85.0 1. 203 x 1O-4
40.3 4.30 x 10-3
7 8 3.77 x 10-5
7 0 6.69 x 1O-5
8 5 5.33 x 10-5
1 0 0 3.50 x 10-4
7 0 4.12 x 1O-5
90.6 8.13 x 1O-5
100. 7 2.75 x 1O-4
110.0 8.92 x 1O-4
7 9 1. 93 x 1o-5
9 8 1. 93 x 1o-4
1 1 8 1. 93 x 10-3
T (K)
2.07 x 1015
90.6 6.9 x 1O-5
100. 7 2.35 x 1O-4
110.0 6.57 x 1O-4
7 0 4.7 x 10-6
8 5 2.6 x 1O-5
1 0 0 1. 55 x 10-4
1 0 0 1. 46 x 1O-4
1 0 0 1. 56 x 1O-4
1 0 0 1. 47 x 10-4
103.4 2.16 x 1O-4
103.4 2.23 x 1O-4
1 0 0 1. 59 x 1o-4
1 0 0 1. 52 x 1O-4
1 0 0 2.5 x 10-5
1 1 5 1. 50 x 10-4
1 3 0 7.39 x 10-4
v24
v24
v24
v24
v25
v25
v25
v25
v25
v26
V26
v26
v26
a
140.6 a
a
a
a
140.6 h
exp[- 13516/RT]
133. 1 h
1 2 2 a
a
a
1 3 8 a
a
a
370
370
370
370
370
370
370
370
370
370
370
370
370
369
369
369
369
370
370
370
370
370
370
370
370
370
370
370
370
370
370
369
369
369
369
328
3 7
126,337
126,337
126,337
3 7
1 3 6
1 3 6
1 3 6
344
344
344
344
1 3 6
1 3 6
1 3 6
3 3 7
3 3 7
3 3 7
270
270
270
2 5 1
2 5 1
270
270
337
337
337
TABLE 6. contd
Peresters and Peroxycarbonates II/51
Number of
C atoms Initiator Solvent T (Cl kti (s-l) E, W/mol) Notes Ref s.
8 (conrd) tert-Butyl permaleic acid Acetone
rerf-Butyl permethacrylate
rerr-Butyl peroxyisopropyl carbonate Benzene
Cyclohexyl peracetate a-Methylstyrene
Diisopropyl peroxalate
Diisopropyl peroxydicarbonate
Ethyl rert-butyl peroxalate
9 reti-Butyl 2-acetoxyperpropionate Ethylbenzene
rerr-Butyl S-bromo-2-pertbenoate Carbon tetrachloride
tert-Butyl 5-chloro-2-perthenoate Carbon tetrachloride
rert-Butyl cyclohutane-
percarboxylate
ter?-Butyl 2,2-dimetbyl-
3-bromoperpropionate
terr-Butyl 2,2-dimethyl-
3-chloroperpropionate
rerr-Butyl 2,2-dimethyl-
3-iodoperpropionate Cyclohexane
tert-Butyl isopropoxyperacetate Ethylbenzene
Pentane
Benzene
Di-n-butyl phthalate
Decane
Ethylbenzene
Mineral spirits
2,2-Oxydiethylene-
bis(ally1 carbonate)
Toluene
Benzene
n-Hexadecane
2,2,4-Trimethyl-
pentane
Cyclohexane
Cyclohexane
70 2.7 x 1O-6
8 5 1.6 x 1O-5
101 6.77 x 1O-5
90 1.92 x 1O-5
1 0 0 7.66 x 1O-5
1 1 0 1.92 x 1O-4
90 6.64 x 1O-6
1 0 0 2.21 x 10-5
1 1 0 6.87 x 1O-5
8 8 . 6 1.63 x 1O-5
93.0 2.30 x 1O-5
9 9 . 3 4.75 x 1o-5
2 5 6.0 x 1O-5
5 4 . 0 5.0 x 10-5
7 7 1.39 x 10-3
8 7 4.09 x 10-3
9 7 1.25 x lo--
1 0 7 3.54 x 10-2
1 1 7 7.98 x lo-*
3 5 6.3 x 1O-6
4 5 2.7 x 10 -5
60 1.85 x 1O-4
5 4 . 3 4.5 x 10-5
5 4 . 3 5.2 x 1O-5
30 2 x 10-6
4 5 1.8 x 1O-5
60 1.28 x 1O-4
75 7.55 x 10-4
40 6.39 x 1O-6
5 0 2.28 x 1O-5
60 9.44 x 10-5
50 3.03 x 10-5
4 5 4.48 x 1O-5
5 5 1.63 x 1O-4
6 5 5.93 x 10-4
91.4 3.60 x 1O-4
9 9 . 2 2.24 x 1O-6
1 1 2 . 0 1.18 x 1O-5
1 2 4 . 5 4.30 x 1o-5
9 9 . 2 2.29 x 1O-6
1 1 2 . 0 9.56 x 1O-6
124.5 4.42 x 1O-5
1 0 2 . 6 4.33 x 10-5
9 2 . 9 1.21 x 10-5
1 0 2 . 6 4.84 x lo-
1 1 3 . 0 1.668 x 10 -4
5 5 9.50 x 10-6
6 5 3.58 x 1O-5
7 5 1.23 x 1O-4
5 5 3.55 x 1o-6
6 5 1.48 x 1O-5
7 5 5.65 x 1O-5
5 5 2.91 x 1O-5
7 5 3.76 x 1O-4
40.0 4.8 x 1O-4
3 9 . 9 4.22 x 1O-4
4 9 . 9 1.39 x 10 -3
5 5 . 3 2.68 x 1O-3
1 1 3
1 3 7 . 0
1 0 9 . 4
1 1 3
m2
Y 16
Y16
Y 16
Y16
Y16
a
a
a
1 1 3
1 1 7 . 6
112.5
143.5
143.5
m2
a
a
a
a
a
a
a
a
c,h
a
a
a
a
a
a
1 5 0 . 4 h
1 1 8 . 2 h,t6 320
t6 320
t6 320
1 2 8 . 6
h,t6 320
t6 320
t6 320
1 1 6 . 9
1 0 0 . 6
9 8 . 9
h,t6
t6
ah
hm
3 3 7
3 3 7
3 3 7
2 1 1
2 1 1
2 1 1
9
9
9
253
253
253
203
60
236
236
236
236
236
337
337
3 3 7
60
60
3 3 7
3 3 7
3 3 7
337
90
90
90
90
31
31
31
328
1 7 6
1 7 6
1 7 6
1 7 6
1 7 6
1 7 6
2 5 5
2 5 5
2 5 5
255
320
320
3 1 5
3 2 8
3 2 8
3 2 8
Notes page II - 69; References page II - 70
II/52 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T (C) kd (S-l) E. Wmol) Notes Refs.
9 (cont'd) lerr-Butyl l-methylcyclopropyl- 2,2,4-Trimethylpentane
percarboxylate
Di-(ret?-butylperoxy)-carbonate Chlorobenzene
fert-Butylperoxy isopropyl
carbonate
1,2-Dichlorobenzene
Cumene
Isopropyl ether
Benzene
rerrButy1 perpivalate
Chlorobenzene
Cyclohexane
Decane
Dioxane/water (90/10)
Dodecane
Hexadecane
Hexane
Heptane
Isooctane
Mineral spirits
fert-Butyl perpivalate-ds
Octane
Tetradecane
Chlorobenzene
1 0 2 . 6 2.30 x 1O-s
1 1 3 . 0 7.47 x 10-5
99.95 6.72 x 1O-5
110.1 2 . 1 3 x 1O-4
120.1 6.05 x 1O-4
120.1 5.98 x 1O-4
99.95 6.72 x 1O-5
99.95 2.76 x 1O-4
85 3.3 x 10-6
1 0 0 2.2 x 10-5
1 1 5 1 . 3 6 x 1O-4
50 9.77 x 10-6
70 1 . 2 4 x 1O-4
85 7.64 x 10-4
50 1.03 x 10-5
55 1.94 x 10-5
60 3.92 x 1O-5
65 7 . 3 1 x 10-5
70 1 . 3 0 x 10-4
48.9 8.4 x 1O-6
58.6 3.35 x 10-5
64.3 7.01 x lo-s
57 1.93 x lo-s
75 1.93 x 10-4
94 1.93 x 10-3
T (K)
7.09 x lOi
74.8 2.79 x 1O-4
60 3.85 x 1O-5
60.6 4.00 x 10-5
74 1.93 x 10-4
45 3.53 x 10-6
55 1.73 x 1o-5
60 2.95 x 1O-5
65 4.53 x 10-5
64.6 5.81 x 1O-5
75.6 2.10 x 10-4
84.6 5.94 x 10-4
70.3 1.11 x 10-4
55 1.03 x 10-5
65 4.02 x 1O-5
75 1.45 x 10-4
50 4.1 x 10-6
70 5.52 x 1O-5
80 2 . 1 8 x 1O-4
60.6 6.26 x 1O-5
80 2.38 x 1O-4
80 2.39 x 1O-4
55 8.42 x 1O-6
60 1.59 x 10-5
65 3.39 x 10-5
70 6 . 1 9 x 1O-5
80 2.33 x 1O-4
60.6 1.97 x 10-5
73.9 8.82 x 1O-5
5.5 1.01 x 10-5
60 2 . 1 5 x 1O-5
65 4.14 x 10-5
70 7.58 x 1O-5
75 1.47 x 10-4
T W) 3.56 x 10 i4
80 2.34 x 1O-4
80 2.27 x 1O-4
60.6 3.24 x 1O-5
74.0 1.57 x 1o-4
133.7 h
133.1
1 3 8 a
a
a
1 1 9 . 7 a
a
a
k
125.5 h
exp[- 123.59fRlJ
1 2 8 . 0
106.7
ah
t9
t9
h
115.5
1 2 2 . 8 h
1 1 7 a
a
t9
exp[- 123/RT]
t9
t9
t9
t9
255
255
27
27
27
27
27
27
337
337
337
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
359
359
359
359
359
249
28
28
344
344
344
344
28
81
1 5 6
1 5 6
1 6 0
1 6 0
362
1 6 0
1 5 9
1 5 9
1 5 9
267
320
320
320
337
337
270
1 5 6
270
270
359
359
359
358
270
165
1 6 5
359
359
359
359
359
376
270
270
1 5 6
1 5 6
TABLE 6. contd
Peresters and Peroxycarbonates II/53
Number of
C atoms Initiator Solvent TV3 kd (s-) E, Wmol) Notes Refs.
9 (confd) k=rt-Butyl perpivalate-de Dioxane/water (90/ 10)
Isooctane
tert-Butyl 2-perthenoate Carbon tetrachloride
6 0 . 6 5 . 0 5 x 10-5
t9 1 5 6
60.6 1.62 x 1O-5 t9 165
73.9 8 . 8 2 x 1O-5
t9
165
9 9 . 2 3 . 3 x 10-6 147.3
m2 1 7 6
1 1 2 . 0 1 . 6 6 x 10-5 m2 1 7 6
124.5 6 . 8 7 x lo-5 m2 1 7 6
90 7.59 x 10-5 141
1 0 0 9 . 9 x 10-4
1 0 0 3 . 7 9 x 10-5
90 1.32 x 1O-5
1 0 0 4 . 9 1 x 10-5
90 3 . 3 x 10-6
1 0 0 1 . 1 0 x 10-5
1 0 0 9 . 0 x 10-6
1 0 0 6 . 0 0 x 1O-3
9 0 9 . 2 4 x 1O-5
1 0 0 3.41 x 10-4
5 1 1.9 x 10-5
5 5 1.93 x 10-5
72 1.93 x 1o-4
9 1 1.93 x 10-3
T 03
4.12 x 1015
5 0 1.05 x 10-5
6 0 3.51 x 10-5
70 1 . 3 0 9 x 10-4
8 0 4.239 x 10 -4
3 5 6 . 9 x 1O-6
4 5 2 . 6 x 1O-5
6 0 1.80 x 1O-4
47 1.93 x 10-5
6 3 1.93 x 10-4
8 2 1.93 x 10-3
T 09
3 . 1 9 x 105
3 0 2 x 10-6
40 1.0 x 10-5
6 0 1 . 3 4 x 10-4
49 1.93 x 10-5
6 5 1.93 x 10-4
8 3 1.93 x 10-3
T (K)
7 . 0 0 x 105
7 4 . 7 1.98 x 1O-4
8 0 . 7 4.37 x 10-4
9 0 . 8 1.25 x 1O-3
4 0 . 3 2.91 x 10 -4
9 9 . 8 1.65 x lo-5
1 1 6 . 6 1.38 x 1O-4
1 2 9 . 9 6 . 8 3 x 1O-4
1 1 3 . 4 km2
m2
t o
m2
a
exp[- 127.76/RT]
1 1 3 a
a
a
exp[- 123.85/RT]
113 a
a
a
exp[- 126.65/RTj
m2
151.3 h
1 4 2
1 4 2
141
14i
141
1 4 2
1 4 2
1 4 2
141
1 4 2
338
344
344
344
3 4 4
362
3 6 2
3 6 2
3 6 2
3 3 7
3 3 7
331
3 4 4
3 4 4
3 4 4
3 4 4
3 3 7
3 3 7
3 3 7
3 4 4
3 4 4
3 4 4
344
3 2 8
3 2 8
3 2 8
3 2 8
2 5 7
2 5 7
2 5 7
1 1 3 . 0 3 . 0 2 x 1O-4
9 2 . 9 2 . 4 7 x 1O-5
1 0 2 . 6 8 . 8 7 x 1O-5
1 1 3 . 0 2 . 8 9 x 1O-4
7 5 1.93 x 10-5
9 3 1.93 x 10-4
1 1 3 1.93 x 10-3
T 03
2 . 4 5 x 1tl15
42.42 9.04 x 10-5
50.30 2.349 x 1o-5
5 7 . 9 5 5.660 x 1O-5
4 4 . 8 5 1 . 8 7 4 x 10 -5
50.10 3.609 x 1O-5
60.20 1 . 3 0 6 x 1O-4
1 4 0 . 8 h
exp[- 134.00/RT]
1 0 0 . 7 h
2 5 5
2 5 5
2 5 5
2 5 5
344
344
344
344
274
274
214
274
274
274
ter&Butyl l-pyrollidine-
percarboxylate
rert-Butyl N-succinimido-
percarboxylate
Chlorobenzene
Acetonitrile
Benzene
Chlorobenzene
10 rerr-Amy1 perpivalate
Cumene
Cyclohexane
Cyclohexene
Methanol
Methylene chloride
Nitrobenzene
Benzene
Chlorobenzene
Cumene
Di-(sec-butyl)peroxy- Decane
Chlorobenzene
Mineral spirits
Di-n-butyl peroxydicarbonate Chlorobenzene
tert-Butyl 2-acetoxy-2-
methyl perpropionate
terr-Butyl [err-butoxyperacetate
tert-Butyl 4-carbomethoxy-
perbutyrate
rerr-Butyl cyclopentyl-
percarboxylate
Ethylbenzene
Ethylbenzene
Cumene
n-Hexadecane
2,2,4-Trimethyl-
pentane
tert-Butyl peroxydiethyl acetate Chlorobenzene
terr-Butyl 2,2-dimethylperbutenoate Cumene
tert-Butyl 2,2-dimethylperbutyrate Cumene
Notes page II - 69; References page II - 70
II/54 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T ((3 ka (s-l) E, Wmol) Notes Refs.
10 (contd) Di(terr-butylperoxy)-oxalate Benzene
tert-Butyl Smethyl-7-perthenoate Carbon tetrachloride
P-Methyl-P-phenyl-p-peroxy-
propiolactone
11
Bis(2-nitro-2-methylpropyl)-peroxy-
dicarbonate
I-Phenylethylperacetate
tert-Butyl 4-chloroperbenzoate
rerr-Butyl-N-(2-chlorophenylperoxy)-
carbamate
rert-Butyl-N-(3-chlorophenylperoxy)-
carbamate
terr-Butyl-N-(4-chlorophenylperoxy)-
carbamate
reti-Butyl cyclohexylperoxy-
carboxylate
rerr-Butyl-N-(2,5-dichlorophenyl-
peroxy) carbamate
rert-Butyl 2,2-dimethylperpentanoate Cyclohexane
[err-Butyl kthyl-2-pertbenoate Carbon tetrachloride
rert-Butyl 2-iodoperbenzoate Chlorobenzene
terr-butyl 4-nitroperbenzoate Phenyl ether
terr-Butyl 3,5dinitroperbenzoate
rert-Butanol
Decane
Dodecane
Octane
n-Pentane
Tetradecane
Styrene
Carbon tetrachloride
Toluene
Benzene
Phenyl ether
Carbon tetrachloride
Toluene
Toluene
Toluene
n-Hexadecane
2,2,4-Trimethyl-
pentane
Toluene
Cumene
Carbon tetrachloride
Carbon tetrachloride
3 5 . 0 6.77 x 1O-5
45.0 2.61 x 1O-4
5 5 . 0 9.3 x 10 -4
2 5 . 0 1.83 x 1O-5
4 1 1.75 x 10-4
4 1 1.81 x 1O-4
4 1 1.79 x 10-4
3 7 . 8 1.01 x 10-4
4 1 1.71 x 1o-4
3 5 5.5 x 10-5
4 5 1.71 x 10-4
5 5 6.01 x 1O-4
9 9 . 2 4.6 x 1O-6
1 1 2 . 0 1.94 x 10-5
124.5 7.95 x 10-5
1 0 6 . 8 5.65 x 1O-6
1 2 6 4.59 x 10-5
1 3 4 9.71 x 10-5
5 0 2.22 x 10-5
1 0 0 1.14 x 1o-4
1 0 0 . 0 3.89 x 1O-6
110.1 1.85 x 1O-5
1 2 0 . 2 6.39 x 1O-5
1 3 0 . 9 2.42 x 1O-4
8 0 4.2 x lo-
8 7 . 0 3.5 x 10-5
9 5 . 5 1.48 x 1O-4
103.3 3.3 x 10-4
78.0 2.6 x 1O-5
8 7 . 0 7.8 x 1O-5
9 6 . 6 2.03 x 1O-4
1 0 2 . 7 4.62 x 10 -4
73.0 5.57 x 10-5
7 8 . 5 1.42 x 1O-4
8 7 . 0 2.75 x 1O-4
9 2 . 5 5.37 x 10-4
9 2 . 9 6.70 x 1O-5
1 0 2 . 6 2.046 x 10 -4
8 2 . 2 1.57 x 10-5
92.9 6.13 x 1O-5
1 0 2 . 6 2.046 x 1O-4
1 1 3 . 0 6.58 x 1O-4
8 8 . 0 2.75 x 1O-5
95.0 5.58 x 1O-5
1 0 3 . 3 1.48 x 1O-4
1 1 4 . 5 4.82 x 1O-4
5 5 1.66 x 10-5
6 5 6.31 x 1O-5
7 5 2.23 x 1O-4
4 5 6.2 x 1O-6
5 5 2.15 x 1O-5
9 9 . 2 5.39 x 10-6
1 1 2 . 0 2.12 x 10-5
124.5 7.91 x 10-5
8 5 . 0 4.02 x 1O-5
1 0 2 . 4 2.58 x 1O-4
1 1 8 . 8 1.32 x 1O-3
110.1 7.56 x 1O-6
1 2 0 . 2 3.19 x 10-5
1 3 0 . 9 1.11 x 1o-4
141.5 3.92 x 10-4
8 0 2.9 x 10-7
8 0 1.1 x 10-7
1 0 6 . 7 ch
C
C
7 5 . 3
1 3 7 . 7
1 3 1 . 8
am 2
am 2
am 2
h,v 9
c,v 9
a
138.7
1 6 4 . 4
157.3 h
115.5 h
1 1 9 . 7 h
1 3 6 . 6
1 3 5 . 8
h
h
1 2 8 . 9 h
120.7 h
1 0 5 . 4
130.5
h
172.8
30
30
30
1 9 7
270
270
270
1 9 7
270
2 1 5
215
2 1 5
1 7 6
1 7 6
1 7 6
195
195
195
90
259
5 3
5 3
5 3
5 3
354
3 6
3 6
3 6
3 6
36
36
3 6
3 6
3 6
36
3 6
2 5 5
2 5 5
2 5 5
255
255
255
36
3 6
3 6
3 6
320
320
320
1 6 0
1 6 0
1 7 6
1 7 6
1 7 6
1 3 4
1 3 4
1 3 4
5 3
5 3
5 3
5 3
354
354
TABLE 6. contd
Peresters and Peroxycarbonates II/ 55
Number of
C atoms Initiator Solvent
T (0 kd (S-l) E. Wmol) Notes Ref s.
11 (contd) fer?-Butyl-N-(3-nitrophenylperoxy)-
carbamate
Toluene
tert-Butyl-N-(4-nitrophenylperoxy)-
carbamate
Toluene
terr-Butyl perbenzoate Acetic acid
Benzene
Bromobenzene
n-Butanol
nSuty1 acetate
rerr-Butylbenzene
n-Butyl ether
Carbon tetrachloride
Chlorobenzene
4-Chlorotoluene
Cumene
Dodecane
Ethylbenzene
Heptane
Hexadecane
Methyl benzoate
Octane
Phenyl ether
Tetradecane
Trimethylbenzene
Xylene
78.0 8.4 x 1O-6
88.7 2.43 x 1O-5
98.0 1.01 x 10-4
106.0 2.36 x 1O-4
73.0 6.4 x 1O-6
87.0 3.11 x 10-5
98.0 8.75 x 1O-5
106.0 2.38 x 1O-4
100.0 3.83 x 1O-5
110.0 1.14 x 10-4
1 0 0 1.07 x 10-5
1 1 5 6.22 x 1O-5
1 3 0 3.50 x 10-4
110.0 3.50 x 10 -5
119.4 1.04 x 10-4
130.0 3.30 x 10-4
119.4 1.37 x 10-4
90.0 9.27 x 1O-5
100.0 2.70 x 1O-4
110.0 1.06 x 1O-4
119.4 2.67 x 1O-4
110.0 3.61 x 1O-5
1 1 9 4 1.1ox 10-4
119.4 1.03 x 10-4
100.0 7.80 x 1O-5
110.0 1.80 x 1O-4
8 0 8.8 x 10-7
110.0 3.83 x 10 -5
119.4 1.11 x 10-4
1 2 0 1.31 x 10-4
1 3 5 6.74 x 1O-4
1 5 0 3.12 x 1O-3
1 0 3 1.93 x 10-5
1 2 2 1.93 x 10-4
1 4 2 1.93 x 10-3
T 6)
2.23 x 1OL6
110.0 3.25 x lo-5
119.4 9.80 x 1O-5
130.0 3.06 x 1O-4
6 0 3.85 x lo-
79.6 7.21 x 10-5
85.0 1.320 x 1O-6
99.3 9.37 x 10 -6
115.0 5.81 x 1O-5
130.2 3.24 x 1O-4
1 0 0 1.4 x 10-5
1 1 5 8.05 x 1O-5
1 3 0 3.56 x 1O-4
1 1 5 6.77 x 1O-5
1 1 5 6.44 x 1O-5
119.4 1.07 x 10-4
1 1 5 7.21 x 1O-5
1 1 5 5.97 x 10-5
119.4 7.80 x 10 -5
1 1 5 7.06 x 1O-5
100.0 6.94 x 1O-6
110. 1 2.28 x 1O-5
120.2 9.00 x 10-5
130.9 2.92 x 1O-4
1 1 5 6.03 x 1O-5
T 6) 2.62 x 10 I6
119.4 1.09 x 10-4
130.0 3.42 x 1O-4
133. 1 h
113. 8 h
130. 1
145.2
144. 3
120. 5
123.4
148. 5
99.2
a
a
a
a
a
a
a
a
a
a
a
a
a
am 2
a,m 2
a
a
a
141.8 a
a
m2
m2
m2
exp[- 151.59/ZUJ
144. 3
140.2
C
C
C
ah
1 3 4 a
a
a
a
a
156.9
exp[- 152.O/RT]
141.4 a
a
3 6
3 6
3 6
3 6
3 6
3 6
3 6
3 6
5 6
5 6
126,337
126,337
126,337
5 6
5 6
5 6
5 6
5 6
5 6
5 6
5 6
5 6
5 6
5 6
5 6
5 6
354
5 6
5 6
2 2
2 2
2 2
344
344
344
344 I
5 5
5 5
5 5
8 1
272
3 4 5
3 4 5
3 4 5
345
337
3 3 7
3 3 7
270
270
5 6
270
270
5 6
270
5 3
5 3
5 3
5 3
270
376
5 6
5 6
Notes page II - 69; References page II - 70
II/56 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
1
Number of
C atoms Initiator Solvent
TW) kd (S-l) E. Wmol) Notes Refs.
r
I
11 (cornd) ferr-Butyl-N-(4-bromophenylperoxy)-
carbamate
Toluene
rerf-Butyl percarboxycyclohexane Chlorobenzene
terr-Butyl per-2-methylphenylacetate
reti-Butyl-N-(phenylperoxy)
carbamate
rert-Hexyl peroxypivalate
1,1,2-Trimethylpropyl perpivalate Cumene
Cumyl peracetate
12 rerr-Amy1 peroxybenzoate
4-Bromocumyl perpropionate Benzene
rerr-Butyl bicyclo[2.2.l]lheptane-
2-percarboxylate
rerr-Butyl endo-bicyclo[2.2.1]-
heptane percarboxylate
Cumene
Isooctane
Toluene
Chlorobenzene
Cumene
Carbon tetrachloride
Toluene
Chlorobenzene
a-Methylstyrene
Cumene
Chlorobenzene
terr-Butyl exo-bicyclo[2.2.1 l]-
heptane-2-percarboxylate
Chlorobenzene
7 0 . 8 3.32 x 1O-5
7 9 . 8 1.04 x 10-4
8 4 . 0 1.75 X 10-4
96.0 7.70 x 10-4
100.1 2.75 x 1O-4
1 1 1 . 4 9.65 x 1O-4
1 2 0 . 0 2.39 x 1O-3
7 9 . 6 1.86 x 10-5
7 9 . 6 1.42 x 1O-5
7 9 . 6 1.15 x 10-5
6 0 . 6 6.60 x 10-5
7 3 . 9 3.233 x 1O-4
5 1 . 2 3.4 x 10-6
6 7 . 7 2.31 x 1O-5
7 7 . 7 1.15 x 10-4
9 0 . 7 6.41 x 1O-4
T W
1.51 x 106
40 2.39 x 1O-6
5 0 8.83 x 1O-6
6 0 3.37 x 10-5
7 0 1.226 x 1O-4
8 0 4.166 x 1O-4
40 3.6 x 1O-6
50 1.59 x 10-5
60 5.14 x 10-5
70 1.921 x 1O-4
1 0 0 4.68 x 1O-5
1 0 0 3.43 x 10-5
9 9 1.93 x 10-5
1 1 8 1.93 x 10-4
1 3 9 1.93 x 10-3
T W)
8.38 x 10 l5
70 1.48 x 10-6
8 0 5.73 x 1o-6
90 1.81 x 1O-5
70 1.99 x 1o-6
8 0 4.93 x 10-6
90 1.55 x 10-5
8 5 1.16 x 1O-6
1 0 0 1.02 x 10-5
1 1 0 3.76 x 1O-5
1 1 0 4.6 x 1O-5
1 2 0 1.56 x 1O-4
1 3 0 4.99 x 10-4
94.0 1.75 x 10-5
1 0 1 . 9 6.20 x 1O-5
1 0 9 . 6 1.7 x 10-4
120.5 5.72 x 1O-4
9 4 . 5 9.69 x 1O-5
1 0 1 . 9 1.96 x 1O-5
1 1 1 . 9 6.53 x 1O-5
100.1 4.61 x 1O-5
1 1 1 . 4 1.96 x 1O-4
1 2 0 . 0 5.40 x 10-4
9 4 . 0 1.87 x 1O-5
1 0 1 . 9 5.30 x 10-5
1 0 9 . 6 1.10 x 10-4
120.3 4.3 x 10-4
9 4 . 5 5.27 x 1O-5
1 0 1 . 9 1.12 x 10-4
1 1 1 . 9 3.57 x 1o-4
9 4 . 5 8.86 x 10-5
1 0 1 . 9 2.28 x 10-4
112.1 8.85 x 1O-4
1 7 7 . 6 h
1 3 1 . 0 h
139.7
z (1)
z (2030)
z (4050)
m2
m2
h
exp[- 136.O/RT]
C
P
exp[- 147.02/RT]
129.7 a
a
a
121.3 a
a
1 5 5 . 2 h
1 6 0
1 5 0 . 2 h
137.2 h
1 4 9 . 0 h
1 5 4 . 0 h
130.1 h
3 6
3 6
1
3 6
3 6
181
181
181
163
163
163
165
165
3 6
3 6
3 6
3 6
40
362
362
362
362
362
362
362
362
362
2 7 1
2 7 1
344
344
344
344
213
213
213
2 1 3
213
213
1 6 0
1 6 0
2 2 3
2 2 3
2 2 3
147
147
147
1 4 7
1 4 7
1 8 2
1 8 2
181
181
181
1 4 7
1 4 7
1 4 7
147
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
,
.
Peresters and Peroxycarbonates II/57
TABLE 6. contd
Number of
C atoms Initiator Solvent T (C) kd (S-1 E, Wmol) Notes Refs.
12 (cmdd)
C u m e n e
terr-Butyl endo-bicyclo[2.2.1]-hept-
Sene-2-percarboxylate
kv?-Butyl exo-bicyclo[2.2.1]-hept-
5-ene-2-percarboxylate
C u m e n e
Ch l o r o b e n z e n e
rerr-Butyl 4-bromophenoxyperacetate Ethylbenzene
rerr-Butyl 4-chlorophenoxyperacetate Ethylbenzene
tert-Butyl 3-chlomphenylperacetate Ch l o r o b e n z e n e
rert-Butyl 4-chlorophenyl peracetate Ch l o r o b e n z e n e
ter?-Butylcycloheptyl percarboxylate
rerr-Butyl 2,4-dichlomphenoxy-
per acet at e
tert-Butyl 2,2-diethyl perbutyrate
tert-Butyl per-2-ethylhexanoate
terf-Butyl 2-methoxy-2-methyl-
pe r pr opi ona t e
ten-Butyl 4-methoxyperbenzoate Phenyl ether
reti-Butyl peroxy-2-methyl-
be nz oa t e
reti-Butyl4-methoxyperbenzoate Carbon tetrachloride
rert-Butyl 4-methylperbenzoate Phenyl ether
C u m e n e
C u m e n e
n- He xa de c a ne
2,2,4-Trimethylpentane
Ethylbenzene
C u m e n e
Be n z e n e
Ch l o r o b e n z e n e
Ch l o r o b e n z e n e
Ch l o r o b e n z e n e
96.0 1.33 x 10-4
100.1 1.90 x 10-4
111.4 6.79 x lO-4
120.0 1.64 x 10-3
84.4 2.19 x lO-5
94.7 7.29 x lO-5
100.1 1.37 x 10-4
108.6 3.6 x lO-4
113.5 6.19 x lO-4
94.5 6.05 x 1O-5
101.9 1.53 x 10-4
112.1 4.72 x 1O-4
94.5 3.11 x 10-5
101.9 7.35 x 10-5
112.0 2.48 x lO-4
94.5 5.59 x 10-5
101.9 1 25 x lO-4
112.1 5.00 x 10-4
94.5 4.48 x lO-5
101.9 1.18 x lO-4
112.1 3.97 x 10-4
70.5 2.6 x 1O-4
70.5 2.9 x 10 -4
79.6 4.05 x 10-5
90.7 1.44 x 10-4
100.5 4.38 x 1O-4
79.6 2.98 x lO-5
79.6 1.99 x 10-5
79.6 8.44 x 1O-5
90.7 2.95 x 1O-4
100.5 8.19 x 1O-4
79.6 6.54 x lO-5
79.6 4.45 x lo-
92.9 1.801 x lO-4
102.6 5.17 x 10-4
92.9 1.703 x 10-4
102.6 5.07 x 10-4
70.5 9.4 x 10-5
4 5 1.23 x lO-5
5 5 4.92 x lO-5
6 5 1.46 x 1O-4
72 1.9 x 10-5
72 1.93 x 10-5
91 1.93 x lo-4
113 1.93 x 10-3
f W)
1.54 x 104
- 14.0 2.05 x 1O-5
- 7.0 6.73 x lo-
- 1.0 1.67 x lO-4
15.0 1.28 x lO-3
100.0 1.07 x 10-5
110.1 4.17 x 10-5
120.2 1.28 x 1O-4
130.9 4.28 x lO-4
96 1.93 x 10-5
115 1.93 x 10-4
1 3 6 1.93 x 10-3
T 6)
8.56 x 10 I5
80 1.0 x 10-6
100.0 9.42 x lO-6
110.1 3.19 x 10-5
120.2 1.06 x 1O-4
129.3 h
129.3 h
131.4 h
136.4 h
138.1 h
123.0
a
a
h
117.2
z (0.98)
z W9W
h
121.5
125.7
z (0.98)
z 6@w
h
h
100.3
a
h
a
exp[- 124.9O/RT]
86.3
m2
m2
m2
m2
149.8 a
a
a
a
expr[- 145.97fRTj
151.0 a
a
a
1 4 7
181
181
181
1 4 7
1 4 7
1 4 7
1 4 7
1 4 7
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
315
315
1 7 8
1 7 8
1 7 8
207
207
1 7 8
1 7 8
1 7 8
207
207
2 5 5
255
t
255
I
255
315
1 6 0
1 6 0
1 6 0
338
344
344
344
344
2 7 5
275
275
2 7 5
5 3
5 3
5 3
5 3
344
344
344
344
354
5 3
5 3
5 3
Notes page II - 69; References page II - 70
II/58 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T ((2 kd (S-l) E, Wmol) Notes Refs.
12 (contd) rert-Butyl 4-methylperbenzoate
tert-Butyl 2-methyl-2-terr-
butylperoxyperpropionate
rert-Butyl 2-methylsulfonyl
perbenzoate
rert-Butyl 2-(methylthio)perbenzoate Chlorobenzene
rert-Butyl 4-(methylthio)perbenzoate Chlorobenzene
rerr-Butyl 4nitrophenoxyperacetate Ethylbenzene
fert-Butyl 4-nitrophenylperacetate Chlorobenzene
fert-Butyl 4-nitrophenylperacetate
Di-terr-butyl per-2-chlorosuccinoate
Phenyl ether
Benzene
Chlorobenzene
Decane
Dodecane
Hexadecane
Octane
Tetradecane
Unknown
rert-Butyl peroctoate
Decane
Di-rerf-butyl persuccinoate Styrene
terr-Butyl phenoxyperacetate Ethylbenzene
terr-Butyl phenylperacetate Chlorobenzene
Cumene
Decane
Dodecane
Hexadecane
Isooctane
1 3 0 . 9
9 . 0
19.0
30. 0
42. 0
105
120
135
150. 6
60
3 9 . 4
50.1
50. 2
6 9 . 8
120. 4
10. 5
19. 6
90. 7
100. 5
80
17. 5
77. 5
1 0 0
77. 5
77. 5
1 0 0
77. 5
105
115
125
70
85
1 0 0
70
85
1 0 0
1 0 5
1 1 5
1 2 5
70. 5
60
17. 0
88. 6
79. 6
90. 1
100. 5
19. 6
19. 6
19. 6
79. 6
85. 0
79. 6
79. 6
79. 6
79. 6
7 9 . 6 1
77. 5
77. 5
77. 5
85. 0
95. 2
3. 25 x 1O-4
6. 66 x 10-5
1.99 x 1o-4
6.94 x 1O-4
2. 43 x 1O-3
6. 68 x 10-6
5. 57 x 10-5
2. 76 x 10m4
2. 05 x 1O-3
8. 08 x 10-4
2.59 x 10-5
2. 42 x 1O-4
1.88 x 1O-4
1.96 x 1O-3
1.75 x 10-4
6. 7 x lo-
2. 5 x 1O-5
8.9 x 1o-5
2. 83 x 1O-4
3. 77 x 10-5
6. 30 x 1O-6
5.81 x 10-6
1.31 x 1o-4
5.11 x 10-6
6. 42 x 1O-6
1.60 x 1O-4
5. 56 x 1O-6
2. 74 x 1O-4
1.22 x 10-5
5.90 x 10-4
3. 83 x 1O-5
1.52 x 1O-3
1.00 x 10-4
1.4 x 10-5
8. 55 x 10-5
4. 55 x 1o-4
6.9 x 1O-6
4.39 x 10-5
2. 64 x 1O-4
1.93 x 10-5
6. 7 x 1O-5
2. 53 x 1O-4
4. 4 x 10-4
6.79 x lO-j
6. 85 x 1O-5
2. 45 x 1O-4
1.05 x 10-4
3. 53 x 10-4
1.003 x 10-3
1.07 x 10-4
9.1 x 10-5
1.02 x 10-4
9.0 x 10-4
1.945 x 1om4
6. 6 x 10-5
5. 6 x 1O-5
6. 78 x 10m5
4. 73 x 10-5
1.1 x 10-5
3. 00 x lo-s
2. 75 x 1O-5
2. 60 x 1O-5
1.08 x 1o-4
3. 527 x 1O-4
78. 8
a
m2
95.0 ah
b
C
m2
1 2 9 . 9 ah
1 2 4 . 7 h
1 0 2 . 9
143.5
1 3 0
x2
x2
x2
x2
x2
x2
a
1 3 0
1 5 4 . 8
113.1
120.1
1 1 7 . 6
116.7
a
Xl
Xl
Xl
ah
a,h
h
m2
h
z (0.98)
z (4050)
z (0.98)
z (4050)
m2
z (0.98)
z (4050)
z (0.98)
z (6090)
53
275
275
275
275
22
22
22
22
9 7
134
134
134
134
134
315
178
178
178
1 6 9
1 6 8
1 6 8
1 6 8
1 6 8
1 6 8
1 6 8
168
214
214
214
214
214
214
337
337
337
337
337
337
215
215
215
315
81
28
28
178
178
178
157
157
163
163
165
157
157
163, 207
163, 207
274
168
168
168
165
165
TABLE 6. contd
Peresters and Peroxycarbonates II/59
Number of
C a t o ms Initiator Solvent
T (C) kd (S-l) E, Wmol) Notes Refs.
12 (contd) cert-Butyl pbenylperacetate
rert-Butyl 2-propylperpenten-2-oate
(cis)
(tram)
rerr-Butyl 2,2,3,3-tetramethyl-
perpropionate
Cumene
tert-Butyl thiophenylperacetate Ethylbenzene
[err-Butyl per-o-toluate Benzene
rert-Butyl per-paratoluate Cumene
rerf-Butyl-N-(3-tolylperoxy)-
carbamate
terr-Butyl 2,4,5-trichloro-
phenoxyperacetate
4-Chlorocumyl perpropionate
Cumyl perpropionate
4-Iodocumyl perpropionate Benzene
4-Nitrocumyl perpropionate Benzene
1,1,3-Trimethylbutyl perpivalate
13 k&Amy1 per-2-ethylhexanoate
Benzyl(rerr-butylperoxy)oxalate
Octane
Paraffin oil
Tetradecane
Cumene
Cumene
Toluene
Ethylbenzene
Benzene
a-Methylstyrene
Benzene
cc-Methylstyrene
whlethylstyrene
a-Methylstyrene
Cumene
Benzene
Chlorobenzene
Benzene
7 1 . 5 3.11 x 10-5
8 5 . 0 1 . 1 5 0 x 10-4
1 1 . 3 2 . 6 6 x 1O-5
9 4 . 9 2 . 7 8 x 1O-5
100.1 5 . 4 x 10-5
100.1 4.26 x 1O-5
100.1 2.31 x 1O-5
110.1 1.72 x 1O-4
9 4 . 9 2 . 4 7 x 1O-5
100.1 4 . 7 x 10-5
100.1 3 . 1 3 x 10-5
100.1 1.42 FH-~
110.1 1.64 x 1O-4
42.2 8 . 7 6 x 1O-6
5 4 . 9 5 . 8 4 x 1O-5
1 0 . 3 3 . 3 6 x 1O-4
7 0 . 5 3 . 8 x 1O-4
9 7 1.9 x 10-5
8 4 . 0 1 . 6 6 0 x 10-6
9 9 . 3 1 . 1 3 9 x 10-5
1 1 5 . 0 6 . 7 7 x 1O-5
6 4 . 0 4 . 5 8 x 10-5
7 0 . 7 9 . 1 7 x 10-5
78.0 2 . 0 3 x 1O-4
88.5 5 . 7 8 x 1O-4
7 0 . 5 5 . 8 x lo-
IO 1.46 x 1O-6
80 5 . 6 8 x 1O-6
90 1.79 X 10-5
70 1.50 x 10-6
8 0 4.54 x 1o-6
90 1.47 x 10-5
7 0 2 . 6 0 x 1O-6
8 0 6 . 1 5 x 1O-6
9 0 1.90 x 10-5
70 6 . 3 1 x 1O-6
8 0 1.71 x 10-5
90 4 . 9 4 x 10-5
70 1.37 x 10-6
8 0 5 . 7 6 x 1O-6
90 1.79 x 10-5
7 0 1.54 x 10-6
8 0 4.96 x 1O-6
90 1 . 6 2 x 1O-5
70 1.36 x 1O-6
8 0 5 . 3 2 x 1O-6
90 1.78 x 1O-5
70 1.35 x 10-6
8 0 4 . 0 7 x 10-6
90 1.43 x 1o-5
40 4.80 x 1O-6
50 1 . 7 7 x 10-5
6 0 6 . 1 8 x 10-5
70 2.344 x 1O-4
IO 1.9 x 10-5
13 1.93 x 10-5
9 1 1.93 x 10-4
111 1.93 x 10-3
T W
1.77 x 1oL5
45 3 . 6 5 x 1O-5
5 5 1.33 x 1o-4
6 5 4 . 6 9 x 1O-4
1 3 7 . 2
1 4 3 . 9
1 1 4
1 0 2 . 9
1 2 9 . 3
118.8
1 0 1 . 7
1 0 6 . 7
133.1
125.5
133.5
124.7
h
z (0.98)
z (1100)
z (4000)
h
z (0.98)
z (1100)
z (3830)
h
a
a
h
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
exp[- 132.11/RT]
1 1 1 . 3 ch
C
1 6 8
165
168
1 7 2
1 7 2
1 7 2
1 7 2
1 7 2
1 7 2
1 7 2
1 7 2
1 7 2
112
2 6 7
267
261
3 1 5
338
3 4 5
3 4 5
345
3 6
3 6
3 6
3 6
3 1 5
2 1 3
213
2 1 3
2 1 3
2 1 3
2 1 3
2 1 3
2 1 3
2 1 3
213
2 1 3
2 1 3
2 1 3
213
2 1 3
2 1 3
2 1 3
213
2 1 3
2 1 3
2 1 3
2 1 3
2 1 3
2 1 3
362
362
362
362
3 3 8
344
344
344
344
31
31
31
Notes page II - 69; References page II - 70
II/60 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent T ((3 ka (S-l) E, Wmol) Notes Refs.
13 (conrd) [err-Butyl benzyloxyperacetate Ethylbenzene
rerr-Butyl benzylthioperacetate Ethylbenzene
rerr-Butyl bicyclo[2.2.2]octane-
I-percarboxylate
rerrButy1 endo-bicyclo[2.2.1]-2-
methylheptane-2-percarboxylate
terr-Butyl exo-bicyclo[2.2.1]-
2-methylheptane-2-percarboxylate
rert-Butyl 1,4-dimethylcyclohexane-
1-percarboxylate (cis)
(tram)
rerr-Butyl 3-methoxyphenyl-
peracetate
fert-Butyl 4- methoxyphenyl-
peracetate
ferr-Butyl 4-methylphenyl peracetate
Di-rerr-butyl perglutarate
rerr-Butylperoxy 2-ethylhexyl-
carbonate
Cumene
Cumene
Cumene
Cumene
Cumene
Chlorobenzene
Chlorobenzene
Cumene
Decane
Dodecane
Ethylbenzene
lsooctane
Octane
Pa&in oil
Tetradecane
Chlorobenzene
Cumene
Decane
Dodecane
Ethylbenzene
Hexadecane
Octane
Tetradecane
Styrene
Chlorobenzene
40.0 1.3 x 10-4
40.0 1.45 x 10-4
5 1 . 0 5 . 0 3 x 10-4
6 0 . 7 1.62 x 1O-3
40.0 2.60 x 1O-5
6 0 . 0 3.31 x 1o-4
70.0 1.14 x 10-3
6 5 7 . 5 x 10-6
7 5 2 . 8 2 x 1O-5
8 5 8 . 4 7 x 1O-5
8 0 5.1 x 10-5
90 1.67 x 1O-4
1 0 0 4.86 x 1O-4
7 5 7 . 3 5 x 10-5
80 1.39 x 10-4
8 5 2 . 6 4 x 10 -4
90 4 . 8 1 x 1O-4
9 5 8.41 x 1O-4
60 7 . 7 8 x 1O-5
6 5 1.44 x 10-4
70 2 . 7 5 x 1O-4
7 5 4.89 x 1O-4
8 0 8 . 9 3 x 1O-4
60.0 7 . 5 2 x 1O-5
70.0 2 . 6 6 x 1O-4
8 0 . 0 8 . 4 9 x 1O-4
6 0 . 0 6 . 9 3 x 1O-5
70.0 2 . 5 2 x 1O-4
8 0 . 0 7 . 7 9 x 10-4
7 9 . 6 9 . 9 x 10-5
9 0 . 7 3 . 4 5 x 10-4
100.5 1.051 x 10-3
5 6 . 0 4 . 5 7 x 10-5
6 0 . 3 9 . 9 x 10-5
7 0 . 2 3 . 0 6 x 10 -4
7 9 . 3 7 . 9 9 x 10-4
48.9 1.93 x 10-5
60 6 . 8 5 x 10-5
60 5.31 x 10-5
7 9 . 6 5.942 x 10 -4
7 7 . 5 2 . 5 2 x 1O-4
7 7 . 5 2 . 6 0 x 1O-4
7 0 . 5 1.4 x 10-3
6 0 . 5 4.72 x 1O-5
7 7 . 5 2 . 5 3 x 1O-4
6 0 . 5 4.20 x 1O-5
7 7 . 5 2 . 6 8 x 1O-4
70.4 8 . 6 7 x 1O-5
79.6 2.37 x 10 -4
9 0 . 7 7 . 9 5 x 1o-4
7 9 . 6 1 . 6 4 9 x 10-4
7 9 . 6 1 . 1 8 0 x 1O-4
7 7 . 5 9 . 0 8 x 1O-5
7 7 . 5 8 . 5 7 x lO-5
7 0 . 5 7 . 2 x 1O-4
7 7 . 5 1 . 0 3 2 x 1O-4
7 7 . 5 8 . 8 3 x 1O-5
7 7 . 5 7 . 7 5 x 10-5
1 0 5 2 . 6 5 x 1O-5
115 1.06 x 1O-4
1 2 5 3 . 0 0 x 10-4
99 1.93 x 10-5
1 1 7 1.93 x 10-4
1 3 7 1.93 x 10-3
1 0 0 . 6 ah
101.8 hmz
108.1 hm
1 1 9 . 2 h
120.1 h
1 2 6 . 8 h
1 1 6 . 7 h
1 1 5 . 2
C
h
116.3
1 2 2 . 2
C
0
C
h
1 0 5 . 4 h
k
z (0.98)
z (4050)
207
1 0 4 . 8 ah
1 1 0 . 9 h
z (0.98)
z (6080)
a
Xl
XI
315
328
3 2 8
328
328
328
328
1 6 0
1 6 0
1 6 0
223
223
223
206
206
206
206
206
206
206
206
206
206
206
206
206
206
206
206
1 7 8
1 7 8
1 7 8
1 7 8
1 7 8
1 7 8
1 7 8
249
207
207
1 6 8
1 6 8
3 1 5
1 6 9
1 6 8
1 6 9
1 6 8
1 7 8
1 7 8
1 7 8
207
207
1 6 8
1 6 8
3 1 5
1 6 8
1 6 8
1 6 8
215
2 1 5
2 1 5
344
344
344
TABLE 6. contd
Peresters and Peroxycarbonates II/61
Number of
C atoms Initiator Solvent T (C) kd (s-l) E, WmoU Notes Ref s.
13 (contd) rert-Butylperoxy 2-ethylhexyl-
carbonate
rert-Butyl 2-phenylperpropionate
tert-Butyl 2,2,4,4-tetra-
methylperbutyrate
rerr-Butylthiobenzylperacetate
terr-Butyl peroxy-3,5,5-tri-
methylhexanoate
4-Nitrobenzyl(rerr-butylperoxy)-
oxalate
14 rert-Amylperoxy 2-ethylhexyl-
carbonate
rert-Butyl di-terr-butylperacetate Cumene
fert-Butyl 2-carbomethoxyphenyl-
peracetate
terr-Butyl 2-(4-chlorophenoxy)-
2-methylperpropionate
terr-Butyl 2-(4.chlorophenyl)-
2-methylperpropionate
ferr-Butyl a-methylpercinnamate
(ci s)
(trans)
rer&Butyl 2-methyl-2-phenylper-
propionate
tert-Butyl pemeodecanoate
tert-Butyl 2-(4.nitrophenyl).
2.methylperpropionate
terr-Butyl permesitoate
tert-Butyl l-phenylcyclo- n-Dodecane
propylpercarboxylate Ethylbenzene
Chlorobenzene T W 4.07 x lOI exp[- 151.72/RT] 344
Cumene
Cumene
Ethylbenzene
Chlorobenzene
4 0 . 7 7 . 8 8 x 10m6
60.1 8 . 4 4 x lo-
80.1 8 . 1 0 x 10m4
4 0 . 8 6 . 1 5 x 1O-6
5 4 . 7 3 . 8 2 x 10m5
7 0 . 7 2 . 7 3 x lO-4
40.0 2 . 6 2 x lo-
9 5 1.93 x 10-5
1 1 4 1.93 x 10-4
135 1.93 x 1o-3
T (K) 1 . 9 4 x 1oL5
4 5 1.30 x 10-5
5 5 4.89 x 1O-5
6 5 1.89 x 10m4
9 5 1.93 x 10-5
113 1.93 x 10-4
1 3 4 1.93 x 10-3
T 6) 2 . 2 2 x 10 l6
5 4 . 7 4 . 3 8 x 1O-6
7 0 . 2 3 . 5 6 x lO-5
8 5 . 4 2 . 4 4 x lO-4
7 0 . 8 1.48 x 10-5
8 5 . 4 8 . 0 7 x 10m5
1 0 1 . 0 4 . 3 8 x 1O-4
40.0 7 . 2 x 1O-4
111 h
1 0 0 . 6 a,h
Benzene
exi[- 140.78/RT]
116.7 c,h
Chlorobenzene
exp[- 148.41/RT]
1 2 5 . 3
Cumene 1 1 6 . 9
Ethylbenzene
Acetonitrile
Benzene
Dodecane
2 7 3
2 7 3
2 7 3
2 6 7
267
267
315
344
344
344
344
31
31
31
344
344
344
344
245
2 4 5
2 4 5
2 5 7
2 5 7
257
3 1 5
5 0 . 0 2 . 5 5 x 1O-4
5 0 . 0 2 . 0 3 x lO-4
5 0 . 0 7 . 9 8 x 1O-5
6 0 . 0 2 . 6 8 x 1O-4
67.0 6.36 x 1O-4
5 0 . 0 8 . 0 0 x 10m5
6 0 . 0 2 . 5 6 x 1O-4
6 7 . 0 5 . 9 6 x lO-4
5 0 . 0 8 . 1 0 x 1O-5
6 0 . 0 2 . 6 5 x 10m4
6 7 . 0 5 . 9 5 x 1o-4
9 9 . 6 1.23 x 10m4
109.8 3 . 7 0 x 10-4
9 9 . 6 3.5 x 10-5
109.8 1.03 x lo-4
34.1 3 . 2 6 x 1O-5
3 9 . 7 5 . 6 3 x 1O-5
4 7 1.9 x 10-5
46 1.93 x 10-5
6 4 1.93 x 1o-4
8 4 1.93 x 10-3
T 6) 1.52 x lOI
5 0 . 0 7 . 5 0 x 1o-5
5 0 . 0 6 . 4 0 x 1O-5
5 0 . 0 2 . 6 3 x 1O-5
6 0 . 0 9 . 2 7 x 1O-5
6 7 . 0 2 . 0 3 x 1O-4
6 7 . 0 1.98 x 10m4
8 4 . 0 1 . 4 6 4 x 1O-5
9 9 . 3 9 . 9 4 x 10-5
1 1 5 . 0 6 . 7 x 10m5
1 1 3 . 0 8 . 6 7 x lO-5
1 2 0 . 0 2 . 4 9 x 1O-4
1 3 0 . 0 7 . 4 9 x 10-4
1 4 0 . 0 2 . 2 2 x 10-3
108.1 h
Hexadecane
Octane
Cumene 1 2 8 . 0 fh
Cumene 125.5 f,h
f
Chlorobenzene
Cumene
Benzene
Chlorobenzene
Acetonitrile
Benzene
Dodecane
exp[- 115.47/RT]
1 0 5 . 2 h
Octane
Cumene
147.5 h,t 1
tl
2 6 5
2 6 5
2 6 5
2 6 5
265
2 6 5
2 6 5
2 6 5
2 6 5
2 6 5
2 6 5
1 5 0
1 5 0
1 5 0
1 5 0
249
249
3 3 8
344
344
344
344
2 6 5
2 6 5
2 6 5
2 6 5
2 6 5
2 6 5
3 4 5
3 4 5
3 4 5
2 5 5
3 2 3
3 2 3
3 2 3
Notes page II - 69; References page II - 70
II/62 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T ((2 ka (S-l) E, Wmol) Notes Refs.
14 (contd) fert-Butyl l-phenylcyclo-
propylpercarboxylate
tert-Butyl phenyldimethylperacetate
terr-Butyl 2-phenyl-3perbutenoate
tert-Butyl4-phenyl-3-perbutenoate
tert-Butyl 2-phenyl-2-methyl-
perpropionate
tert-Butyl 4-vinylphenylperacetate
Hexadecane
Methyl benzoate
Octyl phthalate
Toluene
Cumene
Dibenzyl peroxalate Pentane
Di-tert-butyl adipate Styrene
Dicyclohexyl peroxydicarbonate Benzene
Chlorobenzene
4-Methoxybenzyl (tert-butylperoxy)-
oxalate
I-Methyl-1-phenylethyl 2,2-dimethyl-
peroxyporpionate
15 terr-Amy1 pemeodecanoate
Dibenzoyl monopercarbonate
tert-Butyl l-adamantyl-
percarboxylate
2,2,4-Trimethyl pentane
Chlorobenzene
Isooctane
Chlorohenzene
Chlorobenzene
Acetonitrile
Benzene
Benzophenone
Benzyl benzoate
Butyl phthalate
Chlorobenzene
Cumene
Dodecane
a-Methylstyrene
Mineral spirits
Benzene
Cumene
Benzene
Chlorobenzene
Benzene
Cumene
1 0 2 . 6 2.53 x 1O-5
1 1 3 . 0 8.96 x lo-*
1 2 0 . 4 2.04 x 10-4
60 9.6 x 1O-4
40.6 2.95 x 1O-5
6 0 . 6 3.059 x 10 -4
6 0 . 6 4.064 x 10-4
60 2.9 x 1O-3
60 1.15 x 10-4
5 0 . 0 3.08 x 1O-4
5 0 . 0 2.18 x 1O-4
60 7.73 x 1o-4
60 7.92 x 1O-4
60 6.5 x 1O-4
60 7.00 x 10-4
60 5.25 x 1O-4
5 0 . 0 8.77 x lo-
6 0 . 0 3.00 x 10-4
6 7 . 0 7.13 x 10-4
60 2.88 x 1O-4
60 3.53 x 1o-4
60 7.55 x 10-4
60 5.70 x 10-4
60 5.66 x 1O-4
7 0 . 9 5.54 x 10-5
8 5 . 4 3.00 x 10-4
100.3 1.48 x 1O-3
2 5 6.7 x 1O-5
1 0 . 5 3.50 x 10-5
1 1 5 1.23 x 1O-4
1 2 5 3.05 x 10-4
5 0 5.4 x 10-5
44 1.93 x 10-5
60 1.93 x 10-4
7 7 1.93 x 10-3
T W
3.3 x 106
50 5.9 x 10-5
4 5 2.78 x 1O-5
50 5.58 x 1O-4
60 2.07 x 1O-4
4 5 6.69 x 1O-5
5 5 2.48 x 1O-4
6 5 8.27 x 1O-4
40 6.91 x 1O-6
50 2.80 x 1O-5
60 1.032 x 10 -4
70 3.57 x 1o-4
4 5 1.9 x 1o-5
4 3 1.93 x 10-5
61 1.93 x 10-4
81 1.93 x 10-3
T W)
1.47 x 1o14
60.00 8.05 x 1O-5
4 5 5.15 x 10-5
5 5 2.05 x 1O-5
6 . 5 7.40 x 10-5
6 4 . 6 6.87 x 1O-5
74.6 2.44 x 10-4
8 4 . 6 7.78 x 1O-4
60 5.4 x 10-5
70 2.12 x 10-4
8 0 7.20 x 1O-4
1 4 1 . 2 h
1 0 9 . 2
9 6 . 2
9 8 . 3
ch
t9
t9
mz
c,h
c,h,g
109.3 h
t12
116.5
0
k
1 5 1 . 0
Xl
X l
Xl
C
exp[- 129.O/RT]
1 1 7
1 0 9 . 6
a
a
a
ch
C
C
a
exp[- 114.38/RT]
116.5
115.5
h
h
116.7 h
1 2 4 . 7 h
255
255
255
81
1 6 5
1 6 5
1 6 5
81
81
265
265
334
334
334
334
334
2 6 5
2 6 5
2 6 5
334
334
334
334
334
254
254
254
2 0 3
215
215
215
2 0 1
344
344
344
344
2 0 1
337
3 3 7
337
31
3 1
31
368
368
3 6 8
3 6 8
338
344
344
3 4 4
344
280
1 6 0
1 6 0
1 6 0
1 5 9
1 5 9
1 5 9
223
223
223
TABLE 6. contd
Peresters and Peroxycarbonates II/63
Number of
C atoms Initiator Solvent
T (3 kd (S-l) E, Wmol) Notes Refs.
15 (contd) fen-Butyl 4-(carboethoxy)-
phenoxyperacetate
rert-Butyl u$-dimethyl-
percinnamate @is)
(trans)
rerr-Butyl I-pemaphthoate
rerr-Butyl 2,2-dimethyl-
3-phenylthio perpropionate
teti-Butyl 2-(4-methoxyphenyl)-
2-methylperpropionate
terf-Butyl I-phenylcyclo-n-Dodecane
butylpercarboxylate
terr-Butyl 4-tert-butylperbenzoate Chlorobenzene
Di-rert-butyl perpimelate Styrene
ter&Butyl 2-(4-tolyl)-
2-methylperpropionate
rert-Butyl triisopropylperacetate
l,l-Dimethyl-2-phenylethyl-
perpivalate
16
I-Phenylethyl4-methoxyperacetate Benzene
I-Phenylethyl 3-nitroperbenzoate Benzene
1-Phenylethyl 4-nitroperbenzoate Benzene
1-Phenylethyl perbenzoate Benzene
Dibenzyl peroxydicarhonate Benzene
Di-rert-butyl 2-iodoperisophthalate Chlorobenzene
Di-rerr-hutyl perphthalate Benzene
Ethylbenzene 7 0 . 5 1.6 x 1O-4
Chlorobenzene
Cyclohexane
Acetonitrile
Benzene
Dodecane
Octane
5 2 . 3
Ethylbenzene
n-Hexadecane
2,2,4-trimethyl pentane
Acetonitrile
Benzene
Dodecane
Octane
Cumene
Cumene
Di-n-hutyl phthalate
Chlorobenzene
95.0
1 0 3 . 2
110.1
85.1
95.0
1 0 3 . 7
1 1 0 . 0
1 1 0 . 0
110.1
5 5
6 5
75
50
50
40
50
5 7
50
7.89 x 1O-5
60.0
5 2 . 3
5 2 . 3
6 1 . 6
100.1
1 1 9 . 8
1 3 5 . 9
1 0 5
1 1 5
1 2 5
5 0 . 0
5 0 . 0
50.0
60.0
67.0
6 0 . 0
2 4 . 8
41.6
5 5 . 2
40
50
60
70
9 9 . 7
1 0 0
1 0 0
1 0 0
40
50
60
68.4
8 5 . 4
1 0 1 . 6
1 0 0
1 1 5
1 3 0
1 0 0
115
1 3 0
1 0 7
1 2 5
1 4 6
T 6)
1 . 0 2 x 10-4
2 . 2 9 x 10-4
5 . 1 5 x 10-4
3 . 9 x 10-5
1.17 x 10-4
2 . 8 4 x 1O-4
6 . 0 5 x 1O-4
7.90 x 10-4
8 . 6 9 x 1O-5
1.63 x 1O-5
1.61 x 1O-5
1 . 9 8 x 1O-4
1 . 6 7 5 x 1O-3
9.96 x 1O-4
1.49 x 10-4
4 . 2 1 x 1O-4
1 . 0 2 8 x 1O-3
4 . 1 8 x 1O-4
3 . 6 2 x 1O-4
8.80 x 10 -5
7.69 x 1O-s
2 . 4 6 x 1O-4
3.81 x 1O-5
4.50 x 1o-4
2.38 x 1O-3
4 . 4 5 x 10-5
1.05 x 10-4
5 . 0 6 x 1O-4
6.00 x 1O-4
3 . 8 5 x lO-4
1 . 9 0 x 10-4
5 . 5 8 x 1O-4
1 . 3 2 0 x 1O-3
5 . 4 3 x 10-4
5.32 x 1O-6
6 . 8 4 x 1O-5
3 . 7 8 x 1O-4
4.56 x 1O-6
1 . 8 3 3 x 1O-5
6.1 x lo-
2.51 x 1O-4
3.50 x 10-4
5 . 9 7 x 10-4
4.10 x 10-4
4 . 0 3 x 10-4
2 . 0 x 10-5
6 . 2 5 x 1O-5
2 . 6 7 x 1O-4
8 . 2 4 x 1O-5
4 . 4 5 x 10-4
1.68 x 10 -3
1.1 x 10-5
7.81 x 1O-5
4 . 8 1 x 1O-4
1.08 x 1O-5
7 . 8 x 1O-5
4 . 8 x 1O-4
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
9.39 x 106
1 1 8 . 8
1 2 2 . 6
2 116.9
a
ah
a
a
ah
a
a
a
hv.5
hrt6
t6
93.0 h
1 1 0 . 6
2 5 5
tl
h
1 5 0 . 6
Xl
Xl
XI
1 0 0 . 6 h
1 1 1 . 5 h
134.1
1 3 6 . 2
1 4 6 . 2
1 2 3 . 6
1 1 7
93.9
1 5 9
1 5 5 . 0
exp[- 157.85/RT]
3 1 5
151
151
151
151
151
151
151
151
1 5 4
320
320
320
265
265
265
265
265
265
3 2 3
255
255
2 5 5
1 3 4
1 3 4
1 3 4
2 1 5
2 1 5
2 1 5
2 6 5
265
2 6 5
2 6 5
265
/
265
I
267
2 6 7
267
362
362
362
362
259
259
259
259
3 3 7
3 3 7
337
248
248
248
3 3 7
3 3 7
337
269
269
269
344
344
344
344
Notes page II - 69; References page II - 70
II/64 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T (C) kd (S-l) E. Wmol) Notes Ref s.
16 (contd) Di-[err-butyl perphthalate Cumene
rert-Butyl l-phenyl-l-cyclo-
pentane percarboxylate
tert-Butyl 2,3-dimethyl-
2-phenylperbutyrate
Cumyl N-phenylperoxy carbamate
Dibenzyl peroxydicarbonate
Di-rerf-butyl perphthalate
Di-tert-butyl persuberate
ferr-Butyl l-phenylcyclopentyl-
percarboxylate
1,1,3,3-Tetramethylbutyl-
per-2-ethylhexanoate
Styrene
2,2,4-Trimethyl-
pentane
Benzene
2-Phenylazo-2-propylperbenzoate Chlorobenzene
17
1-Phenylethyl 4-dimethyl-
aminoperbenzoate
Di-terr-butylperhomoterephthalate
tert-Butyl l-phenylcyclo-
hexanepercarboxylate
terr-Butyl 2-(phenylthio)perbenzoate
terf-Butyl dibenzothiophene-4-per-
carboxylate
Di-tert-butyl perazelate Styrene
Ethylbenzene
Ethylbenzene
Xylene
Toluene
Benzene
p-Chlorotoluene
Chloroform-d,
Benzene
Cumene
Toluene
Ethylbenzene
2,2,4-Trimethyl-
pentane
Acetone
Acetonitrile
tert-Butanol
Chlorobenzene
Cyclohexane
DMSO
Ethanol
lsopropanol
Methanol
Chlorobenzene
Chlorobenzene
9 9 . 9 8 . 3 4 x lo-6
1 1 5 . 0 4 . 6 8 x 1O-5
130.1 2 . 6 0 x 1O-4
6 0 . 0 1.52 x 1O-3
140.8 h
t1
269
269
269
3 2 3
5 0 4.30 x 10-5 324
T W 1.26 x lOI
50 2 . 9 2 x 1O-5
1 0 0 1.08 x 10-5
115 7 . 8 3 x 10-5
1 3 0 4.80 x 10-4
1 1 5 7.86 x 10 -5
125 2.81 x 10-4
4 3 . 5 1 . 1 8 4 x 10-4
5 2 . 3 3.51 x 10-4
6 0 1.9 x 10-5
7 0 5.30 x lo-5
8 0 1.38 x 10 -4
10 4 . 5 x 10-4
3 5 1.9 x 10-3
1 0 6 . 4 x 1O-4
10 5.1 x 10-4
1 0 0 2 . 1 6 x 1O-3
exp[- 117.6/RT]
1 5 7 . 7
1 5 9 : o
103.5
a
a
a
a
Xl
Xl
h
101 a
a
a
111.5 h
40
90
1 2 6
1 2 6
1 2 6
2 1 5
2 1 5
2 5 5
2 5 5
337
3 3 7
337
260
260
260
260
259
7 9 . 6 2 . 3 8 x 10m5
1 0 . 6 9 . 4 4 x lo-6
8 0 . 3 2 . 8 0 x 1O-5
100.5 3 . 0 9 x lo-4
6 0 . 0 1.90 x 10-3
4 3 . 5 1.27 x 1O-4
5 2 . 3 3.91 x 10-4
6 1 . 6 1 . 2 1 8 x 1o-3
2 5 1.89 x 1O-5
40 1.22 x 10-4
2 5 1.01 x 10-4
40 5 . 4 4 x 10-4
2 5 5 . 2 6 x 1O-5
40 3 . 2 4 x lO-4
3 9 . 3 4 . 9 8 x 10-5
5 3 . 8 5 . 2 3 x 1O-4
5 3 . 8 4 . 5 8 x 10-4
70.0 2 . 6 2 x 1O-3
2 5 1.76 x 1O-5
40 1.03 x 10-4
2 5 9 . 8 x 10-7
40 6 . 9 x 1O-6
2 5 1.11 x 10-4
40 6 . 0 2 x 1O-4
2 5 2.31 x 1O-4
40 1.65 x 1O-3
2 5 1.33 x 10-4
40 7 . 2 5 x 1O-4
2 5 8.21 x 10-4
40 4 . 7 5 x 10-3
105 2 . 7 9 x lo-
1 1 9 . 4 1.29 x 1O-4
135.1 6 . 0 7 x 1O-4
105 5 . 1 3 x 10-5
115 1.20 x 1o-4
1 2 5 5 . 1 0 x 10-4
9 8 1.93 x 10-5
1 1 6 1.93 x 10-4
137 1.93 x 10-3
T 6)
1.35 x 106
1 2 2 . 3 h
1 0 7 . 7 h
m2
m2
m2
m2
m2
m2
b
m2
1 2 8 . 0
m2
m2
m2
m2
m2
m2
m2
m2
m2
m2
m2
m2
h
1 5 4 . 8
exp[- 147.95/RT]
272
212
272
212
3 2 3
2 5 5
255
2 5 5
2 2
22
2 2
2 2
2 2
2 2
1 3 4
1 3 4
1 3 4
1 3 4
2 2
22
2 2
2 2
2 2
2 2
2 2
22
2 2
2 2
2 2
2 2
2 2
2 2
2 2
2 1 5
2 1 5
2 1 5
344
344
344
344
TABLE 6. contd
Peresters and Peroxycarbonates II/65
Number of
C atoms Initiator Solvent
T ((2 kd (S-l) E, Wmol) Notes Refs.
Benzene
Chlorobenzene
Chlorobenzene
Cumene
2 5 1.84 x 1O-4
1 1 0 2 . 8 8 x 1O-5
60 4.44 x 10-4
4 0 . 3 2 . 7 5 x lo-
49.6 9 . 8 1 x 1O-5
5 9 . 9 3 . 1 0 x 10-4
7 0 . 4 1.04 x 10-3
7 7 . 5 1.66 x 1o-3
7 7 . 5 1 . 6 8 8 x 10-3
7 7 . 5 1 . 6 3 2 x 1O-3
7 7 . 5 1.651 x 1O-3
7 7 . 5 1 . 6 2 7 x 1O-3
40 1.93 x 10-5
5 7 1.93 x 10 -4
76 1.93 x 10-3
T W
3 . 9 7 x 104
P2
1 0 1 . 7 ah
1 0 4 . 6 h
Decane
Dodecane
Hexadecane
Octane
tetradecane
Chlorobenzene
exp[- 115.79/RT]
219
219
81
1 3 6
1 3 6
1 3 6
1 3 6
1 6 8
1 6 8
1 6 8
1 6 8
1 6 8
344
344
344
344
Ethylbenzene 9 5 2.68 x 1O-6
1 0 5 9.10 x 10-6
115 2.97 x lo--
147.5 306
306
306
Ethylbenzene 60.0 2.75 x 1O-3 3 2 3
Cumene
Chlorobenzene
Chlorohenzene
70.9
8 5 . 4
100.3
9 8 . 7
120.1
1 2 0
1 3 5
105
1 1 5
1 2 5
3 . 6 9 x 1O-5
2 . 0 8 x 1O-4
8 . 8 3 x 1O-4
4.64 x lo-s
4.20 x 1O-4
1 . 8 9 x 1O-4
1.15 x 10-3
5 . 1 0 x 10-5
1 . 2 0 x 10-4
5.00 x 1o-4
1.9 x 10-5
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
1.83 x lOI5
5 . 3 x 10-6
3.31 x 10-5
2 . 3 2 x 1O-4
1.3 x 10-5
6.14 x 1O-5
2.31 x 1O-4
6.1 x 1O-6
3 . 8 5 x 1O-5
1 . 7 0 x 1o-4
1 1 2 . 7 U
k
k
1 3 4 . 7 h
156.5 hm
Styrene
m2
1 5 4 . 8
Xl
Xl
Xl
254
254
254
1 5 4
1 5 4
2 2
2 2
2 1 5
2 1 5
2 1 5
Benzene
Chlorohenzene
40
47
64
8 3
T 6)
30
4 5
60
40
50
60
60
7 3 . 5
8 5
a
Decane
exp[- 122.45/RTJ
1 0 5 a
a
Mineral spirits
a
1 2 6 a
Di-n-heptyl persuccinate Styrene 1 3 1 . 0
a
a
XI
Xl
X l
338
344
344
344
344
3 3 7
3 3 7
3 3 7
337
337
337
215
2 1 5
2 1 5
Chlorobenzene
Cumene
103.3 ah
112.1 h
Cumene 1 1 7 . 2 h
Chlorobenzene
6 0 1.9 x 10-3
60.0 2 . 8 x 1O-5
70.0 5 . 5 x 10-5
8 0 . 0 1.68 x 10-4
6 0 . 0 1.6 x 1O-5
7 0 . 0 3 . 9 x 10 -5
8 0 . 0 1.20 x 10-4
34.1 7 . 7 6 x 1O-5
81
204
204
204
204
204
204
249
Benzene 1 0 0 3 . 1 8 x 1O-5
Carbon tetrachloride 1 0 0 3 . 6 0 x 10-5
Benzene 2 5 1.45 x 10-4
Chlorobenzene 1 1 0 3 . 0 3 x 10-5
c,e
c,e
P2
246
246
279
279
18 terr-Butyl 4-benzoylperbenzoate
rert-Butyl diphenylperacetate
2,4,4-Trimethylp-entyl-
cL,o-Di-O,O-tert-butyl-(bis-
persuccinyl)ethylene glycol
rerr-Butyl l-phenyl-l-cyclo-
heptanepercarboxylate
Di-rert-butyl p-phenylene-
reti-Butyl 2-(phenylthiomethyl)-
perbenzoate
rert-Butyl thioxanthone-4-per-
carboxylate
Di-w-r-butyl persebacate
Di-(2-ethylhexyl)peroxy-
dicarbonate
19 rert-Butyl diphenylmethyl-
peracetate
rert-Butyl diphenylperglycidate
(cis)
(Wmw)
ferr-Butyl 2,2-diphenylperpropionate
rert-Butyl 4-hydroxy-3,5-di-
(rert-butyl)perbenzoate
rert-Butyl 4-(4-methylbenzoyl)-
perbenzoate
Notes page II - 69; References page II - 70
II/66 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T (C) ka (S-l) E, &I/mol) Notes Refs.
19 (cent d) rerf-Butyl a-phenylpercinnamate
(cis)
(tram)
Cumyl pemeodecanoate
20 Di-n-heptyl peradipate Styrene
terf-Butyl 2-carbobenzoxy-
phenylperacetate
fert-Butyl 2-methyl-2-phenyl-
perhexanoate
a,w-Di-O,O-rert-butyI-(bis-
persuccinyl)diethylene glycol
21 rert-Butyl S-(phenylthio)-
1 -pemaphthoate
2 2
[err-Butyl 4-(2,4,6-trimethyl-
benzoyl)perbenzoate
terr-Butyl 2,2-diphenyl-
3,3-dimethylperbutanoate
Di-rert-butyl 2-thiophenyl-
perisophthalate
2,5-Dimethylhexyl
2,5-di(peroxybenzoate)
Di-(4-rerf-butylcyclohexyl)-
peroxydicarbonate
2 3 terr-Butyl 2,6-di(phenylthio)-
perbenzoate
fert-Butylperoxy stearyl carbonate
terr-Butyl 2,4,6-tri-ferr-butyl-
perbenzoate
2 4 rerr-Butyl triphenylperacetate
Di-rert-butyl 2,3-diphenyl-
persuccinate
Cumene
Di-n-heptyl persebacate Styrene
2,5-Dimethyl-2,5-bis(2-ethyl.
hexanoylperoxy)hexane
Cumene
Cumene
Benzene
Chlorobenzene
Cumene
Ethylbenzene
Ethylbenzene
Chlorobenzene
Benzene
Chlorobenzene
Toluene (?)
Chlorobenzene
Benzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Cumene
Chlorobenzene
Cumene
Benzene
Chlorobenzene
9 9 . 6 1.52 x 10-4
109.8 4 . 4 1 x 10-4
9 9 . 6 8 . 2 x 1O-5
1 0 9 . 8 2 . 5 9 x 10 -4
3 9 1.9 x 10-5
3 9 1.93 x 10-5
56 1.93 x 10-4
7 5 1.93 x 10-3
T 09
3 . 1 2 x lOI4
60 1.02 x 10-5
7 3 . 5 6 . 5 7 x 10-5
8 5 2 . 9 8 x 1O-4
7 1 . 0 8 . 8 4 x 1O-6
8 5 . 4 5.46 x 10 -5
1 0 2 . 4 4 . 2 3 x 1O-4
5 0 5.01 x 10-5
9 5 2 . 3 4 x 1O-6
105 8 . 8 8 x 10-6
115 3 . 2 7 x 1O-5
5 0 3 . 8 3 x 1O-5
70 3 . 4 4 x 1o-4
70 3 . 1 2 x 1O-4
8 0 9 . 8 2 x 1O-4
2 5 1 . 3 4 x 10-4
1 1 0 1.80 x 1O-5
30 2 . 7 6 x 1O-5
3 9 . 7 1.15 x 10-4
50 5 . 4 5 x 10-4
12.1 1.68 x 10-4
2 5 . 0 6 . 4 5 x 1O-4
40.0 3 . 0 9 x 10-3
1 0 0 1.87 x 1O-5
1 1 5 1.25 x 1O-4
1 3 0 7.14 x 1o-4
48 1.93 x 10-5
64 1.93 x 1o-4
8 2 1.93 x 10-3
T (K) 7 . 4 4 x 105
4 0 . 1 7 . 0 7 x 10 -5
9 8 1.93 x 10-5
1 1 7 1.93 x 10-4
1 3 7 1.93 x 10-3
T 6)
3 . 9 4 x 106
7 0 . 4 5 . 8 4 x 1O-6
8 4 . 0 3 . 5 4 x 10-5
9 9 . 3 2 . 6 7 x 1O-4
1 1 5 . 0 1 . 6 5 6 x 10 -3
3 4 . 9 7 . 8 x 1O-4
2 5 . 7 1.7 x 10-4
3 4 . 9 5 . 8 x 1O-4
45.5 2 . 3 x 1O-3
7 0 . 1 9 . 8 3 x 10 -5
7 9 . 9 3 . 2 9 x 1O-4
9 0 . 0 1 . 2 0 x 10-3
60 1.17 x 10-5
7 3 . 5 7 . 1 3 x 10-5
8 5 3 . 0 3 x 10-5
6 0 6 . 7 x 1O-6
70 2 . 9 2 x 1O-5
8 0 1.14 x 10-4
6 8 1.93 x 10-5
8 6 1.93 x 10-4
1 3 6 . 8 h
1 3 3 . 9 h
a
exp[- 114.59/RlJ
133.1
129.5
Xl
Xl
Xl
h
1 5 5 . 0 h
9 9 . 2 km2
m2
1 1 4 . 8
7 3 . 7
m2
P2
j2
j2
k
h
1 5 4 . 0 a
a
a
exp[- 126.39/RT]
exp[- 151.59/RT]
1 0 0 . 8 h
125.5
1 3 1 . 0
1 4 2
c,h
C
C
Xl
Xl
Xl
a
a
a
1 5 0
1 5 0
1 5 0
1 5 0
3 3 8
344
344
344
344
2 1 5
215
2 1 5
257
257
257
324
306
306
306
1 5 4
1 5 4
1 5 4
1 5 4
279
279
250
250
250
248
248
248
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
344
344
344
344
1 5 4
344
344
344
344
3 4 5
345
3 4 5
3 4 5
1 5 3
153
153
1 5 3
1 9 6
1 9 6
1 9 6
2 1 5
2 1 5
2 1 5
3 3 7
3 3 7
3 3 7
344
344
TABLE 6. conrd
Peresters and Peroxycarbonates II/67
Number of
C atoms Initiator Solvent
T ((2 kd (S-l) E, Wmol) Notes Refs.
24 (cow d )
25
26
36
46
2,5-Dimethyl-2,5-bis(2-ethyl-
hexanoylperoxy)hexane
ten-Butyl 2-(2,2-diphenylvinyl)-
perbenzoate
tert-Butyl 2-percarboxybenzal-
fluorene
cc,w-Di-O,O-caprylyl-(bis
succinyl)ethylene glycol
a,w-Di-O,O-caprylyl-(bis-
persuccinyl)triethylene glycol
Dimyristyl peroxydicarbonate
Dicetyl peroxydicarbonate .
cc,w-Di-O,O-heptanoyl-(bis-
perphthaloyl)triethylene glycol
u,w-Di-O,O-caprylyl-(bis-
persuccinyl)nonaethylene glycol
cc,w-Di-O,O-heptanoyl-(bis-
perphthaloyl)tridecaethylene
glycol
a,w-Di-O,O-caprylyl-(bis-
persuccinyl)tridecaethylene glycol
Chlorobenzene
Chlorobenzene
Cyclohexane
Methanol
Chlorobenzene
Methanol
Ethylbenzene
Ethylbenzene
Chlorobenzene
Chlorobenzene
Ethylbenzene
Ethylbenzene
Ethylbenzene
Ethylbenzene
1 0 6
T 6)
90. 0
90. 3
1 0 0 . 0
105.5
119.3
90. 0
90. 4
90
90
65
75
85
95
6. 5
15
85
95
48
65
84
T (K)
48
65
84
T 6)
65
15
85
95
65
15
85
95
15
85
9. 5
65
15
85
1.93 x 10-3
2 . 1 9 x lOI5
1.32 x 10m4
7. 45 x 10-5
3. 27 x lO-4
4. 64 x lO-4
1.54 x 10-3
3. 5 x 10-5
2. 3 x lO-3
3. 75 x 10-4
2. 41 x lO-3
1.48 x 1O-5
4.10 x 10-5
2 . 1 9 x lO-4
6. 92 x lO-4
2. 74 x lo-
8. 47 x lO-5
2. 95 x 1O-4
8. 92 x lO-4
1.93 x lo-s
1.93 x 10-4
1.93 x 10-3
2. 82 x lOI
1.93 x lo-s
1.93 x lo-4
1.93 x 10-3
3. 02 x lOI5
5. 02 x lO-5
1 . 4 2 0 x lO-4
5 . 1 9 x 10-4
1 . 4 1 0 x 10-3
1.66 x 10-5
6. 57 x lO-5
1. 18 x lO-4
9. 72 x 1O-4
1. 130 x 10-4
3. 50 x 10-4
8. 80 x 10-4
1.28 x 1O-5
4. 46 x lO-5
1.91 x 10-4
exp[- 130.88/RT]
120. 7
1 1 6 . 9
exp[- 124.lO/RT]
exp[- 124.3O/RT]
1 2 4 . 4
1 1 6 . 9
122.3
128. 2
344
344
175
t9 175
175
t9 175
t9 175
115
t9 115
115
175
h 306
306
306
306
306
306
306
306
344
344
344
344
344
344
344
344
306
306
306
306
306
306
306
306
306
306
306
306
306
306
TABLE 7. MISCELLANEOUS INITIATORS
Initiator Sol vent
T CC) ka (s-l) E, Wmol) Notes Refs.
Acetyl cyclohexyl sulfonyl peroxide
N-(l-Cyanocyclohexyl)pentamethylene keteneimine
Dibenzyl hyponitrite
Benzene
Chlorobenzene
Parafhn
30
40
45
80. 0
89. 2
100.1
6 1 . 5
68. 5
15. 5
80. 5
132
1.4 x 10-5
9. 42 x lO-5
2.10 x 10-4
3. 25 x 1O-6
1 . 0 0 1 x lo-s
4. 025 x lO-5
6. 5 x lO-4
3. 7 x 10-3
8. 3 x lO-3
1.45 x 10-2
8. 7 x lo-
1 4 7 a 337
a 337
a 337
119
179
179
240
240
240
240
240
Notes page II - 69; References page II - 70
II/68 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 7. contd
Initiator Sol vent
T (Cl kd (S-l) E, Wmol) Notes Refs.
Di-rerr-butyl hyponitrite
Peroxybenzoylnitrate
2,3-Dimethyl-2,3-diphenylbutane
3,4-Dimethyl-3,4-diphenylhexane
l,CDimethyl-1,4-diphenyl-tetrazene-2
Potassium persulfate
I-Pentanesulfonylazide
1,4-Butanedisulfonyl azide
1,6-Hexanedisulfonyl azide
1,9-Nonanedisulfonyl azide
1 ,lO-Decanedisulfonyl azide
1,4-Dimethylcyclohexane-cr,a-disulfonyl azide
rerr-Butanol
n-Butyl ether
Ethanol (95%)
Isooctane
Nujol
Vapor
Vapor + NO
Vapor + NO
Chlorobenzene
Chlorobenzene
Benzophenone
Cumene
Paraffin
Silicone oil
0. 1 M NaOH
Water (pH 3)
Water
Diphenyl ether
Diphenyl ether
Diphenyl ether
Diphenyl ether
Diphenyl ether
Dipheny 1 ether
6 5 4 . 6 8 x 1O-4
6 5 4.50 x 1o-4
6 5 3 . 9 3 x 10-4
45 2 . 7 2 x 1O-5
5 5 1.07 x 10-4
6 5 4.00 x 10-4
15 1 . 3 3 0 x 10-3
6 5 5 . 1 7 x 1o-4
7 . 6 2 . 7 9 x 1O-6
19.9 1.05 x 10-5
3 0 . 4 2 . 0 2 x lo-s
4 0 . 6 3 . 6 4 x 10-5
5 0 . 1 1.21 x 10-4
6 0 . 5 2 . 7 4 x 1O-4
T (K)
1 x 10
18.1 8 . 1 8 x 1O-5
3 0 . 4 3 . 6 2 x 1O-4
40.6 1.42 x 1O-3
T K) 1.6 x 10 l5
3 0 . 4 1.34 x 10-5
5 0 . 2 7 . 2 2 x 1O-5
6 8 . 5 3.41 x 10-4
T (K) 6 . 3 x 1O-8
237 1.93 x 10-5
259 1.93 x 10-4
284 1.93 x 10-3
T W) 7 . 3 4 x 108
2 0 1 1.93 x lo-s
226 1.93 x 10-4
254 1.93 x 10-3
T W
1.45 x 105
121 3 . 3 x 10-4
1 4 9 3 . 4 5 x 10-3
1 2 0 2 . 3 x 1O-4
1 3 0 6 . 5 x 10 -4
1 4 0 1.67 x 1O-3
1 6 4 . 2 2 . 6 x lo-*
174.3 5 . 6 x lo-*
1 8 6 1.43 x lo-
1 9 4 2 . 5 x lo-
1 2 6 3 . 7 x 10-4
1 3 9 1.92 x 1O-3
50 9 . 5 x 10 -7
60 3 . 1 6 x 1O-6
70 2 . 3 3 x 1O-5
8 0 9.16 x 1O-5
90 3.5 x 1o-4
50 1.66 x 10-6
8 0 6 . 8 9 x 1O-5
80 5 . 7 8 x 10-5
40 1.65 x lo-*
50 4 . 0 2 x lo-*
60 1.08 x 10-1
50 3 . 7 8 x 10 -3
60 2 . 1 8 x 10-2
70 5.01 x 10-2
50 1.1 x 10-6
1 6 6 4.46 x 1O-4
163 5 . 0 2 x 1O-4
1 6 3 5 . 0 2 x 1O-4
1 5 0 8 . 8 4 x 1O-5
1 6 0 2 . 2 5 x 1O-4
1 7 0 4 . 4 5 x 10-4
1 6 3 4 . 4 5 x 10-4
1 6 3 4 . 8 2 x 1O-4
1 1 6 . 9
69.1
exp[- 69.1/RT]
108.5
exp[- 108.5/RT]
79.2
exp[- 79.2/RlJ
exp[- 230.19/RTJ
exp[- 180.32/R7'J
1 4 0 . 2
8 3 . 4
121.5
3 1 7
3 1 7
3 1 7
h 3 1 7
3 1 7
3 1 7
3 1 7
3 1 7
h 261
261
2 6 1
261
261
2 6 1
261
h 2 6 1
2 6 1
2 6 1
2 6 1
h 2 6 1
2 6 1
2 6 1
2 6 1
344
344
344
344
344
344
344
344
240
240
240
240
240
240
240
240
240
240
240
a 242
a 242
a 242
a 242
a 242
a 242
a,vll 1 1 5
a,vll 1 1 5
d3rvn 262
d3rvz 262
ds,v22 262
d3rv23 262
d3,Vz 262
d3,vz3 262
262
1 6 6
1 6 6
1 6 6
1 6 6
1 6 6
1 6 6
1 6 6
1 6 6
m-Xylene-a,a-disulfonyl azide Diphenyl ether
p-Xylene-a,cc-disulfonyl tide Diphenyl ether
Benzenesulfonyl azide Naphthalene
pBromobenzenesulfony1 azide
pChlorobenzenesulfony1 azide
p-Methoxybenzenesulfonylazide
p-Nitrobenzenesulfonyl azide
p-Toluenesulfonyl azide
p-Toluenesulfonyl-p-tolylsulfone
Naphthalene
Naphthalene
Naphthalene
Naphthalene
1,4-Dichlorobutane
Dimethyl terephthalate
Diphenyl ether
Hexanoic acid
Naphthalene
Nitrobenzene
1-Octanol *
Tetradecane
Acetonitrile
Dioxane
1 6 3 6 . 0 9 x 1O-4
1 6 3 5 . 7 8 x 10-4
1 1 0 3 . 6 x 1O-6
1 2 0 1.07 x 1o-5
125 1.97 x 10-5
1 3 0 3.41 x 1o-5
1 7 5 6 . 0 8 x 1o-5
1 2 0 1.36 x 1O-5
1 2 0 1.15 x 10-5
1 2 0 1.31 x 1o-5
1 2 0 1.60 x 1O-5
1 4 . 5 1.70 x 10-4
155 3 . 2 3 x 1O-4
1 3 0 3 . 3 0 x 10-5
1 4 5 1.44 x 1o-4
1 5 5 3 . 4 3 x 1o-4
1 5 5 2 . 9 7 x 1O-4
1 2 0 1.12 x 1o-5
155 3 . 9 7 x 1o-4
1 5 5 3 . 6 3 x 1O-4
1 5 5 3.80 x 1o-4
2 9 . 3 3 . 9 x 1o-5
39.1 1.45 x 10-4
4 9 . 3 5 . 4 x 10-4
2 9 . 3 2.1 x 1o-5
3 9 . 5 1.01 x 1o-4
4 9 . 3 3 . 9 x 1o-4
Not es II/69
152.3
103.8
1 1 5 . 5
1 6 6
1 6 6
2 3 5
2 3 5
2 3 5
2 3 5
235
2 3 5
2 3 5
2 3 5
2 3 5
1 6 6
1 6 6
1 6 6
1 6 6
1 6 6
1 6 6
2 3 5
1 6 6
1 6 6
1 6 6
h 1 4 4
1 4 4
1 4 4
h 1 4 4
1 4 4
1 4 4
C. NOTES
:
bz
C
c2
c3
c4
d
dz
d3
;
kd converted to s-l from authors units
kd values for several concentrations averaged
analyzed from nonisothermal conditions
kd increases with increasing initiator concentration
rate non-linear
hydroperoxide concentration 7.83 x lop3 mol/l
hydroperoxide concentration 2.50 x 10e3 mol/l
kd decreases with increasing initiator concentration
after 1st half life; rate slower initially
rate is second order: units are l/mol sec.
kd listed is for lowest initiator concentration
kd is extrapolated value for zero initiator
concentration
g
it2
h
i
j
j2
k
1
kd # has been corrected for induced decomposition
corrected for uncatalysed reaction (7 x lop5 s-)
AH (not E,)
pressure (number gives mbar)
iodometric analysis
manometer measurement
infrared analysis
kd is limiting value with respect to additive
concentration
ml
3,4-dichlorostyrene added to minimize induced
decomposition
m2
m3
styrene added to minimize induced decomposition
methyl methacrylate added to minimize induced
decomposition
m4
m5
isobutene added to minimize induced decomposition
acenaphthalene added to minimize induced
decomposition
m6
1 mol/l a-methylstyrene added to minimize induced
m7
m8
n
n2
0
P
P2
9
q2
q3
r
S
t1
t2
t3
t4
t5
t6
t7
t8
decomposition
butadiene added to minimize induced decomposition
acrylonitrile added to minimize induced
decomposition
trichloroacetic acid added
3.2 wt.% or about 0.1 monolayer
addition of trichloroacetic acid did not affect kd
degassed
photochemical benzophenone added: 6.56 x 10 l7
quants/min @ 366nm
addition of trichloroacetic acid increased kd several
fol d
pH 2.90
pH 7.05
not inhibited, but initiator concentration low enough
(0.01-0.09 M) so that higher order decomposition is
unimportant
solvent not degassed
2,6-di-tert-butylphenol added to inhibit induced
decomposition
a,a-diphenyl+picrylhydrazyl added to inhibit
induced decomposition
phenyl-a-naphthylamine added to inhibit induced
decomposition
tetrachloroquinone added to inhibit induced
decomposition
1,3,5trinitrobenzene added to inhibit induced
decomposition
12 added to inhibit induced decomposition
O2 added to inhibit induced decomposition
5-20% NO2 added to inhibit decomposition
References page II - 70
II/ 70 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
tg galvanoxyl added to inhibit induced decomposition
t 10 a,y-bisdiphenylene-P-phenylallyl added to inhibit
induced decomposition
t 11 a-naphthylamine added to minimize induced
decomposition
t 12 2,3,5,6-tetra-terbutyl indophenoxy added
t 1s benzoquinone added
t 14 2,6-di-tert-butyl-4-methylphenol added
Ul
in absence of oxygen
u2 from initiation data
u3
in multisurface reaction vessel
u4 rate reduced when nujol layer used to exclude Hg
vapor
ug rate increased when nujol layer used to exclude Hg
vapor
vi acetic acid added
v:! CuC12 added
vg CuCl added
v4 0.1 mol AgC104/mol AIBN added
vg 3.9 mol thiophenol added
vg tert-butyl mercaptan added
v7 2.5 mol cyclohexane added
v8
N 4 x 10m2 mol pyridine added
vg 2 x 10 -2 mol pyridine added
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vt2 saturated with ethyl acetate
~13 3.11 mol CC14 present
vi4 peroxide in P(MMA)
vt5 peroxide in P(sty.)
vr6 0.26 mol piperidine
vr7 0.24 mol triethylamine
v 1s 0.21 mol N,N-diethylaniline
vt9 0.22 mol pyridine
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vqt in presence of 15N0
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v 25 0.10 M pyridine added
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Xl
actual rate divided by 2 because of two identical
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x2 each peroxide group has different kd
Y
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II/76 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
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1
377. M. Buback, C. Hinton, Zeit. Phys. Chem., 193, 61
(1996).
I
Propagation and Termination Constants
in Free Radical Polymerization
M. Kamachi
Department of Applied Physics and Chemistry, Fukui University of Technology, Gakuen, Fukui, Japan
B. Yamada
Department of Applied Chemistry, Faculty of Technology Osaka City University, Sumiyoshi, Osaka, Japan
A. Introduction
B. Tables of Propagation and Termination
Const ant s
Table 1. Dienes
Table 2. Olefins
Table 3. Acrylic Derivatives
Table 4. Methacrylic Derivatives
Table 5. ltaconic Derivatives
Table 6. Fumaric Derivatives
Table 7. Vinyl Halides
Table 8. Vinyl Esters
Table 9. Vinyl Ethers
Table 10. Styrene Derivatives
Table 11. Vinyl Heteroaromatics
Table 12. Aldehydes
Table 13. Others
C. Ref erences
II-77
II-79
II-79
II-79
II-80
II-82
II-85
II-87
II-87
II-87
II-88
II-88
II-90
II-90
II-90
II-91
A. INTRODUCTION
In free radical polymerization the propagation and termina-
tion rate constants describe the reactions
kP
P; +M-I,,, (Al)
2P; kt dead polymer
W)
where P; is a propagating chain of any length n and M is
the monomer. The rate constants are defined by the
following equations:
R, = -7= kr[P][M]
R, = -F = k,[p]2
where
PI = 2 RI1
n=l
(A41
The rate constants k, and kt have usually been assumed to
be independent of chain length. In this chapter termination
constants depending on the length of the polymer radicals
are also reported. In American literature the right hand side
of (A4) is written as 2kt [P] 2. In this chapter the definition
given in Eq. (A4) has been used.
Simultaneous determination of absolute values of both
k, and k, from a single experiment has not been reported. In
practice, the ratio ki/k, is determined from measurements
of molecular weight as a function of rate of polymerization
for a low conversion polymerization or from measurements
of initiation rate and polymerization rate in a low conver-
sion. The ratio k,/k, is determined from nonsteady-state
measurements of the average lifetime, r, of the growing
polymer chain in a photochemically initiated polymeriza-
tion. This lifetime may be defined by noting that the
concentration of chains present must be related to their
average lifetime and rate of disappearance by
[P-]/r = Rt
which, from (A3) and (A4), yields
(A61
By combining the separately determined ratios, ki/k, and
kp/kt, the individual propagation and termination rate
constants may be calculated. Alternatively, the rate of
initiation, Ri, may be measured as the rate of initiator
disappearance and equated to Rt. This gives (from (A6) and
(A311
RP
k, = ~
Rir[M]
(A81
There is a large degree of imprecision inherent in
measuring 7 and in combining data from different
experiments, which helps to explain the scatter in the data
tabulated here.
II/77
II/78 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
k&l O-
100
I O
I
too
3
IO
I
IOOl
kt ( xl 0"
100
18
4 +
l 4
- l i*,
l
: 4 4
+ 4
l *.+
+ +
4s
4 + +
s
l
+
I I I I
a.0 a. 2 a. c a. 0
1000
T
Figure 1. Arrhenius plots of all bulk polymerization data for
styrene for k, (0) and k, (+). Solid lines are least squares obtained
by assuming all points to be of equal value.
The two monomers styrene and methyl methacrylate
have been so extensively studied that their data are
presented as Arrhenius plots (Figs. 1 and 2). Because of
the influence of solvents on the rates, only data of bulk
polymerizations are shown. It remains a wide scatter, which
should serve as a warning against casual acceptance of any
single number. Solid lines are the least squares that have
been calculated assuming all points to be of equal value.
For the termination rate of methyl methacrylate the least-
squares line results in a positive slope and is not shown. In
this case a temperature-independent kt could be a better
representation of the experiments.
The pulse laser polymerization (PLP) method has been
developed as a new method of obtaining k,. In the PLP
method, the value of k, can be estimated from the degree of
polymerization of polymer formed, vr, a knowledge of the
monomer concentration, [Ml, and tf the time between
pulses:
vp = kp[Mltf ( fw
The reproducibility of the PLP method has been recognized
by an IUPAC Working Party on Modeling of Kinetic and
Process of Polymerization, which is establishing a critical
review of the literature values of k,.
P
0
I I I I 1
a. S.k
IO00
a.0
T
Figure 2. Arrhenius plots of all bulk polymerization data for
methyl methacrylate for k, (0) and kr (+). Solid lines are least
squares obtained by assuming all points to be of equal value. The
line for kr is not shown since a horizontal line for a temperature
independent kr could be a better representation.
Classification of the methods for the determination
of rate constants
The tabulated data refer to seven different methods.
Method A uses the following four methods for the
measurement of the lifetime T:
Al - rotating sector or a flashing laser
A2 - flow through a tube with spatially separated light
and dark sections
A3 - spatial intermittent polymerization (SIP)
A4 - intermittent illumination method
Method B effectively measures only a single decrease
(increase), in the radical concentration by the following
methods:
B 1 - dilatometry
B2 - dielectric constant
B3 - interferomety
B4 - temperature change
B5 - viscosity
B6 - light scattering
B7 - monomer pressure
Dienes and Olefins II/79
Method F uses pulse laser photopolymerization (PLP)
met hod
Fl - PLP
F2 - PLP-GPC (MWD)
F3 - PLP-MALDI TOF (-GPC)
Method G refers to the method of measuring molecular
weight (MW) and molecular weight distribution (MWD) by
Gl - gel permeation chromatography (GPC)
G2 - high performance liquid chromatography (HPLC)
B8 - cathetometer
B9 - inhibitor
B 10 - scavenger
Method C uses electron spin resonance (ESR) for the
determination of the radical concentration
Method D refers to values obtained in emulsion polymer-
ization by application of the Smith-Ewart theory
Method E refers to recalculated values
B. TABLES OF PROPAGATION AND TERMINATION CONSTANTS
TABLE 1. DIENES
Monomer k, (VmoVs) k , ( x 10 -6) (l/mol/s) Temp. (C) Method Remarks Refs.
2 8 1 2 5 Al 1 5 2
1 0 D 2 3
1-Acetoxybutadiene
But a di e ne
18.0
k, = 1.2 x lo8
xexp(- 390OO/RT)
150f40 C 2 2 3
Gl 202
5
kt = 1.13 x 104
x exp(-711/7)
45-60
5 0 Ink, = In (3.873 x 10 lo)
-534OO/RT
1 1 1 . 6
k, = 8.05 x 10
x exp(- 35710/RT)
Chl or opr e ne 220
k, = 2.9 x lo9
x exp(- 41OOO/RT)
k, = 1.95 x 10
xexp(- 26630/RlJ
2,3-Dimethyl-1,3-butadiene k, = 8.9 x 10
xexp(- 38000/RT)
Ethyl 4-ethoxy-2,4-pentadienoate 9 . 9
Et hyl 4-methyl-2,4-pentadienoate 2 9 . 7
Ethyl pentadienoate 3 0 . 9
1,3-Hexadiene 20flO
2,4-Hexadiene 16f 12
I s opr e ne 2 . 8
Fl 2 2 1
Fl Solvent: chlorobenzene 2 2 1
F 2 Solvent: chlorobenzene 1 8 7
50
40 D
D
Quoted in Ref. 86 5 9
84
Fl 1 9 8
D 71
9 . 3 2 5 Al
2 3 2 5 Al
1 9 2 5 Al
5 C
5 C
5 D
1 5 2
1 5 2
1 5 2
223
223
Calalyst system: diisopropylbenzene, 2 4
monohydroperoxide-
tetraethylenepentamine
2 2 3
2 2 3 2-Methyl-1,3-pentadiene
125 130 5 C
35 f 10 5 C
TABLE 2. OLEFINS
Monomer k, (Urnok) k, (x 10e6) (YmoVs) Temp. (C) Method Remarks Ref s.
8 3
- 20.01
1 3 0
1 3 0
1 9 0
230
3.2 x lo3 190
Al
Al
Al
Al
C
Fl
Fl
Solvent: benzene
Pressure 1.8 x lo8 Pa
Pressure (5-17.5) x 10 Pa, using
results of Ref. 141
Pressure 1.9 x lO*Pa
Initial pressure 2.27 x lo* Pa
Pressure 2.55 x lo* Pa,
at low or moderate conversion
Pressure 2.50 x lo* Pa,
at conversion 0
5 3
66
1 3 9
1 4 2
135
151
1 6 7
1 6 7
50-150 Radical telomerization 1 2 9
Et hyl e ne 470 f 30 1050f50
18.6f2 455 f 50
5400 200
k, =4.8 x 10
xexp[(-4450+3.1 x 10-6p)/Tj
1.2 x 104 3.9 (7.8) x 10
1.09 x lo4 1.99 x 102
3.08 x lo4 -
Propylene k,=2x106
xexd-320OO/RT)
References page II - 15
II/80 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 3. ACRYLIC DERIVATIVES i
Monomer k, (VmoUs) kt (x 10 -6) (l/moVs) Temp. (C) Method Remarks Ref s. Iv
6000 i 1000
18000 f 1500
8200
220
(7.9 &0.5) x lo4
(4.3 f 0.2) x 104
(3.3 iO.2) x 104
(2.3fO.l) x lo4
k, =7 x 106
x exp[(- 21000f 2000)/RT]
650
3.3 + 0.6
14.5 f 2.0
5 . 5
1.0
660 f 40
350 i 20
230 i 20
160 f 10
Al, Bl Solvent: water, pH 5.5
2 5
19
2 6
3 0
3 0
Al
A
A
Al
Al
Al
Al
Fl
2 . 6 2 3 Al
3150 2 . 6 Al
6600 2 . 7
13 0.018
2100 330
1 9 7 7 3 . 8 4
679 f 66 6.4 f 0.6
2 5
2 5
3 0
25-80
3 0
Al
Al
B 4
Al
Al
Fl
B 5
7 9
4 1
8 9
8 9
1 2 6
1 1 9
1 1 9
1 1 9
1 9 7
Acrylamide
Acrylic acid
-, butyl ester
log 1, ~ k, = 6.0123- 748.4/T
1 3 6 0
963
1 3 2 0
360
2722 f 248
800
12.39 x lo3
ln[(k,(p]/(l.OO + 0.06p)l
= In k, [l]- 0.60~
1.28
1.18
1.07
0.36
3.2 f 0.3
1.76
1 3 9 . 2
3 0 Al
-, cyclohexyl ester
-1
ethyl ester
3 0 Al
5 0 Al
50 Al
-, 2-ethylhexyl ester 155 0 . 2 3 3 5 0 Al
-9 methyl ester 1 3 0 0 7 5 15 Al
880 260 15 Al
1 5 8 0
580
k,= 1.0 x lo*
xexp(- 3OOOO/RT)
1 0 0 0
1 1 6 8 0
21300
(1.5 f0.2) x lo4
5 5
k,=2:, 10
xexp(- 220OO/RT)
3.5550
1 9 4
2 5
2 5
Al 19
Bl 4 8
Al 21
60
Al
Al
Al
G2
(3.7 f 0.6) x lo4 6 0 G2
6.3 x lo4 6 0 G2
(1.4+0.2)x lo4 60 G2
-, 2-(acetoacetoxy-&ethyl)-, ethyl ester 300 1.0 6 0 C
-, 2-cyano-, ethyl ester 1 6 2 2 4 1 1 3 0 Al
1 6 1 0 404 3 0 Al
1 6 1 3 4 1 1 3 0 Al
1 6 0 7 404 3 0 Al
-, 2-chloro-, ethyl ester 1 6 6 0 3 3 3 3 0 Al
1 4 0 8 244 3 0 Al
-, 2-fluoro-, ethyl ester 1 1 2 0 4.8 x 102 3 0 Al
978 435 3 0 Al
-9 2-acetoxymethyl-, methyl ester 350 2.1 6 0 C
Solvent: water
Solvent: water
Solvent: DMSO
Solvent: water 0.38 M
HzO:DMSO (90: 10)
HzO:dioxane (90: 10)
HZ0 : THF (92 : 8)
9 9 Solvent: Water, pH 7.9,
(with 1.2 M NaOH)
Solvent: water,
pH 7.9 (with 1.5 N NaCl)
Solvent: water, pH 11
9 9
9 9
10
5 7
1 0 7
1 3 7
2 0 1
1 2 2
Pressure 5.0 x 10 Pa
Solvent: benzene 1.76 M
k, b]; k, for pressure p (bar),
kt [l] =3.5 x lo6
Solvent: anisole 2.OOM
Solvent: benzene 2.00 M
Solvent: chlorobenzene 2.00M
Solvent: benzonitrile 2.00 M
Solvent: benzene 1.76 M
Solvent: toluene 1.84 M
Solvent: benzene n; molar fractions
of monomer, x = 0.401,
k, and k, also given by other [Ml
Solvent: toluene 1.94 M
From unpublished results of Ross
and Melville
From unpublished results of
Matheson
1 3 8
1 3 8
138
138
1 3 7
1 0 8
171
108
22 ;
2 2
50
1 4 4
1 4 4
1 9 0
Solvent: benzene 2.69 M
Primary propagating step (k,,),
Ph-MA
PhCOz-MA
rerr-BuO-MA
Secondary propagating step (k,~),
Ph-MA-MA, PhCOz-MA-MA,
terc-BuO-MA-MA
Solvent: benseme
AcOHwt.%
1,3-propanesulfone 0.5 wt.%
Optimum value, solvent: AcOH
Optimum value
Solvent: propanesulfone
AIBN 4.88 x 10 - M
Optimum value
1 9 0
1 9 0
1 7 0
1 4 3
1 4 3
123
123
1 4 0
123
1 4 6
123
2 2 5
Optimum value
Solvent: benzene 1 .OO M,
MAIB 0.050 M
TABLE 3. contd
Acrylic Derivatives II/81
Monomer k, (VmoUs) k t ( x 10 -6) (Urnok) Temp. (C) Method Remarks Refs.
-, 2-acetyloxy-, methyl ester 430 60 C
-, 2-benzoyloxy-, ethyl ester 990 2 . 9 60 C
-, 2-(benzyloxymethyl)-, methyl ester 1 8 2 1.6 60 C
-, 2-[2,2-bis(carbomethoxy) ethyl],
methyl ester
4.0 0.038 60 C
-, 2-butoxy-, methyl ester 298 8 60 C
1 8 4
-
60 C
-, 2-butyroxymethyl-, methyl ester 360 1.4 60 C
-, 2-(2-carbomethoxy)- ethyl-,
methyl ester
-, 2-ethyl-, methyl ester
-, 2-ethyl-, cyclohexyl ester
-, 2-isobutyroxymethyl-, methyl ester
19 0 . 5 1 60 C
8 . 6 21 60 C
1.6 1.8 60 C
300 1.1 60 C
-, -2-(methoxycarbonylmethyl)-,
phenetyl ester
11 0 . 0 8 5 0 C
-, 3-methyl, adamantyl ester 0 . 5 7
0 . 7 6
0.11
1.4
6 0 C
60 C
-, 3methy1, dimethyladamantyl ester 0.41 0. 08 1 6 0 C
0.71 1.1 6 0 C
-, 3-methyl, [err-butyl ester 0.90 2 . 3 6 0 C
1.0 4 . 7 6 0 C
-, 2-naphthoyloxymethyl-, ethyl ester
-, 2-pivaroxymethyl-, methyl ester
320 0 . 3 7 60 C
230 0.59 60 C
-9 nuns-2-vinyl-, methyl ester
Acr yl oni t r i l e
1 2 5 60 C
3000-5000
1 2 7
5 2
51
20000
24
12.2
5
1.8
D
B4
B4
B4
D
2 3
0
2 5
2 5
2 5
40
5 0
1 9 6 0 782
1 5 4 0 0 2700
28000 3700
1 9 1 0 290
382 f 230 47.6 + 22
3300 i 300 1200% 170
3200 k 400 300 f 50
3000 i 600 240 i 70
N-Acryloyl-2,2-dimethyl-
5 (R)-phenyl-1,3-dioxazoline
(6.5 f 1.3) x lo3 4700 f 1300
2 8 . 2 0.20
6 0 Al
2 5 Al
2 5 Al
2 5 Al
2 5 Al
50 Al
50 Al
50 Al
50 Al
6 0 C
N-Acryloylpiperidine 273 17.9 3 0 Al
273 11.9 30 Al
N-Acryloylpyrrolidine 8 2 6 7 2200 30 Al
Solvent: 1,1,2-trichloroethane 2.OM
2,2-azobis (4-methoxy-2,4-
dimethylvaleronitrile) O.O30M, k,
also given by other temp.
Solvent: benzene 1.56 M
Solvent: benzene 2.0 M,
AIBN 5.tilK3 M
Bulk AVN 0.05 M,
k, and kr also given by
other temp.
Solvent: benzene 2 M
Solvent: 1 ,1,2-trichloroethane 2.0 M
2,2-azobis (4-methoxy-2,4-
dimethylvaleronitrile) 0.030 M, k,
also given by other temp.
Solvent: benzene 1 .OO M, MAIB
0 . 0 5 0 M
Bulk MAIB 0.05 M, k, and k,
also given by other temp.
Bulk AIBN 0.10 M
Bulk AIBN 0.10 M
Solvent: benzene LOOM,
MAIB 0.050 M
Solvent: benzene 2.22M, k, and kt
also given by other temp.
and [Ml
Bulk 4.8 M
MAIB 0.05 M
Solvent: benzene 2.4 M,
MAIB 0.05 M, k,
also given by other [M]
Bulk 4.0 M, MAIB 0.05 M
Solvent: benzene 2.0 M,
MAIB 0.05 M
Bulk 5.9 M, MAIB 0.05 M
Solvent: benzene 2.0 M,
MAIB 0.05 M
Solvent: benzene 1 .OO M,
MAIB 0.01 M
Solvent: benzene 1 .OO M,
MAIB 0.005 M
Solvent: benzene 1.0 M,
AIBN 0.25 M
Solvent: DMF
Primary radical termination in a
precipitating medium
Solvent: DMF
Solvent: water
Solvent: water
Solvent: DMSO
Solvent: DMF
Solvent: DMF 3.8 M
Solvent: DMSO 3.8 M
Solvent: Ethylene carbonate 3.8 M
224
1 7 2
206
228
1 7 6
224
225
229
230
230
225
232
232
232
232
232
232
226
225
227
42
49
6 3
7 5
42
3 5
4 3
5 4
5 5
70
6 8
8 8
8 8
8 8
Solvent: Mg (Clod)* 12H20 3.04M 8 8
Solvent: benzene 1.08 M, 2 3 1
MAIB 0.05 M, k, and kt
also given by other temp.
145
Optimum value 1 2 3
Optimum value 1 2 3
References page II - 15
II/82 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 3. contd
Monomer k, (VmoVs) kt (x 10e6) (Vmok) Temp. (C) Method Remarks Refs.
WV-Dimethylacrylamide
3-Dimethyl-(acryloyloxyethyl)-
a mmo n i u m s u l f o n a t e
propane
N-Methylactylamide
1 1 0 0 0
27200
29198
15 x 10s
2330 i 230
2760 f 342
9.9 x 10s
3 8
3540
4080
0.540 f 0.053
0.452 f 0.056
5 0
3 0
3 0
2 5
3 0
30
2 5
Al
Al
Al
Fl
A4
Fl
Optimum value
Sol ve nt : water, pH 1.4
Solvent: formamide : 1,Cdioxane
(3 : 1 (v/v))
Sol ve nt : formamide: 1,Cdioxane
(3 : 1 (v/v)), NaCl 0.1 M
Solvent: water, 1.9 pH
74
121
123
1 9 7
1 9 2
1 9 2
1 9 7
TABLE 4. METHACRYLIC DERIVATIVES
Monomer k, (VmoVs) k t ( x 10 -6) (YmoYs) Temp. (C) Method Remarks Refs.
Methacrylamide
Methacrylonitrile
Methacrylic acid
-, benzyl ester
-, bomyl ester 580 3 . 3 6 0 C
-, n-butyl ester 369 10.2
573 18.0
360 1 0
lnk,=6.13+6.33 x 10-9p
lnkr = 15.8-2751/T
2 . 6
ln[(k,[p1/(1.00+0.01p)l
=lnkJl] - 0.73~
Ink, = (14.41 hO.09) - (2472 f 29)/T
3 0 Al
3 0 Al
3 0 Al
30 F 2
12-93 F 2
70 B 5
3 0 B 5
79.6 f 5.6
1.1 x 10s
- 2 1
2 6
k = 106.435026
x exp[(P 29700 f 15OO)/RT]
16.5 it 1.4
- 2 7
21
2 5
2 5
3 0
2 5
Al Solvent: water
Fl Solvent: water, pH 1
Al
6 9
1 9 7
2 6
3 9
670 2.1 2 3 Al Solvent: water, pH 8.0 9 9
1 9 5 0 2 . 2 5
1 4 1 0 41.9
1 1 0 8 0
8 9 5 40
1250 41.9
510 2 . 8 7
3 0
3 2 . 5
3 2 . 5
30
20
Al
Al
C
C
Al
Al
(with 0.22 M NaOH)
pH = 13.6
k, and k, also given as a
function of viscosity
Solvent: benzene l.OM,
AIBN 0.05 M
9 9
101
1 5 3
153
8 7
1 0 3
193
Pressure: 5.0 x lo7 Pa
Pressure 1.0 x lo* Pa
q= 1.92~~
k, [PI; k, for pressure p (bar),
k,[l] = 13.4 x lo6
2 7
1 0 6
1 0 9
216
216
212
1 2 2
10-90 Fl 219
Fl 1 6 9
A3 2 2 5
Al 52
Fl 2 0 3
-, tert-butyl ester
-1 trans-Ctert-butyl-
cyclohexyl ester
-3 cetyl ester
-, p-[p-(cetyloxy)-
benzoyloxyl-
phenyl ester
-, 2-chloroethyl ester
-, 2-cyclohexyl-
ethyl ester
-9 cyclohexyl ester
-, 2-decahydro-
naphthyl ester
k, = 3.44 x lo6 exp(- 233OO/RT)
1 5 7 6
350
9.74
1 4
k, = 107.4*o.4
x exp[- (27.7 f 2.5) x 103/RT]
550
3 0
2 5
9-66
1.9 60 C
510 1.9 60 C
570 f 10 0.5- 2.3 60 C
300 f 90 0. 16f0. 04 30 Al
300 0 . 2 5 50 Al
1 7 0 0 . 3 0 5 0 Al
254 6.71 3 0 Al
1 1 9 0 3 2 . 8 3 0 Al
510
570
5 . 4
3.1
60
60
C
C
Solvent: benzene 1 .O M,
AIBN 0.05 M, tram 100%
t r am 28.9%
Solvent: benzene
Solvent: dioxane 0.2 M
Solvent: toluene 0.2 M
Solvent: benzene 1.0 M,
AIBN 0.05 M
Solvent: benzene 1.0 M,
AIBN 0.05 M
1 9 4
1 9 4
210
1 0 9
97
9 7
8 7
8 7
1 9 3
1 9 3
TABLE 4. contd
Met hacryl i c Deri vat i ves II/83
Monomer k, (VmoUs) k t ( x 10 -6) (l/mol/s) Temp. (C) Method Remarks Refs.
-, 2,6dimethyl-
phenyl ester
-, dodecyl ester
-9
ethyl ester
-, hexadecyl ester
-, isobomyl ester
-9 isobutyl ester
-9 isopropyl ester
-, lauryl ester
-, 2-methoxyethyl ester
-3 methyl ester
6 8 2.1
12
-
1 2 6
-
k,= 1.50 x lo6
x exp(- 20460/RT)
lnk,=(15.11f0.17)-(2753&55)/T
390
2 . 4
0 . 6
1 . 3 5
10
0.16
3 . 5
lnkp=(14.72i0.13)-(2590f42)/T
121 4.52
460 f 140 0.6 f 0.2
k,=2.93 x lo5
x exp(- 16190/RT)
249 9.30
310520 66f4
k,= 5.13 x lo6 k, = 1.36 x lo3
x exp(- 26400/RT) x exp(- 119OO/RT)
1 8 7 7 2 . 1
404 17.6
410 24
13.2 0.488
390
517 3 7 10 Bl
527 2 3 10 Bl
2 8 4.4 10 Bl
260 21 2 5 Al
270 21 2 5 Al
280 19.5 2 5 Al
2 8 5 17.5 2 5 Al
310 17 2 5 Al
330 17 2 5 Al
340 17 2 5 B5
240 11.5 2 5 B5
3 3 5 9 2 5 B5
270 2 2 2 5 B5
330 16 2 5 B 5
250 2 9 2 5 B5
240 2 5 2 5 B 5
280 1 4 2 5 B5
320 2 8 2 5 B5
390 i 40 4 2 1 4 2 5 Al
410f40 29f3 2 5 Al
410f40 26f3 2 5 Al
180f50 20f6 2 0 E
500 f 250 63f32 2 0 B 6
41.6 2 . 6 9 0 B5
6 2 5 D
200 -
20 B 6
1 2 8 8 . 4 4 2 2 Bl
364 4 1 . 8 2 2 . 5 B4
512.6 46.6 2 5 Al
410 4 2 . 7 2 5 Al
248 2 2 . 7 3 0 Al
141 11.6 3 0 A
1 0 6 5 . 7 3 2 B4
1 4 0 40 D
30 Al 1 2 0
30
70
3 0
70
Al
B5
Al
B5
Fl
Optimum value
v = 3.96 cp
17=0.91 cp
123
212
8 7
212
1 6 9
10-90 Fl
70 B 5
60 C
10-90
3 0
3 0
Fl
Al
Al
Fl
v= 7.52 cp
Solvent: benzene l.OM, AIBN
0 . 0 5 M
219
212
193
219
8 7
1 0 9
1 6 9
3 0
2 3 . 6
Al 8 7
Al 9
Al I
3 2 . 5 C
40 Bl
50 E
- 3 0 Bl
20 Al
1 5 3
Solvent: ethyl acetate 51
Using results of Ref. 7 6 2
Solvent: ethyl acetate 7 2
k, also given as a function of temp. 9 2
and of viscosity for other solvents
Solvent: methanol 94
Solvent: pyridine 9 4
Solvent: DMF 94
Solvent: benzene 4.69M 8 5
Solvent: fluorobenzene 4.69 M 8 5
Solvent: chlorobenzene 4.69M 8 5
Solvent: anisole 4.69 M 8 5
Solvent: bromobenzene 4.69 M 85
Solvent: benzonitrile 4.69M 8 5
Solvent: methyl benzoate 4.69 M 9 0
Solvent: methylphenyl acetate 4.69 M 9 0
Solvent: dimethyl phthalate 4.69 M 9 0
Solvent: dimethyl carbonate 4.69M 90
Solvent: diethyl oxalate 4.69 M 90
Solvent: methyl formate 4.69 M 90
Solvent: methyl propionate 4.69 M 90
Solvent: diethyl succinate 4.69 M 90
Solvent: acetonitrile 4.69M 90
Solvent: methanol 50% by vol. 1 0 4
Solvent: n-octane 5% by vol. 1 0 4
Solvent: n-nonane 20% by vol. 1 0 4
m = (2-8) x lo3 using results of 96
Ref. 86
m= (3-5) x 104 96
Assuming biradical initiation 1 1
6 5
k, found as a linear function of M,
Rate of initiation; 1.20 x 10ms
(moles/l/s)
k, and kt also given as a function of
viscosity for other solvents
9 1
2 9
6 0
3 0
9 3
14
8 7
5 8
6 5
References page II - 15
II/84 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Monomer k, (l/mol/s) k t ( x 10 -6) (YmoUs) Temp. (C) Method Remarks Ref s.
0.224
-
45 D
573 2 . 0 60 E
513 11.9 60 E
995 f 83
506 zt 48
450 i 33
456 f 29
448547
498 f 39
614f43
427 i 38
290
1 0 2 0
530
550
43.6 f 4.9
35.6% 3.9
42.Oi3.0
43.8 f 2.0
41.2 f 6.6
42.9 f 4.7
39.9 f 3.3
30.9 i 3.1
21
292
5 5
6 8
80
30
30
60
Al
Al
Al
Al
Al
Al
Al
Al
Al
Al
Al
k,=4.92 x lo5
x exp(- 18210/RT)
315
k,=98
x exp(- 2930/RT)
3 3 . 9
15- 30 A2
25 A2
336 f 90
4 4 1
k,=2.5 x lo6
28f12 25 Al
19.7 30 Al
720 25- 60 C
x exp[(- 23000 f 25OO)/RZJ
k, =k;(0.33 5 wp 5 0.84)
= ki exp[- 29.8 (w,, - 0.84)]
(0.84 5 wp 5 0.99)
(k; =790 f 300)
1 3 0 20.7 f 1 .O
705.6 2 5
1 7 0
306
-
292
50 C wp (weight fraction of polymer) 150
0
60
0. 2 F 3
25 Fl
25 Fl
670 f 30 2 2
Ink, = 14.69-2670/T+
0.201/Tx (1.0 x lo-sp- 1)
lnkJp]=lnkr[l]-0.57~
26. 6 1. 4
5. 8 0. 017
k,(m,n) = 1.22 x lO*(n x m) -.075 2 5
60
20- 90
30
5
5
- 21 70
-
0. 034 50
0. 16 50
k,= 106.6 exp(- 23940/RT) - 1 t o - 7 0
Ink, (l/moYmin) = In k,,o- (3.86 [AIBME]o 60
+0. 8)x(l - qb )-1.6(1-I$ )6.0
m m
131 - 8
680- 820 30
690- 810
Termination by combinat. using
67
33
results of Refs. 7 and 31
Termination by disprop. using results 33
of Refs. 7 and 31
Solvent: benzene 4.7 M
Solvent: anisole 2.OM
Solvent: benzene 2.OM
Solvent: C6Ds 2.OM
Solvent: fluorobenzene 2.OM
Solvent: chlorobenzene 2.0 M
Solvent: benzonitrile 2.0 M
Sol ve nt : be nz e ne 1 . O M
Addition of 1 x 10e3 mol pyridine
Addition of 1 x lo- mol acetone
Addition of 1 x low3 mol
111
133
133
133
133
133
133
133
118
118
118
118
triethanolamine
Fn = 104 1 1 4
k, and kt also given as a
function of Pn
Pressure 5.0 x lo6 Pa
Pressure 5.0 x 10 Pa
1 1 0
127
105
45
Al At high conversions (N 65%) 148
Special evaluation from 134
steady-state and iii,
Solvent: toluene 222
196
Solvent: ethanol (50%) 4.67 M, k,
also given by other [M] and solvents
C 175
Fl 207
B 5
BlO
k&l; kt for pressure p (bar),
k,[l] = 15.4 x lo6
Scavenger DPPH, solvent: DMF,
blank polymn.
Scavenger DPPH, solvent: DMF,
template polymn., template;
it-MMA
122
115
BlO 115
A3
B 5
n: n-mer; m: m-mer, coupling with
n-mer and m-mer
1)=0. 53 CP
147
212
D 149
D
No addition of chain-transfer agent,
Time 7.5-20.5 min.
Addition of 2% CBr4,
Time 7.5-20.5 min.
149
Fl
C AIBME (dimethyl 2,2-
azodiisobutyrate) O.O434M, 4,;
monomer volume fraction
k,,o = 700 (l/moVmin)
Benzoin 7 x 10m4 M
Solvent: toluene, pressure
1.0 x lo* Pa, k,also given by
other pressures
Solvent/2-butanone, pressure
1.0 x 10s Pa
217
158
F 3
Fl
199
208
Fl 208
3.
R
-
T,
-
M
Iti
-,
-,
TABLE 4. contd
ltaconic Der i vat i ves II/85
Monomer k, (VmoVs) kt(x10m6) (Vmolh) Temp. (C) Method Remarks Refs.
-1
octyl ester
-, phenyl ester
-, 2-phenylethyl ester
-, 3-phenylpropyl ester
-1 n-propyl ester
-, 3-tetracyclo-[4.4.02.5.1 ,O]-
dodecyl ester
-1 triphenylmethyl ester
31318. 1
794.0
815.0
957.0
510f 100
299
4 3 1
k,=2.39 x lo6
x exp(- 220OO/RT)
359
12
135
292
200
135f50
1 7 0
3 5
2960
k,= 1.9068 x lo6
x exp(- 21181.07/RT)
k,= 1.2169 x lo6
x exp(- 25203.59/RT)
k,=3.0598 x 10
x exp(- 28008,18/RT)
3 5
1 7 1 0
240 f 80
4 1 1
230 f 15
17658
180*9
223+11
235f8
273f8
228
1 4 9
467
590
2 6 0 . 3 0 1
3 9 1 4
62.4
5 1 . 6
3 8 . 2
25( f 3)
21f2
4 5
50
-
-
2 5 . 6
29.1
6 2 . 6
2. 6f 0. 9
ln[(k,[p]/(l.OO-0.19)]
=lnk,[l]- 1.01~
11.9
2.02 f 0.22
2.06 f 0.21
2.1650.19
2.26 f 0.22
1.72f0.11
1.9610.12
1.88
0.813
4 5 . 1
2 . 6
3-Dimethyl-(methacryloyloxy-ethyl)
ammonium propane sulfonate
1470 f 170 0.499 i 0.058
2760 f 342 0.452 f 0.056
Polyhydroxytetramethylene-a,
w-methacrylate of MW = 700
185 0.034
230 0 . 0 5 3
2 5 Fl
6 0 B 5
60
60
2 5
40
C
C
Al
2 5
5 0
Fl
Fl
C
0 Al
2 5 Fl
2 8 Bl
0 Al
5 0 C
50
3 0 A3
Fl
Fl 30% MMA in benzyl alcohol 227
Fl 30% MMA in NMP 227
50
3 0
3 0
Al
Al
B 5
3 0
3 0
3 0
3 0
3 0
60
Al
Al
Al
Al
Al
Al
Al
Al
Al
Al
C
3 2 . 5 C
3 0 A4
3 0
20
2 0
B 8
B8
Solvent: benzene 3 M
Solvent: chlorobenzene 3 M
Solvent: benzonitrile 3 M
161
204
204
204
1 6 6
191
1 6 0
1 6 0
1 9 8
220
Emulsion polymn., 1 8 4
particle size 260nm, k,
also given by other particle sizes
k,; average value 1 5 9
1 6 4
Values from Chem. Abstr. 8 3
1 6 5
Emulsion polymn., n-butyl acrylate: 1 5 5
MMA: methacrylic acid (8 : 91: l),
particle size (p.s.) 50nm. k, also
given by other temp. and particle sizes
p.s. 500nm 1 5 5
2 2 5
227
p . s . 5 0 0 n m 155
Pressure 5.0 x 1OPa 113
1 0 9
k&l; k, for pressure p (bar), 1 2 2
k,[l] =40.0 x lo6
8 7
Solvent: anisole 2.00M 1 1 6
Solvent: benzene 2.00M 1 1 6
Solvent: fluorobenzene 2.00M 1 1 6
Solvent: chlorobenzene 2.00M 1 1 6
Solvent: bromobenzene 2.00 M 116
Solvent: benzonitrile 2.00 M 116
8 7
8 7
2 8
Solvent: benzene 1 .O M, 193
AIBN 0.05 M
153
Solvent: formamide: 192
1,4-dioxane (3 : 1 (v/v))
Solvent: formamide: 1 9 2
1,4-dioxane (3 : 1 (v/v)), NaCl 0.1 M
Calcd. from nonstationary 125
state kinetics
Calcd. from stationary state kinetics 125
TABLE 5. ITACONIC DERIVATIVES
Monomer k, (I/moUs) k , ( x 10 -6) (VmoVs) Temp. (C) Method Remarks Refs.
Itaconic acid
-, bi s (4-rerr-butyl-cyclohexyl) ester
-, bi s (cyclohexyl-methyl) ester
1.7 2 . 5 x 1O-3 6 0 C Solvent: benzene 0 . 5 M 2 1 3
3 . 9 3 . 4 x 1o-3 60 C Solvent: benzene 1.5 M, 1 8 2
MAlB 0.02 M
References page II - 15
II/86 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 5. contd
Monomer k, (YmoVs) kt (x10m6) (YmoV.9) Temp. (C) Method Remarks Refs.
-, bis (3,5-dimethyl-1-adamantyl) ester
-, bis (2-ethylhexyl) ester
-, diadamantyl ester 0 . 5 6
-, di-n-butyl ester 3 . 5
-, di-set-butyl ester
-, di-reti-butyl ester
-, dicyclohexyl ester
-, diethyl ester
-, diisobutyl ester
-, diisopropyl ester
2 . 7
1.1
-, dimethyl ester 5 . 2
-, a-ethyl-P-hexafluoropropyl ester 5 . 0
-3 a-methyl+isopropyl ester 3 . 4 0 . 0 6 60
-> cc-methyl-S-rerr-butyl ester 4 . 2 0 . 0 5 1 60
-. a-isopropyl-P-methyl ester 1.9 0 . 0 7 6 0
-, a-tert-butyl-S-methyl ester 0 . 9 1 0.056 6 0
N(2,6-dimethylphenyl) itaconimide 26 0.082 50
Methyl N-phenyl-itaconamate 15 0 . 2 9 6 0
0 . 9 2
6 . 8
3 . 4
2 . 0
2.1
2 . 2
2.1
2.1
1.4
3 . 0
0.32 x 1O-3
0 . 0 0 1
0.30 x 10-3
1.59 x 10-2
13 0.11
11
6 . 8
9 . 4
6 . 1
3 . 4
3 . 2
0 . 1 3 50
0 . 0 7 5 0
0.11 50
0 . 0 8 3 50
0.068 50
0 . 1 3 50
1.0 x 10-3 50
5 . 3 8.5 x lo-*
5 . 9
0 . 6
0 . 2
2 . 3
0.053
4.0 x 10-3
5.6 x 1O-3
1.4 x 10-3
7.1
3 . 7
0.24
6.41 x lo-
1.56 x lo-*
5.0 x 10-3
1 0
0.36
0 . 5 9
0 . 2 8
60
5 0
5 0
50
5 0
50
50
50
5 0
50
6 0
60
50
50
5 0
60
60
6 0
50
60
6 0
60
60
50
60
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
Solvent: benzene 1.5 M
Solvent: hexane 1.03 M
Solvent: cyclohexane 1.03 M
Solvent: toluene 1.03 M
Solvent: benzene 1.03 M
Solvent: chlorobenzene 1.03 M
Solvent: ethyl acetate 1.03 M
Solvent: THF 1.03 M
Solvent: acetone 1.03 M
Solvent: benzene 2.0 M,
MAIB 0.05 M
Solvent: benzene 1.5 M, k, and k,
also given by other [M]
Solvent: benzene 1.5 M,
MAIB 0.02M
Solvent: cyclohexane 1.33 M,
MAIB 5.00 x lo-M, k, and k,
also given by other temp.
Solvent: n-hexane 1.33 M
Solvent: chlorobenzene 1.33 M
Solvent: methyl benzoate 1.33 M
Solvent: benzene 1.33 M
Solvent: acetone 1.33 M
Solvent: acetonittile 1.33 M
Solvent: benzene 0.794M,
AIBN 0.05 M k, also given
by other [M]
Solvent: benzene 0.794 M,
MAIB 0.05 M
Solvent: benzene 2.0 M,
MAIB 0.05 M
Solvent: benzene 1.5 M,
MAIB 0.02M
Solvent: benzene 1.5 M,
MAIB 0.02 M
Solvent: benzene 1.5 M,
MAIB 0.02M
Solvent: benzene 2.0 M,
MAIB 0.05 M
Solvent: benzene 1.5 M,
MAIB 0.02 M
Solvent: benzene 1.5 M,
MAIB 0.02M
Solvent: benzene 1.5 M,
MAIB 0.02M
Solvent: benzene 1.5 M,
MAIB 0.02 M
Solvent: benzene 2.0 M,
MAIB 0.05 M
Solvent: benzene 2.0 M,
MAIB 0.05 M, k, and kt
also given by other [M] and temp.
Sol vent : THF 0. 44 M,
AIBN 0.05 M, k, and k,
also given by other [M]
Solvent: DMF 1.4M,
AIBN 0.05 M, k, and kt
also given by other [M] and temp.
2 1 3
1 8 5
185
185
185
1 8 5
185
1 8 5
185
1 7 7
2 1 3
1 8 2
1 6 2
1 6 2
1 6 2
1 6 2
1 6 2
1 6 2
1 6 2
1 5 4
1 5 4
1 7 7
1 8 2
1 8 2
1 8 2
1 7 7
1 8 2
1 8 2
1 8 2
1 9 5
111
233
1 9 5
195
195
1 9 5
234
2 3 5
i
Fumaric Derivatives, Vinyl Halides, and Vinyl Esters II/87
TABLE 6. FUMARIC DERIVATIVES
Monomer k, (l/mol/s) k t ( x 10 -6) (Ymolk) Temp. (C) Method Remarks Refs.
Fumaric acid
-, bis (2-methoxy-ethyl) ester
-, bis (Zchloro-ethyl) ester
-1 tert-butyl methyl ester
-3
rerr-butyl isopropyl ester
0 . 1 9
0 . 2 6
0 . 2 3
0 . 5 1
0 . 3 5
0 . 3 9
0 . 6 1
0.60
0 . 2 1
0.015
330 x 10-6
320 x 1O-6
1 5 0 x 10-6
26 x 1O-6
60
60
60
60
60
Sol ve nt : be nz e ne 1 . O M
Solvent: benzene l.OM
Sol ve nt : be nz e ne 1 . O M
Solvent: benzene 1.OM
AIBN
MAIB
Solvent: benzene 1.0 M
Solvent: benzene 1.0 M
Solvent: benzene l.OM
AVN (2,2-azobis-2,4-
dimethylvaleronitrile),
ACN (1,l -azobiscyclo-hexane-
1-carbonitrile)
ACN, scavenger TPV
(1,3,5&iphenylverdazyl),
sovent: benzene
Sol ve nt : be nz e ne 1 . O M
ACN, scavenger TPV,
solvent: benzene
Solvent: benzene 1 .O M
Solvent: benzene 1 .O M
Solvent: benzene 1.16 M,
MAIB O.lOOM, k, and kt
also given by other [M]
2 1 1
2 1 1
2 1 1
2 1 1
181
181
2 1 1
2 1 1
2 1 1
1 7 3
1.75 x 10-5
30 x 10-6
40 x 10-6
(510- 560) x 1O-6
1.64 x 10-4
6 0 C
6 0 C
60 C
3 0 Al
-, di-reti-butyl ester
-, dicyclohexyl ester
-, diethyl ester
0.029 f 0.003 8 x 10-6 30 BlO 1 7 9
0.46 (80- 100) x 1O-6 60 C
0.31 f0.07 0.84 x 1O-6 3 0 BlO
2 1 1
1 8 0
-, diisopropyl ester
-, dimethyl ester 0.058 430 x 10-6
-, dineopentyl ester 0.028 44 x 10-6
Ethyl o-formylphenyl fumarate 4 . 0 1.4
C
C
C
2 1 1
2 1 1
236
TABLE 7. VINYL HALIDES
Monomer k, (l/mol/s) kt(x10m6) (Ymolk) Temp. (C) Method Remarks Refs.
Tetrafluoroethylene
Vinyl bromide
Vinyl chloride
Vinylidene chloride
7400
2
2 2 . 7
570
k, = 3.3 x 106
x exp(- 15000/R7)
1 1 0 0 0
3130
8 . 6
k,= log
x exp(- 4540/7)
7.4 x 10-5
9 2
3 8 5
k, = 1.3 x lo6
x exp(- 4200/RTj
2100
2300
0.175
k,=106
x exp(- 267017)
40
- 3 0
20
2 5
2 5
2 5
22-75
Al
Al
Al
Al
Al
Al
Large active chain end concentration 8 1
measured by addition of inhibitor
in aqueous solution polymn.
8 0
Quoted in Ref. 80 44
3 2
56
7 7
18
Solvent: N-methylpyrrolidone 2.0 M 1 1 7
TABLE 8. VINYL ESTERS
Monomer k, (Ymolh) k t ( x 10 -6) (YmoVs) Temp. (C) Method Remarks Refs.
4600 220
795 46
556- 586 2860- 3040
670- 770 2500- 3100
700 2600
559 5 1 . 8
1 1 0 0 8 0
1 0 0 0 5 9
8 9 5 24
k,=2.43 x 10 k, =4.16 x lo5
x exp(- 30600/RT) x exp(- 21900/RT)
9500- 19000 380-760
(15-26) x lo2 2 5
2 . 5
15
15.9
15.9
15.9
2 0
2 5
2 5
2 5
B5
Bl
Al
Al
Al
B 4
Al
Al
B 4
Al
Sol ve nt : n-hexane
At 4% conversion
13
4 7
1
3
4
3 7
2
15
3 6
8
Vi nyl acet at e
6 0 E
5 0 Al
Using results of Refs. 8 and 15 64
128
References page II - 15
II/88 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 8. contd
Monomer k, (VmoVs) k , (x 10 -6) (VmoVs) Temp. (C) Method Remarks Ref s.
117512 319f61
113flO 351 f54
481t5 239 f 45
97flO 311 f59
61&9 266 f 75
37&5 412 f 104
8&1 258 zt 76
637 i 101 94.2 i 23.7
7 8 -
1 2 0 310
530 630
1 9 0 0 280
1 4 0 0 -
4 4 3 5 6 4 . 4
k, = 2.0 x 106 2 7 . 5
x exp[(- 19000 f 2900)/RT]
k, =2.7 x lO*
x exp(- 27820/RT)
ln[(k&]/(l.OO-0.07p)l
=lnk,[l]-0.50p
Vi nyl benzoate 106514 253 zt 63
185f8 402 i 32
245 f 13 522 i 48
168 f 18 383 f 76
69f13 257 f 72
3 3 1 3 299 f 44
267 ic 33 451 f65
3 0 Al
Al
Al
Al
Al
Al
Al
Al
32.5 Al
32.5 C
32.5 C
32.5 C
3 0 Al
15-60 C
Fl 209
3 0
3 0
B5 ktb]; k, for pressure p (bar) 1 2 2
Al
Al
Al
Al
Al
Al
Al
Solvent: benzene 2.00M 1 3 0
Solvent: C gD 6 2.00 M 1 3 0
Solvent: anisole 2.00 M 1 3 0
Solvent: fluorobenzene 2.00 M 1 3 0
Solvent: chlorobenzene 2.00 M 1 3 0
Solvent: ethyl benzoate 2.00 M 1 3 0
Solvent: benzonitrile 2.00 M 1 3 0
Solvent: ethyl acetate 2.00M 1 3 0
Solvent: ethyl acetate: ethyl 1 3 0
benzoate (1 : 1 (v/v))
Solvent: benzene
Solvent: benzene 5.41 M
Solvent: ethyl acetate 5.43 M
Pressure 5.0 x 1OPa
153
1 5 3
1 5 3
1 5 3
1 1 2
4 5
.
k,[l] = 52.0 x IO6
Solvent: anisole 1.01 M
Solvent: benzene 1.01 M
Solvent: fluorobenzene 1.01 M
Solvent: chlorobenzene 1.01 M
Solvent: ethyl benzoate 1.01 M
Solvent: benzonitrile 1.01 M
Solvent: ethyl acetate 1 .O 1 M
1 1 6
1 1 6
1 1 6
1 1 6
1 1 6
1 1 6
1 1 6
TABLE 9. VINYL ETHERS
Monomer k, (VmoVs) kt (~10~~) (VmoVs) Temp. (C) Method Ref s.
Monovinyl ether of ethylene glycol 5.0f 1.0 1. 5f 0. 3 5 0 Al 1 3 6
Monovinyl ether of diethylene glycol 3.01tO.8 1.4&0.3 5 0 Al 1 3 6
TABLE 10. STYRENE DERIVATIVES
Monomer k, (UmoVs) kt(x10m6) (VmoVs) Temp. (C) Method Remarks Refs.
Styrene 40f20 8O~t40 15 Al
2 4 14 2 0 Al
5 1 . 9
1 0 8
1 0 6
1 0 2
390
209
18.7
3 9 . 5
k,= 2. 16~10'
x exp(- 32500/RT)
2 2
10. 5
3 2 . 5
1 0 8
-
115
2 . 7 9
5 . 9 6
3 0
3 0
3 0
40
50
50
2 5
2 5
2k, = 2.59 x lo3
x exp(- 9920/R7)
Al
Al
Al
D
D
E
B 5
Bl
Al
5 D
1 3 9
2 2 3
206
40
5 0
5 0
D
D
D
Dimension of k, and kt: kg/mol/s
From copolymn. data with sulfur
dioxide
Quoted in Ref. 86
Using results of Ref. 20
Catalyst: cumene hydroperoxide-
triethylenetetramine
Catalyst: persulfate
46
2 5
16
3 8
7 8
5 9
5
61
6
17
20
2 4
2 4
4 0
6 7
TABLE 10. contcf
Styrene Derivatives II/89
Monomer k, (l/moU.s) k t ( x 10 +) (Vmolh) Temp. (C) Method Remarks Refs.
k, =2.24 x 1014
x exp(- 73510/RlJ
50
8 0
370
25f3
35f7
35f5
29f7
23f8
27f4
k,=1.09 x lo7
x exp(- 31380/RT)
66.6
66.5
k,=2.4 x lo*
x exp(- 38000 f 17OO)/RT
187.1
6 4
915
9f1. 5
19f4
19f3
15f4
l l f 2
31 f0.4
k, = 1.703 x lo3
x exp(- 9489/RT)
22.4
29.4 6 0
2 5 D 6 5
60 Al 1 1 8
2 5 Al
2 5 Al
2 5 Al
2 5 Al
2 5 Al
2 5 Al
15-30 A2
30
2 5
50- 90
8 4
k,=107.630 x exp(- 325lOIRT) - 12- 93 F 2
2 5 Fl
76 2 5 Fl
70 2 5 Fl
380f 110 40 Fl
480 f 10 70 C
16.6-17.0 1 0 0 C
256 1 9 0 50 C
1 0 7
-
2 5 Gl
kt (m,n) = 1.97 x lo* (n x m) -.I* 3 0 A3
-, p-bromo-
-, p-chloro-
-, p-cyano-
-, p-fluoro-
-, p-methoxy-
180f 10
k,=1.99 x lo7 exp(- 30780fRT)
In k, = 17.14-1.873 x 1O-9 p
- 3748/T+2.02 x 1O-6 p/T
77f4.1
79f5.1
187.0
201.0
167.0
641 f48
8 9
1 0 7
9 2
7 8
2 3
In k,= 16.09-2895O/RT (overall)
= 16.47-3003/RT (chain length 2 4)
k = 107.1*0.5
x exp[-729 f 3) x 103/RTJ
k,= 1.8861 x lo7
x exp(- 30737.52/RT)
k,=4.2060 x lOa
x exp(- 37468.93/RT)
k,=4.2458 x 10
x exp(- 39014.90/RT)
1 8 6
1 5 0
219
1 1 2
2.92
7 1
78fl2
96f9
63.2
51.1
37.9
1 3 2
0.6
46 30 Al
7 7 30 Al
3 5 3 0 Al
1 2 7 3 0 Al
1.06 0 B5
3 3 3 0 Al
5
30- 90
2 5 Fl
2 5 Fl
60 B5
91.2
2 5
3 0
2 5
2 5
2 8
Bl 7 3
Addition of 1 x 10m3 mol pyridine
Solvent: dodecane 40% by vol
1 1 8
1 0 4
1 0 0
Al
C
Solvent: bromobenzene 20% by vol 1 0 0
Solvent: diethyl malonate 20% by vol 1 0 0
Solvent: diethyl phthalate 20% by vol 1 0 0
Solvent: dinonyl phthalate 60% by vol 100
m=2500 1 1 4
Pressure 5.0 x lo7 Pa 1 0 2
9 8
9 8
Special evaluation from steady-state 1 3 4
kinetics and iii,
2 1 5
k,also given by other [M] and
s o l v e n t s
1 9 6
Solvent/ethanol (25%) 6.52 M 1 9 6
Solvent: methanol (25%) 6.52 M 1 9 6
Pressure 2.0 x lo8 Pa 1 8 6
Over a range of degree of polymn. 1 8 8
of the oolvmer radical from 40 to 410
Conversion i)-20%
TBP (rert-butyl peroxide)
k, and kt also given by other temp.
Laser-flash-initiated polymn. by
benzoin
1 7 4
1 8 9
1 5 6
n: n-mer, m: m-mer,
coupling with n-mer and m-mer
1 4 7
C
Fl
F2 Pressure 1 x 10s-2.8 x lo* Pa
223
1 6 9
214
Gl
Al
Fl
Fl
Fl
Bl
Fl
Solvent: toluene 50% (v/v)
Solvent: benzene 3 M
Solvent: chlorobenzene 3 M
Solvent: benzonitrile 3 M
Solvent: toluene
k, also given by other temp.
Solvent: benzene 4.33 M
161
161
204
204
204
1 7 8
1 6 0
1 9 8
220
1 6 4
8 3
200
Bl 131
Fl 227
Fl 30% styrene in benzylalcohol 227
Fl 30% styrene in NMP 227
Solvent: dimethylacetamide
7 8
7 8
7 8
7 8
12
7 8
References page II - 15
II/90 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 10. contd
Monomer k, (YmoYs) k t ( x 10 -6) (VmoUs) Temp. (C) Method Remarks Refs.
-,
o-methyl-
-, p-methyl-
Styrene-d s
k, = 1.67 x 10
xexp(- 58240/RT)
84
k,=2.27x 10'
xexp(- 32060/RlJ
k = 105.
x ex;(-23.O/RT)
k,=3.63x 10
x exp(- 31500/RT)
66
kt=2.55 x lo4
x exp(- 14200/R?J
30
24-55
Bl
Al
Bl
Fl
Al
Solvent: toluene 2M
73
78
73
226
1 6 8
TABLE 11. VINYL HETEROAROMATICS
Monomer k, (VmoVs) kt (x 10 -6) (YmoVs) Temp. (C) Method Remarks Refs.
N-Vinylcarbazole 6.0
2-Vinylpyridine 1 8 6
96.6
4-Vinylpyridine 12
5-Vinylpyridine 47
-, 2-methyl- 1 2 2
209
17.3
N-Vinylpyrrolidone 953
220OOf4000
0.306 1 0 Al
33 25 Al
8.9 25 B 4
3 25 B5
3.5 25 B 4
66 20 Bl
43 20 Bl
1.2 20 Bl
65 20 B4
600f200 25 Al
80
76
76
34
75
Sol ve nt : methanol 1.95 M, k, 94
also given as a function of [MI
Solvent: 50% (molar) aqueous methanol 94
Solvent: acetic acid 94
82
Sol ve nt : water 1 3 2
TABLE 12. ALDEHYDES
Monomer k, (VmoVs) k t (x 10 -6) (VmoVs) Temp. (C) Method Remarks Ref s.
Formaldehyde
-
(7-10) x 10-3 - 190 B 4 Solid monomer, gamma irradiation 9 5
TABLE 13. OTHERS
Monomer k, (VmoVs) k,(x10m6) (l/mob) Temp. (C) Method Remarks Refs.
Maleimide
-, N-rerr-amyl-
-1
N-terr-butyl-
-7
N-terr-butyl-dimethylsilyl-
-,
N-rert-octyl-
-, N-trimethylsilyl-
-, N-cyclohexyl-
69
1 0 0
0.048a,0.017b
0.021 a,0.023

b
60
60
1 2 0 0.20a 60
23 0.027a,0.015b 60
1 2 0 0.15,0.23b 60
49 0.054 50
55 0.069
C Solvent: benzene 1 M
C (a) Determined from steady-state
equation k, = (2kdf[I])/[P12,
AIBN 0.005 M;
(b) determined from second order
plot of the decay curve of the
radical concentration, ATMP
(22.azobis-(2,4$trimethyl-
pentane)) 0.02 M, for terr-BMI,
ATMP 0 . 0 1 M
C
C
C
C Solvent: benzene 0.559M,
AIBN 1.39 x IO-* M
Solvent: benzene 0.698 M,
AIBN 1.00 x lo-M, k, and k,
also given by other [Ml and [I]
205
205
205
205
205
163
163
Tic
-
M
-
-9
-3
-,
-,
-,
-,
-,
0 1
-
C,
1
1
1
1
1
1
1
t
i 1
i
i
I
TABLE 13. contd
References II/91
Monomer k, (VmoVs) k t (x 10 -6) (l/mol/s) Temp. (C) Method Remarks Ref s.
-, N-(2,6-diethylphenyl- 2 . 0 0.0078 60 C Solvent: benzene 1 M, 183
AIBN 5 x 1O-3 M
-, N-(2,6-dimethylphenyl)- 14 0.034 60 C Solvent: benzene 1 M, 1 8 3
AIBN 5 x 1O-3 M
-, N-(Cethylphenyl)- 1 2 0 0 3 . 9 60 C Solvent: benzene 1 M, 1 8 3
AIBN 5 x 10-3M
-, N-(2-methylphenyl)- 1 9 0 0 . 5 9 6 0 C Solvent: benzene 1 M, 183
AIBN~x~O-~M
-, N-(2.carboethoxyphenyl)- 9 6 0.10 60 C Solvent: benzene MAIB 0.005 M 237
-, N-dodecyl- 5 4 0.12 5 0 C Solvent: benzene MAIB 0.01 M 238
1 0 4 0 . 4 5 50 C Solvent: toluene MAIB 0.01 M 238
175 1.0 5 0 C Solvent: anisole MAIB 0.01 M 238
8 0 0 . 4 0 5 0 C Solvent: chlorobenzene MAIB 0.01 M 238
1 2 8 0.064 5 0 C Solvent: bromobenzene MAIB 0.01 M 238
1 4 9 0 . 1 7 5 0 C Solvent: methyl benzoate MAIB 238
0 . 0 1 M
386 - 5 0 C Solvent: THF, MAIB 0.01 M 238
250 5 0 C Solvent: dioxane, MAIB 0.01 M 238
235 0 . 5 5 5 0 C Solvent: ethyl acetate MAIB 0.01 M 2 3 8
1 9 6 - 5 0 C Solvent: methyl ethyl ketone MAIB 238
0 . 0 1 M
-, N-octadecyl- 3 3 0.10 5 0 C Solvent: benzene AIBN 0.20M, k, 239
and k, also given by other [I]
Oligotetramethylene glycol dimethacrylic 400 0 . 0 7 5 0 B 9 1 2 4
ester (MW 600)
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Transfer Constants to Monomers,
Polymers, Catalysts and Initiators,
Solvents and Additives, and
Sulfur Compounds in Free
Radical Polymerization+
A. Ueda
Osaka Municipal Technical Research Institute, Osaka, Japan
S. Nagai
Plastics Technical Association, Osaka, Japan
A. Introduction
0. Tables
Table 1. Transfer Constants to Monomers
Table 2. Transfer Constants to Polymers
Table 3. Transfer Constants to Catalysts and
Initiators
Table 4. Transfer Constants to Solvents and
Additives
Table 5. Transfer Constants to Sulfur
Co mp o u n d s
C. Remarks
D. References
II-97
II-98
II-98
II-1 03
II-1 06
II-1 10
II-1 50
II-1 57
II-1 59
A. I NTRODUCTI ON
The transfer reaction in radical polymerization describes a
process in which the polymer radical reacts with another
molecule (monomer, polymer, catalyst, solvent, modifier,
etc.) forming a dead polymer and new radical. This new
radical can continue the kinetic chain:
P;+RX%P,R+X
ki,X
X*+M+Pi
The dimensionless transfer constant is defined by the ratio
Cx = ktr,x/k,
where k, is the rate constant of propagation.
t Based on the tables in the third edition, by K. C. Berger and G. Brandrup.
If it is assumed that
(a) all new radicals X react only by formation of
growing polymer radicals;
(b) all polymer radicals have equal reactivities indepen-
dent of their size;
(c) all rate constants are independent of solvent;
(d) the consumption of monomer by initiation and
transfer is negligible compared with propagation;
(e) a steady-state concentration of polymer radicals is
quickly established (d[P]/dt = 0).
The application of these assumptions to the common
reaction scheme results in the following relationship of
ideal kinetics (Ref. 145):
1
-i+cc,--
[Xl
P,-Pn0 PI
P,, P,,a = number-average degree of polymerization
obtained in the presence or absence, respec-
tively, of transfer agent X.
[Ml, [X] = concentration of monomer or transfer agent,
respectively.
The left-hand side of this equation is obtained by measuring
the number average molecular weight of polymer at
different concentrations of the transfer agent X, all other
variables being kept constant. In many cases the degree of
polymerization was determined by measurement of viscos-
ity (Remark R). It should be noted that the ratio of
I I /97
II/98 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
viscosimetric to number average molecular weight shows a
considerable dependence on the molecular weight distribu-
tion.
The first term Pns of the right-hand side of this equation
is the number average molecular weight measured in the
absence of transfer agent X. This is limited to cases where
the transfer agent is a modifier. In all other cases, PnO is
calculated by combination of several kinetic expressions
and used with its numerical value:
Initiation Ri = 2fkd[I] or therm. Ri = Rt
Termination
Rt = kt[P] 2 = (kt,d + k,c)[P] 2
Propagation
R, = k, WI PI1
Number-average
molecular weight
p
II0
= 20 +fi> R,
-i-TzK
where kt, kt,d, and k,,c are the rate constants of termination,
termination by disproportionation, and termination by
combination, respectively.
The second term of the right-hand side of the above
equation is given by the following expression:
WI PI PI
cx=Ch4+c1-+cs-+cC,-+...
WI [Ml PI
where C, is the constant of chain transfer with added
polymer before starting polymerization.
The transfer constant of very reactive molecules can be
determined from the rate of disappearance of both transfer
agent and monomer:
B. TABLES OF TRANSFER CONSTANTS
TABLE 1. TRANSFER CONSTANTS TO MONOMERS
This decrease of the transfer agent concentration with
increasing monomer conversion is important in practice
because very reactive transfer agents are used up preferen-
tially, giving a broad molecular weight distribution if they
cannot be replenished.
In analogy to quickly decomposing initiators with their
criterion of half-life, one can define, in addition to the
transfer constant Cx, a half-conversion U1iZ as that
monomer conversion where the transfer agent is half
consumed:
u,p = lOO( 1 - 0.5 lcx)
The following table demonstrates (with some examples for
a calibration curve) that the half-conversion U112
decreases with increasing transfer constant Cx:
The Half-Conversion of Transfer Agents
cx U1/2(%) CX U1/2(%b)
0.1 99.9 5 13.0
0.2 96.8 1 0 6.7
0.5 75.0 20 3.4
1 50.0 50 1.4
2 29.3 100 0.7
The transfer agent must be replenished at this monomer
conversion at the latest, if polymerization is to proceed, still
yielding a narrow molecular weight distribution.
Numerous examples are known of polymerization
systems that possibly do not satisfy basic assumptions:
retardation (Remark J), induced decomposition and primary
radical termination by peroxide or hydroperoxide initiation
(Remarks C and B), diffusion control of termination
(Remark X), electron donor/acceptor complexes (Remarks
JJ), etc. Corresponding data in this table have to be used
with caution.
Monomer
T (C) CM (x104) Remarks Refs.
Acetic acid, a l l y 1 ester
80 170 29
700 27
Acrylamide 25 0.12 D 92
0.16 74
0.2 75
0.2 E 103
50 0.558 C2, F13, LL 560
60 0.651 C2, F13, LL 560
60 0.6 E 103
50 1.5 272
55 0.883 291
60 0.905 291
60 0.333 Cl, H, KK 561
60 1.05 Cl, H, KK 561
Acrylamide, N,N-dimethyl-
Acrylic acid, benzyl ester
-, butyl ester
TABLE 1. conrd
Transfer Constants to Monomers II/99
Monomer T (Cl CM (x104) Remarks Refs.
Acetic acid, butyl ester (conrd)
-,
ethyl ester
60
65
50
-, -2 ethylhexyl ester
-, methyl ester
-1 tetrahydrofurfmyl ester
-, 2-chloro-, ethyl ester
thio-, methyl ester
A&ylonitrile
Ally1 bromide
Ammonium chloride, N,N-diallyl-N,N-diethyl-
-, N,N-diallyl-N,N,-dimethyl-
Anisole, p-vinyl
Anthranilic acid, vinyl ester
Benzoic acid, vinyl ester
1,3-Butadiene, 2-chloro-
-, 1,1,2-trichloro-
1 - Bu t e n e
2-Butene, cis-
-, trans-
3-Butene-2-one, 3-methyl-
60
65
70
70
80
50
5 5
60
65
70
75
40
60
60
20
2 5
30
40
50
60
60
60
60
60
60
60
0
60
70
60
80
95
50
25
40
50
60
40
50
60
40
50
60
80
1.25
0.955
0.193
0.90
0.41
0.579
0.332
0.351
0.789
6.28
3.79
0.80
0.275
0.036
0.325
0.10
0.11
0.11
0.37
0.01
01072
0.16
0.18
0.405
0.224
0.25
0.25
4.0
3.0
560
0.18
0.105
1.5
0.17
0.050
0.27
8.2
0.26
0.3
0.333
0.57
1.02
30
1 8
7
0.198
0.74
80
6.0
7.0
2.0
4.0
2.32
1 6
3.1
5.1
7.3
3.2
4.9
11.2
3.0
5.2
10.8
4.00
Cl , H, KK
F 7
C, F17, R
C, F17, R
C, F17, R
C, F17, R
C, F17, R
F 7
,C, AA
B, k~
C, AA
C, AA
C, FlO
C, AA
c AA
C, FlO
B, AA
C, AA
C, AA
c, hi
C, AA
C, FlO
C, AA
C, F2
E
F 8
F18
F17
F16
Cl, H, KK
Cl , H, KK
Cl , H, KK
C, R, HH
Cl, F30
Cl, F30
F2
E
C
561
291
306
510
512
512
306
306
512
512
512
510
2 2 1
221
221
221
1 2 3
221
2 2 1
322
2 2 1
221
221
221
2 2 1
1 2 3
221
319
342
140
299
284
196
284
410
376
362
95
23
561
561
561
505
538
538
1 3
5 3
139
121,393
26
3 2 1
213
1 5 3
230
334
334
334
334
334
334
334
334
334
84
Remarks page II - 157; References page II - 159
II / 100 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 1. contd
Monomer
T (Cl CM (x104) Remarks Refs.
Butyric acid, vinyl ester
Carbamic acid, vinyl-, ethyl ester
Carbazole, N-vinyl-7H-benzo(2)-
Decanoic acid, vinyl ester
Ethylene
50
80
60
70
50
60
8 3
110
-, chloro-
Glutaramic acid, N,N-diisobutyl-,
vinyl ester
-, N,N-diisopentyl-,
vinyl ester
Hexanoic acid, vinyl ester
5-Hexen-3-yn-2-01, 2-methyl-
Isobutyric acid, vinyl ester
Laurie acid, vinyl ester
Maleic anyhydride
Maleic anhydride/methyl methacrylate
Maleimide, N-(3-dimethylamino-6-methyl-phenyl)
Methacrylamide
Methacrylic acid, bomyl ester
-, butyl ester
-,
tert-butyl ester
o-t-butylphenyl est er
1: p-t-butylphenyl ester
-,
n-dodecyl ester
-, 2,3-epoxypropyl est er
-, ethyl ester
-3 o-ethylphenyl ester
-, p-ethylphenyl ester
-, glycidyl ester
-, hexadecyl ester
-, isobomyl ester
130
50-70
20
2 5
30
40
50
60
70
26.7
22.3
0.25
11
45.5
0.4
1.4
4.2
5.0
5.32
1.1
3.5
9.0
0.0
1.6
4.7
11.2
5
3.2
3.2
7.0
6.25
19.4
50
6.4
7.8
8.5
11
13.5
10.8
12.3
12.8
23.8
F4
Y
7 1
200
1 1 7
522
7 1
102
102
102
204
205
102
102
102
259
102
102
102
218
94
315
425
58
463
246
379
379
379
392
58
379
379
379
58
60 42 C, FlO 106
60
70
80
80
60
80
50
75
60
50
60
60
50
60
70
60
60
60
60
45
60
80
90
60
60
60
70
60
5 1
5 1
5 1
36
5.0
46
45.5
750
100
720
10 x 10s
2.85
0.54
120 x 10s
0.14
0.35
30.41
2.01
80 x lo5
0.59
0.248
0.259
0.456
0.442
3.63
1.36
45 x 10s
0.14
1.85
C, FlO
C, FlO
C, FlO
C
F2
JJl
JJl
C
C
JJl
c c
c c
c c
c c
C
C
JJl
107
107
1 0 7
200
226
200
7 1
1 7 5
367
542
515
162
233
515
264
9
550
550
515
1 9 8
1 9 3
1 9 3
1 9 3
1 9 3
550
550
515
1 3 8
162
R, F2
W 5
w4, w5
w4
Q W
Q W
w4, w5
w4, w5
w4
C, F21, W5
w4, w5
w4, w5
w4
w3
Y
F 5
F 3
F4
C, F26
Y
F 3
TABLE 1. contd
Transfer Constants to Monomers II / 101
Monomer T (Cl
CM (x104) Remarks Refs.
Methacrylic acid, isobutyl ester
-, n-nonyl ester
-, phenyl ester
-,
o-tolyl ester
-, p-tolyl ester
Methacrylonitrile
Methyl methacrylate
Naphthalene, I-vinyl-
1,4-Pentadiene, 1,1,2,3,3,4,5,5-octafluoro-
Phemol, o-vinyl-
2-Picoline, 5-vinyl-
I-Propene, 2-chloro-
-, 2-methyl-
Propionic acid, vinyl ester
3 5
50
60
8 0
100
60
21
60
60
60
2 5
60
70
80
0
30
40
50
60
65
70
75
80
90
100
120
50
60
70
110
70
70
80
40
50
60
-
50
0.189
0.179
0.14
0.165
0.224
0.301
0.382
105 x 10s
400
0.61
1.13
1.06
2.08
5.81
8.00
10.05
0.128
0.148
0.117
0.260
0.15
30 x 105
242 x lo5
0.10
0.15
0.477
241 x lo5
0.85
0.07
0.10
0.103
0.18
240 x lo5
0.20
0.17
0.20
0.23
0.265
0.29
0.30
0.45
0.807
1.37
240 x lo5
0.27
0.33
0.60
0.70
0.25
0.40
0.10
0.38
0.58
290
310
300
500
130
6.7
1600
2.5
4.4
6.9
3.6
48.9
DD
DD
F2
DD
DD
DD
JJl
R
C
C
C
Z
Z
Z
Z
D
JJ2
JJl
F2
D
JJl
C
J J O
C, FlO
C, F17
D
JJl
C, FlO
C
C, Fll
C, F2
WlO
1 9 3
1 9 3
264
264
1 9 3
193
1 9 3
515
534
550
550
550
125
125
125
125
69
1 8
69
224
508
525
528
147,327
1 4 5
224
528
69
274
34,290,317
316
145
556
1 2 3
1 2 3
267
1 4 5
440
1 2 3
123
104
224
459
528
1 2 3
1 2 3
1 2 3
1 2 3
1 4 5
1 2 3
147
1 4 5
1 4 5
216
216
216
68
186
11
27
334
334
334
1 5 8
7 1
Remarks page II - 157; References page II - 159
II f 102 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 1. cont' d
Monomer T (2 CM (xlo4) Remarks Refs.
Pyridine, 2-vinyl-
-, 4-vinyl-
2-Pyrrolidinone, l-vinyl-
Stearic acid, vinyl ester
Styrene
15- 35
2 5
20
50
0
25
21
30
45
50
60
67. 8
70
15
80
80. 3
90
99
100
110
117
132
Styrene, p-boromo-
-, o-chloro-
50
30
50
0
6. 1
4. 0
69. 8
0
0. 108
0. 219
0. 358
0. 31
0. 2
0. 32
0. 3
0. 35
0. 40
0. 50
0. 6
0. 62
0. 65
0. 78
0. 07
0. 6
0. 6
0. 6
0. 75
0. 79
0. 85
0. 92
1.1
1.37
20 x 105
1.0
0
0.6
0. 6
0. 8
0. 96
1. 16
1. 35
2. 0
0
1. 6
5. 0
5. 00
0. 7
0. 75
1.00
4. 0
0. 85
1. 25
1. 47
1. 79
1. 5
1. 72
1. 8
1. 83
2. 80
1. 40
2. 45
3. 0
3. 4
5. 33
23
0. 25
0. 25
0. 28
D
BB
A
BB
BB
H
F2
C, H
C
A, K
B, CH
A
C
C
BB
A
A, F
C
JJl
C, FlO
BB
B, H
A
A
C, F2
C, FlO
C
C, F2
C, Fll
BB
BB
C F
A
A
A
A F
A
A
A
A F
A
A
C
C H
38
283
59
71
360
17, 69
69, 245
17
145
318, 360
245
360
354, 355
318, 327
388
145
145
388
146
467
34, 171, 223
145, 240
318, 360
467
145
145
447
53
234
515
34
123
104
360
388
67
145
145
123
123
123
123
123
98
360
318
34
360
145
145
145
98
145
145
145
145
318
145
145
145
145
192
62
60
60
Transfer Constants to Polymers II / 103
TABLE 1. contd
Monomer TV-3 CM (xlo4) Remarks Refs.
Styrene, p-iodo-
Succinimide, N-vinyl-
Valerie acid, 4-methyl-, vinyl ester
Vinyl acetate
50
55
80
- 60
- 4 0
- 20
- 20
0
20
25
40
4 5
50
60
65
70
Vinylidene chloride 50
60
1.9
0.55
24.8
1.9
0.40
0.60
0.70
0.30
0.50
0.90
0.96
0.94
0.90
1.3
1.45
2.4
10.7
1.29
1.32
2.0
0.25
0.41
0.54
0.61
1.29
2
4.55
20
1.75
1.8
1.9
1.91
1.93
2.0
2.1
2.4
2.5
2.5
2.6
2.8
2.1
2.4
2.9
22
38
Fl
C
D
I7
I7
D
w14
w15
C
1 1 2
C
C
C
1 1 3
R
R
56
93
200
158
464
464
464
241
241
86
464
328
241
86
86
202
69
1 2
328
5 1
466
265
265
265
1 2
552
7 1
225
1 2
466
124
328
348
231
145
294
86
1 6 7
167
80
466
403
86
541
541
TABLE 2. TRANSFER CONSTANTS TO POLYMERS
Polymer
T (C)
cp (x104) Remarks Refs.
Acrylamide, N,N-dimethyl-
Poly(N,N-dimethylacrylamide)
Acrylic acid, ethyl ester
Poly(methy1 methacrylate)
-, methyl ester
Poly(isoprene)
-, chlorinated
Poly(methy1 acrylate)
Poly(methy1 methacrylate)
Acrylonitrile
Cellulose
50 0.61 272
60 12800 M6 120
75 12.6 C, F2 308
60 0.5 L 212
1.0 L 105
60 18000 M6 120
60 1.0 L N 361
11 L, M4 361
20 L, M 5 361
Remarks page II - 157; References page II - 159
II / 104 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 2. contd
Polymer T (Cl cp (xlO4) Remarks Refs.
Acrylonitrile, (contd)
Poly(acrylonitrile)
Poly(methy1 methacrylate)
50
60
60
Poly(sarcosine)
1,3-Butadiene
Poly( 1,3-butadiene)
Ethylene
-, chloro-
Poly(viny1 chloride)
Hexanoic acid, vinyl ester
Poly(oxyethylene), dodecyl ether
Methacrylic acid, butyl ester
Poly(methy1 methacrylate)
-, dodecyl ester
Poly(methyl methacrylate)
-, ethyl ester
Poly(isoprene), chlorinated
Poly(viny1 chloride)
Methyl methacrylate
Poly(ethylene)
Poly(isoprene), chlorinated
Poly(methy1 methacrylate)
Poly(propylene)
Poly(styrene)
Poly(viny1 acetate)
Poly(viny1 chloride)
Poly(viny1 urethane)
Rubber, natural
2Pyrrolidinone, 1-vinyl-dextran
Dextran
60
4.7
3.5
0.2
240
900
1270
400
376
1 3 5
2 5
2 5
25
2 5
23
50 11
174.8 108.40
201.6 150.70
215.0 194.81
231.2 214.46
230.3 337.31
229.2 256.85
230.3 195.81
230.4 199.89
230.5 155.78
256.0 348.46
C, W20, F32
C, W20, F32
C, W20, F32
C, W20, F32
C, W22, F32
C, W21, F32
C, W20, F32
C, W19, F32
C, W18, F32
C, W20, F32
142
540
540
540
540
540
540
540
540
540
540
50 5 L 2 1 1
60 780 278
60 7700 120
60 12800
M6
M6
C, F2
C, F28
120
70 18.3
70 21.0
308
308
50
80
40
50
0.6
23.4
1.5
360
0.22
1.5
1.5
360
360
1000
0.1
1.5
2.1
360
2.48
0.22
1000
0.04
1.0
0.42
0.75
2.20
2.95
2.0
2.8
11
10.0
1 7
10.9
11.0
C, F17
N
M
N
N
M
M
N
M
N
209
307
326
326
1 4 7
326
321
326
327
1 4 7
1 0 5
326
262
326
262
1 4 7
147
292
209
292
148
262
262
263
263
250
308
1 5 7
258
258
60
80
90
50
130
50
60
80
60
80
-
70
50
50
50
F14
L
N
M2
M 3
M
M
N
M
C
C, F28
c, F8
C
5 333
5.87 203
TABLE 2. contd
Transfer Constants to Polymer5 II/105
Polymer T (C) cp (x104) Remarks Refs.
St y r e n e
Poly(oxyadipoyloxy-2,2-dibromomethyl trimethylene)
Poly(oxyethylene)
-, dodecyl ether
Poly(oxythexamethyleneoxy sebacoyl)
Poly(methy1 methacrylate)
Poly(propylene)
Poly(styrene)
Poly(viny1 acetate)
Poly(vinyl chloride)
Poly(2-vinylpyridine)
Vinyl acetate
Poly(onyethylene)
130
154
100
130
50
60
-, dodecyl ether 60
Poly(methyl methacrylate)
Poly(styrene)
Poly(viny1 acetate)
60
70
70
60
80
50
60
80
loo
60
66
130
50
55
60
73.5
85
90
100
110
60
75
40
60
75
- 15
0
11
2 1
3 1
40
50
4.05
1 9
1 4
20
1 3
0.4
< 0.3
1110
1140
16.4
17.5
5.7 x 104
32 x lo4
3.74
6.04
0.025
26
0.3
0.30
1.9
4.5
14.0
16.6
1 5
0.8
1.9
3.1
15.4
15.8
16.6
1.0
1.4
5.8
2.0
9.2
10.8
1.8
1.5
6.6
9.2
160
8-10
1 7
40
1 0
40
750
2 1
26
1 2
1 5
1 9
0.36
0.5
1.7
2
4
1 6
11.2
30.9
32.0
0.06
L
Ml0
Ml0
C, N
N
M
N
M
Ml
Ml
M?
M6
C
L
Ml
Ml
C
C
N
N
M
MS
M9
0
0
0
w15
325
562
562
278
394
327
326
326
327
64
64
120
120
262
262
292
486
292
207
44,148
327
327
176
177
105
73
1 0 5
64
64
176
8
8
327
276
1 7 7
176
43
43
263
263
250
279
277
277
277
277
271
263
263
263
263
263
97
97
350
1 4 5
145
145
1 2
43
263
265
Remarks page II - 157; References page II - 159
0.11 w14 265
0.15 265
3 43
10.2 1 2
60 1.2 124
1.4 168,169
1.8 348
1.9 328
2.5 329
3.0 1 6 5
4.0 1 0 5
6.8 1 2
8.0 105
47.0 263
60-70 3.5 P 350
70 2 0 403
4 403
60 0.21 VCL-Part 166
3.0 VOAC-Part 166
II / 106 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 2. contd
Polymer
T (Cl cp (x104) Remarks Refs.
Vinyl acetate (contd)
Poly(viny1 acetate) (cant d)
Poly(viny1 acetate-co-vinyl chloride)
TABLE 3. TRANSFER CONSTANTS TO CATALYSTS AND INITIATORS
Catalyst/Initiator
T (Cl CI Remarks Refs.
Acrylamide
Bisulfite ion
Hydrogen peroxide
Potassium persulfate
-
75 0.17 F13 352
2 5 0.0005 D 92
50 0.0258 F13, LL 560
60 0.028
F13, LL 560
Acrylic acid, benzyl ester
Isobutyronitrile, 2,2-azobis-
-, ethyl ester
Isobutyronitrile, 2,2-azobis-
-. methyl ester
Benzoyl peroxide
2-Butanone, peroxide 65
tert-Butyl hydroperoxide
tert-Butyl peroxi de
Chloroforn-KuCl~
Acrylonitrile
Isobutyronitrile, 2,2-azobis-
Azodiphenylmethane, benzyl-
-> cyclohexyl-
55 0 291
60 0 291
6 5 0 291
65 0 306
55
60
6 5
70
70
75
60
70
65
70
75
120
50 0
60 0
50 0.07
60 0.07
80 0.07
50 0.02
60 0.04
80 0.05
0.0143
0.0246
0.0375
0.01
0.05
0.05
0.05
0.077
0.113
0.113
0.01
0.0266
0.00047
0.00082
0.00111
600
221
221
221
C, FlO 322
221
FlO 123
221
221
FlO 1 2 3
221
221
221
221
221
221
Q(5- 19), Fl 551
F16 362
95
R 536
R 536
R 536
R 536
R 536
R 536
TABLE 3. contd
Transfer Constants to Catalysts and Initiators II / 107
Catalyst/Initiator T (C) CI
Remarks Refs.
Azodiphenylmethane (contd)
-,
l-phenylethyl-
-,
2-propyl-
Benzoic acid, vinyl ester
Benzoyl peroxide
Isobutyronitrile, 2,2-azobis-
3-Buten-2-one, 3-methyl-
Benzoyl peroxide
Et h y l e n e
Azoethane, 1,l -dimethyl-
Ethylene, chloro-
Valeronitrile, 2,2-azobis[2,4,4-trimethyl-
Maleic anhydride
Benzoyl peroxide
Methactylonitrile
Isobutyronitrile, 2,2-azobis-
Methyl methacrylate
Acetophenone, 2-diazo-2-phenyl-
p-Anisoyl peroxide
Benzoyl peroxide
2.Butanone peroxide
tert-Butyl hydroperoxide
terf-Butyl peroxide
Butyronitrile, 2-ethyl-,2,2-azobis-
-, 2-methyl-, 2,2-azobis-
-, 2,3,3&methyl-, 2,2-azobis-
Cinnamoyl peroxide
Cobalt, [bis-[u-[(2,3-butane-dionedioximato)(2-)-0,0]]
tetrafluorodiborato(2-)-N,N,N,N]-
Cyclohexanecarbonitrile, 1,l -azodi-
Cyclopropanecarboxylic acid, l-methyl-
2-(9-anthryl)-, methyl ester
Hydrogen peroxide
Hydroperoxide, a,cc-dimethylbenzyl
Isobutyronitrile, 2,2-azobis-
60
Methane, diazodiphenyl-
Palmitoyl peroxide
70
60
60
50
60
70
60
Peroxide, bis(m-chlorobenzoyl) 60
- bis(o-chlorobenzoyl) 60
-, his@-chlorobenzoyl) 60
-, bis(m-nitrobenzoyl) 60
50 0.1
60 0.1
80 0.1
50 0.02
60 0.04
80 0.05
80
80
80
8 3
0.0527
0
0.0509
0.5
0. 5 1
25
75
60
70
60
50
60
65
70
0.85
2.63 1 7 5
0 1 2 5
75
0.0
0.037
0.01
0
0.02
0.0025
0.00698
0.0033
0.0033
0.0040
0.0092
0.00553
0.00667
0.007 1
0.0089
0.0111
0.0128
1.27 x [cat]
< 0.0001
0
0
0
0.009
36000
80
60
20
60
60
60
60
R 536
R 536
R 536
R 536
R 536
R 536
26
26
84
D;W 204
D. W 205
425
459
316
1 4 5
34
1 2 1 4 5
F2 1 2 3
F17
FlO 1 2 3
Fll 123
1 2 3
Fll 1 2 3
F2 1 2 3
FlO 123
1 2 3
F17 1 2 3
1 2 3
34
C, D 3 5
317
317
317
2500 F17
0 317
0.002
0.046
0.33
0
0
0.0
0
0.16
0.003
0.019
0.35
0.8
0.009
0.012
440
Fll
F2
FlO
Ill
FlO
110
1 2 3
1 2 3
316
563
563
290
34
327
34,290,3 17
267
316
1 4 5
316
316
290
1 4 5
316
316
Remarks page II - 157; References page II - 159
II / 108 TRANSFER CONSTANTS I N FREE RADI CAL POLYMERI ZATI ON
TABLE 3. contd
Catalyst/Initiator T (0 CI
Remarks Refs.
Methyl methacrylate (contd)
-, his@-nitrobenzoyl)
-, bis(m-phenylazobenzoyl)
2-Tetrazene, 1,1,4,4-tetramethyl-
o-Toluoyl peroxide
Valeronitrile, 2-methyl, 2,2-azobis-
Styrene
Acetyl peroxide
p-Anisoyl peroxide
Benzoyl peroxide
Cobalt, [Bis-[y[(2,3-butane-dionedioximato)(2-)-O,O]]
tetrafluorodiborato(2-)-N,N,iV,N]-
Di-3-phenylazo benzoyl peroxide
2-Butanone, peroxide
tert-Butyl hydroperoxide
Butyl peroxide
set-Butyl peroxide
tert-Butyl peroxide
Butyryl peroxide
Cinnamoyl peroxide
Crotonyl peroxide
Cyclohexanone peroxide
Ethyl peroxide
Formamide, 2-cyano-2-propylazo-
Furoyl peroxide
Hexanoyl peroxide
Hydroperoxide, cr,a-dimethylbenzyl
60
50
30
60
6 0
70
70
22
50
60
70
80
50
70
90
50
70
75
60
70
80
60
80
60
80
60
70
80
70
70
70
60
60
80
100
70
70
40
0.144 316
0.00001 C 282
0.038 D 483
0.046 316
0.06 Ill 1 4 5
0 317
0
0.074
0.1
0.13
0.048
0.055
0.101
0
0.075
0.12
0.18
0.13
0.813
1500
D
C
87,217
a7
65
58
1 7 1
240
234
217
87
67
58,65
58,65
F17 530
563
6.7
5.5
4.8
0.46
0.0667
0.1250
0.1670
0.1250
0.1670
0.2000
0.243
0.035
0.05 1
0.060
0.063
0.064
0.066
0.003
0.00076
o.ooo92
0.0029
0.0004
0.0021
0.00023
0.0003
0.0006
0.00086
0.0013
0.039
0.0022
0.0033
0.018
1.10
0.146
0.062
0.00066
0.0024
0.17
*
0.23
0.166
0.052
R 527
R 527
R 527
H 388
F2 1 2 3
FlO 1 2 3
Fll 123
F2 123
FlO 123
Fll 123
123
1 7 1
H 388
399
F6 400
400
F2. F5 400
385
F9 302
F2 302
F9 302
F2 301
F2 301
F9 303
303
F2. F12 303
300
304
F 2 400
F 2 303
385
87
87
87
33
F 2 301
F2 301
47
87
87
388 H
TABLE 3. contd
Transfer Constants to Catalysts and Initiators II / 109
Catalyst/Initiator
T (Cl Cl
Remarks Refs.
Styrene (contd)
Hydroperoxide, a,a-dimethylbenzyl (conrd)
-,
cc,cc-dimethylbenzyl,
p-isopropyl-
Isobutyronitrile,2,2-azobis-
Isopropyl peroxide
Lauroyl peroxide
p-Menth-8-yl hydroperoxide
Myristoyl peroxide
84
5 0
70
2-Naphthoyl peroxide 70
Nickel peroxide 60
Octanoyl peroxide 70
Oleoyl peroxide
Palmitoyl peroxide
Peroxide, his@-acetoxybenzoyl)
-, bis(m-bromobenzoyl)
-, bis(o-[bromobenzoyl)
-, his@-bromobenzoyl)
-, his@-tert-butylbenzoyl)
-, bis(m-chlorobenzoyl)
Peroxide, bis(o-chlorobenzoyl)
-, bis(p-chlorobenzoyl)
-> bis(p-cyanobenzoyl)
-, bis(2,4-dichlorobenzoyl)
-, bis(a,cr-dimethylbenzyl)
-, bis(m-fluorobenzoyl)
-, bis(o-fluorobenzoyl)
-3 his@-fluorobenzoyl)
-, bis(hydroxyhepty1)
-, bis(m-iodobenzoyl)
-, his@-methoxycarbonyloxy-benzoyl)
-, bis(m-nitrobenzoyl)
-, bis(p-nitrobenzoyl)
-, bis(m-phenylazobenzoyl)
-, bis(5-phenyl-2,4-pentadienoyl)
-, bis(2-thiophenecarbonyl)
-I
tert-butoxymaleoyl
-, rert-butoxyphthaloyl
-, butylidenebis[tert-butyl
-1 set-butylidenebis[tert-butyl
-, isobutylidenebis[tert-butyl
-> isopropylidenebis[tert-butyl
Pinanyl hydroperoxide
50
60
70
70
50
60
60
80
70
70
70
70
70
50
70
70
70
70
22
70
70
70
60
70
50
70
70
70
50
70
70
70
70
70
9 0
70
50
70
70
70
80
9 0
80
9 0
8 0
9 0
80
9 0
70
0.069
0.063
0.082
0.10
0.033
0
0
0
0
0.012
0.16
0.0003
0.0015
0
0.024
0
0.048
0
0.116
0.178
0.00265
0
0.098
0.154
0.142
0.187
0.465
1.0
2.17
0.193
0
0.346
2.0
1.91
0.216
0.804
2.9
2.6
0.01
0.246
0.40
0.219
< 0.005
0.262
0.208
6.2
7.4
5.5
4.8
5.24
0.23
0.38
1.52
0.018
0.00077
0.00140
0.00072
0.00115
0.00083
0.00155
0.00040
0.00105
0.026
H
H
H
F2
H
F2
F2
H
C. F2
D
H
H
C
C
388
171
388
3 9 9
388
327
388
1 7 1
318
468
447
301
301
217
8 7
217
388
217
8 7
87
266
217
8 7
8 7
8 7
87
87
58,65
87
87
8 7
8 7
65
87
217
87
217
217
388
87
87
87
388
8 7
8 7
87
87
281
281
87
65
65
87
87
411
411
411
411
411
411
411
411
388
Remarks page II - 157; References page II - 159
II / 110 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 3. cont' d
Catalyst/Initiator
T (Cl CI Remarks Refs.
Styrene (co&d)
Pivalonitrile
Propylene, oxidized
Propyl peroxide
Sorboyl peroxide
Stearoyl peroxide
Succinonitrile, tetramethyl-
2-Tetrazene, 1,1,4,4-tetramethyl-
o-Toluoyl peroxide
p-Toluoyl peroxide
60
60
70
60
70
70
60
30
70
50
70
0. 000038 468
1.01 396
1.14 396
0. 00084 305
1. 19 87
0. 154 87
0. 000037 468
0. 038 D 483
0. 175 87
0. 17 65
0. 003 87
0. 19 65
0. 065 87
0. 59 426
i
9-Undecenoyl peroxide
Valeronitrile, 2,2-azobis[2,4&rimethyl-
Vinyl acetate
Benzoyl peroxide
70
25
60 0. 032 465
0. 09 231
0.15 80
0. 040 466
0. 025 466
0. 055 466
0.10 80
0.10 80
0.17 13 145
0. 24 80
0. 6 13 145
0. 25 80
3. 5 13 145
0. 17 80
0. 17 13 145
65
50
60
60
60
Isobutyronitrile, 2,2-azobis-
Lauroyl peroxide
Palmitoyl peroxide
Peroxide, bis(m-bromobenzoyl) 60
-, bis(o-bromobenzoyl) 60
-, bis(p-bromobenzoyl) 60
-1
bis(o-chlorobenzoyl) 60
TABLE 4. TRANSFER CONSTANTS TO SOLVENTS AND ADDITIVES
Solvent/Additive T (0 cs (XlOQ Remarks Refs.
Acetic acid, ally1 ester
Benzene
p-Benzoquinone
-, 2,3,5,6-tetrachloro-
-, 2,3,5,6-tetramethyl-
-, 2,3,5-trichloro-
Carbon tetrachloride
Phosphorus trichloride
Acrylamide
Acetonitrile
tris(2-Carbamoylethyl)amine
Iron(II1) chloride
Isopropyl alcohol
Methanol
Propionamide
80 21. 0
80 5. 2 x lo5
80 16 x lo5
80 4.14 x 104
80 5. 5 x 105
100 2. 0 x 104
40 1.0 x 104
273
27
27
27
27
210
214
J
J
J
J
C
C, D
5. 5
85
4. 26 x lo4
1 9
7. 2
0. 13
220
64
0. 204
5. 8
F13
F13
564
564
75
353
353
130
103
103
437
444
25
50
80
30
25
60
25
40
F13
F13, S
C, F13
E
E
C, F13
F13
Acrylic acid, butyl ester
Aniline, N,N-dimethyl-
Ethanol
Methanol
Propanol
Iso-propanol
50 380
80 4. 28
80 0. 47
80 3. 78
80 14. 12
161
548
548
548
548
A R
F31, A, R
A, R
A, R
TABLE 4. contd
Transfer Constants to Solvents and Additives II/111
Solvent/Additive
T ((3
cs (x104) Remarks Refs.
Acrylic acid, ethyl ester
Acetic acid
Acetone
Acetonitrile
Aniline, NJ-dimethyl-
Benzene
-, bromo-
-, chloro-
-, ethyl-
2-Butanone
Butyl alcohol
set-Butyl alcohol
rert-Butyl alcohol
Butyric acid
Carbon tetrachloride
Chloroform
Cumene
Cyclohexane
5 0
8 0
100
4 0
6 0
8 0
100
5 0
6 0
8 0
100
5 0
5 0
6 0
8 0
100
6 0
8 0
100
4 0
8 0
100
4 0
6 0
8 0
100
5 0
6 0
8 0
9 0
4 0
6 0
8 0
100
4 5
6 3
8 0
100
4 0
6 0
8 0
100
8 0
4 0
6 0
7 0
8 0
100
4 0
6 0
7 0
8 0
100
5 0
6 0
8 0
9 0
5 0
6 0
0.176
0.537
1.05
0.207
0.27
1.10
2.30
0.158
0.245
0.55
1.43
2 3 0 0
0.016
0.22
0.27
0.45
0.525
2.2
0.163
0.685
3.34
0.054
0.37
1.68
0.668
11.6
16.80
28.7
1.44
0.151
1.92
3.29
4.45
1.28
2.91
5.85
12.6
10.6
18.5
22.20
31.5
0.068
0.17
0.712
1.64
0.855
0.332
0.90
3.2
1.13
1.55
2.80
0.195
0.89
1.57
1.49
4.74
11.7
13.8
22.2
26.0
28.9
0.48
0.61
A
A
C
A
A
A
A
F16
C
C
A
A
A
A
A
A
A
A
C
A
A
A
A
A
A
A
A
A
C
A
A
C
C
A
A
A
A
C
4 7 2
471
4 7 2
4 7 2
134
471
4 7 2
4 7 2
4 7 2
471
4 7 2
2 2 8
4 7 2
4 7 2
1 3 3
134
471
4 7 2
4 7 2
471
4 7 2
4 7 2
471
4 7 2
4 7 2
4 7 2
471
4 7 2
4 7 2
134
4 7 2
471
4 7 2
4 7 2
4 7 2
471
4 7 2
4 7 2
4 7 2
471
4 7 2
4 7 2
4 7 2
471
4 7 2
471
4 7 2
4 7 2
4 1 6
134
471
4 7 2
4 7 2
134
134
471
4 7 2
4 7 2
4 7 2
471
4 7 2
4 7 2
4 7 2
134
Remarks page II- 157; References page II- 159
II / 112 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (Cl
cs (x104) Remarks Refs.
Acrylic acid, ethyl ester (contd)
cyclohexane (contd)
Dimethylformamide
Ethanol
Ethyl acetate
Formic acid
Heaxane
Isobutyl alcohol
Isopropyl alcohol
Methanol
Propanol
To l u e n e
-, 2-ethylhexylester
To l u e n e
-,
methyl ester
Acetone
Acetophenone
Aluminum, triethyl
Aniline
-,
N,N-dimethyl-
-, m-nitro-
-, p-nitro-
Anisole, m-nitro-
Anthracene
Benzene
-, chloro- 80
-, o-dichloro- 80
-, m-dinitro- 50
-9 ethyl- 80
-, nitro- 50
-, 1,3,5trinitro- 50
Benzoic acid, p-nitro- 50
Benzonitrile 50
Copper(I1) chloride 120
Phosphine, tributyl- 60
Phosphorus trichloride 40
Propanol 80
Silane, dimethyphenyl- 60
-, methyldichloro- 60
-, tetraethyl- 60
-, trichloro- 60
80
100
50
80
50
60
80
100
80
50
60
80
100
45
63
80
100
-
80
60
80
80
40
*z
70
80
100
70 28.70
80 2.13
60
80
50
60
50
50
50
50
50
50
80
1.22
3.08
0.1
4.38
0.298
0.448
0.69
0.89
1.82
0.046
0.524
0.593
0.97
1.46
2.1
3.31
4.65
8.06
2 1
28.70
0.32
1.70
0.36
4.73
0.88
0.611
0.929
1.37
1.84
2.60
6.80
0.23
0.622
1.1
<2.5
480
< 1.0
60
42.1
26.7
72.7
1000
0.326
0.45
0.52
0.986
0.71
309
6.056
46.4
2040
107
< 1.0
600
1890
1000
3.92
400
1200
33.1
1600
A
A
F7
A R
C
A
A
A
A
A
A
A
C
A R
C
4
A, R
AR
C, F17, R
C, F17, R
C, F17, R
C
A
A
C, F17, R
C, F17, R
C
C
F2, S
F16
C
C
C
F34
F2
C, D
A R
A R
A, R
F2
A R
471
472
510
548
472
472
134
471
472
471
472
472
471
472
472
472
471
472
445
548
134
472
548
548
472
512
512
512
134
471
471
512
512
470
332
1 1 1
15
156
15
228
15
15
1 5
1 5
332
1 1 1
1 1 1
332
1 1 1
15
332
15
15
15
15
565
156
214
548
539
539
1 5 6
539
TABLE 4. contd
Transfer Constants to Solvents and Additives I I / 113
Solvent/Additive T (Cl cs (x104) Remarks Refs.
Acrylic acid, methyl ester(contd)
-, triethyl-
triphenyl-
i;earic acid, methyl ester
To l u e n e
-, m-nitro-
-, p-nitro-
Triethylamine
Tripropylamine
-1 tetrahydrofurfuryl ester
Carbon tetrachloride
Acrylonitrile
Ac e t a l d e h y d e
Acetamide, N,N-dimethyl-
Acetic acid
Ac e t o n e
Acetonitrile
Acrolein, bis(2-ethoxyethyl)acetal
bis(2-butoxyethyl)acetal
kminum, hydrodiisobutyl
-1 triethyl
triisobutyl
kiline
-, N,N-diethyl-
Aniline, N,N-dimethyl- 40
An t h r a c e n e
Ar a bi nos e
Be n z e n e
-, bromo-
-1 tert-butyl-
-, chloro-
-, ethyl-
-, iodo-
Benzoic acid, vinyl ester
p-Benzoquinone
Borane, tributyl
Z-Butanone
-, 3-methyl-
1-Buten-3-yne
Butyl alcohol
secButy1 alcohol
rerr-Butyl alcohol
60
60
60
60
80
50
50
60
60
40
-
50
50
50
50
60
50
60
60
60
60
60
100
100
40
50
60
40
50
60
50
60
50
60
60
60
60
60
60
60
65
50
60
60
60
50
60
60
60
300
800
0.751
2.7
1.775
2.7
41.2
48.6
400
470
1.0
1 4
47
4.945
5.05
0.81
1.7
1.13
0.7
2.0
120
90.5
3940
590
17.0 x 104
28.0 x lo4
32.0
44.0
9600
1.22 x 104
215
5.81 x lo4
359
9.38 x lo4
547
14.3 x 104
605
1.19 x 104
708
1040
1.5 x 104
1.54 x 104
870
964
2.18 x lo4
1.8 x lo4
13.0
2.46
1.36
1.93
0.79
35.73
5.19
1400
1.3 x 104
6470
6.43
21.08
3800
15.42
97.55
0.44
A, R
A, R
C
F2
c, F2
F
F7
F14
F14
F
F14
F15
F7
F7
F7
F7
F7
F7
F2, G
R J
F16, G, J
F16, G, J
F2, J
F16, G, J
FZ J
F16, G, J
F2, J
F16, G, J
F2, J
F16, G, J
F2, J
F16, J
F16, G, J
J
F2, J
F16, G, J
F8
G
G, S
G
G S
G
3, S
F7
G
G
F7
G
G
G
539
539
441
21,24
332
1 1 1
1 5
1 5
24
156
319
436
377
375
197
377
377
95
377
86
499
156
156
156
247
247
229
229
227,229
229
229
229
229
227,229
229
229
229
229
229
1 6 1
228
227,229
24
229
229
1 5
361
95
95
95
95
95
95
136
1 5
156
95
95
377
95
95
95
Remarks page II - 157; References page II - 159
II/ 114 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (Cl cs (xlO4) Remarks Refs.
Acrylonitrile (contd)
Butyric acid, 4-hydroxy-y-lactone
Cadmium, dibutyl 60
Carbonic acid, cyclic ethylene ester 50
Carbon tetrabromide
Carbon tetrachloride
Chl oroform
Copper(I1) chloride
Copper(I1) sulfate
Crotonaldehyde
Crotononitrile, trans-
Cumene
Cyclohexane
metbyl-
gmethylamine
m-Dioxane, 5,5-dimethyl-2-vinyl-
m-Dioxane, 5,5-dimethyl-2-vinyl-
-, 4-methyl-2-vinyl-
- , 2-vinyl-
1,3,-Dioxolane, 2-vinyl-
1,3-Dioxolane-4-methanol, 2-vinyl-
Diphenylamine-T
Erytbritol
Et hane, 1,2-dichloro-
-, 1,1,2,2-tetrachloro-
-, l,l,l-trichloro-
-, 1,1,2-trichloro-
Ethanol, 2,2-iminodi-
-, 2,2,2-nitrilotri-
Ether, dodecyl vinyl
Ethyl acetate
Formamide, N,N-dimetbyl-
50
60
50
60
60
80
60
80
35
60
3 5
50
50
60
60
60
50
60
60
60
60
60
60
60
60
60
60
60
30
30
50
60
20
25
40
50
60
0.658
0.74
5.5 x 104
0.073
0.33
0.39
0.474
0.5
0.511
1.0
0.128
400
500
1900
0.85
1.13
5.64
5.90
1.8 x IO5
1.9 x 10s
3.2 x IO5
10 x 10s
1900
2800
3000
1.07 x 104
1.35 x 104
3.93 x 104
13.6 x IO4
21.0 x 104
47
1 9
41.41
2.06
2.31
175
2.20
4.40
2.71
16.60
2.40
700
12.8
1.47
3.11
1.25
1.68
10.1
76.0
4.95
2.54
1.4
4.97
3.24
1.0
2.70
2.78
2.8
2.83
1 0
2.412
4.494
5.0
F-l
E
F7, J
G
C
G
C
U(O.01)
U(O.1)
U(1.0)
F 7
F13, J
J, V(O.0001)
J, U(O.01)
J, V(O.001)
J, U(O.1)
J, V(O.01)
J, U(l.0)
J, W.1)
F7
F7
G
G
G
Iv
F7
F7
F7
F7
F 7
F7
F8
G
G
G
G
F13
F13
C
G
C J, fl
Q J
E
F15
375
374
156
293
1 9 7
374
375
404
458
356
293
493
20
24
96
336
95
336
402
402
402
37
402
402
402
402
402
402
402
402
371
377
95
95
95
371
498
498
498
498
498
6 1
361
95
95
95
95
416
476
4
9 5
248
9 1
458
347
374
1 9 7
377
375
356
347
22
8 6
TA
-
Sol
-
A C
1
1
t
(
TABLE 4. contd
Solvent/Additive
T ((3
Transfer Constants to Solvents and Additives II/ 115
cs (x104) Remarks Refs.
Acrylonitrile (contd)
Formamide, N,N-dimethyl- (contd)
-, N-methyl-
Formic acid
Gl uc os e
u,n-Glucoside, met hyl -
-, -1 6-deoxy-6-iodo-
-I -1 6-deoxy-6-mercapto-
-, -, 6-deoxy-6-phthalimido-
-1 -9 2,3-di-o-benzyl-
-1 -1 2,3,4,6-tetra-o-acetyl-
-9 -. 6,-O-(p-toluenesulfonyl)-
-1 -, 6-O-triphenylmethyl-
P,n-Glucoside, methyl-
-, 6-deoxy-6-dipropylamino-
Ghitaronitrile, 2,4-dimethyl-
Glyceraldehyde
Glycerol
2,4,6-Heptanetricarbonitrile
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-
1,5-Hexadien-3-yne
Hydrocyanic acid
Indium, triethyl
Iron(III) chloride
Isobutyl alcohol
I s o b u t y l e n e
Isobutyronitrile
Lactonitrile
Lead, tetraethyl
Magnesium perchlorate
Mercury, diethyl
Methane, dichloro-
-, nitro-
Me t ha nol
Methylamine
2,6-Octadiene, 2,6-dimethyl-
Oxime, acrolein
-9 crotonaldehyde-
-1 ethylisopropenylketone-
-, methacrolein-
-1 metbylacrolein-
-,
methylvinylketone-
-9 methylisopropenylketone-
-9 methylisobutenylketone-
l-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro-
1-Pentanol, 4-methyl-
Piperidine, l-ethyl-
-, l-methyl-
1-Propanol, 2,2,3,3-tetrafluoro-
Silane, tetraetbyl
So r b i t o l
Stibine, tributyl
Suc c i noni t r i l e
Sulfur dioxide
Ti n, t e t r a but yl
To l u e n e
o-Toluidine, N,N-dimethyl-
50
50
60
60
60
60
60
60
60
60
60
60
60
50
60
60
50
60
50
50
60
60
60
60
50
60
50
60
50
60
60
60
50
50
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
50
60
50
60
40
50
1.8
0.5
6.9
20
50
1300
60
90
30
1 0
80
20
1100
0.6
32.1
23.5
1.0
1.9
1.17 x 104
0.81
6.2
2220
3.33 x 104
24.06
70
1.3
1.8
3.5
4.0
1
243
< 0.05
72.2
3.06
6.0
0.5
1 7 5
450
6.26 x lo5
2.05 x lo4
1.03 x 104
9.41 x 104
5.35 x 104
1.2 x 104
1.71 x 104
2.65 x lo4
1.9
11.79
3300
2300
1.5
21.0
6.1
11.1 x 104
0.6
0
80.8
1.153
2.632
3.2
5.83
272
334
F14
F14
F8
F7
F7
F7
F7
F7
F7
F7
F 7
F7
F 7
F14
F8
F8
F14
F2
F7
F14
F
F7
F7
G
F14
I6
F15
F14
F7
F7
G
F15
F14
F7
F2
G
J
F2
F7
F8
F7
F7
G
G
G
F2, J
F2, J
377
377
361
220
220
220
220
220
220
220
220
220
220
376
361
361
376
442
377
377
436
156
1 9
95
553
376
376
1 3 5
86
377
156
376
156
95
86
377
377
6
555
555
555
555
555
555
555
555
442
95
24
24
442
156
361
156
86
362
156
347
347
2 1
24,95
229
229
Remarks page II - 157; References page II - 159
II/ 116 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T CC) cs (x104) Remarks Refs.
Acrylonitrile (contd)
o-Toluidine, N,N-dimethyl- (contd)
Tributylamine
Triethylamine
Trimethylamine
Tripropylamine
Zinc, diethyl
Zinc chloride
Acrylonitrile/styrene (38. 5-61. 5 mol%)
Methanol
Anisole, p-vinyl-
Anisole, p-isopropyl-
Benzonitrile, p-isopropyl-
Cumene
-,p-bromo-
-, p-tert-butyl-
-, p-chloro-
Benzoic acid, vinyl ester
Benzene
Benzoic acid, isopropyl ester
2-Butanone
Carbon tetrachloride
Chl oroform
Cyclohexane
1,3-Butadiene, 2-chloro-
1-Butene, 3-chloro-S-methyl-
2-Butene, 1-chloro-3-methyl-
2,6-Octadiene, 2,7-dichloro-
3-Buten-2-one, 3-methyl-
Benzene
ethyl-
Cyclohexane, methyl-
To l u e n e
Butyraldehyde, divinyl acetal
Aniline, N,N-dimethyl-
Benzene
Butyl alcohol
reti-Butyl alcohol
1,3-Dioxolane, 2-propyl-
Butyric acid, vinyl ester
Benzene
Carbamic acid, vinyl-, ethyl ester
Acetone
Benzene
Chloroprene
3-Chloro-(methyl- 14C)-
1-butene(4- 14C)
3-Chloro-2-pentene-(2,4- 14C)
p-Dioxin, 2,3-dihydro-/maleic anhydride
Benzene
Carbon tetrabromide
Carbon tetrachloride
Chl oroform
p-Dioxane
To l u e n e
m-Xylene
60
60
60
50
60
60
60
50
65 1.4 116
60 3.40 407
60 40.9 407
60 4.28 407
60 11.8 407
60 3.64 407
60 8.52 407
60 1.5 393
80 0.4 26
60 1.0 393
80 29.0 26
80 730 26
80 105 26
80 2.3 26
50 5.47 Fl 152
50 4.57 F2 152
50 5.24 F2 152
80 2.489 C 84
80 6.934 C 84
80 0.500 C 84
80 3.282 C 84
50 1060 430
50 27.7 430
50 3500 430
50 37.2 430
50 708 430
80 3.28 201
60 8.5 1 1 7
60 1.25 1 1 7
50 5.37 F2 509
50 3.94 F2 509
60 11500
60 100 x 10s
60 1.7 x 10s
60 3.6 x lo4
60 1.07 x 104
60 6.0 x lo4
60 9.9 x 104
30200
463
6700
1700
1900
3800
5900
6600
1 7 5
790
4820
1.05 x 104
1.06 x lo4
0.006
F16, G, J
F2, J
J
T
m, J
J
F7
J
F7
J
F7
F13
227,229
229
24
20
20
22
24
24
377
24
156
24
156
410
169
169
169
169
169
169
169
TI
-
SC
-
El
i
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 117
Solvent/Additive T (0 cs (x104) Remarks Refs.
Et h y l e n e
Acetamide, N,N-diethyl-
-I N,N-diisopropyl-
-, N,N-dimethyl-
-, N-ethyl-
-, N-methyl-
Acetic acid, butyl ester
-1 rerz-butyl est er
methyl ester
Letic acid, chloro-
-, -7
methyl ester
Acetic acid, cyano-
methyl ester
,&& aci d, dichloro-
-, -,
methyl ester
Acetic acid, trichloro-
-3 -1 methyl ester
Acetic anhydride 130
Ac e t o n e 130
Acetonitrile
Benzaldehyde
Benzene
130 1 2 5
130 57
130 182
130 1 1 5
130 6 1
130 89
130 40
130 40
90
120
130
130
55
90
120
55
90
120
200
130
130
20
8 3
130
50-70
610
1210
2170
2150
2580
630
1160
1880
1990
2090
1120
1800
7900
11100
13000
1900
6900
9400
10500
2000
5900
8100
11100
700
16100
27500
38000
65700
1000
17000
27700
39000
65200
1200
15400
23600
33000
54100
130
160
1 6 5
168
282
100
1970
0.629
20
2 1
9.4
1 8
c, w5 454
c, w5 454
c, w5 454
c, w5 454
c, w5 454
c, w5 454
c, w5 454
c, w5 454
C Ql 434
C Q2
434
C Q3 434
C Q4 434
C Q5 434
C Ql
434
C Q2 434
C Q3 434
C Q4
434
C Q5 434
c, w5 454
c, w5 454
C Ql 435
C, Q2 435
C Q3 435
C 435
C Ql
435
C, Q2 435
C Q3 435
C 435
C, Ql 435
C Q2 435
C, Q3
435
C 435
C Ql 484
C, Q2
484
C Q3 484
C Q4 484
C 484
C Ql 484
C Q2 484
C Q3
484
C Q4 484
C 484
C Ql 484
C Q2 484
C Q3 484
C Q4 484
C 484
c, w5 454
c, w17 456
C, F21, W5 259
c, w5 456
c, w5 455
C, F21, W5 159
c, w5 457
E, W 1 4 3
D 204
Q W 205
c, w5 260
w3 218
Remarks page II - 157; References page II - 159
II/ 118 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T(C) cs (x104) Remarks Refs.
Ethylene (contd)
-1
ethyl- 130
Benzene-D6
Benzoic acid, butyl ester
-,
ethyl ester
methyl ester
Ltane
-, l-iodo-
2-Butanone
-, 3-methyl-
1-Butene
-, 2-methyl-
-, 3-methyl-
2-Butene
-, l,Cdichloro-
-, 2-met hyl
terr-Butyl alcohol
Butylamine
Butyraldehyde
Butyric acid, methyl ester
Butyronitrile
Carbon tetrachloride
200
130
130
130
130
130
100
130
200
130
130
189
200
130
130
130
130
130
30
130
130
130
130
130
20
50
70
90
95
130
140
430
480
520
560
500
5.6
140
55
53
40
45
9.45 x 104
11.3 x 104
12.6 x lo4
550
600
750
840
330
470
560
900
570
210
530
1200
250
380
4100
470
0
2
220
3250
220
520
215
772
974
7000
32000
740
1210
20200
32500
34000
1250 xk 200
22000 f 1000
43000 f 4000
113oZk700
2000 f 1000
37000 * 3000
9800
1600
1700
1800
2200
22000
23000
30000
36000
38000
39000
60000
c, W17
c, W5
c, w5
c, w5
c, w5
c, W5
c, w5
c, w5
c, w5
C, F21, W5
c, w17
Ql, W14
Q2, W14
Q3, W14
c, w17
C, F21, W5
c, w5
C, F21, W5
c, w5
c, w5
C, F21, W5
B, W5
c, w5
C, F21, W5
C, F21, W5
C, F21, W5
C, F21, W5
c, w5
c, w5
C, F21, W5
E, W4
C, F21, W5
c-w5
c, w5
c, w5
C, F21, W5
E, W
C QL
C, Ql
c, w4
g1, w12
C Ql
Q2, W12
Q3, W12
w12
W23, Q(l)
W23, QG2
W23, Q(3)
W20, Q(l)
W20, Q(Z)
W20, Q(3)
C, F21, W5
C Ql
C, Ql, F19
C, Ql, W13
C, Ql, F20
C, Q2
C, Q2, F19
C, QL ~1
C, 43
C, Q2, F20
C, Q3, F19
C, Q2, W13
456
52
454
52
455
260
454
454
454
259
456
187
1 8 7
187
456
259
455
259
52
52
259
443
455
259
259
259
259
454
454
259
482
259
454
457
454
259
1 4 3
391
391
215
210
453
391
453
453
453
518
518
518
518
518
518
259
170
170
170
170
170
170
170
170
170
170
170
TABLE 4. contd
Transfer Constants to Solvents and Additives II/ 119
Solvent/Additive T ((3 cs (x104) Remarks Refs.
Ethylene (contd)
Carbon tetrachloride (contd)
Chloroacetic acid, methyl ester
60000
61000
70000
90000
100000
110000
130000
140000
180000
90 590, 550, 1200
1680. 2240. 2340
Chloroform 2 8
Cumene 130
Cyclohexane 130
methyl-
Cyclopentane
Cyclopropane
Decane
1-Decene
Dibutylamine
Dichloroacetic acid, methyl ester
Dimethylamine
p-Dioxane
Ethane
-, l,l-bis(dimethylamino)-
-, 1-bromo-Zchloro-
-, chloro-
-, 1,2-dibromo-
-, l,l-dichloro-
7 0
8 0
9 5
1 0 1
103
130
140
2 0 0
130
130
2 0 0
130
130
189
189
130
2100
13000
15000
8000
30000
2470
15500
24900
31200
43900
2OOOf 120
10000*500
16000 & 3000
1150f50
5000 zt 300
8000 f 1000
1500
4 5 0 0
5400
2890
15400
23800
29800
41100
2 9 0 0
3210
15200
22200
28000
37600
5 0 0
8 0
9 0
9 1
190
110
109
127
228
0
120
4 2 5
1090
1070
90 1900, 6900, 9400
130 1900
130 3 2 0
130 6
130 1070
130 3 9 0
7 0 120
130 1250
7 0 1500
C Q3
C, Q3, F20
C, Q4, F20
C, Q4, F20
C, Q2, ~1
C Q3, Wl
C, 43, W13
C Q4, ~1
C
C, Q(l), QG9, Q(3)
C Q(4), Q(5)> Q(6)
E, Ql, W
E, Q2, W
E, Q3, W
c, w4
k, Ql, W12
C, Q2, W12
C, Q3, W12
C, Q4, W12
c, w12
W23, Q(l)
W23, 463
W23, Q(3)
W20, Q(l)
W20, Q(3)
W20, Q(3)
E, QL W
E, Q3, W
E, 42, W
C, Ql, W12
C, Q2, W12
C, Q3, W12
C, Q4, W12
c, w12
C, F21, W5
C, Ql, W12
C, Q2, W12
C, Q3, W12
C, Q4, W12
c, w12
C, F21, W5
C, F21, W5
c, w17
C, F21, W5
c, w5
C, F21, W5
c, w17
c, F21, w5
c, w5
C, F21, W5
C, F21, W5
B, W5
B, W5
c, w5
C Q(l), QC% Q(3)
C, F21, W5
C, F21, W5
C, F21, W5
c, w5
c, w5
c, w4
c, w5
c, w4
170
170
170
170
170
170
170
170
170
557
5 5 7
2 4 4
2 4 4
2 4 4
215
2 1 0
1 0 1
1 0 1
1 0 1
1 0 1
1 0 1
5 1 8
5 1 8
5 1 8
5 1 8
5 1 8
518
2 2 4
2 4 4
2 4 4
1 0 1
1 0 1
1 0 1
1 0 1
1 0 1
2 5 9
1 0 1
1 0 1
1 0 1
1 0 1
1 0 1
2 5 9
2 5 9
4 5 6
2 5 9
4 5 5
2 5 9
4 5 6
2 5 9
455
2 5 9
259
443
443
4 5 4
558
2 5 9
2 5 9
2 5 9
4 5 7
4 5 4
215
4 5 4
215
Remarks page II - 157; References page II - 159
II / 120 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
SolventJAdditive
T (Cl cs (x104) Remarks Refs.
Ethylene (contd)
Ethane, 1,2-dichloro-
-, iodo-
-, l,l,l-trichloro-
Ethanol
Ethyl acetate
Ethylene oxide
Formaldehyde
Fomamide, NJ/-dimethyl-
Formic acid, methyl ester
Furan, tetrahydro-
Heptaldehyde
Heptane
Hexane
1-Hexene
-, 2-ethyl-
Hydrogen
Isobutyronitrile
Isocyanic acid, butyl ester
Isopropanol
Isothiocyanic acid, butyl ester
Methane
-, bromochloro-
130 110
65 1.51 x 105
1.59 x 105
1.65 x lo5
100 1.1 x 105
1.36 x lo5
1.43 x 105
1.48 x lo5
1.49 x 105
70 500
20 5 . 7 1
30 110,210, 270
60 76,240, 280
100 89,270, 340
1 2 5 100,310, 320
130 68
69
75
125-135 190
150 92,260
180 73,350
200 1 3 5
130 45
200 1 2 1
130 7
130 560
130 260
130 42
130 288
289
200 401
130 2600
3900
200 4800
50-70 90
130 80
130 68
189 225
189 900
130 3300
130 159
160
200 400
130 1070
130 212
30 96,410, 520
60 65,310, 380
100 65,300, 350
1 2 5 75,380, 380
130 130
140
144
125-135 570
150 98,470, 460
180 86,440, 500
200 234
130 0
130 0
100 1600
4500
7500
8000
130 10000
140 16.0 x lo5
C, F21, W5
::
;;
Ql, W14
Q2, W14
Q3, W14
Q3
c, w4
:: &,> Q(3L QW
6 Q(l)> Q(3L Q(5)
E> Q(l)> Q(3L Q(5)
6 Q(l), Q(3)> QG)
c, w17
C, F21, W5
c, w5
c, w2
5 Q(l), Q(3)
6 Q(l), Q(3)
c, w5
c, w5
c, w17
C, F21, W5
c, w5
C, F21, W5
c, w5
c, w5
C, F21, W5
c, w5
c, w17
c, w5
c, w5
w 3
C, F21, W5
C, F21, W5
B, W5
B, W5
C, F21, W5
c, w5
C, F21, W5
c, w5
C, F21, W5
c, w5
6 Q(l)> Q(3L Q(5)
E, Q(l). Q(3L Q(5)
5 Q(l), Q(3L Q(5)
6 Q(l), Q(3L Q(5)
c, w17
C, F21, W5
c, w5
c, Wl
6 Q(l), Q(3), Q(5)
E, Q(l)> Q(3k Q(5)
c, w5
c, w5
c, w5
C, Ql, Wll
C, 42, Wll
C, Q3, Wll
C, Q4, Wll
c, w5
Ql, Wll, II
259
189
189
189
452
1 8 8
1 8 8
1 8 8
452
215
1 4 3
523
523
523
523
456
259
454
381
523
523
455
454
455
259
457
259
454
454
259
455
457
457
457
218
259
259
443
443
259
454
259
455
259
454
523
523
523
523
456
259
454
381
523
523
455
454
259
2
2
2
2
454
1
TABLE 4. contd
Solvent/additive
T ((2
Transfer Constants to Solvents and Additives II / 121
cs (XlOq Remarks Refs.
Ethylene (contd)
Methane, bromochloro- (cont&
-, chloro-
-, dichloro-
-, dimethoxy-
-, iodo-
7 0
7 0
130
130
6 5
100
Methanol
Methylamine
1-Octene
Pentane, 2,2,4-trimetbyl- 130
Pentene 189
-, 4,4-dimethyl- 130
-, 4-methyl- 130
Phosphine 130
-, dibutyl 130
-7
tributyl 130
-, triphenyl 130
Phosphorous acid, dimethyl ester 130
Propane 130
3 0
6 0
100
1 2 5
130
150
180
130
130
-, 2-chloro-
Propane, 2-chloro-2-methyl-
-, 2,2-dimetbyl-
-, 2-iodo-
-, 2-methyl-
-, 1 1 1 2 2,3,3,3-octafluoro- 1 1 1 9
1 Propene
Propionaldehyde
Propionic acid, methyl ester
2 0 0
7 0
7 0
130
6 5
100
130
2 0 0
130
130
2 0 0
130
2 0 0
9 0
120
47.0 x 10s
4
7 0 0
3 6 0
7 3
41000
45000
45000
41000
45000
45000
36, 84, 100
46, 100, 140
34, 90, 120
56, 100, 140
2 1
53, 120, 160
37, 120, 160
5 3
3 6 0
3 6 0
6 4
9 0 0
175
3 1 0
207000
36000
4 5 0 0
5 0
5 1 0 0
2 7
27.6
3 1
65.2
2 5 0
4 0
8
5.7 x 10s
5.9 x 10s
6.07 x 10
4.55 x 10s
4.70 x 10s
4.83 x lo5
5 0
7 2
136
4
110
122
150
2 0 0
2 3 0 0
3300
2 8 3 0
63000
92000
1.08 x lo5
630, 420, 780
890, 1030, 1230
78000
1.12 x 10s
1.39 x 10s
780, 430, 1060
1220, 1300, 1410
42, Wll, II
c, w4
c, w4
c, F21, w5
c, w5
::
:;
Q2
:>3Q(U> Q(2), Q(3)
E, Q(l), Q(2), Q(3)
E, Q(l), Q(2), Q(3)
E, Q(l), Q(2h Q(3)
c, F21, w5
E, Q(l), Q(2), Q(3)
E> Q(l), Q(2h Q(3)
c, w5
c, w5
C, F21, W5
C, F21, W5
B, W5
c, w5
c, w5
c, w5
c, w5
c, w5
c, w5
C, F21, W5
C, F21, W5
c, w17
C, F21, W5
c, w5
c, w4
c, w4
C, F21, W5
::
::
::
C, F21, W5
c, w5
c, w5
C, F21, W5
c, w5
c, w5
c, w5
c, w5
c, w17
c, w5
c, w5
C, Ql
C Q3
C, Q5
C, Q(l), Q(2)> Q(3)
C Q(4h Q(5h Q(6)
C, Ql
C, Q3
C Q5
C Q(l), Q(2h Q(3)
C Q(4h Q(5h Q(h)
1
215
2 1 5
2 5 9
4 5 4
189
1 8 9
189
189
189
189
523
523
523
5 2 3
2 5 9
5 2 3
5 2 3
4 5 4
5 2
2 5 9
2 5 9
4 4 3
4 5 4
4 5 4
4 5 7
4 5 4
4 5 4
4 5 4
2 5 9
2 5 9
4 5 6
2 5 9
4 5 5
215
215
2 5 9
189
189
189
189
189
189
2 5 9
4 5 4
4 5 5
2 5 9
5 2
4 5 4
5 2
4 5 5
4 5 7
4 5 7
4 5 7
4 8 5
4 8 5
4 8 5
5 1 6
5 1 6
4 8 5
4 8 5
4 8 5
5 1 6
5 1 6
Remarks page II - 157; References page II - 159
II / 122 TRANSFER-CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T (C)
cs (x104) Remarks Refs.
Ethylene (conrd)
-, 3-cyano-, met hyl est er
Silane, tetramethyl
Tetradecane
1-Tetradecene
To l u e n e
Tributylamine
Trichloroacetic acid, methyl ester
Tridecane
Trimethylamine
Wa t e r
p-Xylene
Ethylene, bromo-
Carbon tetrachloride
Ethylene, chloro-
Acetaldehyde
Aniline, N,N-dimethyl-
Benzene
Butyraldehyde
Carbon tetrabromide 50
Cycl ohexane, 1,2-epoxy-4-vinyl-
Et hane, 1,2-dichloro-
Ether, dodecyl vinyl
Furan, tetrahydro-
Heptane, 2,4,6-trichloro-
Oxalic acid, diethyl ester
Pentane, 2,4-dichloro-
Ethylene, 1, l-dichloro-
Phosphorus trichloride
Ethylene, tetrafluoro-
Ethanol
Isopropanol
Methanol 100
Hexanoic acid, vinyl ester
Benzene
1-Hexene
Carbon tetrachloride
Cyclohexanol
Ethyl alcohol
130
130
189
189
130
200
130
90
130
130
20
130
200
60 50 417
50
50
3 5
50
60
-
2 5
50
50
2 5
40
50
50
2 5
2 5
50
60 1 4 D 214
100
100
80
140
125-135
30-35
790 c, w5 454
0 C, F21, W5 259
580 B, W.5 443
1760 B, W5 443
130 c, w5 52
154 c, w5 454
180 c, w17 456
220 c, w5 455
820 c, w5 454
1000, 1700, 2770 C Q(l), QC% Q(3) 559
140 C, F21, W5 259
180 C, F21, W5 259
330 c, w5 454
1.71 E W 1 4 3
300 C, F21, W5 259
317 c, w5 454
400 c, w17 456
434 c, w5 455
110
2700
1500
350
420
500
580
4.7 x 104
50.0 x 104
3300
1.85 x lo4
7.45 x 104
12.15 x lo4
264
4.0
4.5
156
1 6
30
24
5
1.4
9.0
5
W 8
w7
w15
F26
C. F26
G
164
1 6 1
219
500
500
500
500
492
66
418
418
418
418
428
425
392
4
425
246
164
211
315
315
211
800 C, Q5, W2 3
820 c, Q6, W2 3
860 C Q4, W2 3
880 C 43, W2 3
1540 C Q3, W2 3
1660 C Q4, W2 3
1700 C, Q5, W2 3
350 C Q3, W2 3
390 C, Q4, W2 3
4.9
4.1 x 104
390
170
201
C, Ql, F19 170
C 381
D 381
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 123
Solvent/Additive T CC) cs (x104) Remarks Refs.
I s o b u t e n e
Carbon tetrachloride 100 (7.1 kOo.2) x lo4 E, Q(l) 537
(8.1*0.5) x lo5 E, Q(2)
Isobutyric acid, vinyl ester
Benzene
Maleic acid, diethyl ester
Stearamide, N-allyl-
Maleic anhydride/methyl methacrylate
A c e t o n e
Maleic anhydridelstyrene
Aniline, N,N-dimethyl-
Carbon tetrachloride
Methacrylic acid
Bromotrichloromethane
-, butyl ester
Benzene
-, 2-(diethylamino)ethyl ester/styrene
Carbon tetrachloride
To l u e n e
-3 ethyl ester
Acetic acid
Acetone
Acetophenone
Benzene
-, chloro-
ethyl-
i:Butanone
Butyl alcohol
set-Butyl alcohol
tert-Butyl alcohol
Carbon tetrachloride
80 4.49 201
90 22.4 J 1 7 3
60 1.6 HH 367
60 930
70 1.04 HH
489
365
70 300 566
60 0.158 264
80 23.6 335
80 13.3 335
8 0
80
80
80
80
80
80
80
80
80
80
S
Chl oroform 80
C
C
Cumene 8 0
Cyclohexane 8 0
Et hane, 1,2dichloro- 80
Et hane, 1,1,2,2-tetrachloro- 80
0.095
0.102
0.281
0.081
0.436
1.428
0.252
0.454
1.604
0.417
0.901
5.640
0.703
2.360
2.067
0.928
1.821
0.311
1.820
0.536
0.919
0.429
0.865
0.702
0.445
0.236
0.436
C
C
8 0
80
80
80
80
80
80
80
8 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
1 8 3
8 3
1 8 3
8 3
83
1 8 3
8 3
1 8 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
83
70 0.983
70 2.05
-
1 3 7
1 3 7
60 0.165
80 1.971
80 1.110
80 0.510
80 0.510
C
C
C
C
264
1 8 3
1 8 3
1 8 3
1 8 3
100 900
120 1000
60 30800
60 0.001
60 0.996
A, F7
A ~7
F7
109
1 0 9
1 9
70
2 1
60 6.5
80 0.24 A
86
3 1
-, l,l,l-trichloro-
Ethyl acetate
Ethyl alcohol
Heptane
2-Heptanone
Isobutyl alcohol
2,4-Pentanedione
To l u e n e
-, hexadecyl ester
Carbon tetrachloride
Cumene
-, isobutyl ester
Benzene
Carbon tetrachloride
Chl oroform
Et hane, 1,2-dichloro-
-, 1,1,2,2-tetrachloro-
Methacrylonitrile
Carbon tetrabromide
Iron(II1) chloride
Isobutyraldehyde
To l u e n e
Methyl methacrylate
Acetaldehyde
Acetic acid
Remarks page II - 157; References page II - 1. 59
II / 124 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (I cs (xlO4) Remarks Refs.
Methyl methacrylate (contd)
Acetic acid, monochloro-
-, dichloro-
-, l,l-dimethyl-2,2,2-trinitro-
ethyl ester
-, trichloro-
A c e t o n e
Acetonitrile, (m-bromophenyl)-
-, @-bromophenyl)-
-, (m-chlorophenyl)-
-, @-chlorophenyl)-
-, (p-methoxyphenyl)-
-, phenyl-
-, m-tolyl-
-, p-tolyl-
Acetylene, p-bromophenyl-
-, p-chlorophenyl-
-, p-nitrophenyl-
Aluminum, hydrodiisobutyl
-, triethyl
Aniline
-, N, N-dimethyl-
-, N,N-divinyl-
-, N-methyl-
p-Anisaldehyde
Anisole
-, p-ethynyl-
-, p-isopropyl-
-, p-methyl-
Anthracene
Azobenzene
Benzaldehyde
-,p-bromo-
-, m-chloro-
-, p-chloro-
-, p-cyano-
Benzene
-, allyl-
-, bromo-
-9 rert-butyl-
60 0.64 R 529
60 0.80 R 529
45
60
60
80
60
60
60
60
60
60
60
60
60
60
60
60
50
60
60
80
100
30
50
60
70
80
100
60
60
80
100
60
2 5
60
60
60
50
50
60
60
60
60
60
25
30
50
52
60
75
80
90
60
25
80
520
1.10
0.195
0.225
0.275
3.89
2.78
4.28
3.21
19.0
5.18
5.75
7.83
41.3
38.9
127.5
3600
1550
1240
4.2
6.3
9.0
2.45
1 8
30.4
430
11.3
10.8
17.0
20.0
340
7.0
10.0
13.3
1.11
0
40.3
3.46
0.57
0
100
2.5
0.86
1.43
0.96
1.03
2.06
0
0.01
0.036
0.027
0.040
0.83
0.33
0.075
0.080
0.24
0.036
400
0
0.260
K
K
K
S
R, F2
F2
F2
F2
F16
H
A, F2
A, F2
A, F2
110
R 529
8 1
A 3 1
8 1
462
461
462
461
461
461
462
461
1 5 1
1 5 1
1 5 1
156
547
156
424
424
424
508
228
409
1 6 1
424
270
424
424
82
424
424
424
495
1 6
1 5 1
406
496
1 5
282
86
495
495
495
495
495
1 6
508
147,327
8 1
8 1
1 8 1
1 2 3
3 1
8 1
1 4 5
147
502
1 6
3 1
F2
F2
F2
D
K
C
D
C
C
A
I1
D
A
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 125
Solvent/Additive T (3 cs (x104) Remarks Refs.
Methyl methacrylate (contd)
-, chloro-
-, p-diisopropyl-
-, m-dinitro-
-1 ethyl-
-,
ethynyl- 60
-, fluoro-
Benzene sulfonylchloride
-, p-chloro-
-, p-dimethyl-
Benzonitrile
-, p-hydroxy-
-, p-isopropyl-
p-Benzoquinone
-, 2,3,5,6-tetrachloro-
Benzothiazolethion, 3-allyl-
Benzyl ether
Bibenzyl
Biphenyl, 2,2-methylene-
Borane, tributyl-
Bromoform
Butane, l-chloro-
-, l,l,l-trinitro-
1.4-Butanediol
2 - Bu t a n o n e
1 - Bu t e n e
-, 3,4-epoxy-2-methyl-
2-Butene. cis-
-, trans-
3-Buten-2-01, 1-chloro-3-methyl-
Butyl alcohol
set-Butyl alcohol
rertSuty1 alcohol
Butylamine, N-nitro- 45
Butyl ether 60
1-Butyne, l-phenyl- 60
Bu t y r a l d e h y d e 50
Carbon tetrabromide
2 5
60
80
60
50
52
60
80
2 5
60
60
60
2 5
60
50
60
44.1
50
60
44.1
60
2 5
60
50
60
60
60
77
80
45
60
80
60
70
7 5
80
40
50
80
40
50
40
50
80
60
80
60
80
60
80
30
0
0.074
0.200
0.207
5.72
52
0.501
0.766
1.311
1.350
2.1
21.9
22.3
0
5.16
8.56
4.06
0
0.162
6.0
4.99
5.5 x 104
5.7 x 104
4.5 x 104
2600
1 5 3
10.4
8.0
0.0
41.8
53.5
7.45
2 3
1.20
8300
0.61
1.07
0.45
0.56
0.83
0.70
3.1
5.1
29.6
3.2
4.9
3.0
5.2
18.8
0 . 3 9 4
0.25
0.259
0.85
0.085
0.100
0.152
0
0.8
10.8
1.47
2.25
3.40
2800 * 600
1000 * 100
D
A
A
1 1
K
J
D
R
R
R
D
D
F2
JA C R
A
F24
F24
C
C
C
A
A
A
A
W8
WI
D, R, JJ3a
D, R, JJ3b
1 6
8 1
3 1
8 1
406
1 5
8 1
8 1
8 1
3 1
1 4 5
1 5 1
150
1 6
543
543
543
1 6
150
479
406
194
15
42
194
502
368
368
354
567
567
156
506
3 1
110
421
421
290
1 2 3
1 2 3
3 1
287
287
269
287
287
287
287
269
479
3 1
479
3 1
8 1
3 1
81
110
86
150
500
500
500
521
521
Remarks page II - 157; References page II - 159
II / 126 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (Cl cs (x104) Remarks Refs.
Methyl methacrylate (contd)
Carbon tetrabromide (co&d)
Carbon tetrachloride
Chl oroform 60
Copper(R) chloride
Cumene
-, p-bromo-
-, p-tert-butyl-
-, p-chloro-
Cyclohexane
-9 methyl-
-, truns-l,C, di acet at e
cidtruns-1,4-, dicarboxylic acid dimethylester
Cyclotetrasiloxane, octamethyl-
p-Di oxane
Diphenylamine
Diphenylamine-T
Disiloxane, l,l-dimethoxy-3,3,3-trimethyl-l-phenyl-
-, hexamethyl-
Epibromohydrin
Epichlorohydrin
Et hane, 1,2-dichloro-
-, nitro-
-, 1,1,2,2-tetrachloro-
-, l,l,l-trichloro- 80
-, l,l,l-trinitro- 45
Ethyl acetate 60
60
60
60
80
100
20
30
50
60
IO
80
80
-
60
60
80
60
60
60
60
80
80
60
60
50
79.5
80
44.1
60
19.5
19.5
60
60
60
80
45
60
80
1000 f 500
500 f 200
2700
1500
1900
3300
4600
0.2
20
0.20
0.82
0.925
2.40
5
20.11
18.52
0.42
0.5
1.74
2.393
2.421
3.3
24.4
0.454
1.77
1.129
1.400
1.9
1.9
105 x 10s
1.9
2.56
1.9
2.4
3.71
2.74
3.07
1 2
0.10
0.195
8.46
1.16
2.5
0.080
0.222
0
0.3
0.032
0.104
16.53
9.3
0.35
0.756
2.0
0.155
0.200
0.235
0.600
1400
0.100
0.13
0.132
0.134
0.155
D, R, JJ3c
D, R, JJ3d
F2
F2
F2
C D
D, F2
C
R
R H
R
R H
A
11
D
C
A
11
D
Fl
A
11
A
A
C
C
C
A
F2
R
R
A
A
C
A
C
521
521
109
568
568
109
109
3 5
451
514
514
8 1
1 8 1
86
529
529
568
568
514
3 1
8 1
1 4 5
427
8 1
1 8 1
8 1
3 1
1 4 5
427
36
7
406
3 1
1 4 5
406
406
406
86
3 1
3 1
569
569
450
474
3 1
194
46
474
474
529
529
8 1
8 1
110
8 1
3 1
8 1
3 1
110
316
290,316
216
290
290
TABLE 4. cont' d
Solvent/Additive T ((3
Transfer Constants to Solvents and Additives II / 127
cs (x104) Remarks Refs.
Methyl methacrylate (contd)
Ethyl acetate (contd)
Ethyl alcohol
Ethylene glycol
Germane, diethylchloro-
-, ethyldichloro-
-3 triethyl-
triphenyl-
Gycerol
Heptane
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-
Hydrazyl, 2,2-diphenyl-l-pi@
Hydroquinone
Indium, triethyl-
Isobutyl alcohol
Isobutyric acid
methyl ester
;sbpropyl alcohol
Lead, tetraethyl 60
Malononitrile, furfurylidene- 44.1
Mercury, diethyl 60
Methane. bromotrichloro- 30
-, bromotrinitro-
Methane, dichloro-
-, nitro-
-, trinitro-
-, triphenyl-
Me t ha nol
1 - Na p h t h o l
2,6-Octadiene, 2,6-dimethyl-
Oleic acid, methyl ester
Oxime, acrolein-
-9
crotonaldehyde-
-1 ethylisopropenylketone-
-, methacrolein-
-1
methylacrolein-
-1 methylisobutenylketone-
-9
methylisopropenylketone-
methylvinylketone-
zxolane, cis-3,4-diacetoxy-
Pentane, 2,2,4-trimethyl-
1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro-
2-Pentanone, 4,4-dimethyl-5,5,5-trinitro-
70
75
80
60
80
100
60
80
60
60
60
60
60
50
60
44.1
45
131
60
60
8 0
80
60
60
80
100
130
45
60
80
60
45
60
60
80
100
45
60
60
60
60
60
60
60
60
60
60
60
50
60
45
0.156
0. 46
0. 55
0. 83
0. 240
0. 40
0. 625
0. 80
0. 28
0. 60
22000
39300
5800
18500
0. 152
1. 8
2. 8
200x 10s
7. 0
100
332
0.10
0. 505
0. 229
0. 250
0. 900
0. 26
0. 583
1.907
3. 00
8
43
45
3. 14
1. 2 x 104
0.898
830
1. 2 x 104
4. 5 x 104
1.0 x 104
0.100
0.217
2. 0
5400
4. 0
0. 2
0. 33
0. 45
<5. 0
6. 7
1. 68
8. 0
25500
500
3000
17000
5200
4700
2900
1300
1.39
1.2
2. 36
400
C
1 1 0
C
C
A
A, F2
A, F2
A
F24
F24
A, R
A, R
A, R
A. R
F2
A
A
A
A
C
C
C
S
QQ3
D
D, Q4
A, F2
A, F2
A
C
F2
2 9 0
146
1 2 3
1 2 3
3 1
423
423
49
421
421
539
539
539
539
479
206
442
194
30
398
156
81
479
81
31
31
275
81
81
49
337
337
480
- 156
194
156
311
311
311
110
8 1
8 1
86
110
44
423
423
49
30
324
441
7
555
555
555
555
555
555
555
555
569
206
442
110
Remarks page II - 157; References page II - 159
II / 128 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T (Cl
cs (x104) Remarks Refs.
Methyl methactylate (conr 6)
-, 4-methyl-
3-Pentanone
Pentasiloxane, dodecamethyl-
Phenol
-, o-bromo-
-,p-bromo-
-, o-chloro-
-, o-ethyl-
-, p-ethyl-
-, o-isopropyl-
-, p-isopropyl-
-, p-methoxy-
2,3,4,6-tetramethyl-
Phenyl ether
Phosphine, octyl-
-, phenyl-
tributyl-
&thalic acid, dimethylester
Piperidine, l-nitroso-
Pr opane, 1,2-dichloro-
-, l,l-dinitro-
-, 2,2-dinitro-
-, l-nitro-
1,2Propanediol
1-Propanol, 2,2,3,3-tetrafluoro-
Pr opene, 1,3-diphenyl-
1-Propene, 2-methyl-
Propionic acid, 2,2,2-trinitroethyl ester
Propionitrile, 3-phosphino-
-, 3,3-phosphinylidenedi-
Propyl alcohol
Pyridine
Pyrocatechol
-, p-reti-butyl-
Pyrogallol
Silane, (wbromotolyl)trimethoxy-
-, bromomethylphenyltrimethoxy-
-,
chlorotrimethyl-
-, dichlorodimethyl-
-, dichloromethyl-
-, diethylchloro-
-, dimethoxymethylphenyl-
-, dimethylphenyl-
-, hexamethoxy-(3,3-thiodipropyl)bis-
-1 methyldichloro-
-, (3-mercaptopropylhrimethoxy-
-7 tetraethyl-
-, tetramethyl-
-, trichloro
-3 trichloromethyl-
80
60
80
79.5
50
50
50
50
50
50
50
50
45
45
25
60
60
60
60
30
45
80
45
45
45
60
80
60
60
40
50
45
60
60
60
80
100
70
45
45
45
79.5
79.5
30
50
30
50
79.5
60
79.5
60
79.5
79.5
60
79.5
60
30
50
60
30
50
0.700
0.833
1.729
1.775
2.7
0.145
2.5
5.0
5.0
3.5
7.2
7.5
13.3
13.3
<5.0
11.0
6.42
9.13
2.3 x lo4
16.1 x lo4
30.6
0.2
8.2
0.675
68
1 5
5
0.48
0.86
1.86
15.6
2.5
4.4
3000
1.4 x 104
1.3 x 104
0.69
0.84
1.25
0.176
<5
9
26
29.8
29.8
144
2.2
1 7 5
2.45
15.2
1700
0.20
0.2
300
25.8
15.2
3100
6930
5.75
5.0
1.3
5000
1 8 5
2.7
D
S
A
F24
F24
F2
A 3 1
8 1
8 1
A 3 1
11 1 4 5
474
479
479
479
479
479
479
479
479
30
30
368
368
295
295
156
508
110
3 1
110
110
110
421
421
442
567
287
287
110
295
295
423
423
49
514
30
30
30
474
R 554
D, F2 451
249
D, F2 451
249
474
A, R 539
474
R 554
A, R 539
R 554
R 554
A, R
539
R 554
156
D, F2 451
249
A R 539
D. F2 451
249
A, F2
A, F2
A
TABLE 4. contd
Solvent/Additive T(C)
Transfer Constants to Solvents and Additives II / 129
cs (x104) Remarks Refs.
Methyl methacrylate (co&d)
-, triethyl
-1 triisopropoxymethyl-
-, trimethoxymetbyl-
-3 trimethoxyphenyl-
triphenyl-
&icon chloride
Siloxane, 1,1-dimethoxy-trimethyl-1-phenyl-di-3,3,3-
-, dodecamet hyl penta-
-1
1,1,1,3,5,5,5-heptametbyl-3-phenyltri-
-,
1,1,1,3,5,5,5-heptamethyl-tri-
-, 1,1,1,3,5,5,5-heptamethyl-tri-
-, 1,1,1,3,5,5,5-heptamethyl-3-(3,3,3,3-tri-
-, hexamethyl-di-
-, hexamethyl-phenyl-tri-
-, 1,1,1,5,5,5-bexamethyl-3-(2-phenylpropyl)-tri-
-, 3-(3-mercaptopropyl)-
1,1,1,3,5,5,5-heptamethyl-tri-
-,
octametbyl cyclotetra-
octamethyl tri-
iorbit-2,5-diacetate, 1,4:3,
6-, dianhydro-
Stearamide, N-allyl-
Steak acid, methyl ester
Stibine, tributyl
Tin, tetrabutyl
To l u e n e
-, p-bromo-
-, m-chloro-
-, p-chloro-
-, a-chloro
-, p-ethynyl-
-, p-nitro-
-, 2,4,6-trinitro-
m-Tolunitrile, a-cyano-
p-Tolunitrile
-, a-cyano-
Tributylamine
Triethylamine
Tripropylamine 60
Trisiloxane, 1,1,1,3,5,5,5-heptamethyl- 79.5
-, -, 3-(S-methylphenethyl)- 79.5
-9 -1 3-phenyl- 79.5
-1 -7 3-propyl- 19.5
-1 -1 3-(3,3,3+ifluoropropyl)- 79.5
60
19.5
79. 5
79.5
60
30
50
79.5
19.5
19.5
79.5
79.5
79.5
79.5
79.5
19.5
19.5
79.5 0.08
79.5 0.0316
60 29
9 0
60
60
60
20
52
60
70
80
60
6 0
60
60
60
44.1
44.1
60
60
60
70
20
60
200
0.697
0.697
0.331
0.331
0.053
0.053
1200
256
3.0
0.032
0.145
0.232
0.284
0.189
0.205
0.104
1.84
2.08
1284.5
3.01
0.282
<l.O
1.32
0.04
0.084
0.170
0.190
0.202
0.250
0.26
0.400
0.45
0.561
0.292
0.303
0.52
0.525
0.91
0.58
0.48
0.49
4.17
64.4
0
500
4.55
0.73
1.74
25.1
1.5
8.3
1900
14.6
0.284
2.08
0.232
0.189
0.205
A, R
R
R
R
A, R
D, fl
R
R
R
R
R
R
R
R
R
R
R
R
C
C, J
C D
C
C
C
C
C
C
I1
A
C
C
K
C D
J
5 3 9
474
554
474
554
474
554
539
451
249
554
554
554
554
554
554
554
554
554
554
554
554
569
173
441
156
156
35
8 1
21.81
316
32,316,317
316
275
316
496
123
32
8 1
1 4 5
3 1
1 2 3
496
496
496
1 8 1
1 5 1
194
194
462
496
461
270
35
24
25
156
474
474
414
414
474
Remarks page I I - 157; References page I I - 159
II / 130 TRANSFER CONSTANTS 1N FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T (0
cs (x104) Remarks Refs.
Methyl methacrylate (co&d)
-, 1,1,1,5,5,5-hexamethyl-3-phenyl-
octamethyl-
Gea, thio-
Wa t e r
79.5
79.5
42
60
80.5
60
60
50
1.84
0.032
1.21
0
0.002
0.03
0
0.43
0.50
6.5
A R
F7, F24
474
474
503
268
479
529
48
60 30-50 216
50 11.1 357
60 13.9 357
70 15.2 357
117- 118 270 381
117- 118 520 381
115- 118 230 381
30-35 630 381
120- 125 520 381
116- 120 110 381
55
55
55
3.4
0.35
0.97
313
313
313
70 21.4 11
100
100
(5 -10) x 104
1.03 x 104
C
C
210
210
100
8 0
4800
1.8 x lo4
5.4 x 104
100 17.0 x 104
C
;:
C
210
238
238
210
640000
C, Q(l-3)
570
1.4 1 5 8
50
7 5
100
1 2 5
150
95
1200 QU-4)
517
1400 Q(l) 517
1500
QC9
517
1800
Q(3-4)
517
1700 Q(l) 517
1900
Q(z)
517
1800
Q(3-4)
517
2200 QU-2) 517
2100
Q(3-4)
517
2700
QU-4)
517
17200 f 1100 W23, Q(l) 518
33000 f 15000 W23, Q(z) 518
17000 f 800 W24 Q(l) 518
299000 zt 8000 ~24, ~(2) 518
13800 z!z 800 W20, Q(l) 518
266000 + 10000 W20, QW 518
50 20.7 R 357
70 21.6 R 357
60 8.5 8 6
m-Xylene
p-Xylene
2,4-Xylenol
Naphthalene, l-vinyl-
Naphthalene
Nonanoic acid, vinyl ester
To l u e n e
I-Octene
Butyl alcohol
set-Butyl alcohol
Ethyl alcohol
Isopropyl alcohol
Methanol
Phthalimide, N-vinyl-
Chl oroform
Ethane, l,Zdichloro-
Met hane, dichloro-
2-Picoline, 5-vinyl-
Ally1 ether
1 Propene
Carbon tetrachloride
Chl oroform
1-Propene, 3-chloro-
Carbon tetrachloride
Hydrochloric acid
1-Propene, 2-methyl-
Carbon tetrachloride
-, 3,3,3-trifluoro-
Carbon tetrabromide
Propionic acid, vinyl ester
To l u e n e
Propylene
Bromoethane
Chl oroform
Steak acid, vinyl ester
To l u e n e
Styrene
Acetaldehyde
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 131
Solvent/Additive T (Cl cs (x104) Remarks Refs.
Styrene (contd)
Acetamide, N,N-dimethyl-
Acetic acid
->
methyl ester
-, bromo-
-, chloro-
-, -.
methyl ester
-, dibromo-, ethyl ester
-, monochloro-
50
60
40
100
60
68
68
60
100
90
60
-, dichloro- 60
-, dichloro-, ethyl ester
-, iodo-
-, phenyl-
-, -,
ethyl ester
-, tribromo-
60
68
60
100
-9 -1
ethyl ester
-, trichloro-
-
90
90
-
60
-, -1 ethyl ester
Acetic anhydride
Acetoacetic acid, ethyl ester
-, 2-acetyl, ethyl ester
Ac e t o n e
60
90
100
60
100
100
60
-, oxime
Acetonitrile
m-bromophenyl-
zcetonitrile, p-bromophenyl-
-7 m-chlorophenyl-
-, p-chlorophenyl-
-, p-methoxyphenyl-
-, phenyl-
-1
m-tolyl-
-, p-tolyl-
Acetyl bromide
Acetyl chloride, chloro-
Acetylene, p-bromophenyl-
-, p-chlorophenyl-
-, p-nitrophenyl-
Adipic acid, diallyl ester
-, di-(3,3,5,5-tetramethyl-4-nitrosocyclohexyl) est er
Al l y 1 a l c o h o l
Aluminum, hydrodiisobutyl
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
100
-1 triethoxy-
-, methyl
100
100
-7 triisobutyoxy-
triisobutyl
&line
-, N,N-dimethyl-
- , N, N-divinyl-
100
110
50
60
50
60
0.743
4.6
2.22
0.33
430
300
200
0.3
0.75
2700
28.6
0.76
35.0
1.0
1.3
8000
6.0
8.8
3.0 x 104
2.4 x lo4
10.5 x 104
270
66.0
100
3.75
65.0
90.0
145.0
0.7
1.3
3.0
4.1
<0.5
0.32
2.2
0.44
66.7
68.5
65.2
66.0
51.0
45.1
48.5
49.2
8600
3300
188.5
1 6 1
3130
6.0
1.1 x 104
1.5
26.9 x lo4
28.0 x lo4
<O.l
8.05 x lo4
17.0 x 104
<l.O
28.5 x lo4
20
2.0
1 2
53
130
C
A
A
C
R
R, H
R
R, H
A
A
C
C
A
R
R, H
A
C
A
A
C
A
A
A
A
S
K
K
K
F9, J
A
A
A
A
A
A
F2
A
F2
375
1 1 3
385
72
112
149
149
128
1 2 8
64
529
529
529
529
1 2 8
149
1 2 8
72
178
64
64
1 7 8
1 2 8
529
529
128
64
1 2 8
1 2 8
72
72
182
128
501
1 2 8
1 2 8
462
461
462
461
461
461
462
461
112
112
1 5 1
1 5 1
1 5 1
446
314
128
156
1 5 5
155,156
156
1 5 5
1 5 5
1 5 5
154
1 2 8
154
1 6 1
82
Remarks page II - 157; References page II - 159
II / 132 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T (I
cs (x104) Remarks Refs.
Styrene (conrd)
Aniline, N-methyl-
-, 2,4,6-trinitro-
p-Anisaldehyde
Anisole, p-ethynyl-
-, m-isopropyl-
-, p-isopropyl-
-, p-methyl-
-, 2,4,6-trinitro-
An t h r a c e n e
-, dihydro-
2H-Azepin-2-one, hexahydro-
Azohenzene
Benzaldehyde
-,p-bromo-
-, m-chloro-
-, p-chloro-
-, p-cyano-
Benzene
-9 allyl-
-. bromo-
-1 sec-butyl-
-, rert-butyl-
-, chloro-
-, -9 2,4,6-trinitro-
-, 1,2-dibromoethyl-
-, p-dibutyl
-, p-di-sec-butyl-
-, p-di-rerr-butyl-
-, m-dichloro-
-, o-dichloro- 60
-, p-dichloro- 60
50
50
60
60
60
60
60
50
44.1
50
130
70
60
100
60
60
60
100
60
3 5
40
50
60
70
75
80
100
132
100
60
1 5 5
60
60
80
100
60
80
100
140
50
60
60
60
60
140
1 3
11.8 x lo4
2.86
60.0
5.23
3.23
0.78
20.3 x lo4
2.0 x 104
610
0.61
750
4.54
5.5
2.6
12.2
13.7
8.63
5.6
16.7
3.9
5.8
0.01
0.018
0.023
0.028
0.04
1.92
5.50
6.67
0.061
0.121
0.156
0.184
0.23
0.31
0.42
0.81
0.89
1.5
36
1.78
3
6.22
0.04
0.06
0.193
0.55
0.133
1.50
0.235
0.874
0.54
0.6
58.5 x lo4
1950
1.02
10.70
0.87
0.2
1.4
3.4
2.6
F2
K
J
D
c 1
C
A
A
F2
F2
A
C
A, 15
H
C
C
I5
C
A
A, 15
A
A
A
A
A, 15
A, R
C
A
H
A, I5
A
15
A
C
C
C
15
A
154
370,372
495
1 5 1
405
406
496
370,372
159
271
108
281
495
86
298
495
495
495
298
495
119
119
321
127
79
255
1 4 5
415
123
1 2 3
1 8 5
255
273
1 2 7
1 4 5
235
235
235
127
1 4 5
524
182
237
415
1 4 5
1 2 7
1 8 5
127
255
182
255
1 8 5
235
58
370,372
112
415
415
415
58
61
182
182
TABLE 4. contcl
Transfer Constants to Solvents and Additives II / 133
Solvent/Additive T ((2
cs (x104) Remarks Refs.
Styrene (contd)
Benzene, diethyl-, (mixture)
-, p-diisopropyl-
-,
ethyl- 60
-,
ethynyl- 60
-1 sec-hexyl-
-9
sec-pentyl-
-, tri-sec-butyl-
-, 1,3,5-trinitro-
Benzo[B] chrysene
Benzoic acid
-,
m-(phenylazo)-, methyl ester
-, 2,4,6-trinitro-, ethyl ester
Benzoin
Benzonitrile
-, p-isopropyl
Benzo[A]pyrene
p-Benzoquinone
pBenzoqui none, 2-anilino-
-, 2,5-dimethyl-
-, 2-methyl-
-, 2,3,5,6-tetrachloro-
-, 2,3,5,6-tetramethyl-
-, 2,3,5-trimethyl-
Benzyl ether
Bibenzyl, cc,cc-dibromo-
Bicyclohexyl, 3,3,3,3,5,5,5,5-octamethyl-4,4-dinitroso-
Biphenyl, 2,2-methylene-
Borane, tributoxy-
-, tributyl
Butane, l-bromo-
-, l-chloro-
-, 2-chloro-
-, 2,2-dimethyl-
-, l-iodo-
1,4-Butanediol
100
132
60
80
100
132
60
60
60
40
50
60
44.1
3.35
6.33
5.13
3.30
6.60
0.67
0.70
0.710
0.83
2.7
1.07
1.113
1.38
1.62
2.2
2.33
2.31
2.9
4.9
96.3
98.3
12.76
9.43
13.30
9.48 x lo5
6.43 x lo5
3.51 x 105
1.3 x 10s
70 700
50 5.72 x 10
60 40
60 5.3
60 18.6
44.1 1.4 x 105
60 22.7 x lo5
80 56.6 x lo5
45 53.2 x 10
80 4.3 x 105
80 21.0 x 105
80 95.0 x 10s
80 6700
80 2.6 x lo5
2 5 71.6
60 62.4
60 3020
60 1.12 x 104
80 1.2 x 104
60 142
60 97.9
100 <O.l
100 34.8
60 0.06
100 0.35
60 0.04
100 0.37
60 1.2
100 0.3
60 0.43
60 1.85
100 5.5
60 3.2
80 5.6
100 9.3
A
A
A
A
C
A, 15
C
15
C
A
A
A, 15
A
A
A
A, 15
K
J
H
H
H
J
C
A
J
F9, J
F9, J
A
A
A
A
A, S
A
A
A
F24
F24
F24
235
235
235
497
406
1 2 7
79
255
1 4 5
363
1 8 5
255
235
1 2 7
1 4 5
235
235
127
1 4 5
1 5 1
150
415
415
415
372
370,372,373
372
159
281
370,372
1 2 8
150
406
159
42
27
199
27
27
27
27
27
368
368
112
314
314
567
567
156
156
128
128
128
1 2 8
1 2 8
128
304
1 2 8
1 2 8
422
422
422
Remarks page II - 157; References page II - 159
II / 134 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T (Cl
cs (xlO4) Remarks Refs.
Styrene (contd)
2-Butanone
1-Butene
-, 3,3-dimethyl-2-phenyl-
-, 2,4-diphenyl-
-, 3,4-epoxy-2-methyl-
-, 2-methyl-
-, 3-methyl-
2-Butene
-, l,Cdichloro-
-, 2,3-dimethyl-
-, 2-methyl-
3-Buten-2-01, 1-chloro-3-methyl-
Butyl alcohol
see-Butyl alcohol
rerr-Butyl alcohol
Butylamine
reti-Butyl et her
terf-Butyl isocyanide
1-Butyne, l-phenyl-
Butyraldehyde
-, diallyl acetal
Butyric acid, 4-hydroxy-, y-lactone
Cadmium, dibutyl
Carobonic acid, cyclic ethylene ester
-, diallyl ester
-, di-(3,3,5,5-tetramethyl-4nitrosocyclohexyl) est er
Carbon tetrabromide
60
70
75
100
110
110
80
100
100
100
80
100
100
80
40
50
60
60
50
60
80
100
130
60
60
80
100
60
-
50
60
100
60
50
100
50
60
60
80
40
60
4.98
8.60
12.00
2.6
1 0
70
17.4
3.1
6.9
6.1
2.0
5 1
5.4
5.1
2.9
8.2
11.2
6.5
0.06
1.6
0.562
6.6
0.22
6.65
0.345
0.55
1.0
0.5
2.6
1.0
33.0
34.3
2.7
14.3
2.7
3.7
4.0
4.7
8.0
8.0
11.7
14.3
5.7
11.0
20.2
0.409
1170
0.235
6.2
1.3 x 104
1.4 x 104
1.8 x lo4
1.78 x lo4
2.2 x 104
2.5 x lo4
13.6 x lo4
4.2 x lo4
A
A
A, R
A
C
A
A, R
A
F24
A
A C
A
A
A
A
c, F2
C, F2
W8
F29, W8
F29, W16
F2, W7
F29, W7
F2, W15
F29, w15
F2
F29
A
A
E
F27, J
F9, J
F2
C
F2
Fl
A
(5.09f0.18) x lo5 II2
60 88300
60 40600
70 1.8 x lo4
80 2.3 x lo4 F2
90 2.51 x lo4 C
100 2.35 x lo4 A
182
1 2 3
1 2 3
358
433
433
269
358
358
524
358
112
358
524
358
269
119
430
128
323,385
479
430
422
385
422
261
261
128
301
301
4,75
150
412
412
414
414
413
414
413
414
413
414
128
128
446
375
156
458
446
314
314
109
64
109
109
1 2 8
487
520
568
568
6 1
109
64
128
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 135
Solvent/Additive
T (C)
cs (x104) Remarks Refs.
Styrene (conrd)
Carbon tetrachloride 8 0
-
100
5 0 1 7
2 4 8
6 0 6 9
8 4
8 7
9 0
9 2
9 8
100
109
110
120
122
144.1
130.9
148
6 0 9 2
6 0 110
7 6 1 8
117
8 0 133
8 5 34.1
9 5 148
186
1 8 5
3 0 4
3 0 0
100
132
140
6 0 0.41
0.5
0.566
3.40
4.0
0.50
0.916
3.3
1 1
3 3
4 3
22.1
3 9
<5
0.8
0.82
1.04
3.88
1.31
2.00
2.90
8.29
7.57
3.46
6.90
0.024
0.031
0.04
0.063
8.5
0.066
0.083
0.156
0.16
0.23
Chloroform/acetone
m-Cresol
o-Cresol
p-Cresol
-, u-phenyl-
-, m-bromo- 6 0
-, p-bromo- 6 0
-, p-tert-butyl- 6 0
-, p-chloro- 6 0
Cyclohexane 6 0
6 8
8 0
6 0
50
5 0
6 0
5 0
6 0
6 0
6 0
8 0
100
8 0
100
W8
436
C, W8
C
c, w7
A
C
Q1 4 2
A, X
R
R H
X
C
A
15
Q38
Q1 4 2
A
A
A
A
C
C
15
C
A
A, I5
I5
A
A, 15
A
A, 15
C
F23
15
C
A
A, 15
4 1 2
4 1 2
513
5 1 3
6 3
401
113,183
401
128,129,210
401
3 6 6
6 3
223
4 1 6
114
5 2 9
5 2 9
1 1 5
5 6 8
5 6 8
2 3 6
2 3 6
1 8 5
1 6 3
6 3
6 3
128,129
129
5 8
501
128,210
255
182
149
1 8 5
2 5 5
501
247,248
247,248
1 2 1
247,248
1 2 1
1 2 1
7
127
1 4 5
4 0 6
1 8 5
127
1 4 5
4 0 5
4 0 6
4 0 6
4 0 6
127
7 9
1 4 5
255
119
185
255
273
127
1 4 5
Remarks page II - 157; References page II - 159
II / 136 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (C) cs (x104) Remarks Refs.
Styrene (contd)
Cycl ohexane (co&d)
Cyclohexanone
-, rruns- 1,4-, diacetate
cis/trans-1,4-, dicarboxylic acid dimethylester
C yclopentanone
1-Cyclopentene-1-carboxylic acid, 3,3,5,5-tetramethyl-4-nitroso-,
diester with pyrocatechol
Cyclotetrasiloxane, octamethyl-
1,2,3,4-Dibenzpyrene
1,2,7,&Dibenztetracene
1,2,9,10-Dibenztetracene
p-Dioxane
Diphenylamine-T
Disiloxane, hexamethyl-
Epibromohydrine
Epichlorohydrine
Et hane, 1,2-dibromo-
-,1,2-dichloro-
-, pentaphenyl-
-, 1,1,2,2-tetrachloro-
-, 1,1,2,2-tetrachloro-1,2-difluoro-
-, 1,1,2-trichloro-1,2,2-trifluoro-
Ethanehexacarboxylic acid, hexaethyl ester
1,1,2-Ethanetricarboxyic aci d
Ether, benzyl methyl
-, p-bromobenzyl methyl
-, p-chlorobenzyl methyl
-, p-cyanobenzyl methyl
-, dodecyl vinyl
Ethyl acetate
Ethyl alcohol
Ethylene, l,l-diphenyl-
Ethylene glycol
-, bis(m-phenylazobenzoate)
Ethyl ether
Fluorene
Formamide, N,N-dimethyl-
1 3 2
60
60
60
60
60
80
50
44.4
44.4
44.4
60
100
60
79.5
60
60
60
80
60
70
80
100
60
100
90
90
50
100
68
68
68
68
60
60
70
75
100
60
80
110
60
80
100
70
60
60
100
40
50
60
100
0.31 A 235
12.3
A, R
524
0.81 A 235
0.87 A 1 2 7
1.5 A, 15 1 4 5
7.90 C 182
16.9 C 569
4.2 C 569
3.30 C 182
1.3 x 104
1.0 x 104
4.0
6.0 x lo4
13.0 x 104
13.0 x 104
0
2.28
2.75
0.8
0.9
0.387
67.48
37.87
0.988
1.914
0.333
4.12
1.1
1.137
9.8
3.84
20000
10.8
1.13
0.84
<50
0.94
6.0
6.0
4.0
20.0
3.32
4.11
15.5
5.5
6.67
0.39
1.32
1.611
2.60
450
1.36
2.70
4.70
900
5.64
75.0
124.0
1.09
0.869
4.0
1.08
F27, J
F9, J
C
J
J
J
A, S
C
C
F2
C
C
FlO
C
C
F2
F2
A
F24
F24
F24
C
C
A
A
E
314
314
450
159
159
159
1 2 8
4
182
220
46
474
529
529
255
255
255
182
67
255
112
235
1 2 7
235
1 4
1 4
89
72
1 4 9
1 4 9
149
149
4
4
119
1 2 3
1 2 3
72
423
479
423
432
422
422
422
281
4
127
127
458
375
113
256
Transfer Constants to Solvents and Additives II / 137
TABLE 4. contd
Solvent/Additive T (0
cs (x104) Remarks Refs.
Styrene (conr d)
Furan, tetrahydro-
cc, o-Glucoside, met hyl -
-, -9 6-deoxy-6-mercapto-
-9 -1
2,3-di-o-henzyl-
-9 -, 2,3,4,6-tetra-o-acetyl-
-, -,6-O-@-toluenesulfonyl)-
-1 -9
2,3,4-tri-0-acetyl-6-deoxy-6-iodo-
-1 -, 6-O-triphenylmethyl-
0, D-Glucoside, metbyl-
-, 6-deoxy-6-dipropylamino-
&mane, ethyldichloro-
-, diethylchloro-
-, triethyl-
-, dimethylchloro-
triphenyl-
HLptane
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-
1-Heptene
2-Heptene
Hexane
1 -Hexene
2-Hexene
Hydrochloric acid
Hydroquinone
Hydroxylamine, N,N-dibenzyl-
-9
N-benzyl-N-phenyl-
- , N, N-diethylene-
N-ethyl-N-phenyl-
&mm triethyl
Iron@) chloride
Isobutyl alcohol
Isobutyl alcohol-D
Isobutyraldehyde
Isobutyric acid
Isobutyronitrile
Isophthalic acid, diallyl ester
Isopropyl alcohol
Isopropyl alcohol-D
Isopropyl-l-D alcohol-D
Lead, tetraethyl
Malonic acid, diallyl ester
-, diethyl ester
-, dimethyl ester
-1
acetyl-, diethyl ester
-, bromo-, diethyl ester
-, butyl-, diethyl ester
-, dibromo-, diethyl ester
-, dichloro-, diethyl ester
-, diethyl-, diethyl ester
-7
ethyl-, diethyl ester
50
100 55000 220
100 62 220
100 2.0 220
100 2.0 220
100 50 220
100 2 1 220
100
60
60
60
60
60
60
100
60
100
100
100
100
100
100
60
60
60
60
60
100
60
60
100
130
60
100
130
60
60
80
100
130
100
100
100
60
60
100
100
100
60
100
100
60
60
100
100
100
0.50
22
56900
31600
2400
33500
23000
0.42
0.95
13.33
2.7
3.2
0.9
2.5
2.5
3.6
0
3.6
5000
3.8 x 104
2.5 x lo4
20.5 x lo4
1.7600 x lo4
536.0 x lo4
0.17
0.497
2.9
7.8
8.2
21.0
2.5
4.6
2.7
3.5
3.5
3.05
4.00
1.7
6.0
2.7
1.6
0.78
1.24
5.2
0.47
0.46
0.42
1.2
700
1200
0.82
1.2 x 104
30.0
62.0
0.88
0.72
C
A, R
A, R
A, R
A, R
A, R
A
A
F2
A
A
A
A
A, R
A
A
R
R
R
R
A
A
A
W 8
C
A
A
A
F2
F2
A
F2
A
A
A
A
A
A
A
A
A
449
220
539
539
539
539
539
1 2 7
127
442
358
358
358
358
524
358
238
128
533
533
533
533
156
1 9
385
479
261
261
412
412
385
385
261
261
446
423
423
261
423
261
261
261
156
446
1 2 8
72
72
72
1 2 8
1 2 8
72
1 2 8
128
128
72
72
Remarks page II - 157; References page II - 159
II / 138 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Addition
T ((3 cs (x104) Remarks Refs.
-, dibromo-
-. dichloro-
-, diiodo-
-, diphenyl-
-, nitro-
-,
triphenyl-
Methanetricarboxylic acid
Methanol
-, (4-biphenylyl)phenyl@-vinyl-phenyl)-
-, bis(4-biphenylyl)(p-vinyl-phenyl)-
Naphthalene
-, decahydro-
-, 2-isopropenyl-
-, 2-methoxy- 60
-, 1,2,3,9-tetahydro-l-phenyl- 60
1-Naphthol 60
-, 2,4-dichloro- 60
1-Naphthol-D 60
2-Naphthol 60
Naphtho[2,3-alpyrene 44.4
2,6-Octadiene, 2,6-dimethyl- 60
2-Octene 100
Oleic acid, methyl ester 60
Oxalic acid, diallyl ester
-, diethyl ester
Oxetane, 3,3-bis(chloromethyl)-
Oxime, acrolein
-, crotonaldehyde-
-,
ethylisopropenylketone-
-, methacrolein-
-3 methylacrolein-
-3 methylisobutylketone-
-,methylisopropenylketone-
methylvinylketone-
Gxolane, cis-3,4-diacetoxy-
Pentane, l-chloro-
-, 2,2,4-trimethyl-
2,CPentanedione
Styrene (contd)
Malonic acid, phenyl-, diethyl ester
Mercury, diethyl
Met hane, bis(2-chloroethoxy)-
-, bromotrichloro-
100
100
80
80
60-80
80
60
60
80
100
60
60
100
60
60
80
100
100
60
80
100
50
50
60
60
80
99
70
90
60
60
50
60
60
60
60
60
60
60
60
60
60
100
100
3.5
0.335
6.0 C
7.6 x lo4
D, Q2
7.7 x 104 Q Q2
2.4 x lo6 D, Q3
2.78 x lo6 D, 43
6.5 x lo5
(6.5 f 0.4) x lo5
9 4 5 0
110
0.15
9.5
11.8
710
2.3
4.2
35
1 0
3.5
6.0
8.0
0.91
0.296
0.74
1.10
1.22
3.5
3.5
11
0.4
56
70
69
86
<5.0
10000
480
490
75
77
24.0 x lo5
2.0
2.8
3.15
3.52
455
420
6.64
4.2
13.5
8.0
10800
1500
4300
13000
400
2300
1100
2700
1.89
0.49
< 10
2.0
15
A
C
A
A
A
A R
A
A
F2
F2
F2
A
C
J
C
A
C
C
A
F22
C
72
156
112
312
1 9 5
312
1 9 5
439
504
1 8 5
112
128
112
128
112
1 2 7
1 2 7
524
86
1 2 7
44
127
72
479
423
423
423
57
57
216
1 2 7
98
98
98
98
1 2 1
467
50,121
1 2 1
50,121
122
159
324
358
441
441
239
1 4 1
441
446
119
449
555
555
555
555
555
555
555
555
569
1 2 8
1 5 5
72
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 139
Solvent/Additive
T (Cl cs (x104) Remarks Refs.
Styrene (conrd)
1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro-
3-Pentanone
Pentasiloxane, dodecamethyl-
1-Pentene
-, 4,4-dimethyl-2-phenyl-
-, 2,4-diphenyl-
-, 4-methyl-2,4-diphenyl-
-, 4-methyl-2-phenyl-
-, 2,4,4-triphenyl-
2-Pentene
-, 2-methyl-
4-methyl-
Phenol
-, p-benzyloxy
-, p-terr-butyl-
-, o-chloro-
-, p-chloro-
-, 2,6-di-tert-butyl-
-, 2,6-diisopropyl-
-, p-fluoro-
-1 m-methoxy-
-> o-methoxy-
-, p-methoxy-
-, o-phenyl-
-, 2,3,4,6-tetramethyl-
-, 2,4,6-trinitro-
Phenol-D, p-benzyloxy-
-, 2,3,4,6-tetramethyl-
Phenyl ether
Phosphine, dibutyl
-, diethyl
octyl
Phosphine, phenyl
-, tributyl
Phosphoric acid, tributyl ester
Phosphorus, white (P4)
Phosphorus trichloride
o-Phthalic acid
-, bis(2-methylallyl) ester
-, diallyl ester
-> di-(3,3,5,5-tetramethyl-4-nitrosocyclohexyl) est er
Piperidine
Propane, 1-chloro-2,3-epoxy-
-, 1-chloro-2-methyl
-, 1,1,1,3-tetrabromo-3-phenyl-
-, l,l,l-tribromo-
1,2Propanediol
1,3-Propanediol, 2,2-bis(bromomethyl)-, diacetate
1,3Propanedione, 1,3-diphenyl-
1-Propene, 3-chloro-2-methyl-
-, 2-methyl-
-, 1,3-diphenyl-
Propionaldehyde, diallyl acetal
Propionic acid
60 11.36
60 2.6
79.5 0.285
100 2.3
110 1 0
110 170
110 2900
110 1 0
110 2600
100 4.2
100 6.3
100 6.9
50 8.1
60 1 4
60 290
60 26
60 6.0
60 -11
60 49
60 310
60 54
60 <5
60 43
60 260
60 <5
60 580
50 2.11 x 10s
60 1 0
60 20
25 7.94
60 7.86
100 2.08 x lo4
100 1.35 x 104
60 3.6 x lo4
60 43.9 x 104
100 24.4
100 <O.l
25 400
57 250
75 800
60
60
80
60
50
60
100
90
90
60
80
100
60
60
60
100
60
60
60
6.3
6.3
1.2 x 104
1.32 x lo4
1.0
7.5
1.4
3.0
3.65 x lo4
2.41 x lo4
2.08
3.90
6.80
4.05
7.0
24.0
1.7
87.3
12.3
0.05
4.3
4.5
4.65
F2
A
D
A
A. S
E
C D
F9, J
F27, J
A
C
A
A
C
C
F24
F24
F24
A
A
A
A
C
A
442
385
474
358
433
433
433
433
433
358
358
358
247,248
122
50,121
1 2 1
122
1 2 1
1 2 1
1 2 1
121
1 2 1
122
1 2 1
1 2 1
50,121
371
50
50
368
368
296
296
295
295
156
156
99
214
494
446
446
314
314
1 2 8
449
128
128
64
64
422
422
422
325
1 2 8
1 2 8
358
567
446
1 2 8
385
323
385
Remarks page II - 157; References page II - 159
II/140 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T (Cl
cs (x104) Remarks Refs.
Styrene (contd)
Propionitrile, 3-phosphino-
-, 3,3-phophinylidenedi-
Propyl alcohol
Propylene oxide
2-Propyn- 1-01
Pyridine
Pyrocatechol
-, p-teti-butyl-
Pyrocatechol-D
-, p-rerr-butyl-
Pyrogallol
Pyrogallol-D
Sebacic acid, diallyl ester
Silane, chlorotrimethyl-
-, dichlorodimethyl-
-, diethylchloro-
-, dimethylphenyl-
-, hexamethoxy-(3,3-thiodipropyl) bis-
-3 methyldichloro-
-, 3-mercaptopropyl-trimethoxy-
-, trichloro-
-9 tetraethyl-
-.
tetramethyl-
-, trichloromethyl-
-, triethyl-
-, trimethoxymethyl-
-, triphenyl-
Silicon chloride
Siloxane, hexamethyl-di-
-, dodecamethyl-penta-
octamethyltri-
Sorbit-2,5-diacetate, 1,4:3,6-, dianhydro-
Stamtane, triphenyl-
Stearamide, N-allyl-
60
70
80
50
79.5
79.5
79.5
60
60
90
Steak acid, methyl ester 60
Stibine, tributyl
Stibene, dibromo-
Styrene, u-bromo-
-, j3-bromo-
-, di bromo-
-, cr-ethyl-
-7 u-methyl-
Succinic acid, diallyl ester
Succinonitrile, tetraphenyl-
Sulfonyl chloride, benzene-
-, p-chloro-benzene-
-, p-methyl-benzene-
60
60
60
80
100
50
60
60
60
60
60
60
60
60
60
50
50
60
60
79.5
60
79.5
60
100
50
50
60
70
80
79.5
70
90
1 0 0
60
70
70
60
110
60
74
80
99
110
60
50
60
60
60
50000
50000
2.00
3.14
3.60
1.6
7.0
0.6
1340
3600
260
370
10400
1600
4.8
12.5
17.8
5700
2200
118
9800
5.9 x 104
1.4 x 104
8.12
3.1
19.2
1200
33.4
36.8
0.23
0.230
3700
2.44
1.3
20.0
0.387
0.285
0.069
77
3.3 x 104
5.82
8.30
1.06
526
15.6
0.676
58.0
3020
10000
2000
1950
1 0
0.86
95
3.2
4.9
5.6
8.5
1.67
5.4
28000
4330
7650
3180
A
A
F2
F2
F2
C
A
A
J
J
J
A, R
A, R
R
A, R
R
A. R
A. R
R
A. R
R
R
R
C
A R
A, J
C. J
C
A
A
R
R
R
295
295
423
423
423
449
128
128
50,121
50,121
50
50
50,121
50
446
249
249
539
539
554
539
554
539
156
249
249
539
90
90
474
554
539
90
90
249
554
554
554
569
539
1 7 3
1 7 3
441
239
1 4 1
441
156
112
172
172
112
439
431
343
98
98
98
98
431
446
89
543
543
543
TABLE 4. contd
Solvent/Additive
T ()
Transfer Constants to Solvents and Additives II / 141
cs (xlO4) Remarks Refs.
Styrene (co&d)
Sulfonyl chloride, p-methoxy-benzene-
-, methane-
-, phenylmethane-
a-phenyl-P-(methanesulfonyl)-ethane-
ikephthalamide, N,N-dimethyl-N,N-dinitroroso-
Terephthalic acid, diallyl ester
Tin, tetrabutyl
To l u e n e
-, p-bromo-
-, m-chloro-
-, p-chloro-
-, a-chloro-
-, cc,cc-dichloro-
-, p-etbynyl-
-3 u- H 1, t ol uene
-, PO-* HZ, toluene
-3 c@fl-* H3, toluene
-, craa-trichloro-
-, 2,4,6-trinitro-
p-Toluidine
-, N,N-dimethyl-
-, N-metbyl-
m-Tolunitrile, a-cyano-
p-Tolunitrile
-, a-cyano-
s-Triazine, trimethyl-
Triethylamine
Tripropylamine
Trisiloxane, octamethyl-
Urea, 1,3-bis(3,3,5,5-tetramethyl-4-nitrosocyclohexyl)-
Wa t e r
m-Xylene 60
p-Xylene 60
-, ~,a-dibromo- 60
2,6-Xylenol 60
60
60
60
60
40
60
60
100
60
8 0
100
132
60
60
70
140
60
60
60
60
80
80
80
60
50
50
50
50
60
60
60
60
60
100
19.5
60
80
60
3110 R 543
1180 R 543
3190 R 543
27600 R 543
1400 160
2000 160
4.5 446
3.71 156
0.105 C 255
0.121 21,24,79
0.125 A 1 2 7
0.134 78
0.16 A, 15 1 4 5
0.21 318
0.82 496
1.10 C 363
2.05 363
0.15 C 385
0.298 I5 1 8 5
0.3 C 385
0.308 C 255
0.310 76,71
0.313 78,273
0.813 C, F17 530
0.53 A 235
0.55 C 385
0.645 A 1 2 7
0.72 A 235
0.8 A, I5 1 4 5
1.12 A 235
1.30 496
1.25 496
0.62 67
1.8 67
1.07 496
1.56 A 1 2 8
50.0 A 1 2 8
72.0 K 1 5 1
0.825 C, F17 530
0.820 C, F17 530
0.992 C, F17 530
57.5 A 128
14.6 x lo4 370,372
78 F2 154
1 6 F2 154
11 F2 154
91.4 462
2.07 496
112 461
0.468 88
1.4 w9 364
3.0 W6 364
7.1 24
7.5 363,364
24.2 156
0.069 474
14500 F9, J 314
15000 F9, J 314
0.006 479
0.31 A R 529
0.78 496
0.84 496
150 112
110 1 2 1
Remarks page II - 157; References page II - 159
II / 142 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T ((3 cs (xlO4) Remarks Refs.
St yrene (contd)
Zinc, diethyl
-, p-chloro-
Anisole, p-isopropyl-
Benzaldehyde
-, p-chloro-
Benzene, p-diisopropyl-
100 3660 156
60
100
100
60
3.86
1.9
9.7
3.62
1.24
8.84
52000
45
3.44
5.71
3.52
4.91
A
A
60
60
60
60
60
60
60
F2
406
298
298
491
406
406
109
366
406
406
406
406
50 0.2 56
60
60
60
60
60
60
60
3.27 408
3.67 408
1.34 406
26.0 408
4.12 408
9.23 408
3.59 408
7.67 408
60
60
60
60
60
60
60
60
60
0
0
5.35
0.117
1.09
6.76
1.53
1.61
0.033
1.20
A
469
469
469
469
469
469
469
469
469
469
60 1 5 E F 366
1 1 5 EE 366
55 0.077 C, F25 93
55 0.127 C, F26 93
80 6.2 201
30
45
50
60
400
530
390
0.12
200
220
500
570
660
610
700
40
0.180
0.166
0.200
1.0
1.13
1 0
0.170
J
18
F2
J
70
15
60
50
60
J
C
19
65
F2
C
346
86
460
251
145
232
460
86
86
460
86
86
466
465
466
1 4 5
289
86
466
Benzonitrile, p-isopropyl-
Carbon tetrabromide
Carbon tetrachloride
Cumene
-, p-bromo-
-, p-tert-butyl-
-, p-chloro-
-, p-iodo-
Benzene
-, p-methyl
Anisole, p-isopropyl-
Benzene, p-diisopropyl-
Benzonitrile, p-isopropyl-
Cumene
-, p-bromo-
-, p-tert-butyl-
-, p-chloro-
-, pentafluoro-
Benzene, bromo-
-, chloro-
-, ethyl-
-, fluoro-
2-Butanone, 3-methyl-
Cumene
Furan, tetrahydro-
2-Pentanone, 4-methyl-
To l u e n e
StyreneNyrene, p-chloro-
Carbon tetrachloride
Succinimide, N-vinyl-
Acetic acid
Et hane, 1,2-dichloro-
Valerie acid, 4-methyl-, vinyl ester
Benzene
Vinyl acetate
Acetaldehyde
Acet ami de, N-butyl-
Acetic acid
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 143
Solvent/Additive
T (C) cs (xlO4) Remarks Refs.
Vinyl acetate (conld)
Acetic acid, ally1 ester
-, benzyl ester
-, butyl ester
-1
set-butyl ester
-, tert-butyl est er
-, isobutyl ester
-1 isopropyl ester
-1 methyl ester
-, propyl ester
-, 1,3,3,3-tetrachloropropyl est er
-. bromo-
-, chloro-
-9
cyano-, methyl ester
-, dichloro-, ethyl ester
-, phenyl-
-, trichloro-
-1
ethyl ester
trifluoro-, ethyl ester
Acetic anhydride
Acetoacetic acid, ethyl ester
Ac e t o n e
-, phenyl-
Ac e t o p h e n o n e
-, 3-hydroxy-
-, 3-hydroxy-D-
An i l i n e
-, N,N-dimethyl-
-, N-methyl-
-, p-nitro-
m- An i s a l d e h y d e
o - An i s a l d e h y d e
p - An i s a l d e h y d e
An i s o l e
An t b r a c e n e
-, 9-phenyl-
Benzaldehyde
60
60
5 0
50
60
5 0
60
5 0
50
60
61. 5
75
6 0
50
60
70
6 0
70
70
60
6 0
60
70
6 0
50
60
70
6 0
70
75
6 0
60
50
60
70
45
45
50
50
50
50
60
60
6 0
60
20
30
40
50
60
50
60
70
15
85
94
8 0
13. 2
4. 4
8. 0
1. 5
6. 2
9. 1
3. 5
3. 1
8.0
9. 0
1 0
1.56
1.6
2. 5
6. 2
3. 4
423. 2
489
4450
2550
5000
210
400
1445
4 4 0 0
30
8. 0
80. 4
1. 5
11. 70
12. 0
25. 6
42
1 0
2100
91.5
100
62. 0
1405
1290
149
210
260
360
48600
2500
420
370
1 0
6. 68 x 10s
6. 03 x lo*
4. 55 x 10s
2. 057 x lo5
3. 64x 10s
2. 78 x lo5
2. 73 x lo5
230
460
540
421
600
F 2
J
F2, J
J
J
C
C J
C
C
J
C
C
C
C
C
J
J
C
J
F2
F2
F2
fl, J
J
F2
J
C, J
J
86
86
86
208
208
86
208
232
208
208
145, 232
86
86
86
145, 231
145, 232
86
208
145, 232
389
386
389
389
86
86
86
389
86
71
86
390
86
289
145
330
184
86
86
15
86
390
51
51
15
154
154
154
15
86
86
86
86
41
41
41
15
41
41
41
145, 355
86
86
390
86
Remarks page II - 157; References page II - 159
II / 144 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (3 cs (xlO4) Remarks Refs.
Vinyl acetate (contd)
Benzaldehyde, m-chloro-
-, o-chloro-
-, p-chloro-
-, m-cyano-
-, p-cyano-
-, p-isopropyl-
Benz[A]anthracene
-, bromo-
-9
tert-butyl-
-. chloro-
Benzene, o-dichloro-
-, p-dichloro-
-, m-dinitro-
-, o-dinitro-
-, p-dinitro-
-1 ethyl-
-, nitro-
-, 1,3,5-trinitro-
Benzo[B]chrysene
Benzoic acid
-,
ethyl ester
-, p-nitro-
Benzoic anhydride
Benzoin
Benzonitrile
-1 m-hydroxy-
m-hydroxy-D-
Bknzo[GHl]perylene
Benzophenone
Benzo[A]pyrene
Benzo[E]pyrene
p-Benzoquinone, 2,3,5,6-tetramethyl-
Benzoyl chloride
Benzyl alcohol
Biphenyl
Borane, tributyl
60
60
60
60
60
60
50
60
70
7 5
50
60
70
75
60
60
70
75
75
70
45
50
45
45
50
60
50
45
50
50
60
60
50
60
60
50
45
45
50
50
50
50
45
50
70
70
50
60
1 0
860
390
340
1070
610
540
1.17 x 10s
1.07
1.2
1.2
2.4
2.96
20
5.27
1.4
1.40
3.6
18.9
8.0
9.2
10.0
134.2
25.2
3.61
5.6
6.8
8.0
8.35
80
2.61
12.7
42
11.8
1.05 x 10s
645700
9.6 x lo5
26.7 x 10
662800
55.15
100
110300
8.9 x lo6
434280
2.83 x lo5
50
26
245700
130
800
40.6
820
805
1.82 x lo4
286
3.06 x 10
8400
9.5 x 10s
366
300
556
263
6.4
9000
J
C
C
J
C
w7
w15
C
C
w7
w15
J
C
C
C
C
C J
C, J
C. J
J
C. J
J
J
C
C
86
86
86
86
86
86
4 1
263
86
294
80
289
294
390
86
263
184
1 5
265
265
265
389
184
289
265
265
265
289
86
389
184
184
389
28
1 5
28
28
1 5
289
86
1 5
28
15
4 1
86
86
1 5
86
86
1 5
5 1
5 1
370
1 5
4 1
370
27
1 5
389
390
15
132
1 9 1
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 145
Solvent/Additive
T (Cl
cs (xlO4) Remarks Refs.
Vinyl acetate (cent d)
But ane, l-bromo-
-, l-chloro-
-, l-iodo-
2,3-Butanedione
2-Butanone
-, 3-methyl-
1-Butene, 3-chloro-3-methyl-
2-Butene, 1-chloro-3-methyl-
1-Buten-3-yne
Butyl alcohol
set-Butyl alcohol
rerr-Butyl alcohol
Butyl ether
3-Butyn-2-01, 2-methyl-
Butyraldehyde
Butyric acid, ethyl ester
-,
methyl ester
Carbon tetrabromide
Carbon tetrachloride
Chloral hydrate
Chloroform
2-Chloro-3-(methyl-4C)-lbutene(4- 14C)
3-Chloro-2-pentene-(2,4- 14C)
60
70
60
60
60
60
75
60
50
50
60
60
70
60
70
75
60
70
60
60
40
6 0
70
50
60
60
70
0
20
45
60
70
75
60
70
70
-
30
60
70
50
50
50
1100
1 0
800
670
73.80
1 6 5
118.16
28900
4300
0
20.0
20.39
29.1
31.74
6.21
95.0
0.46
0.5
1.3
12.1
76
400
440
510
590
670
650
1000
388
45
1 8
1 9
7.39 x 106
28740
1500
4700
7600
800
1300
4700
6700
7300
8000
9000
9600
10000
10500
10700
2023
10500
5000
4927
4312
100
140
125.18
130
150
160
170
554
3980
628
C
F2, J
C
F2
F2
J
19
C
C
C
19
C J
J
W8
w7
w15
C
C
F2
C
:;:
C
J
C
C
I9
J
F2
C
F2
F2
86
389
86
86
86
289
184
289
152
152
232
1 4 5
289
390
289
390
184
289
1 4 5
86
390
86
86
500
500
500
500
232,355
86
390
7 1
145,232
86
109,145
389
346
309
86
1 0
1 0
1 0
1 0
86
1 0
1 0
86
210
1 0
1 0
389
86
86
389
389
345
346
289
1 4 5
86
210
86
389
509
509
Remarks page II - 157; References page II - 159
II / 146 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contcf
Solvent/Additive
T (Cl
cs (xlO4) Remarks Refs.
Vinyl acetate (contd)
Chrysene
m-Cresol
m-Cresol-D
p-Cresol
p-Cresol-D
Crotonaldehyde
Cumene
Cyclohexane
-,
methyl-
1,3Cyclohexanedione, 5,5-dimethyl-
Cyclohexanol
Cyclohexanone
Cyclohexene
Dibenz[a,h]anthracene
Dibenzo[def,mno]chrysene
1,2,3,4-Dibenzpyrene
Diethylene glycol
Diethylphosphonate
p-Di oxane
Diphenylamine
Diphenylamine-D
Diphenylamine-T
Et hane, l,l-dibromo-
-, 1 ,Zdibromo-
-, l,l-dichloro-
-, 1,2-dichloro-
-, 1,2-dichloro- 70
-, hexachloro- 70
-, pentachloro- 70
-, 1,1,2,2-tetrabromo- 60
-, 1,1,2,2-tetrachloro- 60
-, l,l,l-trichloro-
-, 1,1,2-trichloro-
1 , 1-Ethanediol, diacetate
Ether, benzyl methyl
-, bis(Zchloroethy1)
-, dodecyl vinyl
e t h y l
l&y1 acetate
50
45
45
45
45
60
60
70
75
60
60
70
70
60
75
60
75
50
40
50
60
50
70
60
60
60
60
60
70
50
60
60
60
60
70
60
60
70
60
60
60
60
70
60
60
20
40
50
60
3360
375
85
710
130
1800
89.9
100
139
356
6.59
7.0
100
11.75
24
5580
127
180
670
620
1600
770
8.7 x lo4
156.5 x lo4
129.2 x lo4
105.4 x 104
73.6 x lo4
85.3
350
910
830
730
20
49.1
138
240
170
230
1100
134
65
5
7
7.18
10.2
1210
1348
6000
107.03
160
67.72
71.11
35.98
40
280
245
57.2
73.5
45.3
1.52
2.11
2.9
1 2
1.07
C
C
19
F2
C
C
F2
C
J
F2
J
J
J
J
J
J
C
Fl
F2
F2
F2
F2
C
C
19
C
C
C
C
F2, J
C
C
C
C
C
370
5 1
6 1
5 1
5 1
355
289
7,86
390
184
289
145
86
289
86
390
390
86
184
86
86
86
370
4 1
4 1
4 1
4 1
390
571
571
571
571
86
390
1 5
46
46
46
86
389
86
86
1 4 5
289
389
389
389
86
289
86
389
289
289
86
86
389
4
4
4
328
328
208
7 1
289
TABLE 4. contd
Solvent/Additive T (C)
Transfer Constants to Solvents and Additives I I / 147
cs (x104) Remarks Refs.
Vinyl acetate (contd)
Ethyl acetate (contd)
Ethyl alcohol
Ethylene, tetrabromo-
-, tetrachloro-
-, tribromo-
-, trichloro-
Ethylene glycol
Fluorene
-, 9-phenyl-
Formamide, N,N,-dimethyl-
Formic acid, ethyl ester
methyl ester
i:Furaldehyde
Furfuryl alcohol
Germane, dietbylchloro-
-, dimethylchloro-
trietbyl-
I:triphenyl-
Glycolic acid, methyl ester
Heptane
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-
1,5-Hexadien-3-yne
Hexanoic acid, 2-ethyl-, ethyl ester
Hydroquinone
-, 2,5-di-terr-butyl-
-, 2,6-dimethyl-
tetramethyl-
;sbbutyl alcohol
Isobutyric acid
Isobutyric acid, ethyl ester
-3 methyl ester
Isobutyronitrile
Isopropyl alcohol
Lactic acid, ethyl ester
methyl ester
&ric acid, ethyl ester
Malonic acid, dimethyl ester
p-Mentha-1,8-dene
Me s i t ol
Methane, bromotrichloro-
-, dichloro-
-, iodo-
-, nitro-
-, tribromo-
-, triphenyl-
Me t ha nol
70
60
70
70
70
70
70
70
60
70
70
60
50
60
60
70
60
60
60
60
60
50
60
60
50
50
50
50
50
60
70
60
50
60
60
70
60
60
50
60
60
50
25
60
70
60
70
60
75
70
60
-
10
60
1.25
2.6
2.96
3.3
3.4
7.8
25
26.3
2800
465
34720
3810
83.0
4700
3610
16240
50
22
3
15000
2520
7800
86600
4500
56000
300
17.0
33.3
0
65
7000
38000
29000
74000
21.75
32.4
5.02
160
58
7 1
86
100
44.6
700
640
105
1 7
1900
5000
29 104
6000
>4 x 10s
6303
4
1230
2300
2600
34760
700
9.0
10.0
10.5
3.4
2.26
C
C
F2
C
C
C
C
C
C, J
J
C J
C
C
J
C, J
A R
A R
A, R
A R
F2
C
C
C
C
J
J
Q S
C
C
C
C
F2, J
J
C
80
145,232
328
86
420
390
86
390
389
389
389
389
390
86
390
390
86
7 1
86
86
390
539
539
539
539
86
208
442
232
7 1
338
338
338
338
289
390
289
7 1
145,232
420
86
86
390
86
86
7 1
86
86
338
39
39
39
389
86
389
86
86
389
45
5
5
5
190
145,231
Remarks page II - 157; References page II - 159
II / 148 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (Cl cs (xlO4) Remarks Refs.
Vinyl acetate (contd)
Methanol (contd)
Naphtbacene
Naphthalene
- , decahydro-
Naphtho[l,2,3,4-deflcbrysene
Nonanoic acid, ethyl ester
2,6-Octadiene, 2,7-dichloro-
-, 2,6-dimethyl-
70
60
50
50
50
60
Octanoic acid, ethyl ester 50
Oleic acid, methyl ester 60
Orthofonnic acid, trimethyl ester
Oxalic acid, diethyl ester
-, dimethyl est er
90
-
30
60
60
Paraldehyde 70
Pentane, 2,2,4-trimethyl- 50
2,4-Pentanedione 60
1-Pentanol, n 2,2,3,3,4,4,5,5-octafluoro- 60
2-Pentanone, 4-methyl- 60
3-Pentanone 60
Pentyl acetate
Pentyl alcohol
Perylene
Phenantbrene
Phenol
-, m-chloro-
-, p-chloro-
-, p-nitro-
-, 2,3,4,6-tetramethyl-
Phenol-D
-, m-chloro-
-, p-chloro-
-, 2,3,4,6-tetrametbyl-
Phosphorus trichloride
Propane, 2-bromo-2-methyl-
-, 2-chloro-2-methyl
1-Propanol, 2,2,3,3-tetrafluoro-
1-Propene, 3-chloro-
-, 3-chloro-2-methyl-
Propionaldehyde
Propionic acid, ethyl ester
-1 methyl ester
Pyrene 50
Pyrocatechol, 4-(1,1,3,3,-tetramethylbutyl)- 50
Pyrogallol 50
Salicylic acid 70
Silane, dimethylphenyl- 60
70
50
50
70
75
75
50
50
70
45
50
60
45
45
50
45
45
45
45
45
60
60
60
60
60
60
60
70
50
60
4.3
6.0
5.5
8.62 x lo6
1150
1457
1715
48
1.35 x 105
80
3200
430
700
70
217
1000
358
7.6
8.0
4.0
1.0
2.0
136
8.0
1 0
26.1
34.52
10.0
114.39
7.2
87.0
56
2.88 x lo5
870
5600
3380
215
120
600
205
400
8.86 x 104
1.13 x 104
35
70
80
800
1.5 x 104
150
26
7.11
3100
400
950
1000
457
40
23
26
11500
11000
50000
296
2200
J
J
C J
J
C
F2
C
J
C
F2
19
C J
J
J
J
J
J
J
C D
F2
J
J
F2
C
C
J
J
J
C
A. R
320
86
320
370
370
1 5
390
86
41
7 1
152
324
7
7 1
441
86
441
345
346
86
86
145,232
390
208
86
442
289
1 4 5
289
390
184
184
4 1
370
1 5
390
5 1
15
86
5 1
5 1
1 5
5 1
5 1
5 1
5 1
5 1
214
86
86
442
86
86
86
86
390
7 1
232
420
370
338
338
390
539
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 149
Solvent/Additive T (Cl cs (xlO4) Remarks Refs.
Vinyl acetate (contd)
Silane, methyldichloro-
-, trichloro-
-, triethyl-
-, triphenyl-
Stearamide, N-allyl-
Steak aci d, ehtyl est er
methyl ester
&cinic acid, diethyl ester
-, dihexyl ester
-, dimethyl est er
m-Tolualdehyde
p-Tolualdehyde
To l u e n e
-, bromo-
-, o-chloro-
-, p-chloro-
-, a-chloro-
Toluene, p-nitro-
p-Toluidine
-, N,N-dimethyl-
-, N-methyl-
Toluonitrile
Triethylamine
Tr i p h e n y l e n e
Ve r a t r a l de yhyde
Xy l e n e
Vinyl chloride
Carbon tetrachloride
Chloroform
Bromotrichloromethane
Vinylidene chloride
N-Methylpyrolidone
2-Vinylpyridine
Silane, diethylchloro-
-, Methyldichloro-
-, trichloro-
-, triethyl-
-, triphenyl-
Vinyltrimethylsilane
Bromoform
60
60
60
60
90
50
60
60
60
60
60
60
50
60
60
70
75
80
50
70
70
60
70
75
50
50
50
50
50
50
60
50
60
50
70
75
60 280
Q(3)
60 290
Q(3)
60 400000
Q(3)
50
60
60
60
60
60
60
5800
8800
1200
2700
620.1
140
38.2
4 1
40
3 1
570
440
3.3
12.0
14.9
100
123
17.8
20.75
20.89
21.6
34
35
49.0
69.0
21.1
21.8
29.2
66
91.6
20.6
92.86
195
450
584
118
106300
750
380
830
38.3
360
370
160
550
14.9
278
166
20
20
5400
8600
12000
2000
4000
1200000
A R
A R
A R
A, R
C J
C
J
J
R
C
R
C
J
F2
w15
R
C
C
F2
F2
F2
F2
J
J
J
C
C
R
R
A R
A, R
A R
A R
A R
539
539
539
539
1 7 3
7 1
441
420
420
420
86
86
158
15
357
7 1
7 1
357
80
21,59,289
357
86
86
265
265
357
390
357
184
273
15
389
389
86
389
184
15
154
154
154
15
154
24,145
370
86
1 5
390
184
511
511
511
541
5 4 1
539
539
539
539
539
C Q(l-2) 572
Remarks page II - 157; References page II - 159
II/l50 TRANSFER CONSTANTS I N FREE RADI CAL POLYMERI ZATI ON
TABLE 5. TRANSFER CONSTANTS TO SULFUR COMPOUNDS
Modifier T(C) cx
Remarks Refs.
Acrylamide, N-octadecyl-lacrylonitrile (1: 1 mol ratio)
1-Dodecanethiol
Acrylic acid
1-Dodecanethiol
-, methyl ester
I-Butanethiol
Ethanethiol
60
45
30
60
50
0.539 C. F24 174
1.9 C, F31 549
6 0
1.53
1.69
0.78
0.94 f 0.07
1.65f0.12
1.57 f 0.09
1.57 f0.18
1.79
5.00
0.544
0.668
0.700
0.656
397
69,397
330
478,507
478,507
508
330,509
330
330
477
477
477
477
50
50
20
30
40
50
80
50
0.73
0.13
0.1
0.47
0.00008 12
0.11
0.29
0.795
0.69
0.97
J
378
378
248
196
458
404
197
375
8 5
378
5 1.5 C. H 380
53.3 C, H
380
5 1.2 C. H 380
5 2.1 C H
380
5 1.1 C H 380
5 1.8 C, H 380
50 1.02 C. H 380
6 0 6.9
6 0 8.1
60 7.5
60 8.3
532
532
532
532
5
50
5
50
50
50
5.3
3.7
21.8
16.0
19.0
3.0
19.5
242
242
242
242
243
242
242
5 0.66 B, H, J 384
5 2.42 J% H, J
383
2Propanethiol
Acrylonitrile
1-Dodecanethiol
Hydrogen sulfide
Methyl sulfoxide
Methyl tetrasulfide
p-Toluenethiol
Acrylonitrile/l,3-butadiene (lo-90%)
1-Hexanethiol,
-, 1,1,3,3,5,5-hexamethyl-
1-Pentanethiol,
-, 1,1,3,3-tetramethyl-
Acrylonitrile/l,3-butadiene (20-80%)
1-Hexanethiol
-, 1,1,3,3,5,5-hexamethyl-
1-Pentanethiol
-, 1,1,3,3-tetramethyl-
Acrylonitrile/l,3-butadiene (30-70%)
1-Hexanethiol
-, 1,1,3,3,5,5-hexamethyl-
1-Pentanethiol
-, 1,1,3,3-tetramethyl-
Acrylonitrilelstyrene (38. 5-61. 5 mol%)
1-Pentanethiol
-, 1,1,3,3,4-pentamethyl-
Butadiene
Xanthogendisulfide, dibutyl-
-, diethyl-
-, di-2-ethylhexyl-
-, di-isopropyl-
1,3-Butadiene
I-Butanethiol, 1,1,3,3-tetramethyl-
1-Octanethiol
-, 1,1,3,3,5,5,7,7-octamethyl-
1-Tetradecanethiol
1,3-Butadienektyrene
1-Dodecanethiol
Formic acid, thio-, dithiobis-
-, -, -3
O,O-dibutyl ester
TABLE 5. contd
Transfer Constants to Sulfur Compounds II/151
Modi fi er T (0 cx
Remarks Refs.
1,3-Butadienelstyrene (contd)
-, -7 -7 0, 0-di-set-butyl ester
-1 -7 - 0, 0-dicyclohexyl ester
-, -7 -7 0, O-diethyl ester
-1 -7 -, O,O-diheptyl est er
-1 -1 -7 O,O-dihexyl est er
-1 -9 -9 O,O-diisobutyl ester
-3 -1 O,O-diisopentyl ester
-9 -1 -1 O,O-diisopropyl ester
-, -9 -9 O,O-dimethyl est er
-3 -1 -1 O,O-dineopentyl ester
-9 -, -9 O,O-dioctyl ester
-1 -3 -1
O,O-dipentyl ester
-1 -1 -1
O,O-dipropyl ester
1-Heptanethiol
-, 1,1,3,3,5,5,6-heptamethyl-
I-Hexanethiol
-, 1,1,3,3,5,Shexamethyl-
1- Oc t a ne t hi ol
-, 1,1,3,5,5,7,7-octamethyl-
p-Dioxin, 2,3-dihydro/maleic anhydride
I-Butanethil
Et h y l e n e
1-Butanethiol
Ethyl sulfide
Methyl sulfoxide
2-Propanethiol, 2-methyl-
Sulfur hexafluoride
Methyl methactylate
Acetic acid, dithiodi-, diethyl ester
mercapto-, methyl ester
Letophenone, 3-mercapto-
-, 4-mercapto-
- 5
50
5
- 5
5
50
5
- 5
50
5
50
5
50
5
- 5
50
5
- 5
50
5
-
- 5
50
5
- 5
50
5
50
5
50
5
- 5
50
5
- 5
50
5 0.64 B, H, J
384
5
5 0.34
B, K J
384
60 6300 R 169
130 5.8 c, w5 457
130 0.027 c, w5 454
130 1 2 C, F21, W5 259
130 15.0 c, w5 457
130 o.oooo C, F21, W5 259
60 0.00065 86
60 0.63 274
45 4.2 30
45 2.6 30
1.75
5.34
1.65
1.565
1.78
3.71
8.43
4.23
16.04
0.41
1.12
0.74
1.78
1.87
1.573
6.43
1.21
7.0
1.85
4.38
2.83
3.4
12.5
0. 40- 1. 31
0. 80- 3. 01
1. 40- 3. 70
1. 80- 3. 50
1. 80-6. 0
9.78
1.185
9.78
16.43
15.86
27.04
1.01
3.40
0.23
0.64
1.45
1.70
3.20
4.42
1.815
9.20
1.22
B, H, J
384
4.1 H 54,55
2.7-4.7 H 54
H
C, H, J
B, H, J
H
B, H, J
C, H, J
B, K J
H
C K J
B, H, J
C K J
B, H, J
C H, J
B, K J
H
C K J
B, K J
B, K J
H
C K J
B, K J
B, H, J
B, H
B, H, J, GG4
B, H, J, GG3
B, H, J, GG2
B, H, J, GGl
B, H, J, GG5
H
C, H, J
B, H, J
H
C, H, J
B, H, J
C, H, J
JA H, J
C, H, J
B, K J
H
C K J
B, K J
H
C H, J
180
382
180
383
383
383
180
382
383
382
383
382
383
180
382
383
341
180
382
383
341
100
100
100
100
100
100
179
180
382
383
180
382
383
382
383
382
383
180
382
383
180
382
Remarks page II - 157; References page II - 159
II / 152 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 5. contd
Modifier T (Cl CX
Remarks Refs.
Methyl methacrylate (contd)
Anisole, 4,4-dithiodi-
p-Anisoyl disulfide
Benzenesulfonic acid
-,
compound with pyridine
-, thio-, Sphenyl est er
Benzenethiol
50 0.0044 285
60 0.0052 285
60 14.6 369
-, m-bromo-
-,p-bromo-
-, m-chloro-
-, p-chloro-
Benzoyl disulfide
Benzyl disulfide
Benzyl sulfide
60
60
45
60
70
45
4.5
4.5
45
60
2 5
50
60
25
50
Benzyl sulfone
Benzyl sulfoxide
Benzyl tetrasulfide
Benzyl trisulfide
1-Butanethiol
60
50
50
50
50
60
Carbanilide, thio- 50
-, -, 4,4-bis(dimethylamino)-
-, -, 4,4-dichloro-
-1 -1 3,3 -dimethoxy-
-1 -1 3,3-dimethyl-
-3 -, 4,4-dimethyl-
-, 3,3-dinitro-
&bon di sul f i de
2,13-Dioxa-7,8-dithia-3,12-disila-tetradecane, 3,3,12,12-tetrameth oxy-
Disulfide, bis(p-bromobenzoyl)-
-, bis (p-bromophenyl)-
-, bis(p-chlorobenzoyl)-
-, bis@-chlorophenyl)-
-, bis(p-cyanobenzoyl)-
-, bis(dimethylthiocarbamoyl)-
-, bis(p-nitrobenzoyl)-
-, bis(o-nitrophenyl)-
-, bis(p-nitrophenyl)-
1-Dodecanethiol
Ethanethiol, 2-amino-, hydrochloride
Ethanol, 2-mercapto-
Ethyl disulfide
Formamidine, N,N-diphenyl-
-, 1,l -dithiobis-
Methyl sufoxide
50
50
50
50
50
50
60
79.5
60
50
60
60
50
60
60
70
60
50
60
50
60
60
70
80
90
50
70
50
60
70
60
50 0.22 C, F2 251
60 0.0000071 A 438
0.00365
0.0196
4.7
2.7
1 5
3.8
5.6
3.5
4.6
10.0
0.134
0.016
0.00627
0.0183
0.0098
0.0098
0.00154
0.0040
0.0039
0.084
0.021
0.66
0.67
0.008
0.22
0.09
0.35
0.33
0.21
0.13
0.55
0.00007
0.00258
16.7
0.0046
0.0098
10.0
0.0072
0.0117
290
0.0115
694
0.0176
0.0508
0.0127
0.0193
0.7
0.55
0.42
0.33
0.17
0.15
0.43
0.62
0.40
0.00013
F2
D
F2
F2, J
F2, J
A
F2
C, F2
C, F2
C, F2
C, F2
C, F2
C, F2
C, F2
A
F7
F7
F2
F2
490
491
30
274
566
30
30
30
30
369
368
354
368
368
252
354
368
252
252
354
354
274
69,397
251
251
251
251
251
251
251
251
288
474
369
285
285
369
285
285
369
104
369
285
285
285
285
573
573
573
573
473
473
473
274
473
310
TABLE 5. contcf
Transfer Constants to Sulfur Compounds I I / 153
Modifier
T (0 CX
Remarks Refs.
Methyl methacrylate (contd)
2-Naphthalenetbiol
I-Penthanethiol
Phenyl disulfide
Phenyl disufone
Phenyl sulfide
Phenyl sulfone
Phenyl sulfoxide
lPropanetbio1, 3-[1,3,3,3-tetramethyl-1-(trimethylsiloxy)disiloxanyl]-
-, 3-(trimethoxy)-
2Propanethiol
-, 2-methyl-
Propionic acid, 3-mercapto-
Sulfide, benzoyl dimethylthiocarbamoyl
Sulfur
Thiosulfuric acid, S-butyl ester
-, -, sodium salt
-, S-isopropyl ester
-3 -, sodium salt
-, S-phenyl ester
-1 -1 compound with pyridine
-1 -, potassium salt
-, S-propyl ester
-, -, sodium salt
m-Toluenethiol
p-Toluenethiol
a-Toluenethiol
p-Toluoyl disulfide
p-Tolyl disulfide
St y r e n e
Acetic acid, dithiodi-
-9 -9 diethyl ester
-, -1 dimethyl est er
-9 -, mercapto-
-, -9 butyl ester
-1 -1 ethyl ester
-, -1 methyl ester
-, phenyl-
-9 -, p,p-dithiodi-
-, t h i o
Aniline, 2,2 dithiodi-
-, 4,4-dithiodi-
-, N-dodecyl-, 4,4-dithiodi-
Anisole, 2,2-dithiodi-
-, 4,4-dithiodi-
-, p-methyl-, u,u-dithiobis-
45
60
50
25
50
60
44.1
50
1.3
3.1
0.8
0.0174
0.0038
0.0007
0.00176
0.0085
0.0110
0.0003
0.00554
0.0064
0.00132
0.0006
0.0013
0.128
0.693
0.38
0.18
0.39
0.38
5.5
0.08
1.3
0.075
0.106
H
D
60
25
50
60
50
50
19.5
79.5
60
60
50
70
20
60
A
A
D
F2
F2
D
A
C
F2, J
30
274
344
368
285
310
368
285
491
491
368
252
368
252
252
414
474
274
274
473
473
280
280
118
194
354
60 0.00226 490
60 0.00167 490
60
60
0.374
0.00537
490
490
60 0.00190
45 4.7
45 7.4
50 0.027
60 11.0
50 0.003 1
60 0.0044
R J
490
30
30
354
369
285
285
50 < 0.005
99 0.2
60 0.015
99 0.1
99 >14.0
50 26.0
60 58.0
60 0.63
99 21.6
J, R
A
A
297
96
86
96
96
146
126
323
96
50
99
25
50
J
15
50
50
50
50
99
0.24
>14.7
3.8
3.0
3.4
3.0
0.24
0.21
3.0
0.18
0.021
89
96
297
297
297
297
89
89
89
89
96
Remarks page II - 157; References page II - 159
II 1154 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 5. contd
Modifier T (Cl CX Remarks
-
Refs.
Styrene (co&d)
p-Anisoyl disulfide
Anthranilic acid, 4,4-dithiobis-
Arylbenzene thiolsulfonate
-, p-chloro-
-, p-methoxy-
-, p-methyl-
Benzenesulfonic acid
-, compound with pyridine
-1 thio-, S-phenyl ester
Benzenethiol
-, o-ethoxy-
-, p-ethoxy-
Benzene thiosulfonate
-, aryl-p-chloro-
-, aryl-p-methoxy-
aryl-p-methyl
i:Benzimidazolethiol
Benzoic acid, 2,2-dithiodi-
-, -1 diethyl ester
-, -,dimethyl ester
-, 4,4-dithiodi-
-1 -, diethyl ester
-, o-mercapto-
-3 -7 methyl ester
-, thio-
Benzothiazole, 2,2-dithiobis-
-, 2,2-thiobis-
2-Benzothiazolethiol
Benzo[B]thiophene, 4,5,6,7-tetrahydro-4(2-thienyl)-
Benzoyl disulfide
Benzyl alcohol, o,o-dithiobis-
-, p,p-dithiobis-
Benzyl diselenide
Benzyl disulfide
Benzyl sulfide
Benzyl sulfone
Benzyl sulfoxide
1-Butanethiol
60 96.0
50 3.0
60 0.95
60 2.22
60 1.872
60 1.237
60 0.00617
50 1.60
60 1.67
99 0.08
99 25.1
99 0.13
60
60
60
99
50
50
99
50
50
99
99
99
25
50
7 5
99
50
50
99
60
50
60
99
50
50
60
50
60
99
25
50
60
50
50
2 5
60
70
80
99
2.597
1.475
1.099
0.21
0.01
< 0.005
0.2
0.11
0.17
0.11
>14.7
17.0
6.23
2.3
2.1
2.3
2.4
2.73
< 0.005
0.03
0.26
0.011
< 0.005
0.010
0.0107
36.0
0.11
0.58
0.09
2.0
0.02
0.03
0.00878
0.01
0.011
0.548
0.069
0.00335
0.052
0. 05 1
5.4
13.2
21.0
22.0
25
15.0
17.0
15.4
R ~2
R, F2
R, F2
R. F2
A
A
R, F2
R, F2
R, F2
J
A
A
D
J A Ql
D
A
A
A
A
369
89
544
544
544
544
490
491
491
96
96
96
544
544
544
96
89
89
96
297
89
89,297
96
96
96
297
297
297
291
96
297
297
96
419
89
545
304
369
96
89
297
128
89
297
368
128
96
368
252
368
252
252
340
340
395
69,397
1 3 1
395
395
96
TABLE 5. contd
Transfer Constants to Sulfur Compounds II / 155
Modifier
T (C) CX
Remarks Refs.
Styrene (contd)
1-Butanethiol, 1,1,3,3-tetramethyl-
1-Butanethiol-D
Butyl disulfide
set-Butyl disulfide
rerr-Butyl disulfide
Butyl sulfide
tert-Butyl sulfide
Carbanilic acid, p,p-dithiodi-diethyl ester
Carbon disulfide
Carbonic acid, dithio-
-1 -3
S,S-bis(carboxymethyl)ester
-, trithio-
-, -I
S,S-bis(carboxymethy1) est er
1-Decanethiol
2,13-Dioxa-7,8-dithia-3,12-disilatetradecane, 3,3,12,12-tetramethoxy-
Diphenyldisulfide
Disulfide, bis(p-bromobenzoyl)
-, bis(cr-bromo-o-tolyl)
-, bis(p-chlorobenzoyl)
-, bis(chlorobenzy1)
-, bis(Zchloroethy1)
-, bis(cc-chloro-o-tolyl)
-, bis(p-cyanobenzoyl)
-, bis(diethylthiocarbamoy1)
-, bis(dimethylthiocarbamoy1)
-, bis(2-ethylhexyl) 50
-, bis(N-ethyl-N-phenylthio-carbamoyl) 60
-, bis(l-methylheptyl) 99
-, bis(morpholinothiocarbony1) 60
-, bis(l-naphthylmethyl) 99
-, bis(p-nitrobenzoyl 60
-, bis(o-nitrophenyl) 50
-, bis(l-phenylethyl) 50
-, bis(P-(2-pyridyl)ethyl) 50
-, bis(2,3,5,6-tetramethylphenyl) 50
-, bis(2,4,6-triisopropylphenyl) 50
1- Dode c a ne t hi ol 60
5
5 0
60
70
80
2 5
5 5
60
99
150
50
50
60
60
60
50
60
5.5
6.4
4.3
5.2
4.0
7.0
0.00079
0.00154
0.0024
0.0068
0.022
< 0.005
< 0.005
0.00014
0.0022
0.025
0.24
0.00066
A
A
242
222
242
395
395
395
448
448
304
96
359
89
89
304
304
304
89
288
50 0.36 297
50
80
80
79.5
60
60
50
60
50
50
50
60
60
60
70
80
C3, H
C3, H
95
1 1 5
130
0.21
4.3
4.2
0.0118
0.147
745
1.0
196
< 0.005
0.01
1.3
3190
0.724
1.11
0.0136
0.568
0.620
0.780
0.860
0.939
1.035
0.984
1.150
< 0.005
1.75
0.0104
6.1
0.033
6650
-
< 0.005
0.03
0.73
0.12
14.8
19.0
1 9
0.69
1.3
13.0
26.0
297
574
574
474
546
369
297
369
297
297
297
369
286
286
104
40
481
481
40
40
481
40
481
297
286
96
286
96
369
89
89
297
297
89
i9,126
59
562
574
574
156
156
A c
70
70
90
100
110
C3, H
C3, H
Remarks page II- 157; References page II- 159
II / 156 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 5. contd
Modifier
T (0 CX
Remarks Refs.
St yrene (contd)
tert-Dodecanethiol
Ethanethiol
Ethanol, 2,2-dithiodi-
-, di(chloroacetate)
Eiher, ethyl 3-mercaptopropyl
Ethyl disulfide
Formamidine, NJdiphenyl-, 1,l -dithiobis-
Formic acid, thio-, dithiobis, O,O-diisopropyl ester
I-Heptanethiol
1 -Hexanethiol
-, 1,1,3,3,5,5hexamethyl-
Hexyl disulfide
Hydrogen sulfide
Isobutyl disulfide
Isopropyl disulfide
Lauryl disulfide
Lepidine, 2,2dithiodi-
Mesityl disulfide
Methyl disulfide
Methyl sulfoxide
Morpholine, 4,4-dithiodi-
1-Naphthalenemethanethiol
I-Naphthalenethiol
2-Naphthalenethiol
1-Naphthoyl disulfide
1-Naphthyl disulfide
2-Naphthyl disulfide
1-Octadecanethiol
Octadecyl disulfide
1-Octanethiol
-, 1,1,3,3,5,5,7,7-octamethyl-
2-Octanethiol
1,4,5-Oxadithiepane
I-Pentanethiol
Phenetole, 2,2-dithiodi-
-, 4,4-dithiodi-
Phenyl disulfide
Phenyl disulfone
Phenyl sulfide
70
90
90
50
50
50
60
100
99
50
50
99
99
99
25
50
7 5
99
70
60
60
60
50
50
60
40
50
60
50
2 5
50
75
99
99
99
50
99
25
50
75
99
99
99
5
50
50
99
150
50
99
99
50
60
50
60
25
50
60
1.5
1.5
1.6
17.1
< 0.005
< 0.005
14.1
21.0
13.7
0.0045
6.72
5.3
7.5
15.1
15.3
3.2
2.9
2.4
0.0104
5.0
0.0020
0.00066
0.00023
0.04
0.69
0.0094
0.0000693
0.548
0.0000242
0.000048
<0.005
12.7
18.3
15.7
24.6
0.15
0.18
0.34
1.57
0.17
0.19
0.29
0.36
14.7
0.024
19.3
23.0
19.0
4.7
3.2
0.057
20.0
0.075
0.33
0.06
0.102
0.0103
0.111
0.147
0.022
0.025
0.0325
0.056
0.00548
C3, H
C3, H
C3, H
A
C, F2
H
H
H
H
A
H
A
A
A
A
D
574
574
574
331
297
297
126
69
69
96
251
297
96
96
96
297
297
297
96
1 4 5
304
304
128
89
89
304
458
375
429
438
297
297
297
297
96
96
96
89
96
297
297
297
96
96
96
339
242
242
242
96
359
344
96
96
297
491
368
491
285
491
491
368
252
368
T A B L E 5 . contcf
Modifier
T (C) CX
Remarks II / 157
Remarks Refs.
Styrene (co&d)
Phenyl sulfone
Phenyl sulfoxide
1-Propanethiol, S-(trimethoxysilyl)-
2Propanethio1, 2-methyl-
50
50
79.5
50
60
60
100
Propionic acid, 3,3-dithiodi-
-, -9 dipropyl ester
-, 2-mercapto-
-, S-mercapto-
Propyl disulfide
Pyridine, 2,2-dithiodi-
Quinoline, 2.2.dithiodi-
Sulfide, ethyl 2,Cdiphenylbutyl
-, ethyl phenethyl
I-Tetradecanethiol
Thiosulfuric acid, S-butyl ester
-, -,
sodium salt
-, S-isopropyl ester, sodium salt
-, S-phenyl est er
-, - potassium salt
-, Spropyl ester, sodium salt
p-Toluenethiol
a-Toluenethiol
-, p-methoxy-
p-Toluoyl disulfide
o-Tolyl disulfide
p-Tolyl disulfide
2,6-Xylyl disulfide
Vinyl acetate
Acetic acid, dithiodi-
15
50
99
50
-, -, diethyl ester 60
Acetic acid, ithio-
-, S-(2-hydroxyethyl)ester, acet at e
2cetyl disulfide
1 - Bu t a n e t h i o l
Butyl disulfide
Butyl sulfide
1,4,5-Oxadithiepane
Su l f u r
u-Toluenethiol
Thiol acetate
50
-
-
50
60
50
50
50
50
50
60 0.173 490
60 0.407 490
60
60
99
99
99
60
25
50
60 0.0132
60 0.29
60 48.0
60 1.0
60 0.026
60 0.25-2.5
45 470.0
IO 0.885
60 0.186
0.021
0.024
5.90
4.0
3.1
3.7
4.6
1.8
2.3
252
252
414
344
261
69,126
59
261
69,126
< 0.005
7.7
9.4
6.0
0.00234
0.01
0.05
30.0
7.15
19.0 H
297
1 7 8
178
291
304
89
89
331
331
242
0.763 490
0.150 490
0.07 96
25.5 96
26.0 96
46.3 369
0.22 297
0.23 291
0.28 291
0.32 291
0.11 291
0.15 96
0.69 291
1.41
1.5
86
351
J
J
J
J
J
C
F20
140
86
140,397
86, 351
351
3 5 1
28
390
515
C. REMARKS
A. Thermal initiation E . y-Ray initiation
B. Hydroperoxide initiation F. Solution polymerization in:
C. Peroxide initiation Fl. Acetonitrile
Cl. Ammonium per-sulfate F2. Benzene
c2. Potassium persulfate F3. Butyl acetate
c3. Sodium persulfate F4. Butyl chloride
D. Photoinitiation F5. Chlorobenzene
References page II - 159
II / 158 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
F6. o-Dichlorobenzene
F7. Dimethylformamide
F8. Dimethyl sulfoxide
F9. p-Dioxane
FlO. Ethyl acetate
Fl 1. Ethyl methyl ketone
F12. Heptane
F13. Water
F14. Magnesium perchlorate
F1.5. Succinonitrile
F16. Sulfur dioxide
F17. Toluene
F18. Zinc chloride
F19. Octane
F20. Methanol
F21. Propane
F22. Diethyl oxalate
F23. Cyclohexane
F24. Butyl alcohol
F25. Acetic acid
F26. 1 ,ZDichloroethane
F27. Ethylbenzene
F28. Cylohexanone
F29. Parabutyr aldehyde
F30. Water-methanol mixture
F3 1. tert-Butyl alcohol
F32. Hexane
F33. 1 -Propanol
F34. Carbon tetrachloride
G. Heterogeneous polymerization
H. Emulsion polymerization
I . Recalculated from data of:
Il. Basu, Sen, and Palit (1950)
1 2 . Baysal and Tobolsky (1952)
13. Chadha and Misra (1958)
14. Dixon-Lewis (1949)
15. Gregg and Mayo (1953)
16. Ham (1956)
17. Kwart, Broadbent, and Bartlett (1950)
18. Matsumoto, et. al. (1959)
1 9 . Palit and Das (1954)
1 1 0 . Palit, Nandi, and Saha (1954)
Ill. Saha, Nandi, and Palit (1956)
1 1 2 . Stein and Schulz (1960)
113. Wheeler, Lavin, and Crozier (1952)
J . Apparent transfer constant; retardation occurred
K. Average value
L . Estimated from model compounds
M. For end groups:
Ml. Tribromomethyl
M2. Butylamino
M3. Diethylamino
M4. Hydroxymethyl
M5. Aldehyde
M6. Thioglycolate
M7. -CH(OH)CH2-SH
M8. Dodecyl
M9. 2-Hydroxyethyl
MlO. -(CH2)i1SH
N. For middle groups
0. For side chain
P. For main chain
Q. Telomerization (number of monomer units in
transferring chain)
R. Calculated from viscosity average molecular
weight
S . Value uncertain
T. In presence of 0.4moVl lithium nitrate
U. In presence of ( ) mol/l sodium chloride
V. In presence of ( ) mol/l sodium bromide
W. Under pressure of:
Wl. 200psi (13.8 bar)
W2. 250 psi (17.2 bar)
w3. 1470psi (101.4bar)
W4. 5000 psi (344.8 bar)
W5. 20000 psi (1379.0 bar)
W6. 26600 psi (1834.1 bar)
W7. 28400 psi (1958.2 bar)
W8. 56000psi (3861.2bar)
W9. 64600 psi (4454.2 bar)
WlO. 168000psi (11583.6bar)
Wll. 6OOpsi (41.4bar)
W12. 2500psi (172.4bar)
W13. 18psi (1.2bar)
W14. 735 psi (50.7 bar)
W15. 14200psi (979.1 bar)
W16. 42600 psi (2937.3 bar)
W17. 34500psi (2378.8 bar)
W18. 3000bar
W19. 2700 bar
W20. 2400 bar
W21. 2000bar
W22. 1800 bar
W23. 150bar
W24. 600 bar
X. Corrected for loss of low molecular weight
polymer
Y. CM = 125 x exp(-7300/RT)
Z. CM = 3.0 x exp(-5673/RT)
AA. CM = 0.4 x exp(-6219/RT)
BB. CM = 0.2 x exp(-5400/RT)
CC. CM = 6.4 x exp(-4120/RT)
DD. CM = 4.77 x exp(-3540/RT)
EE. Radical is styrene
FF. Radical is p-chlorostyrene
GG. l/C varies with polym. rate and emulsifier of:
GGl. K caprate
GG2. K laurate
GG3. K myristate
GG4. K palmitate
GG5. K rosinate
HH. C is combined constant for copolymerization,
= (CSI x RI x Mr + Cs2 x R2 x M2)/
(RI xMt xMrf2xMi xM2
+R2 x M2 x M2)
II. In presence of FeBr2
Re f e r e n c e s II / 159
111. In presence of FE(CO)s
112. In presence of methacrylic acid methyl ester
JJO. Catalyzed by Co(II)-tetramethylhematoporphyrine
JJl. Catalyzed by Co(II)-hematoporphyrine-
tetramethyl ether
JJ2. Catalyzed by Co(II)-tetra4-tert-
butylbenzoporphyrine
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II / 168 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
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Photopolymerization Reactions
J . P. Fouassier
Laboratoire de Photochimie G&r&ale, Mulhouse, Cedex, France
A. Introduction II-1 69 A. INTRODUCTION
B. Tables
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Table 6.
Table 7.
Table 8.
Table 9.
II-1 70
Rate Constants of Cleavage, Electron
Transfer and Monomer Quenching
in Radical Photoinitiators II-1 70
Annex to Table 1. Photoinitiator
Compound Chemi stri es II-1 73
Bimolecular Rate Constants for
the Reaction of Phosphonyl Radicals
with Various Monomers in
Cyclohexane at Room Temperature II-1 76
Bimolecular Rate Constants for
the Reaction of Various Radicals
with Various Olefinic Monomers
at Room Temperature II-I 76
Bimolecular Rate Constants for
the Reaction of PhzP=O and
PhzP = S with Various Monomers II-1 76
Electron Transfer Reaction of Radicals
with Diphenyliodonium Salts II-1 76
Electron Transfer Rate Constants (k,)
Between Photosensitizers and Cationic
Photoinitiators and Quenching Rate
Constants (k,) for Cyclohexene Oxide
in Methanol (M) and Acetonitrile
(AN)
II-1 77
Excitation Transfer Rate Constants
(kr) for Thioxanthones and
Photoinitiators II-1 78
Annex to Table 7. Compound
Chemi stri es II-1 78
Triplet State Lifetimes (7~) of the
Sensitizer (TXI) in Different Media,
and Rate Constant (kr) of the
Interaction between TXI and TPMK II-1 79
Some Values of the Triplet State
Energy Levels of Photoinitiators and
Monomers II-1 79
Table 10. Values of T:, Tr, and k,b
in Solution
Table 11. Rate Constant of Interaction of
Ketones and Light Stabilizers
in Solution
Annex to Table 11
C. References
II-1 79
II-1 79
II-I 79
II-1 80
UV curing technologies use light beams to start photo-
chemical and chemical reactions in organic materials
(monomers, oligomers, prepolymers, polymers), mostly
through a Photo-Induced Polymerization (PIP) reaction.
This leads to the formation of a new polymeric material
whose applications lie in various industrial sectors, such as
coatings, graphic arts, imaging, microelectronics, etc.
Specific advantages of these technologies over the usual
thermal operations are rapid through-cure, solvent-free
formulation, room temperature treatment and low energy
requirements.
This PIP process is concerned with the creation of a
polymer P through a chain radical or cationic reaction
initiated by light in the presence of a photoinitiator (PI) and
a coupled PI/photosensitizer (PS):
light .
P I - R
$-- RM---------P
light
PI -acid species:X
+XM+---P
ps light
-excited PS
hi-
excited PI -R or acid species
The reactivities of PI and PS govern, for a large part, the
practical efficiency of the PIP reaction. The present chapter
reports typical data obtained (through time-resolved laser
spectroscopy experiments) on the excited state processes in
PI and PS occurring after the absorption of the photon. Rate
constants reported in the following tables correspond to the
following processes:
1 .
light
PI - lPI* - 3PI*
(ground singlet first excited triplet state
st at e) singlet state
Ri + R;
cleavage
kc-
PIH t S
Habstraction
SH h
PI t M
!!m!i?+
monomer quenching
M, k,
PIH t A -[PI- AH+]
electron transfer
AK k
II / 169
II / 170 PHOTOPOLYMERIZATION REACTIONS
2. R (or A or S . . .) t M ---!!K- RM
3. 3PI* + light stabilizer
ka
-
(L%
4. 3Ps* t PI
k,
-excitation transfer
5. pi: Triplet state lifetime under the given conditions
(equal to the reciprocal value of the sum of the first-order
rate constants of the different processes)
7~: Triplet state lifetime in the presence of a given
additive
6. 3PS* t cationic photoinitiator Ct
k
-ps+ c
(a) Energy transfer can sometimes occur:
3ps* t c+ -pstc+*
B. TABLES
Ilj
Ilk
Ill
Ilm
Iln
IlP
IQ
Ilr
11s
Ilr
11s
Ilr
11s
Ilr
11s
Ilr
11s
I2a
12b
12c
12d
12e
12f
1%
12h
12i
Ila 1.3 6 6 Ml, AHI, SI 4
Ilb 2.0 150
Ilc 1.2 2.5
Ild 1.2 2
Ile 0.2 1
Ilf 0.07 1 3
m 1 . 5 180
Ilh 0.6 8
Ili 0.27 0.05
Ila 3200 Mz, 552 2 1
3 6 0 Ms. S2 2 1
5.4 M3, S2 2 1
3 4 M4> S2 2 1
Ila 0.003 e 2 2
O.OOlf
Ila 7 S2, AH3 2 6
2 sz. AH4
1.9 S2, AH2
2 S2, AH5
0.56 s2, A&
1 0 s3 2 3
0.5 1500 M7r AH2, S4 2 5
0.9 15. 50
0.0064 = s2 2 6
0.0025 e
0.0056e
0.0043 e
5 6 s6, Ml 2 6
110
5. 500 s6, M2 2 6
7400
5 1 0 0 s6, Ms 2 6
6 5 0 0
4 9 969 M3 2 6
140
9.4 s6, M4 2 6
5 0
2 5 0 MI, AHI, SI 5
2 0
4.5
8
2 2
1 0
2 9
2 0
2 1
7.14
0.87
0.003
0.00025
0.83
0.003
0.67
1.18
0.80
0.26
<O.OOl
0.08
0.20
0.08
0.17
0.15
0.05
(b) Energy and electron transfer can also occur in the
first excited singlet state PS*.
Detailed data are available, especially in several chapters
of two edited books (1) and in a recent monograph (2). Few
data are known on the photopolymerization itself and
largely depend on the practical formulation used as well as
the experimental conditions. Typically, one photon
absorbed can lead to N 10000 polymerized double bonds
(3). Rate constants of propagation k, and termination kt for
a polyurethane acrylate resin containing an acrylate
monomer (weight ratio, 1 : 1) as reactive diluent are
N lo4 l/mol/s and 3 x lo4 l/mol/s respectively (when half
of the double bonds have been polymerized) (3).
TABLE 1. RATE CONSTANTS OF CLEAVAGE, ELECTRON TRANSFER AND MONOMER QUENCHING IN RADICAL PHOTOINITIATORSa
1O-sk, 10m9k, 10-6k, Monomers b/amines /
Compound
(s -9
(VmoVs) (Vmolh) solvents d Refs.
TABLE 1. contd
Rate constants of cleavage, electron transfer and monomer quenching in radical photoinitiators II / 171
t
Compound
lo-sk, 10m9k, 10-6k, Monomers b/aminescl
(s-l) (Ymolh) (VmoVs) solventsd Refs.
1 3 a
1 3 b
13c
I3d
13e
13f
1%
13h
14a
14b
14~
14d
14e
14f
1%
14h
14i
14e
14f
I4g
14h
14i
14f
I@
14h
14i
14f
1%
14h
14i
ISa
16a
I7a
17b
18a
19a
IlOa
Illa
Illb
Illc
Illd
112a
112b
112c
112d
112e
112a
112b
112c
112d
112e
112b
112c
112d
112e
112b
112c
112d
112e
113a
114a
114b
114~
114d
115a
115b
115~
1 0
1
2 5
0.005
1 0
0.006
0.007
0.13
2 100
2 100
2 100
2 100
2 200 MI, AHI, SI 6
2
<lo-4
=10-4
<lo-4
<lo-4
Sl
8100
4 8 0 0
6 5 0 0
1500
190
4 8 0
8 0 0
1000
2 0 0
1 3
6 0
1 7
<l
5.7
1300
7 0 0
3 8 0
180
Mz. S2
MI, S2
7
M3r S2
7
M4r S2 7
2 10
7 x 10-3
8
9
9
9
9
1 0
1 0
0.7
0.05
4 4 0
0.35
1 1
MI, SI
MI, AHI, SI
MI, AHI, SI
MI, AHI, SI
MI, AHI, SI
0.7
6 x 1O-5
0.85
2.5
> 10
0.8
21
0.12
0.01
0.9
0.4
7 0 0
1200
4 8 0
8 0 0
1000
2 0 0
1 3
8100
4 8 0 0
6500
1500
190
6
1 7
<lO
5.7
1300
7 0 0
3 8 0
180
11000
2900
1 5
1200
MI, S2
1 1
M21.92 1 1
M3, S2 1 1
M4, S2 1 1
1.4 1.6 AH2, S2 1 2
MI, AHI, SI 1 3
6.5
6.0
3.5
>5
4
>5
s2
1 4
References page II - 180
II / 172 PHOTOPOLYMERIZATION REACTIONS
TABLE 1. contd
Compound
lo-sk, 10-9k, 10-6k, Monomers b/amines 1
(s-3
(UmoUs) (Vm0V.s) solvents d Refs.
I15d
I16a
I16b
I17a
118a
119a
12Oa
121a
122a
122b
122c
122d
123a
123b
123~
123d
123e
123f
123a
123b
123~
123d
123a
123b
123~
123d
123a
123b
123~
123d
123a
123b
123~
123d
123a
123b
123~
123d
123a
123b
123~
123d
123a
123a
123b
123b
123g
123h
1 2 4
1 2 5
1 2 6
1 2 7
1 2 8
1 2 9
3.3
1.5
0.7
180
300
100
AHl, SI
15
Sl 1 6
Sl
1 7
Sl 1 8
s2
1 8
s2
1 8
s3
1 9
>3
0.05
0.16
0.3
29
60
NlO
- 5
0.02
0.014
93
2.3
2.0
1 5
2
3
3
Ml, AH3, S2
20 6
5
4
4
0.01
0.017
2.5
4H2, s5
Mz, S2, AHz
24
20 3000
6000
6000
6OCG
0.2
0.02
0.03
0.04
4
0.4
1
1
40
30
5
6
1
1
0.3
0.3
M3r S2 20
M4, S2
20
MS> S2
20
M6, s2 20
8
0.85
<10-5
<lo-5
4.4f
0.3
0.015
S2, -4% 26
26
23
Sl, Ma 1 3
Sl, M9
13
S2, AH7
26
S2, AHs 26
M7. S4
25
S2, Ml 37
Szr Mlo
37
S2, MIO 37
s2 39
S7r AH9 4 1
65
37
0.016
0.006
0.007
Compound chemi s t r i es gi ven i n Annex t o Tabl e 1,
b~~Mono~er8: M 1- methyl methacrylate; Mz - styrene; MS - vinyl acetate; Mq - acrylonitrile; MS - vinyl pyrrolidone; Ms - butylvinylether; M, - acrylamide; Ms -
PET& Mg - TMPTA; M 10 - butylmethacrylate.
Amines: AH I - methyl diethanolamine; AHI - triethylamine; AH3 - ethyl-4-(dimethylamino)-benzoate; AH4 - bis-(2-hydroxy ethyl)-methylamine; AH5 - methyl-4-
amino knzoate; AH6 - 1,4-diazabicyclo [2.2.2] octane (DABCO); AH, - dimethylamine; AHs - 2-(dimethyl aminoethyl)-benzoate; AH9 - diethylaniline.
dSolvents: S 1- toluene; S 2 - benzene; S 3 - acetonitrile; S4 - water; S 5 - 2-propanol; S.5 - acetone; S.7 - ethanol.
%ate constant of H abstraction by THF.
Rate constant of H abstraction by isopropanol.
Photoinitiator Compound Chemistries II / 173
ANNEX TO TABLE 1. PHOTOINITIATOR COMPOUND CHEMISTRIES
Compound R
RI R2 R3 R4
4$p4
R3
I l a
Il b
I l c
Il d
Ile
I l f
Ik
Il h
I l i
H
H
H
H
H
NW-Id2
0-4
CH3
H
H
H
H
H
H
H
H
CH3
H
H
H
H
H
H
H
H
CH3
H
H
OCH3
SCH3
S-4
NCHd2
WHd2
0-4
H
4
COOOR I l j
Il k -CH2N(CH3);Cl
I l l -CHzSO;Na+
I l m
Il n
IlP
w
C l
OCH3
F
COOH
I l r COOCH 3
11s
RI
43
P&OR,
0
12a
12b
12c
12d
I2e
12f
1%
12h
12i
H
OCH3
WHd2
SCH3
WH2)2OH
WHd20H
O(CHd$W2H50)3
O(CH2)20COCH=CHz
O(CH2)20COCH=CH2
H
H
H
H
H
H
H
H
COCH-==CH 2
13a
I3b
13c
13d
H
SCH3
OCH3
WH3)2
F-R2
RI
-0
y-753
0 CH-CH,
13e H CsHs WHd2
/
0 N CsH5 NW-Id2
=:
0 N CH=CH2 NCH3)2
E
0
UN
CH=CH2 OEN
I3f
1%
13h
0 OCH,
14a
OCH3
OC4H9
OWCH 3) 2
OH
OCOCH 3
H
CH3
14b
14c
14d
14e
I4f
I+?
14h
14i
0 R
References page II - 180
II / 174 PHOTOPOLYMERIZATION REACTIONS
ANNEX TO TABLE 1. contd
Compound R
Rl RZ R3 R4
$-y-a3
OTR
0-C-OC&H,
Fluorenone
0
p2
FTH
o OR2
ckw43
0 R
ma-rR
0 0
&
R
0
-A-c-p:
OC2Hs
I A &OC2HS
OqH,OCOCH= CH,
0
15a
I6a
I7a
17b
18a
19a
I9b
IlOa
Illa
Illb
Illc
Il l d
I12a
112b
112c
112d
112e
I13a
114a
I14b
I14c
114d
IlSa
115b
1 1 %
115d
116a
H
CHzSOjNa+
OH
OCOCH 3
H
CH3
CH3
H
i-C3H7
OC2H5
z-C4H9
H
CH3
H
H
CH3
CH30
C2H5
H
CH3
H
H
ANNEX TO TABLE 1. contd
Photoinitiator Compound Chemistries II / 175
Compound R
Rl R2 R3 R4
R2
0
R
123a
123b
123~
123d
123e
123f
123g
123h
1 2 4
Ac r i d i n e 1 2 5
Ph e n a z i n e 126
1 2 7
1 2 8
1 2 9
B r
116b
117a
118a
I19a
120a
121a
122a
122b
122c
122d
H
NO2
H
Cl
CH3
CH3(CHdz
H
H
H
H
H
H
Br
Cl
-0CHzCOOH
+
OCHzCH2CHzN(CH3)3SO3Me-
CsHl7
H
0
-&a
Cd25
H
H
H
H
OC3H7
OC3H7
References page II - 180
II / 176 PHOTOPOLYMERIZATION REACTIONS
TABLE 2. BIMOLECULAR RATE CONSTANTSa FOR THE REACTION OF PHOSPHONYL RADICALS WITH VARIOUS MONOMERS IN
CYCLOHEXANE AT ROOM TEMPERATUREb
Radical
Monomer
0
f-o
0
II 943
0
II ,OCH3
0
F
II ,OC2H5
OCH(CH3)2
P,
OCH3
P,
OCH3
P,
OC2H5
Methacrylonitrile 5.0 4.6 4.5 9.2 11
Styrene 6.0 4 . 5 8.0 22 2 5
Methylmethacrylate 8.0 5.0 5.8 5.8 5 . 3
Acrylonitrile 2.0 2.0 0.18 0.58 0.26
Methyl acrylate 3 . 5 2 . 1 1.3 1 . 7 1 . 6
n-Butyl vinyl ether 0.4 0.3 0.23 2 . 1 1 . 4
Vinyl acetate 0.16 0.13 0.082 0.29 0.18
O~RM in 10 l/mol/s.
bRef. 26.
TABLE 3. BIMOLECULAR RATE CONSTANTS FOR THE REACTION OF VARIOUS RADICALS WITH VARIOUS OLEFINIC MONOMERS AT
ROOM TEMPERATURE
Radical
Monomer
Ph-&Ph
AH
Ph2k=0 Ph PhSb2 PhSb3
Styrene 3 . 5 x 10-2 7 x 10-4 1.2 x 10-2 6
Methylmethacrylate 9 x 10e4 5.4 x 10-2 4 x 10-5 0.9 x 10-2 6 18 lo-i lo-It
Acrylonitrile 4 x 10-4 1 . 6 x lo-* 2 x 10-3 2
Methyl acrylate 2
n-Butyl vinyl ether <lo-6 0.5
Vinyl acetate 6 x 1O-4 2 x 10-2 0.2
N-Vinylpyrrolidone 4 x 10-5
kRM in lOl/mol/s.
bRef. 26.
CFrom Ref. 40.
+From Ref. 16.
TABLE 4. BIMOLECULAR RATE CONSTANTSa FOR THE REAC-
TION OF Phzkd AND Ph,is WITH VARIOUS MONOMERSbJ
Radical
Monomer Ph&O Ph$=S
Methacrylonitrile 1 . 9 0.9
Styrene 4.6 0.4
Methylmethacrylate 4 . 1 0.19
Acrylonitrile 1 . 3 0.52
Methyl acrylate 1 . 7 0.62
n-Butyl vinyl ether 5.0 0.15
Vinyl acetate 1 . 4 0.042
akRM in IO7 l/mol/s
bRef. 21.
Experiments were carried out in CH& solution at room temperature.
TABLE 5. ELECTRON TRANSFER REACTION OF RADICALS WITH
DIPHENYLIODONIUM SALTS
Radicals 10 m9k, (l/mol/s)
Ph2Pb 5 10-3
Ph #OH 0.03
(CH3)2k0H 0.06
Refs.
42
43
Electron Rate Constants and Quenching Rate Constants II / 177
TABLE 6. ELECTRON TRANSFER RATE CONSTANTS (k,) BETWEEN PHOTOSENSITIZERS AND CATIONIC PHOTOINITIATORS AND
QUENCHING RATE CONSTANTS (k,) FOR CYCLOHEXENE OXIDE IN METHANOL (M) AND ACETONITRILE (AN)
Photosensitizer Cationic photoinitiator Anion Sol vent
lo-k,
(l/mol/s)
lo-k,
(l/mot/s) Refs.
Chlorothioxanthone
Benzophenone
Ketocoumarin
Chlorothioxanthone
(C6H5)3S+ PF,
off-
CH,- S
I-
@P(C6HS)3
0
0
(~,f4h--4-~~2%%
AH,
BF, 38
(C&5)3Se+AsF; 1 5
AsF,
cl-
PF,
BF,
AsF;
AsF;
AsF,
Cl-
BF,
BF,
PF,
PF,
SbF,
AsF,
BF;
BF;
PF,
AsFi
M 24 0.3 28
24
26
24
AN 290
M 400
36
M 15 0.33
1
47
M 6 . 4 0.04
M 1 4 29
3 5
28
4
8
570
110
1 4
100
References page II - 180
II 1178 PHOTOPOLYMERIZATION REACTIONS
TABLE 6. contd
Photosensitizer Cationlc photoinitiator Anion Solvent
lo-k,
(l/mol/s)
lo-k,
(l/mol/s) Refs.
Xanthone
Michlers ketone
Thioxanthone
lo-Methylacridone
Acridone
Anthracene
Chlorothioxanthone
Pyrene
Benzophenone
lsopropylthioxanthone
cl- M 140
0.7
200
350
740
M 1 3 1
Wzp)zI+ cl- 400 28
130
500
250
TABLE 7. EXCITATION TRANSFER RATE CONSTANTS (kT) FOR THIOXANTHONES AND PHOTOINITIATORS
Thioxanthone Initiator Solvent 10e6k~ (l/mol/s)
T X 1
ETX
I TX
HMK
OMK
TPMK
NMK
TPMK
TPMK
Toluene 100
Methanol 290
Toluene 75
Methanol 380
Toluene 240
Methanol 630
Toluene 4700
Methanol 7900
Toluene 1 2
Methanol 110
Toluene 60
Methanol 55
Ref. 32.
ANNEX TO TABLE 7. COMPOUND CHEMISTRIES
TXs
Triplet state
energy level
R Rl R2 R3 R4
Abbrev. (kcal/mol)
4
RIQI$&
R2
R3
Moks
H Cl H H CTX 62
H
CWCHdz
H H I TX 6 1
CH3 H COOET H ETX 58,5
H H H COOET TX1 6 3
7H3
H
C-y-N20
SCH3
0 CH,
OCH3
WHdz
HMK 65
TPMK 6 1
OMK 65
NMK 63
Triplet State lifetimes, Triplet State Energy levels and Rate Constants II / 179
TABLE 8. TRIPLET STATE LIFETIMES (rT) OF THE SENSITIZER
(TXI) IN DIFFERENT MEDIA, AND RATE CONSTANT (kT) OF THE
INTERACTION BETWEEN TXI AND TPMKb
TABLE 11. RATE CONSTANT OF INTERACTION OF KETONES
AND LIGHT STABILIZERS IN SOLUTION
Photoinitiator Light stabilizer
10 -6ka
(VmoVs) Refs.
Medium
TT
(ns)
9
10-6kT
(cp at 28C) (VmoVs)
Benzophenone
Acetone
LSl 6500 34
LS2 8550
LS3 10300
LS4 15000
LS5 7050
SL6 5900 35
LSl 500 36
LSI 700
TMPTA (100%)
Acrylate (66/33)
Toluene-Ep. acrylate
(50/50)
Toluene-TMPTA (25/75)
Toluene-TMPTA (50/50)
Toluene-TMPTA (75/25)
HDDAd (100%)
HDDA-Ep. acrylate
(50/50)
Toluene-HDDA (50/50)
Tol uene-HDDA-Ep.
acrylate (25150125)
Toluene-PETA (50/50)
Toluene-PETA-Ep.
acrylate (43143114)
Toluene
Methanol
650 40 80
2200 1 8 5 3 1
1500 9.5 3 5
270 5.8 1 3 5
200 1 . 7 <40
280 0.9 150
650 5.2 95
2500 58 22
1000 1 . 2 140
850 5.8 68
ANNEX TO TABLE 11.
Lsl: p#xgg
220 3 . 1 40
360 6.9 69
50 0.53 240
140 0.52 630
Viscosity: q.
*Ref. 33; for formula, see Annex to Table 7.
Trimetbylolpropane triacrylate.
dHexanedioldiacrylate.
ePentaerytbritol triacrylate.
TABLE 9. SOME VALUES OF THE TRIPLET STATE ENERGY
LEVELS OF PHOTOINITIATORS AND MONOMERS
Compound Triplet state energy (AE) (kcaUmo1)
I l a 69
14a 73
I7a 53
I8a 53
19b 59
M2 6 1
I14a 15
124 57
Cited in Ref. 1 3
Cited in Ref. 38
Ls4: -1
TABLE 10. VALUES OF t;, fT, AND kit IN SOLUTION
Photoinitiators
10-6kb
a
$ bs)
ZT ( n s ) (YmoVs)
Ls5:
LS6:
LS7:
4200 4000 0.85
cH$* fmC(Z02-Q- CH3 3300 2000 14
0 CH3
,CH3
$X,-OH
0 CH3
Cl
470 470 15
4000 1750 24
Determined in bulk epoxyacrylate-HDDA (60 :4Ow/w); a in solution b in the
presence of LSl (2%).; Ref. 34.
References page II - 180
II / 180 PHOTOPOLYMERIZATION REACTIONS
C. REFERENCES
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(1990).
10. J. P. Fouassier, D. J. Lougnot, J. Chem. Sot., Faraday Trans., 1,
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11. G. Amirzadeh, R. Kuhlmann, W. Schnabel, J. Photochem., 10,
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12. J. P. Fouassier, D. J. Lougnot, L. Avar, Polymer, 36 (26), 5005
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18. l? J. Wagner, M. J. Lindstrom, Jacs, 109, 3062 (1987).
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(1987).
Free Radical Copolymerization
Reactivity Ratios
Robert Z. Greenley*
Monsanto Co., 544 Oak Valley Drive, St. Louis, MO 63131, USA
A. Introduction
B. Tables
Table 1. Copolymer Reactivity Ratios
Table 2. Listing of Quick Basic (Microsoft)
Program for Calculating Reactivity
Rat i os
C. References
II-1 81
II-1 82
II-1 82
II-288
II-290
A. INTRODUCTION
When a vinyl monomer is copolymerized with a second
monomer, the relationship between the composition of the
initially formed copolymer and the initial monomer mixture
is given by
dml Ml (041 + a)
-=
dm2 M2(r2M2 + Ml)
where ml is the number of moles of monomer 1 entering
the copolymer, m2, the number of moles of monomer 2
entering the copolymer, MI, the number of moles of
monomer 1 in the monomeric mixture, M2, the number of
the moles of monomer 2 in the monomer mixture, and r1
and r2 are the monomer reactivity ratios.
The monomer reactivity ratios, rl and r2, for any
monomer pair are the ratios of the rate constants of the
different propagation reactions:
-M; fM1- -MlM;
kll
N M; + M2- N MlM;
kn
NM; + M2- N M2M;
kn
wM;+M1-wM2M;
k21
with r1 = kll/k
12, r2 = kdh.
N M represents a poly-
mer chain ending in a radical derived from monomer M.
The original compilations of reactivity ratios and their
references were published by L. J. Young in the first two
editions of this Handbook. In the third edition, the original
listings and those through 1986 were re-evaluated. This
fourth edition contains an additional 548 evaluated mono-
mer pairs giving a total of 3,265 such pairs. Only free
*Retired.
radical reactivity ratios are listed. When the original
references were available, they were read. If the experi-
mental data was published, the reactivity ratios were
recalculated according to the methods of Kelen and Tudiis
(803,804). The 95% confidence limits for the reactivity
ratios were also calculated (805). If the authors used this
method for r-value evaluation, including adjustment of the
monomer feeds for total conversion, then the reported
values were utilized. There are a number of reported
reactivity ratios that are not reported here. This is due to the
absence of these values in the abstracts of papers which
were published in journals unavailable to the author.
All of the monomer pairs in Table 1 are cross-referenced.
The full spelling of each monomer was included in its
Monomer 1 citation. Sometimes truncated but distinguish-
able names have been used in the Monomer 2 lists.
If only the reactivity ratios and reference are given, then,
either no experimental data was given or the journal was not
available and the Chemical Abstracts summary was the
source of the data. If a Y or N (yes or no) appears in the
conversion (Conv.) column then the reactivity ratios were
recalculated. If a recalculation was performed but the 95%
confidence columns (95%) are still left blank, it indicates
that only two feed/polymer data pairs were available. In
general, if there is a citation (Y or N) in the Conv. column
but no reactivity ratios are shown in the reactivity ratio
columns, the copolymerization did not follow the copoly-
merization equation (ionic or penultimate effects were
prevalent). In a few cases, the data were too scattered to
allow a reactivity ratio calculation.
Recalculations yield negative reactivity ratios in several
cases. We are aware that this is a physically unrealistic
artifact. When the 95% confidence limits are applied to
these negative numbers, a value of zero usually falls within
these limits. It may be noted that a single reference
sometimes contains a variety of reactivity ratios for one
monomer pair. The reader may assume that these result
from a change of polymerization conditions; e.g., different
polymerization temperatures or polymerization media of
varying polarity.
For those who are interested in using the Kelen-TudBs
calculations, a listing of a simplistic program written in
QuickBasic (Microsoft) is also given (Table 2).
II / 181
II / 182 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
B. TABLES
TABLE 1. COPOLYMER REACTIVITY RATIOS
Monomer 1 Monomer 2
rl
f95% r2 f95% Conv. Refs.
Acenaphtbalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acetamide, N-(4-methacryloyloxyphenyl)-
2-(4-metboxy)
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetanilide, 4-(2-methacryloyloxy)-
ethyloxy)
Acetanilide, 4-(2-methactyloyloxy)-
hexyloxy)
Acetanilide, 4-(methacryloyloxy)-
Acetate, 2-chloro-, vinyl
Acetate, ally1
Acetate, chloro-, ally1
Acetate, dichloro-, ally1
Acetate, isopropenyl
Acetate, trichloro-, ally1
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Aconitate, trimethyl
Aconitate, trimethyl
Aconitate, trimethyl
Aconitate, trimethyl
Aconitate, trimethyl
Acrolein
Acrolein
Acrolein
Acrolein
Acrolein
Acrolein
Acrolein
Acrolein
Acrylate, (-)-menthyl
Acrylonitrile
Carbazole, N-vinyl-
Fumarate, diisopropyl
Maleic anhydride
Maleic anhydride
Mal ei mi de, N-cyclohexyl-
Metbacrylate, (-)-me&y1
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylonitrile
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Stilbene
Styrene
Methacxylate, 2-hydroxyethyl
2.56
6.62
2.51
0.46
0.46
0.57
2.48
1.05
0.99
2.25
2.38
1.77
0.13
0.55
0.14
0.15
0.02
- 0.03
0.06
0.02
- 0.04
0.11
0.316
0.36
0.38
0.44
0.15
0.12
0.05
0.085
0.04
0.04
5.65
0.33
1.49
0.23 - 0.01
3.81
0.61
0.04
645
575
331
1039
1039
26
1039
645
326
326
575
515
326
326
725
525
1 0 5 1
Acrylamide 0.3 1.4 984
Methacrylate, methyl 0.19 2.65 984
Methacrylate, methyl 0.71 1.18 984
Methacrylate, methyl 0.01 2.1 984
Vinyl acetate 5.5 0.6 984
Vinyl acetate 2 1 0 984
Methacrylate, 2-hydroxyethyl 0.67 1.39 1096
Methacrylate, 2-hydroxyethyl 0.87 1.19 1096
Methacrylate, 2-hydroxyethyl
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Fumarate, diisopropyl
Vinyl acetate
Acrylate, methyl
Acrylate, methyl
Acrylonitrile
Isoprene
Maleic anhydride
Methacrylate, methyl
Methacrylate, butyl
Methacrylate, isobutyl
Methacrylate, methyl
Metbactylate, met hyl
Methacrylonitrile
Pyridine, 2-vinyl-
Styrene
Acrylonitrile
Butadiene
Styrene
Vinyl chloride
Vinylidene chloride
Acrylamide
Acrylamide
Acrylate, butyl
Acrylate, butyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, methyl
Acrylate, methyl
1.94
1.18
0.43
0.69
0.54
0.011
0.28
0.212
0.093
0.325
0.1
0.08
0.2
0.21
0.27
1.69
0.07
0.04
0.072
0.01
0.083
26.56
0.016
0.78
0.8
1.8
0.77
0.57
0.67
0.41
0.622
0.664
0.266
3.01
0.06
1.5
1.7
1.9
- 0.06
1.111
0.78
0.062
0.045
0.044
0.16
0.095
0.33
- 0.48
0
- 0.013
0.19
0.15
1.95
1.59
1.86
2.29
1.2
1.98
- 0.07
1.41
0.12
0.11
0.22
0.009
0.02
0.92
0.4
0.091
0.94
0.58
0.1
0.19
0.58
0.44
0.03
0.4
0.324
4.24
0.4
1.026
0.04
64.6
0.8
0.18
0.638
1.12
0.6
1.09
7.86
0.83
23.74
0.23
0.02
0.032
0.41
0.25
3.58
0.12
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
Y
N
N
N
Y
1096
892
1045
1045
1045
1038
1045
60
731
60
648
197
443
565
565
357
732
648
192
357
1 4 7
147
147
1 4 7
149
207
208
291
292
291
292
207
291
Copolymer Reactivity Ratios II / 183
TABLE 1. contd
Monomer 1 Monomer 2
rl f95% r2 f95% Conv. Refs.
Acrolein Acrylate, methyl
Acrolein Acrylic acid
Acrolein Acrylic acid
Acrolein Acrylonitrile
Acrolein Acrylonitrile
Acrolein Acrylonitrile
Acrolein Acrylonitrile
Acrolein Methacrylate, methyl
Acrolein Methacrylate, methyl
Acrolein Methacrylonitrile
Acrolein Methacrylonitrile
Acrolein Pyridine, 2-vinyl-
Acrolein Styrene
Acrolein Styrene
Acrolein Styrene
Acrolein Styrenesulfonate, p-, sodium
Acrolein Styrenesulfonate, p-, sodium
Acrolein Styrenesulfonate, p-, sodium
Acrolein Vinyl acetate
Acrolein Vinyl chloride
Acrolein diethylacetal Acrylonitrile
Acrolein diethylacetal Maleic anhydride
Acrolein, methyl- Acrylate, butyl
Acrolein, methyl- Acrylonitrile
Acrolein, methyl- Acrylonitrile
Acrolein, methyl- Acrylonitrile
Acrolein, methyl- Acrylonitrile
Acrolein, methyl- Methactylate, methyl
Acrolein, methyl- Methacrylonitrile
Acrolein, methyl- Methacrylonitrile
Acrolein, methyl- Methacrylonitrile
Acrolein, methyl- Styrene
Acrolein, methyl- Styrene
Acrolein, methyl- Vinyl acetate
Acrolein, 2-chloro- Styrene
Acryl-2-ethyl-4,5,7-trinitro- Acrylate, N-(Zhydroxyethyl)-
9-flurenone-2-carboxylate carbazolyl
Acryl-2-ethyl-4,5,7-trinitro-9-flurenone- Methacrylate, N-(2-hydroxyethyl)
2-carboxylate carbazolyl
Acrylamide Acet ami de, N-vinyl-
Acrylamide Acrolein
Ac r yl a mi de Acrolein
Ac r yl a mi de Acrylic acid
Ac r yl a mi de Acrylic acid
Ac r yl a mi de Acrylic acid
Ac r yl a mi de Acrylic acid
Ac r yl a mi de Acrylic acid
Acrylamide Acrylic acid
Acrylamide Acrylic acid, cis-3-bromo-
Acrylamide Acrylic acid, cis-3-ethyl-
Acrylamide Acrylic acid, truns-3-bromo-
Acrylamide Acrylic acid, trans-3-ethyl-
Acrylamide Acrylonitrile
Acrylamide Acrylonitrile
Acrylamide Acrylonitrile
Acrylamide Acrylonitrile
Acrylamide Acrylonitrile
Acrylamide Cinnamic acid, cis-
Acrylamide Cinnamic acid, trans-
Acrylamide Crotonic acid
Acrylamide Crotonic acid
Acrylamide Crotonic acid
Acrylamide Crotonic acid
Acrylamide Crotonic acid, cis-
Acrylamide Crotonic acid, truns-
2.54
2.48
0.5
1.16
1.07
1.52
1.28
0.76
0.59
0.68
0.72
2.64
0.216
0.02
0.32
0.395
0.26
0.113
3.04
5.22
0.02
0.18
2.5
1.7
3.8
3.8
1.72
0.4
1.78
1.25
1.25
0.833
0.3
0.98
0.15
0.585
0.93
1.24
0.38
0.28
0.13
0.08
0.07
0.06
0.03
0.01
0.12
0.3
0.12
0.05
0.4
0.05
0.14
0.036
0.01
0.002
0.092
0.16
0.018
0.43
0.13
0.03
0.017
0.02
0.006
0.033
0. 07 1
0.009
0.12
0.11
0.42 0.19
0.07 0.01
0.092
1.08
0.08
1.15
0.88
0.71
0.48
0.6
1.136
1.33
1.17
1.2
-0.12
0.257
0.22
0.205
0.327
0.047
0.01
- 0.02
0.03
11.19
0.07
0.02
0.15
0.15
0.15
0.03
0.1
0.41
0.45
0.45
0.173
0.41
0.15
0.02
0.912
0.017
0.07
0.028
0.05
0.079
0.102 0.022 0.773 0.096
1.4
0.8
0.18
1.08
0.445
1.346
0.598
0.58
1.06
7.64
6.32
4.13
8.19
0.81
1.08
0.5
1.36
1.3
3.84
3.4
3.76
4.23
4.72
5.32
0.23
0.02
0.17
0.075
0.044
0.047
1.67
0.68
0.76
1.09
0.11
0.51
0.26
0.3
1.95
1.59
0.288
1.644
0.341
1.38
3.8
0.29
- 0.2
-0.16
- 0.33
- 0.21
0.863
0.97
1.8
0.88
0.8
0.58
0.1
0.029
0.069
0.012
0.14
0.11
0.1
0.16
0.11
0.033
0.1
0.75
0.68
0.24
0.89
1.37
- 0.24
-0.18
-0.19
0.11
0.12
0.28
0.15
0.14
0.19
7.2 0.33 - 0.085 0.024
N
Y
N
N
N
Y
N
N
N
Y
N
Y
Y
Y
Y
N
N
Y
N
N
Y
Y
N
N
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
292
57
57
207
207
208
504
291
292
208
446
208
291
292
307
57
57
57
207
271
767
767
589
455
587
589
9 1
589
208
587
589
223
589
589
806
715
703
984
207
208
221
278
278
37
869
869
298
298
298
298
228
228
330
421
461
298
298
298
298
569
569
341
341
References page II - 290
II / 184 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1
zt95%
r2
zt95% Conv. Refs.
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acryl ami de, 2-chloro-N,N-dimethyl-
Acryl ami de, 2-chloro-N,N-dimethyl-
Acrylamide, N,N-dibutyl-
Acrylamide, N,N-diethyl-
Acrylamide, N,N-diethyl-
Acrylamide, N,N-dietbyl-
Acrylamide, N,N-diethyl-
Acrylamide, N,N-diethyl-
Acrylamide, N,N-diethyl-
Acrylamide, N,N-dimetbyl-
Acrylamide, N,N-dimethyl-
Acrylamide, N,N-dimetbyl-
Acrylamide, N,N-dimethyl-
Acryl ami de, N,N-dimethyl-
Acrylamide, N,N-dimethyl-
Acrylamide, N,N-dimethyl-
Acrylamide, N,N-dimethyl-
Acrylamide, N-(2-(4-hydroxyphenyl)ethyl)-
Acrylamide, N-(2-(propionamide)-
Acrylamide, N-methyl-
Acrylamide, N-methyl01
Acrylamide, N-methyl01
Acrylamide, N-methyl01
Acryl ami de, N-methyl01
Acryl ami de, N-methyl01
Acryl ami de, N-methyl01
Acrylamide, N-methyl01
Acrylamide, N-methyl01
Acrylamide, N-methyl01
Acrylamide, N-methyl01
Acrylamide, N-methylol-
Acrylamide, N-octadecyl-
Acrylamide, N-octadecyl-
Dioxolane, 1,3,4-methvlene-2-trichloro- 8.6
0.56
0.05
0.14
0.04
Maleic anhydr i de -
Metbacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 3-methoxy-
2-hydroxypropyl
Methacrylate, dimethylaminoethyl
sulfate
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylic acid
Metbacrylic acid
Methacrylic acid
Methylenebutyrolactone
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Succinimide, N-vinyl-
Vinyl chloride
Vinyl methyl ketone
Vinyl methyl ketone
Vinylene carbonate
Vinylmethylphenylsulfonium
tetrafluoro
Vinylsulfonic acid
Methacrylate, methyl
Styrene
Styrene
Acrylic acid
Butanoate, 3-acrylamido-3-methyl-,
sodium
Methacrylate, methyl
Styrene
Styrene
Styrene
Metbacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Styrene
Sulfonate, 2-acrylamido-
2-methylpropane
Vinyl methyl ketone
Methacrylamide, N-(2-hydroxypropyl)-
Styrene
Methacrylate, methyl
Acrylate, butyl
Acrylate, ethyl
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Acrylonitrile
Methacrylate, methyl
Methacrylate, methyl
Styrene
Vinyl chloride
Styrene
Acrylonitrile
Methacrylate, methyl
0.037 616
0 655
1.89 689
0.98 928
3.98 689
0.52
2.29
0.53
0.82
0.9
0.57
0.58
0.56
0.3
0.58
1.32
0.33
0.59
8.97
0.2
1.86
0.05
0.44
0.09
1.07
1.9
2.34
3
2.53
3
1.63
4.4
0.15
2.85
1.17
1.21
1.49
1.13
0.65
1.05
0.17
0.2
0.17
0.09
0.45
0.12
0.13
0.14
0.43
0.06
0.04
0.16
0.03
3.99
1.02
13.8
3.4
0.7
0.13
0.47
0.75
0.05
0.1
0.44
0.23
3.5 0.15 0.3 0.1
- 0.159 0.502 2.71 0.398
- 0.036 0.152 1.29 0.065
0.294 0.058 1.6 0.058
0.35 0.12 0.36 0.04
0.987 0.153 0.22 0.138
0.41
0.39
0.34
0.18
0.57
0.59
0.21
0.12
0.49
0.47
1.108
0.15
0.08
0.09
0.21
0.3
0.15
0.2
0.59
1.65
1.23
1.36
1.54
2.15
2.8
2.64
1.15
1.37
1.32
0.162
0.16
0.08
0.1
0.15
0.35
0.1
0.12
0.949
0.82
0.95
0.86
0.05
0.61
1.4
1.9
1.2
2.33
2.56
0.7
0.7
0.48
0.4
1.4
0.42
0.36
0.09
0.3
0.72
0.1
1.01
1.84
1.14
0.87
1.4
1.3
0.7
0.98
0.22
1.62
1.62
0.03
0.03
0.17
0.11
1.55
1.034
4.119
0.43
0.09
0.21
0.09
0.05
0.02
0.07
N
N
N
N
N
N
N
Y
Y
Y
Y
Y
N
Y
N
N
N
N
N
N
N
Y
Y
N
N
Y
Y
Y
1052
314
314
314
691
1028
852
852
746
295
314
314
314
343
555
600
156
609
609
387
793
1066
917
917
806
205
857
170
739
739
739
315
315
691
170
315
315
857
609
965
295
691
441
442
441
442
577
596
593
596
596
1 5 7
891
119
290
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 185
Monomer 1 Monomer 2
f.1
f95%
r2
Zt95% Conv. Refs.
Acrylamide, N-octadecyl-
Acrylamide, N-octadecyl-
Acrylamide, N-octadecyl-
Acrylamide, N-octyl-
Acrylamide, N-propyl-
Acrylamide, N-propyl-
Acrylamide, N-tert-butyl-
Acrylamide, N-terf-butyl-
Acrylamide, wfluoro-
Acrylamido, l-,-l-deoxy-o-glucitol
Acrylamido, 1-,-1-deoxy-D-glucitol
Acrylamido, l-,-l-deoxy-o-glucitol
Acrylamido, 2-,2-methylpropanesulfonate,
sodium
Acrylamido, 2-,-2-methylpropanesulfonic
acid
Acrylamido, 2-,-2-methylpropanesulfonic
acid
Acrylamido-2-methylpropane sulfonate
sodium salt
Acrylamidomethylamino, p-, azobenzene
Acrylamidomethylamino, p-, azobenzene
Acrylate, (-)-mentbyl
Acrylate, (-)-menthyl
Acrylate, 1.1.5trihydroperlluoroamyl
Acrylate, 2,3-dibromopropyl
Acrylate, 2,4,5-trichlorophenyl
Acrylate, 2,4,5-trichlorophenyl
Acrylate, 2,4,6-tribromophenyl
Acrylate, 2,4dinitrophenyl
Acrylate, 2,4-dinitrophenyl
Acrylate, 2(0-ethyl methylphosphonoxy)-,
methyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroetbyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethw.
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethylglucitol
Acrylate, 2-cyano-, methyl
Acrylate, 2-cyano-, methyl
Acrylate, 2-cyanoethyl
Acrylate, 2-ethylhexyl
Acrylate, 2-ethylhexyl
Acrylate, 2-etbylhexyl
Acrylate, 2-ethylhexyl
Acrylate, 2-etbylhexyl
Acrylate, 2-ethylhexyl
Acrylate, 2-hydroxyethyl
Acrylate, 2-hydroxyethyl
Acrylate, 2-hydroxyetbyl
Acrylate, 2nitrobutyl
Acrylate, 2-nitrobutyl
Acrylate, 2nitrobutyl
Acrylate, 3,4-epoxyhexahydrobenzyl
Styrene 0.54
Vinyl acetate 8.25
Vinylidene chloride 1.4
Styrene 0.258
Acrylate, butyl 0.4
Acrylate, methyl 0.26
Acrylonitrile 1.14
Methactylate, methyl 2.83
Methacrylate, methyl 0.148
Methacrylate, methyl 0.05
Styrene 0.03
Vinyl acetate 0.98
Vinyl acetate 11.6
Methacrylate, 2-hydroxyethyl 0.9 0.86
Methacrylate, 2-hydroxypropyl 1.03 0.89
N-Vinylpyrrolidone
Styrene
Vinyl acetate
Acenaphthalene
Pyridine, .4-vinyl-
Methactylonitrile
Styrene
Pyrrolidone, N-vinyl-
Styrene
Styrene
Acrylate, N-(2-hydroxyethyl)-carbai
Methacrylate, N-(Zhydroxyethyl)-
carbazolyl
Methacrylate, methyl
Acrylate, ethyl
Acrylate, methyl
Acrylonitrile
Itaconate, bis(tri-n-butyltin)
Itaconic anhydride
Itaconic anhydride
Maleic anhydride
Methacrylate, methyl
Fyrrolidone, N-vinyl-
Styrene
Styrene
Styrene
Vinyl butyl ether
Vinyl isobutyl ether
Styrene
Styrene, u-methyl-
Vinyl acetate
Styrene
Acrylate, glycidyl
Methacrylate, glycidyl
Styrene
Styrene
Vinyl acetate
Vinyl chloride
Acrylate, butyl
Acrylate, ethyl
Acrylate, methyl
Acrylonitrile
Methacrylate, methyl
Styrene
Acrylonitrile
0.66
8.5 0.083
12.98 0.126
0.291
0.14
0.16
0.163
0.23
0.1
rolyl 0. 158
0.186
0.44
1.03
1.07
0.87
0.683
- 0.016
0.251
7.15
0.37
0.52
0.1
0.139
0.12
2.01
2.24
0.14
0.001
0.5
0.128
1.12
0.09
0.31
0.26
7.5
4.15
0.9
0.97
0.9
1.76
0.27
0.12
0.388
0.14
1.46
0.11
0.119
0. 08 1
0.09
0.02
0.87
0.017
0.02
0.021
0.015
0.009
0.25
0.022
0.021
0.31
0.17
0.083
0.09
0.074
0.07
0.13
0.6
0.23
0.24
0.13
0.69
0.04
0.01
0.074
2.08
0.004
0.432
2.715
0.8
1.2
0.2
0.25
2.13
3.75
2.42
0.03
0.05
0.13
2.32
1.03
0.42
0.012
0.277
0.2
0.109
0.243
0.73
0.9
0.9
1.03
0.391
2.46
2.61
0.027
2.15
0.03
0.55
0.494
0.54
0
0
0.49
0.05
0.005
0.399
1.18
2.41
0.96
0.94
0.04
0.16
0.3
0.5
0.94
0.67
1.19
0.35
0.25
0.12
0.011
0.008
0.244
0.136
0.24
0.08
0.17
0.45
0.008
0.048
0.026
0.034
0.04
0.38
0.32
0.004
0.47
0.097
0.2
0.032
0.06
0.46
0.3
0.06
0.03
0.04
0.25
0.12
0.03
0.13
Y
Y
Y
Y
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
N
N
N
N
N
N
N
Y
290
119
119
806
730
730
709
709
823
258
258
258
700
618
618
939
858
858
645
667
809
643
840
622
643
716
716
882
726
726
790
940
365
365
117
790
790
140
178
790
790
790
806
452
452
1 7 8
126
674
126
463
570
510
868
868
868
234
234
234
680
References page II - 290
II / 186 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl
f95%
rz
It95% Conv. Refs.
Acrylate, 3,4-epoxyhexahydrobenzyl
Acrylate, 4-acetylphenyl
Acrylate, P-acetoxymethyl-, methyl
Acrylate, P-acetoxymethyl-, methyl
Acrylate, P-chloro-2-hydroxypropyl
Acrylate, P-ethoxy-, ethyl
Acrylate, P-ethoxy-, ethyl
Acrylate, N-(2-hydroxyethyl)-
3,6-dichlorocarbazolyl
Acrylate, N-(2-hydroxyethyl)carbazolyl
Acrylate, N-(2-hydroxyethyl)carbazolyl
Acrylate, N-(2-hydroxyethyl)carbazolyl
/
Acrylate, N-(2-hydroxyethyl)carbazolyl
Acrylate, N-(2-hydroxyethyl)carbazolyl
Acrylate, a-(4-chlorobenzyl)-, ethyl
Acrylate, a-(Ccyanobenzyl)-, ethyl
Acrylate, cc-(4-methoxybenzyl)-, ethyl
Acrylate, a-(O-ethyl methylphosphonoxy)-
methyl
Acrylate, a-(hydroxymethyl)-, methyl
Acrylate, a-[2,2-bis(carbomethoxy)ethyl]-,
methyl
Acrylate, cc-[2,2-bis(carbomethoxy)ethyl]-,
methyl
Acrylate, wacetoxy-, ethyl
Acrylate, cc-acetoxy-, ethyl
Acrylate, a-acetoxy-, ethyl
Acrylate, a-acetoxy-, ethyl
Acrylate, a-acetoxy-, ethyl
Acrylate, a-benzyl-, methyl
Acrylate, a-benzyl-, ethyl
Acrylate, a-benzyl-, methyl
Acrylate, a-benzyl-, methyl
Acrylate, a-bromo-, ethyl
Acrylate, a-butyl-, methyl
Acrylate, a-chloro-, methyl
Acrylate, cc-chloro-, ethyl
Acrylate, wchloro-, ethyl
Acrylate, u-chloro-, ethyl
Acrylate, a-chloro-, ethyl
Acrylate, a-chloro-, ethyl
Acrylate, a-chloro-, ethyl
Acrylate, a-chloro-, ethyl
Acrylate, wchloro-, ethyl
Acrylate, wchloro-, methyl
Acrylate, cr-chloro-, methyl
Acrylate, cl-chloro-, methyl
Acrylate, a-chloro-, methyl
Acrylate, a-chloro-, sodium
Acrylate, wcyano-, methyl
Acrylate, a-cyano-, methyl
Acrylate, a-cyano-, methyl
Acrylate, wcyano-, methyl
Acrylate, cc-cyano-, methyl
Acrylate, wcyano-, methyl
Acrylate, cl-cyclohexyl-, methyl
Acrylate, cl-ethyl-, methyl
Acrylate, a-ethyloxymethyl-, methyl
Acrylate, a-fluoro-, ethyl
Acrylate, a-fluoro-, methyl
Acrylate, cc-hexafluoropropyloxymethyl-,
methyl
Styrene 1.97
Methacrylate, glycidyl 0.292
Methacrylate, methyl 0.24
Styrene 0.19
Acrylonitrile 0.7
Acrylonitrile 0. 26
Styrene 0.21
Methacrylate, 2,4-dinitrophenyl 0.115
0.35
0.141
0.56
0.44
0.029
0.27
0.644
0.91
0.34
0.24
2.42
46.98
1.207
0.3
0.13
1.8
27.03
0.032
Acryl-2-ethyl-4,5,7-trinitro-9-fluorene
Acrylate, 2,4-dinitrophenyl
Acryloyl-P-hydroxyethyl-
3,5-dinitrobenzoate
Methacryloyl-P-hydroxyethyl-
3,5-dinitrobenzoate
Methacryloyl-P-hydroxyethyl-
3,5-dinitrobenzoate
Styrene
Styrene
Styrene
Methacrylate, methyl
0.912 0.079 0.585 0.028
0.109 0.026 0.158 0.015
0.62 0.044 0.361 0.016
N 680
Y 1012
1 0 9 1
1 0 9 1
654
N 194
Y 194
Y 736
Y 715
Y 716
Y 702
1.04 0.14 0.08 0.026 Y 702
0.334 0.022 1.364 0.018
1.03
0.65
0.71
0.44
0.13
0.09
0.24
0.04
0.06
0.33
0.73
0.09
0.05
0.3
Y 719
806
806
806
851
Styrene 0.34 0.36 932
Methacrylate, methyl 0.04 3.7 1092
Styrene 0.09 0.58 1092
Acrylate, a-chloro-, ethyl 0.3
Acrylate, ethyl 0.968
Methacrylate, methyl 0.608
Styrene 0.173
Vinyl acetate 5.621
Styrene 0.175
Styrene 0.9
Metbacrylate met hyl 0.173
Methacrylate methyl 0.09
Styrene 0.44
Styrene 0.205
Methacrylate, methyl 1.13
Acrylate, wmethoxy-, methyl 0.58
Acrylate, a-acetoxy-, ethyl 1.71
Acrylate, cr-fluoro-, ethyl 2.9
Acrylate, methyl 3.22
Acrylonitrile, cc-methoxy- 0.9
Metbacrylonitrile 2
Styrene 0.32
Vinyl acetate 30
Acrylonitrile 1.76
Methacrylate, methyl 1.92
Styrene 0.3
Vinylidene cyanide 0.313
Styrenesulfonate, p-. sodium 0.27
Acrylonitrile 0.68
Acrylate, methyl 0.34
Methacrylate, methyl 0.03
Methacrylate, methyl 0.135
Methacrylonitrile 0.15
Styrene 0.61
Styrene 0.001
Styrene 0.197
Styrene 0.24
Acrylate, a-chloro-, ethyl 0.21
Styrene 0.16
Styrene 0.07
0.033
0.02
0.01
0.094
0.053
0.2
0.022
0.01
0.08
0.053
0.19
0.075
0.12
0.031
0.021
0.028
0.17
0.23
0.19
0.04
0.043
0.24
0.11 0.07
0.18
0.08
0.081
0.09
0.021
0.06
0.09
0.07
0.01
0.016
0.01
0.05
0.034
0.014
0.07
0.31
0.02
0.04
0.02
0.014
0.01
0.01
0.048
0.014
0.11
1.71
0.943
1.65
0.557
0.08
0.57
0.14
2.36
3.9
0.02
0.812
0.31
0.11
0.3
0.21
0.09
0.3
0.45
0.08
0.03
0.122
0.11
0.25
0.066
1.44
0.01
0.02
0.21
0.068
0.18
0.05
1.615
0.758
0.37
2.9
0.66
0.23
0.17
638
Y 244
Y 244
Y 244
Y 244
Y 49
806
Y 610
N 610
806
Y 49
Y 6
638
638
638
638
638
638
806
638
Y 6
N 3 1
74
Y 82
Y 834
N 1 4 1
N 1 4 1
N 1 4 1
Y 182
N 1 4 3
N 1 4 1
Y 49
Y 49
1047
638
806
1047
TABLE 1. contd
copolymer Reactivity Ratios II / 187
Monomer 1 Monomer 2
r1 f95%
r2
Zt95% Conv. Refs.
Acrylate, a-hydroxymethyl-, ethyl
Acrylate, whydroxymethyl-, ethyl
Acrylate, a-hydroxymethyl-, ethyl
Acrylate, a-isobutyl-, methyl
Acrylate, a-isopropyl-, methyl
Acrylate, a-isopropyloxymethyl-, methyl
Acrylate, wmethoxy, methyl
Acrylate, a-methoxy-, methyl
Acrylate, cr-p-chlorobenzyl-, methyl
Acrylate, a-p-methoxybenzyl-, methyl
Acrylate, a-phenoxymethyl-, methyl
Acrylate, CL- phenoxymethyl-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, cl-phenyl-, methyl
Acrylate, cc-phenyl-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, wphenyl-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, wphenyl-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, a-phenyl-, butyl
Acrylate, a-phenyl-, chloroethyl
Acrylate, wphenyl-, propyl
Acrylate, a-propyl-, methyl
Acrylate, cl-propyloxymethyl-, methyl
Acrylate, cc-set-butyl-, methyl
Acrylate, c+tetrafluoropropyloxymethyl-,
methyl
Acrylate, wtetrafluoropropyloxymethyl-,
methyl
A&ate, a-trifluoroethyloxymethyl-,
methyl
Acrylate, a-trifluoromethyl-, methyl
Acrylate, a-trifluoromethyl-, methyl
Acrylate, a-trifluoromethyl-, methyl
Acrylate, a-trifluoromethyl-, methyl
Acrylate, cc-trimethylsiloxy-, methyl
Acrylate, benzyl
Acrylate, benzyl
Acrylate, benzyl
Acrylate, benzyl
Acrylate, benzyl
Acrylate, benzyl
Acrylate, butyl
Ac r yl a t e , but yl
Ac r yl a t e , but yl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Azlactone, 2-vinyl-4,4-dimethyl- 0.668
Methacrylate, methyl 1.34
Styrene 0.546
Styrene 0.202
Styrene 0.036
Styrene 0.26
Acrylate, a-chloro-, ethyl 0.11
Styrene 0.513
Methacrylate, methyl 0.255
Methacrylate, methyl 0.13
Methactylate, met hyl 0.755
Styrene 0.256
Acrylate, methyl 1
Acrylonitrile 6.7
Methacrylate, methyl 0
Methacrylate, methyl 0
Methacrylonitrile 0.25
Styrene 1
Styrene 0.4
Styrene 0.45
Styrene 1.275
Styrene 0.107
Styrene 0.201
Styrene 0.126
Styrene 0.208
Styrene 0.29
Styrene 0.004
Methacrylate, methyl 0.61
Styrene 0.17
Styrene 0.2 0.26
Methacrylate, methyl -0.17
Methacrylate, methyl 0
Methacrylate, methyl 0.1
Styrene, p-chloro- 0
Styrene 1.42
Acrylonitrile 0.72
Acrylonitrile 0.63
Ally1 chloride 9.9
Methacrylate, methyl 0.19
Styrene 0.2
Styrene 0.248
2-Oxazoline, 2-isopropenyl- 0.24
Acrolein 0.638
Acrolein 1.12
Acrolein, methyl- 0.02
Acrylamide, N-propyl- 0.8
Acrylamide, N-methylol- 0.87
Acrylate, 2-hydroxyethyl 0.3
Acrylic acid 1.08
Acrylic acid 0.91
Acrylic acid, a-bromo- 0.19
Acrylonitrile 1.06
Acrylonitrile 0.894
Acrylonitrile 0.82
Acrylonitrile 0.9
Acrylonitrile 1.2
Ally1 acetate 10.2
Ally1 chloride 5.83
Benzofuran, 2-vinyl- 0.041
Butadiene 0.074
Ethylene 13.94
Furan, 2-vinyl-5-methyl 0.118
0.12
0.062
0.127
0.042
0.034
0.058
0.034
0.008
0.061
0.102
0.008
0.055
0.09
0.063
0.07
0.024
0.18
0.1
0.1
0.03
0.16
0.2
0.12
0.041
0.01
0.032
0.41
0.06
0.18
0.13
0.15
0.019
0.13
42.2
0.043
0.03
0.38
0.019
0.389
1.26
0.468
0.974
1.872
0.41
0.58
1.131
1.87
1.71
1.13
0.176
0.06
0.08
0.21
0.3
0.19
0.06
0.03
0.06
1.176
0.04
0.025
0.03
0.821
0.47
2.29
1.43
0.37
1.8
3.2
2.3
0.24
0.46
0.28
1.49
0.06
2.23
0.494
0.534
1.4
1.86
2.29
2.5
0.4
0.61
0.9
0.59
1.31
0.09
1.679
0.781
1.08
1
1
0.039
0.1
7.8
1.04
0.01
0.392
0.229
0.17
0.03
0.022
0.052
0.078
0.222
0.109
0.038
0.05
0.015
0.022
0.015
0.015
0.029
0.068
0.23
0.5
0.2
0.02
0.19
0.14
0.05
0.028
0.08
0.19
0.58
0.23
0.27
0.3
0.058
0.083
0.08
0.066
1.36
0.11
0.003
0. 05 1
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
Y
Y
Y
Y
N
N
N
N
Y
Y
N
N
N
Y
N
Y
1 0 1 1
1 0 2 7
982
49
49
1047
638
806
905
905
1048
1048
141
141
1 4 1
49
1 4 3
1 4 1
399
488
49
488
488
488
49
1047
49
1047
1047
1047
681
825
825
825
1 1 0 1
2 3
385
438
277
1 7 8
277
894
291
292
589
730
441
868
1 8 7
252
733
1 1 8
162
233
513
513
1053
438
1020
257
42
1 1 0 5
References page II - 290
II / 188 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. conrd
Monomer 1 Monomer 2 r1 f95% r2 f95% Conv. Refs.
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
A&ate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, cis-B-cyano-, methyl
Acrylate, cis-B-cyano-, methyl
Acrylate, cresyl
Acrylate, cyclododecyl
Acrylate, cyclododecyl
Acrylate, cyclododecyl
Acrylate, cyclohexyl
Acrylate, cyclohexyl
Acrylate, cyclohexyl
Acrylate, cyclohexyl
Acrylate, cyclohexyl
Acrylate, cyclohexyl
Acrylate, di-, copper
Acrylate, di-, copper
Acrylate, di-, copper
Itaconate, bis(tri-n-butyltin)
Itaconate, dimethyl
Mal ei mi de, N-(2,4-dimethylphenyl)-
Methactylate,
2-(N,N-dimethylcarbamoyloxy)ethyl
Methactylate, 2-chloro-
2,3,3,3-fluoropropyl
Methacxylate, 2-hydroxyethyl
Methacrylate, 2-hydroxypropyl
Methacxylate, 2-hydroxypropyl
Methactylate, butyl
Methacrylate, glycidyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylic acid
Oxazoline, 2,2-isopropenyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 4-vinyl-
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, o-chloro-
Styrene, p-1-(2-hydroxybutyl)-
Styrene, p-octylamine sulfonate
Succinimide, N-vinyl-
Thiophene, J-vinyl
Vinyl acetate
Vinyl bromide
Vinyl bromide
Vinyl chloride
Vinyl fluoride
Vinyl fluoride
Vinyl methyl ketone
Vinyl, p-, benzylethylcarbinol
Vinylanthracene, 9-
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Acrylonitrile
Styrene
Acrylonitrile
Styrene
Styrene
Styrene
N-Vinylpyrrolidone
Styrene
Styrene
Styrene
Styrene
Styrene
Methacrylate, di-, dicyclopentadienyl-
titanium
Styrene
Styrene
0.91 0.422 940
0.4 0.94 398
0.62 0.2 788
0.47 1.89 600
0.079 0.304 0.221 0.636 N 927
0.09
0.171
0.24
0.3
0.083
0.13
0.11
0.43
0.31
0.24
0.1
0.11
0.23
0.25
0.34
0.38
-0.106
0.29
0.18
0.19
0.21
0.15
0.164
0.164
0.2
0.17
0.3
1.54
0.386
3.48
4.07
3.7
4.4
1 9
1 9
0.8
0.17
3.717
0.873
0.46
0.58
0.11
0.041
0.16
0.052
0.15
0.018
0.07
0.1
4.75
5.35
3.3
2.2
2.16
0.92
2.86
1.88
1.25
1.4
2.51
2.59
4.3
0.79
0.79
0.75
1.23
0.44
0.84
0.66
0.82
0.8
0.698
0.698
2.25
0.4
2.3
0.15
0.499
0.018
0.18
0.19
0.07
0.01
0.01
1.81
0.4
0.126
0.934
0.84
0.87
4.2
0.32
6.82
0.57
0.2
0.32
0.4
0.31
0.01
0.04
0.05
0.06
0.05
0.099
0.05
0.03
0.14
0.34
0.08
0.11
0.1
0.21
0.03
0.2
3.39
0.44
0.072
0.16
0.06 0.24
0.046
0.022
0.054
0.006
0.773
0.34
0.31
0.301
1.297
0.272
0.254
0.16
0.17
0.18
1.09
0.067
0.15
0.08
0.072
0.088
0.048
0.141
0.13
0.09
0.07
0.72
0.47
0.54
0.461
0.122
0.913
0.885
0.53
0.7
0.58
0.89
0.12 0.08 5.94
0.56 0.09 1.74
0.15
0.14
0.08
0.07
0.014
0.107
0.102
0.11
0.12
0.1
0.05
0.03
Y 358
Y 333
Y 662
187
Y 674
N 30
Y 639
N 87
N 187
862
236
N 78
N 78
1032
1032
1032
N 1 9
N 20
N 38
38
463
549
612
632
558
548
817
789
1000
Y 301
N 268
268
518
604
606
N 53
591
Y 1 2 3
Y 118
464
464
N 1034
N 1034
Y 363
806
806
806
1 0 6 1
1 0 6 1
806
806
806
806
876
N 829
N 829
TABiE 1 . contd
Copolymer Reactivity Ratios II / 189
Monomer 1 Monomer 2
rl
rt95%
12
*95% Conv. Refs.
Acrylate, di-, nickel
Acrylate, di-, nickel
Acrylate, di-, zinc
Acrylate, di-, zinc
Acrylate, dibutylchlorotin
Acrylate, diethylaluminum
Acrylate, diethylaluminum
Acrylate, dodecyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acjlate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Actylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ferrocenylmethyl
Methacrylate, di-, dicyclo-
pentadienyltitanium
Styrene
Acrylonitrile
Styrene
Acrylate, methyl
Styrene
Styrene
Acrylonitrile
2-Oxazoline, 2-isopropenyl-
Acrolein
Acrolein
Acrylamide, N-methylol-
Acrylate, 2-chloroethyl
Acrylate, 2-hydroxyethyl
Acrylate, a-acetoxy-, ethyl
Acrylate, hydroxyethyl
Acrylic acid
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Ally1 chloride
Benzofuran, 2-vinyl-
Carbazole, N-vinyl-
Ethylene, 1, l-diphenyl-
Imidazolid-2-one, 1,3-divinyl-
Imidazolid-2-one, 1-ethyl-3-vinyl-
Isopropenylisocyanate
Mal ei mi de, 2,3-dimethyl-
N-(2-methacryloyloxy)ethyl
Methacrylate, 2-(sulfonic acid)ethyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, butyl
Methactylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylic acid
Norbomadiene
Oxazoline, 2-, 2-isopropenyl-
Propanesulfonate, S-[diethyl-
2-(2-methacroyloxyethoxy)]ethyl
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 4-vinyl-
Pyrimid-2-one, 1,3-divinylhexahydro-
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene 3-tr-n-butylstannyl-
Tropone, 2-methacryloyloxy-
Vinyl 2chloroethyl ether
Vinyl 2-chloroethyl ether
Vinyl isobutyl sulfide
Vinyl isobutyl sulfide
Vinylanthracene, 9-
Vinylidene chloride
Acrylate, methyl
0.95 0.65 876
0.53
0.24
0.9
0.09
0.046
0.06
0.07
0.035
0.16
0.02
0.25
1.83
0.41
1.1
0.81
- 0.002
0.88
0.19
0.6
1.09
1.4
0.9
0.5
0.943
0.5
1.02
1.2
0.81
4
0.95
1.13
0.015
1.1
0.8
0.41
0.47
0.79
0.28
0.02
0.02
0.016
0.07
0.06
0.44
0.03
0.075
0.05
0.07
0.27
0.24
0.033
0.09
0.08
0.78
0.01 0.334
0.13
0.06
1.15
2.37
1.39
1.2
1.98
1.4
1.03
0.97
0.968
0.88
0.91
0.92
1.16
0.66
0.44
0.08
5.16
0.27
0.5
- 0.08
0.01
0.15
1.55
0.03
0.01
3.06
829
646
829
659
652
652
233
894
291
292
442
126
868
244
890
711
1023
1 9 8
389
542
438
1020
151
65
800
800
434
619
0.3
0.37
0.189
0.273
0.207
0.22
0.41
0.28
0.22
0.008
0.054
0.045
0.17
0.05
0.44
1.03
0.06
3.2
2.1
11.21
13.32
9.08
2.43
1.83
2
2.04
0.43
1.05
3.95
0.39
2.39
0.19
3.97
- 0.01
1.39
0.19
564
657
358
333
662
690
30
469
81
1065
267
862
962
0.21
0.21
0.29
0.59
0.139
0.16
0.19
0.2
0.48
0.152
0.152
10.4
0.387
5
4.65
0.36
0.32
3.498
0.72
0.14
0.28
0.03
0.02
0.1
0.13
0.085
0.03
0.072
0.027 0.528
0.02
0.02
0.041
0.39
0.28
2.25
2.58
- 0.05
0.699
1.01
0.79
0.8
0.8
0.787
0.781
0.01
3.13
0.15
0
0.05
0.05
0.295
0.58
4.46
0.04
0.05
0.056
0.15
N
N
Y
Y
N
N
N
Y
N
N
N
N
Y
Y
Y
Y
Y
N
N
N
Y
N
N
Y
Y
N
N
Y
Y
250
832
832
800
1 7 8
463
530
530
542
673
671
985
1104
439
726
285
336
1 2 3
6 5
293
References page II - 290
II / 190 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl Zt95%
r2
f95% Conv. Refs.
Acrylate, ferrocenylmethyl
Acrylate, ferrocenylmethyl
Acrylate, ferrocenylmethyl
Acrylate, ferrocenylmetbyl
Acrylate, ferrocenylmethyl
Acrylate, ferrocenylmethyl
Acrylate, furfuryl
Acrylate, glycidyl
Acrylate, glycidyl
Acrylate, glycidyl
Acrylate, glycidyl
Acrylate, glycidyl
Acrylate, heptafluorobutyl
Acrylate, heptafluorobutyl
Acrylate, heptafluorobutyl
Acrylate, heptyl
Acrylate, heptyl
Acrylate, hydroxyethyl
Acrylate, hydroxyethyl
Acrylate, hydroxyethyl
Acrylate, isobutyl
Acrylate, isobutyl
Acrylate, isobutyl
Acrylate, isopropyl
Acrylate, m-chlorophenyl
Acrylate, m-nitrophenyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Maleic anhydride
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Styrene
Methacrylate, 2-hydroxyethyl
Acrylate, 2-ethylhexyl
Acrylonitrile
Styrene
Styrene
Vinyl acetate
Butadiene
Methacrylate, methyl
Styrene
Maleimide, N-(2,4-dimethylphenyl)-
Methacrylate, methyl
Acrylate, ethyl
Acrylate, methyl
Acrylate, methyl
Methacrylate, methyl
Methacrylate, glycidyl
Methacrylate, methyl
Styrene
Acrylonitrile
Methacrylate methyl
2-Oxazoline, 2-isopropenyl-
2-Oxazolinium BF4, 3-methyl-
2-isopropenyl-
2-Oxazolinium, 2-isopropenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acrolein
Acrolein
Acrolein
Acrylamide, N-methylol-
Acrylamide, N-propyl-
Acrylate, 2-chloroethyl
Acrylate, 2-hydroxyethyl
Acrylate, a-chloro-, ethyl
Acrylate, a-cyano-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, dibutylchlorotin
Acrylate, ferrocenylmethyl
Acrylate, hydroxyethyl
Acrylate, hydroxyethyl
Acrylate, tributyltin
Acrylic acid, wbromo-
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acryloyl chloride
Ally1 acetate
Ally1 acrylate
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Allylbenzene
Benzophenone, p-vinyl-
Benzophenone, p-vinyl-
Butadiene
Butadiene, 2-chloro-
Carbamate, NJ-diethyl-, vinyl
- 0.3
0.024
0.08
- 0.016
0.02
0.02
0.88
1.18
1
0.17
0.24
7.6
0.073
0.177
0.049
0.14
0.46
0.88
1
0.94
0.135
0.282
0.29
0.195
0.85
1.04
0.16
0.096
0.191
0.622
0.664
7.86
0.83
1.08
1.3
1.2
0.9
0.94
0.09
0.02
0.06
0.81
4.46
1
0.23
0.82
0.24
0.51
0.844
0.85
0.34
5
0.52
8.45
5.45
6.46
9.1
11.35
0.09
1.1
0.07
0.06
4.78
2.96
0.064
0.06
0.19
0.06
0.031
0.013
0.02
0.09
0.1
0.1
0.02
0.026
0.04
0.027
0.036
0.135
0.04
0.057
0. 03 1
0.062
0.045
3.58
0.12
0.38
0.04
0.04
0.1
0.03
0.02
0.037
0.2
0.66
0.02
0.02
0.87
0.22
0.09
2.8
2.9
1.87
2.3
2.5
1.35
1.12
1.01
0.6
0.73
0.003
0.359
0.084
0.31
0.2
2.51
0.5
1
0.23
4.1
1.24
1.04
0.755
1.3
0.928
1.9
0.251
2.08
0.272
0.093
- 0.07
1.41
2.54
1.9
0.26
1.07
0.9
3.22
0.34
1
0.09
0.14
1
0.94
0.03
0.1
0.56
1.54
1.31
2.3
0
0.33
0.05
0.07
0.4
- 0.02
- 0.036
3.6
3.54
1.09
10.4
- 0.027
0.14
0.19
0.17
0.08
0.07
0.34
0.039
0.01
0.13
0.05
0.1
0.03
0.5
0.12
0.08
0.024
0.073
0.248
0.08
0.483
0.327
0.072
0.01
0.03
0.4
0.93
0.13
0.07
0.1
0.1
0.03
0.044
0.08
0.016
1.06
0.077
4.53
0.049
Y
Y
Y
N
N
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
N
Y
N
N
N
Y
N
Y
Y
Y
Y
Y
Y
Y
325
293
293
293
293
576
1063
126
114
114
126
553
206
206
206
788
980
890
890
890
639
674
30
178
363
1074
894
908
908
60
731
207
291
292
441
730
726
868
638
141
1 4 1
659
293
890
890
659
733
1024
1 5 1
233
508
470
578
204
437
437
437
437
351
866
911
257
6 1
92
TABLE 1. contd
Copolymer Reactivity Ratios II / 191
Monomer 1 Monomer 2
r1 f95% r2 &95% Conv. Refs.
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Cinnamate, dibutylchlorotin
Diallyl phthalate
Diallyl phthalate
Diallylcyanamide
Diallylcyanamide
Ethylene
Ethylene
Ethylene 1, l-diphenyl-
Ethylene, l,l-diphenyl-
Ethylene tetrachloro-
Ethylene, trichloro-
Fumarate, diisopropyl
Hexatriene, tetrachloro-
He x e n e - 1
Imidazole, 1-vinyl-Zmethyl-
Indene
Indene
Isoprene
Isoprene, 3-acetoxy-
Isopropenyl, S-1-cyclohexenyl, acetate
Isopropenylisocyanate
Isopropenylisocyanate
Maleic anhydride
Maleic anhydride
Mal ei mi de, N-(4-bromophenyl)-
Mal ei mi de, N-(Cchlorophenyl)-
Mal ei mi de, N-(ctolyl)-
Maleimide, N-phenyl-
Methacrylate, 2,3-epithiopropyl
Methacrylate, 2-(N,N-dimethyl
carbamoyloxy)ethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxypropyl
Methacrylate, ferrocenylmethyl
Methacrylate, methyl
Methacrylate, r-butyl dimethylsilyl
Methacrylic anhydride
Oxazoline, 2-,2-isopropenyl-
Oxazoline, 2-,2-isopropenyl-
Oxazoline, 2-,2-isopropenyl-
4,4-dimethyl
Oxazoline, 2-,4-acryloxy-methyl-
2,Cdimethyl
Oxazoline, 2-P-methacryl-oxy-
2,4-dimethyl
Oxazolinium, 2-, tetrafluoro-borate,
3-methyl
Phthalimide, N-(4-vinylphenyl)-
Phthalimide, N-(methacryloyloxy)-
Propenyl, 2-chloro-, acetate
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-5-ethyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyrrolidone, 1-benzyl-3-methylene-
5-methyl
Styrene
Styrene
0.53
0.43
0.51
1.65
6.208
6.18
6.1
6.1
0.13
0.073
0.069
0.16
0.049
0.11
0.028
- 0.2
0.028
0.038
0.05
0.05
0.029
0:045
0.005
0.008
19.4
0.09
0.12
830
3 3
1.9
0.262
-0.13
1.28
0.63
0.62
0.12
0.27
0.37
0.6
0.799
2.188
2.5
0.429
0.684
0.64
0.554
0.34
0.22
0.01
0.01
0.02
- 0.24
0.21
0
0
0.091
3.19
- 0.67
0.05
0.1
0.12
0.75
5.71
0.57
0.11
0.079
0.012
0
0.39
0.155
0.14
0.103
2.81
1.32
0.15
0.05
0.087
0.6
1.36
0.03
0.049
0.051
0.099
0.052
0.16
0.048
0.047
0.013
0.17
0.052
0.16
0.052
0.29
- 0.005
0.013
1.4
0.4
0.288
0.16
0.16
0.328
0.46
0.036
0.007
0.35
0.12
0.057
8.28
0.083
0.085
0.04
0.21
0.032
2.19
8.67
7.335
0.042
2.15
1.07
4.75
1.9
2.07
1.3
0.191
0.29 0.11
0.4 0.56
0.552 0.043 0.344 0.105
1.14
0.193
0.7
0.18
0.37
0.17
0.2
0.18
0.2
0.15
0.125
0.028
1.56
1.23
0
1
2.13
1.72
2.12
1.32
1.78
2.14
1.58
0.168
0.05
0.4
0.03
0.03
0.004
0.03
0.3
0.54
0.26
0.1
0.03
0.32
0.025 0.24
0.24
0.8 0.21
0.82
0.192 0.057
Y
Y
Y
Y
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
N
Y
N
N
N
N
Y
Y
1 3
551
98
659
291
297
603
604
4 1
168
334
334
402
470
1038
5
60
465
606
606
424
770
770
434
99
260
470
628
628
644
644
187
600
726
358
333
293
324
1069
215
862
877
596
596
596
871
636
979
445
232
2
231
749
231
231
424
633
1 3 9
1 4
References page II - 290
II / 192 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1 It95% r2 Zt95% collv. Refs.
Acrylate, methyl Styrene 0.168
Acrylate, methyl Styrene 0.18
Acrylate, methyl Styrene 0.18
Acrylate, methyl Styrene 0.14
Acrylate, methyl Styrene 0.07
Acrylate, methyl Styrene 0.3
Acrylate, methyl Styrene 0.16
Acrylate, methyl Styrene 0.148
Acrylate, methyl Styrene, 2,5-dichloro- 0.142
Acrylate, methyl Styrene, 2,5-dichloro- 0.288
Acrylate, methyl Styrene, wmethoxy- 0.17
Acrylate, methyl Styrene, m-methyl- 0.14
Acrylate, methyl Styrene, p-1-(2-hydroxybutyl)- 0.18
Acrylate, methyl Styrene, p-N,N-dimethylamino- 0.06
Acrylate, methyl Styrene, p-dimethylamino- 0.192
Acrylate, methyl Styrene, p-methoxy- 0.07
Acrylate, methyl Styrene, p-methyl- 0.17
Acrylate, methyl Succinimide, N-vinyl- 0.357
Acrylate, methyl Vinyl 2chloroethyl ether 3.27
Acrylate, methyl Vinyl acetate 7.28
Acrylate, methyl Vinyl acetate 6.38
Acrylate, methyl Vinyl acetate 2.58
Acrylate, methyl Vinyl acetate 6.7
Acrylate, methyl Vinyl acetate 6.3
Acrylate, methyl Vinyl butyl ether 3.65
Acrylate, methyl Vinyl butyl ether 3.6
Acrylate, methyl Vinyl butylsulfonate 4.14
Acrylate, methyl Vinyl chloride 4.4
Acrylate, methyl Vinyl chloride 7.66
Acrylate, methyl Vinyl chloride 5
Acrylate, methyl Vinyl chloride 4
Acrylate, methyl Vinyl cymantrene 0.46
Acrylate, methyl Vinyl ethyl ether 3.3
Acrylate, methyl Vinyl fluoride 43
Acrylate, methyl Vinyl fluoride 43
Acrylate, methyl Vinyl hendecanoate 3.615
Acrylate, methyl Vinyl isobutyl ether 3.63
Acrylate, methyl Vinyl isobutyl sulfide 0.3
Acrylate, methyl Vinyl isobutyl sulfide 0.29
Acrylate, methyl Vinyl methyl sulfide 0.209
Acrylate, methyl Vinyl phenyl sulfide 0.57
Acrylate, methyl Vinyl stearate 5.8
Acrylate, methyl Vinyl thiolacetate 0.8
Acrylate, methyl Vinyl, 2-bromo-, ethyl ether 16.83
Acrylate, methyl Vinyl, p-, benzylethylcarbinol 0.18
Acrylate, methyl Vinylanthracene, 9- 2.998
Acrylate, methyl Vinylhydroquinone dibenzoate 0.46
Acrylate, methyl Vinylidene chloride 0.95
Acrylate, methyl Vinylidene chloride 0.8
Acrylate, methyl Vinylidene chloride 1
Acrylate, methyl Vinylisocyanate 1.38
Acrylate, mono-, ethylene glycol Acrylonitrile 1.2
Acrylate, o-chlorophenyl Acrylonitrile 1.171
Acrylate, o-chlorophenyl Methacrylate, methyl 0.4
Acrylate, octadecyl Acrylonitrile 1.04
Acrylate, octadecyl Acrylonitrile 1.35
Acrylate, octadecyl Acrylonitrile 0.32
Acrylate, octadecyl Methacrylate, methyl 0.464
Acrylate, octadecyl Styrene 0.37
Acrylate, octadecyl Styrene 0.18
Acrylate, octadecyl Styrene 0.31
Acrylate, octadecyl Styrene 0.18
Acrylate, octadecyl Vinylidene chloride 1
Acrylate, octyl Acrylonitrile 0.84
Acrylate, octyl Styrene 0.01
0.067
0.026
0.054
0.069
0.02
0.01
0.01
0.063
0.37
0.3
0.07
0.58
0.22
0.5
0.14
0.012
0.04
0.01
0.01
0.034
0.1
2.34
0.067
0.21
0.023
0.38
0.4
0.35
0.07
0.12
0.14
0.74
0.53
0.722
0.75
0.75
0.68
0.9
0.65
0.4
0.871
3.93
4.47
0.003
1.65
0.48
0.38
0.372
2
1.54
0.9
0
0.04
0.03
0.405
0.03
0.03
0.01
0
0
0.093
0.002
0
0.06
0.211
0
0.01
0.01
0.033
0
0.05
0.06
0.084
0.02
0.03
0.23
0.79
0.48
0.08
0.75
0.9
0.7
1
0.14
0.8
1.123
1.25
1.91
4.39
1.76
2.477
0.777
0.44
0.79
0.44
0.9
1.98
0.39
0.056
0.022
1.38
0.15
0.01
0.16
0.055
0.17
0.01
0.043
0.01
0.4
0.002
0.01
0.067
0.008
0.002
0.02
0.02
0.086
0.22
0.32
0.092
0.11
0.037
0.1
0.64
0.2
0.024
0.018
0.037
0.3
0.11
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
N
N
N
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
1 5 1
393
397
463
495
496
496
865
136
2
142
558
548
866
911
558
558
80
726
1067
158
25
489
568
345
574
1 8 5
1 5 1
46
470
518
354
470
604
606
1 4 5
347
285
336
1 9 5
1 9 3
537
566
194
591
1 2 3
440
1 0 7
107
377
435
682
363
621
1 1 8
233
290
290
290
290
290
290
118
1 1 8
806
TABLE 1. conrd
Copolymer Reactivity Ratios II / 193
Monomer 1 Monomer 2
rl
*95%
r2
Zt95% Conv. Refs.
Acrylate, octyl Vinyl chloride
Acrylate, octyl Vinylidene chloride
Acrylate, p-(cinnamoylamino)phenyl Styrene
Acrylate, p-bromophenyl Acrylonitrile
Acrylate, p-bromophenyl Methacrylate, methyl
Acrylate, p-chlorophenyl Acrylonitrile
Acrylate, p-chlorophenyl Methacrylate, methyl
Acrylate, p-chlorophenyl Methacrylate, methyl
Acrylate, p-methylphenyl Methacrylate, methyl
Acrylate, pentabromophenyl Styrene
Acrylate, pentachlorophenyl Acrylic acid
Acrylate, pentachlorophenyl Styrene
Acrylate, phenyl Acrylonitrile
Acrylate, phenyl Fumarate, diisopropyl
Acrylate, phenyl Methacrylate, methyl
Acrylate, phenyl Methacrylate, methyl
Acrylate, sodium Vinyl acetate
Acrylate, rert-butyl Methacrylate, glycidyl
Acrylate, tetrahydrofurfuryl Styrene
Acrylate, thio- butyl Styrene
Acrylate, thio-, ethyl Styrene
Acrylate, thio-, rert-butyl Styrene
Acrylate, tributyltin Acrylate, methyl
Acrylate, trifluoro-, methyl Styrene
Acrylate, trifluoro-, methyl Styrene
Acrylate, trifluoro-, methyl Vinyl acetate
Acrylate, trifluoro-, methyl Vinyl acetate
Acrylate, trifluoro-, methyl Vinyl chloride
Acrylate, trifluoro-, methyl Vinyl chloride
Acrylic acid Acrolein
Acrylic acid Acrolein
Acrylic acid Acrylamide
Acrylic acid Acrylamide
Acrylic acid Acrylamide
Acrylic acid Acrylamide
Acrylic acid Acrylamide
Acrylic acid Acrylamide
Acrylic acid Acrylamide, N,N-dimethyl-
Acrylic acid Acrylate, pentachlorophenyl
Acrylic acid Acrylate, butyl
Acrylic acid Acrylate, butyl
Acrylic acid Acrylate, ethyl
Acrylic acid Acrylic acid, 2-benzamido-
Acrylic acid Acrylic acid, N-acetyl-a-amino-
Acrylic acid Carbamate, N,N-diethyl-, vinyl
Acrylic acid Carbamate, N-vinyl-, ethyl
Acrylic acid Imi dazol e, l-vinyl-
Acrylic acid Methacrylate, isopropyl
Acrylic acid Methacrylate, methyl
Acrylic acid Methacrylate, butyl
Acrylic acid N-Vinylimidazole
Acrylic acid Phosphonic acid, u-phenylvinyl-
Acrylic acid Propenyl, 2-chloro-, acetate
Acrylic acid Propylene
Acrylic acid Pyrrolidone, N-vinyl-
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Vinyl acetate
Acrylic acid Vinyl chloride
4.8
0.679
0.35
1.026
0.191
0. 95 1
0.235
0.3
0.223
0.1
1.12
0.9
0.327
3.4
0.45
0.416
0.463
0.489
0.421
0.291
0.368
0.03
0
0
0
0
0
0
0.08
1.15
0.288
1.644
0.341
1.38
3.8
0.29
0.36
0.82
0.59
1.31
0.91
0.48
1.41
5.58
4.69
0.0025
1.03
1.73
0.24
1.932
0.7
1
0.88
0.05
0.08
0.25
0.35
0.136
0.15
0.45
0.25
8.66
6.69
0.057
0.062
0.014
0.063
0.023
0.036
0.045
0.041
0.079
0.196
0.17
0.075
0.055
0.28
0.029
0.069
0.012
0.14
0.04
0.27
0.3
0.32
-
0.096
0.21
0.077
0.13
0.69
0.029
6.63
0.88
0.12
0.851
1.08
0.8
0.926
0.32
1.01
1.09
1.45
0.16
0.82
2.11
0.43
0.07
1.56
1.54
2.096
0.475
0.439
0.18
0.157
0.82
1.4
1.4
0.24
0.24
1.5
1.5
2.48
0.5
1.08
0.445
1.346
0.598
0.58
1.06
0.35
1.12
1.08
0.91
1.02
2.08
0.49
0.097
0.26
0.32
0.68
0.418
3.53
0.187
0.04
0
0.1
0.25
1.1
0.15
0.22
0.253
0.25
0.25
0.15
0.021
0.107
0.018
0.13
0.056
0.056
0.132
0.275
0.13
0.14
0.443
0.186
0.14
0.038
0.034
1.24
0.17
0.075
0.044
0.047
0.12
0.18
0.13
0.068
0.02
0.42
0.025
0.83
0.21
0.069
0.059
0.011
518
Y 1 1 8
685
Y 363
Y 1074
Y 63
Y 1074
621
Y 1074
643
900
900
Y 363
1038
621
Y 672
Y 37
Y 814
806
806
806
806
659
595
598
595
598
595
598
Y 57
57
Y 221
Y 278
Y 278
Y 37
869
869
N 205
900
N 1 8 7
N 252
711
1019
661
Y 92
Y 8 1
955
847
N 964
N 1 8 7
Y 879
Y 132
445
Y 183
N 250
312
312
397
414
Y 47
490
542
561
Y 37
Y 1 3 5
References page II - 290
II / 194 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl It95%
r2
f95% Conv. Refs.
Acrylic acid Vinyl chloride 9.28
Acrylic acid Vinyl chloride 7.04
Acrylic acid Vinyl chloride 6.8
Acrylic acid Vinylhydroquinone 0.29
Acrylic acid Vinylhydroquinone dibenzoate 0.44
Acrylic acid Vinylidene chloride 1.246
Acrylic acid Vinylidene cyanide 0.212
Acrylic acid, 2-benzamido- Acrylic acid 2.08
Acrylic acid, 2-benzamido- Styrene 0.78
Acrylic acid, 2-ethyl Methacrylic acid 0.194
Acrylic acid, 2-ethyl Methacrylic acid 0.069
Acrylic acid, 2-ethyl Methacrylic acid 0.23
Acrylic acid, N-acetyl-a-amino Acrylic acid 0.49
Acrylic acid, N-acetyl-cc-amino- Styrene 0.44
Acrylic acid, a-bromo Methacrylate, methyl 0.11
Acrylic acid, a-bromo Acrylate, butyl 0.09
Acrylic acid, cc-bromo Acrylate, methyl 0.1
Acrylic acid, a-bromo Methacrylate, butyl 0.13
Acrylic acid, a-bromo Pyrrolidone, N-vinyl 0.07
Acrylic acid, cis-3-bromo- Acrylamide - 0.2
Acrylic acid, cis-3-ethyl Acrylamide -0.16
Acrylic acid, truns-3-bromo- Acrylamide - 0.33
Acrylic acid, truns-3-ethyl- Acrylamide - 0.21
Acrylic anhydride Ally1 chloride 11.66
Acrylic anhydride Methacrylonitrile 1
Acrylic anhydride Styrene 0.1
Acrylonitrile 1,3-pentadiene, cis- 0.026
Acrylonitrile 1,3-pentadiene, cis- 0.06
Acrylonitrile 1,3-pentadiene, trans- 0.069
Acrylonitrile 1,3-pentadiene, trans- 0.068
Acrylonitrile 2-Oxazoline, 2-isopropenyl- 0.13
Acrylonitrile Acenaphthalene 0.02
Acrylonitrile Acetylene, phenyl- 0.266
Acrylonitrile Aconitate, trimethyl 4.24
Acrylonitrile Acrolein 0.88
Acrylonitrile Acrolein 0.71
Acrylonitrile Acrolein 0.48
Acrylonitrile Acrolein 0.6
Acrylonitrile Acrolein diethylacetal 11.19
Acrylonitrile Acrolein, methyl- 0.15
Acrylonitrile Acrolein, methyl- 0.15
Acrylonitrile Acrolein, methyl- 0.03
Acrylonitrile Acrylamide 0.863
Acrylonitrile Acrylamide 0.97
Acrylonitrile Acrylamide 1.8
Acrylonitrile Acrylamide 0.88
Acrylonitrile Acrylamide 0.8
Acrylonitrile Acrylamide, N-methylol- 0.7
Acrylonitrile Acrylamide, N-methylol- 0.98
Acrylonitrile Acrylamide, N-methylol- 0.22
Acrylonitrile Acrylamide, N-octadecyl- 1.034
Acrylonitrile Acryl ami de, N-tert-butyl- 0.2
Acrylonitrile Acrylate, 2-chloroethyl 1.03
Acrylonitrile Acrylate, 2-nitrobutyl 0.67
Acrylonitrile Acrylate, 3,4-epoxyhexahydrobenzyl 0.25
Acrylonitrile Acrylate, P-chloro-2-hydroxypropyl 0.24
Acrylonitrile Acrylate, P-ethoxy-, ethyl 2.42
Acrylonitrile Acrylate, a-chloro-, methyl 0.122
Acrylonitrile Acrylate, a-cyano-, methyl 0.01
Acrylonitrile Acrylate, wphenyl-, methyl 0.08
Acrylonitrile Acrylate, benzyl 0.28
Acrylonitrile Acrylate, benzyl 1.49
Acrylonitrile Acrylate, butyl 1.679
Acrylonitrile Acrylate, butyl 0.781
Acrylonitrile Acrylate, butyl 1.08
0.51
0.33
0.11
0.042
0.016
0.027
0.04
0.11
0.1
0.16
0.11
0.56
0.13
0.004
0.173
0.242
0.104
0.096
0.04
0.044
0.92
0.06
0.03
0.01
0.19
0.033
0.1
0.75
0.02
0.25
0.13
1.8
0.081
0.02
0.19
0.083
0.08
0.03
0.024
0.11
0.026
0.95
0.437
0.291
0.48
0.13
1.12
2.29
1.14
1.41
0.91
0.37
0.19
0.24
0.85
0.25
7.64
6.32
4.13
8.19
0.02
0.42
0.16
0.017
0.071
0.018
0.064
0.52
2.56
0.325
- 0.48
1.16
1.07
1.52
1.28
0.02
1.7
3.8
1.72
0.81
1.08
0.5
1.36
1.3
1.2
2.33
2.56
1.4
1.14
0.87
1.76
0.388
0.7
- 0.26
1.76
0.68
6.7
0.72
0.63
1.06
0.894
0.82
0.09
0.069
0.092
0.065
0.042
0.132
0.417
1.67
0.68
0.76
1.09
0.02
0.04
0.01
0.012
0.029
0.01
0.02
0.06
0.083
0.11
0.13
0.08
0.07
0.42
0.11
0.51
0.26
0.17
0.69
0.074
0.56
0.18
0.09
0.16
0.15
0.019
0.13
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
Y
Y
Y
Y
Y
Y
N
N
N
Y
Y
Y
N
Y
N
Y
N
Y
N
N
Y
Y
N
229
288
379
337
444
288
82
1019
1019
1004
1004
961
661
661
733
733
733
733
694
298
298
298
298
219
219
219
912
912
912
912
894
575
60
147
207
207
208
504
767
455
587
9 1
228
228
330
421
461
442
577
596
119
709
790
234
680
654
194
6
1 4 1
1 4 1
2 3
385
1 1 8
162
233
TABLE 1. contd
Copolymer Reactivity Ratios II / 195
Monomer 1 Monomer 2
r1
f95%
r2
lf95% Conv. Refs.
Acrylonitrile Acrylate, butyl
Acrylonitrile Acrylate, butyl
Acrylonitrile Acrylate, cis-P-cyano-, methyl
Acrylonitrile Acrylate, cresyl
Acrylonitrile Acrylate, di-, zinc
Acrylonitrile Acrylate, dodecyl
Acrylonitrile Acrylate, ethyl
Acrylonitrile Acrylate, ethyl
Acrylonitrile Acrylate, ethyl
Acrylonitrile Acrylate, ethyl
Acrylonitrile Acrylate, glycidyl
Acrylonitrile Acrylate, m-chlorophenyl
Acrylonitrile Acrylate, methyl
Acrylonitrile Acrylate, methyl
Acrylonitrile Acrylate, methyl
Acrylonitrile Acrylate, mono-, ethylene glycol
Acrylonitrile Acrylate, o-chlorophenyl
Acrylonitrile Acrylate, octadecyl
Acrylonitrile Acrylate, octadecyl
Acrylonitrile Acrylate, octadecyl
Acrylonitrile Acrylate, octyl
Acrylonitrile Acrylate, p-bromophenyl
Acrylonitrile Acrylate, p-chlorophenyl
Acrylonitrile Acrylate, phenyl
Acrylonitrile Acryloyl chloride
Acrylonitrile Acryloylpyrrolidone
Acrylonitrile Ally1 acetate
Acrylonitrile Ally1 alcohol
Acrylonitrile Ally1 alcohol
Acrylonitrile Ally1 alcohol
Acrylonitrile Ally1 alcohol
Acrylonitrile Ally1 chloride
Acrylonitrile Ally1 chloride
Acrylonitrile Allylbenzene
Acrylonitrile Allylbenzene
Acrylonitrile Allylcyclohexane
Acrylonitrile Allylstearamide, N-
Acrylonitrile Benzothiazole, vinylmercapto-
Acrylonitrile Butadiene
Acrylonitrile Butadiene
Acrylonitrile Butadiene
Acrylonitrile Butadiene
Acrylonitrile Butadiene
Acrylonitrile But adi ene, 1,4-dicarboxylate, diethyl
Acrylonitrile But adi ene, l-(diethylamino)-
Acrylonitrile But adi ene, l-(diethylamino)-
Acrylonitrile Butadiene, l-acetoxy-
Acrylonitrile Butadiene, 1-ethoxy
Acrylonitrile Butadiene, 1-ethoxy
Acrylonitrile Butadiene, 2-chloro-
Acrylonitrile Butadiene, 2-chloro-
Acrylonitrile Butadiene, 2-chloro-
Acrylonitrile Butadiene, 2-fluoro-
Acrylonitrile Butadiene, 2trimethylsilyloxy-
Acrylonitrile Butadiene-1-carboxylate, ethyl
Acrylonitrile Butadiene-1-carboxylic acid
Acrylonitrile Butadiene-1-carboxylic acid
Acrylonitrile Bu t e n e - 1
Acrylonitrile Butene- 1, 4-(p-chlorophenyl)-
Acrylonitrile Butene-1, 4-(p-methoxy-phenyl)-
Acrylonitrile Butene-1, 4-cyclohexyl-
Acrylonitrile Butene-1, 4-phenyl-
Acrylonitrile Butene-2, cis
Acrylonitrile Butene-2, tram
Acrylonitrile Carbazole, N-vinyl-
1
1
0.72
0.41
2.37
0.92
1.16
0.66
0.44
1.01
1.3
0.56
1.54
1.31
0.8
1.123
1.91
4.39
1.76
1.98
0.8
0.32
0.43
1.2
1.56
6.57
2.6
3.9
1.79
2.145
3.45
3.82
5.35
3.81
3.79
0.191
0.046
0.1
0.05
0.06
0.03
0.29
0.481
0.208
0.012
0.02
0.01
0.04
0.05
0.056
0.077
0.036
0.3
0.2
0.03
13.46
4.68
2.56
5.03
4.51
22.32
62.99
0.39
0.15
0.07
0.08
0.78
01073
0.03
0.044
0.08
0.037
0.1
0.64
0.2
0.3
0.13
0.056
0.13
2.11
1.06
0.11
0.049
0.65
1.7
0.3
11.42
0.28
0.014
0.006
0.059
0.02
0.12
0.049
0.049
0.043
0.008
0.008
0.023
0.021
3.61
0.63
1.11
0.76
0.86
10.67
0.04
0.9
1.2
0.773
0.24
0.88
1.2
0.81
4
0.95
1
0.85
0.51
0.844
0.85
1.2
1.171
1.04
1.35
0.32
0.84
1.026
0. 95 1
0.327
1
0.43
- 0.09
0.05
0.1
0.12
-0.152
0.08
- 0.05
- 0.026
-0.18
0.03
0.178
0.358
0.452
0.35
0.1
0.2
2.79
0.426
0.425
0.82
0.065
0.065
5.35
4.8
5.38
0.6
0.065
3.2
4
11
0.24
0.066
- 0.085
0.014
0.024
0.11
0.84
0.09
0.067
0.16
0.07
0.27
0.036
0.02
0.037
0.2
0.023
0.38
0.4
0.35
0.74
0.062
0.063
0.045
0.12
0.16
0.37
0.008
0.03
0.15
0.022
1.01
0.27
0. 08 1
0.046
0.023
0.01
0.9
0.208
0.48
0.68
0.009
0.02
0.45
0.18
0.81
0.044
0.088
0.055
0.069
0.6
0.04
N
Y
N
N
Y
Y
N
Y
Y
N
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
513
513
1034
363
646
233
1023
1 9 8
389
542
114
363
1024
1 5 1
233
682
363
118
233
290
118
363
363
363
580
666
1 0 8
1 0 8
1 0 8
176
300
108
47
24
3 5 1
24
119
763
2 1
255
418
5 0 1
66
327
864
889
9 1
864
889
402
504
6 1
174
993
791
7 9 1
799
211
24
24
24
24
211
2 1 1
269
References page II - 290
II / 196 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contcf
Monomer 1 Monomer 2
r1
f95%
r2
f95% Conv. Refs.
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonittile
Acrylonitrile
Acrylonittile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Actylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Cinnamate, a-cyano-, ethyl
Cinnamon&rile
Cinnamon&rile, a-cyano-
Citraconimide, N-methyl-
Crotonaldehyde
Crotonaldehyde
Crotonate, wchloro-, ethyl
Crotonate, cc-cyano-, ethyl
Crotonate, wmethoxy-, methyl
Crotonate, cc-methyl-, methyl
Crotonate, cc-acetyl-, methyl
Crotonate, wcarboethoxy-, ethyl
Crotonate, ethyl
Crotonic acid
Cyclopentene, 4-, - 1,3-dione
Cyclopropene, 3,3-dimethoxy-
Diallyl phthalate
Diallyl phthalate
Ethylene
Ethylene, 1, l-diphenyl-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, trichloro-
Ethylene, trichloro-
Fumarate, diisopropyl
Fumarate, diethyl
Fumarate, diethyl
Hexatriene, tetrachloro-
He x e n e - 1
Indene
Indene
Isobutylene
Isobutylene
Isobutylene
Isoprene
Isopropenyl methyl ketone
Isopropenyl methyl ketone
Isopropenylisocyanate
Itaconic acid
Itaconic anhydride
Maleate, diethyl
Maleate, diethyl
Maleic anhydride
Mal ei mi de, N-(2-bromophenyl)-
Mal ei mi de, N-(2-chlorophenyl)-
Mal ei mi de, N-(Cchlorophenyl)-
Mal ei mi de, N-2-bromophenyl-
Mal ei mi de, N-2-chlorophenyl-
Mal ei mi de, N-Cchlorophenyl-
Maleimide, N-octadecyl-
Maleimide, N-octadecyl-
Metbacrylamide, N-(p-chlorophenyl)-
12.6 2.3 -0.18 0.15
8.46 0.37 0.36 0.1
0.53
8
25
9.53
11.4
1
2.97
8.68
18.7
25.2
2 1
3.02
1.424
4.23
2.78
7
0.05
456
470
67
62.1
1 6
8
1 0
0.234
2.07
0. 28 1
0.29
1.295
0.98
1.02
0.03
0.3
0.36
0.24
0.59
0.034
1 2
20
6
2.029
0.956
0.972
2.02
0.955
0.972
2.482
2.46
0.399
0.71
0.038
0.15
0.52
0.058
0.037
0.012
0.031
0.01 0.01
0.05
0.6
0
0.01
0
0.06
0
0
0
0
0
0
0.04
0.245
0.04
0.037
0
- 0.02
0
0
0
0
0.2
0
0.1
4.01
- 1.08
0.09
0.07
0
0.02
0
0.45
1.2
0.7
0.1
0.86
4.83
0
0
0
0.338
1.078
0.743
0.348
1.08
0.743
0.389
0.39
0.627
0.559
0.549
2.34
0.71
1 4
1.25
0.05
0.12
0.008
0.25
0.25
0.24
0.002
0.38
0.34
0.014
0.74
0.33
0.214
0.095
0.112
0.205
0.095
0.112
0.119
0.115
0.019
0.019
0.026
0.14
0.085
0.045
0.048
0.048
0.044
0.048
0.048
0.023
0.023
0.051
0.048
0.06
1.07
0.19
Methacrylamide, N-@-methoxyphenyl)-
Methactylamide, N-@-methylphenyl)-
Methacxylamide, N-(p-nitrophenyl)-
Methacrylamide, N-phenyl-
Methacrylate, 2,2,6,6-tetramethyl-
4-piperidinyl
Methacrylate,
2-(NJ+dimethylcarbamoyloxy)ethyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-naphthyl
Metbacrylate, 2-naphthyl
0.337
0.336
0.37
0.381
0.02
0.38 1.89
0.31
0.14
0.2
0.15
0.094
0.2
0.099
2.38
1.3
1
1.17
1.02
0.2
0.19
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
310
310
310
460
429
504
785
785
785
785
785
785
785
402
95
838
1 5 3
1 5 3
415
1 4 3
571
59
470
572
1038
470
640
4
60
360
360
2 1
211
484
417
490
542
434
164
365
470
640
470
863
863
863
915
915
915
863
915
352
352
352
352
352
664
600
657
382
689
611
611
TABLE 1. contcf
Monomer 1 Monomer 2 r1
Copolymer Reactivity Ratios II / 197
+95%
r2
f95% Conv. Refs.
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Methacrylate, 2-naphthyl 0.06
Methacrylate, 2-naphthyl - 0.01
Methacrylate, 3,5-dimethyladamantyl 0.19
Methacrylate, benzyl 0.2
Methacrylate, butyl 0.291
Methacrylate, ferrocenylmethyl 0.15
Methacrylate, glycidyl 0.95
Methacrylate, glycidyl 0.14
Methacrylate, isobutyl 0.217
Methacrylate, methyl 0.138
Methacrylate, methyl - 0.016
Methacrylate, mono-, ethylene glycol 0.19
Methacrylate, phenyl 0.36
Methacrylate, potassium 0.226
Methacrylate, potassium 18-crown- 0.07
6-ether
Methacrylic acid 0.04
Methacrylic.acid 0.092
Methacrylonitrile 0.43
Methacryloyl chloride 0.35
Methaclyloyl acet one 0.01
Methylenebutyrolactone 0.09
N,N-Divinylaniline 0.246
N-Vinylimidazole 3.393
Naphthalene, l-vinyl- 0.107
Norbornadiene 0.48
Norbornadiene 0.66
Ott-1-ene, 6,6-dimethyl-4,8-dioxaspiro 0.985
Oxazoline, 2-,2-isopropenyl- 0.13
Oxazoline, 2-,2-isopropenyl-, 0.24
4-dimethyl
Oxazoline, 2-,4-methacryloxy- 0.11
2,4-dimethyl
Pentadiene, trans- 1,3- 0.06
Pentadiene, cis-1,3- 0.026
Pentadiene, cis-1,3- 0.056
Pentadiene, cis- 1,3- 0.033
Pentadiene, trans- 1,3- 0.07
Pentadiene, truns- 1,3- 0.085
Pentadiene, trans- 1,3- 0.079
Pentadiene, cis-1,3- 0.06
Pentadienoate, trans-4-ethoxy-2,4-, ethyl 0.01
Pentene-1, 5-cyclohexyl- 4.22
Pentene- 1, 5-phenyl- 3.84
Phosphate, diethyl isopropenyl 15.2
Phosphine oxide, diphenylvinyl- 3.8
Phosphonic acid, a-phenylvinyl- 0.34
Phosphonic acid, a-phenylvinyl- 2.36
Phthalide, 3-(4.vinylphenoxy)- 0.084
Phthalimide, N-vinyl- 0.43
Phthalimide, N-(methacryloyloxy)- 0.204
Pinene 0.07
Propene, 2-chloro- 1.164
Propene, 3,3,3-trichloro- 12.2
Pr opene, I-chloro-, cis- 23.37
Propene, 1-chloro-, trans- 19.61
Pyridazinone, 3-(2-vinyl)-6-methyl- 0.32
Pyridazinone, 3-(2-vinyl)-6-methyl-4,5- 0.74
Pyridine, 2-methyl-Svinyl- 0.16
Pyridine, 2-vinyl- 0.05
Pyridine, 2-vinyl- 0.1
Pyridine, 2-vinyl-5-ethyl- 0.02
Pyridine, 2-vinyl-5-ethyl- 0.06
Pyridine, 4-vinyl- 0.11
Pyridine, 4-vinyl- 0.09
0.1
0.16
0.01
0.1
0.039
0.04
0.06
0.037
0.037
0.048
0.04
0.006
0.13
0.06
0.04
0.004
0.014
0.008
0.028
0.27
0.01
0.675
0.064
0.018
0.017
0.017
0.018
0.071
0.45
0.48
0.12
0.053
0.01
0.016
0.01
0.053
2.99
1.72
0.02
0.02
0.01
0.03
0.07
0.04
0.76
0.64
1.3
0.96
0.98
0.82
0.85
1.32
1.05
1.322
1.11
1.5
0.46
0.203
0.175
0.2
2.38
1.67
2.8
3.74
1.1
- 0.006
0.832
0.451
0.05
0.44
1.484
0.52
1.83
0.89
0.095
0.172
0.198
0.188
0.104
0.132
0.114
0.241
5.4
- 0.043
- 0.026
0.03
0.16
- 0.45
0
0.43
0.24
1.45
13.5
- 0.023
0.1
- 0.12
0.01
0.19
0.02
0.31
21.9
0.44
0.43
0.43
0.41
0.34
0.18
0.24
0.23
0.1
0.2
0.42
0.05
0.22
0.05
0.12
0.086
0.018
0.26
0.29
0.12
0.22
0.07
0.044
0.088
0.23
0.05
1.078
0.021
0.012
0.011
0.01
0.009
0.029
0.044
0.046
0.41
0.19
0.02
0.072
0.1
0.062
0.19
0.17
0.04
0.02
0.02
0.08
0.18
0.13
Y
N
N
N
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
N
N
Y
Y
Y
N
Y
N
Y
N
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
N
N
611
6 1 1
335
23
1 6 5
325
114
433
1 6 5
216
681
682
363
808
808
1 6
216
198
580
339
745
45
879
967
267
69
838
862
596
596
867
867
952
997
867
952
997
867
723
24
24
650
843
132
590
721
1046
979
936
1 8 1
402
1 8 1
1 8 1
340
340
232
456
50
1 1 5
50
1 1 5
50
References page II - 290
II / 198 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer< 2
rl f95% r2 zt95% Conv. Refs.
Acrylonitrile Pyrrolidone, N-vinyl-
Acrylonitrile Silane, y-methacryloxypropyltrimethoxy- 0.094
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, 2,4,6-trimethyl-
Styrene, 2,5-dichloro-
Styrene, 2,5-dichloro-
Styrene, 2,5-dichloro-
Styrene, 3-tri-n-butylstannyl-
Styrene, 4-methyl-
Styrene, a-(trimethylsilyloxy)-
Styrene, a-methoxy-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, wmethyl-
Styrene, m-methyl-
Styrene, p-1-(2-hydroxy-butyl)-
Styrene, p-1-(2-hydroxy-propyl)-
Styrene, p-2-(2-hydroxy-propyl)-
Styrene, p-acetoxy-
Styrene, p-chloro-
Styrene, p-chloromethyl-
Styrene p-methyl-
Succinimide, N-vinyl-
Tetrazole, 2-methyl-5-(4~vinyl)phenyl-
Tetrazole, 5-phenyl-2-(4-vinyl)phenyl-
Tetrazole, l-vinyl-
Toluenesulfonamide, N,N-methyl-vinyl-
Triallyl citrate
Tricyclo[4.2.2.0{2,5}]dec-7-ene-
3,4,9,10-tetracarboxylic aci d
Vinyl 12-ketostearate
Vinyl 2-chloroethyl ether
Vinyl 2-ethylhexanoate
Vinyl 3,3-bis(ethoxycarbonyl)propyl
ether
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl benzoate
Vinyl bromide
Vinyl bromide
Vinyl butyl ether
0
0.02
0.05
0.03
0.06
0.05
0.07
0.04
0.17
0.17
0.15
0.17
0.07
0.06
0.03
0.06
0.01
0.874
0.22
0.25
0.26
4.88
0.079
0.05
0.06
0.07
0.04
0.04
0.04
0.063
0.34
0.03
-
0.02
0.07
0.04
0.1
0.05
0.07
- 0.09
0.067
0.05
0.116
0.42
0.32
0.54
0.42
1.76
2.75
3.3
1.09
9.24
1.02
4.05
5.51
5.29
9.2
5.03
2.79
2.25
0.034
0.06
0.594
0.04
0. 05 1
0.01
0.005
0.041
0.15
0.27
0.01
0.06
3.79
0.33
0.29
0.4
0.36
0.39
0.37
0.37
0.4
0.3
0.33
0.33
0.36
0.46
0.41
0.43
0.55
0.35
0.065
0.08
0.07
0.09
0.001
0.227
0
- 0.002
0.08
0.17
0.24
0.14
0.09
0.103
0.14
0.08
0.43
0. 3 1
0.53
0.41
0.4
0.92
0.56
0.33
0.516
1.1
1.4
0.314
0.04
- 0.08
0.25
0.048
0.03
0.005
0.01
0.04
0.021
0.01
0.03
0.03
0.024
0.036
0.07
0.03
0.06
0.024 0.081
0.032
0.12
0.082
0.066
1.04
0.1
0.5
1.96
-0.18
0
- 0.047
0.06
0.36
0.05
0.82 0.04 0.067
0.91
1.13
6.39
1.08
0.2
0.06
- 0.06
- 0.03
0.019
0.06
0.06
0.22
0.08
0.09
0.051
0.04
Y
Y
N
Y
N
Y
N
N
N
Y
Y
N
N
N
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
N
N
213
977
140
1 9 8
269
396
403
417
543
60
727
727
727
727
727
727
727
727
812
58
84
84
84
985
929
970
142
1 7 1
265
265
65
75
75
835
94
378
548
380
547
47
825
1035
378
80
583
583
925
80
367
963
146
597
47
1015
1 5 8
235
6
75
75
47
268
268
345
TABLE 1. contd
Copolymer Reactivity Ratios II / 199
Monomer 1 Monomer 2
rt &95% r2 &95% Conv. Refs.
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Vinyl butyl ether
Vinyl butyl sulfide
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloroacetate
Vinyl chloroacetate
Vinyl chloroethyl ether
Vinyl chloromethyl ketone
Vinyl cymantrene
Vinyl dichloroacetate
Vinyl dichloroacetate
Vinyl dodecyl ether
Vinyl ether
Vinyl ethyl ether
Vinyl ethyl oxalate
Vinyl ethyl sulfide
Vinyl ethyl sulfide
Vinyl ethyl sulfoxide
Vinyl fluoride
Vinyl fluoride
Vinyl formate
Vinyl hendecanoate
Vinyl isobutyl ether
Vinyl isobutyl ether
Vinyl isobutyl ether
Vinyl isobutyl ether
Vinyl isobutyl sulfide
Vinyl isobutyl sulfide
Vinyl isobutyl sulfide
Vinyl isothiocyanate
Vinyl laurate
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl octadecyl ether
Vinyl octyl ether
Vinyl phenyl ether
Vinyl phenyl sulfide
Vinyl phenyl sulfide
Vinyl stearate
Vinyl tert-butyl sulfide
Vinyl trichloroacetate
Vinyl, a-chloro-, triethoxysilane
Vinyl, p-, benzylethylcarbinol
Vinyl, p-, benzylmethylcarbinol
Vinyl-tris(trimethoxysiloxy)-silane
Vinyl-tris(trimethoxysiloxy)-silane
Vinylbenzoate, p-, sodium
Vinylbenzoic acid, p-
Vinylene carbonate
Vinylethynyl-4-piperidinol,
1,2,Qrimethyl
Vinylferrocene
Vinylferrocene
Vinylhydroquinone
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
0.98
0.086
3.26
2.55
2.62
3.62
3.65
4
4.18
0.34
1.04
0.064
0.446
7.45
0.25
0.82
0.94
0.69
1.34
0.09
0.06
1.63
44
24
2.54
1.88
- 0.24
- 0.05
0.98
1.26
0.08
0.062
0.08
0.36
4
0.59
0.63
0.85
0.81
2.5
0.11
0.11
4.639
0.09
7.34
0.04
0.11
3.9
3.85
0.174
0.06
14.9
0.08
0.186
0.16
0.56
0.92
1.04
0.44
0.58
0.65
0.57
0.5
0.13
0.01
0.34
0.12
0.25
0.21
0.22
0.33
0.05
0.019
0.048
0.32
0.12
0.45
0.01
0.01
0.16
1.79
0.44
0.26
0.07
0.15
0.19
0.005
0.004
0.004
0.13
0.01
0.01
0.015
0.024
0.9
0.17
0.04
0.009
0.025
0.36
0.11
0.2
- 0.03
0.041
- 0.01
0.07
0.02
0.044
0.052
0.04
- 0.007
0.09
- 0.02
0.88
- 0.065
0.044
0.18
0
0.02
0.06
0.06
0.06
0.05
- 0.08
0.005
1
- 0.004
0.09
0.7
0.99
- 0.04
- 0.04
0.03
0.022
0.03
1.4
0.04
1.75
1.39
0
0
0.23
0.03
0.03
0.078
0
0.047
0.31
0.54
0.07
0.08
0.23
1.63
0.08
0.38
0.165
0.15
0.04
0.32
0.28
0.4
0.42
0.49
0.69
0.76
0.01
0.028
0.037
0.03
0.08
0.002
0.01
0.016
0.02
0.12
0.093
0.015
0.12
0.03
0.03
0.03
0.14
0.12
0.91
0.09
0.06
0.01
0.02
0.01
0.038
0.01
0.11
0.02
0.01
0.007
0.013
0.039
0.2
0.34
0.42
0.092
0.03
0.14
0.034
N
Y
Y
N
N
Y
Y
Y
N
Y
Y
N
N
N
N
N
Y
Y
Y
N
N
N
N
N
Y
N
Y
N
N
Y
Y
Y
Y
N
Y
Y
Y
N
Y
Y
347
303
140
202
22
238
46
529
362
542
116
356
354
362
542
373
386
194
285
285
336
286
528
590
47
1 4 5
322
322
347
347
285
303
336
542
381
140
504
373
373
556
285
336
1 4 5
303
362
591
48
209
573
1 7 5
1 7 5
579
783
294
294
338
138
238
404
404
404
404
404
References page II - 290
II / 200 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2 rl *95%
r2
Lk95% Conv. Refs.
Acrylonittile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile, 2-chloro-
Acrylonitrile, 2-fluoro-
Acrylonitrile, a-chloro-
Acrylonitrile, a-fluoro-
Acrylonitrile, cc-hydroxymethyl-
Acrylonitrile, cc-methoxy
Acrylonitrile, a-methoxy
Acrylonitrile, a-perfluoropropyl-
Acryloxymethylpentamethyldisiloxane
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl-P-hydroxyethyl-3,5-
dinitrobenzoate
Acryloyl-P-hydroxyethyl-3,5-
dinitrobenzoate
Acryloyloxy, 2-, benzoic acid
Acryloyloxy, 2-, benzoic acid
Acryloylpyrrolidone
Adipate, divinyl
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acrylate
Ally1 acrylate
Ally1 acrylate
Ally1 alcohol
Ally1 alcohol
Ally1 alcohol
Ally1 alcohol
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylisocyanate
Vinylmethyldiacetoxysilane
Vinylmethylphenylsulfonium
tetrafluoroborate
Vinyltriethoxysilane
Vinyltriethoxysilane
Vinyltrimethoxysilane
Vinyltrimethylsilane
Styrene
Styrene
Styrene
Styrene
Styrene
Acrylate, cc-chloro-, ethyl
Styrene
Methacrylate, methyl
Methacrylate, 2-hydroxyethyl
Acrylate, methyl
Acrylonitrile
Methacrylate, 2-hydroxypropyl
Methacrylate, methyl
Methacrylate, methyl
Pyrrolidone, N-vinyl
Styrene
Vinyl chloride
Vinylidene chloride
Acrylate, N-(2-hydroxyethyl))carbazolyl
0.48
0.65
0.65
0.66
0.63
0.63
0.58
0.19
2.246
2.2
6.59
26.83
9.09
4.08
0.087
0.03
0.03
0.528
0.3
0.312
0
0.52
2.3
0.29
1.51
0.05
0.15
0.02
3.03
1.12
0.361
Methacrylate, N-ethyl-
3-hydroxymethylcarbazolyl
Methacrylate, N-methyl-N-phenyl-
2-amino
Styrene
Acrylonitrile
Styrene
Acrylate, butyl
Acrylate, methyl
Acrylonitrile
Isobutylene, 3-chloro-
Maleic anhydride
Methacrylate, ethyl
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl chloride
Vinyl chloride
Vinylidene chloride
Acrylate, methyl
Ally1 chloride
Vinyl acetate
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
0.103
1.82
0.64
0.43
0.011
0.039
0
- 0.09
0.15
- 0.001
- 0.57
- 2.42
0
0.01
0
0.45
0.7
0.7
1.2
0
0
0.33
10.4
17.35
0.05
0.1
0.12
0.054
0.6
29.59
0.76
0.04
0.02
0.086
0.054
0.05
0.02
0.22
0.016
0.015
0.2
0.02
0.011
0.066
0.12
0.007
0.82
37.66
0.05
0.16
0.37
0.95
0.95
1.3
1.74
1.43
1.8
0.39
0.16
-0.11
0.1
0.41
2.69
0.45
0.1
0.014
0.13
0.44
0.205
0.9
0.534
1.9
0.86
0.34
1.2
1.79
0.48
0.42
0.04
0.1
0.02
0.5
0.62
1.425
0.22
0.06
1.56
20.36
10.2
5
6.57
4.5
0.028
81.27
99.24
2 3
62.8
90
0.6
1
1
1.16
6.6
0.52
0.08
0.11
2.6
3.9
1.79
0.23
0.38
2.5
0.27
0.004
0.04
0.029
0.069
0.3
0.05
0.029
0.044
0.09
0.03
0.02
0.26
42.2
2.11
0.019
1.93
24.6
82.7
1.06
0.11
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
N
N
Y
N
Y
Y
N
N
N
N
N
Y
404
404
404
404
404
404
468
435
754
793
209
237
237
209
884
884
806
850
981
638
806
926
822
508
580
649
508
776
599
220
288
288
702
701
651
651
666
815
1053
470
108
412
27
210
210
470
1053
470
140
502
998
470
475
470
578
578
578
1 0 8
1 0 8
176
300
TABLE 1. contd
Copolymer Reactivity Ratios II / 201
Monomer 1 Monomer 2
rl
f95%
r2
f95% conv. Refs.
Ally1 alcohol
Ally1 alcohol
Ally1 butyrate
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloroacetate
Ally1 chloroacetate
Ally1 glycidyl hexahydrophthalate
Ally1 glycidyl phthalate
Ally1 isobutyrate
Ally1 propionate
Ally1 trichloroacetate
Ally1 trimethylacetate
Ally1 valerate
Allylbenzene
Allylbenzene
Allylbenzene
Allylbenzene
Allylbenzene
Allylbenzene
Allylcyclohexane
Allylstearamide, N-
Allylstearamide, N-
Allylstearamide, N-
Allyltriethoxysilane
Allylurea
Azlactone, 2-vinyl-4,4-dimethyl-
Azlactone, 2-vinyl-4,4-dimethyl-
Azobenzene, 4-(acrylamidomethylamino)-
Azobenzene, 4-(acrylamidomethylamino)-
Benzenesulfamide, p-methacrylamide-
Benzimidazole, vinylmercapto-
Benzoate, p-(acryloylethoxy)-,
p-butoxy phenyl
Benzoate, p-(acryloylethoxy)-, phenyl
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-,
p-methoxy phenyl
Methacrylate, ethyl
Methacrylate, methyl
Vinyl acetate
Acrylate, benzyl
Acr yl at e, but yl
Acrylate, ethyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylic anhydride
Acrylonitrile
Acrylonitrile
Ally1 acrylate
Methacrylate, benzyl
Methacxylate, methyl
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl benzoate
Vinyl butyrate
Vinyl formate
Vinyl propionate
Vinylidene chloride
Methacrylic anhydride
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Styrene
Vinyl acetate
Vinyl acetate
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Maleic anhydride
Methacrylonitrile
Triallyl citrate
Acrylonitrile
Acrylonitrile
Vinyl acetate
Vinylidene chloride
Vinyl chloride
Methacrylic anhydride
Acrylate, whydroxymethyl-, ethyl
Styrene
Styrene
Vinyl acetate
Vinyl butyl ether
Styrene
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-, p-butoxy
phenyl
Benzoate, p-(acryloyloxy)-, phenyl
Benzoate, p-(acryloyloxy)-, phenyl
p-butoxyphenyl
- 0.02
- 1.62
0.64
0.06
0.1
0.08
1.92
2.9
107.4
78.79
0.97
9.9
5.83
7.73
5.3
6.5
0.05
0.07
0.4
- 0.02
0.02
-0.152
0.08
0.08
0.02
0.02
0.008
0.03
8.45
5.45
6.46
9.1
11.66
2.145
3.45
10.4
58.7
0.56
0.049
0.65
0.05 0.16 35.55 15.82
0.03
- 2.4
0.61
0.75
0.88
1.15
0.78
0.68
0.24
- 0.01
0.06
0.06
0.14
0.51
0.42
0.81
0.34
0.58
- 0.036
- 0.05
- 0.026
3.21
0.15
0.089
0.15
0.24
0.13
36.8
1.355
0.66
0.34
0.46
0.31
0.57
0.62
3.49
29.76
34.3
34.3
34.8
1.04
1.29
2.32
1.15
1.07
11.35
3.82
5.35
1.4
1 3
0.02 0.15
0.016
0.15
0.022
0.66
1.7
0.3
- 0.061
0.339
-0.18
0.03
0.68
- 0.24
- 0.94
- 0.06
0.389
0.237
8.5
12.98
3.4
0.56
0.36
0.03
0.039
1.01
0.27
0.26
0.19
0.48
0.17
0.229
0.129
1.36
0.5
11.42
0.28
0.092
0.15
0.38
18.48
0.12
0.054
0.1
0.41
16.24
2.01
3.81
3.79
0.923
5.22
1.68
29.01
0.668
0.175
0.083
0.126
0
6.51
0.91
0.51
N
N
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
210
210
998
438
438
438
204
437
437
437
437
219
108
47
578
438
204
1 0
204
438
204
3
438
438
438
438
438
3
106
782
782
782
998
998
913
998
998
351
24
351
351
351
367
24
119
119
119
237
106
1 0 1 1
1 0 1 1
880
880
1005
764
881
0.61 0.32 8 8 1
0.91 0.36 881
0.32 0.61 881
0.49 1.5 881
References page II - 290
II / 202 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl It95% r2 It95% Conv. Refs.
Benzoate, p-(acryloyloxy-ethoxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy-ethoxy)-,
p-methoxy phenyl
Benzoate, p-(acryloyloxy-ethoxy)-,phenyl
Benzoate, p-(methacryloyloxy)-,
p-octyloxy phenyl
Benzoate, p-(methacryloyloxyethoxy)
p-octyloxy phenyl
Benzocyclobutane, a-methylene-
Benzocyclobutane, a-methylene-
Benzocyclobutene, 4-vinyl-
Benzofuran, 2-vinyl-
Benzofuran, 2-vinyl-
Benzofuran, 2-vinyl-
Benzophenone, 2-hydroxy-
4-(methaclyloxy)-
Benzophenone, p-vinyl-
Benzophenone, p-vinyl-
Benzophenone, p-vinyl-
Benzophenone, p-vinyl-
Benzophenone, p-vinyl-
Benzophenone, p-vinyl-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-, phenyl
butoxy phenyl
Benzoate, p-(acryloyloxy)-, phenyl
0.61 0.32 856
1.26 0.23 8 8 1
-1 1.26 0.23 856
Maleic anhydride 0.002
Methacrylate, methyl 0.46
Methacrylate, methyl 1.47
Acrylate, butyl 7.8
Acrylate, ethyl 5.76
Methacrylate, methyl 3.89
Methacrylate, methyl 1.65
Acrylate, methyl
Acrylate, methyl
Styrene, p-N,N-dimethyl-aminomethyl-
Styrene, p-N,N-dimethylamino-
Styrene, p-dimethylamino-
Styrene, p-dimethylaminomethyl-
Acrylonitrile
Fumaronitrile
Maleic anhydride
Methacrylate, methyl
Styrene
Styrene
Vinyl acetate
Vinyl phenyl sulfide
3.6 1.06 0.09 0.02
3.54 0.077 1.1 0.02
2.54 0.136 0.26 0.017
0.84 0.18 0.07 0.05
0.842 0.072 0.176 0.046
2.54 0.259 0.135 0.017
0.178 0.081 0.191 0.014
Benzothiazolone, N-[(methacroyloxy)- Styrene
methyl]
Benzoxazole, vinylmercapto- Styrene
Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Methacrylate, methyl
N-benzyl
Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Methacrylate, methyl
N-benzyl
Bicyclo[2,2,1]hept-2-ene-5,6-dicarboximide, St yrene
N-benzyl
Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, St yrene
N-benzyl
Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Vinyl acetate
N-benzyl
Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Vinyl acetate
N-benzyl
Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Vinyl acetate
N-benzyl
Borazine, P-vinyl Styrene
Butadiene Aconitate, trimethyl
Butadiene Acrylate, butyl
Butadiene Acrylate, heptafluorobutyl
0.43 0.14 1.25 0.083
0.349 0.087 2.171 0.07
0.5 0.095 3.02 0.14
2.53 0.47 0.013 0.037
0.95 0.61 0.24 0.12
3.1 0.01 0.35 0.02
0.24
0
0
0
0
0.35
0.15
0.014
0.001
0.4
1.04
0.359
Benzoate, p-(acryloyloxy)-, phenyl
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-, phenyl
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-, phenyl
Benzoate, p-(acryloyloxy)-, phenyl
Benzoate, p-(acryloyloxy)-,
p-methoxyphenyl
Benzoate, p-(methacryloyloxy)-,
@-octyloxy)phenyl
Benzoate, p-(acryloyloxy-ethoxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy-ethoxy)-,
phenyl
Benzoate, p-(acryloyloxy-ethoxy)-,
p-methoxy phenyl
Benzoate, p-(methacryloyloxy-
ethoxy)-, p-methoxy phenyl
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-, phenyl
1.5 0.49 8 8 1
0.23 1.26 881
0.91 0.36 856
0.32 0.61 856
1.5 0.49 856
0.23 1.26 856
0.36 0.91 856
0.49 1.5 856
1.36
0.334
0.617
0.114
0.025
0.32
0.6
0.041
0.015
0.006
0.315
0.043
0.01
0.02
0.036
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
1083
1083
1085
1020
1020
1020
934
866
911
86
866
911
911
763
763
763
763
764
764
763
763
960
0.12 2.87
30.5
0.19 764
994
108 994
18.2 994
89.2 994
1.26 994
1.46 994
1.99
4.53
0
0.074
0.073
994
0.016
0.4
0.11
0.039
0.62
0.22
0.03
0. 03 1
Y
Y
Y
1018
147
257
206
TABLE 1. contd
Copolymer Reactivity Ratios II / 203
Monomer 1 Monomer 2
rl f95% r2 zt95% Conv. Refs.
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene monoxide
Butadiene, 1,4-dicarboxylate-,diethyl
Butadiene, 1,4-dicarboxylate-, diethyl
Butadiene, 1,4-dicarboxylate-,diethyl
Butadiene, 1-(2-hydroxyethylthio)-
Butadiene, l-(diethylamino)-
Butadiene, l-(diethylamino)-
Butadiene, l-acetoxy-
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Butadiene, 2,3-dimethyl-
Butadiene, 2,3-dimethyl-
Butadiene, 2-chloro-
Butadiene, 2-phthalidomethyl
Cyclobutane, 1,2-dimethylene-
Cyclobutane, 1,2-dimethylene-
Ethylene, trichloro-
Ferrocene, ethyl-a-cylopentadienylide
Fumarate, diethyl
Isoprene
Isoprene
Maleamic acid, N-3-dimethylamino-
6-methyl phenyl
Maleate, diethyl
Methacrylate, 2-(N,N-dimethyl-
carbamoyloxy)ethyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylonitrile
Methyleneglutaronitrile, 2-
Pentadiene, cis- 1,3-
Pentadiene, tram-1,3-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, 2,5-dichloro-
Styrene, 2,5-dichloro-
Styrene, p-chloromethyl
Styrene, a-methyl-
Styrene, p-chloro-
Vinyl chloride
Vinyl chloride
Vinylhendecanoate
Vinyl pelargonate
Vinyl stearate
Vinylferrocene
Vinylidene chloride
Maleic anhydride
Acrylonitrile
Pyridine, 2-vinyl-
Styrene
Styrene, p-chloro-
Acrylonitrile
Acrylonitrile
Acrylonitrile
1.09
0.358
0.452
0.35
0.1
0.2
1.26
0.3
0.06
1.014
0.1
0.1
9.64
0.02
2.13
0.94
0.14
0.37
8.08
1.06
0.75
0.504
0.7
0.39
0.63
1.22
0.61
1.32
1.29
1.44
1.55
1.37
1.35
1.59
1.8
1.4
1.4
0.5
1.38
1.83
1.38
0.449
0.662
0.87
1.5
1.22
8.8
5.27
22.56
26.3
42.5
4.34
1.97
0.05
2.79
0.69
0.55
3.27
0.426
0.425
0.82
4.53
0.046
0.23
0.01
0.92
0.049
0.05
0.21
0.37
0.04
0.024
0.15
0.02
0.56
0.14
0.11
0.41
0.043
0.017
0.13
2.16
3.35
24.54
4.73
0.18
0.25
0.18
0.9
0.23
0.1
0.208
0.48
0.68
0.07
0.046
0.1
0.05
0.06
0.03
0.78
0.86
3.41
1.35
5.76
5.76
0.03
1.51
0.25
1.06
0.608
0.08
0.25
0.027
0.32
0.053
0.26
0.09
0.47
0.72
0.41
0.84
0.37
0.38
0.58
0.44
0.6
0.44
0.38
0.68
0.82
0.83
0.64
0.45
0.187
0.42
0.139
1.6
0.04
0.11
0.22
0.02
0.02
0.16
0.044
0.64
0.29
0.41
0.09
0.24
0. 48 1
0.208
0.012
0.87
0.006
0.059
0.02
0.24
0.45
0.36
0.07
0.062
0.03
0.004
0.016
0.02
0.4
0.25
0.13
0.21
0.17
0.049
0.087
5.7
0.31
1.26
0.27
0.15
0.038
0.06
0.12
0.07
0.014
0.049
0.049
0.043
Y
Y
Y
N
Y
Y
N
Y
N
Y
Y
N
N
Y
N
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
257
2 1
255
418
501
66
1 7 3
8 3
418
735
854
885
89
699
466
1 7 3
8 3
679
466
600
140
257
467
257
196
743
743
462
520
56
140
1 5 9
1 7 3
2 1
418
428
473
486
486
491
56
83
8 3
255
8
1075
70
255
517
717
1 4 5
1 4 5
1 4 5
802
257
1064
327
327
327
810
864
889
9 1
References page II - 290
II / 204 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1 f95% r2 *95% Conv. Refs.
Butadiene, l-chloro-
Butadiene, l-ethoxy-
Butadiene, l-ethoxy-
Butadiene, 1 -phthalimido-
Butadiene, l-succinimido-
Butadiene, 2,3-bis(diethylphosphono)-
Butadiene, 2,3-bis(diethylphosphono)-
Butadiene, 2,3-bis(diethylphosphono)-
Butadiene, 2,3-bis(diethylphosphono)-
Butadiene, 2,3-bis(diethylphosphono)-
Butadiene, 2,3-bis(diethylphosphono)-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dimethyl-
Butadiene, 2,3-dimethyl-
Butadiene, 2,3-dimethyl-
Butadiene, 2,3-dimethyl-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-dichloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-phthalidomethyl-
Butadiene, 2-trimethylsilyloxy-
Butadiene, 2-trimethylsilyloxy-
Styrene
Acrylonitrile
Acrylonitrile
Styrene
Styrene
Mal ei mi de
Mal ei mi de, N-(2-hydroxyethyl)-
Mal ei mi de, N-(Cchlorophenyl)-
Mal ei mi de, N-(4-methoxy-phenyl)-
Mal ei mi de, N-chloromethyl-
Maleimide, N-phenyl-
Butadiene, 2-chloro-
Ethylene, 1, l-diphenyl-
Methacrylate, methyl
Phosphonic acid, cc-phenylvinyl-
Phosphonic acid, a-phenylvinyl-
Styrene
Styrene
Butadiene
Butadiene
Isoprene
Styrene
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Acrylonitrile
Butadiene
Butadiene, 1-(2-hydroxyethyl-thio)-
Butadiene, 2,3-dichloro-
Butadiene, 2-fluoro-
Butadiene, hexafluoro-
Butadiene, hexafluoro-
Ethylene, 1, l-diphenyl-
Fumarate, diethyl
Hexatriene, tetrachloro-
Isoprene
Isopropenyl methyl ketone
Methacrylate, methyl
Maleic anhydride
Methacrylate, isobutyl
Methacrylate, methyl
Methacrylic acid
Phosphonate, vinyl-,dimethyl
Phosphonic acid, a-phenylvinyl-
Phosphonic acid, a-phenylvinyl-
Quinoline, 2-vinyl-
Styrene
Styrene
Vinyl acetate
Vinyl butyrate
Vinyl formate
Vinyl formate
Vinyl propionate
Vinylidene cyanide
Acrylonitrile
Butadiene, 2-chloro-
Butadiene, hexafluoro-
Isoprene
Methacrylate, methyl
Styrene
Styrene
Styrene, u-methyl-
Butadiene
Acrylonitrile
Styrene
1.44
0.065
0.065
1.56
1.68
0.14
0.12
0.03
0.04
0.05
0.05
1.98
3.58
11.04
1.15
7.15
8.65
10.6
0.78
0.86
0.84
1.048
5.19
10.4
5.35
4.8
5.38
3.41
1
0.31
3.7
5.47
5.52
3.4
6.51
3.6
2.82
4.035
11.04
0.026
1.8
6.33
2.52
1.5
7.5
1.5
2.1
7.84
5.98
33.52
1 5
11.91
0.6
0.22
2.93
2.63
1.23
2.1
1.24
2.22
1.35
0.065
1.2
3.1
0.009
0.02
0.63
0.16
0.25
0.24
0.066
0.45
0.12
0.087
0.08
0.03
0.06
0.2
0.5
8.98
3.89
0.18
0.96
1.77
0.12
0.61
0.7
0.45
0.27
0.02
0.01
0.299
0.286
0.43
0.49
0.41
0.47
0.3
0.42
0.31
- 0.08
0.08
0.07
0.07
0.25
0.05
1.26
0.3
1.18
0.534
0.06
0.06
0.04
0.05
0.056
0.06
0.2
1.98
0.22
0.1
0.1
0.03
0.02
0.2
0.06
0.14
0.329
0.9
0.08
- 0.035
0.1
0.1
0.1
0.38
0.05
0.025
- 0.02
- 0.04
- 0.05
0.077
3.7
0.24
0.25
0.76
0.214
0.22
0.72
1.014
0.036
0.64
0.27
0.008
0.008
0.049
0.018
0.12
0.92
0.035
0.023
0.25
0.01
0.107
0.088
0.058
0.047
0.09
0.01
0.021
0.12
0. 11
0.03
0.15
0.24
0.049
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
N
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
695
864
889
1 6 3
1 6 3
759
759
759
159
759
759
122
6 1
6 1
588
597
587
6 1
1 7 3
83
1 7 3
173
451
6 1
402
504
6 1
418
810
122
493
1 2 7
453
6 1
6 1
459
418
259
6 1
1068
1057
6 1
259
594
546
597
456
6 1
8
247
247
127
247
241
82
174
493
453
174
174
174
174
174
135
993
993
TABLE 1. contd
Copolymer Reactivity Ratios II / 205
Monomer 1 Monomer 2 rl zk95% r2 z!?95% Conv. Refs.
Butadiene, hexafluoro-
Butadiene, hexafluoro-
Butadiene, hexafluoro-
Butadiene, hexafluoro-
Butadiene,l-(2-hydroxyethylthio)-
Butadiene- lcarboxylate, ethyl
Butadiene-lcarboxylate, S-(-)a-phene
ammonium
Butadiene-1-carboxylate, ethyl
Butadiene-1-carboxylate, ethyl
Butadiene-1-carboxylic acid
Butadiene-1-carboxylic acid
Butadiene-1-carboxylic acid
Butadiene-1-carboxylic acid
Butanoate, 3-acrylamido-3-methyl-,
sodium
But ene, cis-2-
Bu t e n e - 1
Bu t e n e - 1
Bu t e n e - 1
Bu t e n e - 1
Bu t e n e - 1
Butene-1, 2-ethyl-
Butene- 1, 2-methyl-
Butene-1, 3,3-dimethyl-
Butene-1, 3,3-dimethyl-
Butene- 1, 4-(p-chlorophenyl)-
Butene- 1, 4-(p-methoxyphenyl)-
Butene- 1, 4cyclohexyl-
Butene- 1,4-phenyl-
Butene-2
Butene-2
Butene-2, 2-methyl-
Butene-2, cis-
Butene-2, cis-
Butene-2, cis-
Butene-2, truns-
Butene-2, truns-
Butenoate, 3-phenyl-3-, methyl
Butyrolactone, cl-methylene-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Carbamate, N,N-diethyl-, vinyl
Carbamate, N,N-diethyl-, vinyl
Carbamate, N,N-diethyl-, vinyl
Carbamate, N,N-diethyl-, vinyl
Carbamate, N,N-diethyl-, vinyl
Carbamate, N-phenyl-, vinyl
Carbamate, N-phenyl-, vinyl
Carbamate, N-vinyl-, ethyl
Butadiene, 2-chloro- 0.1
Butadiene, 2-chloro- 0.1
Butadiene, 2-fluoro- 0.24
Isoprene 0.78
Butadiene, 2-chloro- 0.2
Styrene 0.56
Styrene 6.81
Acrylonitrile 3.2
Pyridine, 2-vinyl- 0.8
Acrylonitrile 4
Acrylonitrile 11
Styrene 0.52
Styrene 5.55
Acrylamide, NJ!-dimethyl- 0.22
Mal ei mi de, N-cyclohexyl-
Acrylonitrile
Ethylene
Ethylene
Vinyl acetate
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Ethylene
Vinyl chloride
Vinyl chloride
Acrylonitrile
Vinyl acetate
Vinyl chloride
Acrylonitrile
Vinyl acetate
Styrene
Styrene
Crotonaldehyde
Crotonaldehyde
N-Vinyl pyrrolidone
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyrrolidone, N-vinyl-
Styrene
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl butyl ether
Vinyl isopropyl ether
Vinyl phenyl ether
Acrylate, methyl
Acrylic acid
Maleic anhydride
Styrene
Vinyl acetate
Methacrylate, butyl
Methactylate, di-, triethylene
Acrylic acid
3
0.24
3.25
0.16
0.11
0.12
- 1.05
- 1.18
- 0.44
- 0.07
- 0.066
- 0.085
0.014
0.024
- 1.79
0.3
0.11
0.03
0
0.84
- 0.03
- 0.532
0.85
0.31
0.31
1.7
0.04
0.04
0.12
0 . 1 2
0.1
0.1
1.7
1.02
0.31
2.5
2.5
3.1
0.22
1.3
- 0.027
- 0.097
0.024
- 0.08
0.13
0.329
-glycol 0.034
0.26
1.68
0.138
0.81
0.42
0.12
0.89
1.2
0.28
2.5
0.044
0.088
0.055
0.069
5.22
5.31
0.25
0.6
0.44
0.512
0.06
0.005
0.2
0.01
5.3
1.95
2.43
0.049
0.068
0.066
0.18
0.19
5.47
5.52
2.93
1.19
1
0.12
0.45
0.3
0.4
0.2
0.03
0.15
0.08
0.987
0
13.46
3.6
1.55
3.34
1.56
1.01
5.64
6.18
4.68
2.56
5.03
4.51
7.5
3.3
8.52
22.32
8.27
8.8
62.99
7.2
1.97
0.14
0
0
2.8
11.58
11.58
4.35
4.35
4.43
4.43
2.8
0.2
0.63
0.35
0.35
0.03
0.01
0.26
4.78
5.58
0.025
29.56
1.7
0.418
0.504
4.69
0.13
0.153
3.61
0.24
0.58
0.26
0.31
0.2
13.57
0.63
1.11
0.76
0.86
2.18
10.54
1.05
10.67
1.69
0.364
0.01
0.2
0.01
0.73
0.96
0.37
0.22
0.32
0.034
3.59
0.04
Y
Y
Y
Y
Y
N
N
N
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
1 2 7
453
453
453
810
791
748
791
791
791
799
791
799
857
995
2 1 1
388
407
211
30
329
329
329
6
24
24
24
24
477
329
329
2 1 1
211
230
2 1 1
211
1008
663
875
907
883
589
592
589
592
589
592
859
916
557
859
883
215
215
214
92
92
92
197
1 9 7
833
833
8 1
References page II - 290
II / 206 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rt
It95%
r2
Zt95% Conv. Refs.
Carbamate, N-vinyl-, ethyl Pyrrolidone, N-vinyl-
Carbamate, N-vinyl-, ethyl Vinyl acetate
Carbamate, N-vinyl-, ethyl Vinyl acetate
Carbamate, N-vinyl-, tert-butyl Vinyl acetate
Carbamate, N-vinyl-, tert-butyl Methacrylate, methyl
Carbamate, N-vinyl-, rert-butyl N-Vinylpyrrolidone
Carbazole, 2-butenyl- Carbazole, 9-vinyl-
Carbazole, 9-propenyl- Carbazole, 9-vinyl-
Carbazole, 9-vinyl- Carbazole, 2-butenyl-
Carbazole, 9-vinyl- Carbazole, 9-propenyl-
Carbazole, N-butenyl- Carbazole, N-vinyl-
Carbazole, N-methyl-3-vinyl Styrene
Carbazole, N-propenyl- Carbazole, N-vinyl-
Carbazole, N-vinyl- Acenaphthalene
Carbazole, N-vinyl- Acrylate, ethyl
Carbazole, N-vinyl- Acrylate, methyl
Carbazole, N-vinyl- Acrylate, methyl
Carbazole, N-vinyl- Acrylate, methyl
Carbazole, N-vinyl- Acrylonitrile
Carbazole, N-vinyl- Carbazole, N-butenyl-
Carbazole, N-vinyl- Carbazole, N-propenyl-
Carbazole, N-vinyl- Fumarate, diisopropyl
Carbazole, N-vinyl- Maleate, diethyl
Carbazole, N-vinyl- Maleate, dimethyl
Carbazole, N-vinyl- Methacrylate, methyl
Carbazole, N-vinyl- Methacrylate, methyl
Carbazole, N-vinyl- Methacrylate, methyl
Carbazole, N-vinyl- Methacrylate, methyl
Carbazole, N-vinyl- Metbacrylate, methyl
Carbazole, N-vinyl- Methacrylate, methyl
Carbazole, N-vinyl- Methacrylate, methyl
Carbazole, N-vinyl- Propene, 2,3-dichloro-
Carbazole, N-vinyl- Styrene
Carbazole, N-vinyl- Styrene
Carbazole, N-vinyl- Styrene
Carbazole, N-vinyl- Styrene, p-chloro-
Carbazole, N-vinyl- Succinimide, N-vinyl-
Carbazole, N-vinyl- Vinyl acetate
Carbazole, N-vinyl- Vinyl acetate
Carbazole, N-vinyl- Vinyl acetate
Carbazole, N-vinyl- Vinyl butyrate
Carbazole, N-vinyl- Vinyl chloride
Carbazole, N-vinyl- Vinyl formate
Carbazole, N-vinyl- Vinyl propionate
Carbazole, N-vinyl- Vinyl thiolacetate
Carbazole, N-vinyl- Vinylidene chloride
Carbazole, N-vinyl- Vinylidene chloride
Carbon monoxide Ethylene
Carbon monoxide Ethylene
Carbon monoxide Ethylene
Carbon monoxide Ethylene
Carbon monoxide Vinyl acetate
Carbon monoxide Vinyl chloride
Cinnamat, methyl Styrene
Cinnamate, 2-chloroethyl Styrene
Cinnamate, a-cyano-, 2-ethylhexyl Styrene
Cinnamate, a-cyano-, benzyl Styrene
Cinnamate, cc-cyano-, butyl Styrene
Cinnamate, wcyano-, cyclohexyl Styrene
Cinnamate, a-cyano-, ethyl Acrylonitrile
Cinnamate, wcyano-, ethyl Styrene
Cinnamate, wcyano-, hexyl Styrene
Cinnamate, cl-cyano-, methyl Pyrrolidone, N-vinyl-
Cinnamate, a-cyano-, methyl Styrene
Cinnamate, benzyl Styrene
0.371
2.09
0.4
0.46
0.17
2.4
0.02
0.02
2.6
2.8
0.02
1.404
0.02
- 0.03
0.27
0.049
0.11
0.028
0.09
2.6
2.8
0
0.21
0.51
0.14
0.033
0.06
0.75
0.08
0.33
0. 03 1
1
- 0.02
0.026
0.032
0.02
0.04
2.67
3.02
3.9
1.33
4.77
4.142
1.69
0.44
3.6
3.65
0.32
0.004
-0.15
0
0.33
0.121
0.04
0.01
0.06
-0.16
- 0.09
- 0.24
-0.18
0.05 0.12
0.26
0.03
0.1
0.5
0.003
0.003
0.5
0.5
0.063
0.07
0.2
0.06
0.5
0.5
0.003
0.003
0.146 0.067
0.12 1.77
0.029 0.13
0.045
0.04
0.073
0.04
0.05
0.11
0.03
0.015
1.77
0.39
0.418
1.12
1.87
0.4
2.6
2.8
0.02
0.02
2.6
0.735
2.8
6.62
1.1
0.53
0.43
0.51
0.39
0.02
0.02
0
0
0
1.55
2.12
1.8
0.57
1.84
0.44
2.123
0
6
5.93
5.72
7
0.11
0.126
0.15
0.13
0.07
0.17
0.192
0.081
0.45
- 0.023
- 0.008
0.068
0.025
0.04
0.5
0.24
13.52
1.799
1.394
0.58
0.4
0.47
0.37
12.6
0.01
0.01
0.16
0.14
0.05
0.18
0.022
0.26
0.22
0.048
0.06
0.034
0.057
1.34
1.05
0.4
0.09
0.13
0.83
0.023
0.34 0.12
0.011
0.21
0.28
0.12
0.3
0.65
0.012
0.07
0.001
0.073
0.15
0.068
0.018
0.012
0.006
0.01
0.011
0.13
0.11
0.01
0.17
0.08
0.22
0.15
0.25
0.073
0.068
0.004
0.03
0.03
0.04
2.3
-0.17 0.26 0.39 0.04
- 0.001 0.001 0.044 0.008
- 0.21 0.35 0.4 0.06
0.14 0.13 1.33 0.12
Y
Y
N
N
Y
Y
N
N
N
N
Y
N
N
Y
N
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
N
Y
Y
Y
N
N
N
N
Y
Y
N
Y
N
Y
8 1
629
8 1
827
991
991
904
904
904
904
871
806
8 7 1
331
757
1 3
551
98
269
871
871
1038
361
361
11
1 3
738
738
758
758
98
376
11
1 3
98
551
284
246
246
551
246
427
246
246
97
13
98
5 1
5 1
52
52
474
184
488
488
282
282
282
282
310
134
282
816
282
488
TABLE 1. contd
Copolymer Reactivity Ratios II / 207
Monomer 1 Monomer 2
r1
&95%
r2
&95% Conv. Refs.
Cinnamate, butyl
Cinnamate, dibutylchlorotin
Cinnamate, ethyl
Cinnamate, ethyl
Cinnamate, methyl
Cinnamate, p-chloro-, methyl
Cinnamate, p-methyl-, methyl
Cinnamate, phenyl
Ci nnamat e, tert-butyl
Cinnamic acid, cis-
Cinnamic acid, truns-
Cinnamide, NJ&diethyl-
Cinnamide, p-chloro-, N,N-diethyl-
Cinnamide, p-methyl-, N,N-diethyl-
Cinnamonitrile
Cinnamonitrile
Cinnamon&rile, a-cyano-
Cinnamonitrile, cr-cyano-
Citraconate, di-see-butyl
Citraconate, dibenzyl
Citraconate, dibutyl
Citraconate, dicyclohexyl
Citraconate, diethyl
Citraconate, diisobuty
Citraconate, diisopropyl
Citraconate, dimethyl
Citraconate, dipropyl
Citraconic acid
Citraconic anhydride
Citraconimide, p-iso-, N-(4-acetylphenyl)
Citraconimide, p-iso-, N-(4-acetylphenyl)
Citraconimide, p-iso-,
N-(4-ethoxycarbonylphenyl)-
Citraconimide, p-iso-, N-(4-methoxy-
phenyl)-
Citraconimide, p-iso-, N-(p-tolyl)-
Citraconimide, l&o-, N-phenyl-
Citraconimde, N-( l-menthylcarboxy-
latomethyl)-
Citraconimide, N-(4-acetoxyphenyl)-
Citraconimide, N-(4-acetoxyphenyl)-
Citraconimide, N-(4-chlorophenyl)-
Citraconimide, N-(4-chlorophenyl)-
Citraconimide, N-(4-ethoxycarbonyl-
phenyl)-
Citraconimide, N-(4-ethoxycarbonyl-
phenyl)-
Citraconimide, N-(Cmethoxyphenyl)-
Citraconimide, N-(Cmethoxyphenyl)-
Citraconimide, N-ally1
Citraconimide, N-benzyl-
Citraconimide, N-benzyl
Citraconimide, N-butyl-
Citraconimide, N-butyl-
Citraconimide, N-ethyl-
Citraconimide, N-ethyl-
Citraconimide, N-hexyl-
Citraconimide, N-hexyl-
Citraconimide, N-isobutyl-
Citraconimide, N-isobutyl-
Citraconimide, N-isopropyl-
Citraconimide, N-isopropyl-
Citraconimide, N-methyl-
Citraconimide, N-methyl-
Citraconimide, N-methyl-
Styrene
Acrylate, methyl
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Acrylamide
Acrylamide
Styrene
Styrene
Styrene
Acrylonitrile
Styrene
Acrylonitrile
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
0.04
- 0.2
- 0.076
0.082
0.02
0.04
0
0.029
0.1
- 0.48
- 0.24
0.01
0.01
0.01
0.36
- 0.008
0.15
0.054
0.045
0.055
0.12
0.28
0.15
1.757
1.65
1.52
1.566
1.27
2.24
2.84
1.66
1.692
3.84
3.4
4.17
2.99
4.95
8.46
2.549
0.082
0.31
0.035
0.12
0.087
0.68
0.24
0.1
0.021
0.37
0.092
0.13
0.047
0.054
0.03
0.029
0.03
0.076
0.049
0.027
0
0.021
0
0
0
0.058
2
1.55
2.74
1.88
2.48
1.8
1.62
1.58
2.19
1.36
0.16
0.42
0.28
0.3
0.15
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
488
659
200
488
653
653
653
488
488
298
298
737
737
737
310
134
310
134
8 4 1
8 4 1
841
841
841
841
841
841
841
1 0 2 1
47
608
608
608
Styrene 0 0.27 608
Styrene 0
Styrene 0
Methacrylate, methyl 0.109 0.115
0.4
0.39
3.47 0.335
608
608
950
Methacrylate, methyl
Styrene
Methacrylate, methyl
Styrene
Methacrylate, methyl
0.18 0.13 1.88 0.16
0.015 0.086 0.151 0.054
- 0.01 0.18 2.93 0.4
0.075 0.093 0.181 0.057
- 0.027 0.084 2.72 0.18
728
728
728
728
728
Styrene 0.004 0.033 0.148 0.018 728
Methacrylate, methyl -0. 1
Styrene 0.04
Styrene 0.004
Methacrylate, methyl 0.02
Styrene - 0.066
Methacrylate, methyl -0.12
Styrene 0.03
Methacrylate, methyl - 0.04
Styrene - 0.002
Methacrylate, methyl - 0.08
Styrene - 0.03
Methacrylate, methyl -0.18
Styrene 0.07
Methacrylate, methyl 0.09
Styrene - 0.014
Acrylonitrile 0.6
Methacrylate, methyl 0.15
Styrene 0.24
0.19
0.11
0.14
0.082
0.36
0.045
0.33
0.05
0.28
0.11
0.42
0.14
0.27
0.063
3.16
0.63
0.142
2.77
0.19
2.17
0.169
3.25
0.231
2.38
0.316
1.78
0.326
2.7
0.244
0.53
3.24
0.15
0.73
0.19
0.28
0.087
0.56
0.028
0.79
0.044
0.45
0.086
0.85
0.094
0.51
0.055
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
728
728
959
714
714
714
714
714
714
714
714
714
714
714
714
460
460
460
References page II - 290
II / 208 FREE RADICAL COPOLYMERlZATlON REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
0 &95%
r2
zt95% Conv. Refs.
Citraconimide, N-methyl-
Citraconimide, N-phenyl-
Citraconimide, N-phenyl-
Citraconimide, N-propyl-
Citraconimide, N-propyl-
Citraconimide, N-tert-butyl-
Citraconimide, N-tert-butyl-
Citraconimide, N-tolyl-
Citraconimide, N-tolyl-
Citraconimide, a-iso-; N-(4-acetylphenyl)-
Citraconimide, a-iso-, N-(4-chlorophenyl)
Citraconimide, a-iso-, N-(4-ethoxy-
carbonylphenyl)-
Citraconimide, a-iso-, N-(4-methoxy-
phenyl)-
Citraconimide, a-iso-, N-(p-tolyl)-
Citraconimide, a-iso-, N-phenyl-
Copper diacrylate
Crotonaldehyde
Crotonaldehyde
Crotonaldehyde
Crotonaldehyde
Crotonaldehyde
Crotonaldehyde
Crotonaldehyde
Crotonaldehyde
Crotonaldehyde
Crotonaldehyde
Crotonate, hydrocortisone 2 1 -
Crotonate, a-acetyl-, methyl
Crotonate, a-acetyl-, methyl
Crotonate, a-bromo-, ethyl
Crotonate, wcarboethoxy-, ethyl
Crotonate, a-carboethoxy-, ethyl
Crotonate, a-chloro-, ethyl
Crotonate, a-chloro-, ethyl
Crotonate, a-cyano-, ethyl
Crotonate, a-cyano-, ethyl
Crotonate, a-methoxy-, methyl
Cr ot onat e, a- met hoxy- , met hyl
Crotonate, a-methyl-, methyl
Crotonate, a-methyl-, methyl
Crotonate, ethyl
Crotonate, ethyl
Crotonate, methyl
Crotonic acid
Crotonic acid
Crotonic acid
Crotonic acid
Crotonic acid
Crotonic acid
Crotonic acid
Crotonic acid
Crotonic acid
Crotonic acid
Crotonic acid
Crotonic acid, cis-
Crotonic acid, truns-
Crotononitrile
Crotononitrile
Crotononitrile, a-phenyl-
Cyclobutane, 1,2-dimethylene-
Cyclobutane, 1,2-dimethylene-
Cyclobutane, 1,2-dimethylene-
Styrene 0.24
Methacrylate, methyl 0.001
Styrene - 0.001
Methacrylate, methyl - 0.03
Styrene - 0.014
Methacrylate, methyl 0.038
Styrene 0.045
Methacrylate, methyl 0.003
Styrene - 0.02
Styrene 0
Styrene 0
Styrene 0
Styrene 0
Styrene
Styrene
Titanium, dicylopentadienyl-,
dimethacrylate
Acrylonitrile
Acrylonitrile
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Pyrrolidone, N-vinyl-
Styrene
Styrene
Styrene
Vinyl chloride
Vinylidene chloride
N-Vinyl pyrrolidone
Acrylonitrile
Styrene
Styrene
Acrylonitrile
Styrene
Acrylonitrile
Styrene
Acrylonitrile
S t y r e n e
Acrylonitrile
Styrene
Acrylonitrile
Styrene
Acrylonitrile
Styrene
Styrene
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylonitrile
Pyrrolidone, N-vinyl-
Styrene
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinylidene chloride
Acrylamide
Acrylamide
Styrene
Styrene
Styrene
Butadiene
Butadiene
Styrene
0 1.69 608
0 1.76 608
1.09 0.89 895
0
0.01
0
0
-0.15
0.03
0.07
0.12
- 0.56
0
0.05
0
0
0
0
0
0
0
0.06
0.02
0
0.04
0
0.02
0
0
- 0.27
-0.18
-0.19
0.11
0.12
0
0
0
0.04
0.01
0.001
- 0.2
- 0.085
- 0.012
0
0
5.76
5.76
3.6
0.033
0.023
0.43
0.087
0.072
0.05
0.088
0.18
0.01
0.25
0.05
0.22
0.14
0.19
0.03
0.14
0.1
1.03
0.024
0.06
0.36
0.14
3.081
0.175
3.23
0.196
2.88
0.465
2.75
0. 3 1
0.81
1.03
0.96
0.39
8
2 5
0.31
0. 3 1
0.42
14.7
14.7
14.7
1.55
0.75
8.68
2.7
4.42
18.7
8.24
9.53
5.13
11.4
0.26
1
18.4
2.97
30.7
25.2
27
9.68
3.76
4.23
4.72
5.32
2 1
0.84
20
0.317
0.3
0.31
18.1
7.2
23.29
23.8
0.43
0.1
0.1
0.26
0.074
0.016
0.98
0.062
0.19
0.039
0.19
0.13
0.005
0.02
0.26
0.02
1.86
0.89
1.37
0.07
0. 08 1
0.07
43.7
0.33
1.7
0.05
506
Y 728
Y 728
Y 714
Y 714
Y 714
Y 714
Y 728
Y 728
608
608
608
608
429
504
875
907
N 248
428
428
428
N 271
405
1022
785
785
785
785
785
785
785
785
785
785
785
785
785
785
785
Y 112
Y 298
Y 298
569
569
402
N 245
402
Y 47
526
N 94
Y 47
Y 3 4 1
Y 341
Y 112
785
785
854
885
854
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 209
Monomer 1 Monomer 2
rt f95% r2 *95% Conv. Refs.
Cyclobutane, 1,2-dimethylene-
Cyclopentene, 4-,- 1,3-dione
Cyclopentene, 4-,- 1,3-dione
Cyclopentene, 4-,- 1,3-dione
Cyclopentene, 4-,-1,3-dione
Cyclopentene, 4-,- 1,3-dione
Cyclopropane, l,l-bis(ethoxycarbonyl)-
2-vinyl-
Cyclopropane, l,l-bis(ethoxycarbonyl)-
2-vinyl-
Cyclopropene, 3,3-dimethoxy-
Diallyl P-cyanoethylisocyanurate
Diallyl melamine
Diallyl melamine
Diallyl melamine
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl, 1,3-,5-(2-hydroxy-
3-phenoxypropyl)isocyanate
Diallyl, 1,3-,5-(2-hydroxy-
3-phenoxypropyl)isocyanate
Diallylcyanamide
Diallylcyanamide
Diallylcyanamide
Diallylcyanamide
Diallylcyanamide
Diallylcyanamide
Diallylcyanamide
Diallyldimethylammonium chloride
Dicyclopentadiene
Dihydroxydiphenylsulfone diallyl ether
Dimethyleneheptanedioate, 2,6-,dimethyl
Dioxolane,l,3-,4,4-dimethyl-5methylene-
2-trichloro-
Dioxolane,l,3-,4-methylene-
2-trichloromethyl-
Dioxolane, 1,3-,4-methylene-
2-trichloromethyl-
Diphenyl sulfone,3,3-bisitaconi-
mido-m,m-
Dithiane, 2-methylene- 1,3-
Dithiane, 2-methylene-1,3-
Divinylbenzene, m-
Divinylbenzene, p-
Styrene
Acrylonitrile
Methacrylate, methyl
Styrene
Styrene, p-chloro-
Vinylidene chloride
Methacrylate, methyl
3.6
0.04
0.094
0.28
3.02
8.11
0.014
0.113
0.223
0.294
1.88
4.21
Methacrylate, methyl 0.111
Acrylonitrile
Vinyl acetate
Methacrylate, methyl
Styrene
Vinyl acetate
Acrylate, methyl
Acrylate methyl
Acrylonitrile
Acrylonitrile
Fumarate, dibutyl
Fumarate, diethyl
Fumarate, dioctyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl chloride
Vinylidene chloride
Vinyl acetate
0.245
4.6
0.16
0.058
0.017
0.006
0.027
0.194
0.194
0.037
18.3
1.424
0.06
- 0.32
0.318
0.028
0.038
0.04
0.037
0.02
0.01
0.02
- 0.001
0.029
0.076
0.041
0.026
0.038
0.08
0.09
0.1
0.1
0.13
2.19
1.66
2
0.7
0.2
5.5
0.2
0.073
0.005
0.008
0.012
0.031
0.011
0.026
0.006
0.038
0.071
0.04
0.34
0.16
0.046
36.96
0.68
6.208
6.18
4.23
2.78
1.01
1.25
0.96
26.56
22.73
21.52
36.41
25.59
23.67
18.8
27.5
16.9
23.8
15.1
0.336
0.414
0.72
0.833
5
0.15
Vinyl acetate 3.65 0.16
Acrylate, methyl
Acrylate, methyl
Metbacrylate, methyl
Methacrylate, methyl
Vinyl acetate
Vinyl chloride
Vinyl chloride
Vinyl acetate
Maleic anhydride
Styrene
Methacrylate, methyl
Pyrrolidone, N-vinyl-
0.05
0.05
0.04
0.04
1.62
0.68
0.68
1.95
0.037
0.92
0.53
0.01
0.112
0.16
0.02
6.7
6.7
25
25
0.01
0.44
0.44
0.35
0. 07 1
0.975
2.36
3.87
Acrylamide 0.037 8.6
Pyrrolidone, N-vinyl- 0.04 2.98
Methacrylic acid 0.015 0.058 0.564
Methacrylate, methyl
Styrene
Styrene
Maleic anhydride
4.12
3.35
0.58
0.01
0.04
0.01
0.08
0.03
0.58
0.09
0.05 885
0.71 Y 95
0.38 Y 95
Y 263
0.081 Y 264
0.35 Y 264
0.905 Y 1076
2.5 Y 1076
0.038 Y 838
778
Y 201
4.02 Y 201
0.026 Y 201
0.069 Y 297
0.16 Y 297
0.15 Y 1 5 3
0.52 Y 1 5 3
665
665
665
1.98 Y 1 5 3
1.48 Y 1 5 3
0.39 Y 1 5 3
1.23 Y 152
2.19 Y 152
1.2 Y 152
152
152
152
152
152
0.049 Y 297
0.029 Y 297
509
0.012 Y 296
376
671
676
603
604
603
604
581
602
603
1029
0.045 Y 914
0.015 1016
0.25 N 795
647
616
647
0.032 Y 1042
1 0 3 1
1 0 3 1
0.15 N 262
0.01 943
References page II - 290
II / 210 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1 f95% r2 Zt95% Conv. Refs.
Divinylbenzene, p- Styrene
Ethene, 2-phenyl- 1,l -dicyano- N-Vinylpyrrolidone
Ethylene Acrylate, butyl
Ethylene Acrylate, methyl
Ethylene Acrylate, methyl
Ethylene Acrylonitrile
Ethylene Butene-1
Ethylene Butene-1
Ethylene Butene-2
Ethylene Carbon monoxide
Ethylene Carbon monoxide
Ethylene Carbon monoxide
Ethylene Carbon monoxide
Ethylene Ethylene, tetrafluoro-
Ethylene Ethylene, tetrafluoro-
Ethylene Ethylene, tetrafluoro-
Ethylene Ethylene, tetrafluoro-
Ethylene Fumarate, diethyl
Ethylene Maleate, diethyl
Ethylene Maleic anhydride
Ethylene Methacrylate, di-, zinc
Ethylene Methacrylate, methyl
Ethylene Phosphonate, vinyl-, diphenyl
Ethylene Phosphonate, vinyl-, bis(2-chloroc
Ethylene Phosphonate, vinyl- diisobutyl
Ethylene Propylene
Ethylene Propylene
Ethylene Styrene
Ethylene Vinyl acetate
Ethylene Vinyl acetate
Ethylene Vinyl acetate
Ethylene Vinyl acetate
Ethylene Vinyl acetate
Ethylene Vinyl acetate
Ethylene Vinyl acetate
Ethylene Vinyl acetate
Ethylene Vinyl butyrate
Ethylene Vinyl chloride
Ethylene Vinyl chloride
Ethylene Vinyl chloride
Ethylene Vinyl chloride
Ethylene Vinyl chloride
Ethylene Vinyl chloride
Ethylene Vinyl chloride
Ethylene Vinyl chloride
Ethylene Vinyl chloride
Ethylene Vinyl diethylphosphinate
Ethylene Vinyl diphenylphosphinate
Ethylene Vinyl ethyl ether
Ethylene Vinyl fluoride
Ethylene Vinyl fluoride
Ethylene Vinyl propionate
Ethylene Vinylidene chloride
Ethylene, l,l-dichloro-2,2-difluoro Vinyl acetate
Ethylene, I,1 -diphenyl- Acrylate, ethyl
Ethylene, 1, l-diphenyl- Acrylate, methyl
Ethylene, 1, l-diphenyl- Acrylate, methyl
Ethylene, 1, l-diphenyl- Acrylonitrile
Ethylene, 1,l -diphenyl- Butadiene, 2,3-dichloro-
Ethylene, 1, l-diphenyl- Butadiene, 2-chloro-
Ethylene, 1, l-diphenyl- Methacrylate, methyl
Ethylene, 1, l-diphenyl- Methacrylate, methyl
Ethylene, 1,l -diphenyl- Methacrylonitrile
Ethylene, 1, l-diphenyl- Styrene
Ethylene, l,l-diphenyl- Styrene
1.18
0.01
0.02
0
3.25
3.6
1.5
0.068
0.025
0.04
0.5
0.52
0.575
0.61
0.38
0.11
0.25
0.04
0.19
0.088 0.01 1.66 2.22
:thyl) 0.077 0.003 7.73 2.19
3.43
3.2
0.05
0.16 0.03
0.62
14.88
0.72 1.2
0.28
0.88
0.74
0.67
0.13
0.79
0.7
0.19
0.24
0.34
0.2
0.21
0.21
0.14
0.23
0.16
0.15
0.05
2.7
2.52
1.7
0.67
0.018
-0.13
0.5
- 0.24
0.21
- 0.02
- 0.08
0.03
0.09
0
- 0.45
0.01
- 0.02
0.17
0.003
0.012
0.006
0.01
0.18
0.09
1.14
0.52
0.03
0.01
0.17
0.13
0.13
0.01
0.12
0.01
0.01
0.16
0.01
0.32
0.005
0.36
0.15
0.05
0.01
0.11
0.02
0.01
0.26
13.94
19.4
7
0.16
0.32
0.004
-0.15
0
0.067
0.065
0.02
0.1
1.91
1 0
0
40
1.14
1.03
1.52
3.74
1.23
1.4
1.5
1.99
1.74
4.38
2
3.21
1.85
0.96
1.63
1.55
- 11.99
- 62.84
0
0.01
0.3
1.5
15.71
0.33
0.8
0.09
0.12
0.05
3.58
3.4
2.1
8.7
0.48
0.33
0.34
0.25
0.38
0.65
0.012
0.07
0.12
0.027
3.4
0.77
0.64
0.21
0.42
0.58
0.44
0.1
0.22
0.22
0.18
80.64
34.66
0.15
1.96
0.58
0.01
0.01
0.01
0.1
0.02
0.01
N
Y
N
N
Y
Y
N
N
N
Y
Y
Y
N
N
N
N
N
N
N
N
N
N
N
N
Y
Y
N
Y
Y
N
N
N
Y
Y
N
N
N
262
947
42
4 1
768
415
388
407
477
5 1
5 1
52
52
1093
1094
563
563
4 1
4 1
620
935
4 1
801
8 0 1
801
388
477
615
309
4 1
413
42
559
68
68
766
605
180
270
42
472
536
63
63
64
68
311
311
584
42
590
605
299
6
65
334
334
1 4 3
6 1
6 1
65
901
1 4 3
189
281
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 211
Monomer 1 Monomer 2
rl
zt9S%
r2
&9S% Conv. Refs.
Ethylene, 1, l-diphenyl-
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, dichloro-, cis
Ethylene, dichloro-, cis
Ethylene, dichloro-, cis
Ethylene, dichloro-, cis
Ethylene, dichloro-, cis
Ethylene, dichloro-, cis
Ethylene, dichloro-, cis
Ethylene, dichloro-, cis
Ethylene, dichloro-, cis
Ethylene, dichloro-, cis
Ethylene, dichloro-, cis
Ethylene, p-vinyl- 1, l-diphenyl-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrafluoro-
Ethylene, tetrafluoro-
Ethylene, tetrafluoro-
Ethylene, tetrafluoro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ferrocene, ethyl-a-cyclopentadienylidene
Ferrocene, ethyl-a-cyclopentadienylidene
Formaldehyde-S-vinyl0ethylthioacetal
Fumarate, ally1 methyl
Fumarate, bis(Zbuty1)
Fumarate, bis(3-[tris(trimethylsiloxy)-
silyl)propyl]
Fumarate, bis(3-[tris(trimethylsiloxy)-
silyl)propyl]
Fumarate, bis(3-chloro-2-butyl)
Styrene
Ethylene, tetrafluoro-
Isobutylene
Methacrylate, methyl
Propionate, vinyl
Propylene
Pyrrolidone, N-vinyl-
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl chloride
Vinyl fluoride
Vinylidene chloride
Styrene
Styrene
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinylidene cyanide
Vinylidene cyanide
Styrene
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Methacrylate, methyl
Styrene
Styrene
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Ethylene
Ethylene
Ethylene
Ethylene
Ethylene, chlorotrifluoro-
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Butadiene
Methacrylate, methyl
Styrene
Styrene
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl isobutyl ether
Butadiene
Isoprene
Styrene
Styrene
Styrene
Fumarate, di-tert-butyl
Fumarate, diisopropyl 0.07 0.87
Styrene
1.15
0.01
- 0.074
0.08
0.02
0.3
-0. 1
0.01
0.04
- 0.02
0.01
1.2
0.02
- 3.1
- 2.2
- 0.28
- 0.02
0.067
0.055
0.01
0.058
0.1
1.31
0
0
0
200
0
0
- 0.07
0.067
0.065
0.02
0.1
0
0
0
- 0.03
0
0
0
0
0
- 0.006
- 0.06
- 0.006
0.014
1.51
1.91
0.32
0.03
0
0.21
- 0.06 0.03 0.26
0.02
0.062
0.01
0.08
0.21
0.02
0.12
0.062
0.053
0.024
0.03
0.14
0.15
0.12
0.027
0.07
0.37
0.34
0.019
0.003
0.24
0.02
0.01
0.87
1
0.06
51.36
0.63
0.08
0.38
4.38
5.2
0.68
0.47
2.53
0.8
17.14
3.1
63.1
21.4
161.3
24.75
1.02
6.4
0.898
4.13
0.46
830
456
470
187
1 8 5
4.45
0.52
0.575
0.61
0.38
1
3 3
67
62.1
9.64
100
17.1
16.5
12.1
12.7
1 6
0.607
0.7
0.05
0.02
0.01
7.75
0.25
0.51
0.67
0.03
3.31
0.04
0.07
0.99
0.11
4.9
30.3
2.64
0.27
0.06
1.94
1.87
0.18
0.09
0.21
11
0.076
0.1
0.009
0.68
0.01
0.04
0.04
N
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
N
N
N
901
392
318
236
1097
318
830
236
567
1097
236
454
406
454
1 3 7
1 3 7
40
9
9
1 3 7
1 3 7
9
9
82
82
742
402
571
59
204
204
204
40
40
59
3
59
1093
1094
563
563
392
470
470
572
89
470
40
40
40
40
59
1 5 8
9
332
699
699
273
713
249
1040
1040
249
References page II - 290
II / 212 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl
&95%
r2
&95% Conv. Refs.
Fumarate, di-(2-chloroethyl)
Fumarate, di-(2-cyanoethyl)
Fumarate, di-(2-(methoxyethyl)
Fumarate, di-(2-phenylethyl)
Fumarate, di-set-butyl
Fumarate, di-rert-amyl
Fumarate, di-teti-butyl
Fumarate, di-tert-butyl
Fumarate, di-tert-butyl
Fumarate, di-reti-butyl
Fumarate, dibenzyl
Fumarate, dibutyl
Fumarate, dibutyl
Fumarate, dibutyl
Fumarate, dibutyl
Fumarate, dicyclohexyl
Fumarate, dicyclopentyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diisobutyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, diisopropyl
Fumarate, dimethyl
Fumarate, dimetbyl
Fumarate, dimethyl
Fumarate, dioctyl
Fumarate, dioctyl
Fumarate, dipropyl
Fumarate, dipropyl
Fumarate, isopropyl butyl
Fumarate, isopropyl butyl
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Fumarate, bis(3-[tris(trimethylsiloxy)
silyl)propyl
Fumarate, dimethyl
Maleate, dimethyl
Styrene
Styrene
Diallyl phthalate
Imidazole, l-vinyl-
Styrene
Styrene, tert-butoxy
Styrene
Styrene
Acrylonitrile
Acrylonitrile
Butadiene
Butadiene, 2-chloro-
Diallyl phthalate
Ethylene
Methacrylate, methyl
Methacrylate, methyl
N-Vinylimidazole
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl chloride
Vinyl ethyl ether
Vinyl isobutyl ether
Vinylidene chloride
Styrene
Acenaphthalene
Acetate, isopropenyl
Acrylate, methyl
Acrylate, phenyl
Acrylonitrile
Carbazole, N-vinyl-
Fumarate, bis(3-[tris(trimethylsiloxy)
silyl)propyl
Isobutylene
Methacrylate, methyl
Methacrylonitrile
Styrene
Vinyl acetate
Vinyl chloride
Vinylidene chloride
Fumarate, di-teri-butyl
N-Vinylimidazole
Styrene
Diallyl phthalate
Pyrrolidone, N-vinyl-
Imidazole, l-vinyl-
Styrene
Styrene
Styrene
0 0.18 1038
0.09 0.07 1038
0.03 0.35 1038
0 0.27 1038
0.04 0.55 1038
0.08 0.69 1038
0.61 0.21 1040
1.57
18.2
0.04
0
1.01
0.182
0.04
0.01
0.06
0.06
0
0.1
0.25
0.02
1.25
1.91
0.04
0.05
0.191
0.02
0.081
0.11
0.07
0
0.1
0.02
0.443
0.33
0.48
1.63
0.52
0.012
0.05
0.06
0.67
0.091
0.07
0.2
0
0.87
0.365
6.7
0.227
0.037
0.054
0.156
0.011
0.57
0.32
0.02
0.03
0.35
0.18
0.49
0.3
8
1 0
2.13
6.51
0.01
0.11
40.3
2.1
0.113
0.29
6.3
0.394
0.3
0.31
0.36
0.29
0.011
0.09
0.13
- 0.124
0
12.19
0.37
2.57
0.011
1.9
3.4
1 6
0
0.07
0.01
3.4
0.004
0.022
0.005
0.022
0.01
1.14
0.6
0.019
0.26
0.06
0.02
0.007
0.1
0.16
0.038
0.004
0.1
0.059
1.58
Y
N
N
Y
Y
Y
N
Y
Y
Y
Y
1049
1049
1038
1038
665
614
1038
1077
1038
1038
470
640
466
6 1
665
4 1
28
394
879
1038
139
139
139
249
562
640
1 3 7
718
1 3 7
194
640
59
1038
1039
1038
1038
1038
1038
1038
1040
0.42
0.17
0
0.055
0.9
0.49
0.095
0.156
0.252
0.03
0.96
0.04
0.163
0.02
0.01
0.01
0.227
0.015
0.04
0.69
0
23
8 5
0.4
0.012
0.29
48
1.57
0.133
0.39
0.02
0.02
0.009
0.32
0.42
0.3
0.365
0.021
0.01
0.012
1038
1038
1038
1038
1038
1038
1038
1049
879
1038
665
1 2 1
614
1038
1056
1056
TABLE 1. contd
Copolymer Reactivity Ratios II / 213
Monomer 1 Monomer 2
rl
*95%
r2
Zt95% Conv. Refs.
Fumarate, isopropyl isobutyl
Fumarate, isopropyl methyl
Fumarate, isopropyl see-butyl
Fumarate, methyl butyl
Fumarate, methyl ethyl
Fumarate, methyl isobutyl
Fumarate, methyl isopropyl
Fumarate, methyl propyl
Fumarate, methyl set-butyl
Fumarate, methyl tert-amyl
Fumarate, methyl tert-butyl
Fumarate, mono-2-butyl
Fumarate, tert-butyl 2-ethylhexyl
Fumarate, tert-butyl 4-methyl-2-pentyl
Fumarate, tert-butyl ethyl
Fumarate, tert-Butyl isoamyl
Fumarate, terr-butyl methyl
Fumarate, tert-butyl set-butyl
Fumaric acid
Fumaronitrile
Fumaronitrile
Fumaronitrile
Fumaronitrile
Fumaronitrile
Fumaronitrile
Fumaronitrile
Fumaryl chloride
Fumaryl chloride
Furan, 2,3-dihydro-
Furan, 2-vinyl-5-methyl
Furan, 2-vinyl-5-methyl
Furan, 2-vinyl-5-methyl
Hex-3-yne-5-ene, 2-methyl-tert-butyl
peroxide
Hexatriene, tetrachloro-
Hexatriene, tetrachloro-
Hexatriene, tetrachloro-
Hexatriene, tetrachloro-
Hexatriene, tetrachloro-
Hexatriene, tetrachloro-
Hexatriene, tetrachloro-
Hexene, l-, 3,4-dioic anhydride
Hexene, 2-, 3,4-dioic anhydride
Hexene, 3-, 3,4-dioic anhydride
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
He x e n e - 1
Hexene-1
Hexene-1
Hexene-1, 2,5-dicarboxylate, dimethyl
Imidazole, l-vinyl
Imidazole, l-vinyl-
Imidazole, l-vinyl-
Imidazole, 1 -vinyl-
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
N-vinylimidazole
Benzothiazole, vinylmercapto-
Methacrylate, methyl
Styrene
Styrene
Styrene
Styrene
Styrene, a-methyl-
Styrene
Vinyl acetate
Styrene
Acrylate, butyl
Methacrylate, isobutyl
Methacrylate, methyl
Maleic anhydride
Acrylate, methyl
Acrylonitrile
Butadiene, 2-chloro-
Isoprene
Methacrylate, methyl
Styrene
Vinyl acetate
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Acrylate, methyl
Acrylonitrile
Vinyl chloride
Styrene
Tri azol e, I-N-vinyl-1,2,4-
Acrylic acid
Fumarate, dibutyl
Fumarate, dipropyl
0.01
0.16
0.02
0.02
0.02
0.03
0.16
0.05
0.02
0.06
0.03
- 0.04
0.01
0.01
0.04
0.06
0.03
0.07
0.313
0.03
0.46
0.3
0.54
0.36
0.32
0.32
0.3
0.28
0.45
0.53
0.45
0.33
0.54
0.57
0.25
0.45
0.45
0.55
0.121
0.03
- 0.064
- 0.016
0.006
0
0.012
0.096
0.021
0. 03 1
6.74
0.202
0.294
0.3
0.01
0.79
0.058
0.044
- 0.01 0.078 0.094 0.02
0
0.392
0.716
0.867
0.36
0. 05 1
0.169
0.292
20
0.118
0.105
0.183
0.01
0.019
0.044
0.146
3.19
4.01
0.2
1.58
1.76
0.85
1.36
1.25
0.28
0.22
1
1.17
5.83
0.262
0.234
3.6
0.58
0.504
0.123
0.087
0.05
- 0.052
- 0.08
- 0.54
1.22
1.38
1.52
1.73
1.91
1.91
2.07
2.46
2.69
2.93
3.19
4.11
- 0.67
- 1.08
- 1.72
0.196
0.03
9.23
0.043
8.57
3.63
17.17
0. 03 1
0.049
0.066
0.07
0.171
0.179
0.173
0.121
0.24
0.014
0.044
0.028
- 0.13
2.07
1.54
0.678
0.057
0.042
8.4
5.6
436
0.6
0.98
0.031
0.32
0.03
0.009
0.01
0.012
0.002
0.182
0.163
0.054
0.069
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
N
Y
Y
1056
1056
1056
1056
1056
1056
1056
1056
1056
1056
1056
249
1056
1056
1056
1056
1056
1056
879
763
1 9 1
1 3 7
199
478
77
77
9 1
9 1
806
1105
1105
1 1 0 5
637
5
4
459
459
5
4
4
933
933
933
931
931
931
931
931
931
931
931
931
931
931
931
60
60
329
828
972
955
614
614
References page II - 290
II/214 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
I1 &95% 12 f95% Conv. Refs.
Imidazole, l-vinyl-
Imidazole, l-vinyl-
Imidazole, l-vinyl-
Imidazole, l-vinyl-
Imidazole, l-vinyl-
Imidazole, l-vinyl-
Imidazole, l-vinyl-
Imi dazol e, I-vinyl-
Imidazole, I-vinyl-Zmethyl-
Imidazole, 1-vinyl-2-methyl-
Imidazole, 1-vinyl-2-methyl-
Imidazole, 1-vinyl-Zmethyl-
Imidazole, 1-vinyl-2-methyl-
Imidazole, 1-vinyl-Zmethyl-
Imidazole, N-vinyl-
Imidazole, N-vinyl-
Imidazole, N-vinyl-
Imidazolid-2-one, 1,3-divinyl-
Imidazolid-2-one, 1-ethyl-3-vinyl-
Indene
Indene
Indene
Indene
Indene
Indene
Indene
Indene
Indene
Indene
Indene
Isobutene
Isobutylene
Isobutylene
Isobutylene
Isobutylene
Isobutylene
Isobutylene
Isobutylene
Isobutylene
Isobutylene
Isobutylene
Isobutylene
Isobutylene, 3-chloro-
Isobutylene, 3-chloro-
Isobutylene, 3-chloro-
Isobutylene, 3-chloro-
Isooctene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Maleate, dibutyl
Maleate, dipropyl
Maleate, monomet hyl
Maleic acid
Methacrylate, methyl
Pyrrolidone, N-vinyl-
Styrene
Vinyl acetate
Acrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Vinyl chloride
Silane, methacryloxypropyldimethoxy
methyl-
Silane, methacryloxypropyltrimethoxy-
Styrene, p-trimetbyoxysilyl-
Acrylate, ethyl
Acrylate, ethyl
Acrylate, methyl
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Styrene, p-chloro-
Vinyl acetate
Vinyl 1-mentbyl ether
Vinyl methyl ketone
Vinyl methyl ketone
Vinylidene chloride
Vinylidene chloride
Maleimide, N-cyclohexyl-
Acrylonitrile
Acrylonitrile
Acrylonitrile
Ethylene, chlorotrifluoro-
Fumarate, diisopropyl
Maleic anhydride
Vinyl acetate
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Ally1 acetate
Vinyl acetate
Vinyl chloride
Vinylidene chloride
Maleimide, N-cyclohexyl-
Acetylene, phenyl-
Acrylate, methyl
Acrylonitrile
Butadiene
Butadiene
Butadiene, 2,3-dimethyl-
Butadiene, 2-chloro-
Butadiene, 2-fluoro-
Butadiene, hexafluoro-
Ferrocene, ethyl-a-cycle-pentadienylide
Hexatriene, tetrachloro-
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 4-vinyl-
0.486
0.314
0.4
0.3
0.014
0.96
0. 07 1
1.9
0.05
0.047
0.003
0.09
0.07
2.15
0.079
0.158
0.002
- 0.08
0.01
0.1
0.12
0.09
0.07
- 0.069
8.64
12.64
0.2
0.25
0.293
0.34
0.41
0
0.02
0
0.06
0
0.012
0.17
0.06
0.268
- 0.54
0.08
4.5
0
0
0
0.72
3.01
0.75
0.45
1.06
0.608
1.18
0.06
0.25
1.19
0.01
0.58
0.65
0.64
0.64
0.59
0.58
0.32
0.057
0.028
0.03
0.19
0.029
6.99
0.088
0.064
0.26
0.04
0.03
0.01
0.25
0.24
0.066
2.8
12.59
0.095
0.85
0.002
0.38
0.03
0.19
0.8
0.043
5.8
0.062
0.12
0.23
0.093
0.053
0.6
0.6
4.36
0.16
9.94
-0.11
1.28
4
3.48
8.87
8.97
0.188
1.39
2.27
6.9
0.41
0.47
0.63
0.62
0.281
0.29
2.86
0.39
0.67
2.63
2.9
0.49
- 0.02
0
1.295
0.98
1.02
0.01
0.42
0.065
1.66
2.04
2.12
1.2
1.54
0.15
0.13
0.31
1.1
0
0.1
0.12
0.03
0.94
0.14
0.84
2.82
2.63
0.78
1.91
1.58
0.26
0.25
0.25
0.47
0.46
2.49
0.08
0.035
1.86
0.074
0.24
1.17
0.54
0.62
0.077
1.12
0.13
0.06
0.05
0.12
0.83
0.2
2.82
0.15
1.15
0.008
0.25
0.02
0.18
1.82
0.2
2.05
0.37
0.96
0.21
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
N
Y
Y
Y
614
614
724
635
364
364
364
364
465
364
479
364
479
154
1095
1088
1095
800
800
606
606
360
360
6
360
750
606
606
6
6
995
2 1
211
484
318
1038
988
211
140
1 5 5
329
560
412
415
415
470
995
648
424
417
1 7 3
8 3
1 7 3
418
174
453
699
459
302
698
704
456
458
424
TABLE 1. contd
Monomer 1 Monomer 2
rl
copol ymer React i vi t y Rat i os II / 215
f95%
r2 zt95% Conv. Refs.
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene, 3-acetoxy-
Isoprene, 3-acetoxy-
Isoprene, 3-acetoxy-
Isopropenyl acetate
Isopropenyl acetate
Isopropenyl acetate
Isopropenyl acetate
Isopropenyl methyl ketone
Isopropenyl methyl ketone
Isopropenyl methyl ketone
Isopropenyl methyl ketone
Isopropenyl methyl ketone
Isopropenyl methyl ketone
Isopropenyl, 3-(1-cyclohexenyl), acetate
Isopropenyl, 3-(1-cyclohexenyl), acetate
Isopropenyl, 3-(1-cyclohexenyl), acetate
Isopropenyl-, p-, phenol glycidyl ether
Isopropenylacetophenone, p-
Isopropenylisocyanate
Isopropenylisocyanate
Isopropenylisocyanate
Isopropenylisocyanate
Isopropenylisocyanate
Isopropenylisocyanate
Isopropenylisocyanate
Isopropenylisocyanate
Isopropenylisocyanate
Isopropenyltoluene
Isopropenyltoluene
Isopropylidene, 2,3:4,5-di0,
-l-vinylbenzyl-!.!I-o-fructose
Itaconamate, N-(4-carboethoxyphenyl)-,
butyl
Itaconamate, N-(4-carboethoxyphenyl)-,
ethyl
Itaconamate, N-(4-carboethoxyphenyl)-,
ethyl
Itaconamate, N-(4carboethoxyphenyl)-,
methyl
Itaconamate, N-(4-carboethoxyphenyl)-,
Prowl
Itaconamate, N-(4-carboethoxyphenyl)-,
Prom1
Itaconamate, N-(Cchlorophenyl)-, ethyl
Itaconamate, N-(Cchlorophenyl)-, ethyl
Itaconamate, N-(Cchlorophenyl)-, methyl
Itaconamate, N-(4-chlorophenyl)-, propyl
Itaconamate, N-(4-chlorophenyl)-, propyl
Itaconamate, N-(4-methoxyphenyl)-, butyl
Itaconamate, N-(4-methoxyphenyl)-, ethyl
Itaconamate, N-(4-methoxyphenyl)-, ethyl
Itaconamate, N-(4-methoxyphenyl)-,
methyl
Itaconamate, N-(4-methoxyphenyl)-,
Prowl
Itaconamate, N-(4-methoxyphenyl)-,
Prowl
Itaconamate, N-(Cmethylphenyl)-, propyl
Itaconamate, N-(Cmethylphenyl)-, propyl
Quinoline, 2-vinyl- 1.88
Styrene 1.922
Styrene 1.957
Styrene 1.98
Styrene 2.02
Styrene 1.3
Acrylate, methyl 5.71
Methacrylate, methyl 2.81
Styrene 4.47
Maleic anhydride 0.034
Methacrylate, methyl - 0.09
Vinyl acetate 1.082
Vinyl chloride 0.23
Acrylonitrile 1.2
Acrylonitirle 0.7
Butadiene, 2-chloro- 0.14
Styrene 0.29
Styrene 0.66
Vinylidene chloride 4.06
Acrylate, methyl 0.57
Methacrylate, methyl 0.4
Styrene 0.56
Maleic anhydride 0.003
Styrene 0.84
Acrylate, ethyl 0.15
Acrylate, methyl 0.11
Acrylate, methyl 0.079
Acrylonitrile 0.1
Methacrylate, methyl 0.14
Styrene 0.07
Styrene 0.122
Vinyl chloride 3
Vinylidene chloride 0.31
Methacrylate, methyl 0.04
Methacrylate, methyl 0.04
Styrene 3.26
0.016
0.011
0.53
0.513
0.476
0.44
0.42
0.48
0.27
0.16
0.34
0.002
17.36
1.171
2.26
0.3
0.36
4.035
0.44
0.32
0.134
0.37
0.81
1.59
0.002
0.3
0.79
0.6
0.799
0.24
3.1
8.12
6.84
0.39
0.85
0.68
0.68
0.14
0.02
0.018
0.022
0.12
0.074
0.16
0.011
1.95
0.038
0.13
0.01
0.66
0.59
0.047
0.047
1.12
0.087
0.099
0.18
0.049
0.18
0.055
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
456
366
366
544
544
8 3
770
770
770
260
100
100
100
490
542
259
542
542
47
770
770
770
937
266
434
434
99
434
434
434
99
777
434
688
722
772
Styrene 0.61 0.2 678
Methacrylate, methyl 0.48 1.21 678
Styrene 0.2 0.23 678
Styrene 0.58 0.15 678
Methacrylate, methyl 0.53 1 678
Styrene 0.4 0.26 678
Methacrylate, methyl 0.36 1.24 678
Styrene 0.16 0.35 678
Styrene 0.18 0.38 678
Methacrylate, methyl 0.31 1.26 678
Styrene 0.31 0.39 678
Styrene 0.69 0.12 678
Methacrylate, methyl 0.43 1.31 678
Styrene 0.34 0.33 678
Styrene 0.41 0.26 678
Methacrylate, methyl 0.4 1.03 678
Styrene 0.4 0.38 678
Methacrylate, methyl 0.28 1.11 678
Styrene 0.19 0.54 678
References page II - 290
II / 216 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rt *95%
r2
zt95% Conv. Refs.
Itaconamate, N-(Cmethylphenyl)-, butyl
Itaconamate, N-(4-methylphenyl)-, ethyl
Itaconamate, N-(4-methylphenyl)-, ethyl
Itaconamate, N-(4-methylphenyl)-, methyl
Itaconamate, N-phenyl-, butyl
Itaconamate, N-phenyl-, ethyl
Itaconamate, N-phenyl-, ethyl
Itaconamate, N-phenyl-, methyl
Itaconamate, N-phenyl-, methyl
Itaconamate, N-phenyl-, propyl
Itaconamate, N-phenyl-, propyl
Itaconate, bis(2-ethylhexyl)
Itaconate, bis(tri-n-butyltin)
Itaconate, bis(tri-n-butyltin)
Itaconate, bis(tri-n-butyltin)
Itaconate, bis(tri-n-butyltin)
Itaconate, di-2[-2(2-methoxyethoxy)-
ethoxylethyl
Itaconate, di-p-butyl
Itaconate, diamyl
Itaconate, dibutyl
Itaconate, dibutyl
Itaconate, dibutyl
Itaconate, dibutyl
Itaconate, diethyl
Itaconate, diethyl
Itaconate, diethyl
Itaconate, dimenthyl
Itaconate, dimenthyl
Itaconate, dimenthyl
Itaconate, dimenthyl
Itaconate, dimethyl
Itaconate, dimethyl
Itaconate, dimethyl
Itaconate, dimethyl
Itaconate, dimethyl
Itaconate, dimethyl
Itaconate, dimethyl
Itaconate, dimethyl
Itaconate, dimethyl
Itaconate, dimethyl
Itaconate, dioctyl
Itaconate, dipropy
Itaconate, ethyl hexafluoroisopropyl
Itaconate, glycidyl methyl
Itaconate, mono-methyl
Itaconate, mono-methyl
Itaconate, mono-methyl
Itaconate, mono-methyl
Itaconate, mono-methyl
Itaconate, mono-methyl
Itaconate, mono-methyl
Itaconate, mono-methyl
Itaconate, monomethyl
Itaconic acid
Itaconic acid
Itaconic acid
Itaconic acid
Itaconic acid
Itaconic acid mono@sulfamidoanilide)
Itaconic anhydride
Itaconic anhydride
Itaconic anhydride
Itaconic anhydride
Itaconic anhydride
Styrene 0.31
Methacrylate, methyl 0.63
Styrene 0.26
Styrene 0.16
Styrene 0.49
Methacrylate, methyl 0.47
Styrene 0.21
Styrene 0.52
Styrene 0.18
Methacrylate, methyl 0.15
Styrene 0.18
Maleimide, N-cyclohexyl- 0.38
Acrylate, 2-chloroethyl 0.391
Acrylate, butyl 0.422
Methacrylate,allyl 0.038
N-Vinylpyrrolidone 0.065
Styrene 0.2
Maleimide, N-cyclohexyl
Styrene
Itaconate, dimethyl
Methacrylate, methyl
Methacrylate, methyl
Styrene
Pyridine, 2-methyl-5-vinyl-
Styrene
Vinyl chloride
Maleimide, N-cyclohexyl-
Methacrylate, methyl
Styrene
Vinyl acetate
Acrylate, butyl
Itaconate, dibutyl
Methacrylate, methyl
Methactylonitrile
Pyridine, 2-methyl-5-vinyl-
Styrene
Styrene
Styrene
Styrene, p-chloro-
Vinyl chloride
Styrene
Styrene
Styrene
Styrene
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Styrene
Styrene
Styrene
Styrene
Methacrylate, methyl
Acrylonitrile
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Methacrylate, propargyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylonitrile
Methacrylate, methyl
Styrene
-
0.34
0.5
1.1
0.717
0.4
0.34
0.17
0.34
5.65
0.318
0.156
0.483
0.94 0.4
1.1 1.1
0.3 1.2
0.28 1.26
0.22 0.88
0.14
0.06
0.15
5
0.14
0.28
0.039
0.041
0.31
0.36
0.135
0.04
0.111
0.33
0.33
0.218
0.139
0.86
0
0
0
0.12
0.58
2.46
2.61
4.83
1.17
0.405
0.04
0.015
0.04
0.09
0.11
0.05
0.12
0.213
0.02
0.364
0.12
0.06
0.035
0.079
0.42
0.21
0.028
0.11
0.052
0.15
0.11
0.086
0.103
0.74
0.67
0.05
0.38
0.32
0.33
0.33
0.09
0.19
1.43
0.38
0.3
0.12
1.32
0.45
0.31
0.39
1.13
0.5
0.34
0.683
0.91
1.08
0.21
0.53
0.21
0.36
1.1
1.33
0.8
0.42
0.51
0.23
0.06
0.601
3.34
0.502
0.48
0.5
0.69
0.05
0.33
0.16
0.435
0.376
0.52
0.59
0.223
0.189
0.029
0.34
0.52
0.404
1.1
0.59
1.23
1.14
0.34
0.26
1.65
0.016
0. 25 1
0.034
0.155
0.004
0.013
0.022
0.04
0.05
0.09
0.06
0.11
0.193
0.557
0.188
0.16
0.07
0.025
0.036
0.16
0.14
0.02
0.055
0.077
0.085
0.06
0. 07 1
0.34
0.08
0.02
0.022
0.021
0.014
0.024
0.01
Y
N
N
N
Y
Y
Y
Y
N
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
678
678
678
678
678
678
678
1059
678
678
678
1060
940
940
940
941
1098
1014
39
398
1073
398
39
545
39
480
975
975
975
975
398
398
398
398
545
39
398
586
398
479
39
39
1103
806
613
613
613
613
656
656
656
656
1010
164
260
408
420
76
957
365
365
365
1010
365
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 217
Monomer 1 Monomer 2
r1 f 95% r2 Zt95% Conv. Refs.
Itaconic anhydride
Itaconic anhydride
Itaconic anhydride
Itaconic anhydride
Itaconimide, N-(2-chloroethyl)-
Itaconimide, N-(2-chloroethyl)-
Itaconimide, N-(4-acetoxyphenyl)-
Itaconimide, N-(Cchlorophenyl)-
Itaconimide, N-(4-ethoxycarbonylphenyl).
Itaconimide, N-(p-chlorophenyl)-
Itaconimide, N-(p-tolyl)-
Itaconimide, N-benzyl-
Itaconimide, N-benzyl-
Itaconimide, N-butyl-
Itaconimide, N-ethyl-
Itaconimide, N-ethyl-
Itaconimide, N-isobutyl-
Itaconimide, N-isopropyl-
Itaconimide, N-methyl-
Itaconimide, N-methyl-
Itaconimide, N-naphthyl-
Itaconimide, N-phenyl-
Itaconimide, N-phenyl-
Itaconimide, N-phenyl-
Itaconimide, N-propyl-
Itaconimide, N-tolyl-
Malemic acid, N-3-dimethylamino-
6-methylphenyl-
Malemic acid, N-3-dimethylamino-
6-methylphenyl-
Maleate, chloro-, diethyl
Maleate, dibutyl
Maleate, ally1 methyl
Maleate, butyl stannylallyl
Maleate, di-terr-butyl
Maleate, dibutyl tin
Maleate, dibutyl tin
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, dimethyl
Maleate, dimethyl
Maleate, dimethyl
Maleate, dimethyl
Maleate, dimethyl
Maleate, dimethyl
Maleate, dimethyl
Maleate, dioctyl
Styrene 0.456
Styrene 0.785
Vinyl acetate 1.57
Vinyl acetate 2.87
Methactylate, methyl 0.54
Styrene 0.162
Styrene 0.21
Styrene 0.2
Styrene 0.112
Styrene 0.14
Styrene 0.24
Methacrylate, methyl 1.06
Styrene 0.2
Styrene - 0.019
Methactylate, methyl 0.42
Styrene 0.172
Styrene - 0.03
Styrene 0.045
Methacrylate, methyl 1.12
Styrene 0.12
Styrene 0.35
Styrene 0.109
Styrene 0.08
Styrene 0.998
Styrene 0.04
Styrene 0.219
Butadiene - 0.08
Styrene
Styrene
Imi dazol e, l-vinyl-
Styrene
Styrene
Vinyl acetate
Methacrylate, methyl
Styrene
Acrylonitrile
Acrylonitrile
Butadiene
Carbazole, N-vinyl-
Ethylene
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
N-Vinylimidazole
Styrene
Styrene
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl isobutyl ether
Vinylidene chloride
Carbzole, N-vinyl-
Fumarate, di-tert-butyl
N-Vinylimidazole
Styrene
Styrene
Succinimide, N-vinyl-
Vinyl acetate
Vinyl chloride
-0.19
- 0.043
0.093
0.02
0.06
0.199
- 0.095
0.194
0
0
0.11
0
1 0
-0. 1
0
- 0.02
0.106
- 0.013
0.07
0.01
0.001
0.04
- 0.003
0
0.046
0.17
12.5
0
0.011
0.046
0.15
0.105
- 0.012
0.257
0.608
0.09
0.05
0.3
0.32
0.39
0.092
0.21
0.18
0.054
0.015
0.005
0.045
0.024
0.11
0.045
0.12
0.084
0.032
0.75
0.11
0.04
0.13
0.06
0.11
0.064
0.73
0.12
0.18
0.048
0.03
0.066
0.029
0.11
0.043
0.22
0.069
0.082 0.043
0.123
0.18
0.079
0.03
0.086
0.003
- 0.019
- 0.04
0
0.069
0.35
0.159
0.232
0.15
0.16
0.46
0.056
0.22
0.486
0.232
0.44
0.308
0.38
0.153
0.08
0.116
0.05
0.05
0.28
0.134
0.37
0.248
0.12
0.031
0.04
0.03 0.55 0.03
0.021
0.08
0.01
0.03
0.02
0.199
0.121
2.07
0.486
8.29
0.1
0.005
72.7
2.08
1 2
20
8.08
0.21
0.25
341
20
285.8
0.057
0.14
0.057
0.14
0.02
0.024
5.93
0.118
0.01 0.05
0.05 46
0.015
0.147
35.9
0.028
0.022 6.59
8
6.07
6.592
0.171
0.768
0.8
0.9
0
0.46
0.01 0.07
0.012
0.044
0.025
0.078
0.07 0.11
0.01 0. 5 1 0.11
0.037 18.2 6.7
0.438 0.046 0.046
0.12 10.65 2.81
0.058 0.083 0.015
0.021 1.25 0.16
0.086 - 0.006 0.084
0.099 0.05 0.14
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
N
N
Y
Y
N
N
Y
Y
Y
N
N
Y
Y
Y
Y
N
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
62
62
365
365
642
642
729
729
729
740
740
642
642
642
642
642
642
642
642
642
740
729
740
978
642
729
679
679
1 4
614
713
811
1049
987
987
470
640
466
361
4 1
28
470
873
879
1 4
139
640
874
888
137
137
449
6
640
3
361
1049
879
1 3 7
317
284
1049
3
References page II - 290
II / 218 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
0 f95% r2 195% Conv. Refs.
Maleate, dipropyl
Maleate, monoallyl
Maleate, monoallyl
Maleate, monomethyl
Maleate, tributylstannyl ally1
Maleic Anhydride
Maleic acid
Maleic acid
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anbydride
Maleic anbydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anbydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anbydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Imidazole, l-vinyl-
Maleic anhydride
Styrene
Imidazole, l-vinyl-
Maleic anhydride
Isopropenyl-, p-, phenol glycidyl ether
Imidazole, l-vinyl-
N-Vinylimidazole
Acenaphthalene
Acenaphthalene
Acetylene, phenyl-
Acrolein diethylacetal
Acrylamide
Acrylate, 2-chloroethyl
Acrylate, ferrocenylmethyl
Acrylate, methyl
Acrylate, methyl
Acrylonitrile
Ally1 acetate
Allylbenzene
Benzocyclobutane, a-methylene-
Benzothiazole, vinylmercapto-
Butadiene monoxide
Butadiene, 2-chloro-
Carbamate, N,N-diethyl-, vinyl
Dicyclopentadiene
Divinylbenzene, p-
Ethylene
Hex-3-yne-5-ene, 2-methyl-wt-butyl-
peroxide
Isobutylene
Isopropenyl acetate
Maleate, monoallyl
Maleate, tributylstannyl ally1
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Methacrylate, ferrocenylmethyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, di-, di-n-butylstannyl
Methacrylate, benzyl
Methacrylate, benzyl
Phthalimide, N-vinyl-
Pr opene, I-chloro-, cis-
Propene, 1-chloro-, trans-
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, a-methyl-
0.053
0.027
0.07
0.6
0.095
0.002
0.6
0.094
0.02
- 0.04
0.06
0.07
0
0.027
0.035
0.014
0.02
0.104
0.027
0.05
0.314
0. 05 1
0.14
0.4
0.032
0.003
0.3
0.018
0.46
0.46
0.08
0.18
0.56
7.15
0.012
0
0
0.028
0.004
0.013
0.019
2.788
2.5
6
- 0.001
0.025 0.002
0.64
0.329
0.025
0.071
0.09
0
0.01
0.05
0.026
0.024
0.037
0.01
0.04
0.36
0.065
0.002
0.051
0.032
- 0.095
0.02
0.24
-0.163
- 0.019
0.08
0.02
0.01
0.01
0.01
0.02
0.024
0.011
0.054
0.017
0.106
0.65
0.28
0.027
0.026
1.77
0.004
0.008
0.012
0.034
0.027
0.095
1.08
1.92
0.33
4.18
6.36
0.46
5.2
3.1
3.85
3.4
3.85
0.012
0.372
0.008
0.347
0.28
0.001
0
0.003
0.02
0
0
0.02
0.01
0.001
0.005
0.01
0.02
0.05
0.093
0.012
0.082
0.012
0.008
0.13
0.03
0.01
0.08
- 0.075
0.344
- 0.022
0.05
0.097
0.04
0.02
0
0.02
0.02
0.04
0.04
0.04
0.05
0.02
0.04
0.04
0.04
0.028
0.054
0.01
0.017
0.007
0.13
0.31
2.96
0. 05 1
0.007
0.18
0.03
0.066
0.112
0.01
0.022
0.014
0.104
0.13
11.83
0.65
0.31
0.64
0.69
0.47
0.016
0.088
0.061
0.08
0.015
0.002
0.12
0.003
0.01
Y
N
N
N
Y
N
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
N
N
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
Y
Y
N
Y
N
N
N
614
906
8 1 1
724
906
937
635
879
1039
326
797
767
655
1 1 7
325
260
470
470
27
351
1083
763
1064
1068
92
914
943
620
631
988
260
906
906
990
341
325
169
260
320
3 3
524
524
524
524
954
720
120
284
1 8 1
1 8 1
1 0 5
1 2
1 7
241
384
397
483
506
522
522
522
522
522
923
492
TABLE 1. contd
Copolymer Reactivity Ratios II / 219
Monomer 1 Monomer 2
rl zt95% r2 f95% Conv. Refs.
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride, a-chloro-
Maleimide
Mal ei mi de
Mal ei mi de
Mal ei mi de
Mal ei mi de
Maleimide
Maleimide, N-hydroxymethyl
Mal ei mi de, 2,3-dimethyl-
N-(2-methacryloxyethyl)-
Mal ei mi de, 2,3-dimethyl-
N-(2-methacryloxyethyl)-
Mal ei mi de, 2,3-dimethyl-
N-(2-methacryloxyethyl)-
Mal ei mi de, N-(2,4-dimethylphenyl)-
Mal ei mi de, N-(2,4-dimethylphenyl)-
Mal ei mi de, N-(2,6-diethylphenyl)-
Mal ei mi de, N-(2,6-diethylphenyl)-
Mal ei mi de, N-(2,6-diisopropylphenyl)-
Mal ei mi de, N(2,6-dimethylphenyl)-
Maleimide, N-(2,6-dimethylphenyl)-
Maleimide, N-(2-bromophenyl)-
Mal ei mi de, N-(2-chlorophenyl)-
Mal ei mi de, N-(2chlorophenyl)-
Maleimide, N-(2-chlorophenyl)-
Maleimide, N-(2-chlorophenyl)-
Maleimide, N-(2-chlorophenyl)-
Maleimide, N-(2-chlorophenyl)-
Maleimide, N-(2-hydroxyethyl)-
Maleimide, N-(2-hydroxyethyl)-
Maleimide, N-(2-hydroxyethyl)-
Maleimide, N-(2-hydroxyethyl)-
Maleimide, N-(2-hydroxyethyl)-
Maleimide, N-(2-hydroxyethyl)-
Maleimide, N-(2-methylphenyl)-
Maleimide, N-(3,5-dimethylphenyl)-
Maleimide, N-(3-dimethylaminophenyl)-
Maleimide, N-(3-methylphenyl)-
Maleimide, N-(3-trifluoromethylphenyl)-
Maleimide, N-(4-bromophenyl)-
Maleimide, N-(4-bromophenyl)-
Maleimide, N-(4-carboxyethylphenyl)
Maleimide, N-(4-carboxyethylphenyl)-
a-chloro-
Maleimide, N-(4-carboxyethylphenyl)-
wchloro-
Maleimide, N-(4-chlorophenyl)-
Maleimide, N-(4-chlorophenyl)-
Maleimide, N-(4-chlorophenyl)-
Maleimide, N-(4-chlorophenyl)-
Maleimide, N-(4-chlorophenyl)-a-chloro-
Maleimide, N-(4-chlorophenyl)-c-chloro-
Maleimide, N-(4-hydroxyphenyl)-
Maleimide, N-(C-hydroxyphenyl)-
Maleimide, N-(4.hydroxyphenyl)-
Maleimide, N-(4-hydroxyphenyl)-
Succinimide, N-vinyl-
Vinyl 2-chlorocyclohexyl ketone
Vinyl 4-chlorocyclohexyl ketone
Vinyl acetate
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinylidene cyanide
Styrene
Butadiene, 2,3-bis(diethyl-phosphono)-
Methacrylate, methyl
Methacrylate, methyl
Piperidinol, 4-, N-methyl-
4-(vinylethynyl)-
Styrene
Vinylidene chloride
Methacrylate, methyl
Acrylate, ethyl
0.021
0.83
0.08
- 0.058
- 0.22
0.4
0.67
0
0.43
0.166
0.17
0.49
0.088 0.036 0.057 0.012
0.464 0.083 0.666 0.056
0.263 0.026 1.745 0.03
1.55 3.06 0.28 1.15
Methacrylate, methyl 1.1
Methacrylic acid 1.33
Acrylate, butyl 0.2
Acrylate, heptyl 0.2
Methacrylate, methyl 0.05
Styrene 0.02
Methacrylate, methyl 0.02
Methacrylate, methyl 0.07
Styrene 0.08
Acrylonitrile 0.338
Acrylonitrile 1.078
Methacrylate, methyl 0.1
Styrene 0.013
Styrene 0.028
Styrene 0.01
Styrene 0.006
Butadiene, 2,3-bis(diethyl-phosphono)- 0.49
Methacrylate, methyl 0.201
Pyrrolidone, N-vinyl- 0.038
Styrene 0.011
Vinyl acetate 0.61
Vinyl acetate 0.88
Methacrylate, methyl 0.09
Methacrylate, methyl 0.28
Styrene 0.19
Methacrylate, methyl 0.22
Methacrylate, methyl 0.1
Acrylate, methyl 0.39
Styrene 0.018
Vinyl chloride 3.29
Methacrylate, methyl - 0.004
Styrene
Acrylate, methyl 0.155
Acrylonitrile 0.743
Butadiene, 2,3-bis(diethyl-phosphono)- 0.41
Vinyl chloride 3.65
Methacrylate, methyl 0.02
Styrene 0.019
Methacrylate, methyl 0.345
Styrene 0.13
Vinyl acetate 1.75
Butadiene, 2,3-bis(diethyl-phosphono)- 0.47
0.022
0.027
0.074
0.38
0.047
0.01
3.58
0.1
0.045
0.048
0.002
0.003
0.005
0.003
0.083
0.01
0.027
0.12
0.17
0.17
0.007
0.18
0.168
0.041
0.052
0.048
0.39
0.03
0.038
0.001
0.1
0.17
0.148
1.7
0.12
0.019
0.098
0.04
0.1
0.07
0.14
2.576
2.5
2.05
0.51
0.746
0.62
0.14
4.78
0.19
10.9
3.62
0.14
2.029
0.956
2.1
0.011
0.038
0.013
0.038
0.12
1.396
0.002
0.046
- 0.014
0.01
2.22
1.63
0.03
1.18
1.57
0.429
0.02
0.04
0.472
0.059
0.684
0.972
0.03
0.026
0.562
0.149
1.392
- 0.059
- 0.011
0.04
0.073
0.008
0.042
0.061
0.03
1.66
0.059
0.214
0.095
0.004
0.006
0.012
0.28
0.089
0.002
0.017
0.037
0.041
0.099
0.006
0.03
0.114
0.021
0.052
0.112
0.044
0.025
0.048
0.001
0.041
0.027
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
284
836
836
260
260
521
5 2 1
82
845
759
251
992
948
2 5 1
251
323
619
619
619
788
788
992
992
992
992
992
863
863
992
853
853
910
910
759
323
323
323
323
323
992
992
747
992
992
628
1030
306
973
973
628
863
759
306
973
973
323
323
323
75
References page II - 290
II / 220 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl
f95%
r2
f95% Conv. Refs.
Mal ei mi de, iV-(4-methoxyphenyl)-a-chloro-
Mal ei mi de, N-(4-methoxyphenyl)-cr-chloro-
Mal ei mi de, N-(Cmethylphenyl)-
Mal ei mi de, N-(4-methylphenyl)-
Maleimide, N-(4-methylphenyl)-c-chloro-
Maleimide, N-(4-methylphneyl)-c-chloro-
Maleimide, N-(Ctolyl)-
Maleimide, N-@-chloroethyl)-a-chloro-
Maleimide, N-(j3-chloroethyl)-a-chloro-
Maleimide, N-(fl-chloroethyl)-cx-chloro-
Maleimide, N-(L-menthoxycarbonylmethyl)-
Maleimide, N-(L-menthoxycarbonyl-
methyl)-
Maleimide, iV-2-bromophenyl-
Maleimide, N-2-chlorophenyl-
Maleimide, N-4-chlorophenyl-
Mal ei mi de, N-[N-wmethylbenzyl)
aminocarbonylpentyl]-
Mal ei mi de, N-[TV-a-methylbenzyl)
aminocarbonylpentyll-
Mal ei mi de, N-[N-a-methylbenzyl)
aminocarbonylpentyll-
Maleimide, N-a-methylbenzyl-
Maleimide, N-a-methylbenzyl-
Mal ei mi de, N-allyl-
Maleimide, N-benzyl-
Maleimide, N-benzyl-
Maleimide, N-benzyl-
Maleimide, N-benzyl-a-chloro-
Maleimide, N-butyl-
Maleimide, N-butyl-
Maleimide, N-butyl-
Maleimide, N-butyl-
Mal ei mi de, N-chloromethyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Mal ei mi de, N-ethyl-a-chloro-
Mal ei mi de, N-ethyl-oc-chloro-
Maleimide, N-hexyl-
Maleimide, N-hexyl-
Maleimide, N-hydroxymethyl-
Maleimide, N-hydroxymethyl-
Mal ei mi de, N-methyl-cr-chloro-
Mal ei mi de, N-methyl-o-chloro-
Maleimide, N-octadecyl-
Maleimide, N-octadecyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Methacrylate, methyl 0.064
Styrene 0.049
Methactylate, methyl 0.34
Vinyl chloride 4.49
Methactylate, methyl 0.029
Styrene 0.019
Acrylate, methyl 0.14
Methacrylate, methyl 0.05
Methacrylate, methyl 0.11
Styrene 0
Mal ei mi de, N-benzyl 0.848
Maleimide, N-phenyl- 0.79
Acrylonitrile
Acrylonitrile
Acrylonitrile
Methacrylate, methyl
0.348 0.044 2.02 0.205
1.08 0.048 0.955 0.095
0.743 0.048 0.972 0.112
0.582 0.359 1.37 0.291
Styrene 0.258 0.25 0.198 0.143
Styrene
Maleimide, N-cyclohexyl-
Maleimide, N-phenyl-
Styrene
Mal ei mi de, N-(L-menthoxycarbonyl-
methyl)-
Methacrylate, methyl
Styrene
Styrene
Methacrylate, methyl
Styrene
Styrene
Vinyl chloride
Butadiene, 2,3-bis(diethyl-phosphono)-
Methacrylate, methyl
Acenaphthalene
But ene, cis-2-
Isobutene
Itaconate, bis(2-ethylhexyl)
Itaconate, di-n-butyl
Itaconate, dimenthyl
Mal ei mi de, N-n-methylbenzyl-
Methactylate, methyl
Methacrylate, methyl
Styrene
Styrene
Isooctene
Methacrylate, methyl
Styrene
Methacrylate, methyl
Styrene
Styrene
Vinyl acetate
Methacrylate, methyl
Styrene
Acrylonitrile
Acrylonitrile
Acrylate, methyl
Butadiene, 2,3-bis(diethyl-phosphono)-
Maleic anhydride
Maleic anhydride
Mal ei mi de, N-(L-menthoxycarbonyl-
methyl)-
Maleimide, N-a-methylbenzyl-
1.07
0.683
0.035
0.474
0.03 0.23 1.28 0.23
0.013 0.031 0.058 0.021
0 0.06 0.42 0.06
-0. 1 0.16 1.41 0.19
60
- 12.7
0.3
0.24
0.11
0
0
0.34
0.21
0.601
0.392
0.19
0.106
0.1
0.162
0
0.13
0
0.1
0.09
0.06
1.45
0.11
0
0.389
0.39
0.103
0.42
1.92
1.08
0.798
0.788 0.5 0.683 0.177
0.189
0.061
0.34
0.158
0.078
0.16
0.04
0.05
0.06
0.221
0.261
0.177
0.177
0.087
106.2
0.04
0.193
0.214
0.048
0.054
0.03
0.04
0.15
0.16
0.11
0.21
0.03
0.03
0.023
0.023
0.052
11.83
0.13
0.141
0.556
0.112
0.83
0.022
0.564
0.107
0.64
0.94
0.59
0.29
0.474
0.798
0.392
0.788
0.056
0.848
0.02
0.24
0.05
1.35
0.57
3
0.41
0.38
0.34
0.318
1.07
1.31
2.26
0.102
- 0.01
0.72
0.53
0.9
1.9
- 0.041
- 0.035
0.017
0.63
0.63
2.482
2.46
0.554
0.05
0.02
- 0.095
0.79
0.145
0.031
0.048
0.117
0.048
0.16
0.06
0.06
0.05
0.087
0.141
0.214
0.5
0.221
1.13
0.04
0.213
0.177
0.066
0.017
0.04
0.05
0.2
0.069
0.053
0.037
0.34
0.04
0.119
0.115
0.048
0.65
0.106
0.261
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
973
973
992
306
973
973
644
974
974
974
1089
1089
915
915
915
1099
1099
1099
1055
1055
1003
1089
348
348
974
1 1 5
1 1 5
50
305
759
992
1039
995
995
1060
1014
975
1055
1100
348
1100
348
995
974
974
348
348
323
323
974
974
863
915
644
759
341
990
1089
1055
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 221
Monomer 1 Monomer 2
rl
&95%
r2
&95% Conv. Refs.
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Mal ei mi de, N-phenyl-a-chloro-
Mal ei mi de, N-phenyl-cc-chloro-
Maleimide, N-propyl-
Maleimido-N,N-dimethylaniline,
4-(2-chlorophenyl)azo
Mesaconate, dibenzyl
Mesaconate, di-set-butyldithiol
Mesaconate, diamyl
Mesaconate, dibenzyldithiol
Mesaconate, dibutyl
Mesaconate, dibutyldithiol
Mesaconate, dicyclohexyl
Mesaconate, diethyl
Mesaconate, diethyldithiol
Mesaconate, dihexyl
Mesaconate, diisoamyl
Mesaconate, diisobutyl
Mesaconate, diisobutyldithiol
Mesaconate, diisopropyl
Mesaconate, diisopropyldithiol
Mesaconate, dimethyl
Mesaconate, dimethyldithiol
Mesaconate, dioctyl
Mesaconate, diphenyl
Mesaconate, diphenyldithiol
Mesaconate, dipropyl
Mesaconate, dipropyldithiol
Mesaconic acid
Methacryl-2-ethyl-4,5,7-trinitro-
9-fluorenone-2-carboxylate
Methacrylamide
Methacrylamide
Methacrylamide
Methacrylamide
Methacrylamide
Methacrylamide
Methacrylamide
Methacrylamide
Methacrylamide
Methacrylamide
Methacrylamide, 1-deoxy-D-glucitol
Methacrylamide, N-(2-hydroxypropyl).
Methacrylamide, N-(4-nitro-4-stilbenyl)-
Methacrylamide, N-(4.stilbenyl)-
Methacrylamide, N-(p-chlorophenyl)-
Methacrylamide, N+methoxyphenyl)-
Methacrylamide, N-@methylphenyl)-
Methacrylamide, N-(p-nitrophenyl)-
Methacrylamide, N-[C(4-methoxy-
phenylacetyloxy)phenyl]-
Methacrylamide, N-methoxymethyl-
Methacrylamide, N-p-bromophenyl-
Methacrylamide, N-p-tolyl-
Methacrylamide, N-phenyl
Methacrylamide, N-phenyl-
Methacrylamide, N-phenyl-
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl chloride
Methacrylate, methyl
Styrene
Vinyl chloride
Styrene
0.3
0.164
0.3
0.065
0.98
1.014
0.91
0.06
-
0.044
0.01
1.284
4.01
0.077
0.002
2.38
0.04
0.017
0.046
0.18
0.098
0.073
0.16
0.016
0.07
- 0.003
0.023
0.657
0.087
0.06
0.05
0.004
0.006
0.026
0.083
0.04
0.05
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Methacrylate, N-(2-hydroxy-
ethyl)carbazolyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylic acid
Methacrylic acid
Methacrylic acid
Styrene
Styrene
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl acetate
Acrylamide, N-(2.(4.hydroxyphenyl)-
ethyl)-
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Methacrylate, 2-hydroxyethyl
0.08
0.02
0.02
0.06
0.05
0.05
0.1
0.06
0.03
0.1
0.07
0.1
0.03
0.04
0.05
0.04
0.07
0.01
0.07
0.15
0.05
0.06
0
0.382 0.014
0.73
0.45
1.27
0.28
1.28
0.41
1.25
1.24
0.4
1.51
1.34
1.29
0.41
1.31
0.44
0.98
0.35
1.23
0.45
0.16
1.22
0.39
1.6
0.63
1.27
0.425
0.49
0.33
1.28
0.2
0.48
1.24
3
1.72
0.56
1.01
0.24
0.085
0.11
0.074
0.25 0.28
0.014
0.2
0.38
0.18
0.26
0.09
0.13
0.17
0.12
0.24
0.09
1.57
1.39
1.65
2.73
1.55
2.006
1.4
1.42
0.25
0.28
0.16
0.95 0.09
0.593
0.7
0.627
0.559
0.549
2.34
0.29
0.047
0.23
0. 05 1
0.048
0.06
1.07
1.474
1.842
0.399
0.337
0.336
0.37
1.47
0.05
0.062
0.019
0.019
0.026
0.14
Methacrylate, methyl 0.265 0.009 1.678 0.048
Methacrylate, methyl 0.38 0.2 3.48 0.2
Methacrylate, methyl 0.78 0.2 1.43 0.2
Methacrylate, methyl 0.28 0.2 1.95 0.2
Acrylonitrile 0.71 0.19 0.381 0.085
Methacrylate, methyl 0.56 0.12 1.42 0.096
323
328
992
1026
328
992
328
306
973
973
305
747
658
624
658
624
658
624
658
658
624
658
658
658
624
658
624
658
624
658
658
624
658
624
1 0 2 1
703
316
54
5 5
190
527
5 5
316
316
609
609
258
965
342
342
352
352
352
352
1 0 5 1
227
968
968
968
352
352
References page II - 290
II / 222 FREE RADICAL COPOLYMERlZATlON REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl
ZlY95%
r2
Zt95% Conv. Refs.
Methacrylamide, N-phenyl-
Methacrylamide, 1 -deoxy-D-glucitol
Methacrylamide, 1-deoxy-n-glucitol
Methacrylamide, N-p-nitrophenyl-
Methacrylate, 2-ethylhexyl
Methacrylate, ferrocenylmethyl
Methacrylate, ferrocenylmethyl
Methacrylate, octyl
Methacrylate, potassium 18-crown-
6-ether
Methacrylate, tert-butyl
Methacrylate, (- )-menthyl
Methacrylate, (2,2-dimethyl-
1,3-dioxolane-4-yl)methyl
Methacrylate, 1,1-diphenylethyl
Methacrylate, 1 -naphthyl
Methacrylate, 1-naphthyl
Methacrylate, 1-naphthyl
Methacrylate, 1-naphthyl
Methacrylate, 2,2,6,6-tetramethyl-
4-piperidinyl
Methacrylate, 2,2,6,6-tetramethyl-
4-piperidinyl
Methacrylate, 2,2,6,6-tetramethyl-
4-piperidinyl
Methacrylate, 2,2,6,6-tetramethyl-
4-piperidinyl
Methacrylate, 2,2-dimethylaminoethyl
Methacrylate, 2,3-epithiopropyl
Methacrylate, 2,3-epithiopropyl
Methacrylate, 2,3-epithiopropyl
Methacrylate, 2,3-epithiopropyl
Methactylate, 2,4,6-trinitrophenyl
Methacrylate, 2,4-dinitrophenyl ethyl
Methacrylate, 2,4-dinitrophenyl
Methacrylate, 2,6-(diphenyl)phenyl
Methacrylate, 2-(2-carboxybenzoyl-
oxy)ethyl
Methacrylate, 2-(2-carboxybenzoyl-
oxy)ethyl
Methacrylate, 2-(N,N-dimethyl-
carbamoyloxy)ethyl
Methacrylate, 2-(N,N-dimethyl-
carbamoyloxy)ethyl
Methacrylate, 2-(N,N-dimethyl-
carbamoyloxy)ethyl
Methacrylate, 2-(N,N-dimethyl
carbamoyloxy)ethyl
Methacrylate, 2-(N,N-dimethyl-
carbamoyloxy)ethyl
Methacrylate, 2-acetoxyethyl
Methacrylate, 2-acetoxyethyl
Methacrylate, 2-acetoxyethyl
Methacrylate, 2-acetylsalicylicoyloxy-
3-hydroxypropyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-chloro-2,3,3,3-fluoro-
prowl
Styrene 0.88
Methacrylate, methyl 0.04
Styrene 0.005
Methacrylate, methyl 0.29
Methacrylate, 2-hydroxypropyl 0.083
Maleic anhvdride
Pyrrolidone: N-vinyl-
0.33
2.57
Methacrylonitrile 0.61
Acrylonitrile 0.175
Methacrylate, 2-chloroethyl 0.98
Acenaphthalene 0.316
Methacrylate, methyl 1.1
0.17 1.24
4.2
2.09
0.2 5.05
0.006 4.56
0.65 0.24
2.77 0.073
0.05 0.75
0.018 0.07
0.22 1.18
0.085 2.48
0.9
0.11
0.55
Y 179
Y 645
807
Methacrylate, methyl 0.77 0.72
Methacrylate, methyl 1.8 0.73 0.77
Methacrylate, methyl 1.68 0.38 0.809
Methacrylate, methyl 2.62 0.47 0.851
Methacrylate, methyl 1.52 0.61
Acrylonitrile 1 4 0.02
0.14
0.078
0.084
761
Y 752
Y 752
Y 752
761
664
Styrene 0.3 0.63 664
Vinyl acetate
Vinyl methyl ketone 0.53 0.41 664
Methacrylate, methyl
Acrylate, methyl
Methacrylate glycidyl
Methacrylate, methyl
Styrene
Methacrylate, 2-naphthyl
Acrylate, N-(2-hydroxyethyl)-oxy)
3,6-dichloro
Methyacrylate, N-(2-hydroxyethyl)-
3,6-dichloro
Methacrylate, methyl
Methacrylate, butyl
1.01 0.54 0.42
2.81 0.34
0.78 0.81
0.97 0.83
0.28 0.41
0.02
1.207
1.112
0.071
0.85
0.032 0.115
0.026 0.126
0.004 1.42
0.75
0.029
0.026
0.06
N 691
787
787
787
787
Y 744
Y 736
Y
1079
1009
Methacrylate, butyl 0.85 0.75 1 0 4 1
Acrylate, butyl 1.89 0.47 600
Acrylate, methyl 1.32 0.22
Acrylonitrile 1.89 0.38 600
Butadiene 0.35 1.06
Methacrylate, methyl 0.42 0.59 600
Methacrylate, 2-hydroxyethyl 0.99 0.02 1.02
Methacrylate, methyl 1.12 0.06 0.94
Styrene 0.58 0.04 0.44
N-Vinylpyrrolidone 0.85 0.34
Acrylate, ethyl
Acrylonitrile
Methacrylate, methyl
Pyrrolidone, N-vinyl-
Styrene
Vinyl butyl ether
Acrylate, butyl
2.7 0.37
2.38 0. 3 1
1.18 0.79
2.44 0.02
0.41 0.32
13.7 0
0.221 0.636 0.079
13.7 0.2
0.06
0.2
0.18
0.28
0.096
0.04
0.006
0.01
0.02
0.02
0.304
N 352
258
258
968
Y 708
Y 325
Y 325
N 44
Y 808
664
N 346
N 346
N 346
1080
657
657
657
657
657
657
N 927
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 223
Monomer 1 Monomer 2
rl
k95%
r2
Lk95% Conv. Refs.
Methacrylate, 2-chloro-2,3,3,3-fluoro-
Prom1
Methacrylate, 2-chloro-2,3,3,3-fluoro-
prowl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-ethylhexyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methactylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, methyl 0.583
Styrene 0.243
Acrylate, methyl
Acrylonitrile
Methacrylate, benzyl
Methacrylate, butyl
Methacrylate, isobutyl
Methacrylate, methyl
Methacrylate, methyl
Metbacrylate, phenyl
Methacrylate, terr-butyl
Styrene
Styrene
Styrene
Methacrylate, tributyltin
Methacrylate, 2-hydroxypropyl
Acetamide, N-(4-methacryloyloxy-
phenyl)-2-(4-methoxy)
Acetanilide, 4-(2-(methacryloyloxy)
ethyloxy)
Acetanilide, 4-(2-(methacryloyloxy)
hexyloxy)
Acetanilide, 4-(methacryloyloxy)-
Acrylamide
Acrylamide
Acryl ami do, 2-,2-methylpropanesulfonic
Acrylate, butyl
2.19
1.3
0.989
0.82
0.85
0.97
0.48
1.02
1.18
0.341
0.34
0.23
0.53
0.083
0.61
1.39 0.67
1.19 0.87
0.78
1.89
0.98
0.86
4.75
Acrylate, ethyl 11.21
Acrylate, furfuryl 1.35
Acrylate, methyl 8.61
Acrylonitrile 1
Acryloxymethylpentamethyl disiloxane 0.86
Methacrylate, 2-hydroxypropyl 0.55
Met hacryl ami de, N-(4~nitro-4-stilbenvl)- 1. 474
Methacrylamide, N-(4-stilbenyl)-
Methacrylamide, N-[4-(4-methoxy-
phenylacetyloxy)phenyl]-
Methacrylate, 2-acetoxyethyl
Methacrylate, dodecyl
Methacrylate, dodecyl
Methacrylate, dodecyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methactyloxymethylpentamethyl
disiloxane
Pyridine, 2-vinyl-
Pyridine, 3-vinyl-
Pyridine, 4-vinyl-
Pyrrolidone, N-vinyl-
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Acrylamido, 2-, 2-methylpropane-
sulfonic
Acrylate, butyl
Acrylate, butyl
Acrylate, ethyl
Acrylate, ethyl
1.842
1.47
0.05
0.062
1.94
0.05
0.14
0.9
0.09
0.189
0.88
0.005
0.2
0.52
1.82
0.593
0.7
0.29
0.047
0.23
1.02
11.2
1.6
0.8
0.63
0.81
1.5
0.97
0.01 0.99
0.7
0.5
0.8
0.824
0.192
0.75
0.33
0.02
0.076
1.02
0.01
0.09
0.56
0.69
0.62
4.841
0.54
0.856
0.65
1.65
0.53
0.59
1.65
0.89
0.04
0.01
0.04
0.133
0.03
0.018
0.64
0.73
0.9
0.019
0.44
0.332
0.57
0.5
0.59
0.53
0.5
1.03
0.16
0.04
0.09
0.046
0.02
0.006
5.35 0.32 0.171 0.041
3.3 6.82 0.24 0.16
13.32 1.05 0.213 0.054
9.08 3.95 0.207 0.045
1.17
0.15
0.098
0.041
0.14
0.18
0.21
0.11
0.075
0.08
0.16
0.006
4.2
0.43
0.08
8.28
0.984
0.121
0.29
0.14
1.068
1.086
1.014
1.156
0.55
0.785
0.98
0.35
0.345
0.42
0.2
4.56
1.49
0.395
0.068
0.042
0.02
0.064
0.082
0.083
0.22
0.046
0.048
0.444
0.18
0.11
0.008
0.19
0.036
N
N
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
N
Y
Y
N
N
N
Y
N
Y
Y
Y
Y
Y
927
927
726
382
179
179
179
179
382
179
179
179
179
382
945
692
1 0 5 1
1096
1096
1096
689
928
618
358
358
1063
358
689
822
686
342
342
1 0 5 1
346
837
837
837
350
358
710
822
342
342
342
840
346
350
463
878
878
903
903
618
333
662
333
662
References page II - 290
II / 224 FREE RADICAL COPOLYMERlZATlON REACTIVITY RATIOS
TABLE 1. cont' d
Monomer 1 Monomer 2
0 &95% r2 I ! z95% Conv. Refs.
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl-, methyl
Methacrylate, 2-naphthyl-, methyl
Methacrylate, 2-naphthyl-, methyl
Methacrylate, 2-naphthyl-, methyl
Methacrylate, 2-sulfonic acid)ethyl
Methacrylate, 2-sulfonic acid)ethyl
Methacrylate, 2-sulfonic acid)ethyl
Methacrylate, 2-sulfonic acid)ethyl
Methactylate, 2-methoxyethyl
Methacrylate, 3,5-dimethyladamantyl
Methacrylate, 3,5-dimethyladamantyl
Methacrylate, 3,5-dimethyladamantyl
Methacrylate, 3,5-dimethyladamantyl
Methacrylate, 3-methoxy-2-hydroxypropyl
Methacrylate, 5-oxo-pyrrolidinylmethyl
Methactylate, 5-oxo-pytrolidinylmethyl
Methacrylate, P-(2-benzothiazolylthio)
ethyl
Methacrylate, N-(2-hydroxyethyl)-
3,6-dichlorocarbazolyl
Methacrylate, N-(2-hydroxyethyl)-
carbazolyl
Methacrylate, iV-(2-hydroxyethyl)-
carbazolyl
Methacrylate, N-(2-hydroxyethyl)-
carbazolyl
Methacrylate, N-wbenzothiazolonylmethyl
Methacrylate, N-ethyl-
3-hydroxymethylcarbazolyl
Methacrylate, N-ethyl-3-
hydroxymethylcarbazolyl
Methacrylate, N-methyl-N-phenyl-
2-aminoethyl
Methacrylate, N-methyl-N-phenyl-
2-aminoethyl
Methacrylate, N-methyl-N-phenyl-
2-aminoethyl
Acrylate, methyl
Acryloyl chloride
Methacrylate, 2-ethylhexyl
Methacrylate, 2-ethylhexyl
Methacrylate, 2-hydroxyethyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, methyl
Methacrylate, tributyltin
Methacrylic acid
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Itaconate, mono-methyl
Itaconate, mono-methyl
Itaconate, mono-methyl
Itaconate, mono-methyl
Methactylate, 2,4,6-trinitrophenyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Styrene
Styrene
Styrene
Acrylate, ethyl
Methacrylate, ethyl
Styrene
Vinylidene chloride
Styrene
Acrylonitrile
Methactylate, methyl
Styrene
Vinyl chloride
Acrylamide
Methacrylate, methyl
Styrene
Vinyl chloride
Methacrylate, 2,4-dinitrophenyl
Acryl-2-ethyl-4,5,7-trinitroflourenone
Acrylate, 2,4-dinitrophenyl
Methacryl-2-ethyl-4,5,7-trinitro-
9-fluorenone
Methacrylate, methyl
Acryloyl-P-hydroxyethyl-
3$dinitrobenzoate
Methacryloyl-fi-hydroxyethyl-
3,5-dinitrobenzoate
Acryloyloxy, 2-, benzoic acid
Methactylic aci d
Methacryloyloxy, 2-,benzoate, methyl
7. 335
1.79
4. 56
4. 56
1. 82
2. 35
2. 35
1. 878
1. 844
1. 055
1. 81
0. 31
1. 17
1.02
0. 76
0. 64
0. 52
0. 59
0. 223
0. 189
0. 083 0. 007
0. 18
0. 18
0. 006
0. 006
0. 13
0. 13
0. 056
0. 039
0. 04
0. 275
0. 007
0. 007
0. 007
0. 005
0. 017
0. 517
0. 2
0. 19
0. 18
0. 24
0. 16
0. 14
0. 02
0. 055
-
0. 013
0. 29
0. 083
0. 083
0. 55
0. 158
0. 158
0. 245
0. 267
0. 402
0. 728
0. 99
0. 15
0. 094
0. 06
0.01
0.31
0. 36
0. 135
0. 04
0. 2
0. 099
0.1
0.16
0. 42
0. 21
0. 028
0.11
0. 85
2. 57
2. 53
1. 91
4. 41
3. 83
0. 534
0. 113
0. 321
0. 576
0. 216
3. 2
2
0. 6
3. 6
0. 48
1. 3
0. 45
0. 63
1. 85
3. 98
0. 694
0. 411
0. 26
0. 34
0. 48
0. 27
0. 6
0. 76
0. 57
0. 099
0. 126
0. 098
0. 477
0. 422
0.16
0. 059
0. 023
0. 055
0. 051
0. 048
0. 025
0. 16
0. 117
0. 195
0. 225
0. 23
0. 16
0. 21
8. 87
0. 087
0. 033
0. 75
0. 602
0. 581
0. 532
0. 614
0. 623
0. 56
0. 786
0. 486
0. 61
0. 384
0. 3
1
0. 37
0. 22
0. 46
0. 19
0. 68
0. 89
0. 21
0. 04
0. 421
0. 342
0. 64
0.01
0. 04
0. 14
0. 04
0. 033
0. 013
0. 126 0. 026 1.112 0. 026
0. 773 0. 096 0.102 0. 022
0. 243 0. 034 0.186 0. 009
0. 63 0. 041 0. 382 0. 014
0. 6 0. 02 0. 5 0.01
1. 425 0. 09 0. 103 0.015
0. 729 0. 051 0. 554 0.019
0. 22 0. 03 1. 82 0. 2
0. 2 0.01 2. 16 0. 18
0. 55 0. 04 1.11 0. 18
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
333
649
692
708
686
692
708
692
708
333
945
886
611
611
611
611
613
613
613
613
744
540
760
760
760
760
760
540
924
924
924
924
564
564
564
564
918
335
335
335
335
689
633
633
741
736
703
716
703
887
701
701
651
651
651
TABLE 1. contd
copolymer Reactivity Ratios II / 225
Monomer 1 Monomer 2
r1
f95%
r2
Zk95% Conv. Refs.
Methacrylate, N-methyl-N-phenyl-
2-aminoethyl
Methacrylate, N-methyl-N-phenyl-
2-aminoethyl
Methacrylate, qsdimethylbenzyl
Methacrylate, a-naphthoyloxy-, ethyl
Methacrylate, acetonyl
Methacrylate, ally1
Methacrylate, amyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Metbacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzylmethylaminoethyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Metbacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, chloromethyl
Methacrylate, chloromethyl
Methacryloyloxy, 2-,benzoic acid 0.2
Styrene 0.58
Methacrylate, methyl
Styrene
Styrene
Itaconate, bis(tri-n-butyltin)
Styrene
Acrylonitrile
Ally1 chloride
Maleic anhydride
Maleic anhydride
Methacrylate, 2-chloroethyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, phenyl
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Vinylidene chloride
Methacrylate, methyl
Acetylene, phenyl-
Acrylate, butyl
Acrylate, ethyl
Acrylic acid
Acrylic acid, cc-bromo-
Acrylonitrile
Carbamate, N-phenyl-, ally1
Metbacrylate, 2-(2-carboxy-
benzoyloxy)ethyl
Methacrylate, 2-(2-carboxy-
benzoyloxy)ethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, ethyleneglycol-
N-phenylcarbamate
Methacrylate, glycidyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylic acid
Methacrylic acid
Methacrylonitrile
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, o-chloro-
Styrene, p-chloro-
Styrene p-chloro-
Styrene chloromethyl-
Styrene p-octylamine sulfonate
Thioindigoid
Vinyl acetate
Vinyl chloride
Vinylidene chloride
Methacrylate, methyl
Styrene
0.92
0.242
0.505
1.08
0.46
0.96
58.7
- 0.075
1.068
1.112
1.05
1.38
0.67
0.658
0.467
0.51
0.42
0.3
0.5
3.3
0.296
1.7
2.2
2.43
3.53
0.85
0.98
0.418
0.75
0.75 0.85
1.086
0.158
0.158
0.395
0.85
2.11
1.2
1.26
1.15
0.75
0.31
2.52
0.47
0.64
0.64
0.59
0.32
0.564
0.38
0.7
11.5
30.18
13.5
2.07
1.02
0.298
0.01
0.02
0.018
0.115
0.2
0.1
0.088
0.042
0.093
0.06
0.084
0.048
0.38
0.123
0.39
0.42
0.2
0.02
0.007
0.007
0.03
0.08
0.12
0.12
0.07
0.2
1.1
0.1
0.131
14.47
0.18
0.16
0.03
2.6
0.44
0.81
0.216
0.285
0.038
0.52
0.2
0.02
0.372
0.989
0.808
0.93
0.78
1.42
0.463
0.435
0.45
0.48
0.8
0.45
0.34
0.523
0.21
0.3
0.22
0.24
0.13
0.291
0.329
0.85
0.82
2.35
2.35
0.299
0.94
0.52
1.27
0.8
0.73
0.56
0.56
- 0.05
0.52
0.63
0.54
0.74
1.24
1.025
1.46
1.5
0.5
- 0.003
0.05
0.35
0.477
0.208
0.08
0.04
0.043
0.041
0.11
0.1
0.093
0.098
0.03
0.09
0.041
0.026
0.32
0.134
0.17
0.21
0.039
0.041
0.13
0.13
0.06
0.07
0.16
0.2
0.15
0.12
1.09
0.1
0.124
0.15
0.03
0.029
0.006
N
N
Y
Y
N
Y
Y
Y
Y
N
Y
Y
Y
Y
N
Y
Y
Y
Y
N
N
N
N
N
Y
N
N
Y
Y
Y
Y
651
651
761
1102
958
940
1 7 9
2 3
438
720
720
179
1 1 1
32
540
32
1 1 1
179
487
540
602
806
432
1 0 8 1
565
1 8 7
690
1 8 7
733
1 6 5
833
1009
1 0 4 1
179
692
708
833
224
30
844
1 8 7
224
44
179
43
463
530
530
835
558
872
966
1035
817
1007
1 6 5
519
3
712
712
References page II - 290
II / 226 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl f95%
r2
Zt95% Conv. Refs.
Methacrylate, cyanomethyl
Methacrylate, cyanomethyl
Methacrylate, cyclohexyl
Methacrylate, cyclohexyl
Methacrylate, decyl
Methacrylate, di-, di-n-butylstannyl
Methacrylate, di-, di-n-butylstannyl
Methacrylate, di-, zinc
Methacrylate, di-, dicyclopentadienyl-
titanate
Methacrylate, di-, dicyclopentadienyl-
titanate
Methacrylate, di-, ethylene glycol
Methacrylate, di-, triethyleneglycol
Methacrylate, di-, triethyleneglycol
Methacrylate, diethylaminoethyl
Methacrylate, diethylaminoethyl
Methacrylate, dimethylaminoethyl
Methacrylate, dimethylaminoethyl sulfate
Methacrylate, diphenylmethyl
Methacrylate, diphenylmethyl
Methacrylate, diphenylmethyl
Methacrylate, diphenylmethyl
Methacrylate, diphenylmethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyleneglycol-
N-phenylcarbamate
Methacrylate, ethyleneglycol-
N-phenylcarbamate
Methacrylate, ferrocenylmethyl
Methacrylate, ferrocenylmethyl
Methacrylate, ferrocenylmethyl
Methacrylate, ferrocenylmethyl
Methacrylate, ferrocenylmethyl
Methacrylate, furfuryl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, methyl 0.73
Styrene 0.28
Methacrylate, tributyltin 0.891
Styrene 0.57
Oxazolidone, N-vinyl- 12.19
Maleic anhydride 0.012
Vinyl acetate 0.013
Ethylene 40
Acrylate, di-, copper 0.89
Acrylate, di-, nickel 0.65
Styrene
Carbamate, N-phenyl-, ally1
Methacrylate, ethylene-glycol
N-phenylcarbamate
Methacrylate, methyl
Methacrylic acid
Methacrylate, methyl
Acrylamide
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, dodecyl l
Methacrylate, methyl
Styrene
Ally1 acetate
Ally1 alcohol
Methacrylate, 2-(sulfonic acid)ethyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, tributyltin
Methacrylic acid
Methacrylonitrile
Styrene
Styrene
Styrene
Styrene
Styrene, o-chloro-
Styrene, p-chloromethyl-
Vinyl acetate
Vinylidene chloride
Methactylate, butyl
0.67
0.504
0.59
0.08 0.39
0.034
0.24
1.44
2.34
1.2
1.9
0.5
0.8
0.7
1.07
0.3
81.27
107.4
1,
0.245
0.267
0.085
1.59
0.154
0.2
0.1
1.93
5.3
0.007
0.005
0.843
0.63
0.699
0.52
1.6
0.8
11.2
0.81
0.528
- 0.57
- 0.02
2
1.878
1.844
1.08
1
0.601
0.71
0.83
0.36
0.26
0.29
0.33
0.45
0.36
131.8
2.18
0.299
0.09
0.123
0.05
0.12
29.8
0.1
1.08
1.16
0.299
0.57
0.46
0.55
0.67
0.65
0.55
1.34
1.29
- 0.77
0.353
0.395
Methacrylate, di-, triethyleneglycol 0.24 0.59
Acrylate, methyl 0.042
Acrylonitrile 0.82
Styrene - 0.01
Styrene 0.01
Vinyl acetate 1.52
N-Vinylpyrrolidone 5.16
Acrylate, 2-ethylhexyl 2.41
Acrylate, 4-acetylphenyl 0.644
Acrylate, butyl 2.16
Acrylate, isobutyl 1.24
Acrylate, terr-butyl 2.096
Acrylonitrile 0.85
Acrylonitrile 1.32
Methacrylate, 2,3-epithiopropyl 0.81
Methacrylate, butyl 0.94
Methacrylate, methyl 0.52
Methacrylate, methyl 0.934
0.085
0.42
0.14
1.4
0.15
1.13
0.46
0.13
0.57
0.12
0.443
0.05
0.06
0.06
0.085
3.6
0.2
0.0036
0.09
0.292
0.083
0.282
0.463
0.95
0.14
0.78
0.85
0. 7 1
0.726
0.11
0.041
0.136
0.28
1.35
0.016
0.036
0.399
0.144
0.395
0.586
- 0.052
0.024
0.013
0.19
1.09
0.95
0.019
0.011
0.428
0.088
0.049
0.008
0.018
0.15
0.128
1.47
0.051
0.05
0.05
0.82
1.92
0.056
0.039
0.19
0.607
0.04
0.062
5.29
0.02
0.35
0.04
3.63
0.02
0.13
0.141
0.052
0.026
0.079
0.06
0.03
0.08
0.042
Y
Y
N
Y
Y
Y
Y
N
Y
Y
Y
Y
N
N
Y
Y
N
N
N
N
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
Y
Y
625
625
945
179
36
954
949
935
876
876
262
833
833
1 0 8 1
1 6
1 0 8 1
1052
837
837
837
761
1 7 9
210
210
564
692
708
32
844
87
945
820
44
179
530
530
570
558
1035
210
3
833
833
293
325
293
576
293
1050
674
1012
674
674
814
114
433
787
224
1 1 3
226
TABLE 1. contd
copolymer Reactivity Ratios II / 227
Monomer 1 Monomer 2
rl
*95%
r2
*95% Conv. Refs.
Methactylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methactylate, hexyl
Methacrylate, hydroxyethyl
Methacrylate, hydroxyethyl
Methacrylate, iso-butyl
Methacrylte, isobomyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, m-chlorophenyl
Methacrylate, m-nitrophenyl
Methacrylate, methoxymethyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylic acid
N-Vinylpytrolidone
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Vinyl phenyl ketone
Vinyl, mono-, ethylene glycol ether
Styrene
Methacrylate, tetra(2-hydroxypropyl)
ethylenediamine
Methacrylate, tributyltin
Butadiene, 2-chloro-
Styrene
Acetylene, phenyl-
Acrylic acid
Acrylonitrile
Furan, 2-vinyl-5-methyl
Methacrylate, 2-chloroethyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylic acid
Methacrylonitrile
Methacrylonitrile
Styrene
Styrene
Styrene
Styrene
Styrene
Vinyl acetate
Styrene
Styrene
Styrene
2-Oxazoline, 2-isopropenyl-
3-Pyridazone, 2-vinyl
3Pyridazone, 2-vinyl-6-methyl-
3-Pyridazone, 2-vinyl-6-methyl-
4,5-benz-3-
3Pyridazone, 2-vinyl-6-phenyl-
4H-1,3-Oxazinium FsCSOs, 3-methyl-
2-vinyl-5,6-dihydro-
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acrolein
Acrolein
Acrolein, methyl-
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acryl ami de, 2-chloro-N,N-dimethyl-
1.05
0.501
1.2
4.29
0.16
0.539
0.46
0.54
0.55
0.74
0.73
0.514
0.719
4.41
0.44
0.606
0.027
0.1
0.498
0.03
0.04
0.08
0.1
0.284
0.098
0.8
0.688
0.98
0.003
0.54
0.278
0.47
0.44
0.45
0.31
0.11
0.435
0.697
0
0.58
1.44
2.33
0.9
0.24
1.9
0.68
1.05
0.105
1.014
1.88
1.2
0.488
0.47
0.68
0.94
0.271
0.58
0.42
0.4
0.74
29.7
0.209
0.185
0.586
0.69
0.63
0.16
1.65
0.13
0.416
0.185
0.088
0.3
0.22
0.044
0.064
0.07
0.029
0.05
0.12
0.036
24.16
0.013
0.054
0.069
0.02
0.282
1.8
0.61
0.27
1.03
0.217
0.716
0.85
0.62
0.89
0.92
2.01
0.74
0.43
0.509
0.56
0.5
0.55
0.47
0.06
0.375
0.44
0.395
0.99
1.56
0.3
0.27
0.58 0.49
0.37 0.31
0.36
0.38
0.44
2.65
1.18
2.1
- 0.06
1.5
1.111
1.136
1.33
0.1
2.34
3
2.53
3
2.71
0.04
0.04
0.16
0.095
0.05
0.4
0.17
0.09
0.45
0.398
1.05
0.99
2.25
0.19
0.71
0.01
1.69
0.2
0.07
0.76
0.59
0.4
2.29
0.53
0.82
0.9
0.159
0.076
0.16
0.018
0.07
0.086
0.02
0.04
0.045
0.033
0.07
1
0.424
0.06
0.45
0.037
0.169
0.14
0.08
0.15
0.07
0.08
0.014
0.22
0.05
0.16
0.014
0.07
0.14
0.15
26.56
0.016
0.12
0.3
0.44
0.09
1.07
0.502
Y
N
N
Y
N
N
N
Y
Y
Y
N
N
Y
Y
Y
N
Y
N
N
Y
Y
Y
Y
Y
N
N
Y
Y
Y
N
N
N
N
Y
463
639
224
1017
114
217
225
225
463
849
893
999
946
780
1 7 9
996
945
1057
806
565
847
1 6 5
1105
179
30
541
639
847
44
44
179
463
463
487
541
1 6 5
1 7 7
1 7 7
821
894
897
897
897
897
909
326
326
575
984
984
984
357
443
732
291
292
589
314
314
314
691
917
References page II - 290
II / 228 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1
f95%
r2
It95% Conv. Refs.
Methacrylate, methyl
Metbacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methactylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Metbacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methactylate, methyl
Acrylamide, N,N-dimethyl-
Acrylamide, N,N-dimethyl-
Acrylamide, NJ-dimethyl-
Acrylamide, NJ-dimethyl-
Acrylamide, N-methyl-
Acrylamide, N-methylol-
Acryl ami de, N-methyl01
Acrylamide, N-octadecyl-
Acrylamide, N-tert-butyl-
Acryl ami de, a-fluoro-
Acryl ami do, l-,-I-deoxy-~glucitol
Acrylate, a-benzyl-, methyl
Acrylate, a-chloro-methyl
Acrylate, ferrocenylmethyl
Acrylate, 2-(O-ethyl methyl-
phosphonoxy)-, methyl
Acrylate, 2-chloroethyl
Acrylate, 2nitrobutyl
Acrylate, P-acetoxymethyl-, methyl
Acrylate, a-(O-ethyl methylphos-
phenoxy)
Acrylate, a-[2,2-bis(carbomethoxy)-
ethyl]-, methyl
Acrylate, cl-acetoxy-, ethyl
Acrylate, a-benzyl-, methyl
Acrylate, cc-chloro-, methyl
Acrylate, cr-cyano-, methyl
Acrylate, a-cyano-, methyl
Acrylate, a-hydroxymethyl-, ethyl
Acrylate, cr-phenoxymethyl-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, wphenyl-, methyl
Acrylate, wtetrafluoropropyloxymethyl-,
methyl
Acrylate, a-trifluoromethyl-, methyl
Acrylate, a-trifluoromethyl-, methyl
Acrylate, wtrifluoromethyl-, methyl
Acrylate, benzyl
Acrylate, butyl
Acrylate, butyl
A&ate, butyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ferrocenylmethyl
Acrylate, heptafluorobutyl
Acrylate, heptyl
Acrylate, isobutyl
Acrylate, isobutyl
Acrylate, m-nitrophenyl
Acrylate, methyl
Acrylate, o-chlorophenyl
Acrylate, octadecyl
Acrylate, p-bromophenyl
Acrylate, p-chlorophenyl
Acrylate, p-chlorophenyl
Acrylate, methylphenyl
Acrylate, phenyl
Acrylate, phenyl
Acrylate, cc-p-chlorobenzyl-, methyl
Acrylate, cr-p-methoxybenzyl-, methyl
Acrylic acid
Acrylic acid, a-bromo-
Acrylonitrile
Acrylonitrile, a-trifluoromethyl-
1.65
2.15
2.8
2.64
1.14
1.62
1.62
4.119
0.25
2.13
3.75
3.9
0.11
2.9
0.73
2.15
1.19
0.91
0.73
3.7
1.65
2.36
0.31
0.21
0.068
1.26
1.13
0.21
0.3
1.43
1.8
3.2
2.3
2.23
0.92
2.86
1.88
1.83
2
2.04
2.8
1.387
2.51
1.04
4.1
0.928
2.15
1.25
2.477
0.926
1.01
1.09
1.45
1.56
1.54
1.87
1.71
0.418
0.37
1.322
1.11
0.16
0.08
0.1
0.15
0.09
0.07
0.136
0.24
0.19
0.09
0.04
0.12
0.12
0.23
0.24
0.02
0.014
0.17
0.038
0.23
0.5
0.2
0.14
0.2
0.32
0.4
0.28
0.19
0.072
0.13
0.08
0.5
0.248
0.04
0.024
0.056
0.132
0.275
0.14
0.222
0.109
0.02
0.05
0.12
0.41
0.57
0.59
0.21
0.05
0.7
0.7
0.42
2.83
0.148
0.05
0.09
1.92
0.08
0.44
0.37
0.27
0.24
0.44
0.04
0.608
0.173
1.13
0.03
0.135
1:34
0.755
0
0
0.61
0.17
0
0.1
0.19
0.13
0.11
0.43
0.47
0.28
0.22
0.024
0.177
0.46
0.29
0.135
1.04
0.4
0.4
0.464
0.191
0.235
0.3
0.223
0.45
0.416
0.255
0.13
1.73
0.11
0.138
0.016
0.15
0.08
0.09
0.21
0.72
0.11
0.081
0.09
0.01
0.08
0.25
0.04
0.02
0.022
0.19
0.01
0.016
0.062
0.061
0.18
0.1
0.1
0.2
0.15
0.018
0.07
0.05
0.064
0.084
0.02
0.04
0.02
0.135
0.12
0.07
0.014
0.023
0.036
0.041
0.034
0.008
0.096
0.037
0.048
N
N
N
N
N
Y
Y
N
N
N
N
Y
Y
Y
N
Y
N
Y
Y
N
N
Y
N
Y
N
N
Y
Y
N
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
170
315
315
691
691
593
596
290
709
823
258
610
3 1
293
882
790
234
1 0 9 1
851
1092
244
610
6
1 4 1
182
1027
1048
1 4 1
49
1047
681
825
825
277
30
639
(87
30
469
8 7
293
206
980
30
639
1074
324
621
290
1074
1074
621
1074
621
672
905
905
964
733
216
681
TABLE 1. contd
Copolymer Reactivity Ratios II / 229
Monomer 1 Monomer 2 rl It95%
rz
&95% Conv. Refs.
Methacrylate, methyl Acrylonitrile, cr-perfluoropropyl- 1.9
Methacrylate, methyl Acryloyl chloride 0.48
Methacrylate, methyl Acryloyl chloride 0.42
Methacrylate, methyl Ally1 acetate . 99.24
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Ally1 acetate
Ally1 alcohol
Ally1 chloride
Benzocyclobutane, cc-methylene-
Benzocyclobutene, 4-vinyl-
Benzofuran, 2-vinyl-
Benzophenone, 2-hydroxy-
4-(methacryloxy)-
Benzothiazole, vinylmercapto-
Bicyclo[2,2,l]hept-2-ene-
5,6-dicarboximide, N-benzyl
Bicyclo[2,2,l]hept-2-ene-
5,6-dicarboximide, N-benzyl
Butadiene
Butadiene
Butadiene
Butadiene, 2,3-dichloro-
Butadiene, 2-chloro-
Butadiene, 2-fluoro-
Carbamate, N-vinyl-r-butyl-
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Citraconimide, N-(4-acetoxyphenyl)
Citraconimide, N-(4-chlorophenyl)-
Citraconimide, N-(4-ethoxycarbonyl-
phenyl)-
Citraconimide, N-(4-methoxyphenyl)-
Citraconimide,
N-( 1 -menthylcarboxylatomethyl)-
Citraconimide, N-benzyl-
Citraconimide, N-butyl-
Citraconimide, N-ethyl-
Citraconimide, N-hexyl-
Citraconimide, N-isobutyl-
Citraconimide, N-isopropyl-
Citraconimide, N-methyl
Citraconimide, N-phenyl
Citraconimide, N-propyl
Citraconimide, N-tert-butyl-
Citraconimide, N-tolyl-
Cyclopentene, 4-,-1,3-dione
Cyclopropane, l,l-bis(ethoxy-
carbonyl)2-vinyl-
Cyclopropane, l,l-bis(ethoxy-
carbonyl)-2-vinyl-
Diallyl melamine
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallylcyanamide
Diallylcyanamide
Dimethyleneheptanedioate,
2,6-dimethyl
Ditiane, 2-methylene- 1,3-
Ethylene
2 3
18.79 6.5
0
1.51
0.05
- 2.42
0
- 1.62 2.9
0.32
0.6
0.006
0.315
0.02
0.036
0.46
1.41
3.89
1.65
0.617
0.114
1.25
30.5
0.083 0.43
0
0.14
1 0 8 0
0.25
0.027
0.32
0.08
0.08
0.76
1.87
1.55
2.12
1.8
0.57
1.84
0.44
2.123
1.88
2.93
2.72
0.004
0.75
0.504
0.7
11.04
6.33
1.23
0.17
0.14
0.033
0.06
0.75
0.08
0.33
0. 03 1
0.18
- 0.01
- 0.027
0.024
0.77
0.2
0.16
0.14
1.77
0.1
0.03
0.015
0.26
0.22
0.048
0.16
0.4
0.18
0.05
0.18
0.022
0.13
0.18
0.084
3.16 0.73 -0. 1 0.19
3.47 0.335 0.109 0.115
2.17
2.17
3.25
2.38
1.78
2.7
3.24
3.081
3.23
2.88
2.75
8.11
4.21
0.28
0.56
0.79
0.45
0.85
0.51
0.02
-0.12
- 0.04
-0.18
-0.18
0.09
0.15
0.001
- 0.03
0.038
0.003
0.094
0.223
0.14
0.36
0.33
0.28
0.42
0.27
0.074
0.98
0.19
0.19
0.38
0.905
0.033
0.43
0.072
0.088
0.017
0.194
18.3 2.5 0.111 0.194
26.56
22.13
21.52
2 5
2 5
2.36
1.98
1.48
0.39
- 0.001
0.029
0.076
0.04
0.04
0.53
0.011
0.026
0.006
0.25 0.02
0.08 4.12
0.3
24.6
0.05
31.66 N
N
Y
N
Y
Y
Y
Y
Y
Y
N
Y
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
926
508
776
210
410
210
204
1083
1085
1020
934
763
994
994
1 4 0
257
467
6 1
6 1
174
991
11
13
138
738
158
758
98
728
7 2 8
128
728
950
714
714
714
714
714
714
460
728
714
714
728
95
1076
1076
201
1 5 3
1 5 3
1 5 3
603
604
195
1 0 3 1
4 1
References page II - 290
II / 230 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1
&95%
r2
ik95% Conv. Refs.
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Metbacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Metbacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Ethylene, 1, l-diphenyl-
Ethylene, l,l-diphenyl-
Ethylene, chlorotrifluoro-
Ethylene, tetrachloro-
Ethylene, trichloro-
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diisopropyl
Fumaronitrile
Furan, 2-vinyl-Smethyl
Hexatriene, tetrachloro-
Imi dazol e, l-vinyl-
Imidazole, 1-vinyl-Zmethyl-
Imidazole, 1-vinyl-Zmethyl-
Isoprene
Isoprene
Isoprene
Isoprene, 3-acetoxy-
Isopropenyl acetate
Isopropenyl, 3-( 1-cyclohexenyl), acetate
Isopropenylisocyanate
Isopropenyltoluene
Isopropenyltoluene
Itaconamate, N-(4-chlorophenyl)-, ethyl
Itaconamate, N-(4-chlorophenyl)-,
Prwl
Itaconamate, N-(4-methoxyphenyl)-,
ethyl
Itaconamate, N-(4carboethoxyphenyl)-
ethyl
Itaconamate, N-(4-methylphenyl)-, ethyl
Itaconamate, N-(4-methoxyphenyl)-,
propel
Itaconamate, N-(4-methylphenyl)-,
prom1
Itaconamate, N-phenyl-, ethyl
Itaconamate, N-phenyl-, propyl
Itaconamate, N-(4-carboethoxyphenyl)-
Prwl
Itaconate, dibutyl
Itaconate, dibutyl
Itaconate, dimethyl
Itaconate, dimethyl
Itaconate, monomethyl
Itaconic acid
Itaconic acid
Itaconic anhydride
Itaconimide, N-(2-chloroethyl)-
Itaconimide, N-benzyl-
Itaconimide, N-ethyl-
Itaconimide, N-methyl-
Maleate, dibutyl tin
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Mal ei mi de
Mal ei mi de
2.1
8.7
51.36
100
40.3
2.1
2 3
6.14
0.183
0.504
4.36
4
3.48
0.26
0.25
0.25
0.16
17.36
0.81
3.1
0.68
0.68
1.24
1.26
1.31 0.43 678
1.21 0.48 678
1.43
1.03
1.11 0.28 678
1.32
1.13
1.33
0.8
3.34
1.2
1.1
1.23
1.14
0.155
0
0.46
0.486
0.38
12.7
341
20
285.8
4.18
6.36
0.46
5.2
3.1
3.85
3.4
3.85
2.576
2.5
3.31
0.6
0.79
0.146
0.057
1.86
0.54
0.21
1.95
0.09
0.557
0.071
0.024
0.11
0.18
0.066
0.22
5.93
46
35.9
0.31
0.64
0.69
0.47
0.061
0.09
0
- 0.074 0.062
0
0.04
0.05
0.17
- 0.064
0.867
1.76
0.014
0.047
0.003
0.65
0.64
0.64
2.81
- 0.09
0.4
0.14
0.04
0.04
0.36
0.31
0.004
0.096
0.292
0.28
0.03
0.088
0.23
0.12
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
65
901
236
204
470
28
394
1038
1 9 1
1105
5
364
364
4 1 9
302
698
704
770
100
770
434
688
722
678
618
0.63 678
0.4 678
0.47 678
0.15 678
0.53 678
0.717
0.4
- 0.156
0.3
0.139
0
0
1.17
0.54
1.06
0.42
1.12
- 0.095
-0.1
0
- 0.02
-0.163
- 0.019
0.08
0.02
0.01
0.01
0.01
0.02
0.166
0.17
0.11
0.02
0.103
0.33
0.39
0.75
0.13
0.73
0.199
0.05
0.015
0.027
0.026
1.77
0.004
0.047
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
N
N
Y
1073
398
975
398
1010
260
408
1010
642
642
642
642
987
28
470
813
1 6 9
260
320
3 3
524
524
524
524
2 5 1
992
TABLE 1. contd
copolymer Reactivity Ratios II / 231
Monomer 1 Monomer 2
rl
*95%
r2
f95% Conv. Refs.
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Mal ei mi de, 2,3-dimethyl-
N-(2-methacryloyloxyetbyl)
Maleimide, N-(4-hydroxyphenyl)-
Maleimide, N-(2-hydroxyethyl)-
Mal ei mi de, N-(2,6-diethylphenyl)-
Mal ei mi de, N-(2,6-diisopropylphenyl)-
Mal ei mi de, N-(2,6-dimethylphenyl)-
Mal ei mi de, N-(2-chlorophenyl)-
Mal ei mi de, N-(2-methylphenyl)-
Mal ei mi de, N-(3,5-dimethylphenyl)-
Maleimide, N-(3-methylphenyl)-
Mal ei mi de, N-(3-trifluoromethylphenyl)-
Mal ei mi de, N-(4-carboxyethylphenyl)-
a-chloro-
Mal ei mi de, N-(4-chlorophenyl)-c-chloro-
Mal ei mi de, N-Cmethoxyphenyl)-
a-chloro-
Maleimide, N-(4-methylphenyl)-
Maleimide, N-(4-methylphenyl)-
a-chloro-
Mal ei mi de, N-(P-chloroethyl)-a-chloro-
Mal ei mi de, N-(P-chloroethyl)-a-chloro-
Mal ei mi de, N-[N-(a-methylbenzyl)
aminocarbonylpentyl]-
Mal ei mi de, N-benzyl
Mal ei mi de, N-butyl
Mal ei mi de, N-cyclohexyl
Maleimide, N-cyclohexyl
Mal ei mi de, N-cyclohexyl
Mal ei mi de, N-ethyl-a-chloro-
Mal ei mi de, N-hexyl-
Mal ei mi de, N-hydroxymethyl-
Mal ei mi de, N-methyl-wchloro-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Mal ei mi de, N-phenyl-a-chloro-
Maleimide, N-phenyl-
Metbacrylate, 2-acetoxyethyl
Methacrylate, cyanomethyl
Metbacrylate, diphenylmethyl
Methacrylamide
Methacrylamide
Metbacrylamide
Methacrylamide
Methacrylamide, N-metboxymethyl-
Methacrylamide, N-p-bromophenyl-
Methacrylamide, N-p-tolyl-
Methacrylamide, N-phenyl
Metbacrylamide, N-phenyl-
Methacrylamide, 1-deoxy-o-glucitol
Methacrylamide, N-p-nitrophenyl-
Methacrylate, rerr-butyl
Methacrylate, a,wdimethylbenzyl
Methacrylate, (2,2-dimethyl-
1,3-dioxolane)
Methacrylate, l,l-diphenylethyl
Methacrylate, 1 -naphthyl
Methacrylate, 1-naphthyl
Methacrylate, 1-naphthyl
Methacrylate, 1-naphthyl
Methacrylate, 2,2-dimethylaminoethy
Methacrylate, 2,3-epithiopropyl
Methacrylate, 2,6-(diphenyl)phenyl
Methactylate, 2-(NJV-dimethyl-
carbamoyloxy)ethyl
0.51
1.392
1.396
4.78
10.9
3.62
2.1
2.22
1.63
1.18
1.57
0.472
0.562 0.025 0.02 0.03
0.556 0.145 0.064 0.189
0.83
0.564 0.117
0.34
0.029 0.158
0.94 0.06 0.05 0.04
0.59 0.06 0.11 0.05
1.37 0.291 0.582 0.359
1.28
1.41
1.35
1.31
2.26
0.53
1.9
1.745
0.63
0.98
0.91
0.657
1.014
0.94
0.399
0.81
1.57
1.7
1.39
1.65
1.678
3.48
1.43
1.95
1.42
4.2
5.05
0.96
0.81
0.9
0.23
0.19
0.23
0.16
0.066
0.04
0.2
0.03
0.34
0.048
0.03
0.15
0.026
0.03
0.083
0.06
0.02
0.019
0.03
0.1
0.24
0.19
0.106
0.13
0.1
0.263
0.11
0.3
0.3
0.077
0.164
1.12
0.73
1.07
1.27
0.44
0.425
0.49
0.265
0.38
0.78
0.28
0.56
0.04
0.29
1.35
0.92
1.1
0.098
0.065
0.06
0.11
0.11
0.04
0.074
0.24
0.06
0.085
0.048
0.2
0.2
0.2
0.096
0.2
0.009
0.2
0.2
0.2
0.12
0.2
0.72
0.77
0.809
0. 85 1
0.61
0.42
0.83
1.42
0.59
0.14
0.078
0.084
0.73
0.38
0.47
0.02
0.06
0.77
1.8
1.68
2.62
1.52
1.01
0.97
0.071
0.42
0.54
0.004
1.66
0.001
0.089
0.114
1.1
0.345
0.201
0.05
0.02
0.07
0.1
0.09
0.28
0.22
0.1
0.004
3.58
0.001
0.083
0.168
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
N
N
Y
Y
Y
Y
Y
Y
N
619
323
323
992
992
992
992
992
992
992
992
973
973
973
992
973
974
974
1009
348
1 1 5
992
1100
348
974
348
323
974
323
992
973
328
346
625
761
316
316
54
55
227
968
968
968
352
258
968
761
761
807
7 6 1
752
752
752
761
691
787
1079
600
References page II - 290
II / 232 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2 rl It95% r2 195% Conv. Refs.
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methaqlate, met hyl
Methactylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methactylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methactylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-chloro-
2,3,3,3-fluoropropyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-naphthyl
Methacrylate, 2-phenylethyl
Methacrylate, 3,5dimethyladamantyl
Methacrylate, 5-oxo-pyrrolidinylmethyl
Methacrylate, N-a-benzothiazolonyl-
methyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzylmethylaminoethyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, chloromethyl
Methacrylate, diethylaminoethyl
Methacrylate, dimethylaminoethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isopropyl
Methacrylate, methyl diphenylsilyl
Methacrylate, methylthiomethyl
Methacrylate, p-acetylphenyl
Methacrylate, p-chlorophenyl
Methacrylate, p-methoxyphenyl
Methacrylate, p-tolyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, propyl
Methacrylate, sulfolanyl
Methacrylate, t-butyl dimethylsilyl
Methacrylate, t-butyl diphenylsilyl
Methacrylate, tributyltin
Methacrylate, tributyltin
Methacrylate, trimethyltin
Methacrylate, trimethyltin
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
0.79
0.984
1.156
0.55
0.824
0.192
0.75
0.402
0.602
0.581
0.532
0.614
0.623
0.75
0.68
0.421
0.5
0.808
0.93
0.78
0.523
0.52
1.27
0.477
0.843
0.699
0.81
1.08
1.16
0.71
0.726
0.8
0.688
0.62
0.92
0.89
0.438
0.639
0.47
0.54
0.72
0.59
0.53
0.58
0.56
0.66
0.55
1.21
1.07
0.897
0.636
0.58
0.62
0.63
0.6
0.63
0.1
0.78
0.31
0.27
0.1
0.78
0.32
0.395
0.082
0.01
0.09
0.017
0.059
0.023
0.055
0. 05 1
0.048
0.16
0.04
0.033
0.01
0.03
0.134
0.07
0.029
0.128
0. 05 1
0.22
0. 19
0.08
0.042
0.076
0.08
0.15
0.075
0.057
2.48
0.05
0.014
0.03
0.01
0.03
0.02
0.03
0.01
0.03
0.02
1.18
0.583
0.97
0.48
0.63
0.81
1.5
1.055
2.57
2.53
1.91
4.41
3.83
0.85
0.45
0.694
0.6
1.112
I .05
1.38
0.296
2.11
1.2
1.02
1.44
1.2
0.86
1.08
1
0.52
0.934
1.05
0.501
1.88
0.488
1.2
0.38
1.1
0.67
1.08
1.19
1.28
1.67
1.69
1.72
1.55
0.99
1.24
7.16
0.725
0.396
0.62
0.87
1.07
0.68
0.25
1.06
0.33
0.63
0.46
1.06
0.33
0.63
1.17
0.18
0.076
1.02
0.04
0.48
0.27
0.6
0.76
0.57
0.34
0.16
0.087
0.02
0.093
0.123
0.08
0.16
0.085
0.154
0.12
0.09
0.06
0.085
0.027
0.07
0.029
0.178
0.356
23.7
0.455
0.257
0.05
0.02
0.02
0.02
0.03
0.02
0.02
0.02
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
N
Y
Y
Y
N
N
Y
Y
Y
N
Y
Y
Y
N
Y
Y
657
927
179
382
350
358.
710
333
760
760
760
760
760
540
335
633
887
111
32
540
1 0 8 1
30
844
712
1 0 8 1
1 0 8 1
32
844
87
1 1 3
226
463
639
30
639
541
1069
920
769
769
769
769
32
32
32
761
769
844
359
1069
1069
1082
1082
1082
1082
1 0 7 1
1072
1072
1072
1072
1087
1087
1087
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 233
Monomer 1 Monomer 2
r1
f95%
r2
f95% Conv. Refs.
Methacrylate, methyl
Methacrylate, methyl
Methactylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacxylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methactylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methactylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methactylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methactylate, methyl
Methactylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methactylic aci d
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic anhydride
Methacrylophenone, u-
Methacrylophenone, w
Methacryloyl chloride
Methacryloyl chloride
Methacryloyl fluoride
Methacryloyl fluoride
Methactyloyl isocyanate
Methacryloyloxy-, o-, benzoic acid
Methylenebutyrolactone
Methyleneglutaronitrile, 2-
Methyleneglutaronitrile, 2-
Myrcene
N,N-divinylaniline
N-Vinylimidazole
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
Naphthalene, l-vinyl-
Norbornadiene
Oxazolidone, N-vinyl-
Oxazolidone, N-vinyl-
Oxazoline, 2-,2-isopropenyl
4,4-dimethyl
Oxazoline, 2-,2-isopropenyl
Oxazoline, 2-,4-actyloxymethyl
2,4-dimethyl
Oxazoline, 2-,4-methacryloxy-
2,4-dimethyl
Pentadiene, trans-1,3-
Pentenoate, 3-oxo-4-, ethyl
Pentenoate, 3-oxo-4-, ethyl
Pentenoate, 3-oxo-4-, ethyl
Pentenoate, 3-oxo-4-, ethyl
Pentenoate, 3-oxo-4-, ethyl
Pentenoate, 3-oxo-4-, ethyl
Pentenoate, 3-oxo-4-, ethyl
Pentenoate, 3-oxo-4-, ethyl
Pentenoate, 3-oxo-4-, ethyl
Pentenoate, 3-oxo-4-, ethyl
Pentenoate, 4-methyl-3-oxo-4-, ethyl
Pentenoate, 4-methyl-3-oxo-4-, ethyl
Pentenoate, 4-methyl-3-oxo-4-, ethyl
Pentenoate, 4-methyl-3-oxo-4-, ethyl
Pentenoate, 4-methyl-3-oxo-4-, ethyl
Pentenoate, 4-methyl-3-oxo-4-, ethyl
Pentenoate, 4-methyl-3-oxo-4-, ethyl
Pentenoate, 4-methyl-3-oxo-4-, ethyl
Pentenoate, 4-methyl-3-oxo-4-, ethyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
0.87
1.81
0.56
0.29
1.28
0.77
0.36
1.18
0.55
0.209
1.25
0.48
0.22
1.79
1.74
0.45
0.45
0.405
0.53
0.75
0.908
0.6
1.36
1.27
0.256
1.06
4.306
4.78
5.93
2.07
4.04
0.321
14.68
6.75
9.46
0.53
0.05
0.16
0.23
0.04
0.1
0.05
0.08
0.05
2.16
1.63
0.99
1.18
0.48
1.84
1.38
0.63
1.55
1.26
0.78
0.68
1.58
0.11
0.119
0.2
0.2
0.43
0.9
0.35
1.37
1.67
0.12
0.12
0.448
0.005
0.663
0.006
0.014
0.027
0.066
0.574
0.5
0.04
0.027
0.82
0.28
6.25
0.55
0.19
0.1
0.24
0.27
0.2
0.02
0.07
0.22
0.06
0.02
0.009
0.037
0.06
0.12
0.16
0.252 0.64
0.28 0.74
0.013
0.18
0.185
0.236
0.198
0.247
0.956
0.096
16.78
0.37
0.39
-
0.06
0.018
0.104
2.29
0.899
0.062
3.96
0.073
0.52
0.13
0.008
0.69 0.99
0.41 0.11
1.17 0.19
0.404 0.038 0.379 0.013
0.555 0.032 3.39 0.263
0.424 0.022 2.02 0.141
0.591 0.046 3.06 0.349
0.443 0.032 1.67 0.183
0.34 0.03 1 1.24 0.168
0.57 0.023 1.72 0.123
0.606 0.045 1.69 0.236
0.269 0.027 0.72 0.12
0.715 0.048 1.55 0.224
0.528 0.02 1.09 0.09
0.597 0.03 2.56 0.218
0.38 0.034 0.748 0.155
0.513 0.022 1.14 0.109
0.43 0.034 0.952 0.164
0.474 0.023 1.67 0.143
0.581 0.025 1.04 0.111
0.616 0.024 1.05 0.108
0.663 0.023 0.725 0.08
0.528 0.02 1.09 0.09
2.37 0.046 0.486 0.088
2.23 0.047 0.521 0.138
1.87 0.086 0.946 0.436
N
N
Y
N
N
N
N
Y
N
N
Y
Y
N
Y
N
Y
Y
Y
N
Y
Y
Y
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
203
210
216
276
276
312
313
313
424
54
630
819
275
798
798
591
593
617
660
944
938
746
196
196
1062
45
879
1084
1084
1084
1084
967
267
102
36
596
862
596
596
1058
1033
1033
1033
1033
1033
1033
1033
1033
1033
1 0 3 3
1033
1033
1033
1033
1033
1033
1033
1033
1033
971
971
971
References page II - 290
II / 234 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
J.1 &95% r2 It95% Conv. Refs.
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methaclylate, met hyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphonate, cL-bromovinyl-,diethyl
Phosphonate, cl-carboethoxyvinyl-,
diethyl
Phosphonate, wcarbomethoxyvinyl-,
diethyl
Phosphonate, isopropenyl-, dimethyl
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, diethyl
Phosphonic acid, a-phenylvinyl-
Phthalimide,-N-)methacryloyloxy)-
Pinene, cc-
Propene, 2,3-dichloro-
Propene, 2-chloro-3-hydroxy-
Propenyl, 2-chloro-, acetate
Propenyl, 2-methyl, acetate
Pyridazinone, 3-(2-vinyl)-6-methyl-4,5-
Pyridazinone 3-(2-vinyl)-6-methyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-Vinyl-S-ethyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyrrolidone, I-benzyl-3-methylene-
5-methyl
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, a-methylene-N-methyl-
Silane, y-methacryloxypropyltrimethoxy-
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
1.97 0.029
2.1 0.045
2.56 0.094
2.04 0.012
1.25 0.04
4.7
30
29.9
11.1
1.362
0.69
1 0
6.02
4.4
1 0
1.19
0.86
0.42
0.42
0.4
0.35
0.31
0.27
0.39
0.57
0.54
0.387
5.62
4.63
4.36
4.04
0.577
0.788
0.5
0.46
0.46
0.42
0.45
0.46
0.47
0.48
0.5
0.22
0.32
0.418
0.54
0.478
0.45
0.45
0.49
0.47
0.48
0.46
0.42
0.5
0.46
0.44
0.49
0.49
0.04
0.084
0.048
1.66
0.04
0.02
0.09
0.02
0.19
0.04
0.02
0.02
0.01
0.07
0.3
0.34
0.61
0.61
0.058
0.082
0.13
0.085
0.029
0.011
0.01
1.16 0.248
0.42 0.097
0.258 0.226
0.0701 0.052
0.05
0.01
0.2
0.26
- 0.063
1.45
0.08
0.18
0
0
0
0.08
0.56
0.54
0.73
0.86
0.76
0.64
1.1
0.68
0.77
0.99
2.28
0.03
0.04
0.19
0.06
0.12
0.08
0.06
0.07
0.18
0.47
- 0.05
- 0.032
- 0.052
0.01
0.24
2.06
0.5
0.52
0.52
0.48
0.52
0.49
0.45
0.58
0.44
0.396
0.42
0.49
0.564
0.585
0.44
0.47
0.54
0.52
0.38
0.52
0.54
0.44
0.52
0.5
0.56
0.53
0.08
0.068
0.028
0.15
0.14
0.309
0.048
0.14
0.047
0.007
0.08
N
N
N
N
Y
Y
N
N
N
N
N
Y
N
N
N
N
Y
Y
N
Y
Y
N
Y
Y
Y
Y
Y
Y
N
971
971
971
971
684
684
684
684
410
684
1 3 1
979
48
11
445
445
470
340
340
232
231
532
6
623
749
231
231
691
3 3
213
320
321
36
691
6 4 1
977
1 3 8
139
179
20
2 1
2 1
2 1
2 1
2 1
241
241
254
254
287
324
324
403
416
451
463
492
492
505
531
531
534
TABLE 1. contd
Copolymer Reactivity Ratios II / 235
Monomer 1 Monomer 2
rl Zk95%
r2
Zk95% Conv. Refs.
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methaclylate, methyl
Methacrylate, methyl
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, 2,4,6-trimethyl-
Styrene, 2,4,6-trimethyl-
Styrene, 2,5-dichloro-
Styrene, 2,6-dichloro-
Styrene, 3-methyl
Styrene, 3-methyl
Styrene, 3-methyl
Styrene, 3-tri-n-butylstannyl-
Styrene, 4-methyl-
Styrene, a-methoxy-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, cr-methyl-
Styrene, cc-methyl-
Styrene, m-bromo-
Styrene, m-chloro-
Styrene, m-methyl-
Styrene, m-nitro-
Styrene, p-chloro-
Styrene, o-chloro-
Styrene, p-1-(2-hydroxypropyl)
Styrene, p-N,N-dimethylamino-
Styrene, p-bromo-
Styrene, p-chloro-
Styrene, p-chloro-
Styrene, p-chloro-
Styrene, p-chloromethyl-
Styrene, p-cyano-
Styrene, p-methoxy-
Styrene, p-methyl-
Styrene, p-octylamine sulfonate
Styrene, p-tert-butyl-
Styrene, pentachloro-
Succinamete, potassium N-vinyl-
Succinimide, N-vinyl-
Succinimide, N-vinyl-
Tetrazole, l-Vinyl-
Tetrazole, 2-methyl-5-vinyl-
Tetrazole, 2-phenyl-5(4-vinyl) phen
Thiophene, 3-vinyl
Thioxanthone, 2-(acryloyloxy)-
Toluenesulfonamide, N,N-methyl-
vinyl-
Triallyl cyanurate
Triallyl isocyanurate
Tri azol e, 1,2,3-, l-p-bromophenyl-
4-vinyl
Tri azol e, 1,2,3-, 4(5)-vinyl-
Urea, N-vinyl-N-ethyl-
0.409
0.504
0.611
0.59
0.6
0.63
0.58
0.64
0.41
0.454
0.464
0.422
0.41
0.314
1.511
1.45
0.44
1.98
0.48
0.38
0.41
0.69
0.345
2.5
0.48
0.55
0.55
0.5
0.42
0.41
0.48
0.02
0.026
0.028
0.072
0.16
0.13
0.16
0.04
0.03
0.04
0.008
0.39
0.02
0.485
0.48
0.371
0.62
0.52
0.5
0.55
0.55
0.41
0.472
0.497
0.432
0.57
0.275
0.083
- 0.01
2.66
-0.15
0.53
0.36
0.51
0.03
0.46
- 0.02
0.27
0.51
0.6
0.14
0.22
0.48
1.17
0.052
0.059
0.055
0.045
0.11
0.38
0.27
0.04
0.06
0.05
0.022
0.04
0.07
0.512
0.35
0.5
0.46
0.26
0.204
0.4
0.334
0.42
0.43
0.408
0.22
0.29
0.4
0.6
0.44
3.65
1.1
9.94
0.01
7.13
1.026
0.7
0.563
1.36
1.87
0.036
0.11
0.022
0.016
0.038
0.85
0.17
0.27
0.031
0.093
0.029
0.19
0.486
0.8
1.37
1.34
1
0.101
1.1
0.17
0.89
0.47
0.91
1.41
0.32
0.44
2.6
0.5
0.3
- 0.02
0.048
- 0.059
0.262
0.486
0.4
0.25
0.5
- 1.83
0.02
0.32
0.016
0.12
0.15
0.05
0.12
0.026
0.096
0.026
0.075
0.26
16.12 0.56 - 0.005 0.05
16.88 6.64 - 0.49 0.94
0.832 0.022 0.266 0.058
0.839 0.055 0.27 0.13
1.85 0.23 - 0.008 0.029
Y
Y
Y
Y
Y
Y
N
Y
N
N
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
751
751
751
753
753
753
753
753
753
824
824
824
835
860
58
58
3
324
1087
1087
1087
985
929
142
265
265
265
532
835
899
256
150
256
222
532
558
380
256
256
150
256
476
756
256
3 5
256
817
634
7
771
104
693
925
670
583
1000
986
80
2 0 1
201
670
670
1 0 1
References page II - 290
II / 236 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl rfr95% r2 Z!Z95% Conv. Refs.
Methacrylate, methyl Vinyl 2-chloroethyl ether
Methacrylate, methyl Vinyl 4-chlorocyclohexyl ketone
Methacrylate, methyl Vinyl acetate
Methacrylate, methyl Vinyl acetate
Methacrylate, methyl Vinyl acetate
Methacrylate, methyl Vinyl acetate
Methacrylate, methyl Vinyl acetate
Methacrylate, methyl Vinyl benzoate
Metbacrylate, methyl Vinyl bromide
Methacrylate, methyl Vinyl bromide
Methacrylate, methyl Vinyl bromide
Methacrylate, methyl Vinyl bromide
Methacrylate, methyl Vinyl butyl ether
Methacrylate, methyl Vinyl butyrate
Methacrylate, methyl Vinyl chloride
Methacrylate, methyl Vinyl chlorometbyl ketone
Methacrylate, methyl Vinyl ether
Methacrylate, methyl Vinyl ethyl ether
Methacrylate, methyl Vinyl ethyl ketone
Methacrylate, methyl Vinyl ethyl oxalate
Methactylate, methyl Vinyl ethyl sulfide
Methacrylate, methyl Vinyl ethyl sulfide
Methacrylate, methyl Vinyl ethyl sulfoxide
Methacrylate, methyl Vinyl isobutyl sulfide
Methacrylate, methyl Vinyl isobutyl sulfide
Methacrylate, methyl Vinyl isobutyl sulfide
Methacrylate, methyl Vinyl isopropyl ketone
Methactylate, methyl Vinyl isopropyl ketone
Methacrylate, methyl Vinyl isopropyl sulfide
Methacrylate, methyl Vinyl isothiocyanate
Methacrylate, methyl Vinyl m-cresyl ether
Methacrylate, methyl Vinyl methyl sulfide
Methacrylate, methyl Vinyl o-cresyl ether
Methacrylate, methyl Vinyl p-cresyl ether
Methacrylate, methyl Vinyl phenyl ether
Methacrylate, methyl Vinyl phenyl ether
Metbacrylate, methyl Vinyl phenyl ketone
Methacrylate, methyl Vinyl phenyl sulfide
Methacrylate, methyl Vinyl phenyl sulfide
Methacrylate, methyl Vinyl propionate
Methacrylate, methyl Vinyl sulfone
Metbacrylate, methyl Vinyl rert-butyl ketone
Methacrylate, methyl Vinyl, 4-, dithiobenzoate, methyl
Methacrylate, methyl Vinyl, p-,benzylmethylcarbinol
Methacrylate, methyl Vinyl-tris(trimethoxysiloxy)silane
Methacrylate, methyl Vinylacetophenone, p-
Methacrylate, methyl Vinylanthracene, 9-
Methacrylate, methyl Vinylbenzoic acid, p-
Methacrylate, methyl Vinylbenzyl chloride
Methacrylate, methyl Vinylene carbonate
Methacrylate, methyl Vinylferrocene
Methacrylate, methyl Vinylhydroquinone
Methacrylate, methyl Vinylhydroquinone dibenzoate
Methacrylate, methyl Vinylidene chloride
Methacrylate, methyl Vinylidene chloride
Methacrylate, methyl Vinylidene chloride
Methacrylate, methyl Vinylidene chloride
Methacrylate, methyl Vinylidene chloride
Methacrylate, methyl Vinylidene chloride
Methacrylate, methyl Vinylidene chloride
Methacrylate, methyl Vinylidene chloride
Methacrylate, methyl Vinylidene chloride
Methacrylate, methyl Vinylidene chloride
Methacrylate, methyl Vinylidene cyanide
Methactylate, methyl Vinylisocyanate
18.8
0.11
2.71
1,37.5
26
28.6
22.21
20.3
14.11
17.1
25.1
19.84
2 5
8.99
0.121
4.9
37
0.42
4.74
1.03
2.1
11.17
0.89
0.985
0.88
0.81
0.54
0.822
0.85
3.3
1
1.8
2.6
11.34
2.8
0.71
0.79
0.85
24
4.5
1.21
0.151
0.24
34
0.33
4.068
0.398
0.46
126
1.22
0.49
0.34
2.6
2.38
2.16
2.5
2.5
2.1
1.8
2.83
1.23
2.17
3.3
0.25
5.9
0.67
0.88
2.58
2.91
0.021
0.99
0.17
2.95
0.11
0.48
0.01
0.077
0.02
0.22
0.064
5.16
0.6
0.06
0.49
0.11
0.092
0.26
0.36
0.04
0.097
298
0.21
0.02
0.06
0.95
0.06
0.012
0
0.51
- 0.2
-0.81
0.03
0.04
0.07
0.07
0.12
0.33
0.052
0.05
0.03
0.07
0.593
- 0.15
0.01
0.65
- 0.05
0.036
0.3
0.37
0.05
0.021
0.03
1.44
0.6
0.046
0.6
0.2
0.03
0.1
0
0.01
0
0.59
0.06
0.08
0.03
0.1
0.65
0.3
0.98
0.02
1.65
0.117
1.16
1.02
- 0.04
0.52
0.02
0.41
0.3
0.36
0.18
0.5
0.34
0.09
0.094
0.19
0.02
0.21
0.01
0.01
1.17
0.06
0.026
0.074
0.047
0.092
0.16
0.42
0.44
0.017
0.06
0.03
0.034
0.02
0.47
0.025
0.32
1.9
0.09
0.16
0.15
0.29
0.28
3.81
0.043
0.3
0.85
0.13
0.03
0.18
0.032
0.01
0.013
N
N
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
N
Y
N
Y
Y
L
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
Y
N
Y
597
668
158
210
272
383
471
212
268
268
34
34
127
212
3
356
45
106
194
124
303
507
286
285
303
336
601
794
303
422
605
106
605
605
172
605
794
239
239
212
45
794
691
48
482
266
1 2 3
266
792
1 0 3
294
331
440
138
324
324
426
432
538
65
762
762
786
82
422
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 237
Monomer 1 Monomer 2
rl
rt95%
12 f-95% Conv. Refs.
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl diphenylsilyl
Methacrylate, methylthiomethyl
Methacrylate, methylthiomethyl
Methacrylate, mono-,ethylene glycol
Methacrylate, octyl
Methacrylate, octyl
Methacrylate, octyl
Methacrylate, p-(cinnamoylamino)phenyl
Methacrylate, p-acetylphenyl
Methacrylate, p-carbomethoxyphenyl
Methacrylate, p-chlorophenyl
Methacrylate, p-chlorophenyl
Methacrylate, p-methoxyphenyl
Methacrylate, p-methoxyphenyl
Methacrylate, p-methylphenyl
Methacrylate, p-methylphenyl
Methacrylate, p-tolyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, potassium
Methacrylate, propargyl
Methacrylate, propyl
Methacrylate, propyl
Methacrylate, sodium (2-sulphoxyethyl)-
Methacrylate, sulfolanyl
Methacrylate, sulfolanyl
Methacrylate, sufolanyl
Methacrylate, t-butyl dimethylsilyl
Methacrylate, t-butyl dimethylsilyl
Methacrylate, t-butyl diphenylsilyl
Methacrylate, tert-butyl
Methacrylate, tert-butyl
Methacrylate, tetra(2-hydroxypropyl)-
ethylenediamine
Methacrylate, tetra(2-hydroxypropyl)-
ethylenediamine
Methacrylate, tributyltin
Methacrylate, tributyltin
Methacrylate, tributyltin
Methacrylate, tributyltin
Methacrylate, tributyltin
Methacrylate, tributyltin
Methacrylate, triethyltin
Methacrylate, trimethyltin
Methacrylate, triphenyltin
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Vinylphenyldimethylsilane 29.79
Vinyltrimethylsilane 35.66
Xanthate, S-methacryloyl O-ethyl 0.76
Methacrylate, methyl 0.38
Methacrylate, methyl 1.1
Styrene 0.512
Acrylonitrile 1.5
Styrene 0.56
Styrene 0.68
Vinyl chloride 1 4
Styrene 0.31
Methactylate, met hyl 0.67
Styrene 0.178
Methacrylate, methyl 1.08
Styrene 0.243
Methacrylate, methyl 1.19
Styrene 0.244
Styrene 0.225
Styrene 0.185
Methacrylate, methyl 1.28
Acrylonitrile 0.46
Methacrylate, 2-chloroethyl 0.785
Methacrylate, benzyl 1.42
Methacrylate, methyl 1.67
Methacrylate, methyl 1.69
Methacrylate, methyl 1.12
Methacrylate, methyl 1.55
Methacrylate, methyl 0.99
Methacrylic, acid 1.89
Methacrylic, acid 0.589
N-Vinylpyrrolidone 4.17
Styrene 0.48
Styrene 0.55
Styrene 0.51
Acrylonitrile 0.203
Itaconic acid mono@-sulfamidoanilide) 1.65
Methacrylate, methyl 1.24
Styrene 0.38
Methacrylic, acid 1.2
Methacrylate methyl 7.16
Methacrylic, acid 0.81
Styrene - 0.2
Acrylate, methyl 1.07
Methacrylate, methyl 0.725
Methacrylate, methyl 0.396
Methacrylate, methyl 1.35
Styrene 0.61
Methacrylate, hydroxyethyl 1.44
Methacrylic acid 0.328
Methacrylate, 2-ethoxyethyl 0.2
Methacrylate, 2-hydroxypropyl 0.728
Methacrylate, cyclohexyl 0.395
Methacrylate, ethyl 0.299
Methacrylate, hydroxyethyl 0.282
Methacrylate, methyl 0.62
Methacrylate, methyl 0.87
Methacrylate, methyl 1.07
Methacrylate, methyl 0.68
Acrylamide 1.63
Acrylamide 4.4
Acrylamide 0.15
Acrylate, butyl 1.25
1.89
0.85
0.04
0.178
0.356
0.05
0.16
0.027
0.022
0.026
0.04
0.039
0.083
0.09
0.17
0. 08 1
0.756
0.23
0.33
0.086
0.02
0.11
0.19
23.7
0.24
2.46
0.21
0.455
0.257
0.51
1
0.181
0.444
0.517
0.428
0.607
0.424
0.31
- 0.009
0.028
0.6
0.438
0.639
0.338
0.19
0.65
0.56
0.04
0.62
0.47
0.482
0.54
0.34
0.72
0.499
0.49
0.223
0.59
0.36
1.02
0.67
0.53
0.58
0.56
0.66
0.55
0.211
0.398
- 0.026
0.246
0.241
0.26
0.226
0.58
1.21
0.565
0.78
1.07
0.81
0.2
0.288
0.897
0.636
0.96
0.545
0.606
1.56
0.53
1.81
0.891
0.601
2.33
0.58
0.62
0.63
0.6
0.57
0.58
0.56
0.31
0.034
0.016
0.08
0.075
0.057
0.01
0.1
0.084
0.11
0.089
0.25
0.09
0.21
0.06
0.018
0.019
0.032
0.049
0.064
0.04
0.05
0.081
0.08
2.48
0.03
0.1
0.057
0.05
0.014
0.054
0.416
0.237
0.16
0.275
0.136
0.123
0.185
0.1
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
Y
Y
Y
Y
Y
Y
N
N
N
N
N
N
482
482
1086
1069
920
920
682
1 7 9
463
5 1 1
685
769
1 7 7
769
1 7 7
769
1 7 7
1 7 7
1 7 7
769
363
179
32
32
32
32
761
769
8 8
8 8
1013
1 7 7
179
463
808
957
844
179
745
359
359
359
1069
1069
1069
761
1 7 9
996
996
945
945
945
945
945
1082
1082
1082
1082
1028
852
852
1 8 7
References page II - 290
II / 238 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2 r1 It95% r2 f95% Conv. Refs.
Methacrylic acid
Methacrylic acid
Methacrylic acid
Metbacrylic acid
Methacrylic acid
Methacrylic acid
Methaclylic aci d
Metbacrylic acid
Methacrylic acid
Met haql i c aci d
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Metbacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methaqlic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Metbacrylic acid
Acrylate, ethyl
Acrylic acid, 2-ethyl
Acrylic acid, 2-ethyl
Acrylic acid, 2-ethyl
Acrylonitrile
Acrylonitrile
Butadiene, 2-chloro-
Diphenyl sulfone,
3,3-bisitaconimido-m,m-
Mal ei mi de, 2,3-dimethyl-
N-(2-methacryl)
Methacrylamide
Methacrylamide
Methacrylamide
Methacrylate, 2-hydroxypropyl
Methacrylate, N-methyl-N-phenyl-
2-amino
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, diethylaminoethyl
Methacrylate, ethyl
Methacrylate, glycidyl
Methacrylate, isopropyl
Metbacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, phenyl
Methacrylate, phenyl
1.12
2.29
1.14
0.2
2.38
- 0.035
0.564
0.132
0.417
0.194
0.069
0.23
0.04
0.092
2.52
0.015
0.027
0.04
0.26
0.29
0.058
0.032
0.13
0.06
0.2
0.058
0.746 0.059 1.33 0.1
2.73
1.55
2.006
0.99
2.16
0.28 0.25
0.09 0.014
0.18
0.33
1.28
0.2
0.31
0.2 0.01
0.8
0.73
0.63
0.57
0.98
2.01
0.25
1.06
0.33
0.63
0.46
1.06
0.33
0.63
2.16
1.63
0.99
1.18
0.48
1.84
1.38
0.63
1.55
1.26
0.78
0.68
0.211
0.398
0.16
0.2
1.47
0.12
0.12
1.59
0.16 0.1
0.05
0.02
0.02
0.02
0.03
0.02
0.02
0.02
0.28
6.25
0.55
0.19
0.1
0.24
0.27
0.03
0.01
0.03
0.02
0.03
0.01
0.03
0.02
0.05
0.16
0.23
0.04
0.1
0.05
0.08
0.2
1.26
1.15
2.34
0.71
1.2
0.47
0.63
0.1
0.78
0.31
0.27
0.1
0.78
0.32
0.87
1.81
0.56
0.29
1.28
0.77
0.36
1.18
0.55
0.209
1.25
0.48
1.89
0.589
1.2
0.81
0.328
0.05
0.018
0.019
0.08
0.03
0.237
0.1
3.71
0.034
0.16
0.17
0.081
0.19
0.24
0.181
0.07
0.32
0.022
0.3
Met hacryl at e, sodi um (2-sulphoxyethyl)- 0. 78
Methacrylate, sulfolanyl 0.81
Methacrylate, tetra(2- 1.56
hydroxypropyl)ethylenediamine
Methacrylonitrile
Methacrylonitrile
N-Vinylimidazole
Phosphonate, vinyl-, diethyl
Phosphonic acid, a-phenylvinyl-
Pipetylene, cis-
Piperylene, truns-
Propene, 2,3-dichloro-
Propene, 2-chloro-3-hydroxy-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Styrene
Styrene
Styrene
Styrene
1.74
0.54
1.384
1.9
1.49
0.4
0.38
4
4.5
0.43
0.58
0.44
0.55
0.64
0.66
0.49
0.21
0.66
0.08
0.64
0.52
0.145
0.15
0.17
0.38
0.33
0
0
0.85
1.69
1.38
0.21
0.22
0.2
0.15
0.71
0.02
0.04
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
Y
N
N
N
Y
N
N
N
N
Y
Y
Y
N
N
Y
N
N
Y
Y
Y
N
N
1065
1004
1004
961
1 6
216
259
1042
619
190
527
55
886
651
1 8 7
224
1 6
820
224
847
1 0 7 1
1072
1072
1072
1072
1087
1087
1087
203
210
216
276
276
312
313
313
424
54
630
819
88
88
745
359
996
44
8 5
879
431
130
773
773
445
445
552
1 5
498
166
166
203
312
TABLE 1. contd
Copolymer Reactivity Ratios !I/239
Monomer 1 Monomer 2 rl &95% r2 Zt95% Conv. Refs.
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic anhydride
Methacrylic anhydride
Methacrylic anhydride
Methacrylic anhydride
Methacrylic anhydride
Methacrylic anhydride
Methacrylic anhydride
Methacrylic anhydride
Methacrylic anhydride
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, 3-methyl
Styrene, 3-methyl
Styrene, 3-methyl
Styrene, o-chloro-
Sulfonic acid, o-methacryloylamino-
benzene-
Sulfonic acid, o-methacryloylamino-
benzene-
Sulfonic acid, p-methacryloylamino-
benzene-
Sulfonic acid, p-methacryloylamino-
benzene-
Vinyl acetate
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl, mono-, diethyleneglycol ether
Vinylethynyl-4-piperidinol,
1,2,5-trimethyl
Vinylidene chloride
Acrylate, methyl
Ally1 chloroacetate
Allylurea
Methacrylate, methyl
Methacrylonitrile
Styrene
Styrene
Vinyl benzyl sulfide
Vinyl chloroethyl ether
Acenaphthalene
Acetylene, phenyl-
Acrolein
Acrolein
Acrolein, methyl-
Acrolein, methyl-
Acrolein, methyl-
Acrylate, 1,1,5-trihydroperfluoroamyl
Acrylate, a-chloro-, ethyl
Acrylate, cl-cyano-, methyl
Acrylate, wphenyl-, methyl
Acrylic anhydride
Acrylonitrile
Allylbenzene
Butadiene
Ethylene 1, l-diphenyl-
Fumarate, diisopropyl
Itaconate, dimethyl
Methacrylate, butyl
Methacrylate, ethyl
Methacrylate, isobutyl
Methacrylate, isopropyl
Methacrylate, octyl
Methacrylic acid
Methacrylic acid
Methacrylic anhydride
Phosphonic acid, cr-phenylvinyl-
0.56
0.28
0.602
0.85
0.631
0.6
0.44
0.39
0.12
0.35
0.18
0.51
0.622
0.203
0.188
0.156
0.155
0.2
23.52
23.26
9.05
0
0.4
3.368
4.15
29.76
29.01
1.58
1.45
0.27
0.33
0.97
0.15
0.78
1.17
1.2
0.41
0.45
0.45
1.03
0.45
0.18
0.19
0.42
1.67
16.24
0.053
0.48
8 5
1.26
0.56
0.46
0.74
0.43
0.75
0.64
0.52
0.26
2.24
0.19
0.088
0.146
0.249
0.089
0.199
0.118
0.08
0.02
0.01
0.058
0.067
0.076
0.081
0.052
0.98
0.96
0.098
1 3
18.48
0.06
0.18
0.02
0.27
0.05
0.01
0.01
0.04
0.12
1.36
0.016
0.1
0.15
0.04
0.07
0.08
0.04
0.07
0.32
0.06
0.2
0.38
0.124
0.17
0.041
0.067
0.627
0.55
0.221
0.06
0.33
0.42
0.101
0.217
0.523
1.08
1.65
0.01
0.064
- 0.022
0.07
2.2
0.05
0.154
0.16
- 0.01
- 0.06
0.22
0.26
0.13
0.1
- 0.048
2.38
0.04
0.68
0.72
1.78
1.25
1.25
0.14
2
0.15
0.25
1
0.43
- 0.061
0.39
- 0.45
0
0.28
0.75
0.83
0.68
0.94
0.61
1.74
0.54
1.45
0
0.04
0.092
0.03
0.046
0.031
0.06
0.048
0.03
0.02
0.01
0.034
0.122
0.195
0.338
0.27
0.008
0.02
0.047
0.13
0.17
0.02
0.06
0.01
0.033
0.12
0.07
0.01
0.13
0.04
0.03
0.15
0.11
0.07
0.05
0.05
0.12
0.05
0.1
3.71
0.18
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
Y
Y
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
N
N
313
313
47
812
842
842
842
842
842
1087
1087
1087
6
1006
1006
1006
1006
377
1 3 5
229
46
831
734
6
275
106
106
275
219
219
275
106
106
575
648
208
446
208
587
589
809
638
1 4 3
1 4 3
219
1 9 8
3 5 1
251
1 4 3
1038
398
44
44
44
44
44
44
8 5
219
590
References page II - 290
II / 240 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
f-l f9.5% r2 It95% Conv. Refs.
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methactylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylophenone, cc-
Methacrylophenone, CL-
Methacryloxymethylpentamethyldisiloxane
Methacryloxypropyltrimethoxysilane
Methacryloyl chloride
Methacryloyl chloride
Methactyloyl chloride
Methacryloyl chloride
Methacryloyl chloride
Methacryloyl fluoride
Methacryloyl fluoride
Methacryloyl fluoride
Methacryloyl fluoride, perfluoro-
Methacryloyl isocyanate
Methacryloyl-P-hydroxyethyl-
3,5-dinitrobenzoate
Methacryloyl-P-hydroxyethyl-
3,5-dinitrobenzoate
Methacryloyl-P-hydroxyethyl-
3,5-dinitrobenzoate
Methacryloylacetone
Methacryloylacetone
Methacryloylacetone
Methacryloyloxy, 2-benzoate methyl
Methacryloyloxy, 2-benzoate methyl
Methacryloyloxy, 2-benzoic acid methyl
Methacryloyloxy, 2-benzoic acid
Methacryloyloxy,
4-,2,2,6,6-tetramethylpiperidine
Methacryloyloxy-, o-, benzoic acid
Methacryloyloxy-, o-, benzoic acid
Methylenebutyrolactone
Methylenebutyrolactone
Methylenebutyrolactone
Methylenebutyrolactone
Methyleneglutaronitrile, 2-
Methyleneglutaronitrile, 2-
Methyleneglutaronitrile, 2-
Methyleneglutaronitrile, 2-
Methyleneglutaronitrile, 2-
Methyleneglutaronitrile, 2-
Methyleneglutaronitrile, 2-
Myrcene
Myrcene
Myrcene
N-N-Divinylaniline
N-N-Divinylaniline
N-N-Divinylaniline
N-N-Divinylaniline
N-N-Divinylaniline
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, a-methoxy-
Styrene, a-methyl-
Styrene, o-chloro-
Vinyl acetate
Vinyl cinnamate
Vinylidene chloride
Vinylidene chloride
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, 2-hydroxyethyl
Styrene
Acrylonitrile
Methacrylate, methyl
Methacrylate, methyl
Pyrrolidone, N-vinyl-
Vinyl chloride
Methacrylate, methyl
Methacrylate, methyl
Styrene
Vinylidene fluoride
Methacrylate, methyl
Acrylate, N-(2-hydroxyethyl)carbazolyl
0.41
0.42
0.28
0.21
0.25
0.21
0.83
0.21
0.86
1 2
4.6
2.43
2.38
0.11
0.119
0.33
0.58
2.8
0.2
0.2
0.58
n
i.43
0.9
0.164
0.02
0.35
0.08
Acrylate, N-(2-hydroxyethyl)carbazolyl 1.364
Methacrylate, N-ethyl-3-hydroxymethyl- 0.554
carbazolyl
Acrylonitrile
Pyrrolidone, N-vinyl-
Styrene
Methacrylate, N-methyl-N-phenyl-
2-amino ethyl
Styrene
Methacrylate, N-methyl-N-phenyl-
2-amino ethyl
Styrene
Styrene
Methacrylate, methyl
Vinylchloride
Acrylamide
Acrylonitrile
Methacrylate, methyl
Styrene
Butadiene
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Styrene
Vinyl methyl ketone
Methacrylate, methyl
Styrene
Styrene p-fluoro-
Acrylonitrile
Methacrylate, methyl
Styrene
Styrene, p-methyl-
Vinyl acetate
3.74
5.66
1.66
1.11
0.48
2.6
1.17
0.32
1.37
11.26
2.85
1.1
1.67
0.7
0.12
0.12
- 0.02
0.02
0.25
1.24
0.448
1.38
0.87
- 0.006
0.005
0.033
0.06
3.99
0.04
0.1
0.05
0.02
0.009
0.12
0.16
0.045
0.026
0.018
0.019
0.22
0.4
0.16
0.18
0.02
0.08
0.03
0.64
3.5
0.74
1.3
0.06
0.081
0.143
0.07
0.018
0.067
0.03
0.12
-
0.37
0.38
0.43
0.34
0.25
0.34
0.02
0.15
0.78
0.01
0.15
0.3
0.36
1.79
1.74
0.97
0.36
0.35
0.45
0.45
0.05
0.3
0.405
0.53
0.069
7.6
0.75
1.04
0.334
0.729
0.01
0.008
0.067
0.55
0.27
0.2
0.15
0.6
0.908
0.004
0.3
0.09
0.6
0.09
1.36
1.27
0.42
0.5
0.85
5.05
0.256
0.891
0.362
0.246
1.06
5.38
6.15
0.058
0.005
0.1
0.05
0.07
0.22
0.037
0.06
0.014
0.14
0.022
0.051
0.004
0.004
0.007
0.04
0.04
0.01
0.04
0.252
0.052
0.28
0.52
0.013
0.015
0.022
0.014
0.18
0.36
0.16
0.009
N
N
N
N
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
Y
Y
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
3 1 1
311
542
707
75
835
1 4 3
542
44
75
200
7 8 1
781
798
798
822
951
580
591
593
599
432
617
660
660
669
944
702
719
701
339
339
339
651
651
651
651
687
938
938
746
745
746
746
196
196
196
196
1 9 6
512
512
1062
1062
1062
45
45
45
45
45
TABLE 1. contd
Copolymer Reactivity Ratios II / 241
Monomer 1 Monomer 2
r1
f95%
r.2 &95% Conv. Refs.
N-Vinylimidazole
N-Vinylimidazole
N-Vinylimidazole
N-Vinylimidazole
N-Vinylimidazole
N-Vinylimidazole
N-Vinylimidazole
N-Vinylimidazole
N-Vinylimidazole
N-Vinylimidazole
N-Vinylimidazole
N-Vinylpyrolidone
N-Vinylpyrolidone
N-Vinylpyrrolidone
N-Vinylpytrolidone
N-Vinylpyrrolidone
N-Vinylpytrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
N-Vinylpytrolidone
N-Vinylpyrrolidone
Naphthalene, l-vinyl-
Naphthalene, l-vinyl-
Naphthalene, l-vinyl-
Naphthalene, I-vinyl-Cchloro-
Naphthalene, 2-vinyl-
Naphthalene, 2-vinyl-6-chloro-
Naphthalene, 6-vinyl-2-rerr-butyl
Nickel diacrylate
Norbomadiene
Norbomadiene
Norbomadiene
Norbomadiene
Norbomadiene
Norbomadiene
Norbomadiene
Norbomadiene
Ott-1-ene, 4,8-dioxaspiro(2.5)-
Ott-1-ene, 6,6-dimethyl-
4,8-dioxaspiro(2.5)-
Ott-1-ene, 6,6-dimethyl-
4,8-dioxaspiro(2.5)-
Ott-1-ene, 6,6-dimethyl-
4,8-dioxaspiro(2.5)-
Ott-1-ene, 6,6-dimethyl-
4,8-dioxaspiro(2.5)-
Octene- 1
Oxazi ni um F3CS03, 3-methyl-2-vinyl-
5,6-dihydro-4H- 1,3-
Acrylic acid
Acrylonitrile
Fumarate, diethyl *
Fumarate, dimethyl
Fumaric acid
Maleate, diethyl
Maleate, dimethyl
Maleic aci d
Methacrylate, methyl
Methacrylic acid
Styrene
Caprolactam, N-vinyl-
Crotonate, hydrocortisone 21-
2-Oxazoline, 2-isopropenyl-
Acrylamido-2-methylpropane sulfonate
sodium salt
Acrylate, cyclohexyl
Carbamate, N-vinyl-r-butyl-
Ethene, 2-phenyl- 1,l -dicyano-
Itaconate, bis(tri-n-butyltin)
Methacrylate, 2-acetylsalicylicoyloxy-
3-hydroxypropyl
Methacrylate, furfuryl
Methacrylate, glycidyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, phenyl
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-vinyl-
Pyridine, 4-vinyl-
Quinine
Styrene sulfonate, sodium salt
Vinyl trimethylammonioetbyl ether
iodide
Acrylonitrile
Metbacrylate, methyl
Styrene
Styrene
Styrene
Styrene
Styrene
Titanium, dicylopentadienyl-,
dimethacrylate
Acrylate, ethyl
Acrylonitrile
Acrylonitrile
Methacrylate, methyl
Styrene, p-chloro-
Vinyl acetate
Vinyl chloride
Vinylidene chloride
Styrene
Acrylonitrile
Pyridine, 2-vinyl-
Pyrrolidone, N-vinyl-
Styrene
Vinyl chloride
Methacrylate, methyl
0.187
0.832
0.113
0.133
0.121
0.057
0.046
0.018
0.663
0.145
0.68
2.8
0.75
0.01
0.13
0.025
0.044
0.019
0.021
0.01
0.028
0.046
0.007
0.104
0.022
0.02
0.2
0.02
0.02
1.932
3.393
0.191
0.252
0.313
0.106
0.046
0.094
4.306
1.384
8.377
1.7
0.05
3.5
0.66
0.077
0.008
0.022
0.015
0.012
0.147
0.438
0.027
0.185
0.034
0.149
0.2
0.05
1.2
0.122 0.014 1.297 0.088
0.4 0.06 2.4 0.5
0.21
0.34
0.013 0.065
0.85
0.04
0.0036
0.003
0.006
0.014
0.027
0.066
- 0.026
0.039
0.014
0.01
2.2
0.084
11.6
0.02
0.018
2.29
0.899
0.062
3.96
0.032
0.006
0.002
0.002
1.13
0.498
0.236
0.198
0.247
0.956
0.756
2
2.3
1.5
0.03
5.16
4.29
4.78
5.93
2.07
4.04
4.17
1 3
12.4
9.8
0.37
7.19
0 0.02
0.451
0.574
2.02
0.75
1.345
2.44
1.014
0.95
0.088
0.073
0.401
0.45
0.093
1.38
0.244
0.107
0.321
0.699
0.76
0.395
0.39
0.616
0.65
0.028
0.096
0.233
0.68
0.049
0.6
0.069
- 0.01 0.03 2.39 0.44
0.05 0.23 0.48 0.27
0.44 0.05 0.66 0.01
- 0.5 0.52 14.68 16.78
0 0.12 69.93 24.19
1.354 0.07 0.818 0.019
0.41 0.01 0.67 0.02
0.09 0.17 1.36 0.63
0.246 0.024 1.831 0.027
1.484 1.078 0.985 0.675
0.073
0.552
0.271
- 0.57
0.31
0.04
0.075
0.109
0.85
2.216
- 0.009
1.93
3.26
0.37
0.062
0.018
0.098
0.45
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
Y
Y
N
N
Y
Y
Y
Y
Y
N
879
879
879
879
879
879
879
879
879
879
879
883
1022
894
939
1 0 6 1
991
947
941
1080
1050
1017
1084
1084
1084
1084
1013
1070
1070
1070
922
939
1037
967
967
967
806
806
806
806
895
267
267
69
267
1 8 8
1 8 8
267
267
838
838
838
838
838
329
909
References page II - 290
II / 242 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Oxazolidone, N-vinyl-
Oxazolidone, N-vinyl-
Oxazolidone, N-vinyl-
Oxazolidone, N-vinyl-
Oxazolidone, N-vinyl-
Oxazolidone, N-vinyl-
Oxazolidone, N-vinyl-
Oxazolidone, N-vinyl-
Oxazoline, 2-, 2-isopropenyl-
Oxazoline, 2-, 2-isopropenyl-
Oxazoline, 2-, 2-isopropenyl-
Oxazoline, 2-, 2-isopropenyl-
Oxazoline, 2-, 2-isopropenyl-
Oxazoline, 2-, 2-isopropenyl-
Oxazoline, 2-, 2-isopropenyl-
Oxazoline, 2-, 2-isopropenyl-
Oxazoline, 2-, 2-isopropenyl-
Oxazoline, 2-, 2-isopropenyl-
4,4-dimethyl-
Oxazoline, 2-, 2-isopropenyl-
4,4-dimethyl-
Oxazoline, 2-, 2-isopropenyl-
4,4-dimethyl-
Oxazoline, 2-, 2-isopropenyl-
4,4-dimethyl-
Oxazoline, 2-, 4-acryloxymethyl-
2,4-dimethyl-
Oxazoline, 2-, 4-acryloxymethyl-
2,4-dimethyl-
Oxazoline, 2-, 4-acryloxymethyl-
2,4-dimethyl-
Oxazoline, 2-, 4-acryloxymethyl-
2,4-dimethyl-
Oxazoline, 2-, 4-methacryloxy-
2,4-dimethyl-
Oxazoline, 2-, 4-methacryloxy-
2,4-dimethyl-
Oxazoline, 2-, 4-methacryloxy-
2,4-dimethyl-
Oxazoline, 2-, 4-methacryloxy-
2,4-dimethyl-
Oxazoline, 2-isopropenyl-2-
Oxazoline, 2-isopropenyl-2-
Oxazoline, 2-isopropenyl-2-
Oxazoline, 2-isopropenyl-2-
Oxazoline, 2-isopropenyl-2-
Oxazoline, 2-isopropenyl-2-
Oxazoline, 2-isopropenyl-2-
Oxazoline, 2-isopropenyl-2-
Oxazol i ni um BFJ, 3-methyl-
2-isopropenyl-2-
Oxazol i ni um BF4, 3-methyl-
2-isopropenyl-2-
Oxazolinium, 2-, tetrafluoroborate
3-methyl-2-isopropenyl-
Oxazolinium, 2-, tetrafluoroborate
3-methyl-2-isopropenyl-
Oxazolinium, 2-isopropenyl-2-
Oxi rane, 4-vinylphenyl-
Pentadiene, cis- 1,3-
Pentadiene, cis- 1,3-
Pentadiene, cis-1,3-
Pentadiene, cis-1,3-
Pentadiene, cis-1,3-
Pentadiene, cis-1,3-
Methacrylate, decyl
Methacrylate, methyl
Methacrylate, methyl
Styrene
Vinyl acetate
Vinyl acetate
Vinyl chloride
Vinylidene chloride
Acrylate, butyl
Acrylate, ethyl
Acrylate, methyl
Acrylate, methyl
Acrylonitrile
Methacrylate, methyl
Pyrrolidone, N-vinyl-
Styrene
Vinyl acetate
Acrylate, methyl
- 0.052
0.04
0.027
- 0.029
1.55
2.04
0.822
0.091
1.4
1.39
1.9
2.07
0.52
0.99
3.5
0.64
7.1
1.3
0.049
0.13
0.008
0.014
0.28
0.13
0.048
0.077
0.191
12.19
6.75
9.46
29.42
0.602
0.55
0.313
1.42
0.24
0.19
0.16
0.328
0.13
0.69
0.01
0.67
0.25
0.46
1.35
0.37
0.39
2.19
0.038
0.18
0.095
0.11
0.032
Y 36
Y 102
Y 36
Y 36
Y 102
Y 36
Y 36
Y 1 0 2
862
862
862
Y 877
862
862
862
862
862
596
Acrylonitrile 1.83 0.24 596
Methacrylate, methyl 0.82 0.53 596
Styrene 0.68 0.55 596
Acrylate, methyl 0.11 0.29 596
Methacrylate, methyl 0.11 0.41 596
Styrene 0.14 0.56 596
Vinyl acetate 1.41 0.03 596
Acrylate, methyl 0.56 0.4 596
Acrylonitrile 0.89 0.11 596
Methacrylate, methyl 0.19 1.17 596
Vinyl acetate 6.2 0.05 596
Acrylate, butyl 1.4 0.08 0.24 0.01 894
Acrylate, ethyl 1.39 0.06 0.19 0.02 894
Acrylate, methyl 1.9 0.08 0.16 0.04 894
Acrylonitrile 0.52 0.06 0.13 0.04 894
Methacrylate, methyl 0.99 0.07 0.69 0.02 894
N-Vinylpyrrolidone 3.5 1.2 0.01 0.02 894
Styrene 0.64 0.03 0.67 0.02 894
Vinyl acetate 7.1 2 0.25 0.04 894
Acrylate, methyl 0.251 0.483 0.096 0.057 Y 908
Vinyl acetate 0.413 0.005 0.114 0.021
Acrylate, methyl 0.344 0.105 0.552 0.043
Vinyl acetate 0.366 0.151 0.43 0.057
Acrylate methyl
Styrene
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
2.08
1.06
0.172
0.241
0.017
0.071
0.198
0.188
0.327 0.191
0.78
0.026
0.06
0.026
0.06
0.056
0.033
0.031
0.012
0.029
0.012
0.029
0.018
0.071
0.173
0.242
0.011 0.017
Y 908
Y 877
Y 877
Y 908
1 0 0 1
Y 867
Y 867
Y 912
Y 912
952
N 997
TABLE 1. contd
Monomer 1 Monomer 2
n
copol ymer React i vi t y Rat i os II/243
*95%
r2
zt95% Conv. Refs.
Pentadiene, cis-1,3- Butadiene 0.26
Pentadiene, cis- 1,3- Pentadiene, tram-1,3- 0.86
Pentadiene, rrans-1,3- Acrylonitrile 0.104
Pentadiene, tram- 1,3- Acrylonitrile 0.095
Pentadiene, trans- 1,3- Acrylonitrile 0.018
Pentadiene, tram- 1,3- Acrylonitrile 0.064
Pentadiene, trans-1,3- Acrylonitrile 0.132
Pentadiene, tram-1,3- Acrylonitrile 0.114
Pentadiene, tram- 1,3- Butadiene 0.09
Pentadiene, tram- 1,3- Methacrylate, methyl 0.379
Pentadiene, tram- 1,3- Pentadiene, cis-1,3- 0.37
Pentadienoate, trans-4-ethoxy-2,4-,ethyl Styrene 12.2
Pentadienoate, trans-4-ethoxy-2,4-,ethyl Acrylonitrile 5.4
Pentadienoate, trans-4-ethoxy-2,4- Styrene 11.8
Penten-2,4-one Styrene - 0.033
P e n t e n e - 1 Vinyl chloride 0.001
P e n t e n e - 1 Vinyl chloride 0.81
Pentene- 1, 2-methyl- Vinyl chloride - 1.16
Pentene-1, 5-cyclohexyl- Acrylonitrile - 0.043
Pentene-1, 5-phenyl- Acrylonitrile - 0.026
Pentenoate, 3-oxo-4-, ethyl Styrene 3.29
Pentenoate, 3-oxo-4-, ethyl Styrene 1.57
Pentenoate, 3-oxo-4-, ethyl Styrene 1.29
Pentenoate, 3-oxo-4-, ethyl Styrene 1.4
Pentenoate, 3-oxo-4-, ethyl Styrene 0.923
Pentenoate, 3-oxo-4-, ethyl Styrene 0.147
Pentenoate, 3-oxo-4-, ethyl Styrene 0.635
Pentenoate, 3-oxo-4-, ethyl Styrene 1.12
Pentenoate, 3-oxo-4-, ethyl Styrene 0.568
Pentenoate, 3-oxo-4-, ethyl Methacrylate, methyl 3.39
Pentenoate, 3-oxo-4-, ethyl Methacrylate, methyl 2.02
Pentenoate, 3-oxo-4-, ethyl Methacrylate, methyl 3.06
Pentenoate, 3-oxo-4-, ethyl Methacrylate, methyl 1.67
Pentenoate, 3-oxo-4-, ethyl Methacrylate, methyl 1.24
Pentenoate, 3-oxo-4-, ethyl Methacrylate, methyl 1.72
Pentenoate, 3-oxo-4-, ethyl Methacrylate, methyl 1.69
Pentenoate, 3-oxo-4-, ethyl Methacrylate, methyl 0.12
Pentenoate, 3-oxo-4-, ethyl Methacrylate, methyl 1.55
Pentenoate, 3-oxo-4-, ethyl Methacrylate, methyl 1.09
Pentenoate, 4-methyl-3-oxo-4-, ethyl Methacrylate, methyl 2.56
Pentenoate, 4-methyl-3-oxo-4-, ethyl Methacrylate, methyl 0.748
Pentenoate, 4-methyl-3-oxo-4-, ethyl Methacrylate, methyl 1.14
Pentenoate, 4-methyl-3-oxo-4-, ethyl Methacrylate, methyl 0.952
Pentenoate, 4-methyl-3-oxo-4-, ethyl Methacrylate, methyl 1.67
Pentenoate, 4-methyl-3-oxo-4-, ethyl Methacrylate, methyl 1.04
Pentenoate, 4-methyl-3-oxo-4-, ethyl Methacrylate, methyl 1.05
Pentenoate, 4-methyl-3-oxo-4-, ethyl Methacrylate, methyl 0.725
Pentenoate, 4-methyl-3-oxo-4-, ethyl Methacrylate, methyl 1.09
Phenol, 3-(methacryloylamino)- Styrene 0.99
Phenol, 4-(methacryloylamino)- Styrene 0.86
Phosphate diethyl isopropenyl Acrylonitrile 0.03
Phosphate diethyl isopropenyl Vinyl acetate 0.44
Phosphate, 2-(acryloyloxy)ethyl diethyl Methacrylate, methyl 0.486
Phosphate, 2-(acryloyloxy)ethyl diethyl Methacrylate, methyl 0.521
Phosphate, 2-(acryloyloxy)ethyl diethyl Methaqlate, met hyl 0.946
Phosphate, 2-(acryloyloxy)ethyl diethyl Methacrylate, methyl 1.16
Phosphate, 2-(acryloyloxy)ethyl diethyl Methacrylate, methyl 0.42
Phosphate, 2-(acryloyloxy)ethyl diethyl Methacrylate, methyl 0.258
Phosphate, 2-(acryloyloxy)ethyl diethyl Methacrylate, methyl 0.0701
Phosphate, 2-(acryloyloxy)ethyl diethyl Styrene 0.171
Phosphate, 2-(acryloyloxy)ethyl diethyl Styrene 0.15
Phosphate, 2-(acryloyloxy)ethyl diethyl Styrene 0.146
Phosphate, 2-(acryloyloxy)ethyl diethyl Styrene 0.168
Phosphate, 2-(acryloyloxy)ethyl diethyl Styrene 0.094
Phosphate, 2-(acryloyloxy)ethyl diethyl Styrene 0.23
0.01
0.021
0.01
0.02
0.009
0.013
0.055
5.2
2.31
0.044
0.046
0.712
0.193
0.309
0.322
0.075
0.073
0.068
0.112
0.035
0.263
0.141
0.349
0.183
0.168
0.123
0.236
0.12
0.224
0.09
0.218
0.155
0.109
0.164
0.143
0.111
0.108
0.08
0.09
0.04
0.03
0.088
0.138
0.436
0.248
0.097
0.226
0.052
0.01
0.05
0.073
0.355
0.02
0.187
0.63
0.37
0.07
0.06
0.069
0.068
0.085
0.079
1.22
0.404
0.86
0.04
0.01
0.08
13.84
4
2.08
1.59
4.22
3.84
0.233
0.161
0.215
0.189
0.179
0.164
0.162
0.178
0.217
0.555
0.424
0.591
0.443
0.34
0.51
0.606
0.269
0.715
0.528
0.597
0.38
0.513
0.43
0.474
0.581
0.616
0.663
0.528
0.5
0.71
15.2
1.56
2.31
2.23
1.87
1.97
2.1
2.56
2.04
0.629
0.612
0.595
0.597
0.633
0.61
0.017
0.064
0.104
0.096
0.018
0.038
0.57
1.78
0.68
0.45
0.48
0.069
0.028
0.051
0.05
0.014
0.015
0.015
0.02
0.009
0.032
0.022
0.046
0.032
0. 03 1
0.023
0.045
0.027
0.048
0.02
0.03
0.034
0.022
0.034
0.023
0.025
0.024
0.023
0.02
0.06
0.04
0.046
0.047
0.086
0.029
0.045
0.094
0.012
0.003
0.004
0.005
0.044
0.002
0.018
Y
Y
Y
Y
N
Y
Y
N
N
N
Y
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
143
743
867
867
912
912
952
997
743
1058
743
723
723
123
112
3
329
329
24
24
930
930
930
930
930
930
930
930
930
1033
1033
1033
1033
1033
1033
1033
1033
1033
1033
1033
1033
1033
1033
1033
1033
1033
1033
1033
896
896
650
650
971
971
971
971
971
971
971
971
971
971
971
971
971
References page II - 290
II/244 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rt
Zt95%
rt
It95% Conv. Refs.
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphate, vinyl bis(chloroethy1)
Phosphate, vinyl diethyl
Phosphate, vinyl diethyl
Phosphate, vinyl diphenyl
Phosphate, vinyl diphenyl
Phosphazene, isopropenylpentafluoro-
Phosphazene, isopropenylpentafluoro-
Phosphine oxide, diphenylvinyl-
Phosphine oxide, diphenylvinyl-
Phosphonate, 2-(4-vinylphenyl)ethyl,
diethyl
Phosphonate, 4-vinylphenyl, diethyl
Phosphonate, a-bromovinyl-, diethyl
Phosphonate, u-carboethoxyvinyl-, diethyl
Phosphonate, a-carboethoxyvinyl-, diethyl
Phosphonate, a-carboethoxyvinyl-, diethyl
Phosphonate, isopropenyl-, dimethyl
Phosphonate, isopropenyl-, dimethyl
Phosphonate, isopropenyl-, dimethyl
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, dibutyl
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, diisobutyl
Phosphonate, vinyl-, diisobutyl
Phosphonate, vinyl-, diisopropyl
Phosphonate, vinyl-, dimethyl
Phosphonate, vinyl-, dimethyl
Phosphonate, vinyl-, dimethyl
Phosphonate, vinyl-, dimethyl
Phosphonate, vinyl-, dimethyl
Phosphonate, vinyl-, dimethyl
Phosphonate, vinyl-, dimethyl
Phosphonate, vinyl-, diphenyl
Phosphonate, vinyl-, diphenyl
Phosphonate, vinyl-, dipropyl
Phosphonic acid, a-phenylvinyl
Phosphonic acid, wphenylvinyl-
Phosphonic acid, wphenylvinyl-
Phosphonic acid, wphenylvinyl-
Phosphonic acid, cr-phenylvinyl-
Phosphonic acid, a-phenylvinyl-
Phosphonic acid, a-phenylvinyl-
Phosphonic acid, a-phenylvinyl-
Phosphonic acid, wphenylvinyl-
Phosphonic acid, cl-phenylvinyl-
Phosphonic acid, u-phenylvinyl-
Styrene 0.108
Styrene 0.03
Vinyl chloride 0.15
Vinyl chloroacetate 0.374
Vinyl chloride 0.327
Vinyl chloroacetate 0.53
Styrene -0.121
Styrene, p-chloromethyl- - 0.048
Acrylonitrile 0.16
Vinyl acetate 1.7
Styrene 1.36
Styrene
Methacrylate, methyl
Methacrylate, methyl
Phosphonate, vinyl-, diethyl
Methacrylate, methyl
Methacxylate, methyl
Styrene
Vinyl acetate
Ethylene
Methacrylate, methyl
Styrene
Styrene
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl acetate
Styrene
Methacrylate, methyl
Methacrylic acid
Phosphonate, a-carbomethoxyvinyl
diethyl
Styrene
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Ethylene
Styrene
Styrene
Butadiene, 2-chloro-
Styrene
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Ethylene
Styrene
Styrene
Vinylidene cyanide
Acrylic acid
Acrylonitrile
Acrylonitrile
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Methacrylate, methyl
Methacrylic acid
Methacrylonitrile
1.4
0.04
0.05
0.55
0.01
0.2
0.23
0.99
7.73
0.26
0.02
0.16
0.2
0.18
0.18
0.85
0.85
0.47
-0.12
0.04
0.15
0.62
-0.15
- 0.52
0.02
0
0.74
0.6
- 0.32
- 0.52
0.1
0.4
0.15
0.02
0.74
0.74
1.66
- 0.38
- 0.41
0.1
0.04
- 0.45
0
0.07
0.07
0.1
0.1
- 0.063
0.17
0
0.034
0.23
0.047
0.046
0.023
0.12
0.088
0.067
2.19
0.39
2.33
2.18
0.22
1.46
2.52
2.22
0.29
0.72
0.83
0.41
0.077
0.3
0.599
2.47
3.4
2.01
3.009
1.42
1.6
1.64
3.8
0.38
0.55
0.7
1.25
1
0.62
4.7
30
8.6
0.14
0.077
29.9
2.46
2.3
2.2
6.32
6.32
0.09
0.09
0.33
4.97
11.1
1.9
0.55
4.36
1.59
2.45
3.88
0.04
0.09
3.87
2.57
7.5
4.61
2.45
2.45
0.04
0.04
0.088
1.74
3.81
4.58
0.7
0.34
2.36
7.75
7.75
7.5
7.5
1.362
1.49
2.24
0.002
0.78
0.21
0.2
0.077
0.15
0.27
0.58
0.003
0.43
3.44
4.27
0.24
1.59
2.13
0.01
0.16
0.68
0.13
0.12
0.084
0.16
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
971
1 3 3
779
779
779
779
765
765
843
843
796
796
684
684
684
684
684
684
684
8 0 1
410
1 3 3
410
485
592
594
592
594
595
1 2 9
684
431
684
129
1 8
592
684
592
684
801
129
129
594
1 2 9
129
592
594
592
594
801
129
129
921
132
132
590
588
597
546
597
1 3 1
130
590
TABLE 1. contd
Monomer 1 Monomer 2
rl
Copolymer Reactivity Ratios II / 245
Zt95%
r2 Zt95% Conv. Refs.
Phthalide, 3-(4-vinylphenyl)-
Phthalimide, N-(4.vinylphenyl)-
Phthalimide, N-(methacryloyloxy)-
Phthalimide, N-(methacryloyloxy)-
Phthalimide, N-(methacryloyloxy)-
Phthalimide, N-vinyl-
Phthalimide, N-vinyl-
Phthalimide, N-vinyl-
Pinene
Pinene, c(-
Piperidinol, 4-, N-methyl-4-(vinylethynyl)
Piperylene, cis-
Piperylene, truns-
Propanesulfonate, 3-[diethyl-
[2-(2-methacroyloxyethoxy)ethyl
Propene, 3,3,3-trichloro-
Propene, 3,3,3-trichloro-
Propene, 3,3,3-trichloro-
Propene, l-chloro-cis-
Propene, l-chloro-cis-
Propene, l-chloro-cis-
Propene, l-chloro-cis-
Propene, l-chloro-trans-
Propene, l-chloro-trans-
Propene, l-chloro-trans-
Propene, l-chloro-trans-
Propene, 2,3-dichloro-
Propene, 2,3-dichloro-
Propene, 2,3-dichloro-
Propene, 2,3-dichloro-
Propene, 2,3-dichloro-
Propene, 2-chloro-
Propene, 2-chloro-
Propene, 2-chloro-
Propene, 2-chloro-
Propene, 2-chloro-
Propene, 2-chloro-3-hydroxy-
Propene, 2-chloro-3-hydroxy-
Propene, 2-chloro-3-hydroxy-
Propene, 3-chloro-2-chloromethyl-
Propenyl methyl ketone
Propenyl, 2-, acetate
Propenyl, 2-chloro-, acetate
Propenyl, 2-chloro-, acetate
Propenyl, 2-chloro-, acetate
Propenyl, 2-chloro-, acetate
Propenyl, 2-chloro-, acetate
Propenyl, 2-methyl-, acetate
Propenyl, 2-chloro-, acetate
Propenyl, 2-methyl-, acetate
Propenyltriethoxysilane
Propiolactam, N-phenyl-cr-methylene-
Propionate, vinyl
Propylene
Propylene
Propylene
Propylene
Propylene
Propylene
Propylene
Propylene
Propylene
Pyrazole, 3-methyl-l-vinyl-
Pyrazole, 5-methyl-l-vinyl-
Pyrazole, N-vinyl-3,5-dimethyl-
Acrylonitrile 0.43
Acrylate, methyl 1.56
Acrylate, methyl 1.23
Acrylonitrile 1.45
Methacrylate, methyl 1.45
Acrylonitrile 0.24
Maleic anhydride 0.344
Styrene 0.07
Acrylonitrile 13.5
Methacrylate, methyl 0.08
Mal ei mi de 2.05
Methacrylic acid 0.38
Methacrylic acid 0.33
Acrylate, ethyl 0.19
Acrylonitrile
Styrene
Vinyl acetate
Acrylonitrile
Maleic anhydride
Vinyl acetate
Vinyl chloride
Acrylonitrile
Maleic anhydride
Vinyl acetate
Vinyl chloride
Carbazole, N-vinyl-
Methacrylate, methyl
Methacrylic acid
Styrene
Styrene
Acrylonitrile
Vinyl acetate
Vinyl chloride
Vinyl chloride
Vinylidene cyanide
Methacrylate, methyl
Methacrylic acid
Styrene
Styrene
Styrene
Vinyl chloride
Acrylate, methyl
Acrylic acid
Methacrylate, methyl
Styrene
Vinyl chloride
Methacrylate, methyl
Styrene
Vinylidene chloride
Vinyl chloride
Styrene
Ethylene, chlorotrifluoro-
Acrylic acid
Ethylene
Ethylene
Ethylene, chlorotrifluoro-
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Pyrazole, S-methyl-l-vinyl-
Pyrazole, S-methyl-l-vinyl-
Styrene
0.1
0
0.19
-0.12
- 0.022
- 0.012
0.1
0.01
0.05
0.011
0.33
0
0.18
0
0.05
0.036
- 0.023
1.65
4.75
0.58
0.001
0
0
0
0.01
0.08
0.25
0
0
0
0
0
0
0
0
0.406 0.106 0.626 0.025
0.63 0.04 0.08 0.01
0.62
0.08
0.196
3.1
- 0.02
0.09
0.42
1.35
0.049
0.19
0.168
0.072
0.151
0.02
0.061
0.11
0.1
0.03
0.02
0.19
0.08
0.061
0.63
0.17
0.015
0.074
0.4
0.1
0.01
0.062
0.36
5.12
0.003
0.1
0.3
0.07
0.023
0.21
0.04
0.011
0.084
1.14
0.193
0.204
0.69
0.43
0.008
6.27
0.07
1 0
0.49
0.4
0.38
3.97
12.2
6.9
0.19
23.37
0.347
7.08
11.52
19.61
0.28
3.13
4.45
1
6.02
4
3.51
3
1.164
0.186
0.095
0.75
0.204
4.4
4.5
12.5
3.37
18.12
2.2
0.7
1
1
4.1
0.7
1 0
7 1
2.4
3.43
3.2
0.02
2.35
- 0.05
5.16
2.45
2.9
1.35
0.42
8.663
0.053
0.028
0.016
0.048
0.01
0.012
0.66
0.01
0.01
1.03
2.99
0.082
0.35
2.14
1.72
0.012
0.15
0.81
1.66
0.18
0.053
0.091
0.085
0.079
0.73
6.09
0.08
0.14
0.1
0.06
0.196
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
Y
Y
Y
N
Y
N
N
721
636
979
979
979
1046
284
1 6 3
936
848
948
773
773
962
402
402
402
1 8 1
1 8 1
181
181
1 8 1
1 8 1
1 8 1
1 8 1
376
11
445
11
983
1 8 1
1 8 1
1 8 1
517
82
445
445
445
806
806
1 8 9
445
445
445
445
445
470
470
470
237
1002
1097
1 8 3
388
477
318
1 5 5
329
355
560
588
898
898
806
References page II - 290
II / 246 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contcf
Monomer 1 Monomer 2
rt
Zt95%
r2 Zt95% Conv. Refs.
Pyridazinone, 3-(2-vinyl)-6-methyl-
Pyridazinone, 3-(2-vinyl)-6-methyl-
Pyridazinone, 3-(2-vinyl)-6-methyl-
Pyridazinone, 3-(2-vinyl)-6-methyl-
4,5-dihydro-
Pyridazinone, 3-(2-vinyl)-6-metbyl-
4,5-dihydro-
Pyridazinone, 3-(2-vinyl)-6-methyl-
4,5-dihydro-
Pyridazone, 2-vinyl-3-
Pyridazone, 2-vinyl-3-
Pyridazone, 2-vinyl-6-methyl-3-
Pyridazone, 2-vinyl-6-methyl-3-
Pyridazone, 2-vinyl-6-methyl-4,5-benz-3-
Pyridazone, 2-vinyl-6-methyl-4,5-benz-3-
Pyridazone, 2-vinyl-6-phenyl-3-
Pyridazone, 2-vinyl-6-phenyl-3-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine. 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Acrylonitrile 0.19
Methacrylate, methyl 0.56
Styrene 0.85
Acrylonitrile 0.02
Methacrylate, methyl 0.08
Styrene
Methacrylate, methyl
Styrene
Methacrylate, methyl
Styrene
Methacrylate, methyl
Styrene
Methacrylate, methyl
Styrene
Acrylate, methyl
Acrylonitrile
Butadiene
Butadiene
Butadiene
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Itaconate, diethyl
Itaconate, dimethyl
Metbacrylate, methyl
Methacrylic acid
N-Vinylpyrrolidone
Styrene
Styrene
Styrene
Styrene
Sulfonic acid, o-methacryloyl-
aminobenzene-
Sulfonic acid, p-methacryloyl-
aminobenzene-
Vinyl acetate
Acetylene, phenyl-
Acrolein
Acrylate, butyl
Acrylate, butyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Butadiene, 1,4-dicarboxylate-, diethyl
Butadiene, 1-carboxylate, ethyl
Butadiene, 2-chloro-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Isoprene
Isoprene
Methacrylate, 2-hydroxyethyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylic acid
Metbacrylic acid
N-Vinylpyrrolidone
0.13
1.56
0.43
0.3
1.2
0.21
0.24
0.49
1.45
1
0.31
0.47
0.72
0.41
11.58
11.58
0.51
0.88
0.54
0.85
1 3
0.75
0.68
1.2
0.78
- 0.002
- 0.054
9
-0.12
2.51
2.59
0.28
2.25
2.13
1.72
2.12
21.9
0.44
0.41
0.4
0.06
4.35
4.35
0.47
0.46
0.64
0.73
0.86
0.76
0.64
1.1
1.69
1.38
12.4
0.04
0.04
0.05
0.02
0.03
0.03
0.3
0.02
0.02
0.19
2
0.08
0.03
0.031
0.048
0.03
0.14
0.1
0.54
0.26
0.1
0.08
0.07
0.16
0.06
0.12
0.08
0.71
2.3
0.32
0.86
0.9
0.74
1.19
5.92
0.63
0.53
0.16
0.9
1.65
0.7
0.58
0.51
0.18
0.16
0.61
1.32
1.29
0.04
0.04
0.17
0.22
0.42
0.43
0.039
0.74
0.6
0.72
0.73
1.83
2.72
0.11
2.64
0.1
0.11
0.21
0.21
0.37
0.17
0.2
0.05
0.1
0.69
0.8
5.19
0.12
0.12
0.59
0.58
0.56
0.42
0.4
0.35
0.31
0.27
0.58
0.44
0.014
0.02
0.02
0.03
0.02
0.04
0.1
0.05
0.01
0.02
0.09
0.006
0.03
0.03
0.218
0.525
0.14
0.01
0.06
0.4
0.03
0.03
0.03
0.23
0.04
0.02
0.19
0.04
0.21
0.002
N
N
N
N
N
N
N
N
N
N
N
N
Y
Y
Y
N
N
N
Y
N
N
N
N
N
Y
N
Y
340
340
340
340
340
340
897
897
897
897
897
897
897
897
232
232
462
520
56
589
592
545
545
232
552
1070
232
500
514
56
1006
1006
812
192
208
236
78
250
832
2
231
749
456
50
327
791
457
589
592
456
458
342
231
532
6
623
749
1 5
498
1070
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 247
Monomer 1 Monomer 2
r1
Zt95%
r2
*95% Conv. Refs.
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-5-ethyl-
Pyridine, 2-vinyl-5-ethyl-
Pyridine, 2-vinyl-5-ethyl-
Pyridine, 2-vinyl-5-ethyl-
Pyridine, 2-vinyl-5-ethyl-
Pyridine, 3-ethynyl-6-methyl-
Pyridine, 3-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, N-oxide-, 2-vinyl-5-ethyl-
Pyrimidine-2-one, 1,3-divinylhexahydro-
Pyrimidine, 2-N-N-dimethylamino-4-vinyl-
Pyrimidine, 4-vinyl-
Pyrrolidone, 1-benzyl-3-methylene-
5-methyl-
Pyrrolidone, 1-benzyl-3-methylene-
5-methyl-
Pyrrolidone, 1-benzyl-3-methylene-
5-methyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidope, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Ott-1-ene, 6,6-dimethyl-4,8-dioxaspiro 2.216
0.75
1.27
1.81
1.33
1.14
0.62
13.65
30
1.32
0.43
0.43
0.68
1.09
0.15
0.73
2.32
4.3
2.58
1.78
2.14
0.41
0.34
4.43
4.43
2.49
0.9
0.77
0.99
9.8
0.69
1.04
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, 2,5-dichloro-
Vinyl acetate
Vinyl acetate
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Methacrylate, methyl
Styrene
Styrene
Methacrylate, 2-hydroxyethyl
Acrylate, (-)-menthyl
Acrylate, butyl
Acrylate, ethyl
Acrylate, methyl
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Isoprene
Methacrylate, 2-hydroxyethyl
Methacrylate, methyl
Methacrylate, methyl
N-Vinylpyrrolidone
Styrene
Styrene
Vinyl chloride
Vinyl ether
Vinylhydroquinone
Styrene
Acrylate, ethyl
Styrene
Styrene
Acrylate, methyl
Methacrylate, methyl
Styrene
Acenaphthalene
Acrylate, 2,4,5-trichlorophenyl
Acrylate, 2-chloroethyl
Acrylic acid
Acrylic acid, a-bromo-
Acrylonitrile
Acryloyl chloride
Caprolactam, N-vinyl-
Carbamate, N-vinyl-, ethyl
Cinnamate, a-cyano-, methyl
Crotonaldehyde
Crotonic acid
Dioxolane, 1,3,4-methylene-2-trichlor
32
0.53
2.27
- 0.05
1.404
2.38
1.58
2.28
0.71
0.012
0.03
0.1
0.25
0.04
2.8
1.77
0.044
0.42
0.84
2.98
Di oxol ane, 1,3-, 4,4-dimethyl-5-methyl 3.87
Ethylene, chlorotrifluoro- 0.38
Fumarate, dioctyl 0.02
Imi dazol e, l-vinyl- 0.16
Maleimide, N-(2-hydroxyethyl)- 0.002
Methacrylate, 2-bromoethyl 0.02
Methacrylate, 2-hydroxyethyl - 0.019
0.062
0.32
0.12
3.64
0.03
0.18
0.06
0.12
0.04
0.45
0.34
0.32
0.13
0.09
0.07
0.18
1.5
0.16
0.22
0.4
0.88
0.03
0.071
1.06
0.24
0.47
0.17
0.008
0.21
0.12
0.008
0.02
0.07
0.01
0.074
0.002
0.046
0.073
0.46
0.5
0.55
0.57
0.55
0.14
-0.11
0
0.18
0.02
0.06
0.39
0.74
2.3
0.69
0.291
0.23
0.29
0.2
0.15
0.11
0.09
0.1
0.1
0.32
0.62
0.57
0.54
0.01
0.52
- 0.73
0.03
- 0.23
0.06
0.59
0.338
0.219
0.125
0.387
0.555
0.163
0.52
0.88
0.07
0.15
1.7
0.371
- 0.001
-0.15
0
0.04
0.01
0.3
0.04
0.96
0.038
2.44
4.841
0.04
0.15
0.18
0.17
0.004
0.07
0.02
0.05
0.01
0.017
0.04
0.03
0.04
0.04
0.02
0.01
0.002
0.07
1.09
0.36
0.11
0.13
0.017
0.095
0.025
0.07
0.053
0.02
0.69
0.05
0.001
0.01
0.03
0.04
0.19
0.01
0.133
Y
N
N
Y
N
N
N
N
N
Y
N
N
N
N
N
N
N
Y
Y
Y
N
Y
Y
Y
Y
Y
N
Y
N
Y
Y
Y
N
N
N
Y
Y
Y
838
231
4 1
456
499
532
2
6
6
231
1 1 5
50
231
231
784
342
667
78
832
2 3 1
424
1 1 5
50
589
592
424
342
2 3 1
691
1070
231
79
154
395
337
806
800
243
243
633
633
633
326
840
790
250
694
213
599
859
8 1
816
248
245
647
647
830
1 2 1
364
323
657
840
References page II - 290
II / 248 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl
*95%
r2
195% Conv. Refs.
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone. N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, a-methylene-N-methyl-
Quinine
Quinoline, 2-vinyl-
Quinoline, 2-vinyl-
Quinoline, 2-vinyl-
Quinoline, 2-vinyl-
S-Ethyl N-vinyl-N-methylthiolcarbamate
S-Ethyl N-vinyl-N-methylthiolcarbamate
S-Vinyl N, N-diethylthiolcarbamate
S-Vinyl N, N-diethylthiolcarbamate
Silane, y-methacryloxypropyltrimethoxy-
Silane, y-methacryloxypropyltrimethoxy-
Silane, y-methacryloxypropyltrimethoxy-
Silane, methacryloxypropyldimethoxy-
methyl-
Silane, methacryloxypropyltrimethoxy-
Stilbene
Stilbene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
S t y r e n e
Styrene
Styrene
Styrene
Methacrylate, ferrocenylmethyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacryloyl chloride
Methacryloylacetone
Ott-1-ene, 6,6-dimethyl-4$dioxaspiro
Oxazoline, 2-, 2-isopropenyl-
Styrene
Succinimide, N-vinyl-
Triazine, 2-allyloxy-4,6-dichloro-
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl benzoate
Vinyl butyl ether
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl cinnamate
Vinyl cyclohexyl ether
Vinyl cymantrene
Vinyl ethylene glycol glycidyl ether
Vinyl ethyleneglycol glycidyl ether
Vinyl isopropyl ether
Vinyl phenyl ether
Vinylene carbonate
Vinylferrocene
Methacrylate, methyl
N-Vinylpytrolidone
Butadiene, 2-chloro-
Isoprene
Styrene
Styrene
Styrene
Vinyl acetate
Styrene
Vinyl acetate
Acrylonitrile
Methacrylate, methyl
Styrene
Imidazole, N-Vinyl-
Imidazole, N-Vinyl-
Acenaphthalene
Styrene
2-Oxazoline, 2-isopropenyl-
3-Pyridazone, 2-vinyl-
3-Pyridazone, 2-vinyl-6-methyl-
3Pyridazone, 2-vinyl-6-methyl-
4,5-benz-3-
3-Pyridazone, 2-vinyl-6-phenyl-
4-Pentenoate, 3-oxo-, ethyl
4-Pentenoate, 3-oxo-, ethyl
4-Pentenoate, 3-oxo-, ethyl
4-Pentenoate, 3-0x0., ethyl
4-Pentenoate, 3-oxo-, ethyl
4-Pentenoate, 3-oxo-, ethyl
4-Pentenoate, 3-oxo-, ethyl
4-Pentenoate, 3-oxo-, ethyl
4-Pentenoate, 3-0x0., ethyl
Acenaphthalene
Acetylene, phenyl-
0.073 0.096 2.57 2.77
- 0.05
- 0.032
- 0.052
0.01
0.05
0.008
- 0.009
0.01
0.057
0.97
0.98
1.06
1.75
3.4
2.507
1.49
0.38
0.34
0.73
0.01
1.91
0.037
1.4
1.4
0.87
4.48
1.08
0.364
0.24
0.37
0.38
0.53
2.09
2.69
-0.11
1.22
0.1
1.89
3.79
2.06
0.868
1.39
0.08
0.068
0.028
0.15
0.3
0.34
0.61
0.61
0.004
0.018
0.4
0.075
0.028
0.42
1.55
0.89
0.25
2.79
0.21
0.039
0.95
0.25
1.77
0.057
0.03
0.063
9.39
0.03
0.59
0.053
9.3
0.1
0.11
0.068
0.14
2.09
0.007
0.059
0.16
0.058
0.26
1.17
0.34
0.77
0.594
0.309
0.096
5.62
4.63
4.36
4.04
0.58
5.66
0.552
3.5
17.2
3.67
0.5
0.26
0.19
0.195
0.408
- 0.027
0.53
0.55
0.74
1.2
-0.11
0.093
0.06
0.06
0.03
0.253
0.056
0.71
0.577
2.2
2.1
1.88
0.49
0.49
1 0
0.67
4.45
0.133
0.094
0.788
0.425
0.079
1.72
0.1
0.48
0.025
0.034
0.082
0.048
2.27
- 0.01
0
0.67
0.53
0.9
0.7
1.12
0.04
0.09
0.02
0.158
5.65
3.92
0.64
0.43
1.2
0.24
0.04
0.23
0.17
0.03
0.51
0.233
0.161
0.215
0.189
0.179
0.164
0.162
0.178
0.217
3.81
0.324
0.069
0.028
0. 05 1
0.05
0.014
0.015
0.015
0.02
0.009
0.02
1.45
3.29
1.57
1.29
1.4
0.923
0.747
0.635
1.12
0.568
0.33
0.33
0.712
0.193
0.309
0.322
0.075
0.073
0.068
0.112
0.035
0.12
Y
Y
N
Y
Y
N
Y
Y
Y
N
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
N
N
N
N
N
N
N
Y
325
213
320
3 2 1
36
691
599
339
838
862
36
96
826
1 0 3
1 2 1
36
253
215
40
582
582
200
214
308
369
818
215
214
1 0 3
308
641
922
456
456
456
458
1 9 7
1 9 7
197
1 9 7
977
977
977
1095
1088
125
725
894
897
897
897
897
930
930
930
930
930
930
930
930
930
525
357
TABLE 1. contd
Copolymer Reactivity Ratios I I / 249
Monomer 1 Monomer 2
rl
f95%
r2
Zt95% Conv. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Aconitate, trimethyl
Acrolein
Acrolein
Acrolein
Acrolein, 2-chloro-
Acrolein, methyl-
Acrolein, methyl-
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acryl ami de, 2-chloro-N,N-dimetbyl-
Acrylamide, N,N-dibutyl-
Acrylamide, NJ-diethyl-
Acrylamide, NJ-diethyl-
Acrylamide, NJ-diethyl
Acrylamide, NJ-dimethyl-
Acrylamide, N,N-dimethyl-
Acrylamide, N,N-dimethyl-
Acrylamide, N-(2-propionamido)-
Acrylamide, N-methylol-
Acrylamide, N-methylol-
Acrylamide, N-octadecyl-
Acrylamide, N-octyl-
Acrylamido, l- , -1-deoxy-D-glucitol
Acrylamidomethylamino, p-, azobenzene
Acrylate, 2,3-dibromopropyl
Acrylate, 2,4,Mrichlorophenyl
Acrylate, 2,4,6-tribromophenyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroetbylglucitol
Acrylate, 2-cyanoethyl
Acrylate, 2-ethylhexyl
Acrylate, 2-ethylhexyl
Acrylate, 2-nitrobutyl
Acrylate, 3,4-epoxyhexahydrobenzyl
Acrylate, [3-acetoxymethyl-, methyl
Acrylate, P-ethoxy-, ethyl
Acrylate, a-(4-chlorobenzyl)-, ethyl
Acrylate, a-(4-cyanobenzyl)-, ethyl
Acrylate, w(4-methoxybenzyl)-, ethyl
Acrylate, w(hydroxymethyl)-, methyl
Acrylate, cL-[2,2-bis(carbomethoxy)-
ethyl]-, methyl
Acrylate, a-acetoxy-, ethyl
Acrylate, a-benzyl-, ethyl
Acrylate, a-benzyl-, methyl
Acrylate, a-bromo-, ethyl
Acrylate, a-butyl-, methyl
Acrylate, a-chloro-, ethyl
Acrylate, u-chloro-, methyl
Acrylate, a-cyano-, methyl
Acrylate, u-cyclohexyl-, methyl
Acrylate, a-ethyl-, methyl
Acrylate, a-ethyloxymethyl-, methyl
Acrylate, cr-fluoro-, methyl
1.026
0.257
0.22
0.205
0.02
0.173
0.41
1.17
1.21
1.49
1.13
0.65
1.05
1.29
1.6
1.23
1.36
1.54
1.15
1.37
1.32
1.84
0.03
1.55
2.08
2.715
2.42
0.083
0.42
0.277
0.2
0.55
0.494
0.54
0.49
0.399
0.96
0.94
0.35
0.27
0.34
46.98
0.04
0.06
0.33
0.36
0.58
0.557
0.14
0.57
0.02
0.812
0.08
0.25
0.05
1.615
0.758
0.37
0.66
Acrylate, a-hexafluoropropyloxymethyl-, 0.23
methyl
Acrylate, whydroxymethyl-, ethyl 0.468
Acrylate, a-isobutyl-, methyl 0.974
0.091
0.017
0.02
0.006
0.05
0.017
0.06
0.04
0.16
0.03
0.065
0.058
0.35
0.1
0.12
0.21
0.05
0.12
0.244
0.08
0.048
0.47
0.097
0.2
0.032
0.3
0.03
0.3
27.03
0.09
0.05
0.3
0. 03 1
0.17
0.028
0.04
0.043
0.07
0.01
0.048
0.014
0.17
0.03
0.022
- 0.013
0.216
0.02
0.32
0.15
0.833
0.3
0.58
1.32
0.33
0.59
8.97
0.2
- 0.036
0.294
0.39
0.34
0.18
0.12
0.49
0.47
0.86
0.48
0.4
0.54
0.258
0.03
8.5
0.16
0.23
0.1
0.1
0.139
0.12
0.14
0.128
0.31
0.26
0.12
1.97
0.19
- 0.21
1.03
0.65
0.71
0.34
0.09
0.009
0.036
0.01
0.002
0.07
0.092
0.12
0.13
0.14
0.43
0.152
0.058
0.3
0.15
0.2
0.3
0.03
0.14
0.119
0.02
0.021
0.17
0.083
0.09
0.074
0.6
0.01
0.35
0.44
0.13
0.09
0.24
0.173
0.9
0.175
0.44
0.205
0.32
0.3
0.61
- 0.001
0.197
0.24
0.16
0.07
0.01
0.2
0.053
0.08
0.053
0.11
0.05
0.034
0.014
0.11
0.546 0.127
0.202 0.042
Y
Y
N
Y
Y
N
N
N
N
Y
N
N
N
N
Y
N
Y
Y
Y
Y
N
N
N
Y
Y
Y
Y
N
Y
Y
Y
Y
1 4 7
291
292
307
806
223
589
295
314
314
314
343
555
917
806
739
739
739
170
315
315
295
596
8 9 1
290
806
258
858
643
622
643
140
1 7 8
790
806
1 7 8
126
463
234
680
1 0 9 1
194
806
806
806
932
1092
244
806
49
806
49
806
74
1 4 1
49
49
1047
806
1047
982
49
References page II - 290
II / 250 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2 rl &95% 12 +95% Conv. Refs.
Styi-ene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
S t y r e n e
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Acrylate, a-isopropyl-, methyl
Acrylate, cc-isopropyloxymethyl-,
methyl
Acrylate, wmethoxy-, methyl
Acrylate, a-phenoxymethyl-, methyl
Acrylate, a-phenyl-, chloroethyl
Acrylate, a-phenyl-, methyl
Acrylate, cr-phenyl-, methyl
Acrylate, cc-phenyl-, methyl
Acrylate, wphenyl-, methyl
Acrylate, cc-phenyl-, propyl
Acrylate, cl-phenyl-, butyl
Acrylate, wpropyl-, methyl
Acrylate, wpropyloxymethyl-, methyl
Acrylate, a-set-butyl-, methyl
Acrylate, a-tetrafluoropropyloxymethyl-,
1.872
0.41
1.131
0.176
0.025
0.06
0.03
0.06
1.176
0.03
0.04
0.821
0.47
2.29
0.37
methyl
Acrylate, cc-trifluoroethyloxymethyl-,
methyl
Acrylate, a-trimethylsiloxy-, methyl
Acrylate, benzyl
Acrylate, benzyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, cis-S-cyano-, methyl
Acrylate, cyclododecyl
Acrylate, cyclododecyl
Acrylate, cyclododecyl
Acrylate, cyclohexyl
Acrylate, cyclohexyl
Actylate, cyclohexyl
Acrylate, cyclohexyl
Acrylate, cyclohexyl
Acrylate, di-, copper
Acrylate, di-, copper
Acrylate, di-, nickel
Acrylate, di-, zinc
Acrylate, diethylaluminum
Acrylate, diethylaluminum
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ferrocenylmethyl
Acrylate, ferrocenylmethyl
Acrylate, ferrocenylmethyl
Acrylate, glycidyl
Acrylate, glycidyl
Acrylate, heptafluorobutyl
Acrylate, isopropyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
0.26 0.2
0.46
0.494
0.534
0.79
0.79
0.75
1.23
0.44
0.84
0.66
0.82
0.8
0.698
0.698
0.05
0.028
0.08
0.11
0.1
0.21
0.03
0.2
1.42
0.2
0.248
0.25
0.34
0.38
0.106
0.29
0.18
0.19
0.21
0.15
0.164
0.164
0.12
0.041
0.05
0.06
0.05
0.099
0.05
0.03
0.47 0.14 0.34 0.15
0.54 0.08 0.31 0.08
0.461 0.07 0.301 0.072
0.913 0.107 0.272 0.048
0.885 0.102 0.254 0.141
0.53 0.11 0.16 0.13
0.7 0.12 0.17 0.09
0.58 0.1 0.18 0.07
1.74 0.03 0.56 0.09
5.94 0.05 0.12 0.08
1.83 0.02 0.53 0.06
1.1 0.02 0.9 0.07
- 0.002 0.016 0.046 0.035
0.699
1.01
0.79
0.8
0.8
0.787
0.787
1.87
2.3
2.5
0.6
0.73
0.31
0.755
0.82
0.192
0.722
0.072
0.17
0.34
0.01
0.024
0.057
0.056
0.139
0.16
0.19
0.2
0.48
0.152
0.152
0.016
0.02
0.02
0.17
0.24
0.049
0.195
0.24
0.8
0.168
0.085
0.06
0.58
0.013
0.027
0.21
0.067
0.052
0.078
0.05
0.015
0.015
0.015
0.022
0.029
0.068
0.036
0.26
0.513
0.256
0.201
1
0.4
0.45
1.275
0.126
0.107
0.208
0.29
0.004
0.17
0.034
0.058
0.102
0.09
0.008
0.063
0.055
0.07
0.024
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
N
N
N
N
Y
Y
Y
Y
N
Y
Y
Y
Y
49
1047
806
1048
488
1 4 1
399
488
49
488
488
49
1047
49
1047
1047
1 1 0 1
1 7 8
277
1032
1032
1032
1 9
20
38
3 8
463
549
612
632
1034
806
806
806
1 0 6 1
806
806
806
806
829
829
829
829
652
652
1 7 8
463
530
530
542
673
677
293
293
576
1 1 4
1 2 6
206
1 7 8
1 3 9
1 4
151
TABLE 1. contd
Copolymer Reactivity Ratios II / 251
Monomer 1 Monomer 2
rl
595%
r2
*95% Conv. Refs.
Styrene Acrylate, methyl
Styrene Acrylate, methyl
Styrene Acrylate, methyl
Styrene Acrylate, methyl
Styrene Acrylate, methyl
Styrene Acrylate, methyl
Styrene Acrylate, methyl
Styrene Acrylate, octadecyl
Styrene Acrylate, octadecyl
Styrene Acrylate, octadecyl
Styrene Acrylate, octadecyl
Styrene Acrylate, octyl
Styrene Acrylate, p-(cinnamoylamino)phenyl
Styrene Acrylate, pentabromophenyl
Styrene Acrylate, pentachlorophenyl
Styrene Acrylate, tetrahydrofurfuryl
Styrene Acrylate, thio-, butyl
Styrene Acrylate, thio-, ethyl
Styrene Acrylate, thio-, tert-butyl
Styrene Acrylate, trifluoro-, methyl
Styrene Acrylate, trifluoro-, methyl
Styrene Acrylic acid
Styrene Acrylic acid
Styrene Acrylic acid
Styrene Acrylic acid
Styrene Acrylic acid
Styrene Acrylic acid
Styrene Acrylic acid
Styrene Acrylic acid
Styrene Acrylic acid, 2-benzamido-
Styrene Acrylic acid, N-acetyl-a-amino-
St y r e n e Acrylic anhydride
St y r e n e Acrylonitrile
Styrene Acrylonitrile
Styrene Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile
St y r e n e Acrylonitrile- 2-chloro-
St y r e n e Acrylonitrile, 2-fluoro-
St y r e n e Acrylonitrile, a-chloro-
St y r e n e Acrylonitrile, wfluoro-
St y r e n e Acrylonitrile, a-hydroxymethyl-
St y r e n e Acrylonitrile, a-methoxy-
Styrene Acryloyl chloride
Styrene Acryloyloxy, 2-, benzoic acid
Styrene Adipate, divinyl
Styrene Ally1 acetate
Styrene Ally1 acetate
Styrene Ally1 chloride
Styrene Ally1 chloride
Styrene Ally1 chloride
Styrene Ally1 glycidyl hexahydrophthalate
Styrene Ally1 glycidyl phthalate
0.75
0.75
0.68
0.9
0.65
0.4
0.871
0.777
0.44
0.79
0.44
0.39
1.08
0.16
2.11
0.475
0.439
0.18
0.157
1.4
1.4
0.25
1.1
0.15
0.22
0.253
0.25
0.25
0.15
0.13
0.91
0.16
0.33
0.29
0.4
0.36
0.39
0.37
0.37
0.4
0.3
0.33
0.33
0.36
0.46
0.41
0.43
0.55
0.35
0.014
0.022
0.018
0.11
0.186
0.14
0.038
0.034
0.069
0.01
0.04
0.004
0.18
0.18
0.14
0.07
0.3
0.16
0.148
0.37
0.18
0.31
0.18
0.01
0.35
0.1
0.9
0.489
0.421
0.291
0.368
0
0
0.05
0.08
0.25
0.35
0.136
0.15
0.45
0.25
0.78
0.44
0.1
0
0.02
0.05
0.03
0.06
0.05
0.07
0.04
0.17
0.17
0.15
0.17
0.07
0.06
0.03
0.06
0.01
0.087
0.13
0.44
0.205
0.534
0.1
0.06
20.36
62.8
90
35.55
0.04
0.029
0.069
0.05
0.02
0.26
82.7
15.82
0.03
0.03
0.528
0.312
0.02
0.64
0.011
0.01
0
0.05
36.8 0.03
34.3 0.06
34.8 0.14
0.026
0.12
0.53
0.196
0.17
0.075
0.055
0.029
0.004
0.06
0.04
0.02
0.086
0.054
0.02
0.02
0.011
0.05
0.16
393
397
463
495
496
496
Y 865
Y 290
290
290
290
806
685
643
900
806
806
806
806
595
598
312
312
397
414
Y 41
490
542
561
1019
661
N 219
140
N 198
269
396
403
417
543
60
727
727
727
727
727
727
727
727
812
Y 884
Y 884
806
850
Y 981
806
N 220
N 651
Y 815
N 1053
470
Y 1 0
Y 204
438
782
782
References page II - 290
II/252 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. cont' d
Monomer 1 Monomer 2
rt
f 95%
r2 &95% Conv. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
S t y r e n e
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Ally1 trichloroacetate
Azlactone, 2-vinyl-4,4dimethyl-
Azobenzene,
4-(acrylamidomethylamino)-
Benzimidazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazolone,
N-[(methacroyloxy)methyl]
Benzoxazole, vinylmercapto-
Bicyclo[2,2,1]hept-2-ene-
5,6dicarboximide, N-benzyl
Bicyclo[2,2,1]hept-2-ene-
5,6-dicarboximide, N-benzyl
Borazine, P-vinyl
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene, 1,4-dicarboxylate-, diethyl
Butadiene, l-chloro-
Butadiene, l-phtbalimido-
But adi ene, l-succinimido-
Butadiene, 2,3-dichloro-
Butadiene, 2,3dichloro-
Butadiene, 2,3dimethyl-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-trimetbylsilyloxy-
Butadiene- 1 -carboxylate,
S(-)-wphenethyl
Butadiene-1-carboxylate, ethyl
Butadiene-1-carboxylic acid
Butadiene- 1 -carboxylic acid
Butenoate, 3-phenyl-3-, methyl
Bntyrolactone, wmethylene-
Caprolactam, N-vinyl-
Carbamate, N, N-diethyl-, vinyl
Carbazole, N-methyl-3-vinyl-
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Cinnamate, 2-chloroethyl
Cinnamate, a-cyano-, 2-ethylhexyl
Cinnamate, cl-cyano-, benzyl
Cinnamate, u-cyano-, butyl
Cinnamate, cl-cyano-, cyclohexyl
Cinnamate, a-cyano-, ethyl
Cinnamate, a-cyano-, hexyl
Cimtamate, a-cyano-, met hyl
Cinnamate, benzyl
Cinnamate, butyl
Cinnamate, ethyl
Cinnamate, ethyl
2. 32 0. 15
0. 175 0. 054
0. 083 8. 5
0. 81 0. 02
0. 237 0. 129
6. 51 0. 51 0. 56 0. 41
2. 171 0. 07 0. 349 0. 087
3. 02 0. 14 0. 5 0. 095
0. 35 0. 02 3. 1 0.01
2. 87
18. 2
0. 19 0. 24
0
0.12
89. 2 0
4. 53
0. 84
0. 37
0. 38
0. 62
0. 4
0. 25
0.001
1.44
1.55
1.37
0.016
0. 56
0. 14
0. 58
0. 44
0. 6
0. 44
0. 38
0. 68
0. 82
0. 83
0. 64
0. 09
0. 27
0. 299
0. 286
0. 25
0. 05
0. 534
0. 05
0. 025
0. 214
0. 22
0. 64
0. 45
0. 13
0. 21
0.11
0.41
0. 014
0. 27
0. 049
0. 018
0.1
3.1
0. 63
0. 16
0. 035 0. 066
0. 047
0. 03
0. 15
0. 13
1. 35
1. 59
1. 8
1. 4
1. 4
0. 5
1. 38
1. 83
1. 38
0. 55
1.44
1.56
1.68
8. 65
10. 6
1. 048
7. 84
5. 98
2. 1
1. 24
1. 2
6. 81
0. 5
0. 12
0. 61
1. 68
0.12
0.15
0. 08
1. 97
0. 14
0. 2
29. 56
0. 735
6
5. 93
5. 72
1. 394
0. 58
0. 4
0. 47
0. 37
0. 364
0.01
0.01
3. 59
0. 067
1. 34
1. 05
0. 4
0. 068
0. 004
0. 03
0. 03
0. 04
0. 56
0. 52
5. 55
- 0. 532
0. 85
1. 02
- 0. 08
1. 404
- 0. 02
0. 026
0. 032
0.01
- 0. 06
- 0. 16
- 0. 09
- 0. 24
0. 512
0. 06
0.01
0.18
0.146
0. 06
0. 034
0. 057
0.11
0.01
0.17
0. 08
0. 22
0. 39 0. 04 - 0. 17 0. 26
0. 4 0. 06 - 0. 21 0. 35
1. 33 0. 12 0. 14 0. 13
1. 757 0. 082 0. 04 0. 15
1. 52 0. 31 - 0. 076 0. 054
1. 566 0. 035 0. 082 0. 045
Y
Y
Y
Y
Y
Y
N
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
N
Y
Y
Y
N
N
N
N
Y
N
N
Y
Y
Y
Y
913
1 0 1 1
880
764
764
764
960
764
994
994
1018
140
159
1 7 3
2 1
418
428
473
486
486
491
56
83
83
327
695
163
163
587
61
173
61
8
174
174
993
748
791
791
799
1008
663
916
197
806
11
13
98
488
282
282
282
282
134
282
282
488
488
200
488
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 253
Monomer 1 Monomer 2
rl It95%
r2
zt95% cow. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
St y r e n e
Styrene
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Cinnamate, methyl
Cinnamate, methyl
Cinnamate, p-chloro-, methyl
Cinnamate, p-methyl-, methyl
Cinnamate, phenyl
Ci nnamat e, terr-butyl
Cinnamide, N,N-diethyl-
Cinnamide, p-chloro-, NJVdiethyl-
Cinnamide, p-methyl-, N,N-diethyl-
Cinnamonitrile
Cinnamonitrile, a-cyano-
Citraconate, di-see-butyl
Citraconate, dibenzyl
Citraconate, dibutyl
Citraconate, dicyclohexyl
Citraconate, diethyl
Citraconate, diisobutyl
Citraconate, diisopropyl
Citraconate, dimethyl
Citraconate, dipropyl
Citraconic acid
Citraconic anhydride
Citraconimide, p-iso-,
N-(4-acetylphenyl)-
Citraconimide, b-iso-,
N-(4-chlorophenyl)-
Citraconimide, b-iso-,
N-(4-ethoxycarbonylphenyl)-
Citraconimide, f3-iso-,
N(4-methoxyphenyl)-
Citraconimide, p-iso-, N-(p-tolyl)
Citraconimide, p-iso-, N-phenyl-
Citraconimide, N-(4-acetoxyphenyl)
Citraconimide, A-(4-chlorophenyl)-
Citraconimide,
N-(4-ethoxycarbonylphenyl).
Citraconimide, N-(4-methoxyphenyl)-
Citraconimide, N-ally1
Citraconimide, N-benzyl-
Citraconimide, N-butyl-
Citraconimide, N-ethyl-
Citraconimide, N-hexyl-
Citraconimide, N-isobutyl-
Citraconimide, N-isopropyl-
Citraconimide, N-methyl-
Citraconimide, N-methyl-
Citraconimide, N-phenyl-
Citraconimide, N-propyl-
Citraconimide, N-terr-butyl-
Citraconimide, N-tolyl-
Citraconimide, cc-iso-,
N-(4.acetylphenyl)-
Citraconimide, cc-iso-,
N-(4-chlorophenyl)-
Citraconimide, wise-,
N-(4-ethoxycarbonylphenyl)-
Citraconimide, cc-iso-,
N-(4-methoxyphenyl)-
Citraconimide, cc-iso-, N-(p-tolyl)-
Citraconimide, a-iso-, N-phenyl-
Crotonaldehyde
Crotonaldehyde
Crotonaldehyde
Crotonate, a-acetyl-, methyl
Crotonate, cc-bromo-, ethyl
1.799
1.27
2.24
2.84
1.66
1.692
4.17
2.99
4.95
2.549
0.073
0.12
0.087
0.04
0.02
0.04
0
0.029
0.1
0.01
0.01
0.01
- 0.008
0.13
0.055
0.12
0.092 0.021
2
1.55
2.74
1.88
2.48
1.8
1.62
1.58
2.19
1.36
0.16
0.42
0.15
0.13
0.047
0.054
0.03
0.029
0.03
0.076
0.049
0.027
0
0.021
0
0.058
488
653
653
653
488
488
737
737
737
134
134
8 4 1
8 4 1
8 4 1
8 4 1
841
8 4 1
841
8 4 1
8 4 1
1 0 2 1
47
608
0.28 0 608
0.3 0 608
0.27 0
0.4
0.39
0.151
0.181
0.148
0.054
0.057
0.018
0
0
0.015
0.075
0.004
0.63
0.142
0.19
0.169
0. 23 1
0.316
0.326
0.244
0.15
0.14
0.175
0.196
0.465
0.31
0.81
0.19
0.087
0.028
0.044
0.086
0.094
0.055
0.016
0.062
0.039
0.13
0.04
0.004
- 0.066
0.03
- 0.002
- 0.03
0.07
- 0.014
0.24
0.24
- 0.001
- 0.014
0.045
- 0.02
0
1.03
0.96
0.39
1.69
1.76
14.7
14.7
14.7
2.7
4.42
0
0
0
0
0
0.03
0.07
0.12
0
0
608
608
608
0.086 Y 728
0.093 Y 728
0.033 Y 728
0.11 Y 728
959
0.082 Y 714
0.045 Y 714
0.05 Y 714
0.11 Y 714
0.14 Y 714
0.063 Y 714
460
506
0.023 Y 728
0.087 Y 714
0.05 Y 714
0.18 Y 728
608
608
608
608
608
608
428
428
428
785
785
References page II - 290
II / 254 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl It95% r2 *95% Conv. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
S t y r e n e
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
S t y r e n e
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Crotonate, a-carboethoxy-, ethyl
Crotonate, a-chloro-, ethyl
Crotonate, a-cyano-, ethyl
Crotonate, wmethoxy-, methyl
Crotonate, cl-methyl-, methyl
Crotonate, ethyl
Crotonate, methyl
Crotonic acid
Crotononitrile
Crotononitrile
Crotononitrile, wphenyl-
Cyclobutane, 1,2-dimethylene-
Cyclobutane, 1,2-dimethylene-
Cyclopentene, 4-, -1,3-dione
Diallyl melamine
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Diallyl phthalate
Dihydroxvdiphenylsulfone diallyl ether
Dithiane, s2-keth$lene-1,3- -
Divinylbenzene, m-
Divinylbenzene, p-
Ethylene
Ethylene, l,l-diphenyl-
Ethylene, 1,l -diphenyl-
Ethylene, l-diphenyl-
Ethylene, chlorotrifluoro-
Ethylene, dichloro-, cis-
Ethylene, dichloro-, cis-
Ethylene, dichloro-, cis-
Ethylene, dichloro-, cis-
Ethylene, dichloro-, cis-
Ethylene, p-vinyl-l, l-diphenyl-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, tetrafluoro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Ethylene, trichloro-
Formaldehyde,-S-vinyl-O-
ethylthioacetal
Fumarate, ally1 methyl
Fumarate, bis(2-butyl)
Fumarate, bis(3-chloro-2-butyl)
Fumarate, di-(2-chloroethyl)
Fumarate, di-(2-cyanoetbyl)
Fumarate, di-(2-methoxyethyl)
Fumarate, di-(Zphenylethyl)
Fumarate, di-set-butyl
Fumarate, di-terl-amyl
Fumarate, di-tert-butyl
Fumarate, dibenzyl
Fumarate, dibutyl
Fumarate, dicyclohexyl
Fumarate, dicyclopentyl
0.03
0.58
0.26
14.88
0.34
0.87
0.33
4.38
3.1
63.1
21.4
161.3
24.75
0.46
4.02 - 0.32
1.23 0.041
2.19 0.026
1.2 0.038
0.08
0.09
0.1
0.1
0.13
0.015 0.92
3.35
0.15 0.58
0.25 1.18
0.05
0.01 - 0.02
1.15
0.02 0.01
0.99 -0. 1
- 3.1
- 2.2
4.9 - 0.28
30.3 - 0.02
2.64 0.067
1.31
200
1 8 7 0
1 8 5 0
5.2 0.01
17.1 0
16.5 0
12.1 0
12.7 0
1 6 11 - 0.006
7.75 0.68 0.32
0.25 0.01 0.03
0.51 0.04 0
0.26 0.04 - 0.06
0.18 0
0.07 0.09
0.35 0.03
0.27 0
0.55 0.04
0.69 0.08
0.57 0.04
0.32 0
0.35 0.04
0.49 0.06
0.3 0.06
8.24 0
5.13 0
0.26 0.02
18.4 0.04
30.7 0.02
27 0
9.68 1.86 - 0.27
20 0
23.29 1.7 - 0.012
23.8 0
0.43 0
0.26 3.6
0.28 0.05 3.6
36.96
36.41
25.59
23.67
18.8
27.5
16.9
23.8
15.1
0.975
0.22
0.06
0.16
0.2
0.038
0.071
0.04
0.16
0.04
0.17
0.01
0.02
0.21
0.12
0.062
0.053
0.37
0.24
0.02
0.01
0.03
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
785
785
785
785
785
785
112
402
112
785
785
854
885
263
201
152
152
1 5 2
152
152
152
1 5 2
1 5 2
1016
1 0 3 1
262
262
615
281
901
1 8 9
236
1 3 7
1 3 7
40
9
9
742
204
204
40
40
59
567
40
40
40
40
59
273
713
249
249
1038
1038
1038
1038
1038
1038
1 0 3 8
1 0 3 8
1 0 3 8
1038
1 0 3 8
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 255
Monomer 1 Monomer 2
rl
*95%
r2
f95% Conv. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
S&ene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diisobutyl
Fumarate, diisopropyl
Fumarate, dimethyl
Fumarate, dipropyl
Fumarate, isopropyl butyl
Fumarate, isopropyl ethyl
Fumarate, isopropyl isobutyl
Fumarate, isopropyl methyl
Fumarate, isopropyl see-butyl
Fumarate, methyl butyl
Fumarate, methyl ethyl
Fumarate, methyl isobutyl
Fumarate, methyl isopropyl
Fumarate, methyl propyl
Fumarate, methyl set-butyl
Fumarate, methyl tert-amyl
Fumarate, methyl tert-butyl
Fumarate, mono-2-butyl
Fumarate, tert-butyl 2-ethylhexyl
Fumarate, rerr-butyl 4-methyl-2-pentyl
Fumarate, rert-butyl ethyl
Fumarate, rert-butyl isoamyl
Fumarate, tert-butyl methyl
Fumarate, tert-butyl see-butyl
Fumaronitrile
Fumaronitrile
Fumaronitrile
Fumaronitrile
Fumaronitrile
Fumaryl chloride
Furan, 2,3-dihydro-
Hexatriene, tetrachloro-
Hexene, l-, 3,4-dioic anhydride
Hexene, 2-, 3,4-dioic anhydride
Hexene, 3-, 3,4-dioic anhydride
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5, 2,4-dione
Hexene, 5, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene, 5-, 2,4-dione
Hexene-1,5-dicarboxylate, dimethyl
Imi dazol e, l-vinyl-
Imidazole, 1-vinyl-2-methyl-
Imi dazol e, I-vinyl-2-methyl-
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene
Isoprene, 3-acetoxy-
Isopropenyl methyl ketone
0.29
6.3
0.394
0.3
0.31
0.36
0.29
0.37
0.4
0.39
0.32
0.42
0.3
0.46
0.3
0.54
0.36
0.32
0.32
0.3
0.28
0.45
0.53
0.45
0.33
0.54
0.57
0.25
0.45
0.45
0.55
0.202
0.294
0.3
20
0.123
8.57
3.63
17.17
0.031
0.049
0.066
0.07
0.171
0.179
0.173
0.121
0.24
0.014
0.044
0.028
0.678
9.94
8.87
8.97
0.513
0.476
0.44
0.42
0.48
0.34
0.44
0.26
0.06
0.02
0.03
0.058
0.044
0.0428
8.4
5.6
436
0.031
0.24
0.62
0.02
0.018
0.02
0.081
0.11
0.07
0
0.1
0.02
0.05
0.055
0.03
0.02
0.01
0.01
0.01
0.16
0.02
0.02
0.02
0.03
0.16
0.05
0.02
0.06
0.03
- 0.04
0.01
0.01
0.04
0.06
0.03
0.07
- 0.016
0.006
0
0
0.85
- 0.052
- 0.08
- 0.54
1.22
1.38
1.52
1.73
1.91
1.91
2.07
2.46
2.69
2.93
3.19
4.11
0.196
0.071
0.09
0.07
1.922
1.957
1.98
2.02
1.3
4.47
0.29
0.005
0.022
0.01
0.03
0.021
0. 03 1
0.22
1
1.17
5.83
0.043
0.029
0.064
0.016
0.011
Y
Y
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
1038
139
139
139
249
562
640
1038
1038
1038
1038
1056
1056
1056
1056
1056
1056
1056
1056
1056
1056
1056
1056
1056
249
1056
1056
1056
1056
1056
1056
1 3 7
1 9 1
199
478
77
9 1
806
4
933
933
933
931
931
931
931
931
931
931
931
931
931
931
931
828
364
364
479
366
366
544
544
8 3
770
542
References page II - 290
II / 256 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
. TA BLE 1. contd
Monomer 1 Monomer 2
r1
zt95%
r2
*95% Conv. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Isopropenyl methyl ketone
Isopropenyl, 3-(1-cyclohexenyl), acetate
Isopropenylacetophenone, p-
Isopropenylisocyanate
Isopropenylisocyanate
Isopropylidene, 2,3:4,5-d&O-,
-l-vinylbenzyl-
Itaconamate, N-(4-carboethoxyphenyl).,
butyl
Itaconamate, N-(4-carboethoxyphenyl)-,
ethyl
Itaconamate, N-(4-carboethoxyphenyl)-,
methyl
Itaconamate, N-(4-carboethoxyphenyl)-,
Prowl
Itaconamate, N-(4-chlorophenyl)-, ethyl
Itaconamate, N-(4-chlorophenyl)-,
methyl
Itaconamate, N-(-chlorophenyl)-, propyl
Itaconamate, N-(4-methoxyphenyl-,
butyl
Itaconamate, N-(4-methoxyphenyl)-,
ethyl
Itaconamate, N-(4-methoxyphenyl)-,
methyl
Itaconamate, N-(4-methoxyphenyl)-,
Prwl
Itaconamate, N-(4-methylphenyl)-,
butyl
Itaconamate, N-(4-methlyphenyl)-,
ethyl
Itaconamate, N-(4-methylphenyl)-,
methyl
Itaconamate, N-(4-methylphenyl)-,
prwl
Itaconamate, N-phenyl, methyl
Itaconamate, N-phenyl-, butyl
Itaconamate, A-phenyl, ethyl
Itaconamate, N-phenyl-, methyl
Itaconamate, N-phenyl-, propyl
Itaconate, di-2[-2(2-methoxyethoxy)-
ethoxylethyl
Itaconate, diamyl
Itaconate, dibutyl
Itaconate, diethyl
Itaconate, dimenthyl
Itaconate, dimethyl
Itaconate, dimethyl
Itaconate, dimethyl
Itaconate, dioctyl
Itaconate, dipropyl
Itaconate, ethyl hexafluoroisopropyl
Itaconate, glycidyl methyl
Itaconate, mono-methyl
Itaconate, mono-methyl
Itaconate, mono-methyl
Itaconate, mono-methyl
Itaconic acid
Itaconic acid
Itaconic anhydride
Itaconic anhydride
Itaconic anhydride
Itaconimide, N-(Zchloroethyl)-
Itaconimide, N-(4-acetoxyphenyl)-
Itaconimide, N-(l-chlorophenyl)-
0.32
1.59
0.3
8.12
6.84
0.14
0.18
0.18
0.055
0.66
0.56
0.84
0.07
0.122
3.26
0.59
0.047
1.12
Y
Y
Y
542
770
266
434
99
772
0.2 0.61 678
0.23 0.2 678
0.15 0.58 678
0.26 0.4 678
0.35 0.16 678
0.38 0.18 678
0.39 0.31 678
0.12 0.69 678
0.33 0.34 678
0.26 0.41 678
0.38 0.4 678
0.19 0.31 678
0.38 0.26 678
0.3 0.16 678
0.54 0.19 678
0.39
0.12
0.45
0.31
0.5
0.53 0.022
0.18
0.49
0.21
0.52
0.18
0.2 0.015
678
678
678
1059
678
1098
0.36 0.05 0.5 0.09
0.42 0.06 0.34 0.05
0.23 0.11 0.34 0.12
0.502 0.188 0.483 0.364
0.48
0.5
0.33
0.16
0.435
0.376
0.029
0.34
0.52
0.404
0.34
0.26
0.004
0.086
0.003
0.069
0.35
0.159
0.16
0.07
0.025
0.036
0.039
0.077
0.085
0.06
0.08
0.01
0.015
0.005
0.045
0.12
0.084
0.14
0.06
0.14
0.28
0.039
0.041
0.111
0.33
0.33
0.218
0
0.12
0.405
0.456
0.785
0.162
0.21
0.2
0.052
0.15
0.11
0.086
0.67
0.09
0.09
0.05
0.092
0.21
0.18
N
N
N
Y
N
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
3 9
39
39
975
39
398
586
3 9
39
1103
806
656
656
656
656
420
76
365
62
62
642
729
729
TABLE 1. contd
Copolymer Reactivity Ratios II / 257
Monomer 1 Monomer 2
rl
&95%
r2 &95% Conv. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
S t y r e n e
Styrene
Styrene
Styrene
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Itaconimide,
N-(4-ethoxycarbonylphenyl)
Itaconimide, N-(p-chlorophenyl)-
Itaconimide, N-@-tolyl)-
Itaconimide, N-benzyl-
Itaconimide, N-butyl-
Itaconimide, N-ethyl
Itaconimide, N-isobutyl-
Itaconimide, N-kopropyl-
Itaconimide, N-methyl-
Itaconimide, N-naphthyl-
Itaconimide, N-phenyl-
Itaconimide, N-phenyl-
Itaconimide, N-phenyl-
Itaconimide, N-propyl-
Itaconimide, N-tolyl-
Maleamic acid,
N-3-dimethylamino-6-methyl
Maleate, ally1 methyl
Maleate, butyl stannyl, ally1
Maleate, chloro-, diethyl
Maleate, dibutyl tin
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, diethyl
Maleate, dimethyl
Maleate, dimethyl
Maleate, monoallyl
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride
Maleic anhydride, a-chloro-
Mal ei mi de
Mal ei mi de, N-(2,6-diethylphenyl)-
Maleimide, N-(2,6-dimethylphenyl
Mal ei mi de, N-(2-chlorophenyl)-
Mal ei mi de, N-(2-chlorophenyl)-
Maleirnide, N-(2-chlorophenyl)-
Mal ei mi de, N-(Zchlorophenyl)-
Mal ei mi de, N-(2-hydroxyethyl)-
Mal ei mi de, N-(3-dimethylaminophenyl)-
Mal ei mi de, N-(Cbromophenyl)-
Mal ei mi de, N-(4-carboxyethylphenyl)-
a-chloro-
Mal ei mi de, N-(4-chlorophenyl)-
a-chloro-
Maleimide, N-(4-hydroxyphenyl)-
-
Maleimide, N-(4-methoxyphenyl)-
a-chloro-
Maleimide, N-(4-methylphenyl)-
a-chloro-
Mal ei mi de, N-(P-chloroethyl)-a-chloro-
0.232 0.032 0.112 0.054
0.15
0.16
0.056
0.22
0.232
0.44
0.308
0.153
0.08
0.116
0.05
0.05
0.28
0.134
0.55
8.29
0.1
2.07
2.08
6.59
8
6.07
6.592
10.65
0.083
0.14
0.097
0.04
0.02
0
0.02
0.02
0.04
0.04
0.04
0.05
0.02
0.04
0.04
0.07
0.057
0.19
0.14
0.011
0.038
0.013
0.038
0.046
0.03
0.02
0.059
0.149
0.059
0.112
0.107
0.29
0.048
0.03
0.029
0.11
0.043
0.069
0.14
0.24
0.2
- 0.019
0.172
- 0.03
0.045
0.12
0.35
0.109
0.08
0.998
0.04
0.219
-0.19
0.11
0.04
0.06
0.11
0.064
0.12
0.043
0.248
0.12
0. 03 1
0.03
0.14
0.02
0.14
0.118
0.46
0.02
0.06
- 0.043
0.194
- 0.013
0.082
0.123
0.18
0.079
0.03
0.01
0.03
0.021
0.121
0.022
0.07
2.81
0.015
0.01
0.002
0.12
0.003
0.01
0.07
0.01
0.001
0.15
0.105
0.07
0.001
0
0.003
0.02
0
0
0.02
0.01
0.001
0.005
0.01
0.02
0.05
0.01
0.12
0.058
0.02
0.008
0.13
0.03
0.01
0.012
0
0.088
0.02
0.08
0.013
0.028
0.01
0.006
0.011
0.19
0.018
0.022
0.036
0.004
0.006
0.012
0.028
0.017
0.002
0.003
0.005
0.003
0.027
0.006
0.021
0.007
0.041
0.048 0.019 0.038
0.041 0.13 0.1
0. 03 1 0.049 0.061
0.048 0.019 0.078
0.05 0 0.06
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
N
N
N
Y
Y
Y
Y
N
Y
Y
N
N
Y
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
729
740
740
642
642
642
642
642
642
740
729
740
978
642
729
679
713
811
1 4
987
139
1 4
640
874
888
1 3 7
317
811
1 0 5
1 2
1 7
241
384
397
483
506
522
522
522
522
522
923
845
251
992
992
853
853
910
910
323
747
1030
973
973
323
973
973
974
References page II - 290
II / 258 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1 Ik95% r2 Z!Z95% Conv. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
S t y r e n e
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Mal ei mi de, N-[N-(a-methylbenzyl)-
aminocarbonylpentyll-
Mal ei mi de, N-[N-(a-methylbenzyl)-
aminocarbonylundecyll-
Maleimide, N-ally1
Mal ei mi de, N-benzyl-
Mal ei mi de, N-benzyl-wchloro-
Maleimide, N-butyl-
Maleimide, N-butyl-
Maleimide, N-cyclohexyl-
Maleimide, N-cyclohexyl-
Maleimide, N-ethyl-a-chloro-
Maleimide, N-hexyl-
Mal ei mi de, N-hydroxymethyl-
Mal ei mi de, N-methyl-a-chloro-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-
Maleimide, N-phenyl-a-chloro-
Maleimide-N,N-dimethylaniline,
4-(2-chlorophenyl)-
Mesaconate, di-set-butyldithiol
Mesaconate, diamyl
Mesaconate, dibenzyl
Mesaconate, dibenzyldithiol
Mesaconate, dibutyl
Mesaconate, dibutyldithiol
Mesaconate, dicyclohexyl
Mesaconate, diethyl
Mesaconate, diethyldithiol
Mesaconate, dihexyl
Mesaconate, diisoamyl
Mesaconate, diisobutyl
Mesaconate, diisobutyldithiol
Mesaconate, diisopropyl
Mesaconate, diisopropyldithiol
Mesaconate, dimethyl
Mesaconate, dimethyldithiol
Mesaconate, dioctyl
Mesaconate, diphenyl
Mesaconate, diphenyldithiol
Mesaconate, dipropyl
Mesaconate, dipropyldithiol
Mesaconic acid
Methacrylamide
Methacrylamide
Methacrylamide, 1-deoxy-D-glucitol
Methacrylamide, N-phenyl-
Methacrylate, 2,2,6,6,-tetramethyl-
4-piperidinyl
Methacrylate, 2,3-epithiopropyl
Methacrylate, 2-(sulfonic acid)ethyl
Methacrylate, 2-acetoxyethyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-chloro-
2,3,3,3-fluoropropyl
Methacrylate, 2chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
0.198 0.143 0.258 0.25 Y 1099
Y 1099
0.056
0.058
0.42
0.021
0.06
0.035
0.013
0
0.031
0.06
0.02
0.102
- 0.01
0.9
- 0.041
- 0.035
0.63
0.06
0.1
0.162
0
0.09
0.06
0
0.016
0.07
0.087
0.05
0.017
0.05
0.069
0.053
0.04
0.004
0.04
0.044
0.01
- 0.002
0.04
0.054
0.04
0.16
0.11
0.03
0.017
0.073
1003
Y 348
974
Y 1 1 5
50
1100
Y 348
974
Y 348
Y 323
974
N 1026
Y 328
992
Y 973
747
0.45
1.27
0.73
0.28
1.28
0.41
1.25
1.24
0.4
1.51
1.34
1.29
0.41
1.31
0.44
0.98
0.35
1.23
0.45
0.16
1.22
0.39
1.6
1.4
1.42
2.09
1.24
0.63
0.13
0.17
0.06
0.02
0.02
0.08
0.06
0.05
0.05
0.1
0.06
0.03
0.1
0.07
0.1
0.03
0.04
0.05
0.04
0.07
0.01
0.07
0.15
0.05
0.06
0
0.48
1.24
0.005
0.88
0.3
0.2
0.38
0.17
624
658
658
624
658
624
658
658
624
658
658
658
624
658
624
658
624
658
658
624
658
624
1 0 2 1
N 316
N 316
258
N 352
664
0.41
0.37
0.44
0.32
0.121
0.02
0.28
0.6
0.58
0.41
0.243
0.04
0.068 0.15
787
564
N 346
657
N 927
0.35
0.345
0.42
0.44
0.332
0.57
0.5
0.59
0.53
0.046
0.048
0.075
0.08
0.02
0.006
0.341
0.34
0.23
0.54
0.856
0.65
1.65
0.53
0.59
0.03
0.018
Y 179
Y 179
382
N 346
Y 350
463
878
878
903
TABLE 1. contd
Copolymer Reactivity Ratios II / 259
Monomer 1 Monomer 2
r1
Zt95%
r2
*95% Conv. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
St y r e n e
St y r e n e
St y r e n e
Styrene
Styrene
Styrene
St y r e n e
St y r e n e
St y r e n e
St y r e n e
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-methoxyethyl
Methacrylate, 2-naphthyl-, methyl
Methacrylate, 2-naphthyl-, methyl
Methacrylate, 2-naphthyl-, methyl
Methacrylate, 2-naphthyl-, methyl
Methacrylate, 2-phenethyl
Methacrylate, 3,5dimethyladamantyl
Methacrylate, 5-oxo-pyrrolidinylmethyl
Methacrylate, N-methyl-N-phenyl-
2-aminoethyl
Methacrylate, a-naphthoyloxy-, ethyl
Methacrylate, acetonyl
Methacrylate, amyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, benzyl
Methacrylate, bomyl
Methactylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, butyl
Methacrylate, chloromethyl
Methacrylate, cyanomethyl
Methactylate, cyclohexyl
Methacrylate, di-ethylene glycol
Methacrylate, dodecyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacrylate, ethyl
Methacxylate, ethyl
Methacrylate, ferrocenylmethyl
Methacrylate, ferrocenylmethyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, glycidyl
Methacrylate, hexyl
Methacrylate, isobomyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methacrylate, isobutyl
Methactylate, isopropyl
Methacrylate, isopropyl
Methacrylate, m-chlorophenyl
Methacrylate, m-nitrophenyl
Methacrylate, methoxymethyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
-
0.5
0.46
0.786
0.486
0.61
0.384
0.56
0.89
0.342
0.44
0.216
0.285
0.52
0.463
0.435
0.45
0.48
0.8
0.45
0.56
0.05
0.52
0.63
0.54
0.74
0.208
0.144
0.586
0.39
0.528
0.55
0.67
0.65
0.55
3.63
3.6
0.54
0.278
0.47
0.44
0.45
0.31
0.11
0.435
0.58
0.61
0.509
0.56
0.55
0.5
0.47
0.375
0.44
0.395
0.5
0.52
0.52
0.48
0.52
0.49
0.45
0.58
0.44
0.396
0.16
0.117
0.195
0.225
0.025
0.14
0.013
0.04
0.043
0.041
0.11
0.041
0.026
0.32
0.12
1.09
0.006
0.011
0.088
0.15
0.05
0.062
0.14
0.07
0.086
0.02
0.04
0.045
0.033
0.07
0.45
0.014
0.05
0.16
0.014
0.048
-
1.65
0.48
0.113
0.321
0.576
0.216
0.534
0.63
0.411
0.58
0.242
0.505
0.46
0.658
0.467
0. 5 1
0.42
0.3
0.5
0.31
2.52
0.47
0.64
0.64
0.59
0.298
0.28
0.57
0.67
0.3
0.36
0.26
0.29
0.33
0.019
0.01
0.16
0.539
0.46
0.54
0.55
0.74
0.73
0.514
0.44
0.24
0.271
0.58
0.4
0.42
0.74
0.209
0.185
0.586
0.5
0.46
0.46
0.42
0.45
0.46
0.47
0.48
0.5
0.22
0.126
0.098
0.477
0.422
0.099
0.21
0.033
0.02
0.018
0.115
0.2
0.084
0.048
0.38
0.2
1.1
0.03
0.041
0.28
0.08
0.1
0.12
0.022
0.03
0.04
0.08
0.1
0.284
0.098
0.13
0.3
0.036
0.013
0.054
0.069
0.13
Y
Y
Y
Y
Y
N
Y
N
Y
Y
Y
Y
Y
N
Y
Y
Y
N
Y
Y
Y
N
Y
N
N
N
Y
Y
Y
Y
Y
Y
Y
903
918
924
924
924
924
540
335
633
651
1102
958
1 7 9
111
1 7 9
487
540
602
806
179
43
463
530
530
835
712
625
179
262
179
179
530
530
570
293
576
114
217
225
225
463
849
893
999
179
806
1 7 9
463
487
463
541
1 7 7
177
821
138
1 3 9
179
20
2 1
2 1
2 1
2 1
2 1
241
References page II - 290
II / 260 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1
zt95%
r2
It95% Conv. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Methacrylate, methyl
Methacrylate, methyl
Metbacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Metbacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Metbacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Metbacxylate, met hyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methylthiomethyl
Methacrylate, octyl
Methacrylate, octyl
Methacrylate, p-(cinnamoylamino)-
phenyl
Methacrylate, p-carbomethoxypheq
Methacrylate, p-chlorophenyl
Methacrylate, p-methoxyphenyl
Methacrylate, p-methylphenyl
Methacrylate, p-nitrophenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, phenyl
Methacrylate, propyl
Methacrylate, sulfolanyl
Methacrylate, teri-butyl
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Metbacrylic acid
Methacrylic acid
Metbacrylic aci d
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic acid
Methacrylic anhydride
Methacrylic anhydride
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
Methacrylonitrile
0.42
0.49
0.564
0.585
0.44
0.47
0.54
0.52
0.38
0.52
0.54
0.44
0.52
0.5
0.56
0.53
0.485
0.48
0.371
0.62
0.52
0.5
0.55
0.55
0.41
0.472
0.497
0.432
0.57
0.275
0.338
0.65
0.56
0.62
0.482
0.34
0.499
0.49
0.223
0.246
0.247
0.26
0.565
0.2
0.545
0.21
0.22
0.2
0.15
0.2
0.38
0.124
0.17
0.041
0.067
0.627
0.55
0.221
0.13
0.1
0.37
0.38
0.43
0.34
0.14
0.047
0.007
0.08
0.052
0.059
0.055
0.1
0.084
0.11
0.089
0.25
0.09
0.049
0.064
0.081
0.1
0.054
0.02
0.04
0.04
0.092
0.03
0.046
0.03 1
0.06
0.048
0.01
0.32
0.418
0.54
0.478
0.45
0.45
0.49
0.47
0.48
0.46
0.42
0.5
0.46
0.44
0.49
0.49
0.409
0.504
0.611
0.59
0.6
0.63
0.58
0.64
0.41
0.454
0.464
0.422
0.41
0.314
0.512
0.56
0.68
0.31
0.178
0.243
0.244
0.225
0.185
0.48
0.55
0.51
0.38
- 0.2
0.61
0.55
0.64
0.66
0.49
0.56
0.28
0.602
0.85
0. 63 1
0.6
0.44
0.39
0.12
0.27
0.33
0.41
0.42
0.28
0.21
0.085
0.029
0.011
0.01
0.02
0.026
0.028
0.05
0.16
0.027
0.022
0.026
0.04
0.039
0.23
0.33
0.11
2.46
0.51
0.66
0.08
0.19
0.088
0.146
0.249
0.089
0.199
0.118
0.02
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
N
N
N
Y
Y
Y
Y
Y
Y
N
241
254
254
287
324
324
403
416
451
463
492
492
505
531
531
534
751
7 5 1
751
753
753
753
753
753
753
824
824
824
835
860
920
179
463
685
1 7 7
1 7 7
1 7 7
1 7 7
1 7 7
1 7 7
179
463
1 7 9
359
179
166
166
203
312
313
313
47
812
842
842
842
842
842
219
275
3 1 1
3 1 1
542
707
TABLE 1. contd
Copolymer Reactivity Ratios II / 261
Monomer 1 Monomer 2
rl
*95%
r2 Zt95% Conv. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
0.25
0.34
0.36
0.069
0.067
0.27
0.15
0.6
0. 09
0.42
0.5
0.85
0.891
5.38
a.377
0.699
0.76
0.395
0.39
0.616
1.831
1.93
29.42
0.55
0.56
Methacrylonitrile
Methacrylonitrile
Methacryloxypropyltrimethoxysilane
Methacryloyl fluoride
Methacryloylacetone
Methacryloyloxy, 2-, benzoate, methyl
Methacryloyloxy, 2-, benzoic acid
Methacryloyloxy, 4-,
2,2,6,6-tetramethyl
Methylenebutyrolactone
Methyleneglutaronitrile, 2-
Methyleneglutaronitrile, 2-
Methyleneglutaronittile, 2-
Myrcene
NJCDivinylaniline
N-Vinylimidazole
Naphthalene, l-vinyl-
Naphthalene, 1-vinyl-4-chloro-
Naphthalene, 2-vinyl-
Naphthalene, 2-vinyl-6-chloro-
Naphthalene, 6-vinyl-2-tert-butyl
Ott-1-ene, 4&dioxaspiro(2,5)-
Ott-1-ene, 6,6-dimethyl-4,8-dioxaspiro
Oxazolidone, N-vinyl-
Oxazoline, 2-, 2-isopropenyl-
4,4-dimethyl
Oxazoline, 2-, 4-acryloxymethyl-
2,4-dimethyl
Oxazoline, 2-isopropenyl-
Oxi rane, 4-vinylphenyl-
Pentadienoate, truns-4-ethoxy-2,4-, ethyl
Pentadienonitrile, truns-4-ethoxy-2,4-
Penten, 2-, -Cone
Phenol, 3-(methacryloylamino)-
Phenol, 4-(methacryloylamino)-
Phosphat e, 2-(acryloyloxy)ethyl di et hyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphate, 2-(acryloyloxy)ethyl diethyl
Phosphate, vinyl bis(chloroethy1)
Phosphazene, isopropenylpentafluoro-
Phosphonate, 2-(4-vinylphenyl)ethyl,
diethyl
Phosphonate, 4-vinylphenyl, diethyl
Phosphonate, a-carbomethoxyvinyl-,
diethyl
Phosphonate, isopropenyl-, dimethyl
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(Zchloroethy1)
Phosphonate, vinyl-, bis(Zchloroethy1)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, dibutyl
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, diisobutyl
Phosphonate, vinyl-, diispropyl
Phosphonate, vinyl-, dimethyl
0.67
0.78
0.04
0.08
13.84
0.5
0.71
0.629
0.612
0.595
0.597
0.633
0.61
0.599
2.47
1.6
0.55
0.7
3.88
8.6
2.46
2.3
2.2
6.32
6.32
4.97
4.36
1.59
2.45
3.87
2.57
Phosphonate, vinyl-, dimethyl 4.61 0.4
Phosphonate, vinyl-, dimethyl 2.45 0.15
Phosphonate, vinyl-, dimethyl 2.45 0.02
0.014
0.007
0.04
0.04
0.52
0.015
0.36
0.149
0.233
0.68
0.049
0.6
0.069
0.027
0.098
2.19
0.57
0.06
0.04
0.003
0.004
0.005
0.044
0.002
0.018
0.002
0.78
0.27
0.43
3.44
4.27
0.24
1.59
2.13
0.25
0.21
0.58
0.164
1.66
0.48
1.17
0.32
0.7
- 0.02
0.02
0.25
1.38
0.033
0.68
2.02
0.75
1.345
2.44
1.014
0.246
0.271
- 0.029
0.68
0.14
0.64
1.06
12.2
11.8
- 0.033
0.99
0.86
0.171
0.15
0.146
0.168
0.094
0.23
0.108
0.03
-0.121
1.36
1.4
0
0.23
0.02
0.16
0.2
0.18
0.18
-0.12
- 0.15
- 0.52
0.02
- 0.32
- 0.52
0.045
0.16
0.02
0.03
0.081
0.067
0.02
0.401
0.45
0.093
1.38
0.244
0.024
0.109
0.014
0.055
0.04
0.03
0.01
0.05
0.073
0.355
0.02
0.187
0.034
0.23
0.088
2.33
2.18
0.22
1.46
2.52
Y
Y
N
N
N
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
7 5
835
951
660
339
651
6 5 1
687
746
1 9 6
196
512
1062
45
879
967
806
806
806
806
838
838
36
596
596
862
1 0 0 1
723
723
112
896
896
971
971
971
971
971
971
971
1 3 3
765
796
796
684
684
1 3 3
410
485
592
594
1 2 9
129
1 8
592
129
129
129
129
592
594
References page II - 290
II / 262 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rt
f95%
12
*9.5% COIN. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Phosphonate, vinyl-, diphenyl
Phosphonate, vinyl-, dipropyl
Phthalimide, N-vinyl-
Propene, 2,3-dichloro-
Propene, 2,3-dichloro-
Propene, 2-chloro-3-hydroxy-
Propene 3,3,3-trichloro-
Propene, 3-chloro-2-chloromethyl-
Propneyl methyl ketone
Propenyl, 2-chloro-, acetate
Propenyl, 2-methyl, acetate
Propiolactam, N-phenyl-a-methylene-
Pyrazole, N-vinyl-3,5dimethyl-
Pyridazinone, 3-(2-vinyl)-6-methyl-
Pyridazinone, 3-(2-vinyl)-6-methyl-
4.5dihydro
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-5-ethyl-
Pyridine, 3-ethynyl-6-methyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyridine, N-oxide-, 2-vinyl-5-ethyl-
Pyrimidine, 2-N,N-dimethylamino-
4-vinyl
Pyrimidine, 4-vinyl-
Pyrrolidone, 1-benzyl-3-methylene-
5-methyl
Pyrrolidone, N-vinyl-
Quinoline, 2-vinyl-
Quinoline, 2-vinyl-
S-Ethyl N-vinyl-N-methylthiol-
carbamat e
S-Vinyl N,N-diethylthiolcarbamate
Silane, y-methacryloxypropyl-
trimethoxy-
Stilbene
Styrene, 2,4-dibromo-
Styrene, 2,5-dichloro-
Styrene, 2,5-dichloro-
Styrene, 2,5-dichloro-
Styrene, 2,5-dichloro-
Styrene, 2,4,5-tribromo-
Styrene, 3-mri-n-butylstannyl-
Styrene, 4-(t-butyldimethylsilyloxy)-
Styrene, 4-(trimethylsilyl)-
Styrene, 4-phenoxy-
Styrene, a-(trimethylsilyloxy)-
Styrene, a-methoxy-
Styrene, a-methyl-
Styrene, wmethyl-
Styrene, cr-methyl-
Styrene, cr-methyl-
Styrene, cr-methyl-
Styrene, cr-methyl-
Styrene, m-amino-
Styrene, m-amino-
Styrene, m-bromo-
Styrene, m-bromo-
1 .I4
3.81
6.21
3.51
3
12.5
6.9
3.31
18.12
4.1
7 1
0.626
8.663
0.9
5.92
0.74
0.6
0.72
0.73
0.46
0.5
0.55
0.57
0.55
0.74
2.3
0.52
- 0.73
0.06
0.338
0.219
0.555
17.2
0.49
0.49
1 0
4.45
0.425
3.92
0.14
0.268
0.18
0.23
0.26
0.23
18.5
0.877
0.48
1.38
1.48
2.51
1.21
0.96
1.09
1.13
1.08
1.12
1.04
0.786
0.5
0.55
0.16
0.68
0.66
0.18
0.73
6.09
0.025
0.196
0.03
0.1
0.03
0.03
0.15
0.05
0.07
1.09
0.11
0.017
0.095
0.053
1.55
1.72
0.48
0.048
0.17
1.61
0.08
0.17
0.351
0.34
0.41
0.03
0.11
0.01
- 0.38
- 0.41
0.07
0.05
0.036
0
0
0.01
0.08
0
0
0.406
0.049
0.85
0.13
0.75
0.68
1.2
0.78
0.75
1.27
1.81
1.33
1.14
1.09
0.15
0.69
1.04
2.27
1.404
2.38
0.71
0.057
2.09
2.69
-0.11
0.1
0.868
0
0.91
0.81
0.25
2.2
0.14
2.78
0.03
0.863
0.28
0.94
0
0.07
0.14
0.05
0.3
0.4
0.521
0.63
1.16
1.18
1.6
1.05
0.29
0.72
0.11
0.01
0.1
0.3
0.106
0.011
0.05
0.03
0.08
0.23
0.32
0.12
0.16
0.22
0.88
0.071
1.06
0.17
0.028
0.26
0.34
0.096
0.09
2.88
0.14
0.04
0.193
0.05
0.06
0.13
0.084
0.007
Y
Y
Y
N
Y
N
N
N
N
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
N
Y
N
N
N
Y
Y
129
129
1 6 3
11
983
445
402
806
806
445
470
1002
806
340
340
232
500
514
56
231
4 1
456
499
532
231
784
231
19
806
243
243
633
36
456
458
197
1 9 7
971
725
806
1 4
411
419
84
1054
985
976
1036
602
970
1 4 2
1 7 1
281
281
281
289
289
175
989
1 6 8
256
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 263
Monomer 1 Monomer 2
r1
*95%
r2
&95% Conv. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
St y r e n e
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, m-chloro- 0.57
Styrene, m-chloro- 0.64
Styrene, m-cyano- 0.851
Styrene, m-diethylaminoethyl- 1.2
Styrene, m-dimethylamino- 1.027
Styrene, m-hydroxy- 0.78
Styrene, m-methoxy- 1.742
Styrene, m-nitro- 0.279
Styrene, m-sulfonic acid fluoride 0.788
Styrene, p-2-methoxyphenyl ketone 0.23
Styrene, p-Cmethoxyphenyl ketone 0.423
Styrene, p-phenyl ketone 0.11
Styrene, p-phenyl ketone 0.13
Styrene, p-1-(2-hydroxypropyl)- 0.97
Styrene, p-2-(2-hydroxypropyl)- 0.5
Styrene, p-2-(2-hydroxypropyl)- 0.79
Styrene, p-acetoxy- 0.835
Styrene, p-acetoxy- 0.887
Styrene, p-amino- 0.41
Styrene, p-amino- 0.876
Styrene, p-bromo- 0.7
Styrene, p-bromo- 0.67
Styrene, p-bromo- 0.71
Styrene, p-bromo- 0.71
Styrene, p-bormo- 0.69
Styrene, p-chloro- 0.62
Styrene, p-chloro- 0.744
Styrene, p-chloro- 0.816
Styrene, p-chloro- 0.74
Styrene, p-chloro- 0.39
Styrene, p-chloro- 0.76
Styrene, p-chloro- 0.74
Styrene, p-chloromethyl- 0.622
Styrene, p-chloromethyl- 0.62
Styrene, p-chloromethyl- 0.6
Styrene, p-cyano- 0.24
Styrene, p-cyano- 0.28
Styrene, p-decyl- 0.88
Styrene, p-diethylaminoethyl- 1.12
Styrene, p-ethoxy 0.98
Styrene, p-fluoromethyl- 0.474
Styrene, p-formyl- 0.2
Styrene, p-formyl- 0.16
Styrene, p-iodo- 0.485
Styrene, p-iodo- 0.629
Styrene, p-mercapto- 0.607
Styrene, p-methoxy- 0.85
Styrene, p-methoxy- 1.14
Styrene, p-methoxy- 1.16
Styrene, p-methoxy- 1.05
Styrene, p-methyl- 0.891
Styrene, p-nitro- 0.193
Styrene, p-octylamine sulfonate 0.7
Styrene, p-sulfonic acid fluoride 0.171
Styrene, p-trimethoxysilyl- 0.774
Styrene, p-trimethylsilyl- 1.26
Styrene, pentachloro- 1.33
Succinimide, N-vinyl- 10.74
Succinimide, N-vinyl- 10.09
Succinimide, N-vinyl- 2.31
Succinimide, N-vinyl- 0.052
Terpyridinyl, 4-vinyl-2,2:6,2- 0.53
Tetrazole, l-vinyl- 3.85
Tetrazole, 2-methyl-5-(4-vinyl)phenyl 0.65
Tetrazole, 2-methyl-5-vinyl- 1.124
0.534
0.28
0.248
0.07
0.456
0.055
0.183
0.07
0.071
0.15
0.02
0.029
0.034
0.007
0.03
0.09
0.14
0.1
0.08
0.029
0.043
0.047
0.15
0.3
0.07
0. 22
0.19
0.19
0.151
0.093
0.039
0.188
0.19
0.6
0.086
0.092
0.045
0.126
0.47
0.19
0.49
0.46
0.98
0.032
0.384
0.045
0.081
2.3
1.09
0.363
1.21
0.617
1.33
0.661
0.5
1.268
1.52
1.85
2.58
0.55
0.91
0.56
1.25
1.305
1.218
0.22
1.07
1.05
1.1
0.99
1.05
1
1.08
1.029
1.062
1.03
0.76
1.76
1.02
1.12
1.12
1.66
1.22
1.16
0.26
0.59
0.71
1.399
3
1.43
1.044
0.965
0.907
0.69
1.01
0.82
0.79
0.993
1.13
2.7
1.372
1.581
1.15
0.07
0.045
0.045
0.01
7
1.26
0.184
1.3
0.62
0.08
0.26
0.264
0.06
0.232
0.14
0.236
0.58
0.93
0.83
9.44
0.05
0.069
0.004
0.07
0.05
0.11
0.07
0.056
0.014
0.12
0.17
0.2
0.46
0.11
1.32
0.19
0.14
0.236
0.159
0.124
0.223
0.1
1.27
0.028
0.13
0.188
0.342
0.72
0.1
0.036
0.072
0.23
1.6
0.33
0. 03 1
0.21
N
Y
Y
N
N
Y
N
Y
Y
Y
Y
N
Y
N
N
Y
Y
N
Y
Y
Y
Y
N
Y
Y
1 6 8
256
806
806
806
3 5
806
222
806
806
806
806
806
380
390
547
806
806
775
989
125
1 2 8
256
447
554
1 2 8
139
139
140
150
523
554
756
806
806
1 2 8
256
806
806
806
806
1025
956
806
839
806
1 2 8
160
256
535
261
256
817
806
806
806
7
104
1 6 3
693
80
953
925
583
670
References page II - 290
II f 264 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
0
It95%
r2
It95% Conv. Refs.
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Tetrazole, 2-phenyl-5-(4-vinyl)phenyl-
Tetrazole, 5-phenyl-2-(4vinyl)phenyl-
Tetrazole, 5-vinyl-
Tetrazole, 5-vinyl-
Toluenesulfonamide, NJ-methyl-vinyl-
Triallyl citrate
Triallyl cyanurate
Triallyl isocyanurate
Tri azi ne, 1,3,5-, 2-amino-4-(N-methyl-
p-aminoanilino)-
Tri azi ne, 1,3,5-, 2-amino-4-(N-methyl-
p-nitroanilino)-
Tri azi ne, 1,3,5-, 2-amino-4-(p-nitroanil)-
Triazine, 4,6-diamino-2-vinyl-
Triazole, 1,2,3-, I-p-bromophenyl-4-vi
Tri azol e, 1,2,3-, 4(5)-vinyl-
Urea, 1,3-divinyl-1,3-diphenyl-
Urea, N-acryloyl-N-benzoyl-
Urea, N-vinyl-N-ethyl-
Valerolactone, cc-methylen-
Valerolactone, wmethylene-
Vinyl 2-, 1, 1-dichlorocyclopropane
Vinyl 2-, 2-methyl-4,4,6-6-tetraphenyl
cyclotrisiloxane
Vinyl 2-chloroethyl ether
Vinyl 4, dithiobenzoate methyl
Vinyl 4-chlorocyclohexyl ketone
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetoxymethyl ketone
Vinyl benzoate
Vinyl benzoate
Vinyl benzyl sulfide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl butyl ether
Vinyl butyl sulfide
Vinyl butylsulfonate
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloroacetate
Vinyl chloroacetate
Vinyl chloromethyl ketone
Vinyl cymantrene
Vinyl dichloroacetate
Vinyl dodecyl ether
Vinyl dodecyl ether
Vinyl ether
Vinyl ethyl ether
Vinyl ethyl ether
Vinyl ethyl ketone
Vinyl ethyl ketone
Vinyl ethyl ketone
Vinyl ethyl ketone
Vinyl ethyl oxalate
Vinyl ethyl sulfide
0.95
0.48
0.78
0.78
5.6
20.02
32.45
28.6
0.306
0.169 0.013 1.676 0.065
0.257
1.104
1.32
1.48
3.62
0.404
10.78
0.097
0.096
17.98
0.11
160
0.111
0.53
42.48
18.8
56
48
60
57.8
0.103
34.8
31.56
2.32
16.88
18
1 5
21.25
2.69
1.74
27.54
17.24
23.92
2 5
12.4
14.7
14.57
45
0.127
2.324
20
27
56
152
90
1 1 1
13.83
0.2
0.29
0.665
5.62
4.76
0.3
1.13
0.81
1.27
1.39
0.054
0.062
0.157
0.15
0.12
0.98
2.07
0.59
0.009
26.85
2.87
0.011
29.3
4.33
0.25
0.94
8.26
16.53
0.25
0.27
7.35
1.12
3.6
5
29.2
62.41
0.047
0.06
1 8 5
15.5
1.44
0.08
0.16
0.021
1.06
0.2
1
2.2
0.31
0.31
- 0.58
0.076
0.22
- 0.05
0.44
0.91
0.538
0.73
0.52
- 1.76
0.053
- 0.33
1.42
1.44
0
0.8
0.07
2.08
0.58
- 0.04
0.02
0.01
0.05
0.16
0.08
0.368
- 0.02
0.06
0.04
0.012
0.06
0.09
- 0.08
- 0.06
0
- 0.06
0.058
0.16
0.005
0.04
0.01
- 0.04
0.03
0.507
0.096
0.28
0
0
1.2
0
- 0.122
- 0.033
0.43
0.332
0.122
-0.12
0.113
0.02
0.44
0.041
0.12
0.11
0.12
0.18
0.141
0.4
0.26
1.36
0.33
0.034
0.81
0.072
0.12
0.018
1.62
0.15
0.17
0.049
0.2
0.78
0.18
0.16
0.08
0.003
0.08
0. 03 1
0.87
0.24
0.039
0.014
5.3
0.066
0.023
0.06
0.043
0.017
0.19
0.032
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
N
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
583
583
870
902
80
367
201
201
364
364
364
806
670
670
800
1090
101
919
855
806
626
597
697
668
1 5 8
241
481
481
481
812
806
26
696
303
34
34
368
241
303
1 8 5
109
238
242
46
516
59
212
542
353
354
542
374
374
45
1 4 0
194
112
344
353
550
1 2 4
303
TABLE 1. contd
Copolymer Reactivity Ratios II / 265
Monomer 1 Monomer 2
r1 *95% r2 f95% Conv. Refs.
Styrene Vinyl ethyl sulfide
Styrene Vinyl ethyl sulfioxde
Styrene Vinyl ethyl sulfoxide
Styrene Vinyl hendecanoate
Styrene Vinyl iodide
Styrene Vinyl isobutyl ether
Styrene Vinyl isobutyl ether
Styrene Vinyl isobutyl ether
Styrene Vinyl isobutyl sulfide
Styrene Vinyl isopropyl ketone
Styrene Vinyl isopropyl ketone
Styrene Vinyl isopropyl ketone
Styrene Vinyl isopropyl sulfide
Styrene Vinyl isothiocyanate
Styrene Vinyl isothiocyanate
Styrene Vinyl methyl ketone
Styrene Vinyl methyl ketone
Styrene Vinyl methyl ketone
Styrene Vinyl methyl sulfide
Styrene Vinyl methyl sulfide
Styrene Vinyl methyl sulfide
Styrene Vinyl methyl sulfone
Styrene Vinyl methyl sulfoxide
Styrene Vinyl octyl ether
Styrene Vinyl pelargonate
Styrene Vinyl phenyl ether
Styrene Vinyl phenyl ketone
Styrene Vinyl phenyl ketone
Styrene Vinyl phenyl sulfide
Styrene Vinyl phenyl sulfide
Styrene Vinyl phenyl sulfone
Styrene Vinyl stearate
Styrene Vinyl sulfone
Styrene Vinyl lert-butyl ketone
Styrene Vinyl rert-butyl ketone
Styrene Vinyl reti-butyl sulfide
Styrene Vinyl thiolacetate
Styrene Vinyl, 1-cyano, acetate
Styrene Vinyl, 2-bromo-, ethyl ether
Styrene Vinyl, p-benzylmethylcarbinol
Styrene Vinyl-tri~(trimethoxysiloxy)silane
Styrene Vinyl-&(trimethoxysiloxy)silane
Styrene Vinylacetophenone, p-
Styrene Vinylanthracene, 9-
Styrene Vinylanthracene, 9-
St y r e n e Vinylbenzoic acid, p-
St y r e n e Vinylene carbonate
St y r e n e Vinylene carbonate
St y r e n e Vinylferrocene
St y r e n e Vinylferrocene
St y r e n e Vinylhydroquinone dibenzoate
St y r e n e Vinylidene chloride
St y r e n e Vinylidene chloride
St y r e n e Vinylidene chloride
Styrene Vinylidene chloride
Styrene Vinylidene chloride
Styrene Vinylidene chloride
Styrene Vinylidene cyanide
Styrene Vinylidene cyanide
Styrene Vinylisocyanate
Styrene Vinylisocyanate
Styrene Vinylmethyldiacetoxysilane
Styrene Vinylmethyldiethoxysilane
Styrene Vinylmethyldiethoxysilane
Styrene Vinylphenyldimethylsilane
6
9.64
6
24.89
7.401
11.58
11.96
50
2.38
0.46
0.36
0.4
4.61
0.65
0.8
0.288
0.237
0.35
4.5
4.46
5
1.146
3.57
65
49.5
1.7
0.24
0.21
3.63
3.96
1.562
15.96
0.731
0.3
0.36
4.36
4
0.181
0.98
26
24
0.246
2.12
2.12
0.282
411
21.03
4.37
2.76
0.22
1.81
1.79
1.8
1.839
1.81
1.7
0.015
0.003
8.13
6.9
4.08
5.68
11.29
32.53
0.54
1.22
0.315
1.91
2.32
0.41
0.05
0.1
0.18
0.092
0.023
0.11
0.24
0.087
b.04
0.042
0.12
0.27
0.091
13.32
0.058
0.31
0.11
0.76
0.409
0.32
0.072
0.011
23.45
1.44
0.22
0.35
0.14
0.024
0.12
0.007
0.001
0.14
0.1
0.43
0.49
0.25
0.101
0.1
-0.17
0.126
0.65
0.29
0.01
-0.11
0.26
0.272
0.3
0.16
0.37
0.5
0.349
0.348
0.27
0.15
0.066
0.046
- 0.22
0.01
0
0.01
0.01
0.3
0.465
0.019
0.26
- 0.31
- 0.39
- 0.027
3.2
0.248
0.158
0.25
0.147
0.94
0
0.01
1.12
0.25
0.3
1.029
3.16
- 0.73
0.2
0.14
0.43
0.134
0.098
1.5
0.87
0.15
0.11
0.72
0.001
0.08
0.1
0
0.08
- 0.08
0.024
0.044
0.18
0.035
0.39
0.33
0.2
0.07
0.046
0.068
0.068
0.009
0.056
0.084
0.17
0.02
0.03
0.054
0.18
0.16
b . 7 1
0.047
0.46
0.05
0.073
0.033
0.15
0.42
0.06
0.98
0.1
0.14
0.48
0.01
0.007
0.005
0.16
0.001
0.15
0.14
0.2
0.016
Y
Y
N
N
Y
N
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
N
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
507
286
286
1 4 5
806
349
349
490
303
344
353
599
303
422
542
140
353
550
1 9 3
1 9 5
303
1 9 5
737
374
1 4 5
423
344
353
1 9 3
239
1 9 3
1 4 5
45
344
353
303
566
806
194
48
209
482
266
1 2 3
48
266
1 0 3
120
274
294
440
1 3 8
238
393
59
812
93
134
82
435
533
754
754
754
482
References page II - 290
II / 266 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl
&95%
r2
I t 95% COIN. Refs.
Styrene Vinylphenylpropanol, 2- p-
Styrene Vinyltriethoxysilane
Styrene Vinyltrimethylsilane
Styrene Vinyltrimethylsilane
Styrene Vinyltrimethylsilane
Styrene Xanathate, S-methacryloyl O-ethyl
Styrene sulfonate, sodium salt N-Vinylpyrrolidone
Styrene, 2,4,6-trimethyl- Acrylonitrile
Styrene, 2,4,6-trimethyl- Methacrylate, methyl
Styrene, 2,4,6-trimethyl- Methactylate, met hyl
Styrene, 2,4,6-trimethyl- Styrene, p-chloro-
Styrene, 2,4-dibromo- Styrene
Styrene, 2,5-dichloro- Acrylate, methyl
Styrene, 2,5-dichloro- Acrylate, methyl
Styrene, 2,5-dichloro- Acrylonitrile
Styrene, 2,5dichloro- Acrylonitrile
Styrene, 2,5-dichloro- Acrylonitrile
Styrene, 2,5dichloro- Butadiene
Styrene, 2,5-dichloro- Butadiene
Styrene, 2,5dichloro- Methacrylate, methyl
Styrene, 2,5-dichloro- Fyridine, 2-vinyl-
Styrene, 2.5-dichloro- Styrene
Styrene, 2,5-dichloro- Styrene
Styrene, 2,5-dichloro- Styrene
Styrene, 2,5-dichloro- Styrene
Styrene, 2,5-dichloro- Styrene, 2,5-dimethyl-
Styrene, 2,5-dichloro- Styrene, cc-methyl-
Styrene, 2,5-dichloro- Vinyl methyl ketone
Styrene, 2,5-dichloro- Vinylidene cyanide
Styrene, 2,5-dimethyl- Styrene, 2,5dichloro-
Styrene, 2,6-dichloro- Methacrylate, methyl
Styrene, 2,4,5-tribromo- Styrene
Styrene, 3-tri-n-butylstannyl- Acrylate, ethyl
Styrene, 3-tri-n-butylstannyl- Acrylonitrile
Styrene, 3-tri-n-butylstannyl- Methacrylate, methyl
Styrene, 3-tri-n-butylstannyl- Styrene
Styrene, 3-tri-n-butylstannyl- Vinyl acetate
Styrene, 4-(tert-butyldimethylsilyloxy). Styrene
Styrene, 4-(trimethylsilyl)- Styrene
Styrene, 4-methyl- Acrylonitrile
Styrene, 4-methyl- Methacrylate, methyl
Styrene, 4-phenoxy- Styrene
Styrene, a-(trimethylsilyloxy)- Acrylonitrile
Styrene, a-(trimethylsilyloxy)- Styrene
Styrene, n-methoxy- Acrylate, methyl
Styrene, cc-methoxy- Acrylonitrile
Styrene, cc-methoxy- Methacrylate, methyl
Styrene, wmethoxy- Methacrylonitrile
Styrene, a-methoxy- Styrene
Styrene, a-methyl- Acrylate, 2-cyano-, methyl
Styrene, cc-methyl- Acrylonitrile
Styrene, a-methyl- Acrylonitrile
Styrene, a-methyl- Acrylonitrile
Styrene, a-methyl- Acrylonitrile
Styrene, cc-methyl- Acrylonitrile
Styrene, cc-methyl- Acrylonitrile
Styrene, cc-methyl- Acrylonitrile
Styrene, cc-methyl- Acrylonitrile
Styrene, wmethyl- Butadiene
Styrene, cc-methyl- Butadiene, 2-fluoro-
Styrene, a-methyl- Fumaronitrile
Styrene, wmethyl- Maleic anhydride
Styrene, n-methyl- Methacrylate, methyl
Styrene, wmethyl- Methacrylate, methyl
Styrene, cc-methyl- Methacrylate, methyl
0. 48 0. 3 0.41 0. 4
20. 86 1.99 - 0. 09 0.14
14.66 5.15 -0.19 0. 36
5. 98
0. 44
7.19
0. 065
0. 083
- 0.01
0. 34
0.91
3. 93
4. 47
0. 08
0. 07
0. 09
0. 45
0.187
2. 66
0.14
0.81
0. 25
2. 2
0.14
1.543
3
2
0. 026
0. 263
-0.15
2. 78
0.01
0.001
0. 03
0. 03
0. 38
0. 863
0. 28
0. 227
0. 46
0. 94
0
0
0. 003
- 0. 002
- 0. 02
- 0. 02
0. 07
0. 05
0. 08
0.14
0.17
0. 24
0. 09
0.103
0.14
0. 08
0.139
0. 72
0. 094
0.04
0. 27
0.51
0. 6
0.18
0. 06
0. 025
0. 08
0. 048
0. 045
0.11
1.05
2. 88
1.38
0.15
0. 03
0.051
0. 072
0.16
5. 24
1.61
0. 054
0. 069
0.01
0.17
0. 049
0. 38
0.18
0.14
0. 043
0.017
0.13
0.12
0.08
0.04
0. 068
0.17
0. 022
0. 006
0. 022
0. 27
0. 009
0. 068
0.16
0.193
0. 049
0. 36
0. 084
0. 874
1.511
1.45
17.83
0.14
0.142
0. 288
0. 22
0. 25
0. 26
0. 449
0. 662
0. 44
0. 62
0. 268
0.18
0. 23
0. 26
0. 263
0.14
0. 5
0. 005
1.543
1.98
0. 23
10.4
4. 88
0. 69
18.5
5. 33
0. 877
0. 48
0. 079
0. 345
1.38
0. 05
1.48
0.17
0. 06
2. 5
0. 83
2.51
0.001
0. 07
0. 04
0. 04
0. 04
0. 063
0. 34
0. 03
- 0. 02
1.5
2. 22
- 0.01
0. 08
0. 48
0. 55
0. 55
0. 35 1
0.021
0. 022
0. 005
0.008
0.01
0.01
0.04
0. 005
0. 05
0. 02
0.01
0. 39
0.04
0. 34
0. 03
0. 03
0. 04
0. 005
0. 024
0. 036
0.041
0.15
0. 07
0. 087
0. 24
0. 02
0. 27
0.13
0. 7
0. 078
0. 07 0. 02
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
N
Y
N
Y
Y
Y
N
Y
Y
Y
N
N
N
N
N
N
N
Y
Y
N
Y
Y
Y
N
7 2
209
209
482
7 3
1086
939
5 8
5 8
5 8
5 8
806
136
2
8 4
8 4
8 4
255
8
3
2
1 4
411
419
8 4
9 1
377
375
8 2
9 1
324
1054
985
985
985
985
985
976
1036
929
929
602
970
970
1 4 2
1 4 2
142
1 4 3
142
452
1 7 1
265
265
265
7 5
7 5
835
9 4
7 0
174
7 7
492
265
265
265
Copolymer Reactivity Ratios II / 267
TABLE 1. cont' d
Monomer 1 Monomer 2 rl zt95% r2 zt95% Conv. Refs.
Styrene, a-methyl- Methacrylate, methyl
Styrene, cc-methyl- Methacrylate, methyl
Styrene, wmethyl- Methacrylate, methyl
Styrene, wmethyl- Methacrylonitrile
Styrene, a-methyl- Styrene
Styrene, cr-methyl- Styrene
Styrene, a-methyl- Styrene
Styrene, a-methyl- Styrene
Styrene, a-methyl- Styrene
Styrene, a-methyl- Styrene
Styrene, wmethyl- Styrene, 2,5-dichloro-
Styrene, a-methyl- Styrene, p-chloro-
Styrene, a-methyl- Vinyl chloromethyl ketone
Styrene, a-methyl- Vinylhydroquinone dibenzoate
Styrene, m-amino- Styrene
Styrene, m-amino- Styrene
Styrene, m-amino- Styrene, p-amino-
Styrene, m-bromo- Methacrylate, methyl
Styrene, m-bromo- Styrene
Styrene, m-bromo- Styrene
Styrene, m-bromo- Styrene, p-methoxy-
Styrene, m-bromo- Methacrylate, methyl
Styrene, m-chloro- Styrene
Styrene, m-chloro- Styrene
Styrene, m-chloro- Styrene, p-methoxy-
Styrene, m-cyano- Styrene
Styrene, m-diethylaminoethyl- Styrene
Styrene, m-dimethylamino- Styrene
Styrene, m-hydroxy- Styrene
Styrene, m-methoxy- Styrene
Styrene, m-methyl Methacrylate, methyl
Styrene, m-methyl Methacrylate, methyl
Styrene, m-methyl Methacrylate, methyl
Styrene, m-methyl Methacrylic acid
Styrene, m-methyl Methacrylic acid
Styrene, m-methyl Methacrylic acid
Styrene, m-methyl Acrylate, methyl
Styrene, m-methyl- Acrylonitrile
Styrene, m-methyl- Methacrylate, methyl
Styrene, m-nitro- Methacrylate, methyl
Styrene, m-nitro- Styrene
Styrene, m-nitro- Styrene, p-chloro-
Styrene, m-sulfonic acid fluoride Styrene
Styrene, o-chloro- Acrylate, butyl
Styrene, o-chloro- Indene
Styrene, o-chloro- Methacrylate, butyl
Styrene, o-chloro- Methacrylate, ethyl
Styrene, o-chloro- Methacrylate, methyl
Styrene, o-chloro- Methacrylate, methyl
Styrene, o-chloro- Methacrylic acid
Styrene, o-chloro- Methacrylonitrile
Styrene, p-2-methoxyphenyl ketone Styrene
Styrene, p-phenyl ketone Styrene
Styrene, p-phenyl ketone Styrene
Styrene, p-l-(Z-hydroxybutyl)- Acrylate, butyl
Styrene, p-1-(2-hydroxybutyl)- Acrylate, methyl
Styrene, p- l -(2-hydroxybutyl)- Acrylonitrile
Styrene, p-1-(2-hydroxypropyl)- Acrylonitrile
Styrene, p-1-(2-hydroxypropyl)- Methacrylate, methyl
Styrene, p-1-(2-hydroxypropyl)- Styrene
Styrene, p-1-(2-hydroxypropyl)- Styrene, p-chloro-
Styrene, p-2-(2-hydroxypropyl)- Acrylonitrile
Styrene, p-2-(2-hydroxypropyl)- Styrene
Styrene, p-2-(2-hydroxypropyl)- Styrene
Styrene, p-2-(2-hydroxypropyl)- Styrene, p-chloro-
0.14
0. 22
0. 48
0. 15
0. 14
0. 05
0. 3
0. 4
0. 521
0. 63
0. 14
0. 21
0. 009
0.11
1.16
1.18
0. 63
1. 17
1. 6
1. 05
1. 4
2. 3
1. 09
1. 9
0. 363
1. 21
0. 617
1. 33
0. 661
0. 53
0. 36
0. 51
0. 06
0. 33
0. 42
1.65
0. 43
0. 486
0. 8
0. 5
1. 73
1.268
2. 25
2. 86
1. 24
1. 34
1. 37
1. 34
0. 101
0. 78
1. 52
2. 58
0. 55
0. 4
0. 48
0. 31
0. 53
1
0.91
0. 63
0. 41
0. 56
1. 25
0. 53
0. 06
0. 13
0. 084
0. 2
0.01
0. 007
0. 08
0. 26
0. 264
0. 06
0. 232
0. 04
0. 06
0. 05
0. 03
0. 02
0.01
0. 02
0. 32
0. 14
0. 47
0. 236
0. 83
0. 034
0. 58
0. 83
9. 44
-
0. 5
0. 42
0. 47
0. 21
1. 21
0. 96
1. 09
1. 13
1.08
1.12
3
1. 56
0. 386
0. 3
1. 04
0. 786
0. 49
0. 48
0. 5
0. 55
0. 25
0. 57
0. 64
0. 2
0. 851
1. 2
1.027
0. 78
1. 742
0. 48
0. 38
0. 41
0. 35
0. 18
0. 51
0. 14
0. 07
0. 512
0. 35
0. 279
0. 3
0. 788
0. 2
0. 069
0. 32
0. 45
0. 5
0. 46
0. 622
0. 86
0. 23
0.11
0.13
0.17
0.18
0. 04
0.1
0. 26
0. 97
0. 91
0. 05
0. 5
0. 79
1. 24
0.41
0. 03
0.11
0. 42
0. 034
0.01
0. 534
0. 28
0. 248
0. 07
0. 456
0. 04
0. 03
0. 04
0. 08
0. 02
0.01
0. 036
0.11
0. 055
0. 14
0. 183
0. 066
0. 058
0. 07
0. 15
0. 02
532
835
899
542
171
281
281
281
289
289
377
218
356
440
775
989
774
256
168
256
168
150
168
256
168
806
806
806
35
806
1087
1087
1087
1087
1087
1087
558
378
256
222
222
222
806
558
6
558
558
532
558
6
44
806
806
806
548
548
548
380
380
380
380
547
390
547
547
References page II - 290
II / 268 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1
+95%
r2 Ik95% Conv. Refs.
Styrene, p-4-methoxyphenyl ketone Styrene 1.85
Styrene, p-NJ+dimethylamino- Acrylate, methyl 0.38
Styrene, p-N,N-dimethylamino- Benzophenone, p-vinyl- 0.07
Styrene, p-Nfl-dimethylamino- Methacrylate, methyl 0.101
Styrene, p-N,N-dimethylaminomethyl- Benzophenone, p-vinyl 0.26
Styrene, p-acetoxy- Acrylonitrile 0.4
Styrene, p-acetoxy- Styrene 1.305
Styrene, p-acetoxy- Styrene 1.218
Styrene, p-amino- Styrene 0.22
Styrene, p-amino- Styrene 1.07
Styrene, p-amino- Styrene, m-amino- 0.49
Styrene, p-bromo- Methacrylate, methyl 1.1
Styrene, p-bromo- Styrene 1.05
Styrene, p-bromo- Styrene 1.1
Styrene, p-bromo- Styrene 0.99
Styrene, p-bromo- Styrene 1.05
Styrene, p-bromo- Styrene 1
Styrene, p-bromo- Styrene, p-methoxy- 1.15
Styrene, p-chloro- Acrylate, a-trifluoromethyl-, methyl 0.24
Styrene, p-chloro- Acrylonitrile, a-trifluoromethyl- 0.92
Styrene, p-chloro- Butadiene 1.6
Styrene, p-chloro- Butadiene, 1-(2-hydroxyethylthio)- 0.24
Styrene, p-chloro- Carbazole, N-vinyl- 7
Styrene, p-chloro- Cyclopentene, 4-, -1,3-dione 0.294
Styrene, p-chloro- Itaconate, dimethyl 0.69
Styrene, p-chloro- Methacrylate, butyl 1.036
Styrene, p-chloro- Methacrylate, butyl 1.025
Styrene, p-chloro- Methacrylate, methyl 0.77
Styrene, p-chloro- Methacrylate, methyl 0.89
Styrene, p-chloro- Methacrylate, methyl 0.47
Styrene, p-chloro- Norbornadiene 69.93
Styrene, p-chloro- Styrene 1.08
Styrene, p-chloro- Styrene 1.029
Styrene, p-chloro- Styrene 1.062
Styrene, p-chloro- Styrene 1.03
Styrene, p-chloro- Styrene 0.76
Styrene, p-chloro- Styrene 1.76
Styrene, p-chloro- Styrene 1.02
Styrene, p-chloro- Styrene, 2,4,6-trimethyl- 17.83
Styrene, p-chloro- Styrene, cc-methyl- 1.56
Styrene, p-chloro- Styrene, m-nitro- 0.3
Styrene, p-chloro- Styrene, p-1-(2-hydroxypropyl)- 0.91
Styrene, p-chloro- Styrene, p-2-(2-hydroxypropyl)- 1.24
Styrene, p-chloro- Styrene, p-cyano- 0.26
Styrene, p-chloro- Styrene, p-methoxy- 0.47
Styrene, p-chloro- Styrene, p-methoxy- 0.86
Styrene, p-chloro- Styrene, p-methyl- 1.15
Styrene, p-chloro- Vinyl methyl sulfoxide 6.46
Styrene, p-chloro- Vinyl, p-, benzylmethylcarbinol 1
Styrene, p-chloromethyl- Acrylonitrile 0.56
Styrene, p-chloromethyl- Butadiene 0.42
Styrene, p-chloromethyl- Methacrylate, butyl 1.46
Styrene, p-chloromethyl- Methacrylate, ethyl 1.29
Styrene, p-chloromethyl- Methacrylate, methyl 0.91
Styrene, p-chloromethyl- Phosphazene, isopropenylpentafluoro- 1.64
Styrene, p-chloromethyl- Styrene 1.12
Styrene, p-chloromethyl- Styrene 1.12
Styrene, p-chloromethyl- Styrene 1.66
Styrene, p-cyano- Methacrylate, methyl 1.41
Styrene, p-cyano- Styrene 1.22
Styrene, p-cyano- Styrene 1.16
Styrene, p-cyano- Styrene, p-chloro 1.28
Styrene, p-cyano- Styrene, p-methoxy- 0.89
Styrene, p-decyl- Styrene 0.26
Styrene, p-diethylaminoethyl- Styrene 0.59
0.93
0.16
0.05
0.016
0.017
0.03
0.05
0.069
0.004
0.07
0.05
0.11
0.08
0.02
0.06
5.7
0.081
0.1
0.124
0.12
24.19
0.07
0.056
0.014
0.12
5.24
0.42
0.14
0.08
0.16
0.15
0.58
0.17
0.2
0.46
0.11
0.13
0.03
1.32
0.19 1.12
0.423
0.06
0.84
0.204
2.54
0.07
0.835
0.887
0.41
0.876
0.63
0.4
0.7
0.67
0.71
0.71
0.69
0.44
0
- 0.09
1.22
3.27
0.02
0.014
0.15
0.517
0.564
0.334
0.42
0.43
0
0.62
0.744
0.816
0.74
0.39
0.76
0.74
0.34
0.21
1.73
0.63
0.53
1.28
0.41
0.56
0.61
0.01
1
0.067
0.87
0.38
0.36
0.408
- 0.048
0.622
0.62
0.6
0.22
0.24
0.28
0.26
0.14
0.88
0.071
0.01
0.18
0.022
0.136
0.01
0.029
0.034
0.007
0.03
0.09
0.14
0.02
0.03
0.06
2.16
0.006
0.1
0.131
0.016
0.12
0.1
0.08
0.029
0.043
1.05
0.2
0.47
0.13
0.08
0.038
0.067
0.047
0.15
0.3
0.07
0.08
0.05
0.22
0.19
Y
Y
Y
Y
N
Y
N
N
Y
N
N
N
Y
Y
N
Y
Y
N
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
N
N
N
806
866
866
256
86
47
806
806
775
989
774
256
1 2 5
1 2 8
256
447
554
1 2 8
825
825
255
810
551
264
398
872
966
150
256
476
1 8 8
1 2 8
139
139
140
150
523
554
58
218
222
380
547
128
128
256
256
737
48
1035
1075
1035
1035
756
765
756
806
806
256
1 2 8
256
1 2 8
1 2 8
806
806
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 269
Monomer 1 Monomer 2
0
*95%
r2
f95% Conv. Refs.
Styrene, p-dimethylamino- Acrylate, methyl 0.372
Styrene, p-dimethylamino- Benzophenone, p-vinyl- 0.176
Styrene, p-dimethylaminomethyl. Benzophenone, p-vinyl- 0.135
Styrene, p-ethoxy- Styrene 0.71
Styrene, p-fluoro- Myrcene 0.362
Styrene, p-fluoromethyl- Styrene 1.399
Styrene, p-formyl- Styrene 3
Styrene, p-formyl- Styrene 1.43
Styrene, p-iodo- Styrene 1.044
Styrene, p-iodo- Styrene 0.965
Styrene, p-mercapto- Styrene 0.907
Styrene, p-metboxy- Acrylate, methyl 2
Styrene, p-methoxy Methacrylate, methyl 0.32
Styrene, p-methoxy Styrene 0.69
Styrene, p-methoxy Styrene 1.01
Styrene, p-methoxy Styrene 0.82
St yrene, p- methoxy Styrene 0.79
Styrene, p-methoxy Styrene, m-bromo- 0.25
Styrene, p-methoxy Styrene, m-chloro- 0.2
Styrene, p-methoxy Styrene, p-bromo- 0.44
Styrene, p-methoxy Styrene, p-chloro- 0.41
Styrene, p-methoxy Styrene, p-chloro- 0.56
Styrene, p-methoxy Styrene, p-cyano- 0.14
Styrene, p-methyl Acrylate, methyl 1.54
Styrene, p-methyl Acrylonitrile 0.33
Styrene, p-methyl Methacrylate, methyl 0.44
Styrene, p-methyl N,N-Divinylaniline 6.15
Styrene, p-methyl Styrene 0.993
Styrene, p-methyl Styrene, p-chloro- 0.61
Styrene, p-methyl Vinyl methyl sulfoxide 2.73
Styrene, p-nitro Styrene 1.13
Styrene, p-octylamine sulfonate Acrylate, butyl 2.3
Styrene, p-octylamine sulfonate Methacrylate, butyl 1.5
Styrene, p-octylamine sulfonate Methacrylate, methyl 2.6
Styrene, p-octylamine sulfonate Styrene 2.7
Styrene, p-sulfonic acid fluoride Styrene 1.372
Styrene, p-tert-butyl- Methacrylate, methyl 0.5
Styrene, p-tert-butyl- Styrene 1.581
Styrene, p-trimethoxysilyl- Imidazole, N-vinyl- 6.9
Styrene, p-trimethylsilyl- Styrene 1.15
Styrene, pentachloro- Methacrylate, methyl 0.3
Styrene, pentachloro- Styrene 0.07
Styrene, pentachloro- Vinyl chloride 5.3
Styrene, tert-butoxy- Fumarate, dibutyl 0.18
Styrenesulfonate, p-, sodium Acrolein 0.047
Styrenesulfonate, p-. sodium Acrolein 0.327
Styrenesulfonate, p-, sodium Acrolein 0.01
Styrenesulfonate, p-, sodium Acrylate, cc-chloro-, sodium 1.44
Succinamate, potassium N-vinyl- Methacrylate, methyl 0.02
Succinimide, N-vinyl- Acrylamide 0.17
Succinimide, N-vinyl- Acrylate, butyl 0.15
Succinimide, N-vinyl- Acrylate, methyl 0.9
Succinimide, N-vinyl- Acrylonitrile 0.516
Succinimide, N-vinyl- Carbazole, N-vinyl- 0.11
Succinimide, N-vinyl- Maleate, dimethyl 1.25
Succinimide, N-vinyl- Maleic anhydride 0.148
Succinimide, N-vinyl- Methacrylate, methyl 0.048
Succinimide, N-vinyl- Methacrylate, methyl 0.059
Succinimide, N-vinyl- Pyrrolidone, N-vinyl- 3.67
Succinimide, N-vinyl- Styrene 0.045
Succinimide, N-vinyl- Styrene 0.045
Succinimide, N-vinyl- Styrene 0.01
Succinimide, N-vinyl- Styrene 7
Succinimide, N-vinyl- Vinyl acetate 5.68
Succinimide, N-vinyl- Vinyl acetate 4.49
0.055
0.046
0.017
0.14
0.022
0.236
0.159
0.124
0.223
0.1
1.27
0.02
0.08
0.05
0.16
0.028
0.13
0.188
0.342
0.72
0.05
0.1
0. 07 1
0.033
0.009
0.31
0.12
0.17
0.081
0.83
0.16
0.073
0.026
0.096
0.89
0.036
0.072
0.23
1.6
0.12
9.49
0.192
0.842
2.54
0.98
0.87
0.474
0.2
0.16
0.485
0.629
0.607
0.07
0.29
0.85
1.14
1.16
1.05
1.4
1.9
1.15
0.47
0.86
0.89
0.17
0.05
0.4
0.06
0.891
1.15
0.01
0.193
0.3
0.7
0.6
0.7
0.171
0.44
0.774
0.002
1.26
3.65
1.33
0.43
0.01
0.26
0.395
0.113
0.27
1.1
1.86
1.54
0.357
0.116
0.04
- 0.012
0.021
9.94
0.01
0.97
10.74
10.09
2.31
0.052
0.072
0.18
0.01
0.072
0.259
0.19
0.143
0.151
0.093
0.039
0.188
0.19
0.6
0.08
0.16
0.03
0.03
0.086
0.092
0.045
0.126
0.47
0.85
0.19
0.16
0.092
0.018
0.06
0.17
0.063
0.024
0.09
0.021
0.027
0.27
0. 03 1
0.42
0.49
0.46
0.98
0.32
0.009
0.54
Y
Y
Y
Y
Y
N
N
N
N
N
Y
Y
Y
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
911
911
911
806
1062
806
1025
956
806
839
806
558
3 5
1 2 8
160
256
535
168
1 6 8
1 2 8
1 2 8
256
1 2 8
558
378
256
45
261
256
737
256
817
817
817
817
806
634
806
1095
806
7
7
516
1077
57
57
57
834
771
600
789
80
80
284
284
284
104
693
96
104
1 6 3
693
80
104
1 6 7
References page II - 290
II / 270 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1
f95%
r2
f95% Conv. Refs.
Succinimide, N-vinyl-
Succinimide, N-vinyl-
Succinimide, N-vinyl-
Sulfonate, 2-acrylamido-
2-methylpropane-, s odi um
Sulfonic acid, o-methacryloylamino-
be nz e ne -
Sulfonic acid, o-methacryloylamino-
be nz e ne -
Sulfonic acid, o-methacryloylamino-
be nz e ne -
Sulfonic acid, p-methacryloylamino-
be nz e ne -
Sulfonic acid, p-methacryloylamino
be nz e ne -
Sulfonic acid, p-methacryloylamino
benzene-
Terpyridinyl 4-vinyl:2,2:6,2-
Tetrazole, l-vinyl-
Tetrazole, l-vinyl-
Tetrazole, l-vinyl-
Tetrazole, 2-methyl-5-(4-vinyl)phenyl-
Tetrazole, 2-methyl-5-(4-vinyl)phenyl-
Tetrazole, 2-methyl-5-(4-vinyl)phenyl-
Tetrazole, 2-methyl-5-vinyl-
Tetrazole, 2-methyl-5-vinyl-
Tetrazole, 2-methyl-5-vinyl-
Tetrazole, 2-phenyl-5-(4-vinyl)phenyl-
Tetrazole, 2-phenyl-5-(4-vinyl)phenyl-
Tetrazole, 2-phenyl-5-(4-vinyl)phenyl-
Tetrazole, 2-phenyl-5-(4-vinyl)phenyl-
Tetrazole, 2-phenyl-5-(4-vinyl)phenyl-
Tetrazole, 2-phenyl-5-(4-vinyl)phenyl-
Tetrazole, 5-vinyl-
Tetrazole, 5-vinyl-
Thioindigoid
Thiophene, 3-vinyl
Thiophene, 3-vinyl
Thioxanthone, 2-(acryloyloxy)-
Titanium, dicylopentadienyl-,
dimethacrylate
Titanium, dicylopentadienyl-,
dimethacrylate
Toluenesulfonamide, N,N-methyl-vinyl-
Toluenesulfonamide, N,N-methyl-vinyl-
Toluenesulfonamide, N,N-methyl-vinyl-
Toluenesulfonamide, N,N-methyl-vinyl-
Triallyl citrate
Triallyl citrate
Triallyl citrate
Triallyl citrate
Triallyl citrate
Triallyl cyanurate
Triallyl cyanurate
Triallyl cyanurate
Triallyl isocyanurate
Triallyl isocyanurate
Triallyl isocyanurate
Triazine, 4,6-diamino-2-vinyl-
Tri azi ne, 1,3,5-2-amino-4-(N-methyl-
p-aminoanilino)-6-isopropenyl-
Triazine, 1,3,5-2-amino-4-(N-methyl-
p-aminoanilino)-6-isopropenyl-
Tri azi ne, 1,3,5-2-amino-
4-@-nitroanilino)-6-isopropenyl-
Vinyl acetate 1.99
Vinyl thiolacetate 0.17
Vinylidene chloride 0.311
Acrylamide, N,N-dimethyl- 0.162
0.43
0.15
0.058
0.949
0.122
0.195
0.218
0.338
0.27
0.525
0.33
0.066
0.026
0.031
0.229
2.47
1.441
1.108
80
97
104
857
Methacrylic acid 0.217 0.203 1006
Methacrylic acid 0.523 0.188 1006
Pyridine, 2-methyl-5-vinyl- 1.83 - 0.002 1006
Methacrylic acid 1.08 0.156 1006
Methacrylic acid 1.65 0.155 1006
Pyridine, 2-methyl-5-vinyl- 2.72 - 0.054 1006
Styrene
Acrylonitrile
Methacrylate, methyl
Styrene
Acrylonitrile
Styrene
Vinylidene chloride
Methacrylate, methyl
Styrene
Vinyl acetate
Methacrylate, methyl
Styrene
Vinylidene chloride
Acrylonitrile
Styrene
Vinylidene chloride
Styrene
Styrene
Methacrylate, butyl
Acrylate, butyl
Methacrylate, methyl
Methacrylate, methyl
Copper diacrylate
1.26
0.314
0.262
0.184
1.1
1.3
1.9
0.486
0.62
28.51
0.4
1
1.8
1.4
2.2
1.9
0.31
0.31
0.5
0.499
0.25
0.5
0.89
0.075
0.21
31.34
0.53
0.54
7.13
3.85
0.42
0.65
0.13
1.026
1.124
0.04
0.7
0.95
0.25
0.32
0.48
0.11
0.78
0.78
11.5
0.386
0.563
1.36
1.09
0.06
0.37
0.061
0.59
0.067
0.076
0.031
0.081
0.052
0.048
0.384
0.032
0.093
0.045
0.029
0.081
0.16
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
0.02 0.3
953
925
925
925
583
583
583
670
670
670
583
583
583
583
583
583
870
902
1007
1000
1000
986
895
Nickel diacrylate 0.65 0.95 895
Acrylonitrile
Methactylate met hyl
Styrene
Vinyl butyl ether
Acrylonitrile
Allylbenzene
Styrene
Vinyl acetate
Vinyl chloride
Methacrylate, methyl
Styrene
Vinyl acetate
Methacrylate, methyl
Styrene
Vinyl acetate
Styrene
Styrene
0.04 1.04 0.42 0.12
- 1.83 0.26 1.87 0.19
- 0.58 0.44 5.6 1.13
-0.31 0.29 3.37 1.65
- 0.08 0.1 1.76 0.082
2.01 0.5 0.339 0.039
0.076 0.041 20.02 0.81
2.97 0.38 0.222 0.025
1.03 0.17 0.605 0.033
- 0.005 0.05 16.12 0.56
0.22 0.12 32.45 1.27
1.29 0.42 0.197 0.053
- 0.49 0.94 16.88 6.64
- 0.05 0.11 28.6 1.39
1.95 0.42 0.278 0.043
0.538 0.141 1.104 0.157
0.44 0.12 0.306 0.054
80
80
80
80
367
367
367
367
367
201
2 0 1
201
201
201
201
806
364
Styrene
Styrene
1.676 0.065 0.169 0.013
0.91 0.18 0.257 0.062
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
364
364
TABLE 1. contd
Copolymer Reactivity Ratios II / 271
Monomer 1 Monomer 2
0
f95%
r2
*95% conv. Refs.
Triazine, 2-allyloxy-4,6-dichloro-
Triazine, 4,6-diamino-2-vinyl-
Triazole, 1,2,3-, 1-p-bromophenyl-4-vinyl-
Triazole, 1,2,3-, 1-p-bromophenyl-4-vinyl-
Triazole, 1,2,3-, 1-p-bromophenyl-4-vinyl-
Triazole, 1,2,3-, 4(5)-vinyl-
Tri azol e, 1,2,3-, 4(5)-vinyl-
Triazole, l-N-vinyl- 1,2,4-
Tricyclo[4,2,2,0{2,5}]dec-7-ene-
3,4,9,10-tetracarboxylicacid
Tropone, 2-methacryloyloxy-
Urea, 1,3-divinyl-1,3-diphenyl-
Urea, N-acryloyl-N-benzoyl-
Urea, N-vinyl-N-ethyl-
Urea, N-vinyl;N-ethyl-
Urea, N-vinyl-N-ethyl-
Urea, N-vinyl-N-ethyl-
Urea, N-vinyl-N-ethyl-
Valerolactone, wmethylene-
Valerolactone, u-methylene-
Vinyl 1-cyano- acetate
Vinyl 12-ketostearate
Vinyl 12-ketostearate
Vinyl 12-ketostearate
Vinyl 12-ketostearate
Vinyl 2-, l,l-dichlorocyclopropane
Vinyl 2-bromo-ethyl ether
Vinyl 2-bromo-ethyl ether
Vinyl 2-chlorocyclohexyl ketone
Vinyl 2-chloroethyl ether
Vinyl 2-chloroethyl ether
Vinyl 2-chloroethyl ether
Vinyl 2-chloroethyl ether
Vinyl 2-chloroethyl ether
Vinyl 2-chloroethyl ether
Vinyl 2chloroethyl ether
Vinyl 2-chloroethyl ether
Vinyl 2-ethylhexanoate
Vinyl 3,3-bis(ethoxycarbonyl)propyl
ether
Vinyl 4-dithiobenzoate methyl
Vinyl 4-dithiobenzoate methyl
Vinyl 4-chlorocyclohexyl ketone
Vinyl 4-chlorocyclohexyl ketone
Vinyl 4-chlorocyclohexyl ketone
Vinyl 4-chlorocyclohexyl ketone
Vinyl 4-chlorocyclohexyl ketone
Vinyl N,N-methylacetamide
Vinyl cr-chloro-, triethoxysilane
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Pyrrolidone, N-vinyl-
Vinyl methyl ketone
Methacrylate, methyl
Styrene
Vinyl acetate
Methacrylate, methyl
Styrene
Imidazole, l-N-vinyl
Acrylonitrile
Acrylate, ethyl
Styrene
Styrene
Methacrylate, methyl
Styrene
Vinyl acetate
Vinyl acetate
Vinyl acetate
Styrene
Styrene
Styrene
Acrylonitrile
Vinyl acetate
Vinyl chloride
Vinylidene chloride
Styrene
Acrylate, methyl
Styrene
Maleic anhydride
Acrylate, ethyl
Acrylate, ethyl
Acrylate, methyl
Acrylonitrile
Methacrylate, methyl
Styrene
Vinyl acetate
Vinyl chloride
Acrylonitrile
Acrylonitrile
Methacrylate, methyl
Styrene
Maleic anhydride
Methacrylate, methyl
Styrene
Vinyl acetate
Vinyl cyclohexyl ketone
Vinyl acetate
Acrylonitrile
2-Oxazoline, 2-isopropenyl-
2-Oxazolinium BF4, 3-methyl-
2-isopropenyl-
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetate, 2-chloro-, vinyl
Acetate, ally1
Acetate, chloro-, ally1
Acetate, dichloro-, ally1
Acetate, trichloro-, ally1
Acrolein
Acrolein, methyl
Acrylamide, N-octadecyl-
Acryl ami do, I-, -l-deoxy-D-glucitol
Acrylamido, 2-, -Zmethylpropane-
sulfonate
0.5
1.35
0.266
0.73
42.47
0.27
0.52
0.68
0.058
0.4
9.84
0.13
0.26
0.98
0.17
0.832
1.32
-0.011
0.839
1.48
0.25 2.75
3.13
- 1.76
0.053
- 0.008
- 0.33
0.621
3.61
1.45
1.42
1.44
0.147
-0.18
- 0.28
-0.01
0.26
0
- 0.79
0.528
1.36
0.029
0.33
0.081
0.033
0.36
2.61
0.034
0.32
0.387
3.62
0.404
1.85
10.78
0.463
0.16
0.38
0.097
0.096
0.181
3.3
0.18
0.03
4.4
17.98
16.83
1.7
0.15
0
0
0
0
0.07
0.16
- 0.07
- 0.047
0.06
0.11
0.05
0.83
5
4.65
3.27
1.09
18.8
160
2.36
2.46
9.24
1.02
0.3
2.08
0.12
0.51
0.58
0.15
0.5
0.93
0.29
0.81
0.151
0.111
0.08
0.77
0.53
0.1
1.6
0.49
0.25
0.114
0.04
0.021
0.12
0.011
0.17
7.1
0.413
0.6
0
0.8
1.8
0.77
0.57
0.41
- 0.02
0.15
0.004
0.03
0.05
5.5
2 1
1.18
0.43
0.69
0.54
0.28
3.04
0.98
8.25
0.98
11.6
0.11
0.022
0.15
0.008
0.055
0.12
0.027
0.98
0.23
2.07
0.029
0.409
0.5
4.8
0.59
2.34
0.52
1.96
0.092
0.009
2
0.005
0.43
1.46
0.87
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
N
826
243
670
670
670
670
670
972
963
1104
800
1090
1 0 1
1 0 1
1 0 1
683
683
919
855
806
146
146
146
146
806
194
194
.836
439
726
726
597
597
597
597
304
47
1015
697
697
836
668
668
668
668
631
237
894
908
984
984
892
1045
1045
1045
1045
207
589
119
258
700
References page II - 290
II / 272 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2 rl f95%
r2
Zt95% Conv. Refs.
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Acrylamidomethylamino, p-,
azobenzene
Acrylate, 2-cyano-, methyl
Acrylate, 2-ethylhexyl
Acrylate, cl-acetoxy-, ethyl
Acrylate, cc-chloro-, ethyl
Acrylate, butyl
Acrylate, glycidyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, sodium
Acryl at e, t ri fl uoro-, met hyl
Actylate: trifluoro-, methyl
Acrylic acid
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acrylate
Ally1 butyrate
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 isobutyrate
Ally1 propionate
Ally1 trimethylacetate
Ally1 valerate
Allystearamide, N-
Azobenzene, 4-(acrylamidomethyl-
amino)-
Benzothiazole, vinylmercapto-
Bicyclo[2,2,l]hept-2-ene-
5,6-dicarboximide, N-benzyl
Bicyclo[2,2,l]hept-2-ene-
5,6-dicarboximide, N-benzyl
Bicyclo[2,2,l]hept-2-ene-
5,6-dicarboximide, N-benzyl
Butadiene, 2-chloro-
Bu t e n e - 1
Butene-2, cis-
Butene-2, trans-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Caprolactam, N-vinyl-
Carbamate, N,N-diethyl-, vinyl
Carbamate, N-vinyl-, ethyl
Carbamate, N-vinyl-, ethyl
Carbamate, N-vinyl-, rerr-butyl
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Carbon monoxide
Crotonic acid
Crotonic acid
Crotonic acid
Diallyl P-cyanoethylisocyanurate
Diallyl melamine
Diallyl phthalate
0.126 12.98 858
0.005
0.04
0.08
0.03
0.018
0.003
0.04
0.03
0.405
0.03
0.03
0.021
0.072
0.01
0.043
0.05
7.5
5.621
30
3.48
7.6
7.28
6.38
2.58
6.7
6.3
0.094
3.39
0.37
0.3
0.24
0.24
0.021
0.04
0.06
- 0.06
- 0.03
0.6
1
1
0.11
0.97
1.355
0.66
0.34
1.04
1.29
1.15
1.07
0.923
0.126
0.059
0.067
0.22
0.08
0.09
0
0
8.66
4.05
5.51
5.29
9.2
0.45
0.7
0.7
17.35
0.64
- 2.4
0.61
0.75
0.51
0.42
0.34
0.58
0.68
12.98
6.63
0.82
0.91
1.13
6.39
0.089
0.15
3.21
0.15
0.092 0.26
452
570
244
638
301
553
1067
1 5 8
2 5
489
568
37
595
598
37
1 5 8
235
6
7 5
75
140
502
998
578
998
204
3
438
998
998
998
998
1 1 9
880
0.013
1.26
0.037 2.53
0.35
0.47 763
994
1.46 0.15 994
1.99 0.014 994
- 0.02
1.55
8.27
7.2
0.63
0.35
0.35
1.7
0.39
0.418
0.07
0.126
0.15
0.13
0.24
0.317
0.3
0.31
0.06
0.68
0.336
0.09
0.24
1.05
1.69
8.98
0.42
0.25
0.44
0.04
0.063
1.12
0.023
0.19
0.26
0.03
0.13
0.081
0.07
0.026
0.049
33.52
0.11
0.03
- 0.03
0.31
2.5
2.5
0.13
2.09
0.4
0.46
2.67
3.02
3.9
0.33
0.04
0.01
0.001
4.6
0.318
2.19
0.14
0.1
0.073
0.34
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
N
Y
Y
N
Y
Y
247
211
211
2 1 1
557
859
883
1 9 7
629
81
827
246
246
551
474
47
526
94
778
201
297
TABLE 1. contd
Copolymer Reactivity Ratios II / 273
Monomer 1 Monomer 2
f.1 f95% r2
zt95% Conv. Refs.
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Diallyl phthalate
Diallyl phthalate
Diallyl, 1,3-, 5-(2-hydroxy-
3-phenoxypropyl)
Diallyl, 1,3-, 5-(2-hydroxy-
3-phenoxypropyl)
Diallylcyanamide
Diallyldimethylammonium chloride
Ethylene
Ethylene
Ethylene
Ethylene
Ethylene
Et hyl ene
Ethylene
Ethylene
Ethylene
Ethylene, chlorotrifluoro-
Ethylene, chlorotrifluoro-
Ethylene, dichloro-, cis-
Ethylene, dichloro-, cis-
Ethylene, dichloro-, cis-
Ethylene, dichloro-, cis-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, trichloro-
Ethylene, trichloro-
Fumarate, diethyl
Fumarate, diethyl
Fumarate, diisopropyl
Fumaryl chloride
Hexatriene, tetrachloro-
Imi dazol e, l-vinyl-
Indene
Isobutylene
Isobutylene, 3-chloro-
Isopropenyl acetate
Itaconate, dimentbyl
Itaconic anhydride
Itaconic anhydride
Maleate, di-tert-butyl
Maleate, diethyl
Maleate, dimethyl
Maleic anhydride
Mal ei mi de, N-(2-hydroxyethyl)-
Mal ei mi de, N-(2-hydroxyethyl)-
Mal ei mi de, N-(Zhydroxyphenyl)-
Mal ei mi de, N-hydroxymethyl-
Maleimide, Nphenyl-
Methacrylamide, 1-deoxy-D-glucitol
Methacrylate, 2,2,6,6-tetramethyl-
4-piperidinyl
Methacrylate, butyl
Methacrylate, di-, di-n-butylstannyl
Methacrylate, ethyl
Methacrylate, ferrocenylmethyl
Methacrylate, isobutyl
Methacrylate, methyl
Metbactylate, met hyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate acid
Methacrylonitrile
NJGDivinylaniline
0.414
0.12
0.15
0.029 1.66
2
5.5
0.16 Y 297
509
671
0.16 3.65 676
0.01
0.35
0.72 1.2
1.62
1.95
0.16 0.03
1.14
1.03
1.52
3.74
1.23
1.4
0.33
0.68
0.41
1.02
6.4
0.898
4.13
4.45
0.77
0.28
0.88
0.74
0.67
0.13
0.79
-0.13
0.04
- .0.02
0.055
0.01
0.058
0.1
- 0.07
0.52
0.64
0.21
0.03
0.01
0.58
0.11
0.36
0.02
0.27 0.024
0.06
1.94
1.87
0.607
0.7
0.011
0.09
0.012
0.076
0.1
0.004
- 0.06
- 0.006
0.443
0.33
0.9
-0.11
0.39
1.66
0.13
1.171
1.17
0.2
0.18
1.9
8.64
0.17
0
1.082
6.99
2.8
0.19
0.038 0.074
- 0.019
- 0.04
0.005
0.171
- 0.006
0.019
- 0.014
0.01
-0.011
0.017
- 0.003
0.16
0.2
0.045
0.024
0.024
0.025
0.084
0.008
0.037
0.041
0.027
0.037
0.006
1.57
2.87
0.199
0.04
0.257
- 0.058
0.61
0.88
1.75
1.45
1.284
0.56
13.7
0.36
0.32
0.02
0.012
0.086
0.074
0.12
0.17
0.17
0.21
0.046
581
1029
309
4 1
413
42
559
68
68
766
6
1097
236
1 3 7
137
9
9
3
59
1 5 8
9
1 3 7
718
1038
9 1
4
364
360
211
475
100
975
365
365
1049
1 3 7
1049
260
323
323
323
323
328
258
664
- 0.003
0.013
- 0.71
0.2
- 0.06
- 0.2
- 0.81
0.03
0.04
0.07
0.01
0.01
0.058
0.15
0.018
5.29
0.22
0.01
1.17
0.009
30.18
0.013
131.8
1.52
29.7
2.71
137.5
26
28.6
22.21
0.2
1 2
3.99
14.47
0.036
29.8
24.16
0.25
5.9
0.12
N
N
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
N
Y
1 6 5
949
210
293
165
158
210
272
383
471
377
75
45
References page II - 290
II / 274 FREE RADICAL COPOLYMERlZATlON REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1
It95%
r2
Zt95% Conv. Refs.
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Norbomadiene
Oxazolidone, N-vinyl-
Oxazolidone, N-vinyl-
Oxazol i ne, 2-, 2-isopropenyl-
Oxazoline, 2-, 4-acryloxymethyl-
dimethyl-2,4-dimethyl
Oxazoline, 2-, 4-methacryloxy-
2,4-dimethyl
Oxazolinium, 2- tetrafluoroborate,
3-methyl
Phosphate, diethyl isopropenyl
Phosphine oxide, diphenylvinyl-
Phosphonate, u-carbomethoxyvinyl-,
diethyl
Phosphonate, isopropenyl-, dimethyl
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, bis(2-chloroethyl)
Phosphonate, vinyl-, diethyl
Phosphonate, vinyl-, dimethyl
Phosphonate, vinyl-, dimethyl
Propene, 1-chloro-, cis-
Propene, 1-chloro-, trans-
Propene, 2-chloro-
Propene, 3,3,3-trichloro-
Pyridine, 2-methyl-5-vinyl-
Pvridine, 2-vinvl-
P&dine, 2-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
S-Ethyl N-vinyl-N-methylthiolcarbamate
S-Vinyl N,N-diethylthiolcarbamate
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, 3-tn-n-butylstannyl-
Succinimide, N-vinyl-
Succinimide, N-vinyl-
Succinimide, N-vinyl-
Tetrazole, 2-methyl-5-vinyl-
Triallyl citrate
Triallyl cyanurate
Triallyl isocyanurate
Triazole, 1,2,3-, l-p-bromophenyl-
4-vinyl-
Urea, N-vinyl-N-ethyl-
Urea, N-vinyl-N-ethyl-
Urea, N-vinyl-N-ethyl-
Vinyl 12-ketostearate
Vinyl 2-chloroethyl ether
Vinyl 4-chlorocyclohexyl ketone
Vinyl benzenesulfonate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl bromide
Vinyl bromide
Vinyl bromide
0.818
0.602
0.55
0.25
0.03
0.05
0.43 0.057 0.366 0.151
1.56 0.44 650
0.38 1.7 843
0.09 0.6 684
0.14
0.09
0.09
0.33
0.04
0.04
0.04
7.08
3.13
0.186
0.19
0.11
-0.11
-
0
0.26
0.19
0.195
0.67
0.133
0.04
0.02
0.01
0.05
0.16
0.08
5.33
0.072
0.18
0.229
0.04
0.222
0.197
0.278
0.011
0.463
0.16
0.38
0.18
2.36
0.1
0.628
0.455
0.35
0.78
0.7
0.66
0.24
0.41
0.6
0.38
0.019
0.038
0.18
0.35
0.15
0.091
0.17
0.25
1.77
0.057
0.1
0.025
0.072
0.12
0.009
0.54
0.06
0.16
0.025
0.053
0.043
0.008
0.029
0.036
0.069
0.52
0.2
0.13
0.09
1.354
1.55
2.04
7.1
1.41
6.2
0.99
0.85
0.85
0.47
0.74
0.74
0.74
- 0.012
0.011
1.65
0.19
9
13.65
30
1.06
1.75
3.4
1.22
1.89
42.48
18.8
56
48
60
57.8
0.38
5.68
4. 49
1.99
28.51
2.97
1.29
1.95
42.47
0.621
3.61
1.45
- 0.28
0.16
0.15
- 1.34
1.07
0.99
1.64
1.13
1.74
1.98
5.26
1.92
3
0.07
0.28
0.13
0.061
0.074
0.36
3.64
0.25
2.79
0.21
1.17
0.77
26.85
2.87
0.12
9.49
0.43
31.34
0.38
0.42
0.42
9.84
0.081
1.7
0.27
1.93
0.98
1.23
0.35
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
N
1 8 8
1 0 2
36
862
596
596
877
684
592
594
595
592
592
594
1 8 1
1 8 1
181
402
812
6
6
1 0 3
1 2 1
36
1 9 7
1 9 7
1 5 8
241
481
481
481
812
985
104
167
80
670
367
201
201
670
1 0 1
683
683
146
597
668
942
253
253
26
272
430
696
1 5 8
268
268
TABLE 1. contd
Copolymer Reactivity Ratios II / 275
Monomer 1 Monomer 2
rt
295%
r2
Zt95% Conv. Refs.
Vinyl acetate Vinyl butyl ether
Vinyl acetate Vinyl butyl ether
Vinyl acetate Vinyl butyl ether
Vinyl acetate Vinyl butylsulfonate
Vinyl acetate Vinyl butyrate
Vinyl acetate Vinyl butyrate
Vinyl acetate Vinyl chloride
Vinyl acetate Vinyl chloride
Vinyl acetate Vinyl chloride
Vinyl acetate Vinyl chloride
Vinyl acetate Vinyl chloride
Vinyl acetate Vinyl chloride
Vinyl acetate Vinyl chloride
Vinyl acetate Vinyl chloroacetate
Vinyl acetate Vinyl chloroacetate
Vinyl acetate Vinyl chloroacetate
Vinyl acetate Vinyl chloroformate
Vinyl acetate Vinyl chloroformate
Vinyl acetate Vinyl chloromethyl ketone
Vinyl acetate Vinyl cinnamate
Vinyl acetate Vinyl cyclohexyl ketone
Vinyl acetate Vinyl cymantrene
Vinyl acetate Vinyl dodecyl ether
Vinyl acetate Vinyl ethyl ether
Vinyl acetate Vinyl ethyl ketone
Vinyl acetate Vinyl ethyl oxalate
Vinyl acetate Vinyl fluoride
Vinyl acetate Vinyl formate
Vinyl acetate Vinyl formate
Vinyl acetate Vinyl isopropyl ketone
Vinyl acetate Vinyl isopropyl ketone
Vinyl acetate Vinyl laurate
Vinyl acetate Vinyl methanesulfonate
Vinyl acetate Vinyl methyl ketone
Vinyl acetate Vinyl methyl sulfone
Vinyl acetate Vinyl octadecyl ether
Vinyl acetate Vinyl octyl ether
Vinyl acetate Vinyl phenyl carbonate
Vinyl acetate Vinyl phenyl carbonate
Vinyl acetate Vinyl phenyl ketone
Vinyl acetate Vinyl phenyl sulfone
Vinyl acetate Vinyl propionate
Vinyl acetate Vinyl propionate
Vinyl acetate Vinyl stearate
Vinyl acetate Vinyl stearate
Vinyl acetate Vinyl terr-butyl sulfide
Vinyl acetate Vinyl tert-butyl sulfide
Vinyl acetate Vinyl thiolacetate
Vinyl acetate Vinyl, N-, N-methylacetamide
Vinyl acetate Vinylene carbonate
Vinyl acetate Vinylene carbonate
Vinyl acetate Vinylene carbonate
Vinyl acetate Vinylene carbonate
Vinyl acetate Vinylene carbonate
Vinyl acetate Vinylene carbonate
Vinyl acetate Vinylidene chloride
Vinyl acetate Vinylidene chloride
Vinyl acetate Vinylidene chloride
Vinyl acetate Vinylidene chloride
Vinyl acetate Vinylidene chloride
Vinyl acetate Vinylidene cyanide
Vinyl acetate Vinylidene fluoride
Vinyl acetoxymethyl ketone Styrene
Vinyl benzenesulfonate Vinyl acetate
Vinyl benzoate Acrylonitrile
3.12
0.71
2.5
0.025
1
1.35
0.43
0.981
0.24
0.263
0.25
0.65
0.26
0.83
0.803
0.8
0.67
0.66
0.044
0.04
0.08
0.072
3.67
3.42
-0.13
1.35
3.5
0.94
1.41
0.3
- 0.154
1.4
0.639
0
4.5
3.47
0.85
0.85
- 0.06
0.171
0.98
0.9
0.953
0.9
1 3
1 3
0.05
0.49
3.2
3
7.16
7.3
3.83
3.92
0.03
0.05
0.05
- 0.002
0.12
0.003
6
0.368
- 1.34
0.019
0.09
0.006
0.14
0.036
0.15
0.028
0.15
0.14
0.12
0.089
0.16
0.12
0.054
0.003
0.18
0.84
0.14
0.073
0.014
0.02
0.23
0.23
0.057
0.064
0.015
0.62
0.64
0.18
0.32
0.1
0.026
0.002
0.018
1.7
0.051
0.01
0.2
0.16
0.13
0.97
1.25
1.63
1.032
1.84
2.13
1.64
1.35
2.3
1.39
0.88
1.18
0.579
0.586
49.52
1.2
13.76
7.21
0
0.26
10.18
9.89
0.25
0.98
0.68
7.87
6.47
0.7
0.206
0.355
0
0
0.384
0.384
5.81
- 0.35
0.98
1
0.96
0.73
0.07
0.07
5.5
0.93
0.3
0.27
0.05
0.13
0.044
0.08
4.66
6.7
5
3.49
4.7
0.1
0.08
0.103
0.628
5.03
0.02
0.33
0.32
0.097
0.68
0.2
0.12
0.64
0.3
0.19
0.076
0.052
15.79
1.01
6.62
8.44
0.06
2.18
0.427
0.21
0.083
0.083
0.96
0.37
0.17
0.3
0.16
0.039
0.11
0.26
0.17
0.11
0.011
0.036
1.08
References page II - 290
N
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
345
448
553
1 8 5
272
515
1 0 9
1 4 8
1 5 8
283
3
450
86
7 1
779
861
675
706
356
200
846
354
372
158
794
124
755
272
401
601
794
503
942
9 1
1 9 5
372
372
675
705
794
1 9 3
272
425
1
537
598
601
566
631
1 0 3
1 0 3
120
120
144
90
3
432
436
59
812
82
627
806
942
47
II / 276 FREE RADICAL COPOLVMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
0
f95%
r2
It95% Conv. Refs.
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzoate
Vinyl benzyl sulfide
Vinyl benzyl sulfide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl bromide
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl ether
Vinyl butyl sulfide
Vinyl butyl sulfide
Vinyl butylsulfonate
Vinyl butylsulfonate
Vinyl butylsulfonate
Vinyl butylsulfonate
Vinyl butylsulfonate
Vinyl butyrate
Vinyl butyrate
Vinyl butyrate
Vinyl butyrate
Vinyl butyrate
Ally1 chloride
Methacrylate, methyl
Pyrrolidone, N-vinyl-
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl p-bromobenzoate
Vinyl p-chlorobenzoate
Vinyl p-cyanobenzoate
Vinylidene chloride
Vinylidene cyanide
Methacrylic anhydride
Styrene
Acrylate, butyl
Acrylate, butyl
Acrylonitrile
Acrylonitrile
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl acetate
Acrylate, 2-chloroethyl
Acrylate, methyl
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Benzenesulfamide, p-methacrylamide-
Caprolactam, N-vinyl-
Methacrylate, 2-bromoethyl
Methacrylate, methyl
Pyrrolidone, N-vinyl
Styrene
0.46
0.07
0.408
- 0.02
0.06
1.07
0.99
1.64
1.13
1.74
1.98
0.343
0.5
0.28
0.716
0.832
0.659
0.065
0
- 0.048
0.04
0.18
0.19
0.06
0.06
0.12
0.33
0.052
0.05
0.012
0.06
0.09
5.26
1.92
3
0
0.01
0
- 0.03
0
0.03
0
Toluenesulfonamide, N,N-methyl-vinyl-
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl chloride
Vinyl chloroacetate
Vinylidene chloride
Acrylonitrile
Styrene
-
Acrylate, methyl
Styrene
Vinyl acetate
Vinyl chloride
Vinyl chloride
Ally1 chloride
Butadiene, 2-chloro-
Carbazole, N-vinyl-
Ethylene
Methacrylate, methyl
- 0.027
- 0.08
3.37
0.01
0.2
0.16
0.023
0.12
0.004
0.041
0.06
0
0
0.13
0.267
0.083
0.31
0.07
1.5
0.03
0.03
1.62
0.15
0.27
1.93
0.98
0.036
0. 03 1
0.028
0.033
0.093
0.017
0.033
0.17
0.16
0.04
0.06
0.026
0.074
0.049
0.2
1.23
0.35
0.01
0.01
0.73
0.063
0.78
1.65
0.02
0.001
4.39
0.001
0.028
0.18
0.14
0.16
0.33
0.046
0.096
0.12
0.88
20.3
2.507
34.8
31.56
0.455
0.35
0.78
0.7
0.66
0.24
1.66
1.7
0.72
1.17
0.81
0.878
5.58
0.061
0.97
2.32
4.07
3.7
2.25
2.79
14.11
17.1
25.1
19.84
16.88
1 8
15
0.41
0.6
0.38
2.01
3.65
3.6
0.98
3.4
3.1
13.7
1.49
21.25
-0.31
3.72
0.71
2.5
2.084
1.49
1.75
0.086
2.69
4.14
1.74
0.025
0.325
8.47
1.15
1.33
0.7
25
0.039
29.3
4.33
0.069
0.52
0.2
0.16
0.13
0.072
0.094
1.76
0.047
0.27
0.25
0.44
0.2
0.67
0.88
2.58
0.94
8.26
0.13
0.09
0.07
0.13
0.1
5.3
0.95
16.53
0.29
0.09
0.016
34.5
0.11
0.01
0.25
0.58
0.27
0.006
0.013
0.86
0.34
Y
Y
N
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
Y
Y
Y
N
Y
N
N
N
N
Y
N
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
438
272
253
26
696
253
253
26
272
430
696
283
450
519
110
110
110
47
82
106
303
268
268
268
286
268
268
34
34
34
34
368
158
268
268
790
345
574
345
347
1005
215
657
1 2 7
215
241
80
345
448
553
279
212
279
303
303
1 8 5
1 8 5
1 8 5
1 8 5
1 8 5
438
247
246
605
272
TABLE 1. contd
Copolymer Reactivity Ratios II / 277
Monomer 1 Monomer 2 rl Zt95% r2 *95% Conv. Refs.
Vinyl butyrate Vinyl acetate
Vinyl butyrate Vinyl acetate
Vinyl butyrate Vinyl chloride
Vinyl butyrate Vinyl chloride
Vinyl butyrate Vinyl chloride
Vinyl caproate Vinyl chloride
Vinyl chloride Aconitate, trimethyl
Vinyl chloride Acrolein
Vinyl chloride Acrylamide
Vinyl chloride Acrylamide, N-methylol-
Vinyl chloride Acrylate, 2-ethylhexyl
Vinyl chloride Acrylate, butyl
Vinyl chloride Acrylate, methyl
Vinyl chloride Acrylate, methyl
Vinyl chloride Acrylate, methyl
Vinyl chloride Acrylate, methyl
Vinyl chloride Acrylate, octyl
Vinyl chloride Acrylate, trifluoro-, methyl
Vinyl chloride Acrylate, trifluoro-, methyl
Vinyl chloride Acrylic acid
Vinyl chloride Acrylic acid
Vinyl chloride Acrylic acid
Vinyl chloride Acrylic acid
Vinyl chloride Acrylonitrile
Vinyl chloride Acrylonitrile
Vinyl chloride Acrylonitrile
Vinyl chloride Acrylonitrile
Vinyl chloride Acrylonitrile
Vinyl chloride Acrylonitrile
Vinyl chloride Acryloyl chloride
Vinyl chloride Ally1 acetate
Vinyl chloride Ally1 acetate
Vinyl chloride Allyltriethoxysilane
Vinyl chloride Butadiene
Vinyl chloride Butadiene
Vinyl chloride Bu t e n e - 1
Vinyl chloride Butene- 1, 2-ethyl-
Vinyl chloride Butene- 1, 2-methyl-
Vinyl chloride Butene-1,3, 3-dimethyl-
Vinyl chloride Butene-1,3, 3-dimethyl-
Vinyl chloride Butene-2
Vinyl chloride Butene-2, 2-methyl-
Vinyl chloride Butene-2, cis-
Vinyl chloride Carbazole, N-vinyl-
Vinyl chloride Carbon monoxide
Vinyl chloride Crotonaldehyde
Vinyl chloride Diallyl phthalate
Vinyl chloride Diallylcyanamide
Vinyl chloride Diallylcyanamide
Vinyl chloride Ethylene
Vinyl chloride Ethylene
Vinyl chloride Ethylene
Vinyl chloride Ethylene
Vinyl chloride Ethylene
Vinyl chloride Ethylene
Vinyl chloride Ethylene
Vinyl chloride Ethylene
Vinyl chloride Ethylene
Vinyl chloride Ethylene
Vinyl chloride Ethylene, chlorotrifluoro-
Vinyl chloride Fumarate, diethyl
Vinyl chloride Fumarate, diisopropyl
Vinyl chloride Hexene-1
Vinyl chloride Imidazole, 1-vinyl-2-methyl-
Vinyl chloride Isobutylene
0.97
1.25
0.302
0.55
0.65
0.348
0.04
0.03
0.16
0.07
0.093
0.002
0
0.06
0.12
1.5
1.5
0.107
0.03
0.024
0.11
0.01
0.07
0.02
0.044
0.052
0.04
0.02
1.2
1.16
1.68
0.04
.O.ll
3.34
1.56
1.01
5.64
6.18
3.3
8.52
8.8
0.17
13.52
1.55
0.833
0.44
0.44
3.82
1.99
1.74
4.38
2
3.21
1.85
0.96
1.63
1.55
2.53
0.13
0.29
1.54
0.188
2.04
0.013
0.05
0.11
0.002
0.01
0.011
0.09
0.069
0.037
0.03
0.08
0.002
0.01
0.029
0.38
0.31
0.58
0.26
0.31
0.2
13.57
2.18
10.54
0.25
0.26
0.012
0.59
0.42
0.58
0.44
0.1
0.22
0.22
0.18
0.1
0.98
0.077
1.82
1
1.35
2.092
1.75
1.35
2.26
0.19
5.22
4.15
4.4
4.4
7.66
5
4
4.8
0
0
6.69
9.28
7.04
6.8
3.26
2.55
2.62
3.62
3.65
4
3.03
0
- 0.94
8.8
5.27
0.12
- 1.05
- 1.18
- 0.44
- 0.07
- 1.79
0.3
0
4.77
0.121
- 0.56
0.7
0.68
0.68
0.02
0.19
0.24
0.34
0.2
0.21
0.21
0.14
0.23
0.16
0.01
0.48
0.49
- 1.72
2.15
0.06
0.074
0.22
0.13
0.22
0.5
0.88
0.51
0.33
0.34
0.12
0.25
0.21
0.22
0.22
0.48
3.35
0.12
0.89
1.2
0.28
2.5
5.22
5.31
0.011
0.25
0.046
0.06
0.17
0.13
0.13
0.01
0.12
0.01
0.01
0.1
9.23
0.26
0.8
Y
Y
Y
N
Y
Y
Y
Y
Y
N
Y
Y
N
N
Y
Y
Y
Y
Y
Y
N
N
N
Y
N
N
Y
N
Y
N
N
N
N
N
N
N
N
Y
N
Y
Y
272
515
283
400
494
283
1 4 7
2 7 1
1 5 6
1 5 7
510
518
151
46
470
518
518
595
598
1 3 5
229
288
379
140
202
22
238
46
529
288
470
475
237
517
717
230
329
329
329
6
329
329
230
427
184
271
296
602
603
1 6 1
180
270
42
472
536
63
63
64
68
454
1 3 7
1038
329
154
140
References page II - 290
II / 278 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl
Zt95%
r2
&95% Conv. Refs.
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Isobutylene
Isobutylene
Isobutylene
Isobutylene, 3-chloro-
Isopropenyl acetate
Isopropenylisocyanate
Itaconate, diethyl
Itaconate, dimethyl
Maleate, dietbyl
Maleate, diethyl
Maleate, diethyl
Maleate, dioctyl
Maleic anhydride
Maleic anhydride
Maleic anhydride
Mal ei mi de, N-(4-carboxyethylphenyl)-
Mal ei mi de, N-(Cchlorophenyl)-
Mal ei mi de, N-(Cmethylphenyl)-
Mal ei mi de, N-butyl-
Maleimide, N-phenyl-
Mal ei mi de, N-propyl-
Methacrylate, 3,5dimethyladamantyl
Methacrylate, S-(2-benzothiazolylthio)-
ethyl
Metbacrylate, butyl
Methacrylate, methyl
Methacrylate, octyl
Methacrylic acid
Methacrylic acid
Methacrylic acid
Metbacryloyl chloride
Methacryloyloxy-, o-, benzoic acid
Norbornadiene
Octene-1
Oxazolidone, N-vinyl-
P e n t e n e - 1
P e n t e n e - 1
Pentene- 1, 2-methyl-
Phosphate, vinyl diethyl
Phosphate, vinyl diphenyl
Propene, 1-chloro-, cis-
Propene, 1-chloro-, trans-
Propene, 2-chloro-
Propene, 2-chloro-
Propenyl, 2-, acetate
Propenyl, 2-chloro-, acetate
Propenyltriethoxysilane
Propylene
Propylene
Propylene
Propylene
Propylene
Pyridine, 4-vinyl-
Pyrrolidone, N-vinyl-
Pyrrolidone, iv-vinyl-
Pyrrolidone, N-vinyl-
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, pentachloro-
Triallyl citrate
Vinyl 12-ketostearate
-
2.12
1.2
1.54
0.31
2.26
0.39
0.06
0.05
0.768
0.8
0.9
0.05
0.098
0.04
0.1
0.04
0.026
0.022
0.24
0.023
0.06
0.21
0.64
0.05
0.07
0.04
0.064
0.022
0.07
0.3
0.004
0.67
3.26
0.313
4
2.08
1.59
3.4
3.009
11.52
4.45
0.095
0.75
2.2
0.7
2.35
.0.05
5.16
2.45
2.9
0.53
0.55
0.74
.0.06
0.058
0.16
0.005
0.04
0.01
0.43
0.605
0.03
0.2
2.05
0.13
0.078
0.11
0.14
0.042
0.03
0.044
0.048
1.13
0.026
0.05
0.04
0.047
0.008
0.02
0.052
0.02
0.45
0.095
1.78
0.68
0.21
0.077
2.14
0.81
0.085
0.14
0.1
0.06
0.08
0.003
0.08
0.031
0.87
0.033
-
0.268
- 0.54
0.08
0
0.23
3
5.65
5
- 0.003
0
0.046
0.608
- 0.22
0.4
0.67
3.29
3.65
4.49
12.7
4.01
2.38
1.85
0.26
13.5
8.99
1 4
23.52
23.26
9.05
2
11.26
0.41
- 0.57
0.822
0.001
0.81
- 1.16
0.15
0.327
0.1
0.33
4.75
0.58
0.25
0
0.196
3.1
- 0.02
0.09
0.38
0.34
0.73
27.54
17.24
23.92
2 5
12.4
14.7
5.3
1.03
- 0.01
0.043
5.8
0.16
0.044
0.07
0.099
0.38
0.18
0.39
0.34
106.2
0.18
0.16
8.87
2.97
0.98
0.96
3.5
0.01
0.85
0.048
5.2
2.31
0.047
0.023
0.63
0.4
5.12
0.023
0.21
0.04
7.35
1.12
3.6
5
29.2
0.17
Y
N
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
N
N
Y
Y
Y
Y
N
N
Y
Y
N
N
Y
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
N
Y
Y
Y
Y
1 5 5
329
560
475
100
777
480
479
1 3 7
449
6
3
260
5 2 1
521
306
306
306
305
306
305
335
741
519
3
511
1 3 5
229
46
432
938
267
329
36
3
329
329
779
779
181
1 8 1
1 8 1
517
189
445
237
1 5 5
329
355
560
588
154
40
582
582
109
238
242
46
516
59
516
367
146
TABLE 1. contd
Copolymer Reactivity Ratios II / 279
Monomer 1 Monomer 2
rt
Zt95%
r2
Yt95% Conv. Refs.
Vinyl chloride Vinyl 2-chloroethyl ether 2.46
Vinyl chloride Vinyl acetate 1.63
Vinyl chloride Vinyl acetate 1.032
Vinyl chloride Vinyl acetate 1.84
Vinyl chloride Vinyl acetate 2.13
Vinyl chloride Vinyl acetate 1.64
Vinyl chloride Vinyl acetate 1.35
Vinyl chloride Vinyl acetate 2.3
Vinyl chloride Vinyl benzoate 1.66
Vinyl chloride Vinyl benzoate 1.7
Vinyl chloride Vinyl benzoate 0.72
Vinyl chloride Vinyl butyl ether 2.084
Vinyl chloride Vinyl butylsulfonate 0.325
Vinyl chloride Vinyl butylsulfonate 8.47
Vinyl chloride Vinyl butyrate 2.092
Vinyl chloride Vinyl butyrate 1.75
Vinyl chloride Vinyl butyrate 1.35
Vinyl chloride Vinyl caproate 2.26
Vinyl chloride Vinyl chloroacetate 1.64
Vinyl chloride Vinyl dichloroacetate 1.3
Vinyl chloride Vinyl dodecyl ether 1.93
Vinyl chloride Vinyl fluoride 11
Vinyl chloride Vinyl fluoride 11.6
Vinyl chloride Vinyl hendecanoate 1.081
Vinyl chloride Vinyl isobutyl ether 2.19
Vinyl chloride Vinyl laurate 7.4
Vinyl chloride Vinyl m-cresyl ether 1.23
Vinyl chloride Vinyl methyl ketone 0.1
Vinyl chloride Vinyl o-cresyl ether 1.33
Vinyl chloride Vinyl octadecyl ether 2.1
Vinyl chloride Vinyl octyl ether 1.9
Vinyl chloride Vinyl p-chlorophenyl ether 1
Vinyl chloride Vinyl p-cresyl ether 1.17
Vinyl chloride Vinyl p-rerr-butylphenyl ether 1.08
Vinyl chloride Vinyl p-vinyloxybenzoate 0.58
Vinyl chloride Vinyl pelargonate 1.16
Vinyl chloride Vinyl phenyl ether 1.28
Vinyl chloride Vinyl phenyl ether 1.06
Vinyl chloride Vinyl phenyl ether 1.21
Vinyl chloride Vinyl propionate 1.6
Vinyl chloride Vinyl propionate 1.35
Vinyl chloride Vinyl stearate 0.71
Vinyl chloride Vinyl rerr-butyl sulfide 3
Vinyl chloride Vinyl rerr-butyl sulfide 3
Vinyl chloride Vinyl valerate 2.006
Vinyl chloride Vinylene carbonate 4.82
Vinyl chloride Vinylene carbonate 15.38
Vinyl chloride Vinylene carbonate 17.81
Vinyl chloride Vinylethyldiethoxysilane 0.94
Vinyl chloride Vinylidene chloride 0.071
Vinyl chloride Vinylidene chloride 0.14
Vinyl chloride Vinylidene chloride 0.25
Vinyl chloride Vinylidene chloride 0.3
Vinyl chloride Vinylidene chloride 0.2
Vinyl chloride Vinylidene chloride 0.2
Vinyl chloride Vinylidene chloride 0.16
Vinyl chloride Vinylidene chloride 0.205
Vinyl chloride Vinylidene cyanide 0.01
Vinyl chloride Vinylidene cyanide 0.016
Vinyl chloride Vinylisocyanate 0.46
Vinyl chloride Vinylphenylisocyanate, p- 0.01
Vinyl chloride Vinyltriethoxysilane 0.82
Vinyl chloride Vinyltrimethoxysilane 0.93
Vinyl chloroacetate Acrylonitrile - 0.007
Vinyl chloroacetate Acrylonitrile 0.09
0.52
0.32
0.097
0.68
0.2
0.12
0.64
0.16
0.016
0.013
0.86
0.074
0.22
0.34
0.55
0.016
1.43
0.04
0.02
0.04
0.02
0.06
0.06
0.14
0.03
0.097
0.071
0.49
1.44
7.84
1.53
0.025
0.32
0.003
0.002
0.16
0.016
- 0.07
0.43
0.981
0.24
0.263
0.25
0.65
0.26
0.343
0.5
0.28
0.023
0.267
0.083
0.302
0.55
0.65
0.348
0.421
0.91
0.15
0.05
0.11
0.38
0.04
0.2
0.13
8.3
0.14
-0. 1
0.1
0.63
0.13
0.14
0.78
0.28
0.01
0.16
0.17
0.6
0.65
0.24
0.15
0.15
0.277
0.03
0.069
0
- 0.44
2.06
3.39
8.92
3.2
4.5
1.8
4.5
3.068
0.72
0.6
3.7
11.9
- 0.04
0.09
4.18
0.34
0.11
0.14
0.036
0.15
0.028
0.15
0.14
0.036
0.001
0.046
0.096
0.013
0.05
0.055
0.49
0.022
0.37
0.02
0.01
0.05
0.01
0.02
0.07
0.59
0.03
0.64
0.014
0.12
0.068
0.22
2.97
0.32
1.16
0.076
0.068
0.44
0.33
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
N
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
304
109
1 4 8
158
283
3
450
86
283
450
519
279
1 8 5
1 8 5
283
400
494
283
283
283
370
590
755
1 4 5
47
450
279
375
279
370
370
279
279
279
497
1 4 5
172
279
280
400
450
1 4 5
598
601
283
103
319
319
237
238
29
3
470
517
539
585
67
409
82
777
777
237
237
362
542
References page II - 290
II / 280 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Vinyl chloroacetate Phosphate, vinyl diethyl
Vinyl chloroacetate Phosphate, vinyl diphenyl
Vinyl chloroacetate Styrene
Vinyl chloroacetate Styrene
Vinyl chloroacetate Vinyl acetate
Vinyl chloroacetate Vinyl acetate
Vinyl chloroacetate Vinyl acetate
Vinyl chloroacetate Vinyl butyl ether
Vinyl chloroacetate Vinyl chloride
Vinyl chloroacetate Vinyl ethyl ether
Vinyl chloroacetate Vinyl phenyl ether
Vinyl chloroacetate Vinylidene cyanide
Vinyl chloroethyl ether Acrylonitrile
Vinyl chloroethyl ether Methacrylic anhydride
Vinyl chloroformate Vinyl acetate
Vinyl chloroformate Vinyl acetate
Vinyl chloromethyl ketone Acrylonitrile
Vinyl chloromethyl ketone Methacrylate, methyl
Vinyl chloromethyl ketone Styrene
Vinyl chloromethyl ketone Styrene, cc-methyl-
Vinyl chloromethyl ketone Vinyl acetate
Vinyl chloromethyl ketone Vinylidene chloride
Vinyl cinnamate Methacrylonitrile
Vinyl cinnamate Pyrrolidone, N-vinyl-
Vinyl cinnamate Vinyl acetate
Vinyl cyclohexyl ether Pyrrolidone, N-vinyl-
Vinyl cyclohexyl ketone Vinyl 4-chlorocyclohexyl ketone
Vinyl cyclohexyl ketone Vinyl acetate
Vinyl cjrmantrene Acrylate, methyl
Vinyl cymantrene Acrylonitrile
Vinyl cymantrene Pyrrolidone, N-vinyl-
Vinyl cymantrene Styrene
Vinyl cymantrene Vinyl acetate
Vinyl dichloroacetate Acrylonitrile
Vinyl dichloroacetate Acrylonitrile
Vinyl dichloroacetate Styrene
Vinyl dichloroacetate Vinyl chloride
Vinyl diethylphosphinate Ethylene
Vinyl diethylphosphinate Ethylene
Vinyl dodecyl ether Acrylonitrile
Vinyl dodecyl ether Styrene
Vinyl dodecyl ether Styrene
Vinyl dodecyl ether Vinyl acetate
Vinyl dodecyl ether Vinyl chloride
Vinyl dodecyl ether Vinylidene chloride
Vinyl ether Acrylonitrile
Vinyl ether Methacrylate, methyl
Vinyl ether Pyridine, 4-vinyl-
Vinyl ether Styrene
Vinyl ethyl ether Acrylate, methyl
Vinyl ethyl ether Acrylonitrile
Vinyl ethyl ether Ethylene
Vinyl ethyl ether Fumarate, diethyl
Vinyl ethyl ether Methacrylate methyl
Vinyl ethyl ether Styrene
Vinyl ethyl ether Styrene
Vinyl ethyl ether Vinyl acetate
Vinyl ethyl ether Vinyl chloroacetate
Vinyl ethyl ether Vinylidene chloride
Vinyl ethyl ketone Methacrylate, methyl
Vinyl ethyl ketone Styrene
Vinyl ethyl ketone Styrene
Vinyl ethyl ketone Styrene
Vinyl ethyl ketone Styrene
Vinyl ethyl ketone Vinyl acetate
2.01
1.42
- 0.04
0.03
1.39
0.88
1.18
1.49
0.421
1.92
0.84
0
- 0.02
0.579
0.586
0.88
0.593
0.507
0.386
49.52
6.8
0.15
1 . 2
1.2
-0.11
1.6
13.76
0.211
- 0.065
0.093
0.096
7.21
0.044
0.18
0.28
0.91
- 11.99
- 62.84
0
0
0
0
0.15
0
0.02
-0.15
0.03
1.2
0
0.06
0
-0.124
0.01
0
-0.122
0.26
0.43
0
0.65
- 0.033
0.43
0.332
0.122
10.18
0.2
0.15
0.24
0.3
0.19
34.5
0.055
17.19
1.67
0.006
0.02
0.076
0.052
0.12
0.092
0.039
0.034
15.79
0.3
0.59
0.067
0.093
0.053
0.014
1.01
0.015
0.49
80.64
34.66
0.16
5.3
0.12
0.059
0.066
3.9
0.42
0.023
0.06
0.043
0.017
6.62
0.374
0.53
14.57
45
0.83
0.803
0.8
0.12
1.64
0.43
0.55
0.137
1.04
0.67
0.66
0.064
0.121
0.127
0.009
0.044
0.018
4.6
0.01
0.04
1.91
0.5
0.08
0.46
0.446
0.037
2.324
0.072
7.45
0.25
20
1.3
0.15
0.05
0.82
27
56
3.67
1.93
1.3
0.94
4.9
32
1 5 2
3.3
0.69
2.7
1.63
37
90
1 1 1
3.42
1.92
3.2
0.42
13.83
0.2
0.29
0.665
-0.13
0.046
0.12
62.41
0.12
0.089
4.39
0.34
3.9
0.61
0.037
0.05
0.16
0.12
0.019
0.021
0.047
0.01
0.054
0.009
9.39
0.14
0.048
0.03
0.06
0.003
0.32
0.55
0.16
0.01
0.99
1 8 5
0.12
0.16
15.5
17.19
0.17
1.44
0.08
0.16
0.021
0.18
779
779
212
542
7 1
779
8 6 1
212
283
212
212
82
116
106
675
706
356
356
353
356
356
356
200
200
200
214
668
846
354
354
308
354
354
362
542
542
283
311
3 1 1
373
374
374
372
370
371
386
45
395
45
470
194
584
194
106
140
194
1 5 8
212
470
794
1 1 2
344
353
550
794
TABLE 1. contd
Copolymer Reactivity Ratios II / 281
Monomer 1 Monomer 2
rl
f95%
r2
f 95% Conv. Refs.
Vinyl ethyl oxalate Acrylonitrile
Viny1 ethyl oxalate Methacrylate, methyl
Vinyl ethyl oxalate Styrene
Vinyl ethyl oxalate Vinyl acetate
Vinyl ethyl sulfide Acrylonitrile
Vinyl ethyl sulfide Acrylonitrile
Vinyl ethyl sulfide Methacrylate, methyl
Vinyl ethyl sulfide Methacrylate, methyl
Viny1 ethyl sulfide Styrene
Vinyl ethyl sulfide Styrene
Viny1 ethyl sulfoxide Acrylonitrile
Vinyl ethyl sulfoxide Methacrylate, methyl
Viny1 ethyl sulfoxide Styrene
Viny1 ethyl sulfoxide Styrene
Vinyl ethylene glycol glycidyl ether Pyrrolidone, N-vinyl-
Vinyl ethylene glycol glycidyl ether Pyrrolidone, N-vinyl-
Viny1 fluoride Acrylate, butyl
Vinyl fluoride Acrylate, butyl
Vinyl fluoride Acrylate, methyl
Vinyl fluoride Acrylate, methyl
Vinyl fluoride Acrylonitrile
Vinyl fluoride Acrylonitrile
Vinyl fluoride Ethylene
Vinyl fluoride Ethylene
Vinyl fluoride Ethylene, chlorotrifluoro-
Vinyl fluoride Vinyl acetate
Vinyl fluoride Vinyl chloride
Vinyl fluoride Vinyl chloride
Viny1 fluoride Vinylidene chloride
Vinyl formate Acrylonitrile
Vinyl formate Ally1 chloride
Vinyl formate Butadiene, 2-chloro-
Viny1 formate Butadiene, 2-chloro-
Vinyl formate Carbazole, N-vinyl-
Vinyl formate Vinyl acetate
Vinyl formate Vinyl acetate
Vinyl hendecanoate Acrylate, methyl
Vinyl hendecanoate Acrylonitrile
Vinyl hendecanoate Butadiene
Vinyl hendecanoate Styrene
Viny1 hendecanoate Vinyl chloride
Viny1 hendecanoate Vinylidene chloride
Vinyl iodide Styrene
Vinyl isobutyl ether Acrylate, 2-chloroethyl
Vinyl isobutyl ether Acrylate, methyl
Vinyl isobutyl ether Acrylonitrile
Vinyl isobutyl ether Acrylonitrile
Vinyl isobutyl ether Acrylonitrile
Vinyl isobutyl ether Acrylonitrile
Vinyl isobutyl ether Ethylene, trichloro-
Vinyl isobutyl ether Fumarate, diethyl
Vinyl isobutyl ether Maleate, diethyl
Vinyl isobutyl ether Styrene
Vinyl isobutyl ether Styrene
Vinyl isobutyl ether Styrene
Vinyl isobutyl ether Vinyl chloride
Vinyl isobutyl ether Vinylene carbonate
Viny1 isobutyl sulfide Acrylate, ethyl
Vinyl isobutyl sulfide Acrylate, ethyl
Vinyl isobutyl sulfide Acrylate, methyl
Vinyl isobutyl sulfide Acrylate, methyl
Vinyl isobutyl sulfide Acrylonitrile
Vinyl isobutyl sulfide Acrylonitrile
Vinyl isobutyl sulfide Acrylonitrile
Viny1 isobutyl sulfide Methacrylate, methyl
0
- 0.05
-0.12
9.89
0.06
0.05
0.036
0.3
0.113
0.25
- 0.08
- 0.037
0.101
0.1
0.06
0.06
0.01
0.01
0.01
0.01
0.005
0.01
0.3
0.8
0.25
0.05
0.11
0.16
- 0.004
0.57
- 0.04
- 0.05
0.192
0.98
0.68
0.033
0.09
- 0.22
-0.17
0.38
0.04
0.126
0
0
0.7
0.99
- 0.04
- 0.04
0.05
0
0
0.65
0.29
0.01
0.04
0.18
0.05
0.05
0.05
0.06
0.03
0.022
0.03
0.05
0.28
0.44
0.19
8.44
0.03
0.03
0.017
0.032
0.14
0.06
0.044
0.15
0.12
0.01
0.001
0.06
0.008
0.91
1.26
0.18
0.022
0.16
0.035
0.002
0.09
0.06
0.01
0.02
0.009
0.39
0.33
0.37
0.04
0.05
0.02
0.02
0.01
0.038
0.01
0.03
1.34
4.74
5.62
1.35
0.09
0.06
1.03
2.7
4.76
6
1.63
11.17
9.64
6
1.4
1.4
1 9
1 9
43
43
44
24
2.52
1.7
1.2
3.5
11
11.6
6
2.54
0.78
1 5
11.91
4.142
0.94
1.41
3.615
1.88
22.56
24.89
1.081
2.72
7.401
2.24
3.63
- 0.24
- 0.05
0.98
1.26
0.014
0.52
0.17
11.58
11.96
50
2.19
0.16
0.36
0.32
0.3
0.29
0.08
0.062
0.08
0.89
0.45
2.95
1.06
0.84
0.01
0.01
0.11
0.2
0.16
0.48
0.54
0.32
1.79
3.89
0.011
0.14
0.012
0.44
24.54
1.22
0.016
0.37
0.315
0.04
0.26
0.07
0.15
0.19
0.003
1.91
2.32
1.43
0.02
0.02
0.01
0.01
0.005
0.004
0.004
0.01
Y
Y
Y
Y
N
N
Y
Y
Y
Y
Y
N
Y
N
Y
N
Y
Y
Y
Y
Y
Y
N
N
N
N
N
Y
N
N
Y
N
N
N
N
N
Y
N
N
124
124
124
124
285
336
303
507
303
507
286
286
286
286
369
818
604
606
604
606
528
590
42
590
406
755
590
755
607
47
438
1 2 7
247
246
272
401
1 4 5
1 4 5
1 4 5
1 4 5
1 4 5
1 4 5
806
790
347
322
322
347
347
332
640
640
349
349
490
47
322
285
336
285
336
285
303
336
285
References page II - 290
II / 282 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1
* 95%
r2
Zt95% Conv. Refs.
Vinyl isobutyl sulfide
Vinyl isobutyl sulfide
Vinyl isobutyl sulfide
Vinyl isopropyl ether
Vinyl isopropyl ether
Vinyl isopropyl ketone
Vinyl isopropyl ketone
Vinyl isopropyl ketone
Vinyl isopropyl ketone
Vinyl isopropyl ketone
Vinyl isopropyl ketone
Vinyl isopropyl ketone
Vinyl isopropyl sulfide
Vinyl isopropyl sulfide
Vinyl isothiocyanate
Vinyl isothiocyanate
Vinyl isothiocyanate
Vinyl isothiocyanate
Vinyl l-methyl ether
Vinyl laurate
Vinyl laurate
Vinyl laurate
Vinyl m-cresyl ether
Vinyl m-cresyl ether
Vinyl m-cresyl ether
Vinyl methanesulfonate
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl methyl sulfide
Vinyl methyl sulfide
Vinyl methyl sulfide
Vinyl methyl sulfide
Vinyl methyl sulfide
Vinyl methyl sulfide
Vinyl methyl sulfone
Vinyl methyl sulfone
Vinyl methyl sulfoxide
Vinyl methyl sulfoxide
Vinyl methyl sulfoxide
Vinyl mono-diethyleneglycol ether
Vinyl mono-ethyleneglycol ether
Vinyl o-cresyl ether
Vinyl o-cresyl ether
Vinyl o-cresyl ether
Methacrylate, methyl
Methacrylate, methyl
Styrene
Caprolactam, N-vinyl-
Pyrrolidone, N-vinyl-
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Methacrylate, methyl
Styrene
Acrylonitrile
Methacrylate, methyl
Styrene
Styrene
Indene
Acrylonitrile
Vinyl acetate
Vinyl chloride
Methacrylate, methyl
Vinyl chloride
Vinylidene chloride
Vinyl acetate
Acrylamide
Acrylamide
Acrylamide, N,N-dimethyl
Acrylate, butyl
Acrylonitrile
Acrylonitrile
Indene
Indene
Methacrylamide
Methacrylamide
Methacrylate, 2,2,6,6-tetramethyl-
4-piperidinyl
Methyleneglutaronitrile, 2-
Styrene
Styrene
Styrene
Styrene, 2,5-dichloro-
Triazine, 4,6-diamino-2-vinyl-
Vinyl acetate
Vinyl chloride
Vinyl phenyl ether
Vinyl phenyl ketone
Vinylidene chloride
Acrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Styrene
Vinylene carbonate
Styrene
Vinyl acetate
Styrene
Styrene, p-chloro-
Styrene, p-methyl-
Methacrylic acid
Methacrylate, glycidyl
Methacrylate, methyl
Vinyl chloride
Vinylidene chloride
0.021
0.03
0.11
0.01
0.03
1.44
0.6
0.26
0.272
0.3
7.87
6.47
0.046
0.16
1.4
0.6
0.37
0.5
0.67
0.04
0.7
0.2
0.2
0.13
0.04
0.206
0.47
0.75
0.1
1.81
1.75
1.39
2.63
2.9
0.25
0.28
0.41
5.05
0.349
0.348
0.27
0.5
0.17
8.3
4.4
0.74
1.8
0.084
0.03
0.15
0.066
0.046
7.72
0.22
0.55
0.01
0.01
0.01
2.2
0
0.1
0.14
0.04
0.034
0.02
0.2
0.96
2.09
0.47
0.07
0.046
2.18
0.025
0.068
2.82
0.02
0.004
0.427
0.44
0.23
0.43
0.24
0.11
0.12
0.24
0.068
0.009
0.11
0.086
0.056
0.084
1.68
0.17
0.21
0.01
0.01
0.985
0.88
2.38
0.22
0.87
0.81
0.54
0.46
0.36
0.4
0.3
0.154
0.822
4.61
0.36
0.85
0.65
0.8
12.64
4
1.4
7.4
3.3
1.23
1.95
0.639
3.99
1.02
0.82
0.8
0.59
0.63
0.2
0.25
3
1.72
0.53
1.24
0.288
0.237
0.35
2
1.35
0.1
0.01
0.671
0.55
0.209
1
4.5
4.46
5
0. 08
1.146
0
3.57
6.46
2.73
0
4.41
1.8
1.33
2.1
0.077
0.02
0.41
1.95
9.3
0.22
0.05
0.1
0.073
0.064
0.18
12.59
0.04
0.07
0.014
0.7
0.13
0.36
0.06
0.13
0.18
0.26
0.092
0.023
0.68
0.034
0.11
0.24
0.17
0.087
0.02
0.02
0.1
Y
N
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
303
336
303
215
215
601
794
344
353
599
601
794
303
303
542
422
422
542
750
381
503
450
605
279
279
942
609
609
609
53
140
504
606
606
609
609
664
512
140
353
550
375
243
9 1
375
423
946
375
1 9 5
106
1 9 3
195
303
120
1 9 5
1 9 5
737
737
737
831
780
605
279
279
TABLE 1. contd
copolymer Reactivity Ratios II / 283
Monomer 1 Monomer 2
rl
f95%
r2
?c95% Conv. Refs.
Vinyl octadecyl ether Acrylonitrile 0
Vinyl octadecyl ether Vinyl acetate 0
Vinyl octadecyl ether Vinyl chloride -0. 1
Vinyl octadecyl ether Vinylidene chloride 0
Vinyl octyl ether Acrylonitrile 0
Vinyl octyl ether Styrene 0
Vinyl octyl ether Vinyl acetate 0
Vinyl octyl ether Vinyl chloride 0.1
Vinyl p-benzylethylcarbinol Acrylate, butyl 0.4
Vinyl p-benzylethylcarbinol Acrylate, methyl 0.48
Vinyl p-benzylethylcarbinol Acrylonitrile 0.31
Vinyl p-benzylmethylcarbinol Acrylonitrile 0.54
Vinyl p-benzylmethylcarbinol Methacrylate, methyl 0.98
Vinyl p-benzylmethylcarbinol Styrene 0.94
Vinyl p-benzylmethylcarbinol Styrene, p-chloro- 1
Vinyl p-bromobenzoate Vinyl benzoate 1.17
Vinyl p-bromobenzoate Vinyl p-cyanobenzoate 0.83
Vinyl p-bromobenzoate Vinyl p-methoxybenzoate 1.08
Vinyl p-bromobenzoate Vinyl p-methylbenzoate 1.05
Vinyl p-chlorobenzoate Vinyl benzoate 0.81
Vinyl p-chlorobenzoate Vinyl p-cyanobenzoate 0.813
Vinyl p-chlorobenzoate Vinyl p-methoxybenzoate 1
Vinyl p-chlorobenzoate Vinyl p-methylbenzoate 0.853
Vinyl p-chlorophenyl ether Vinyl chloride 0.63
Vinyl p-chlorophenyl ether Vinylidene chloride 0.14
Vinyl p-cresyl ether Methacrylate, methyl 0
Vinyl p-cresyl ether Vinyl chloride 0.13
Vinyl p-cresyl ether Vinylidene chloride 0.03
Vinyl p-cyanobenzoate Vinyl benzoate 0.878
Vinyl p-cyanobenzoate Vinyl p-bromobenzoate 0.901
Vinyl p-cyanobenzoate Vinyl p-chlorobenzoate 1.031
Vinyl p-cyanobenzoate Vinyl p-methoxybenzoate 0.63
Vinyl p-cyanobenzoate Vinyl p-methylbenzoate 0.81
Vinyl p-methoxybenzoate Vinyl p-bromobenzoate 0.72
Vinyl p-methoxybenzoate Vinyl p-chlorobenzoate 0.699
Vinyl p-methoxybenzoate Vinyl p-cyanobenzoate 0.685
Vinyl p-methylbenzoate Vinyl p-bromobenzoate 0.594
Vinyl p-methylbenzoate Vinyl p-chlorobenzoate 0.682
Vinyl p-methylbenzoate Vinyl p-cyanobenzoate 0.624
Vinyl p-tert-butylphenyl ether Vinyl chloride 0.14
Vinyl p-tert-butylphenyl ether Vinylidene chloride 0.05
Vinyl p-vinyloxybenzoate Vinyl chloride 0.78
Vinyl pelargonate Butadiene 0.02
Vinyl pelargonate Styrene 0.01
Vinyl pelargonate Vinyl chloride 0.28
Vinyl pelargonate Vinylidene chloride 0
Vinyl phenyl carbonate Vinyl acetate 0.384
Vinyl phenyl carbonate Vinyl acetate 0.384
Vinyl phenyl ether Acrylonitrile 0.23
Vinyl phenyl ether Caprolactam, N-vinyl- 0.26
Vinyl phenyl ether Methacrylate, methyl 0.01
Vinyl phenyl ether Methacrylate, methyl 0
Vinyl phenyl ether Pyrrolidone, N-vinyl- 0.253
Vinyl phenyl ether Styrene 0.01
Vinyl phenyl ether Vinyl chloride 0.01
Vinyl phenyl ether Vinyl chloride 0.16
Vinyl phenyl ether Vinyl chloride 0.17
Vinyl phenyl ether Vinyl chloroacetate 0.55
Vinyl phenyl ether Vinyl methyl ketone 0.01
Vinyl phenyl ether Vinylidene chloride 0.433
Vinyl phenyl ether Vinylidene chloride 0.04
Vinyl phenyl ketone Methacrylate, glycidyl 0.697
Vinyl phenyl ketone Methacrylate, methyl 0.59
Vinyl phenyl ketone Styrene 0.3
Vinyl phenyl ketone Styrene 0.465
0.2
0.28
0.15
0.13
0.021
0.29
0.17
0.072
0.014
0.14
0.054
0.05
0.01
0.01
0.004
0.094
0.034
0.028
0.22
0.1
0.1
0.057
0.075
0.045
0.021
0.04
0.02
0.004
0.07
0.083
0.083
0.37
0.32
0.007
0.59
0.03
0.61
0. 05 1
0.03
1.9
0.02
0.03
0.85
4.5
2.1
1.5
0.81
65
3.47
1.9
0.17
0.18
0.04
0.11
0.24
0.98
1
0.716
0.901
0.72
0.594
0.832
1.031
0.699
0.682
1
2.44
2.6
1.17
1.97
0.659
0.83
0.813
0.685
0.624
1.08
1
0.63
1.05
0.853
0.81
1.08
2.04
0.58
26.3
49.5
1.16
4.08
0.85
0.85
2.5
1.3
11.34
2.8
4.48
1.7
1.28
1.06
1.21
0.84
4.4
2.45
2.11
0.719
0.71
0.24
0.21
0.17
0.26
0.32
0.031
0.034
0.1
0.045
0.028
0.028
0.057
0.021
0.04
0.04
0.02
0.06
0.033
0.021
0.014
0.075
0.04
0.29
0.14
0.22
0.17
0.054
0.1
0.06
0.06
0.06
0.23
0.23
2.43
5.76
0.1
0.14
0.03
1.67
0.34
0.11
0.6
0.04
0.042
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
N
Y
Y
N
Y
N
Y
373
372
370
371
373
374
372
370
5 9 1
591
591
48
48
48
48
110
110
110
110
110
110
110
110
279
279
605
279
279
110 (
110
110
110
110
110
110
110
110
110
110
279
279
497
1 4 5
1 4 5
1 4 5
1 4 5
675
705
556
214
172
605
214
423
172
279
280
212
423
240
280
946
794
344
353
References page II - 290
II / 284 FREE RADICAL COPOLVMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
0 f95% r2 f95% Conv. Refs.
Vinyl phenyl ketone
Vinyl phenyl ketone
Vinyl phenyl sulfide
Vinyl phenyl sulfide
Vinyl phenyl sulfide
Vinyl phenyl sulfide
Vinyl phenyl sulfide
Vinyl phenyl sulfide
Vinyl phenyl sulfide
Vinyl phenyl sulfide
Vinyl phenyl sulfone
Vinyl phenyl sulfone
Vinyl propionate
Vinyl propionate
Vinyl propionate
Vinyl propionate
Vinyl propionate
Vinyl propionate
Vinyl propionate
Vinyl propionate
Vinyl propionate
Vinyl stearate
Vinyl stearate
Vinyl stearate
Vinyl stearate
Vinyl stearate
Vinyl stearate
Vinyl stearate
Vinyl stearate
Vinyl sulfone
Vinyl sulfone
Vinyl tert-butyl ketone
Vinyl tert-butyl ketone
Vinyl tert-butyl sulfide
Vinyl tert-butyl sulfide
Vinyl tert-butyl sulfide
Vinyl tert-butyl sulfide
Vinyl tert-butyl sulfide
Vinyl tert-butyl sulfide
Vinyl teti-butyl sulfide
Vinyl thiolacetate
Vinyl thiolacetate
Vinyl thiolacetate
Vinyl thiolacetate
Vinyl thiolacetate
Vinyl thiolacetate
Vinyl trichloroacetate
Vinyl trimethylammonioethyl ether iodide
Vinyl valerate
Vinyl, 2-, 2-methyl-4,4,6,6-tetraphenyl-
cyclotrisiloxane
Vinyl-tris(trimethoxysiloxy)silane
Vinyl-tris(trimethoxysiloxy)silane
Vinyl-tris(trimethoxysiloxy)silane
Vinyl-tris(trimethoxysiloxy)silane
Vinyl-tris(trimethoxysiloxy)silane
Vinylacetophenone
Vinylacetophenone
Vinylanthracene, 9-
Vinylanthracene, 9-
Vinylanthracene, 9-
Vinylanthracene, 9-
Vinylanthracene, 9-
Vinylanthracene, 9-
Vinylbenzoate, p-, sodium
Vinyl acetate
Vinyl methyl ketone
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Benzothiazole, vinylmercapto-
Methactylate, methyl
Methactylate, methyl
Styrene
Styrene
S t y r e n e
Vinyl acetate
Ally1 chloride
Butadiene, 2-chloro-
Carbazole, N-vinyl-
Ethylene
Methacrylate, methyl
Vinyl acetate
Vinyl acetate
Vinyl chloride
Vinyl chloride
Acrylate, methyl
Acrylonitrile
Butadiene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl chloride
Vinylidene chloride
Methacrylate, methyl
Styrene
Methacrylate, methyl
Styrene
Styrene
Acrylonitrile
Styrene
Vinyl acetate
Vinyl acetate
Vinyl chloride
Vinyl chloride
Acrylate, methyl
Carbazole, N-vinyl-
Styrene
Succinimide, N-vinyl-
Vinyl acetate
Vinylene carbonate
Acrylonitrile
N-Vinylpyrrolidone
Vinyl chloride
Styrene
5.81
0.671
- 0.02
0.03
0.03
0.24
0.06
0.08
0.019
0.26
- 0.31
- 0.35
0.62
0.08 1
1.5
0.03
0.98
1
0.6
0.65
0.03
0.078
0.02
- 0.39
0.96
0.73
0.24
0.08
0.1
- 0.027
0.65
3.2
0.248
0
0.158
0.07
0.07
0.15
0.15
0.23
0.45
0.25
2.47
5.5
13.57
0.047
0
0.277
0.8
Acrylonitrile 0.07
Acrylonitrile 0.08
Methacrylate, methyl 0.02
Styrene 0
Styrene 0.01
Methacrylate, methyl 1.65
Styrene 1.12
Acrylate, butyl 0.126
Acrylate, ethyl 0.295
Acrylate, methyl 0.08
Methacrylate, methyl 0.117
Styrene 0.25
Styrene 0.3
Acrylonitrile 0.23
0.96
0.22
0.02
0.01
0.12
0.09
0.054
0.18
0.16
0.37
0.073
0.007
0.21
0.71
0.17
0.64
0.17
0.16
0.047
0.15
0.46
0.05
0.013
0.073
0.15
0.37
1.04
0.039
0.02
0.014
3.81
0.42
0.054
0.056
0.092
0.043
0.34
- 0.06
0.74
0.57
0.11
0.11
0.95
0.79
0.85
3.63
3.96
1.562
0.171
0.68
1.69
0.67
24
0.98
0.9
1.6
1.35
5.8
4.639
42.5
15.96
0.953
0.9
0.71
3.92
4.5
0.731
1.21
0.3
0.36
0.09
4.36
1 3
1 3
3
3
0.8
0.44
4
0.17
0.05
0.041
7.34
11.6
2.006
0.11
3.9
3.85
34
26
24
0.33
0.246
3.717
3.498
2.998
4.068
2.12
2.12
0.174
0.057
0.1
0.01
0.01
0.61
0.06
0.12
0.27
0.091
0.064
0.21
0.015
4.73
13.32
0.015
0.097
0.14
0.49
0.058
0.11
0.31
0.11
0.024
0.76
0.28
0.15
0.01
0.9
0.03
0.071
0.36
0.072
0.046
0.041
0.067
0.04
0.04
Y
Y
N
N
Y
N
Y
N
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
194
946
1 9 3
285
336
163
239
239
1 9 3
239
1 9 3
1 9 3
438
247
246
605
212
272
425
400
450
537
1 4 5
14.5
1 4 5
1
537
1 4 5
1 4 5
45
45
794
344
353
303
303
598
601
598
601
566
91
566
97
566
186
362
1037
283
626
209
513
482
209
482
266
266
1 2 3
1 2 3
1 2 3
1 2 3
1 2 3
48
1 7 5
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 285
Monomer 1 Monomer 2
r1
Zt95%
r2
195% Conv. Refs.
Vinylbenzoic acid, p-
Vinylbenzoic acid, p-
Vinylbenzoic acid, p-
Vinylbenzyl chloride
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylene carbonate
Vinylethyldiethoxysilane
Vinylethynyl-4-piperidinol,
1,2,5-trimethyl-4-
Vinylethynyl-4-piperidinol,
1,2,5-trimethyl-4-
Vinylferrocene
Vinylferrocene
Vinylferrocene
Vinylferrocene
Vinylferrocene
Vinylferrocene
Vinylferrocene
Vinylhydroquinone
Vinylhydroquinone
Vinylhydroquinone
Vinylhydroquinone
Vinylhydroquinone dibenzoate
Vinylhydroquinone dibenzoate
Vinylhydroquinone dibenzoate
Vinylhydroquinone dibenzoate
Vinylhydroquinone dibenzoate
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Acrylonitrile 1.63
Methacrylate, methyl 1.16
Styrene 1.029
Methacrylate, methyl 1.02
Acrylamide 0.05
Acrylonitrile 0.08
Methacrylate, methyl 0. 04
Pyrrolidone, N-vinyl- 0.056
Styrene 3.16
Styrene 0. 73
Vinyl acetate 0.3
Vinyl acetate 0.27
Vinyl acetate 0.05
Vinyl acetate 0.13
Vinyl acetate 0.044
Vinyl acetate 0.08
Vinyl chloride 0.03
Vinyl chloride 0.069
Vinyl chloride 0
Vinyl isobutyl ether 0.16
Vinyl 1-menthyl ether 0.14
Vinyl methyl sulfide 0. 08
Vinyl thiolacetate 0.041
Vinyl chloride 0. 44
Acrylonitrile 0.38
Methacrylic acid 0.05
Acrylonitrile
Acrylonitrile
Butadiene
Methacrylate, methyl
Pyrrolidone, N-vinyl-
Styrene
Styrene
Acrylic acid
Acrylonitrile
Methacrylate, methyl
Pyridine, 4-vinyl-
Acrylate, methyl
Acrylic acid
Methacrylate, methyl
Styrene
Styrene, a-methyl-
Aconitate, trimethyl
Acrylamide, N-octadec
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, ethyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, octadecyl
Acrylate, octyl
Acrylic acid
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
0.165
0.15
0.16
0.52
0.71
0.2
0.14
0.026
0.04
0.02
- 0.23
0.75
0.95
0.41
0.43
0.3
64.6
0.432
0.934
0.84
0.87
0.58
0.9
0.7
1
0.9
0.851
0.437
0.32
0.28
0.4
0.42
0.49
0.69
0.76
0.95
0.95
0.42
0.3
0.06
0.85
0.059
0.98
0.3
0.16
0.039
0.11
0.12
0.068
0.22
1.91
0.17
0.01
2.97
0.092
0.15
0.16
0.1
0.14
0.092
0.03
0.13
0.36
23.74
0.008
0.006
0.15
0.11
0.037
0.018
0.065
0.14
0.034
0.06
0.398
0.282
0.46
13.8
14.9
126
1.08
411
21.03
3.2
3
7.16
7.3
3.83
3.92
4.82
15.38
17.81
0.18
0.25
7.72
13.57
0.94
0.08
0.4
0.186
0.16
4.34
1.22
0.364
4.37
2.76
0.29
0.56
0.49
0.53
0.46
0.44
0.34
0.22
0.11
0.15
1.4
0.873
0.46
0.58
0.72
0.95
0.8
1
1
0.679
1.246
0.92
1.04
0.44
0.58
0.65
0.57
0.5
0.48
0.65
0.009
0.097
0.011
298
0.11
23.45
0.62
0.64
0.18
0.32
0.49
1.44
7.84
3.32
1.68
1.04
1.53
0.025
0.18
0.068
1.44
0.22
0.11
0.36
0.21
0.4
0.94
0.11
0.022
0.39
0.21
0.14
0.057
0.042
0.11
0.2
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
1 7 5
266
266
792
387
579
1 0 3
1 0 3
1 0 3
120
1 0 3
1 0 3
1 2 0
120
1 4 4
90
1 0 3
319
319
322
750
120
186
237
783
734
294
294
802
294
308
274
294
337
338
337
337
440
444
440
440
440
149
119
1 1 8
464
464
65
107
1 0 7
377
1 1 8
1 1 8
288
1 3 8
238
404
404
404
404
404
404
404
References page II - 290
II / 286 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl
f95%
r2
f95% Conv. Refs.
Vinylidene chloride Acrylonitrile
Vinylidene chloride Acrylonitrile
Vinylidene chloride Acrylonitrile
Vinylidene chloride Acrylonitrile
Vinylidene chloride Acrylonitrile
Vinylidene chloride Acryloyl chloride
Vinylidene chloride Ally1 acetate
Vinylidene chloride Ally1 chloride
Vinylidene chloride Allylstearamide, N-
Vinylidene chloride Butadiene
Vinylidene chloride Carbazole, N-vinyl-
Vinylidene chloride Carbazole, N-vinyl-
Vinylidene chloride Crotonaldehyde
Vinylidene chloride Crotonic acid
Vinylidene chloride Cyclopentene, 4-, 1,3-dione
Vinylidene chloride Diallyl phthalate
Vinylidene chloride Ethylene
Vinylidene chloride Ethylene chlorotrifluoro-
Vinylidene chloride Fumarate, diethyl
Vinylidene chloride Fumarate, diisopropyl
Vinylidene chloride Indene
Vinylidene chloride Indene
Vinylidene chloride Isobutylene, 3-chloro-
Vinylidene chloride Isopropenyl methyl ketone
Vinylidene chloride Isopropenylisocyanate
Vinylidene chloride Maleate, diethyl
Vinylidene chloride Mal ei mi de
Vinylidene chloride Methacrylate, 2-(sulfonic acid)ethyl
Vinylidene chloride Methacrylate, benzyl
Vinylidene chloride Methacrylate, butyl
Vinylidene chloride Methacrylate, ethyl
Vinylidene chloride Methacrylate, methyl
Vinylidene chloride Methacrylate, methyl
Vinylidene chloride Methacrylate, methyl
Vinylidene chloride Methactylate, methyl
Vinylidene chloride Metbacrylate, methyl
Vinylidene chloride Methacrylate, methyl
Vinylidene chloride Methacrylate, methyl
Vinylidene chloride Methacrylate, methyl
Vinylidene chloride Methacrylate, methyl
Vinylidene chloride Methacrylate, methyl
Vinylidene chloride Methacrylic acid
Vinylidene chloride Methacrylonitrile
Vinylidene chloride Methacrylonitrile
Vinylidene chloride Norbornadiene
Vinylidene chloride Oxazolidone, N-vinyl-
Vinylidene chloride Eropenyl 2-methyl, acetate
Vinylidene chloride Styrene
Vinylidene chloride Styrene
Vinylidene chloride Styrene
Vinylidene chloride Styrene
Vinylidene chloride Styrene
Vinylidene chloride Styrene
Vinylidene chloride Succinimide, N-vinyl-
Vinylidene chloride Tetrazole, 2-methyl-5-(4-vinyl)phenyl-
Vinylidene chloride Tetrazole, 2-phenyl-5-(4-vinyl)phenyl-
Vinylidene chloride Tetrazole, 5-phenyl-2-(4-vinyl)phenyl-
Vinylidene chloride Vinyl 12-ketostearate
Vinylidene chloride Vinyl acetate
Vinylidene chloride Vinyl acetate
Vinylidene chloride Vinyl acetate
Vinylidene chloride Vinyl acetate
Vinylidene chloride Vinyl acetate
Vinylidene chloride Vinyl benzoate
Vinylidene chloride Vinyl butyl ether
1.3
1.74
1.43
1.8
0.39
0.5
6.6
3.49
5.22
- 0.044
- 0.023
- 0.008
18.1
1.88
5
15.71
17.14
12.19
48
0.49
- 0.02
1.1
0.134
0.85
12.5
0.666
0.22
0.34
0.35
0.353
0.3
0.36
0.18
0.5
0.34
0.09
0.094
0.19
0.02
0.27
0.154
0.3
0.036
1.36
1.42
2.4
0.134
0.098
1.5
0.087
0.15
0.11
1.441
0.13
0.25
0.11
4.4
4.66
6.7
5
3.49
4.7
5.58
1.75
1.4
0.15
0.038
0.068
0.018
43.7
0.35
1.96
1.58
0.15
1.15
0.099
0.056
0.03
0.02
0.03
0.18
0.032
0.01
0.047
0.1
0.05
0.63
0.11
0.048
0.01
0.007
0.005
0.061
4.8
0.26
0.17
1.76
0.11
0.65
0.66
0.63
0.63
0.58
1.12
0
0.24
- 0.24
1.97
3.6
3.65
0
- 0.2
0.113
0.2
0.018
0.02
0.012
0.095
0.293
0.34
0
4.06
0.31
0.464
3.6
3.3
2.07
2.18
2.6
2.38
2.16
2.5
2.5
2.1
1.8
2.83
1.23
2.77
3.368
2.43
2.38
0.09
0.091
0
1.81
1.79
1.8
1.839
1.81
1.7
0.311
1.9
1.8
1.9
0.26
0.03
0.05
0.05
- 0.002
0.12
0.065
0.004
0.24
0.19
0.25
0.12
0.3
1.03
0.027
0.005
0.038
0.095
0.85
0.66
0.083
0.18
0.1
0.02
0.06
0.95
0.06
0.098
0.1
0.05
0.17
0.077
0.35
0.14
0.024
0.12
0.058
2.61
0.1
0.026
0.093
0.001
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
Y
N
Y
N
N
N
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
404
404
404
404
468
288
470
3
119
257
1 3
98
405
47
264
376
299
454
59
1038
6
6
470
47
434
3
251
564
432
3
3
1 3 8
324
324
426
432
538
65
762
762
786
6
781
781
267
1 0 2
470
1 3 8
238
393
59
812
9 3
104
583
583
583
1 4 6
3
432
436
5 9
812
47
279
TABLE 1. contd
Copolymer Reactivity Ratios II / 287
Monomer 1 Monomer 2
rl
f 95%
r2 r t 9S% Conv. Refs.
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene cyanide
Vinylidene fluoride
Vinylidene fluoride
Vinylisocyanate
Vinylisocyanate
Vinylisocyanate
Vinylisocyanate
Vinylisocyanate
Vinylisocyanate
Vinylisocyanate
Vinylmethyldiacetoxysilane
Vinylmethyldiacetoxysilane
Vinylmethyldiethoxysilane
Vinylmethyldiethoxysilane
Vinylmetbylphenylsulfonium
tetrafluoroborate
Vinylmethylphenylsulfonium
tetrafluoroborate
Vinylphenyldimethylsilane
Vinylphenyldimethylsilane
Vinylphenylisocyanate, p-
Vinylphenylpropanol, 2- p-
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloromethyl ketone
Vinyl dodecyl ether
Vinyl ethyl ether
Vinyl fluoride
Vinyl hendecanoate
Vinyl m-cresyl ether
Vinyl methyl ketone
Vinyl o-cresyl ether
Vinyl octadecyl ether
Vinyl p-chlorophenyl ether
Vinyl p-cresyl ether
Vinyl p-tert-butyl phenyl ether
Vinyl pelargonate
Vinyl phenyl ether
Vinyl phenyl ether
Vinyl stearate
Vinylidene cyanide
Vinylisocyanate
Acrylate, wchloro-, methyl
Acrylic acid
Butadiene, 2-chloro-
Ethylene, dichloro-, cis-
Ethylene, dichloro-, cis-
Maleic anhydride
Methacrylate, methyl
Phosphonic acid, 1-phenylvinyl
Propene, 2-chloro-
Styrene
Styrene
Styrene, 2,5dichloro-
Vinyl acetate
Vinyl benzoate
Vinyl chloride
Vinyl chloride
Vinyl chloroacetate
Vinyl chloride
Methacryloyl fluoride, perhuoro-
Vinyl acetate
Acrylate, methyl
Acrylonitrile
Methacrylate, methyl
Styrene
Styrene
Vinyl chloride
Vinylidene chloride
Acrylonitrile
Styrene
Styrene
Styrene
Acrylamide
2. 06
3. 39
8. 92
3. 2
4. 5
1.8
4. 5
3. 068
0.018
1.3
3. 2
6
2. 72
1.95
0.55
2.1
1.5
2. 44
1.97
2. 04
4. 08
2. 45
2.11
3. 92
0. 009
1.46
0. 066
0.291
0. 32
1.16
0. 076
0. 009
0. 37
0. 07
0.1
0. 04
0. 06
0. 06
0. 34
0.11
0.14
0.001
0. 07
0. 042
0.071
0.14
0. 25
0. 3
0. 2
0. 2
0.16
0. 205
6. 8
0
0
0.16
0. 04
0. 04
1.8
0. 04
0
0.14
0. 03
0. 05
0
0. 433
0. 04
0. 08
0. 049
0. 33
0.313
0.212
0. 028
4. 58
0. 204
0. 72
0.001
0. 005
0.1
0.061
0. 72
0. 6
0.137
0. 049
7. 6
0. 08
0.14
0.16
0.01
0. 08
0.1
3. 7
0. 33
-0.11
0
0. 08
- 0. 08
0.1
0.013
0. 079
0.16
0.001
0. 009
0.11
0. 047
0. 068
0. 037
0. 02
0. 23
0.15
0.14
0. 2
0. 057
0.1
0.001
0.015
0. 003
0. 026
0. 003
0
0.01
0.016
0
0. 009
0. 02
6
1.38
0.19
3. 3
8.13
6. 9
0. 46
1.46
2. 246
4. 08
5. 68
11.29
3. 4
Acrylonitrile 0.1 2. 2
Methacrylate, methyl
Styrene
Vinyl chloride
Styrene
- 0. 009
0. 024
11.9
0.41
0. 034
0.016
0. 4
29. 79
32. 53
0.1
0. 48
0. 025
0. 32
0. 003
0. 3
0.16
0. 004
0.01
0.01
0.004
0. 004
0.051
0. 03
0.17
0. 02
0.021
0.016
0.012
0. 03
0. 007
0.001
0. 006
0. 002
0.017
0. 002
0. 006
0.001
0. 054
0.14
0.1
0. 43
1.89
0. 49
0. 3
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
238
2 9
3
470
517
539
585
6 7
356
371
470
607
145
279
375
279
3 7 1
279
279
279
145
240
280
1 4 5
8 2
435
8 2
8 2
8 2
8 2
8 2
8 2
8 2
921
8 2
134
8 2
8 2
8 2
8 2
409
8 2
8 2
8 2
669
627
435
435
422
435
533
777
435
754
754
754
754
793
793
482
482
777
7 2
References page II - 290
II / 288 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl
195%
f-2 Zt95% Conv. Refs.
Vinylsulfonic acid Acrylamide
Vinyltriethoxysilane Acrylonitrile
Vinyltriethoxysilane Acrylonitrile
Vinyltriethoxysilane Styrene
Vinyltriethoxysilane Vinyl chloride
Vinyltrimethoxysilane Acrylonitrile
Vinyltrimethoxysilane Vinyl chloride
Vinyltrimethylsilane Acrylonitrile
Vinyltrimethylsilane Methacrylate, methyl
Vinyltrimethylsilane Styrene
Vinyltrimethylsilane Styrene
Vinyhrimethylsilane Styrene
Xanthate, S-methacryloyl O-ethyl Methacrylate, methyl
Xanthate, S-methacryloyl O-ethyl Styrene
0.3
0.41
2.69
- 0.09
- 0.04
0.45
0.09
0.1
0.028
-0.19
0.049 0.025
0.6 0.08
0.36 0.08
0.1
0.38
2.5
0.14
0.44
0.27
0.016
0.36
3.5 0.15 1066
6.59 0.6 Y 209
26.83 29.59 Y 231
20.86 1.99 Y 209
0.82 0.16 Y 237
9.09 Y 2.37
0.93 Y 231
4.08 0.76 Y 209
35.66 0.85 Y 482
14.66 5.15 Y 209
Y 482
5.98 0.18 Y 13
0.76 0.04 1086
0.44 0.06 1086
TABLE 2. LISTING OF QUICK BASIC (MICROSOFT) PROGRAM FOR CALCULATING REACTIVITY RATIOS*
100 OPTI ON BASE 1
110 DI M et a ( 20)
120 DIM ksi (20)
130 DI M gee ( 20)
140 DIM ef (20)
150 DIM t (20)
151 FOR b=l TO 20
152 READ t(b)
153 NEXT b
170 DATA 12.71,4.3,3.18,2.78,2.57,2.45,2.37,2.31,2.26,2.23,2.2,2.18,2.16,2.14,2.13,2.12,2.11,2.1,2.09,2.09
180 DEF FNLog 1 O(X) = LOG(X)/LOG( I 0#)
190 PRINT Calculation of reactivity ratios by the method of Kelen and Tudos
210 PRINT Enter 0 for monomer 1 in the feed to start the calculation
220 REM initialize all of the summing addresses
230 n=O
231 m=O
232 var=O
233 sumasi = 0
2 3 4 sumi=O
2 3 5 suma=
236 sumsqi = 0
237 sumnegi = 0
238 sum2i = 0
250 INPUT Do you wish to stop (Y/N)?;fS
260 IF fS = y THEN GO TO 1510
270 REM enter the names and molecular weights of the monomers
280 INPUT Monomer 1 is:; mone$
290 INPUT Monomer 2 is:; mtwo$
340 REM enter the feed, polymer and conversion values
350 PRINT Are the feed and polymer values in mol fractions (mol),
mol ratios (ratio) or weight fractions (wt) ?
370 INPUT type$
380 IF type$ = ratio THEN GOT0 1210
390 IF type$ = wt THEN GOT0 1360
400 PRINT Mol fraction of; mone$; in the feed =
410 INPUT ml0
420 IF ml 0 = 0 THEN GOT0 800
430 n=n+l
440 m20 = l-ml0
450 PRINT Mol fraction of; mone$; in the polymer =
460 INPUT pl
470 p2 = l-p1
480 PRINT Conversion, weight fraction = ? (If none given enter 0)
490 INPUT w
500 IF w = 0 THEN GOT0 680
* Method of Kelen and Tiidos (803,804).
Quick Basic (Microsoft) Program for Calculating Reactivity Ratios II / 289
510
520
530
540
550
560
510
580
590
600
610
620
630
640
650
660
670
680
690
700
710
720
730
740
750
760
770
780
790
800
810
820
830
840
850
860
870
880
890
900
910
920
930
940
950
960
970
980
990
1 0 0 0
1 0 1 0
1020
1 0 3 0
1 0 4 0
1050
1060
REM calculate G and F
X = mlO/m20
y=pl/p2
mu = mw2/mw 1
zeta2 = w *(mu + X)/(mu + y)
zeta1 = (y/X) *zeta2
z = (FNLoglO(l-zetal))/(FNLoglO(l-zeta2))
g=(y-l)/z
f = yl(z2)
IFn-1 THENfmin=f
IFn=l THENfmax=f
IF fmin>f THEN fmin = f
IF fmax<f THEN fmax = f
gee(n) = g
ef(n) = f
GOT0 380
REM calculate G and f without conversion data
X = mlO/m20
y=pl/p2
g=((y-l)*xYY
f = (X2)N
IFn=l THENfmin=f
IFn=l THENfmax=f
IF fmin>f THEN fmin = f
IF fmax<f THEN fmax = f
gee(n) = g
ef(n) = f
GOT0 380
REM calculate eta and ksi
alpha = SQR(fmin *fmax)
m= m+ l
a = gee (m)/(alpha + ef(m))
si = ef(m)/(alpha + ef(m))
REM sum variables for least squares
sumasi = (a * si) + sumasi
sumi = si + sumi
suma = a + suma
sumsqi = (siA2) + sumsqi
sumnegi = (1-si) + sumnegi
sum2i = si*( 1-si) + sum2i
eta(m) = a
ksi(m) = si
IF m = n THEN GOT0 960
GOT0 810
REM calculate the reactivity ratios
rl = (sumasi*(n-sumi)-suma*(sumi-sumsqi))/((n*sumsqi)-(sumiA2))
r2 = (alpha*((sumasi*sumi)-(suma*sumsqi)))/((n *sumsqi)-(sumiA2))
REM calculate S squared
m=O
m= m+ l
smin = ((eta(m)-(rl *ksi(m))) + ((r2/alpha)*(l-ksi(m))))2
var = smin + var
IF m = n THEN GOT0 1050
GOT0 1000
d = sumsqi *(sumnegi2)-(sum2iA2)
REM calculate the delta rs
1070 deltrl = t(m-2) *SQR((var/(n-2)) *((sumnegiA2)/d))
1080 deltr2 = alpha*t(m-2)*SQR((var/(n-2))*(sumsqi/d))
1090 REM print out the answers
1100 PRINT Reactivity ratios for; mone$; (Ml) and; mtwo$; (M2)
1 1 1 0 PRINT rl = ; rl; delta rl = ; deltrl
1 1 2 0 PRINT r2 = ., r2; delta r2 = ; deltr2
1130 PRINT alpha = ; alpha
1140 PRI NT ks i ; et a
1150 m=O
1160 m=m+l
1170 PRINT ksi(m), eta (m)
1180 IF m=n THEN GOT0 220
1190 GOT0 1160
References page II - 290
II / 290 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
1200 REM calculation of Ml and M2 from mol ratios
1210 PRINT Mol ratio of; mone$; in the feed = ;
1220 INPUT qf
1230 IF qf = 0 THEN GOT0 800
1240 n=n+l
1250 mlO=qf/(qf+ 1)
1260 m20 = l-ml0
1270 PRINT Mole ratio of; mone$ in the polymer =
1280 INPUT qp
1290 pl = qp/(qp+l)
1300 p2 = l-p1
1310 PRINT Weight fraction conversion =
1320 I NPUT w
1330 IF w = 0 THEN GOT0 680
1340 GOT0 510
1350 REM calculation of Ml and M2 from weight fractions
135 1 PRINT The molecular weight of; mone$; is
1352 INPUT mwl
1353 PRINT The molecular weight of; mtwo$; is
1354 INPUT mw2
1360 PRINT Weight fraction of; mone$ in the feed =
1370 INPUT rfl
1380 If rfl = 0 THEN GOT0 800
1390 n=n+l
1400 rf2 = 1-rfl
1410 ml0 = (rfl/mwl)/((rfl/mwl) + (fl/mw2))
1420 m20 = l-ml0
1430 PRINT Weight fraction of; mone$; in the polymer =
1440 INPUT rpl
1450 rp2 = 1-rpl
1460 pl = (rpl/mwl)/((rpl/mwl) + (rp2/mw2))
1470 PRINT Weight fraction conversion =
1480 INPUT w
1490 IF w = 0 THEN GOT0 680
1500 GOT0 510
1510 PRINT FINI
1520 END
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143 (1961).
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24. C. Aso, T. Kuni t ake, K. Wat anabe, Kogyo Kagaku Zasshi ,
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Q and e Values for Free Radical
Copolymerizations of Vinyl
Monomers and Telogens
Robert Z. Greenley*
Monsanto Co., 544 Oak Valley Drive, St. Louis, MO 63131, USA
A. Introduction
6. Q and e Values for Free Radical
Copolymerizations
Table 1. Monomers
Table 2. Telogens
Table 3. Monomers Arranged by Q Values
Table 4. Monomers Arranged by e Values
C. References
II-309
II-310
II-31 0
II-314
II-314
II-31 7
II-31 9
A. INTRODUCTION
The Alfrey and Price Q and e equation (Al) is well known:
Q2 = (Qllrl)exp{-el(el - 4)
(Al)
Q and e are measures of the reactivity and polarity,
respectively, of a vinyl monomer and rt = k II/~ 12, a
reactivity ratio. This equation may be arranged to a
logarithmic form (A2) which provides a more convenient
linear solution:
{[ln(Ql/rl)] - ef} = -wl + lnQ2. (A4
When monomer 2 is the one to be characterized, its Q and e
values may be determined from the slope (-e2) and
intercept (In Q2) of the equation.
The first requirement for the use of Eq. (A2) is the
selection of a small group of common monomers for which
Q and e could be independently established. Since, by
definition the Q and e scheme is based on styrene (Q = 1.0
and e = - O.S), the average Q and e values of these primary
monomers were calculated using Eqs. (Al) and (A3)
(Ref. 1).
e2 = e 1 f (-lnrlr2) 12
W)
utilizing only their reactivity ratios with styrene. The six
primary monomers (Group I) - acrylic acid, acrylonitrile,
*Retired.
butadiene, methyl acrylate, methacrylonitrile and methyl
methacrylate - were chosen because their reactivity ratios
had been narrowly defined by several investigators. These
primary reactivity ratios were taken from the compilation in
the second edition of this Handbook.
The Q and e values of a secondary group (Group II) of
ten common vinyl monomers were determined using
Eq. (A2), with the primary monomer group supplying the
Q i and e i values. The Q and e values were then calculated
for a tertiary set (Group III) of reactivity ratios for which a
set of reactivity ratios with four or more of the primary and
secondary monomers was available. For all groups except
Group I, recalculated reactivity ratios (see the preceding
chapter) were used when available. Otherwise, reported
values were included.
The Q and e values developed for the three groups during
the first pass through the data were subsequently used to
recalculate the Q and e values for Groups II and III. Group I
was not redetermined so that the styrene bias of the system
could be better maintained. After four iterations, no
significant changes were observed. During the iterative
process, a number of reactivity ratio citations were dropped
due to a lack of fit with the majority of data points.
The final Q and e values for these three groups were
then used to determine the Q and e values of other
monomers with four or more reactivity ratio citations
with at least three comonomers (Group IV), and monomers
with three citations with three different comonomers
(Group V).
By replacing rl in Eq. (A2) with the reciprocal of the
chain transfer constant, 1 /C, (3), Q and e values of telogens
may also be estimated (4) from their coreactivity with vinyl
monomers.
The Monomer Table lists the monomer group designa-
tion, the Q and e values, and the correlation coefficient (r)
for the regression. The Number column (n) represents the
number of ri values actually used in the regression. If the
monomer is in Group V, the number is understood to be 3.
The data are listed alphabetically as well as in increasing
values of Q and e.
II / 309
II / 310 Q AND e VALUES FOR FREE RADICAL COPOLYMERIZATIONS OF VINYL MONOMERS AND TELOCENS
Recent work by Jenkins (5) has uncovered another he was able to calculate three coefficients which appear to
approach to characterizing the copolymerization character allow a more precise prediction of the actual reactivity
of vinyl monomers. By deriving data from 1-1 and r2 values, ratios.
6. Q AND e VALUES FOR FREE RADICAL COPOLYMERIZATIONS
TABLE 1. MONOMERS
Monomer Group
Q
e n r
Acenaphthalene
Acetylene, phenyl-
Aconitate, trimethyl
Acrolein
Acrolein, methyl-
Acrylamide
Acrylamide, N-methylol-
Acrylamide, N-octadecyl-
Acrylamide, N,N-diethyl
Acryl ami de, N,N-dimethyl-glucitol
Acrylate, wacetoxy-, ethyl
Acrylate, a-chloro-, ethyl
Acrylate, wchloro-, methyl
Acrylate, cr-cyano-, methyl
Acrylate, cr-phenyl-, methyl
Acrylate, benzyl
Acrylate, butyl
Acrylate, ethyl
Acrylate, ferrocenylmethyl
Acrylate, glycidyl
Acrylate, heptafluorobutyl
Acrylate, methyl
Acrylate, octadecyl
Acrylate, octyl
Acrylate, trifluoro-, methyl
Acrylate, 2-chloroethyl
Acrylate, 2-ethylhexyl
Acrylate, 2-nitrobutyl
Acrylic acid
Acrylic acid, a-bromo-
Acrylic anhydride
Acrylonitrile
Acryloyl chloride
Ally1 acetate
Ally1 acrylate
Ally1 alcohol
Ally1 chloride
Allylbenzene
N-Allylstearamide
I V
I V
III
I V
I V
I V
I V
I V
I V
V
V
V
I V
I V
I V
I V
II
III
I V
I V
V
I V
V
V
V
I V
V
V
V
I V
III
V
I V
III
I V
V
0.12 - 1.88
0.45 0.10
0.25 2.27
0.80 1.31
1.83 0.71
0.23 0.54
0.52 1.15
0.66 1.64
0.48 -0.31
0.22 0.61
0.52 0.77
1.00 - 1.03
2.43 0.35
4.91 0.91
5.19 0.96
0.33 1.13
0.38 0.85
0.41 0.55
0.15 0.51
0.48 1.28
0.96 1.34
0.45 0.64
0.33 1.26
0.63 2.01
0.048 1.20
0.49 1.03
0.37 0.24
0.69 1.09
0.83 0.88
3.07 1.37
1.46 0.31
0.48 1.23
1.82 1.92
0.24 - 1.07
0.32 - 0.99
0.005 - 1.48
0.026 - 0.60
0.038 0.40
0.024 - 0.41
Benzothiazole, vinylmercapto- I V 0.36 - 0.44
Bicyclo[2.2.1 Jhept-2-ene-5,6-dicarboxamine, N-benzyl- I V 0.01 - 0.36
Butadiene I 1.70 - 0.50
Butadiene- 1-carboxylate, ethyl V 1.67 1.26
Butadiene, l,Cdicarboxylate, diethyl V 1.94 1.39
Butadiene, 2,3-dichloro- V 9.08 0.14
Butadiene, 2,3-dimethyl- V 1.42 - 0.43
Butadiene, hexafluoro- I V 0.82 0.58
Butadiene, 2-chloro- II 10.52 1.20
Butadiene, 2-fluoro- III 1.88 0.63
Butene-1 I V 0.007 - 0.06
Butene-2 I V 0.002 - 0.29
Carbamate, N-vinyl-, ethyl V 0.037 - 1.12
Carbamate, N,N-diethyl-, vinyl I V 0.028 - 1.11
Carbazole, N-vinyl- III 0.26 - 1.29
Carbon monoxide V 0.013 1.68
5
6
5
1 6
5
1 7
6
4
5
4
4
8
5
20
1 2
4
4
7
5
4
6
8
5
1 2
4
4
6
24
4
1 0
6
5
6
4
1 2
0.98
0.75
0.63
0.97
0.98
0.64
0.91
0.93
0.56
0.68
0.99
0.87
0.38
0.99
0.90
0.92
0.94
0.91
0.65
0.87
0.81
0.97
0.99
0.55
0.95
0.37
0.98
0.99
0.37
0.90
0.85
0.96
0.98
0.93
0.60
0.62
0.95
0.47
0.82
0.99
0.99
0.93
0.58
0.93
0.98
0.77
0.08
0.44
0.91
0.95
0.99
0.70
TABLE 1. contd
Monomer s II/311
Monomer Group
Q
e n r
Citraconimide, N-methyl-
Crotonaldehyde
Crotonic acid
4-Cyclopentene-1,3-dione
I V
I V
III
I V
0.87 1.58 4 0.94
0.023 0.84 5 0.82
0.017 0.89 6 0.98
0.42 2.43 4 0.96
Diallyl melamine
Diallyl phthalate
Diallycyanamide
N,N-Divinylaniline
V 0.059 - 1.57
I V 0. 03 1 - 0.26
I V 0.14 2.41
II 0.26 - 0.68
20
4
5
0.99
0.50
0.96
0.78
Ethylene III 0.016 0.05 6 0.52
Ethylene, 1, l-diphenyl- I V 0.17 - 1.71 5 0.84
Ethylene, chlorotrifluoro- III 0.026 1.56 5 0.99
Ethylene, tetrachloro- III 0.001 1.24 7 0.99
Ethylene, tetrafluoro- I V 0.032 1.63 4 0.99
Ethylene, trichloro- III 0.010 1.29 11 0.94
Fumarate, diethyl I V 0.25 2.26 1 0 0.91
Fumarate, diisopropyl I V 0.11 2.58 8 0.84
Fumaronitrile I V 0.29 2.73 5 0.96
Hexatriene, tetrachloro- I V 1.83 0.94
He x e n e - 1 V 0.035 0.92
Imi dazol e, l-vinyl- V 0.11 - 0.68
Imidazole, 1-vinyl-2-methyl- I V 0.14 - 0.98
Indene IV 0.13 - 0.71
Isobutylene III 0.023 - 1.20
Isobutylene, 3-chloro- I V 0.17 - 0.86
Isoprene II 1.99 - 0.55
Isoprene, 3-acetoxy- V 1.91 -0.11
Isopropenyl acetate I V 0.023 - 0.94
Isopropenyl methyl ketone III 1.03 0.64
Isopropenyl, 3-( 1-cyclohexenyl), acetate V 0.57 - 0.66
Isopropenylisocyanate III 0.18 - 1.05
Itaconate, dibutyl V 0.82 0.57
Itaconate, diethyl V 1.04 0.88
Itaconate, dimethyl III 0.73 0.57
Itaconic acid I V 0.78 1.07
Maleate, diethyl
Maleic anhydride
Maleimide
Maleimide, 2,3-dimethyl-N-(2-methacryloxyethyl)-
Maleimide, N-(2-hydroxyethyl)-
Maleimide, N-(2-chlorophenyl)-
Maleimide, N-(4-chlorophenyl)-
Maleimide, N-butyl-
Maleimide, N-phenyl-
Methacrylamide
Methacrylamide, N-phenyl-
Methacrylamide, 1-deoxy-D-glucital
Methaqlate, 2-chloro-2,3,3,3-tetrafluoropropyl
Methacrylate, 2,2,6,6-tetra-methyl-4-piperidinyl
Methacrylate, 2,3-epithio-propyl
Methacrylate, benzyl
Methacrylate, butyl
Methacrylate, ethyl
Methacrylate, ferrocenylmethyl
Methacrylate, glycidyl
Methacrylate, isobutyl
Methacrylate, isopropyl
Methacrylate, methyl
Methacrylate, phenyl
Methacrylate, sulfolanyl
I V
I V
V
V
V
I V
V
V
I V
I V
V
V
V
I V
I V
I V
III
III
I V
III
III
I V
I V
V
0.053 1.08
0.86 3.69
0.94 2.86
2.54 1.64
1.26 1.07
2.29 2.87
2.98 2.75
0.88 3.70
2.81 3.24
0.40 - 0.05
0.40 0.19
0.15 -0.16
2.09 0.62
0.52 - 1.09
1.04 0.29
0.88 0.35
0.82 0.28
0.76 0.17
0.22 0.65
0.96 0.20
0.82 0.27
0.97 0.10
0.78 0.40
1.25 0.79
1.18 0.95
6
6
8
7
4
11
4
6
8
8
5
1 2
25
5
4
8
4
4
1 0
1 0
7
7
9
5
4
7
0.98
0.69
0.98
0.93
0.45
0.99
0.98
0.86
0.10
0.98
0.78
0.98
0.94
0.88
0.98
0.90
0.99
0.87
0.98
0.99
0.98
0.68
0.96
0.99
0.92
0.99
0.29
0.70
0.19
0.56
0.68
0.84
0.97
0.68
0.62
0.85
0.92
0.76
0.46
0.91
0.95
References page II - 3 19
II / 312 Q AND e VALUES FOR FREE RADICAL COPOLYMERIZATIONS OF VINYL MONOMERS AND TELOCENS
TABLE 1. contd
Monomer Group
Q
e n r
Methacrylate, 2-naphthyl
Methacrylate, 2-(AJ,N-dimethyl-carbamoyloxy)ethyl
Methacrylate, 2-(sulfonic acid)ethyl
Methacrylate, 2-acetoxyethyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxypropyl
Methacrylic acid
Methacrylic anhydride
Methacrylonitrile
Methacryloyl chloride
Methacryloylacetone
Methylenebutyrolactone
2-Methyleneglutaronitrile
IV
I V
I V
V
I V
I V
I V
I V
III
I V
I
V
V
V
I V
1.04 - 0.09
1.14 0.84
1.09 0.25
0.60 0.51
1.18 0.74
1.04 0.31
1.78 - 0.39
4.38 1.86
0.98 0.62
3.00 0.56
0.86 0.68
2.04 1.54
5.47 - 0.76
2.48 0.83
0.41 1.25
Norbornadiene III 0. 05 1 - 1.48
Ott-1-ene, 6,6-dimethyl-4,8-dioxaspiro(2.5)-
Oxazolidone, N-vinyl-
Oxazoline, 2,-2-isopropenyl-4,4-dimethyl-
Oxazoline, 2-isopropenyl-2-
Oxazoline, 2-,4-acryloxymethyl-2,4-dimethyl-
Oxazoline, 2-,4-methacryloxymethyl-2,4-dimethyl-
V
III
I V
I V
I V
I V
0.25 0.61
0.087 - 1.70
0.87 0.34
0.59 - 0.64
0.97 -0.51
0.44 - 0.70
Pentadiene, trans-1,3- I V 1.28 -0.13
Phosphonate, a-carbomethoxyvinyl-, diethyl V 0.14 - 0.04
Phosphonate, isopropenyl-, dimethyl V 0.032 0.96
~ Phosphonate, vinyl-, bis(2-chloroethyl) V 0.044 1.64
Phosphonate, vinyl-, diethyl V 0.27 - 0.40
Phosphonate, vinyl-, dimethyl V 0.24 - 0.25
Phosphonic acid, wphenyl-vinyl- I V 0.65 0.52
Phthalimide, N-(methacryloyloxy)- V 1.89 0.96
Propene, 3,3,3-trichloro- V 0.030 1 .oo
Pr opene, I-chloro-, cis- V 0.003 - 0.46
Propene, I-chloro-, frans- V 0.006 -0.16
Propene, 2-chloro- V 0.073 -0.16
Propene, 2-chloro-3-hydroxy- V 0.091 - 0.95
Propene, 2,3-dichloro- I V 0.12 - 0.40
Propenyl, 2-chloro-, acetate IV 0.20 - 0.85
Propenyl, 2-methyl-, acetate V 0.040 - 2.08
Propylene V 0.009 - 1.69
Pyridazinone, 3-(2-vinyl)-6-methyl- V 0.57 0.24
Pyridazinone, 3-(2-vinyl)-6-methyl-4,5-dihydro- V 0.18 - 0.32
Pyridine, 2-methyl-5-vinyl- III 1.32 - 0.66
Pyridine, 2-vinyl- II 1.41 - 0.42
Pyridine, 2-Vinyl-S-ethyl- IV 1.29 - 0.91
Pyridine, 4-vinyl- III 2.47 0.84
Pyrrolidone, 1-benzyl-3-methylene-5-methyl- V 1.50 - 0.59
Quinoline, 2-vinyl- I V 1.04 - 0.09
Silane, y-methacryloxypropyl-trimethoxy
Styrene
Styrene, 2,4,6-trimethyl-
Styrene, 2,5-dichloro-
Styrene, 3-tri-n-butylstannyl-
Styrene, wmethoxy-
Styrene, wmethyl-
Styrene, m-bromo-
Styrene, m-chloro-
Styrene, m-methyl-
Styrene, m-nitro-
Styrene, p-bromo-
Styrene, p-chloro-
V
I V
II
I V
I V
III
I V
I V
V
IV
I V
III
1.08 0.07
1.00 - 0.80
0.15 - 0.58
1.50 0.94
0.014 -0.61
0.39 - 1.02
0.97 -0.81
1.25 - 0.27
2.46 - 0.90
1.57 - 0.03
2.66 1.57
1.30 - 0.68
1.33 - 0.64
8
5
4
4
7
7
7
2 3
5
6
7
5
4
5
7
9
1 2
4
7
4
4
1 2
4
5
15
4
4
7
7
1 2
0.46
0.74
0.52
0.80
0.96
0.79
0.67
0.81
0.73
0.93
0.94
0.79
0.90
0.83
0.90
0.82
0.95
0.65
0.54
0.71
0.99
0.54
0.96
0.98
0.89
0.54
0.53
0.76
0.74
0.99
0.84
0.28
0.99
0.99
0.67
0.61
0.97
0.84
0.58
0.35
0.95
0.97
0.94
0.86
0.98
0.46
0.35
0.41
0.96
0.51
0.77
0.98
0.98
0.87
0.06
0.85
0.99
0.92
TABLE 1. contd
Monomer s II / 313
Monomer Group
e
e n r
Styrene, p-chloromethyl-
Styrene, p-cyano-
Styrene, p-metboxy-
Styrene, p-methyl-
Styrene, p-1-(2-hydroxybutyl)-
Styrene, p-1-(2-hydroxypropyl)-
Styrene, p-2-(2-hydroxypropyl)-
Styrene, pentachloro-
Succinimide, N-vinyl-
I V
I V
III
III
V
I V
I V
V
III
1.39 - 0.38
2.93 - 0.38
1.53 - 1.40
1.10 - 0.63
0.70 - 0.97
1.08 - 0.35
1.15 - 0.49
0.20 0.79
0.19 - 1.42
0.74
0.75
0.99
0.98
0.65
0. 5 1
0.91
0.87
0.96
Tetrazole, l-vinyl-
Tetrazole, 2-methyl-5-(4-vinyl)phenyl-
Tetrazole, 2-methyl-5-vinyl-
Tetrazole, 2-phenyl-5-(4-vinyl)phenyl-
Tetrazole, 5-phenyl-2-(4-vinyl)phenyl-
Toluenesulfonamide, N&methyl-vinyl-
Triallyl citrate
Triallyl cyanurate
Triallyl isocyanurate
V
V
V
V
V
V
I V
V
V
0.13 -0. 14
0.86 0.51
0.55 - 0.46
0.84 - 0.52
1.11 0.53
0.18 - 0.53
0.054 0.26
0.14 2.41
0.035 - 0.23
4
0.39
0.49
0.85
0.97
0.53
0.78
0.50
0.17
0.35
Urea, N-vinyl-N-ethyl- V 0.17 - 1.88 0.98
Vinyl acetate II 0.026 - 0.88
Vinyl benzoate III 0.030 - 0.89
Vinyl bromide I V 0.038 - 0.23
Vinyl butyl ether I V 0.038 - 1.50
Vinyl butylsulfonate Iv 0.16 1.06
Vinyl butyrate I V 0.024 - 0.89
Vinyl chloride II 0.056 0.16
Vinyl chloroacetate I V 0.039 - 1.61
Vinyl chloromethyl ketone I V 16.00 1.78
Vinyl cinnamate I V 0.18 0.76
Vinyl cymantrene I V 0.39 - 0.57
Vinyl dichloroacetate V 0.059 - 1.38
Vinyl dodecyl ether I V 0.041 - 1.69
Vinyl ether I V 0.029 - 1.16
Vinyl ethyl ether III 0.018 - 1.80
Vinyl ethyl oxalate Iv 0.056 - 0.65
Vinyl ethyl sulfide Iv 0.27 - 1.31
Vinyl ethyl sulfoxide I V 0.065 0.05
Vinyl fluoride I V 0.008 0.72
Vinyl formate III 0.043 - 1.19
Vi nyl hendecanoat e III 0.056 - 0.84
Vinyl isobutyl ether I V 0.030 - 1.27
Vinyl isobutyl sulfide I V 0.49 - 0.95
Vinyl isopropyl ketone V 0.58 - 1.16
Vinyl isotbiocyanate I V 0.59 0.37
Vinyl laurate V 0.011 - 0.54
Vinyl-m-cresyl ether V 0.016 - 6.33
Vinyl methyl ketone II 0.66 1.05
Vinyl methyl sulfide I V 0.42 - 1.66
Vinyl methyl sulfoxide V 0.60 - 1.79
Vinyl o-cresyl ether V 0.010 - 8.53
Vinyl octadecyl ether I V 0.024 - 1.93
Vinyl octyl ether I V 0.020 - 1.57
Vinyl p-cresyl ether V 0.015 - 6.86
Vinyl pelargonate Iv 0.046 - 1.22
Vinyl phenyl ether I V 0.046 -2.16
Vinyl phenyl ketone I V 1.16 1.02
Vinyl phenyl sulfide I V 0.33 - 0.99
Vinyl propionate I V 0.027 - 0.68
Vinyl stearate III 0.043 - 0.97
Vinyl tert-butyl sulfide I V 0.046 - 2.20
Vinyl thiolacetate I V 0.27 - 0.52
49
9
1 0
1 0
4
8
38
5
4
4
4
6
4
8
4
6
4
8
5
5
7
4
8
5
4
4
4
5
0.87
0.95
0.94
0.87
0.97
0.91
0.37
0.98
0.97
0.99
0.88
0.95
0.83
0.80
0.90
0.53
0.96
0.21
0.71
0.99
0.82
0.98
0.99
0.44
0.77
0.81
0.99
0.98
0.99
0.46
0.97
0.87
0.98
0.99
0.79
0.95
0.95
0.96
0.82
0.85
0.72
0.85
References page II - 3 19
II / 314 Q AND e VALUES FOR FREE RADICAL COPOLYMERIZATIONS OF VINYL MONOMERS AND TELOCENS
TABLE 1. contd
Monomer Group
Q
e R r
Vinyl 4chlorocyclohexyl ketone I V 0.66 - 0.82 0.50
Vinyl 2-chloroethyl ether I V 0.019 - 1.64 9 0.96
Vinyl-tris(trimethoxysiloxy)silane I V 0.022 -0. 12 5 0.75
pVinylbenzylethylcarbino1 V 0.69 - 0.98 0.67
p-Vinylbenzylmethylcarbinol V 1.70 - 1.27 0.98
9-Vinylanthracene I V 0.14 0.82 5 0.90
Vinyl N,N-diethylcarbamate I V 0.028 - 1.10 4 0.95
p-Vinylbenzoic acid V 5.17 1.08 0.95
N-Vinylcaprolactam I V 0.14 - 1.18 4 0.72
Vi nyl ene car bonat e III 0.004 - 0.49 9 0.73
Vinylferrocene IV 0.31 - 1.34 6 0.91
Vinylhydroquinone V 4.30 2.26 0.87
Vinylhydroquinone dibenzoate I V 1.73 0.84 5 0.87
Vinylidene chloride II 0.31 0.34 40 0.68
Vinylidene cyanide I V 14.22 1.92 9 0.82
Vinylisocyanate III 0.14 - 0.95 6 0.98
N-Vinylpyrrolidone II 0.088 - 1.62 1 2 0.95
Vinyltriethoxysilane V 0.021 0.82 0.61
Vinyltrimethylsilane V 0.027 0.19 0.58
TABLE 2. TELOGENS
Telogen Temp. ( C) Q ( x lo41 e No. r
Acetone 60 0.11 0.35 5 0.80
80 0.32 0.45 5 0.68
J Benzene 60 0.05 - 1.21 1 6 0.94
80 0.07 - 0.61 9 0.72
-, chloro- 60 0.07 0.08 7 0.30
80 0.13 - 0.06 5 0.30
-7
ethyl- 60 0.95 - 1.02 8 0.84
80 0.91 -0.61 7 0.86
-7
methyl- 60 0.16 - 0.95 1 2 0.93
80 0.34 - 0.87 11 0.94
Benzoyl peroxide 60 36 - 1.89 4 0.93
Butanol 60 0.53 - 0.57 6 0.63
Butanone 60 0.82 0.53 4 0.60
80 1.40 1 .oo 7 0.80
Cyclohexane 60 0.11 - 0.64 6 0.86
80 0.14 - 1.41 7 0.77
1,2-Dichloroethane 60 0.62 1.34 3 0.96
80 1.1 2.07 6 0.96
Ethyl acetate 60 0.07 - 0.87 11 0.97
Mercaptan, alkyl- 60 14500 2.44 11 0.99
Mercaptoacetate, alkyl- 60 15100 3.27 4 0.99
Met hane, dichloro- 60 0.10 - 0.68 4 0.82
-, nitro- 60 3.26 - 1.50 4 0.92
-, tetrabromo- 60 7300 2.90 8 0.99
Methane, tetrachloro- 60 3.64 3.21 1 3 0.99
80 5.15 3.41 9 0.99
-, trichloro- 60 1.18 0.47 8 0.95
80 1.24 0.70 1 0 0.82
Methanol 60 0.18 - 0.93 5 0.76
Triethylamine 60 28.8 - 2.39 7 0.99
TABLE 3. MONOMERS ARRANGED BY Q VALUES
Monomer
Q
e Monomer
Q
e
Ethylene, tetrachloro- 0.001 1.24 Vinylene carbonate 0.004 - 0.49
Butene-2 0.002 - 0.29 Ally1 alcohol 0.005 - 1.48
Propene, 1-chloro-, cis- 0.003 - 0.46 Propene, 1-chloro-, WU~S- 0.006 -0.16
Monomers Arranged by Q Val ues II / 315
TABLE 3. contd
Monomer
Q
e
Butene-1
Vinyl fluoride
Propylene
Bicyclo[2.2.l]hept-2-ene-
5,6 di carboxami ne, N-benzyl-
Ethylene, trichloro-
Vinyl o-cresyl ether
Vinyl laurate
Carbon monoxide
Styrene, 3-tri-n~butylstannyl-
Vinyl p-cresyl ether
Ethylene
Vinyl m-cresyl ether
Crotonic acid
Vinyl ethyl ether
Vinyl 2-chloroethyl ether
Vinyl octyl ether
Vinyltriethoxysilane
Vinyl-tris(trimethoxysiloxy)silane
Crotonaldehyde
Isobutylene
Isopropenyl acetate
N-Allylstearamide
Vinyl butyrate
Vinyl octadecyl ether
Ally1 chloride
Ethylene, chlorotrifluoro-
Vinyl acetate
Vinyl propionate
Vinyltrimethylsilane
Carbamate, N,N-dietbyl-, vinyl
Vinyl N,N-diethylcarbamate
Vinyl ether
Propene, 3,3,3-trichloro-
Vinyl benzoate
Vinyl isobutyl ether
Diallyl phthalate
Ethylene, tetrafluoro-
Phosphonate, isopropenyl-, dimethyl
He x e n e - 1
Triallyl isocyanurate
Carbamate, N-vinyl-, ethyl
Allylbenzene
Vinyl bromide
Vinyl butyl ether
Vinyl chloroacetate
Propenyl, 2-methyl-, acetate
Vinyl dodecyl ether
Vinyl formate
Vinyl stearate
Phosphonate, vinyl-, bis(2-chloroethyl)
Vinyl pelargonate
Vinyl phenyl ether
Vinyl terr-butyl sulfide
Acrylate, trifluoro-, methyl
Norbomadiene
Maleate, diethyl
Triallyl citrate
Vinyl chloride
Vinyl ethyl oxalate
Vinyl hendecanoate
Diallyl melamine
Vinyl dichloroacetate
Vinyl ethyl sulfoxide
Propene, 2-chloro-
0.007 - 0.06
0.008 0.72
0.009 - 1.69
0.010 - 0.36
0.010 1.29
0.010 - 8.53
0.011 - 0.54
0.013 1.68
0.014 - 0.61
0.015 - 6.86
0.016 0.05
0.016 - 6.33
0.017 0.89
0.018 - 1.80
0.019 - 1.64
0.020 - 1.57
0.021 0.82
0.022 -0.12
0.023 0.84
0.023 - 1.20
0.023 - 0.94
0.024 - 0.41
0.024 - 0.89
0.024 - 1.93
0.026 - 0.60
0.026 1.56
0.026 - 0.88
0.027 - 0.68
0.027 0.19
0.028 - 1.11
0.028 - 1.10
0.029 - 1.16
0.030 1.00
0.030 - 0.89
0.030 - 1.27
0.031 - 0.26
0.032 1.63
0.032 0.96
0.035 0.92
0.035 - 0.23
0.037 - 1.12
0.038 0.40
0.038 - 0.23
0.038 - 1.50
0.039 - 1.61
0.040 - 2.08
0.041 - 1.69
0.043 - 1.19
0.043 - 0.97
0.044 1.64
0.046 - 1.22
0.046 - 2.16
0.046 - 2.20
0.048 1.20
0. 05 1 - 1.48
0.053 1.08
0.054 - 0.26
0.056 0.16
0.056 - 0.65
0.056 - 0.84
0.059 - 1.57
0.059 - 1.38
0.065 0.05
0.073 -0.16
Monomer
Q
e
Oxazolidone, N-vinyl-
N-Vinylpyrrolidone
Propene, 2-chloro-3-hydroxy-
Fumarate, diisopropyl
Imi dazol e, l-vinyl-
Propene, 2,3-dichloro-
Indene
Tetrazole, 1 -vinyl-
N-Vinylcaprolactam
Diallylcyanamide
Imi dazol e, I-vinyl-2-methyl-
Phosphonate, wcarbomethoxyvinyl-diethyl
Triallyl cyanurate
9-Vinylanthracene
Vinylisocyanate
Acrylate, ferrocenylmethyl
Methacrylamide, 1-deoxy-D-glucitol
Styrene, 2,4,6-trimethyl-
Vinyl butylsulfonate
Ethylene, 1, l-diphenyl-
Isobutylene, 3-chloro-
Urea, N-vinyl-Nethyl-
Isopropenylisocyanate
Pyridazinone, 3-(2-vinyl)-6-methyl-
4,5-dihydro-
Toluenesulfonamide, N,N-methyl-vinyl-
Vinyl cinnamate
Succinimide, N-vinyl-
Propenyl, 2-chloro-, acetate
Styrene, pentachloro-
1-Acrylamido-1-deoxy-o-glucitol
Methacrylate, ferrocenylmethyl
Acrylamide
Ally1 acetate
Phosphonate, vinyl-, dimethyl
Aconitate, trimethyl
Fumarate, diethyl
Ott-1-ene, 6,6-dimethyl-4,8-dioxaspiro(2,5)-
Carbazole, N-vinyl-
N,N-Divinylaniline
Phosphonate, vinyl-, diethyl
Vinyl ethyl sulfide
Vinyl thiolacetate
Fumaronitrile
Vinylferrocene
Vinylidene chloride
Ally1 acrylate
Acrylate, benzyl
Acrylate, octadecyl
Vinyl phenyl sulfide
Benzothiazole, vinylmercapto-
Acrylate, 2-ethylhexyl
Acrylate, butyl
Styrene, a-methoxy-
Vinyl cymantrene
Methacrylamide
Methacrylamide, N-phenyl-
Acrylamide, N,N-dimethyl-
Acrylate, ethyl
2-Methyleneglutaronitrile
4-Cyclopentene- 1,3-dione
Vinyl methyl sulfide
Oxazoline, 2-,4-methacryloxymethyl-
2,4-dimethyl-
Acetylene, phenyl-
0.087 - 1.70
0.088 - 1.62
0.091 - 0.95
0.11 2.58
0.11 - 0.68
0.12 - 0.40
0.13 - 0.71
0.13 -0.14
0.14 - 1.18
0.14 2.41
0.14 - 0.98
0.14 - 0.04
0.14 2.41
0.14 0.82
0.14 - 0.95
0.15 0.51
0.15 -0.16
0.15 - 0.58
0.16 1.06
0.17 - 1.71
0.17 - 0.86
0.17 - 1.88
0.18 - 1.05
0.18 - 0.32
0.18 - 0.53
0.18 0.76
0.19 - 1.42
0.20 - 0.85
0.20 0.79
0.22 0.61
0.22 - 0.65
0.23 0.54
0.24 - 1.07
0.24 - 0.25
0.25 2.27
0.25 2.26
0.25 0.61
0.26 - 1.29
0.26 - 0.68
0.27 - 0.40
0.27 - 1.31
0.27 - 0.52
0.29 2.73
0.31 - 1.34
0.31 0.34
0.32 - 0.99
0.33 1.13
0.33 1.26
0.33 - 0.99
0.36 - 0.44
0.37 0.24
0.38 0.85
0.39 - 1.02
0.39 - 0.57
0.40 - 0.05
0.40 0.19
0.41 - 0.26
0.41 0.55
0.41 1.25
0.42 2.43
0.42 - 1.66
0.44 - 0.70
0.45 0.10
References page II - 3 19
II / 316 Q AND e VALUES FOR FREE RADICAL COPOLYMERIZATIONS OF VINYL MONOMERS AND TELOCENS
TABLE 3. contd
Monomer
Q
e Monomer
Q
e
Acrylate, methyl
Acrylamide, N,N-diethyl
Acrylate, glycidyl
Acrylonitrile
Acrylate, 2-chloroethyl
Vinyl isobutyl sulfide
Acrylamide, N-methylol-
Acrylate, a-acetoxy-, ethyl
Methacrylate, 2,2,6,6-tetramethyl-
4-piperidinyl
Tetrazole, 2-methyl-5-vinyl-
Isopropenyl, 3-( 1-cyclohexenyl)acetate
Pyridazinone, 3-(2-vinyl)-6-methyl-
Vinyl isopropyl ketone
Oxazoline, 2-isopropenyl-2-
Vinyl isothiocyanate
Methacrylate, 2-acetoxyethyl
Vinyl methyl sulfoxide
Acrylate, octyl
Phosphonic acid, a-phenyl-
Acrylamide, N-octadecyl-
Vinyl methyl ketone
Vinyl 4-chlorocyclohexyl ketone
Acrylate, 2nitrobutyl
p-Vinylbenzylethylcarbinol
Styrene, p-l-(2-hydroxybutyl)-
Acenaphthalene
Itaconate, dimethyl
Metiiacrylate, ethyl
Itaconic acid
Methacrylate, methyl
Acrolein
Butadiene, hexafluoro-
Itaconate, dibutyl
Methacrylate, butyl
Methacrylate, isobutyl
Acrylic acid
Tetrazole, 2-phenyl-5-(4-vinyl)-phenyl-
Maleic anhydride
Methacrylonitrile
Tetrazole, 2-methyl-5-(4-vinyl)-phenyl-
Citraconimide, N-methyl-
Oxazol i ne, 2-, 2-isopropenyl-4,4-dimethyl-
Mal ei mi de, N-butyl-
Methacrylate, benzyl
Mal ei mi de
Acrylate, heptafluorobutyl
Methacrylate, isopropyl
Oxazoline, 2-,4-acryloxymethyl-2,4-dimethyl.
Styrene, a-methyl-
Methacrylic acid
Acrylate, a-chloro-, ethyl
Styrene
Isopropenyl methyl ketone
Itaconate, diethyl
Methacrylate, 2-naphthyl
Methacrylate, 2,3-epithiopropyl
Methacrylate, 2-chloroethyl
Quinoline, 2-vinyl-
Silane, y-methacryloxypropyl-trimethoxy
Styrene, p-1-(2-hydroxypropyl)-
Methacrylate, 2-(sulfonic acid)ethyl
Styrene, p-methyl-
0.45 0.64
0.48 - 0.31
0.48 1.28
0.48 1.23
0.49 1.03
0.49 - 0.95
0.52 1.15
0.52 0.17
0.52 - 1.09
0.55 - 0.46
0.57 - 0.66
0.57 0.24
0.58 - 1.16
0.59 - 0.64
0.59 0.37
0.60 0.51
0.60 - 1.79
0.63 2.01
0.65 0.52
0.66 1.64
0.66 1.05
0.66 - 0.82
0.69 1.09
0.69 - 0.98
0.70 - 0.97
0.12 - 1.88
0.73 0.57
0.76 0.17
0.78 1.07
0.78 0.40
0.80 1.31
0.82 0.58
0.82 0.57
0.82 0.28
0.82 0.27
0.83 0.88
0.84 - 0.52
0.86 3.69
0.86 0.68
0.86 0.51
0.87 1.58
0.87 0.34
0.88 3.70
0.88 0.35
0.94 2.86
0.96 0.20
0.97 0.10
0.97 -0.51
0.97 -0.81
0.98 0.62
1.00 - 1.03
1.00 - 0.80
1.03 0.64
1.04 0.88
1.04 - 0.09
1.04 0.29
1.04 0.31
1.04 - 0.09
1.08 0.07
1.08 - 0.35
1.09 0.25
1.10 - 0.63
Tetrazole, 5-phenyl-2-(4-vinyl)-phenyl-
Methacrylate, 2-(N,N-dimethylcarbam-
0yloxy)ethyl
Styrene, p-2-(2-hydroxypropyl)-
Vinyl phenyl ketone
Methacrylate, sulfolanyl
Methacrylate, 2-bromoethyl
Methacrylate, phenyl
Styrene, m-bromo-
Maleimide, N-(Zhydroxyethyl)-
Pentadiene, truns- 1,3-
Pyridine, 2-vinyl-5-ethyl-
Styrene, p-bromo-
Pyridine, 2-methyl-5-vinyl-
Styrene, p-chloro-
Styrene, p-chloromethyl-
Pyridine, 2-vinyl-
Butadiene, 2,3-dimethyl-
Acrylic anhydride
Pyrrolidone, 1-benzyl-3-methylene-5-methyl-
Styrene, 2,5-dichloro-
Styrene, p-methoxy-
Styrene, m-methyl-
Butadiene-1-carboxylate, ethyl
Butadiene
p-Vinylbenzylmethylcarbinol
Vinylhydroquinone dibenzoate
Methacrylate, 2-hydroxyethyl
Acryloyl chloride
Acrolein, methyl-
Hexatriene, tetrachloro-
Butadiene, 2-fluoro-
Phthalimide, N-(methacryloyloxy)-
Isoprene, 3-acetoxy-
Butadiene, 1,4-dicarboxylate, diethyl
Isoprene
Methacryloyl chloride
Methacrylate, 2-chloro-
2,3,3,3-tetrafluoropropyl
Styrene, m-nitro-
Mal ei mi de, N-(Zchlorophenyl)-
Acrylate, cr-chloro-, methyl
Styrene, m-chloro-
Pyridine, 4-vinyl-
Methylenebutyrolactone
Mal ei mi de, 2,3dimethyl-
N-(2-methacryloxyethyl)-
Styrene, o-chloro-
Maleimide, N-phenyl-
Styrene, p-cyano-
Mal ei mi de, N-(Cchlorophenyl)-
Methacrylic anhydride
Acrylic acid, a-bromo-
Vinylhydroquinone
Methacrylate, 2-hydroxypropyl
Acrylate, cl-cyano-, methyl
p-Vinylbenzoic acid
Acrylate, cr-phenyl-, methyl
Methacryloylacetone
Butadiene, 2,3-dichloro-
Butadiene, 2-chloro-
Vinylidene cyanide
Vinyl chloromethyl ketone
1.15
1.16
1.18
1.18
1.25
1.25
1.26
1.28
1.29
1.30
1.32
1.33
1.39
1.41
1.42
1.46
1.50
1.50
1.53
1.57
1.67
1.70
1.70
1.73
1.78
1.82
1.83
1.83
1.88
1.89
1.91
1.94
1.99
2.04
2.09
2.19
2.29
2.43
2.46
2.47
2.48
2.54
2.66
2.81
2.93
2.98
3.00
3.07
4.30
4.38
4.91
5.17
5.19
5.47
9.08
10.52
14.22
16.00
- 0.49
1.02
0.95
0.74
0.79
- 0.27
1.07
-0.13
- 0.91
- 0.68
- 0.66
- 0.64
- 0.38
- 0.42
- 0.43
0.31
- 0.59
0.94
- 1.40
- 0.03
1.26
- 0.50
- 1.27
0.84
- 0.39
1.92
0.71
0.94
0.63
0.96
-0.11
1.39
- 0.55
1.54
0.62
0.20
2.87
0.35
- 0.90
0.84
0.83
1.64
1.57
3.24
- 0.38
2.75
0.56
1.37
2.26
1.86
0.91
1.08
0.96
- 0.76
0.14
1.20
1.92
1.78
Monomers Arranged by e Val ues II / 317
TABLE 4. MONOMERS ARRANGED BY e VALUES
Monomer
Q
e
Vinyl ethyl sulfoxide 0.065
Ethylene 0.016
Silane, y-methacryloxypropyl-trimethoxy 1.08
Acetylene, phenyl- 0.45
Methacrylate, isopropyl 0.97
Butadiene, 2,3-dichloro- 9.08
Vinyl chloride 0.056
Methacrylate, ethyl 0.76
Vinyltrimethylsilane 0.027
Methacrylamide, N-phenyl- 0.40
Methacrylate, glycidyl 0.96
Styrene, m-nitro- 2.19
Acrylate, 2-ethylhexyl 0.37
Pyridazinone, 3-(2.vinyl)-6-methyl- 0.57
Methacrylate, 2-(sulfonic acid)ethyl 1.09
Methacrylate, isobutyl 0.82
Methacrylate, butyl 0.82
Methacrylate, 2,3-epithiopropyl 1.04
Methacrylate, 2-chloroethyl 1.04
Acrylic anhydride 1.46
Vinylidene chloride 0.31
Oxazoline, 2-,2-isopropenyl-4,4-dimethyl- 0.87
Methacrylate, benzyl 0.88
Acrylate, wchloro-, methyl 2.43
Vinyl isothiocyanate 0.59
Allylbenzene 0.038
Methacrylate, methyl 0.78
Acrylate, ferrocenylmethyl 0.15
Methacrylate, 2-acetoxyethyl 0.60
Tetrazole, 2-methyl-5-(4-vinyl)-phenyl- 0.86
Phosphonic acid, a-phenylvinyl- 0.65
Tetrazole, 5-phenyl-2-(4-vinyl)-phenyl- 1.11
Acrylamide 0.23
Acrylate, ethyl 0.41
Methacrylic anhydride 3.00
ltaconate, dimethyl 0.73
ltaconate, dibutyl 0.82
Butadiene, hexafluoro- 0.82
1-Acrylamideo-1-deoxy-D-glucitol 0.22
Ott-1-ene, 6,6-dimethyl-4,8-dioxaspiro(2.5)- 0.25
Methacrylic acid
Butadiene, 2-fluoro-
Acrylate, methyl
lsopropenyl methyl ketone
Methacrylonitrile
Acrolein, methyl-
Vinyl fluoride
Methacrylate, 2-bromoethyl
Vinyl cinnamate
Acrylate, a-acetoxy-, ethyl
Styrene, pentachloro-
Methacrylate, phenyl
Vinyltriethoxysilane
9-Vinylanthracene
Methylenebutyrolactone
Vinylhydroquinone dibenzoate
Crotonaldehyde
Methacrylate, 2-(N,N-dimethylcarbam-
0yloxy)ethyl
Pyridine, 4-vinyl-
Acrylate, butyl
Acrylic acid
Itaconate, diethyl
Crotonic acid
Acrylate, a-cyano-, methyl
0.98
1.88
0.45
1.03
0.86
1.83
0.008
1.18
0.18
0.52
0.20
1.25
0.021
0.14
2.48
1.73
0.023
1.14
0.05
0.05
0.07
0.10
0.10
0.14
0.16
0.17
0.19
0.19
0.20
0.20
0.24
0.24
0.25
0.27
0.28
0.29
0.31
0. 3 1
0.34
0.34
0.35
0.35
0.37
0.40
0.40
0.51
0.51
0. 5 1
0.52
0.53
0.54
0.55
0.56
0.57
0.57
0.58
0.61
0.61
0.62
0.63
0.64
0.64
0.68
0.71
0.72
0.74
0.76
0.77
0.79
0.79
0.82
0.82
0.83
0.84
0.84
0.84
2.47 0.84
0.38 0.85
0.83 0.88
1.04 0.88
0.017 0.89
4.91 0.91
Monomer
Q
e
He x e n e - 1
Styrene, 2,5-dichloro-
Hexatriene, tetrachloro-
Methacrylate, sulfolanyl
Phosphonate, isopropenyl-, dimethyl
Phthalimide, N-(methacryloyloxy)-
Acrylate, a-phenyl-, methyl *
Propene, 3,3,3-trichloro-
Vinyl phenyl ketone
Acrylate, 2-chloroethyl
Vinyl methyl ketone
Vinyl butylsulfonate
Itaconic acid
Maleimide, N-(2-hydroxyethyl)-
p-Vinylbenzoic acid
Maleate, diethyl
Acrylate, 2-nitrobutyl
Acrylate, benzyl
Acrylamide, N-methylol-
Acrylate, trifluoro-, methyl
Butadiene, 2-chloro-
Acrylonitrile
Ethylene, tetrachloro-
2-Methyleneglutaronitrile
Acrylate, octadecyl
Butadiene-1-carboxylate, ethyl
Acrylate, glycidyl
Ethylene, trichloro-
Acrolein
Acrylate, heptafluorobutyl
Acrylic acid, a-bromo-
Butadiene, 1,4-dicarboxylate, diethyl
Methacryloyl chloride
Ethylene, chlorotrifluoro-
Styrene, o-chloro-
Citraconimide, N-methyl-
Ethylene, tetrafluoro-
Phosphonate, vinyl-, bis(2-chloro-ethyl)
Acrylamide, N-octadecyl-
Mal ei mi de, 2,3-dimethyl&
(2-methacryloxyethyl)-
Carbon monoxide
Vinyl chloromethyl ketone
Methacrylate, 2-hydroxypropyl
Vinylidene cyanide
Acryloyl chloride
Acrylate, octyl
Methacrylate, 2-chloro-
2,3,3,3-tetrafluoropropyl
Vinylhydroquinone
Fumarate, diethyl
Aconitate, trimethyl
Fumarate, diisopropyl
Triallyl cyanurate
Diallylcyanamide
4-Cyclopentene-1,3-dione
Fumaronitrile
Mal ei mi de, N-(4-chlorophenyl)-
Mal ei mi de
Mal ei mi de, iV-(2-chlorophenyl)-
Maleimide, N-phenyl-
Maleic anhydride
Mal ei mi de, N-butyl-
Styrene, m-methyl-
Phosphonate, a-carbomethoxyvinyl-, diethyl
0.035 0.92
1.50 0.94
1.83 0.94
1.18 0.95
0.032 0.96
1.89 0.96
5.19 0.96
0.030 1.00
1.16 1.02
0.49 1.03
0.66 1.05
0.16 1.06
0.78 1.07
1.26 1.07
5.17 1.08
0.053 1.08
0.69 1.09
0.33 1.13
0.52 1.15
0.048 1.20
10.52 1.20
0.48 1.23
0.001 1.24
0.41 1.25
0.33 1.26
1.67 1.26
0.48 1.28
0.010 1.29
0.80 1.31
0.96 1.34
3.07 1.37
1.94 1.39
2.04 1.54
0.026 1.56
2.66 1.57
0.87 1.58
0.032 1.63
0.044 1.64
0.66 1.64
2.54 1.64
0.013 1.68
16.00 1.78
4.38 1.86
14.22 1.92
1.82 1.92
0.63 2.01
0.62 2.09
4.30 2.26
0.25 2.26
0.25 2.27
0.11 2.58
0.14 2.41
0.14 2.41
0.42 2.43
0.29 2.73
2.98 2.75
0.94 2.86
2.29 2.87
2.81 3.24
0.86 3.69
0.88 3.70
1.57 - 0.03
0.14 - 0.04
References page II - 3 19
II / 318 Q AND e VALUES FOR FREE RADICAL COPOLYMERIZATIONS OF VINYL MONOMERS AND TELOCENS
TABLE 4. contd
Monomer
Q
e
Methacrylamide 0.40
Butene-1 0.007
Methacrylate, 2-naphthyl 1.04
Quinoline, 2-vinyl- 1.04
Isoprene, 3-acetoxy- 1.91
Vinyl-tris(trimethoxysiloxy)silane 0.022
Pentadiene, truns-1,3- 1.28
Tetrazole, l-vinyl- 0.13
Propene, 1-chloro-, trans- 0.006
Propene, 2-chloro- 0.073
Methacrylamide,l-deoxy-D-glucitol 0.15
Triallyl isocyanurate 0.035
Vinyl bromide 0.038
Phosphonate, vinyl-, dimethyl 0.24
Triallyl citrate 0.054
Diallyl phthalate 0.031
Acrylamide, N,N-dimethyl- 0.41
Styrene, m-bromo- 1.25
Butene-2 0.002
Acrylamide, N,N-diethyl 0.48
Pyridazinone, 3-(2-vinyl)-6-methyl- 0.18
Styrene, p-1-(2-hydroxypropyl)- 1.08
Bicyclo[2.2.l]hept-2-ene-
5,6 di carboxami ne, N-benzyl- 0.01
Styrene, p-chloromethyl- 1.39
Styrene, p-cyano- 2.93
Methacrylate, 2-hydroxyethyl 1.78
Propene, 2,3-dichlom- 0.12
Phosphonate, vinyl-, diethyl 0.27
N-Allylstearamide 0.024
Pyridine, 2-vinyl- 1.41
Butadiene, 2,3-dimethyl- 1.42
Benzothiazole, vinylmercapto- 0.36
Tetrazole, 2-methyl-5-vinyl- 0.55
Propene, 1-chloro-, cis- 0.003
Vinylene carbonate 0.004
Styrene, p-2-(2-hydroxypropyl)- 1.15
Butadiene 1.70
Oxazoline, 2,4-acryloxymethyl-2,4-dimethyl- 0.97
Vinyl thiolacetate 0.27
Tetrazole, 2-phenyl-5-(4-vinyl)-phenyl- 0.84
Toluenesulfonamide, N,N-methyl-vinyl- 0.18
Vinyl laurate 0.011
Isoprene 1.99
Vinyl cymantrene 0.39
Styrene, 2,4,6-trimethyl- 0.15
Pyrrolidone, 1-benzyl-3-methylene-5-methyl- 1.50
Ally1 chloride 0.026
Styrene, 3-tri-n-butylstannyl- 0.014
Styrene, p-methyl- 1.10
Oxazoline, 2-isopropenyl-2- 0.59
Styrene, p-chloro- 1.33
Vinyl ethyl oxalate 0.056
Methacrylate, ferrocenylmethyl 0.22
Isopropenyl, 3-( 1-cyclohexenyl)-acetate 0.57
Pyridine, 2-methyl-5-vinyl- 1.32
Vinyl propionate 0.027
Imidazole, l-vinyl- 0.11
N,N-Divinylaniline 0.26
Styrene, p-bromo- 1.30
Oxazoline, 2-,4-methacryloxymethyl- 0.44
2,4-dimethyl-
Indene 0.13
Methacryloylacetone 5.47
Styrene 1.00
Styrene, a-methyl- 0.97
- 0.05
- 0.06
- 0.09
- 0.09
-0.11
-0.12
-0.13
-0. 14
-0. 16
-0.16
-0.16
- 0.23
- 0.23
- 0.25
- 0.26
- 0.26
- 0.26
- 0.27
- 0.29
- 0.31
- 0.32
- 0.35
- 0.36
- 0.38
- 0.38
- 0.39
- 0.40
- 0.40
- 0.41
- 0.42
- 0.43
- 0.44
- 0.46
- 0.46
- 0.49
- 0.49
- 0.50
- 0.51
- 0.52
- 0.52
- 0.53
- 0.54
- 0.55
- 0.57
- 0.58
- 0.59
- 0.60
- 0.61
- 0.63
- 0.64
- 0.64
- 0.65
- 0.65
- 0.66
- 0.66
- 0.68
- 0.68
- 0.68
- 0.68
- 0.70
- 0.71
- 0.76
- 0.80
-0.81
Monomer
Q
e
Vinyl 4-chlorocyclohexyl ketone 0.66
Vinyl hendecanoate 0.056
Propenyl, 2-chloro-, acetate 0.20
Isobutylene, 3-chloro- 0.17
Vinyl acetate 0.026
Vinyl butyrate 0.024
Vinyl benzoate 0.030
Styrene, m-chloro- 2.46
Pyridine, 2-vinyl-5-ethyl- 1.29
Isopropenyl acetate 0.023
Vinylisocyanate 0.14
Vinyl isobutyl sulfide 0.49
Propene, 2-chloro-3-hydroxy- 0.091
Vinyl stearate 0.043
Styrene, p-l(Zhydroxybutyl)- 0.70
p-Vinylbenzylethylcarbinol 0.69
Imidazole, 1-vinyl-2-methyl- 0.14
Vinyl phenyl sulfide 0.33
Ally1 acrylate 0.32
Styrene, a-methoxy- 0.39
Acrylate, a-chloro-, ethyl 1.00
Isopropenylisocyanate 0.18
Ally1 acetate 0.24
Methacrylate, 2,2,6,6-tetramethyl-piperidinyl 0.52
Vinyl N,N-diethylcarbamate 0.028
Carbamate, N,N-diethyl-, vinyl 0.028
Carbamate, N-vinyl-, ethyl 0.037
Vinyl ether 0.029
Vinyl isopropyl ketone 0.58
N-Vinylcaprolactam 0.14
Vinyl formate 0.043
Isobutylene 0.023
Vinyl pelargonate 0.046
Vinyl isobutyl ether 0.030
p-Vinylbenzylmethylcarbinol 1.70
Carbazole, N-vinyl- 0.26
Vinyl ethyl sulfide 0.27
Vinylferrocene 0.31
Vinyl dichloroacetate 0.059
Styrene, p-methoxy- 1.53
Succinimide, N-vinyl- 0.19
Ally1 alcohol 0.005
Norbornadiene 0.051
Vinyl butyl ether 0.038
Vinyl octyl ether 0.020
Diallyl melamine 0.059
Vinyl chloroacetate 0.039
N-Vinylpyrrolidone 0.088
Vinyl 2-chloroethyl ether 0.019
Vinyl methyl sulfide 0.42
Vinyl dodecyl ether 0.041
Propylene 0.009
Oxazolidone, N-vinyl- 0.087
Ethylene, 1,l -diphenyl- 0.17
Vinyl methyl sulfoxide 0.60
Vinyl ethyl ether 0.018
Urea, N-vinyl-Nethyl- 0.17
Acenaphthalene 0.72
Vinyl octadecyl ether 0.024
Propenyl, 2-methyl-, acetate 0.040
Vinyl phenyl ether 0.046
Vinyl terl-butyl sulfide 0.046
Vinyl m-cresyl ether 0.016
Vinyl p-cresyl ether 0.015
Vinyl o-cresyl ether 0.010
- 0.82
- 0.84
- 0.85
- 0.86
- 0.88
- 0.89
- 0.89
- 0.90
- 0.91
- 0.94
- 0.95
- 0.95
- 0.95
- 0.97
- 0.97
- 0.98
- 0.98
- 0.99
- 0.99
- 1.02
- 1.03
- 1.05
- 1.07
- 1.09
- 1.10
- 1.11
- 1.12
- 1.16
- 1.16
- 1.18
- 1.19
- 1.20
- 1.22
- 1.27
- 1.27
- 1.29
- 1.31
- 1.34
- 1.38
- 1.40
- 1.42
- 1.48
- 1.48
- 1.50
- 1.57
- 1.57
- 1.61
- 1.62
- 1.64
- 1.66
- 1.69
- 1.69
- 1.70
- 1.71
- 1.79
- 1.80
- 1.88
- 1.88
- 1.93
- 2.08
- 2.16
- 2.20
- 6.33
- 6.86
- 8.53
References II / 319
C. REFERENCES
1. T. Alfrey, C. C. Price, J. Polym. Sci., 2, 101 (1947). 4. R. Z. Greenley, J. Macromol. Sci. A: Chem., 11, 933
2. R. Z. Greenley, J. Macromol. Sci. A: Chem., 9, 505 (1975). (1977).
3. L. J. Young, in: J. Brandrup, E. H. Immergut (Eds.), Polymer 5. A. D. Jenkins, J. Polym. Sci.: Part A: Polym. Chem., 34,3495
Handbook, 2nd ed., Wiley, New York, 1975. (1996).
&
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.
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_
Patterns of Reactivity (U,V) Parameters
for the Prediction of Monomer Reactivity
Ratios and Transfer Constants
in Radical Polymerization
Aubrey D. Jenkins, Jitka Jenkins
School of Chemistry, Physics and Environmental Science,
University of Sussex, Brighton, Sussex, BNl 9QJ, UK
A. Introduction II-321
B. Example I I-322
C. Transfer Constants II-322
D. Tables of Parameters I I-323
Table 1. Monomers II-323
Table 2. Transfer Agents II-326
E. References II-327
A. INTRODUCTION
The relation between monomer reactivity ratios and the
Alfrey-Price Q-e parameters is explained in the introduc-
tion to the tables of monomer reactivity ratios and Q-e
values, compiled by Robert Z. Greenley and published in
the present volume (1,2). Although very widely used, the
Q-e scheme is well known to have serious limitations (3),
which have prompted several attempts to improve upon it.
One such endeavour was the Patterns of Reactivity
scheme, first described as long ago as 1959 (4-7), when the
Q-e scheme was only about ten years old; despite the
indisputably more satisfactory basis of this procedure, it did
not achieve popularity but recent revisions have greatly
improved both its accessibility and its accuracy (3,8,9).
In the Q-e scheme, four parameters (Q 1, Q2, e 1, e;?; two
for each monomer) are necessary for the prediction of a
monomer reactivity ratio (e.g. r12 = kll/k12, where sub-
script 1 refers to the radical and subscript 2 to the
monomer) but the same four parameters also facilitate the
prediction of the partner monomer reactivity ratio
(121 = k22/k21) because identical Q and e parameters are
used to characterise both a given monomer and its derived
radical. This device is certainly economical on input data
but it introduces an approximation of very doubtful validity.
In the Patterns scheme (to use the abbreviated title),
different parameters are designated for the monomer and its
conjugate radical. Hence, while four input parameters are
again necessary for the calculation of a single monomer
reactivity ratio, eight are required to calculate both r-i2 and
r21. The reward for the greater input of data is a substantial
increase in the precision of the result; furthermore, all four
parameters for each monomer/radical conjugate pair are
experimentally determined from polymerization data,
specifically monomer reactivity ratios from Greenleys
tabulation, so no arbitrary assignment is involved, as it is
with the Q-e scheme.
The fundamental equation for the calculation of a
reactivity ratio, r12, is given below.
logri2 = logris - ~2~1 - ~2.
(Al)
Here, the symbol S denotes the monomer styrene, and
log rls is the counterpart of Q 1 in the Q-e scheme. The
counterpart of e 1 is the polarity parameter rri; this is
usually almost exactly equal to the Hammett (T parameter
for the substituent(s) present on the a-carbon atom of the
radical derived from monomer 1 but it is best calculated (8)
from monomer reactivity ratio data according to Eq. (A2).
~1 = 0.385 log[(rlA)/O.377(r,s)]
( w
Here, the symbol A denotes the monomer acrylonitrile. It
is truly an astonishing fact that the Hammett c parameter,
derived originally from studies of the dissociation of
substituted benzoic acids, is equal in value to a simple
quantity derived from a knowledge of the monomer
reactivity ratios for the reactions of a monomer 1 with
(separately) acrylonitrile and styrene.
The values of 2.~2 and ~2, the respective counterparts of
the Q-e schemes e2 and Q2, are determined by reference
to data for the (separate) copolymerizations of monomer 2
with the members of a Basic Monomer Set. These are five
monomers for which reliable data exist in the literature:
styrene (S); methyl methacrylate (MM); methyl acrylate
II / 321
II / 322 PATTERNS OF REACTIVITY (U,V) PARAMETERS FOR THE PREDICTION OF MONOMER REACTIVITY RATIOS
(MA); methacrylonitrile (MAN); and acrylonitrile (A).
Ideally, monomer reactivity ratios should be known for the
copolymerization of the monomer of interest (labelled 2 in
this case) with each of these five reference monomers. If the
reference monomer is monomer 1 in this context, a plot is
made of [log ~12 - log his] against ~1; the slope of the
resulting straight line is -u:! and the intercept on the
ordinate axis is -v2, in conformity with Eq. (Al).
If data for reactions with all five members of the Basic
Monomer Set are not available, use can be made of such
data as exists, always provided that styrene and acrylonitrile
are among the monomers included. This condition ensures
that the data are spread over a wide range of radical
polarity, represented by rri, because styrene has a very low
value (zero), while acrylonitrile has one of the highest
values known (0.701).
In Table 1, each monomer is designated either as Basic
or assigned to a category according to the number of
members of the Basic Monomer Set for which data have
been employed in the determination of its z.42 and ~2; for
category 5, all five Basic monomers were involved, and so
on down to category 2, where data for only styrene and
acrylonitrile are available. Clearly, the higher the category
number, the more reliable the u2 and v2 values. The
procedure described thus far is known as the Patterns U,V
Scheme (3).
) For Group 2 monomers, there is no need to make a plot
because the use of just two data points permits algebraic
solutions to be found. In fact, it can be shown (3) that the
following relations hold.
U2 = [log t-AS - log rA2 + log f-S2]/rA and V2 = -log Y,Q
( w
Substitution in Eq. (Al) leads to the following relation-
ships (A4, A5), giving the two monomer reactivity ratios
for the copolymerization of any two monomers, 1 and 2.
log(r12) = bd(~IS)h2)1
_ ~10~~(rAS)(rS2)/(rA2)I)(log[(YSA)o/(rlA~~~ (A4)
10dhS)hA)l
log(r21) = log[(r2s)(w)l
Application of Eqs. (A3-A5) corresponds to the
Patterns A,S Scheme (4), so-called, because data for
reaction with only acrylonitrile and styrene are involved.
According to the Patterns A,S Scheme, it is possible to
calculate the two monomer reactivity ratios for copolymer-
ization of monomers 1 and 2, if each of them has separately
been copolymerized with acrylonitrile and styrene. (The
two monomer reactivity ratios for copolymerization of
acrylonitrile and styrene are also required. These are taken
t0 be: T.&s = 0.04, TsA = 0.38 (3).)
The rr, u, and v values listed in the table below have been
derived as explained above, with the Patterns U,V Scheme
being used for the monomers in categories 3-5 and the
Patterns A,S Scheme for those in category 2. The r is values
are mean values from the figures supplied in Greenleys
table, making due allowance for the consistency of the data.
B. EXAMPLE
Suppose one wants to evaluate the monomer reactivity
ratios for the copolymerization of 2-chlorobutadiene (CB)
and 2-vinylpyridine (VP). To use the Patterns U,V Scheme
for this purpose, it is first necessary to consult Greenleys
table of monomer reactivity ratios for data characterizing
the copolymerizations of each of these monomers with as
many members of the Basic Monomer Set as possible. In
fact, in both~cases, values exist for reactions with styrene,
methyl methacrylate, methyl acrylate and acrylonitrile, but
not methacrylonitrile. The rr values for the four useful basic
monomers are, respectively, 0.000, 0.339, 0.423 and 0.701.
The relevant monomer reactivity ratios are listed in the
table below.
MONOMER REACTIVITY RATIOS FOR 2XHLOROBUTADIENE
AND 2-VINYLPYRIDINE AND MEMBERS OF THE BASIC
MONOMER SET
Monomer
reactivity
ratio 2Xhlorobutadiene
rx,s
6.91
rX,A
5.18
rs,x
0.038
rA,X
0.05
rmf,x
0.08
m.4,x
0.06
X = 2-chlorobutadiene or 2-vinylpyridine.
2-Vinylpyridine
1.26
0.44
0.53
0.10
0.35
0.25
Plots of [log r12 - log rls] against T 1, where 2 = CB or
VP, are linear with slopes and intercepts that provide the
following u and v values (9). For CB, u = - 2.18, v = 1.44,
and for VP, u = - 0.982 and v = 0.323. All the data are now
available for substitution in Eq. (Al), first for CB =
monomer 1 and VP=monomer 2, and secondly with the
monomers roles reversed, to obtain values of r12 and r21.
The results are r12 = 4.26 and r21 = 0.04. The Patterns A,S
Scheme can be applied by simply substituting the appro-
priate monomer reactivity ratio data in Eqs. (A4) and (A5),
giving r12 =4.71 and r21 =0.05. The corresponding
experimental results are r12 = 5.19 and r21 =0.06, while
the Q=e scheme predicts that r12 = 1.07 and r21 =0.07.
C. TRANSFER CONSTANTS
Transfer constants can be predicted by exactly parallel
reasoning (3). It is necessary only to realise that whereas
the rate constant for the propagation step of a radical with
its own parent monomer appears in the numerator of a
monomer reactivity ratio (r 12 = k 11 /k 12), where both rate
Monomers II / 323
constants refer to propagation reactions, it figures in the
denominator of a transfer constant because (Cz) I=
k12/kll, where k 12 represents a transfer reaction between
the radical derived from a monomer (species 1) and a
transfer agent (species 2); the equations for calculating
transfer constants are thus easily obtained from the
equations above by replacing log r12 by - log (C2) 1. The
only formal difference between the two cases is that, for
transfer, there is no symmetrical counterpart of the
equations representing reaction of a radical of type 2 with
a transfer agent of type 1. Thus, the equivalent of Eq. (Al),
for transfer is Eq. (A6), and this enables the Patterns U,V
Scheme to be applied to chain transfer.
-log(Cz) 1 = log rls - 242~1 - v2
W)
For use of the Patterns A,S Scheme in transfer, a parallel
derivation to that used in copolymerization leads to the
following equation, where (C2)s and (C2) A are, respec-
tively, the (known) transfer constants for reaction of the
same transfer agent (species 2) with radicals derived from
styrene and acrylonitrile (species 1).
log(C2) 1 = log[(C2) Jwl
+ (~I/~A)10g[rAS(c2)A/(c2)S1
WY
Since TA =0.701 and rAs =0.04, this equation can be
reduced to Eq. (A8) for general use.
log(C2) 1 = log[(C2)s/wl
+ (1.43T1) 1og[o.04(c2),/(c2),]
W)
The transfer constants used here are taken from two
tabulations, one due to Eastmond (10) and one in the
Polymer Handbook (11).
D. TABLES OF PARAMETERS
As explained above, each monomer or transfer agent is
assigned to a category, designated by Basic or the number
2, 3, 4, or 5, according to the number of members of the
TABLE 1. MONOMERS
Basic Monomer Set with which this reagent has been
reacted to obtain data for the evaluation of u, v and (in the
case of monomers) 7r. Although it must be true that the
higher the category, the more reliable the derived
parameters, the difference between Categories 2 and 5 is
not so great as might appear at first sight. In all cases, two
of the basic monomers involved are styrene, S, (the least
polar) and acrylonitrile, A, (the most polar), so the role
played by other basic monomers is merely to add
intermediate points to what should be a straight line joining
the data points for S and A; if the data for these two latter
monomers are accurate, intermediate points add little or no
value beyond confirmation of the slope and intercept. They
do contribute valuable weighting when there are some
discrepancies in the data, but parameters have not been
recorded here in cases where the discrepancies are large.
Where either rls or r1A was reported as zero, the value
0.05 has been assigned arbitrarily in order to make it
possible to calculate an approximate value for the 7r
parameter but the values of the u and v parameters are not
influenced by this device; entries of this type are printed in
italics in Table 1. Sometimes both rls and r1A are reported
to be zero; when this happens, 7r cannot usefully be
estimated but u and v can still be determined, if positive
values of rs1 and rAl are available.
Nomenc lature In the tables below, compounds are listed
in alphabetical sequence in accordance with the following
rules:
The primary listing is based on the root name of the
compound and the secondary sequence on the name(s) of
the substituent(s) or the esterifying moiety. For example,
the compounds, p-methyl styrene, N-vinyl carbazole, and
ethyl acrylate, will be found listed under Styrene, p-methyl,
Carbazole, N-vinyl, and Acrylate, ethyl, respectively.
In deciding on the appropriate order of names, all
prejixes (alphanumeric, Greek or whatever) and spaces are
ignored, and reliance is placed solely on the alphabetical
priority of the strictly chemical part of the name. In styrene,
p-methyl, for example, the prefix p- plays no part in
determining the place of this name in the list; this is
governed by the m in methyl.
Monomer Cat egory
rlS rlA rA1 01 log (r 1s) 7r ll V
Acenaphthalene 4
Acetylene, phenyl 5
Aconitate, trimethyl 2
Acrolein 5
Acrolein, methyl 4
Acrylamide 3
Acrylamide, N-methyl01 4
Acrylamide, N-octadecyl 3
Acrylate, benzyl 3
Acrylate, butyl 3
Acrylate, 2-chloroethyl 4
Acrylate, a-chloro-, methyl 3
0.33 2.56
0.33 0.33
0.27 1.11
0.60 3.10
0.70 1 . 1 0
0.48 2.43
0.54 1 . 4 0
0.20 0.72
0.18 0.97
0.12 0.87
0.30 1.76
0.02 3 . 8 1
0.27 0.32
4.24 1.026
0.78 0.23
0.15 0.26
0.90 1 . 2 0
0.60 0.03
1 . 0 3 2.08
1 . 4 9 0.49
1.11 0.77
1 . 0 3 0.53
0.12 0.25
- 0.4815
- 0.4815
- 0.5686
- 0.2219
- 0.1549
- 0.3188
- 0.2676
- 0.6990
- 0.7447
- 0.9208
- 0.5229
0.506 1 . 3 3 - 0.46
0.159 - 1 . 8 8 0.37
- 2.88 - 0 . 0 1
0.397 - 2.75 0.59
0.436 - 1 . 7 3 0.77
0.237 - 1 . 8 2 - 0.07
0.432 - 3.94 1 . 1 8
0.321 - 1 . 5 6 - 0.35
0.376 - 2.68 0.28
0.443 - 2.22 0.12
0.492 - 2.38 0.25
0.457 - 1 . 5 5 0.64
References page II - 327
II / 324 PATTERNS OF REACTIVITY (U,V) PARAMETERS FOR THE PREDICTION OF MONOMER REACTIVITY RATIOS
TABLE 1. contd
Monomer Category r1s r1A rA1 01 1% (TlS)
n u V
Acrylate, a-cyano-, methyl
Acrylate,
3,4-epoxyhexahydrobenzyl
Acrylate, P-ethoxy-, ethyl
Acrylate, ethyl
Acrylate, methyl
Acrylate, octadecyl
Acrylate, octyl
Acrylate, 2-nitrobutyl
Acrylate, a-phenyl-, methyl
Acrylate, di-zinc
Acrylonitrile
Acryloyl chloride
Ally1 acetate
Ally1 chloride
Aniline, N,N-divinyl
Benzothiazole, vinylmercapto-
Butadiene
Butadiene- 1-carboxylic acid
Butadiene-1-carboxylate, ethyl
Butadiene-1,4-dicarboxylic
acid
Butadiene, 1 ,Cdicarboxylate-,
diethyl
Butadiene, 2-chloro-
Butadiene, 2-fluoro-
Butadiene,
2+imethylsilyloxy-
Carbazqle, N-vinyl
Cinnamonitrile
Citraconimide, N-methyl-
Crotonaldehyde
Crotonate, a-acetyl-, methyl
Crotonate, a-carboethoxy-,
ethyl
Crotonate, a-chloro-, ethyl
Crotonate, cc-cyano-, ethyl
Crotonate, ethyl
Cmtonate, cl-methoq-,
methyl
Crotonate, cc-methyl-,
methyl
Crotonic acid
Diallyl phthalate
Ethylene
Ethylene, tetrachloro-
Ethylene, trichloro-
Ethylene, diphenyl-
Fumarate, dietbyl
Fumarate, diisopropyl
Hexatriene, tetrachloro-
Imidazole, N-vinyl
Isoprene
Isopropenyl isocyanate
Isopropenyl methyl ketone
Itaconic acid
Itaconic anhydride
Maleate, diethyl
Maleic anhydride
Mal ei mi de, N-(2-chlorophenyl)-
Methacrylamide, N-phenyl-
Methacrylate, benzyl
Methacrylate, 2-bromoethyl
Methacrylate, butyl
Methacrylate, isobutyl
5
2
2
3
B
3
2
3
5
2
B
4
3
3
2
3
5
2
2
2
2
4
3
2
4
2
3
2
2
2
2
2
2
2
2
2
4
3
3
4
5
3
5
4
3
4
3
2
3
2
3
4
3
3
3
3
4
4
0.61 0.68 0.01 0.05 - 0.2147 0.180 - 1.09 1.20
1.97 0.39 0.25 0.27 0.2945 -0.110 - 1.95 0.57
0.17 0.87
0.18 0.85
0.26 1.20
0.125 0.84
0.12 1.76
1.28 6.70
0.90 0.24
0.04 1.00
0.02 1 .oo
0.436
0.421
0.417
0.482
0.610
0.438
- 0.060
0.701
0.815
0.04 0.04
0.033 0.05
0.42 0.18
1.40 0.29
5.55 7.5
0.3 3.2
0.52 4.00
2.42 46.98
0.80 0.81
1.42 0.75
3.15 0.61
1.98 0.39
0.67 0.35
0.08 0.06
0.41 1.10
1.00 0.38
1.20 0.10
6.57 90
2.80 36
0.246 5.38
0.19 2.6
0.06 0.57
0.12 0.115
0.3 0.12
0.20 0.15
0.162
0.231
0.020
- 0.100
0.213
0.559
0.502
-0.16 - 1.67
- 1.99 0.08
- 2.34 0.16
- 3.01 0.24
- 3.01 0.41
- 2.39 0.44
- 2.13 1.20
- 1.39 - 0.04
- 2.60 0.42
- 3.50 1.09
- 0.37 - 1.97
- 0.39 - 1.53
- 0.08 -0.73
- 0.38 - 0.38
- 0.30 0.41
- 2.00 0.94
- 2.57 0.92
- 2.18 0.82
0.55 2.79 0.29 0.09
6.91 5.18 0.05 0.038
1.67 0.60 0.077 0.22
1.20 0.07 0.036 0.64
- 0.7696
- 0.7447
- 0.5850
- 2.0000
- 0.9208
0.1072
- 0.0458
- 1.3980
- 1.6990
- 1.3980
- 1.482
- 0.3768
0.1461
0.7443
- 0.5229
- 0.2840
- 0.2596
0.8395
0.2227
0.0792
0.433 - 2.73 1.05
0.113 - 2.18 1.44
- 0.0095 - 1.32 0.51
- 0.324 - 0.21 0.19
0.05 0.36
0.24 0.60
0.07 0.01
0.39 5.82
8.46 2.55
0.53 0.145
2 5 14.7
8.68 2.7
18.7 8.24
- 1.3010 0.491
- 0.6198 0.315
- 1.1549 - 0.164
- 0.25 - 0.58
-2.74 - 0.41
- 2.77 0.59
- 2.33 - 1.17
- 2.72 - 0.43
- 2.51 - 0.92
0.02 0.06 0.345
0.04 0.05
9.53 5.13
11.4 0.26
25.2 27
1.00 18.4
- 1.6990
- 1.3980
- 1.699
- 1.301
- 1.12
- 1.301
0.199
- 2.38 -0.71
- 4.35 0.59
- 1.96 - 1.43
- 0.19 - 1.26
0.02 0.05 2. 97 30. 7 0.315 - 0.55 - 1.49
0.076 0.0385
0.05 0.05
0.06 0.05
0.055 0.20
0.85 4.01
0.68 0.832
1.84 0.45
0.096 0.1
0.48 0.95
0.12 0.86
0.55 4.83
0.04 0.05
0.011 0.05
0.021 1.078
0.88 0.71
0.47 0.96
0.41 2.38
0.53 0.98
0.42 1.05
2 1 20
3.5 23.5
7 14.88
463 195
64.5 14.6
0.05 0.335
9 0.33
1 6 0.4
0.234 0.123
3.39 8.38
0.03 0.458
0.24 7.48
0.33 0.38
0.59 0.26
0.034 0. 03 1
16 7.03
6 0.36
0.956 0.0245
0.381 1.24
0.2 0.52
0.31 0.32
0.291 0.6
0.217 0.54
0.048
0.162
- 1.222 0.131
- 1.26 0.377
- 0.0706 0.421
- 0.1675 0.195
0.2648 - 0.074
- 1.0177 0.170
- 0.3188 0.276
- 0.9208 0.491
- 0.2596 0.526
- 1.398 0.199
- 1.959 0.416
- 1.688 0.826
- 0.0555 0.126
- 0.3279 0.281
- 0.3872 0.455
- 0.2757 0.267
- 0.3768 0.315
- 2.03 - 1.30
- 0.77 - 1.35
- 1.57 - 1.23
- 2.60 - 2.36
- 2.87 - 1.20
- 0.74 0.23
- 4.05 0.56
-4.31 0.17
- 2.39 0.86
- 1.44 - 0.92
- 0.32 0.34
0.14 - 0.87
- 1.91 0.42
- 2.50 0.54
- 2.06 1.51
- 2.51 - 0.83
-5. 20 1.22
- 4.23 1.32
- 1.26 - 0.08
- 1.40 0.26
- 1.97 0.47
- 1.49 0.26
- 1.43 0.27
TABLE 1. contd
Monomers II / 325
Monomer Category r1s r1A rA1 r.31 log hs)
72 U V
Methacrylate, 2-chloroethyl
Methacrylate, ferrocenylmethyl
Methacrylate, glycidyl
Methacrylate, 2-hydroxyethyl
Methacrylate, methyl
Methacrylate,
3,5-dimethyladamantyl
Methacrylate,
2,2,6,6-tetramethyl-
4-piperidinyl-
Methacrylate, phenyl
Methacrylic acid
Methacrylonitrile
Methacryloylacetone
Methylenebutyrolactone
Naphthalene, l-vinyl-
Ott-1-ene,6,6-dimethyl-
4&dioxaspiro(2,5)-
Oxazoline, 2,2-isopropenyl-
Oxazoline, 2,2-isopropenyl-
4,4-dimethyl-
Pentadienoate, tmns-Cethoxy-
2,4-,ethyl
Phthalimide, N-vinyl-
Propene, 3,3,3-trichloro-
Pyridazinone,
3-(2-vinyl)-6-methyl-
Pyridazinone,
jr 3-(2-vinyl)-6-methyl-
4,5-dihydro-
Pyridine, 2-methyl-%vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-5-ethyl-
Pyridine, 4-vinyl-
Silane, 3-methacryloxypropyl,
trimethoxy-
Styrene
Styrene, p-acetoxy-
Styrene, 3-tri-n-butylstannyl-
Styrene, 2,5-dichloro-
Styrene, p-chloromethyl-
Styrene,
p-1-(2-hydroxypropyl)-
Styrene, cr-methoxy
Styrene, cl-methyl
Styrene, p-methyl
Succinimide, N-vinyl
Tetrazole, l-vinyl-
Tetrazole, 5-phenyl-2-
(4-vinyl)-phenyl-
Toluenesulfonamide,
N,N-methyl-vinyl-
Triallyl citrate
Vinyl acetate
Vinyl benzoate
Vinylbenzoic acid, p-
Vinyl benzyl methyl carbinol
Vinyl bromide
Vinyl isobutyl ether
Vinyl butyl sulfide
Vinyl isobutyl suljide
Vinyl tert-butyl suljide
Vinyl chloride
Vinyl chloroacetate
Vinyl dichloroacetate
3
2
3
3
B
3
2
3
4
B
2
3
2
2
4
4
2
2
2
3
3
4
4
4
4
2
B
2
2
4
2
3
5
3
4
4
2
2
3
2
5
3
3
3
3
3
2
4
2
4
2
2
0. 3 1. 30 0. 14 0. 37 - 0. 5229 0. 406 - 1. 39 0. 42
0.01 0. 82 0. 15 3. 6 - 2 0. 898 - 0. 03 - 0. 56
0. 5 1. 32 0. 14 0. 415 - 0. 301 0. 325 - 1. 32 0. 34
0. 64 1 0. 2 0. 48 - 0. 1938 0. 238 - 1. 45 0. 34
0. 46 1.32 0. 138 0. 5 - 0. 3372 0. 339 - 1. 18 0. 23
0. 63 1.30 0. 19 0. 89 - 0. 2007 0. 283 - 1. 04 0.10
0. 30 1 4 0. 02 0. 63 - 0. 5229 0. 806 0. 14 0. 20
0. 51 0. 46 0. 36 0. 25 - 0. 2924 0. 146 - 2. 22 0. 62
0. 524 0. 2 0. 04 0. 24 - 0. 2807 0. 002 - 0. 95 0. 39
0. 33 1. 67 0. 43 0. 38 - 0. 4815 0. 432 - 2. 08 0. 44
1. 66 3. 74 0.01 0. 067 0. 2202 0. 297 - 0. 82 1. 17
0. 1 1.10 0. 09 0. 09 - 0. 1549 0. 237 - 1. 98 0. 88
2. 02 0.451 0. 107 0. 699 0. 3054 - 0. 089 - 0. 83 0. 16
0. 271 1.484 0. 985 1. 93 - 0. 567 0. 446 - 1. 58 - 0. 29
0. 64 0. 52 0. 13 0. 67 - 0. 1938 0. 127 - 0. 95 0. 19
0. 68 1. 83 0. 24 0. 55 - 0. 1675 0. 327 - 1. 51 0. 31
12. 2 5. 40 0.01 0. 04 1. 0864 0. 025 - 1. 14 1.40
0. 07 0. 24 0. 43 6. 27 - 1. 155 0. 367 - 0. 33 - 0. 80
0. 05 0.10 12. 2 6. 9 - 1.301 0. 277 - 2. 35 - 0. 84
0. 85 0.19 0. 32 0. 90 - 0. 0706 - 0. 089 - 1. 36 0. 09
0. 13 0. 02 0. 74 5. 92 - 0. 8861 - 0. 151 - 0. 73 - 0. 57
0. 85 0. 31 0. 16 0. 70 - 0. 0706 - 0. 007 - 1. 04 0. 28
1. 26 0. 44 0.10 0. 53 0.1004 - 0. 014 - 0. 98 0. 32
1. 09 0. 43 0. 04 0. 74 0. 03743 0. 006 - 0. 20 0. 12
0. 69 0. 375 0.10 0. 52 - 0. 1612 0. 06 - 0. 94 0. 30
0. 868 3. 79 0. 094 0. 425 - 0. 0615 0. 408 - 1. 06 0. 37
1 .oo 0. 38 0. 04 1.00 0 0 0. 00 0. 00
1.26 0. 40 0. 07 0. 86 0. 1004 - 0. 030 - 0. 44 0. 07
0. 03 0.001 4. 88 18. 5 - 1. 5229 - 0. 407 - 1. 17 - 1. 27
0. 40 0. 08 0. 24 0. 236 - 0. 3979 - 0. 107 - 1. 98 0. 67
1. 12 0. 56 0. 067 0. 62 0. 0492 0. 046 - 0. 62 0. 21
0. 91 0. 53 0.10 0. 97 - 0.041 0. 071 - 0. 60 0. 16
0. 07 0. 05 0. 06 2. 51 - 1.1549 0. 105 0. 41 - 0. 49
0. 60 0. 143 0. 047 1.1 - 0.2219 - 0. 077 - 0. 04 - 0. 03
0. 993 0. 33 0. 05 0.891 - 0. 003 1 - 0. 021 - 0. 20 0. 08
0. 033 0. 516 0. 116 7.71 - 1.4815 0. 623 0. 75 - 1. 02
0. 184 0. 314 0. 54 3. 85 - 0. 7352 0. 25 1 - 0. 78 - 0. 59
2. 2 1. 4 0. 32 0. 48 0. 3424 0. 088 - 1. 75 0. 32
0. 05 0. 04 0. 42 5. 6 - 1.301 0.126 - 0. 40 - 0.66
0. 076 0. 05 1.76 20 - 1.12 0. 092 - 0. 49 - 1.30
0. 02 0. 05 4. 78 48 - 1.699 0. 315 - 0. 44 - 1. 56
0. 06 0. 019 5. 03 31. 56 - 1.222 - 0. 03 1 - 0. 86 - 1. 45
1. 03 1. 63 0. 06 0. 282 0.0124 0. 238 - 1. 03 0. 50
0. 94 0. 54 0.11 0. 98 - 0. 027 0. 069 - 0. 66 0. 18
0. 054 0. 06 2. 52 16. 6 - 1. 268 0. 179 - 0. 82 - 1. 27
0. 32 0. 40 0. 49 24. 5 - 0. 495 0. 200 0.41 - 1.41
0. 05 0. 041 0. 086 2. 69 - 1. 301 0. 128 0. 14 - 0.43
0. 05 0. 027 0. 074 2. 38 - 1.301 0. 059 0.18 - 0.36
0.158 0. 05 0. 09 4. 36 - 0.8013 - 0. 029 0.41 - 0.64
0. 055 0. 045 3. 29 18. 7 - 1. 26 0. 128 - 0. 90 - 1. 16
0. 03 0. 09 0. 34 45 - 1. 523 0. 345 1.04 - 1. 65
0. 28 0. 04 3. 85 20 - 0. 553 - 0. 162 - 0. 98 - 1. 30
References page II - 327
II/326 PATTERNS OF REACTIVITY (U,V) PARAMETERS FOR THE PREDICTION OF MONOMER REACTIVITY RATIOS
TABLE 1. contd
Monomer Category rlS rlA rA1 TSl 1% (r 1s)
72 u V
Vinyl 2-chloroethyl ether
Vinyl chloromethyl ketone
Vinyl cymantrene
Vinyl dodecyl ether
Vinylene carbonate
Vinyl ethyl ether
Vinyl ethyl oxalate
Vinyl ethyl sulfide
Vinyl ethyl muoxide
Vinylferrocene
Vinyl hendecanoate
Vinylidene chloride
Vinyl isocyanate
Vinyl isothiocyanate
Vinyl methyl ketone
Vinyl phenyl ether
Vinyl phenyl sulfide
Vinyl stearate
Vinyltriethoxysilane
Vinyl-tris(trimethoxysiloxy)
silane
Vinyltrimethylsilane
4 0.07 0.05 1.09 160 - 1.155 0.105 1.18 - 2.06
3 0.507 0.88 0.064 0.127 - 0.295 0.255 - 1.58 0.97
2 0.096 0.05 0.446 2.32 - 1.018 0.053 - 0.97 - 0.37
2 0.82 41.5 0.44 - 1.62
3 0.05 0.08 14.9 70 0.29 0.252 - 1.03 - 1.95
4 0.05 0.06 0.69 100 - 1.301 0.192 1.11 - 2.00
3 1.34 5.62 - 1.11 -0.71
3 0.182 0.055 0.075 5.38 - 0.740 - 0.038 0.66 - 0.77
3 0.10 0.05 I.63 7.82 - I.000 0.046 - 1.02 - 0.94
3 0.17 0.158 0.173 3.57 - 0.7696 0.149 -0.12 - 0.50
3 0.05 0.09 1.88 24.89 - 1.301 0.260 - 0.34 - 1.33
5 0.1075 0.32 0.64 1.79 - 0.9686 0.346 - 1.34 - 0.24
3 0.08 0.16 0.19 8.13 - 1.097 0.277 0.29 - 0.90
3 0.435 1.40 0.36 0.725 - 0.3615 0.357 - 1.56 0.18
2 0.32 1.57 0.61 0.29 - 0.495 0.427 - 2.46 0.54
3 0.01 0.23 2.50 1.70 - 2.000 0.685 - 2.23 - 0.30
3 0.14 0.03 0.11 3.8 - 0.854 - 0.090 0.20 - 0.58
3 0.05 0.078 4.64 15.96 - 1.301 0.236 - 1.19 - 1.15
2 0.05 0.41 6.59 20.86 - 1.301 0.513 - 1.28 - 1.32
3 0.005 0.075 3.90 25 - 2.301 0.616 - 0.84 - 1.46
3 0.05 0.10 4.08 10.32 - 1.301 0.277 - 1.41 - 1.15
TABLE 2. TRANSFER AGENT
Transfer agent Category
cs C A
u V
Acetaldehyde
Acet ami de, NJWimethyl-
Acetic acid
Acetone
Acetonitrile
Ally1 chloride
Aluminium, hydrodiisobutyl
Aluminium, triethyl
Aluminium, triisobutyl
Aniline
Aniline, NJ-dimethyl-
Anthracene
Benzene
Benzene, bromo-
Benzene, tert-butyl-
Benzene, chloro-
Benzene, ethyl-
p-Benzoquinone
Borane, tributyl
Butanone
Butyl alcohol
set-Butyl alcohol
rert-Butyl alcohol
Butyl mercaptan
Butyric acid, 4-hydroxy-y-lactone
Cadmium, dibutyl
Carbonic acid, cyclic ethylene ester
Carbon tetrabromide,
Carbon tetrachloride,
Chloroform
Copper(H) chloride
Cumene
Cyclohexane
3
2
3
4
2
2
3
4
2
4
4
3
4
3
3
4
4
3
3
3
3
3
3
4
2
2
2
0.00085
0.00046
0.000222
0.000032
0.000044
0.00151
27.5
12.5
28.5
0.0020
0.0053
~.000003
0.000178
0.000005
0.000041
0.00007
227
0.00348
0.0005
0.00016
0.000056
0.00003
21.99
0.00004
0.117
0.000024
See methane, tetrabromo-
See methane, tetrachloro-
0.00005
10300
0.00009
0.000005
0.0047 - 0.93 - 3.12
0.0005 - 1.94 - 3.34
0.000081 - 2.61 - 3.80
0.000113 - 1.28 - 4.59
0.0002 - 1.06 - 4.36
0.000595 - 2.57 - 2.82
0.394 - 4.60 1.21
0.059 - 5.46 0.79
2 8 - 2.01 1.45
0.0050 - 1.43 - 2.70
0.0547 - 0.55 - 2.20
1.8 - 2.29 - 0.01
0.000246 0.80 - 5.65
0.000136 - 2.07 - 4.73
0.000193 0.26 - 5.20
0.000079 - 1.49 - 4.51
0.003573 0.49 - 4.28
1.3 -5.19 2.29
0.647 1.29 - 2.95
0.000643 - 1.82 - 3.55
0.001542 - 0.57 - 4.05
0.009755 1.23 - 4.62
0.000044 - 1.75 - 4.62
0.409 - 4.42 1.23
0.00007 - 1.66 - 4.39
5.5 0.39 - 0.93
0.000013 - 2.36 - 4.63
0.000577 - 0.49 -4.17
67.19 - 4.61 4.33
0.004141 0.38 - 4.07
0.000206 0.25 - 4.63
TABLE 2. contd
References II / 327
Transfer agent Category
CS CA
U V
Dimethyl sulfoxide
Diphenylamine-T
Ethane, 1,2-dichloro-
Ethane, 1,1,2,2-tetrachloro-
Ether, dodecyl vinyl
Ethyl acetate
Formamide, N,N-dimethyl-
a-n-Glucoside,
met hyl , 6-deoxy-6-mercapd-
a-n-Glucoside,
methyl-, di-O-benzyl-
a-n-Glucoside, methyl-,
2,3,4,6-tetra-u-acetyl-
a-D-Glucoside, methyl-,
6-(p-toluene sulfonyl)-
cr-rr-Glucoside, methyl-,
6-O-triphenylmethyl-
fl-n-Glucoside, met hyl -,
6-deoxy-6-dipropylamino-
Glycerol
Heptanol, dodecafluoro-
Indium, triethyl
Iron(II1) chloride
Isobutyl alcohol
Isobutyronitrile
Lead, tetraetbyl
Mercury, diethyl
Methane, dichloro-
Methane, tetrabromo-
Methane, tetrachloro-
Methane, nitro-
Methanol
Octadiene, 2,6-dimethyl-
Oxime, acrolein-
Oxime, crotonaldehyde-
Oxime, ethyl isopropenyl ketone-
Oxime, methacrolein-
Oxime, methylacrolein-
Oxime, methyl isopropenyl ketone-
Oxime, methyl vinyl ketone-
Pentanol, octafluoro-
Silane, tetraetbyl
Stibine, tributyl
Tin, tetrabutyl
Toluene
Triethylamine
Tripropylamine
Zinc, diethyl
0.00005 0.000029 - 2.32
0.00009 0.07 2.18
0.0002 0.000147 -2.17
0.00108 0.0003 11 - 2.73
0.000372 0.000495 - 1.82
0.00155 0.000254 - 3.07
0.0001 0.000278 - 1.36
5.5 0.13 -4.31
- 4.44
- 4.57
- 3.82
- 3.39
- 3.43
- 3.28
- 4.00
0.74
2 0.0062 0.009 - 1.76 - 2.21
- 0.32 - 3.70
- 1.00 - 3.70
2 0.0021 0.008 - 1.17 - 2.68
0.43 - 2.66
0.002864 0.00235 - 2.12
0.001333 0.00019 - 3.20
1.76 0.222 - 3.25
536 3.33 - 5.44
0.00005 0.002406 0.41
0.00027 0.00029 - 1.95
0.000124 0.0243 1.28
0.000034 0.00722 1.35
0.000015 0.000306 -0.13
2.2 0.085 - 4.04
0.01 0.000099 - 4.85
0.001 0.0006 - 2.30
0.000074 0.00005 - 2.23
0.0002 0.045 1.37
1.08 62.6 0.53
0.15 2.05 - 0.35
0.43 1.03 - 1.45
1.3 9.41 - 0.77
0.04 5.35 1.03
0.11 1.71 - 0.30
0.27 1.20 - 1.06
0.001136 0.00019 - 3.10
0.000812 0.0021 - 1.30
0.0058 11.1 2.78
0.00037 1 0.00808 - 0.06
0.000012 0.00032 0.26
0.00071 0.304 1.85
0.00242 0.428 1.32
0.366 1.6 - 1.08
- 2.54
- 2.85
- 0.08
2.43
- 4.54
- 3.57
- 3.91
- 4.60
- 4.82
0.37
- 2.09
- 3.09
-4.18
- 3.79
- 0.02
- 1.06
- 0.37
0.13
- 1.25
- 0.90
- 0.67
- 2.93
- 3.02
- 3.27
- 3.69
- 4.84
- 3.04
- 2.89
- 0.44
2
2
2 0.0002 0.003
2 0.0002 0.001
2 0.0022 0.11
2
3
3
3
3
2
2
3
2
4
3
3
3
3
3
3
3
3
3
3
3
3
4
3
3
5
4
4
2
E. REFERENCES
1. R. Z. Greenley, Polymer Handbook, this volume, p. 181.
2. R. Z. Greenley, Polymer Handbook, this volume, p. 309.
3. A. D. Jenkins, J. Polymer Sci., 34, 3495 (1996).
4. C. H. Barnford, A. D. Jenkins, R. Johnston, Transactions.
Farad. Sot., 55, 418 (1959).
5. C. H. Bamford, A. D. Jenkins, J. Polymer Sci., 53, 149 (1961).
6. C. H. Bamford, A. D. Jenkins, Transactions. Farad. Sot., 58,
530 (1962).
7. A. D. Jenkins, Eur. Polymer J., 1, 177 (1965).
8. A. D. Jenkins, Macromol. Chem. Phys. Rapid Commun., 17,
275 (1996).
9. A. D. Jenkins, J. Jenkins, Macromol. Chem. Phys., Macromol.
Symp., 111, 159 (1996).
10. G. C. Eastmond, Comprehensive Chemical Kinetics,
(C. H. Bamford, C. F. H. Tipper (Eds.)), 14A, 105 (1976).
11. A. Ueda, S. Nagai, Polymer Handbook, this volume, p. 97.
Copolymerization Parameters of
Metallocene-Catalyzed Copolymerizations
Gerhard Fink, Wolf Jtirgen Richter
Max-Planck-lnstitut fur Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45466 Mtilheim an der Ruhr, FR Germany
A. Introduction II-329
B. A Brief Theoretical Outline of Copolymerization
React i ons II-329
1. First-Order Markov Model II-330
2. Second-Order Markov Model II-330
C. Calculation of the Copolymerization
Paramet ers I I - 331
1. First-Order Markov Model I I - 331
1 .I. Copolymerization Parameters Deduced
from the Mayo-Lewis Equation I I - 331
1. 2. Determination of Copolymerization
from the Sequence Distribution
(Triad Distribution) Parameters I I - 331
2. Second-Order Markov Model II-332
3. Example II-332
D. Table of Copolymerization Parameters II-333
E. List of CataIysts/CocataIysts Used II-336
F. References II-336
A. INTRODUCTION
In contrast to radical and ionic polymerization reactions in
which the incoming monomer always adds to the end of the
growing chain
the most distinct feature of Ziegler-Natta-catalysis is the
attachment of a monomer molecule to a highly structured
catalyst complex (which may be homogeneously solvated
or heterogeneously fixed to a surface) and its insertion
between the catalyst complex and the growing chain:
Since the structural features of the catalyst - in
particular the steric bulk of ligauds, the bite angle of
metallocenes, the configuration and conformation on the
one hand, and the increasing space-filling demand of the
growing chain and of the various monomers on the other -
do influence the addition of the monomers, elucidation of
the copolymerization behavior, and, in particular, determi-
nation of copolymerization parameters requires correct
modeling, i.e. adequate Markov-statistics.
B. A BRIEF THEORETICAL OUTLINE OF
COPOLYMERIZATION REACTIONS
Various mathematical models have been applied to
copolymerization reactions induced by Ziegler-catalysts.
Wall (1) assumed the velocity of the monomer addition M i
and M2 to be independent of the previously integrated
monomeric unit (zero-order Markov model):
R-Kat + M i kl R-M i -Kat
R-Kat + M2 2 R-M,-Kat
R = Polymer chain
This scheme gives rise to the following equation for a
copolymerization reaction:
dW11 [MI] kl
d[M2l=l-
r=-
[M21 k2
Mayo and Lewis (2) extended this model by including the
influence of the last built-in monomer into the chain during
the subsequent step (first-order Markov model):
R-Ml-Kat + Ml kR-Mi-Mi-Kat
R-Ml-Kat + M2 -% R-Ml-M2-Kat
R-Mz-Kat + Ml 2 R-M2-Ml-Kat
R-MT-Kat + M2 % R-M2-M2-Kat
This results in the so-called Mayo-Lewis equation,
d[21 _ h421 rdbb]/[Ml]) + 1
dbbl
[Ml] ([M2]/[Ml]) + rl
with rl =kll/k12 and r2 = k22/k21. Taking the effect of
II 1329
II 1330 COPOLYMERIZATION PARAMETERS OF METALLOCENE-CATALYZED COPOLYMERIZATIONS
the last two built-in monomers into account, Merz, et al. (3)
developed a second-order Markov model. This penultimate
model necessarily results in a more complex kinetic
scheme:
R-MI-MI-Kat + Ml kill R-MI-Ml-Ml-Kat
R-MI-Mt-Kat + MT kR-Ml-Ml-Mz-Kat
R-M2-Ml-Kat + MI %R-Mz-Ml-Ml-Kat
R-M2-Mt-Kat + M2 % R-M2-MI-M2-Kat
R-it-M2-Kat + Ml %R-MI-M2-MI-Kat
R-MI-M2-Kat + M2 k R-MI-M2-M2-Kat
R-M2-M2-Kat + MI %R-MZ-M2-MI-Kat
R-M2-M2-Kat + M2 % R-M2-M2-M2-Kat
With ~11 = kttt/k
112, ~21 = k2ll/k212, ~22 = km/km and
Y t2 = k 122/k t2t, the following copolymerization equation is
obtained:
4Md
1+ r2lx(l+ rllx)/(l +r21X)
_
d[Mz] 1 + (02,~) (1 + r22/-4/(1 + y12/x)
with x = [Mt]/[M2].
Expanding this model even further to the influence of the
last three monomeric units, Ham (4) proposed a third-order
Markov model. However, due to the many parameters
involved, it has been of little practical use.
Thus, most authors restrict themselves to first- or second-
order Markov models when dealing with Ziegler-Natta-
catalysis for copolymerization, and this is elaborated
below.
1. First-Order Markov Model
The Mayo-Lewis equation describes the composition of a
copolymer as a function of the composition of the monomer
mixture and their respective copolymerization parameters.
These parameters not only determine the composition of the
resulting copolymer, but also its microstructure, e.g. the
distribution of the sequence length.
A knowledge of the ratio of the starting monomers and
their copolymerization parameters enables the sequence
length distribution to be calculated. The reactivity prob-
abilities PC are defined (5,6) that give the probability of the
monomer j adding to the polymer chain with the termina-
ting monomer i:
kll[R-Ml-Kat][Ml]
11 = ktt[R-Ml-Kat][Mt] + ktz[R-Ml-Kat][Mz]
= rl + ,$,[Ml]
kl2[R-Ml-Kat][M2]
12 = ktt[R-MI-Kat][Mt] + ktT[R-Ml-Kat][Mz]
1
= rI[Ml]/[M2] + 1
k21 [R-Mz-Kat] [M 11
p21 = k21 [R-Mz-Kat] [MI] + kz,[R-M2-Kat][M2]
1
= 1 + dM2]/[Ml]
= k21 [R-Mz-Kat] [M t] + k22[R-M2-Kat] [M2]
=b41l/[G2] + r2
with P11 + P12 = 1 and P21 + P22 = 1
The proportion of the M 1 and M2 units (P 1 or P2) in
the copolymer is also determined by reactivity probabil-
ities:
Pl = lPlPll+ lP2P21
lP2 = PIP12 + lP2P22
giving Pl = p21,p12 fP21)
and
92 = p12,
(P 12 +P21).
All the potential sequence distributions can thus be
calculated. Consider, for example, the triad distributions:
MlMlMl = %PllPll
= [P21(1 - p12)2],[p12 + p211
MlMlMz + M2MlMl = 2 PlP11P12
= 2[P21(1 - P12)Pl2],[P12 +p21]
M2MlM2 = 1P2f21P12
= [p:2p211,[p12 +p211
MNN2= 92P22P22
= [P12(1 - p21)2],[p12 + p211
MzMzMl + MlM2M2 = 2 P1P12P22
= qp21p12(1 - P21)],[Pl2 +p211
MlMNl = 1W12P21
= [p;,p12l,[f?2 +p211
The triad distribution allows the calculation of the true
copolymerization parameters. For a given polymer, the triad
distribution is deduced from experimental 13C-NMR
spectra (7) (see below).
2. Second-Order Markov Model
The kinetic scheme for this model gives rise to eight
reaction probabilities Pqk that result from the probability of
the monomer k adding to the polymer chain with the
terminating monomers ij. The reactivity probability P 121 is
j
i
i
I
given for instance as
Calculation of the Copolymerization Parameters II / 331
1. First-Order Markov Model
1
I
= 1 + 732([~2]/[M1])
I
with PHI +P112 = 1, P222 + P221 =1, P122 + P121 = 1,
p211 +p212 = 1.
The triad distribution is calculated in a manner
/
analogous to the first-order Markov model:
!
MIMIMI = lP~~P~~~
I
MlMlMz + M2MlM1 = 2 PllP112
MzMlM2 = P21P212
MN2M2 = P22P222
MzMzMl + MlM2M2 = 2 P22P221
MIMZMI = P12P121
I
Pd is the frequency of the diad ij, and is calculated as
t
1
follows:
Pll = lfwlll + P21P211
922 = 922P222 + P12P122
+12 = 1Pllh12 + 921P212
+21 = 922p221 + 1P12P121
I
It results in
i
P*1 =
(1 - Plll)(l - P222)
2(1 - Plll)(l - P222) +P21l(l - P222) + PI&l - P1,1)
I
PI I =
(1 - P222)P211
2(1 - Plll)(l -P222) +Pz11(1 - P222) + Pm(1 -PI,,)
I
P*2 =
(1 - Plll)Pl22
,
2(1 - Plll)(l - P222) +P211(1 - P222) +Pm(1 - PI I ,)
The diad frequency Pij is PI2 = lP21 and
Pll + 2lP12 + 1P22 = 1
1
C. CALCULATION OF THE COPOLYMERIZATION
PARAMETERS
Once the copolymerization parameters of a catalyst system
1
with a given ratio of monomers are known, the composition
of the copolymer and all its sequence distributions result,
e.g., the complete microstructure of the copolymer is
1
revealed. These parameters characterize any catalyst system
and enable different systems to be compared. The major
practical problem is the choice of the adequate statistical
model.
1.1. Copolymeriza tion Parameters Deduced from the
Mayo-Lewis Equation The Mayo-Lewis equation cal-
culates the composition of the copolymer formed as a
function of the ratio of the monomer concentration at a
given time. At arbitrary intervals these values are generally
inaccessible; thus a sufficiently small interval (a small
percent of the total conversion) is taken and the relative
change of the monomer concentration d[Mz]/d[M1] is
assumed to be the composition of the copolymer
([ml], [mz]) itself according to
lim(d[M$d[Md = [m]/[ml]
dU-0
It is advisable to keep the monomer ratio [Mz]/[M 11
constant during polymerization by constantly feeding
both monomers, or at least the most reactive monomer.
To determine the copolymerization parameters the experi-
ments are run with varying ratios of the starting monomers,
and their compositions are subsequently measured. The
data obtained can be analyzed by linear or nonlinear
methods.
Linear Methods: Mayo and Lewis (2), Fineman and Ross
(8), Kelen and Ttidos (9)
Nonlinear Methods: Behnken (lo), Tidwell and Mortimer
(1 l), Braun et al. (12)
Independent of the analytical methods the copolymer-
ization parameters derived from the Mayo-Lewis equation
have some major drawbacks, but do enable a part of the
information contained in each copolymerization experiment
to be extracted, namely the integral composition of the
copolymer. A series of experiments is necessary to obtain
the copolymerization parameters. Furthermore, using this
approach it cannot be decided whether the application of
the first-order Markov model is valid or not. One may even
obtain a nearly perfect Fineman-Ross plot, where other
methods show that a first-order Markov model cannot be
applied.
1.2. Determination of Copolymeriza tion Parameters
from the Sequence Distribution (Triad Distribution)
As mentioned above, a knowledge of the copolymerization
parameters enables all the sequence distributions to be
calculated. Or inversely, experimentally determined
sequence distributions yield the copolymerization para-
meters. In the simplest case, intensities of appropriate
single sequences can be compared. The results are even
more reliable, if the determination of the copolymerization
parameters is based on the maximal accessible information
on the microstructure of the copolymer. To derive the r-
parameters from the overall triad distribution is the safest
way (13). This may be done by calculating a triad
distribution based on a first-order Markov model and
optimizing by variation of the reaction probabilities P,
until the best fit between calculated and experimental data
References page II - 336
II / 332 COPOLYMERIZATION PARAMETERS OF METALLOCENE-CATALYZED COPOLYMERIZATIONS
is reached. Based on the optimized reaction probabilities
the copolymerization parameters ri and r2 are calculated
according to the following equations:
rl = ([W121 - l)([M21/[Ml])
r2 = ([l/f211 - l)([Ml]/[M21)
This, procedure for determining the copolymerization
parameters is superior to the Mayo-Lewis approach. While
the latter requires several experiments, using the above
approach, all the information can be obtained from one
experiment.
To determine the copolymerization parameters from the
triad distribution, six variables are available, five of which
are independent. The system is over-determined and thus
allows critical evaluation.
2. Second-Order Markov Model
The second-order Markov model gives four copolymeriza-
tion parameters, which are gained from the sequence
distribution (full triad distribution) with a high degree of
reliability. The calculated triad distribution from the
second-order Markov model is optimized by varying the
reaction probabilities PUk until the best fit is reached. The
four copolymerization parameters are calculated from
reaction probabilities P$ as follows (l3- 15):
m = ([l/P1121 - l)([M2]/[Ml])
~21 = ([l/P2121 - l)([Mz]/[Ml])
r22 = ([l/P2211 - l)([Mll/[M21)
~12 = ([l/P1211 - l)([Ml]/[M2])
The second-order Markov model results in four copoly-
merization parameters from six variables based on triad
distribution. A higher degree of determination clearly is
desirable to justify this copolymerization model. However,
the complete distribution is not obtained from 13C-NMR
spectra of ethenela-olefin copolymers. The full triad
distribution does not exhaust the full information of the
spectra, since some peaks exhibit tetrad or even pentad
sensitivity. Cheng (16,17) suggested that all recorded peaks
of a 13C-NMR spectrum should be included to calculate the
copolymerization parameters. Arbitrarily chosen reaction
probabilities give rise to a polymer chain built at random,
and its 13C-NMR spectrum is calculated. This spectrum is
superimposed on the experimental one and optimized by
varying the starting values, until the minimal difference is
reached. Since the 13C-NMR spectra of ethenela-olefin
copolymers display many overlapping peaks, the quality of
the spectra simulation very much influences the success of
this method.
Randall (7) found a way to avoid this problem by
creating a collective assignment method. Here the
complete triad distribution results from combining the
experimental spectral information with the relation between
different n-ades. In the first step the 13C-NMR spectrum of
an ethenela-olefin copolymer is split into several spectral
areas given by signal overlap. The 13C-NMR spectra of
ethene/propene copolymers, for example, are divided into
eight appropriate spectral areas A to H, as shown in Fig. 1.
The integrals TX of different spectral areas are expressed by
the number of contributing triads ending up in the complete
triad distribution by appropriately combining several
TX-data. Randall exemplified this method in detail for
ethene/propene-, ethene/l-butene-, and ethene/l-hexene-
copolymerizations (7).
The resulting triad distribution allows the composition of
the copolymer
[ml] =MlMlMl +M&flM2+MNlMl +MlMlM2
[mz] = M2M2Mz +MiMMi +M&I&Ii +MiMM2
and the average sequence length:
n(Mi) = [mi]/[M2MiM2 + 0.5 (M2M1M1 + M~M~M~)]
n(M2) = [mz]/[MiM2Mi + 0.5 (M2M2M2 + M2M2M1)]
to be calculated.
3. Example
To demonstrate which model describes the experimental
results best, the following table from a recent publication by
Fink is reproduced (15). It is based on ethene/l-octene
copolymerization experiments using a homogeneous metal-
locene/MAO catalyst.
a r e a C
area B
a r e a D
ar ea A
Fi gure 1. 13C-NMR spectrum of an ethene/propene copolymer.
Copolymerization Parameters II / 333
COMPARISON BETWEEN THE EXPERIMENTAL MEASURED TRIAD DISTRIBUTION AND THE CALCULATED TRIAD
DISTRIBUTION ACCORDING TO THE FIRST- (Ml) AND THE SECOND-ORDER (M2) MARKOVIAN-STATISTIC OF
THE ETHYLENE (E)/l-OCTADECENE (0) COPOLYMERIZATIONU
KWEI
in solution Model EEE EEO + OEE OEO 0 0 0 EOO + OOE EOE Rb (x 106)
0.28
1.39
1. 41
2.84
7.14
14.18
Exp. 0.976 0.014 0.000 0.000 0.001 0.008
-
Ml 0.980 0.004 0.000 0.011 0.004 0.000 5 0
M2 0.976 0.014 0.001 0.000 0.001 0.008 0.22
Exp. 0.878 0.077 0.004 0.000 0.004 0.038
-
Ml 0.878 0.078 0.002 0.000 0.004 0.038 0
M2 0.878 0.078 0.003 0.000 0.004 0.039 0.3
Exp. 0.883 0.074 0.005 0.000 0.005 0.033
-
Ml 0.883 0.074 0.002 0.000 0.006 0.035 0
M2 0.882 0.072 0.003 0.000 0.006 0.036 6.27
Exp. 0.795 0.118 0.011 0.006 0.008 0.063
-
Ml 0.798 0.124 0.005 0.000 0.010 0.062 2 0
M2 0.795 0.117 0.010 0.006 0.008 0.064 0.64
Exp. 0.878 0.143 0.020 0.011 0.011 0.084
-
Ml 0.738 0.158 0.008 0.001 0.014 0.080 9 0
M2 0.731 0.143 0.019 0.011 0.011 0.085 0.27
Exp. 0.718 0.112 0.046 0.010 0.030 0.084
-
Ml 0.733 0.153 0.008 0.005 0.035 0.066 6 1 0
M2 0.718 0.111 0.045 0.010 0.031 0.085 0.60
T, = 6OC, Kat: iPr(CpFlu)ZrC12 and MAO, [Zr] = 7.56 x 10 -6 m&l, Al/Zr = 9800.
*R is the sum of the least squares divided by the number of measured values.
If the experimentally determined triad distribution is Second-order Markov statistics is only applicable
compared with the calculated values based on a first-order when there is a sufficiently high comonomer concentra-
or alternatively on a second-order Markov model (Mi or tion in solution, and enables the formation of a-olefinl
M2 of the table), both models give a reasonable good fit up a-olefin dual-blocks. Now the insertion of another
to a monomer/comonomer ratio in solution of 1.5. Beyond a a-olefin unit into this dual-block sequence is preferred
ratio of 3, however, the second-order Markov model proves to that into in a single-block. The complete triad dis-
to be the better approximation as indicated by the sum of tribution is gained by this procedure and it has to be
the error squares divided by the number of experimental performed over a wide range of the monomer/comonomer
values (R of the table). ratio in solution.
D. TABLE OF COPOLYMERIZATION PARAMETERS
Monomer/
comonomer r1 r2 J.11 r21 r22
CatJ Model Analytical
r-12 cocat. Remarks
TPoly (C)
tested method * Refs.
Ethenelpropene
6.26
6.61
18.6
2.57
2.90
15.7
1 6 . 1
20.6
12.43
5.1
1 . 3
5.60
4.23
25.42
13.75
16.53
19.61
2 4
0.11
0.06
0.032
0.39
0.28
0.009
0.025
0.074
0.08
0.14
0.2
0.13
0.12
-
0.18
-
-
0.0085
3.4 2.2 0.270 0.153 19 2 5 Ml; M2 C. T. A. 1 3
4.1 3.9 0.153 0.065 28 2 5 Ml; M2 C. T. A. 1 3
2 4 2 5 Ml F.-R. 1 8
2 4 5 0 Ml F.-R. 1 8
2 3 6 Ml F.-R. 1 9
2 4 5 0
-
See Ref. 20 2 0
2 5 5 0
-
See Ref. 20 2 0
1 5 0
-
See Ref. 20 2 0
7 5 0
-
See Ref. 20 2 0
3 5 5 0
-
See Ref. 20 2 0
2 9 A a 120-220 Ml F.-R. 2 1
2 4 0 Ml F.-R. 2 2
1 9 2 5 Ml F.-R. 2 2
2 4 Bb 4 0 Ml See Ref. 24 2 3
2 8 B 4 0 Ml See Ref. 24 2 3
1 3 B 4 0 Ml See Ref. 24 2 3
1 2 B 4 0 Ml See Ref. 24 2 3
7 B 4 0 Ml See Ref. 24 2 3
1 1 B 4 0 Ml See Ref. 24 2 3
4 5 0 Ml F.-R. 2 5
*C.T.A. - Complete Triad Analysis (7); D.A. - Diad Analysis (28); F.-R. - Fineman-Ross (8); K.-T. - Kelen-Tiidas (9); M.-L. - Mayo-Lewis (2).
References page II - 336
II/334 COPOLYMERIZATION PARAMETERS OF METALLOCENE-CATALYZED COPOLYMERIZATIONS
Monomer/ Cat./ Model Analytical
comonomer rt r2 r11 r21 r22
r12 cocat. Remarks
TPoly (0
tested met hod Refs.
Ethene/
I-butene
19.5
5 0
4 8
2 4
2. 50
6 0
3.9
4.4
5.5
19.4
23.6
29.2
5.4
6.6
6.8
Ethenel
1 -hexene
32.67 0.027
44.75 0
62.31 0.003
74.60 0
31.00 0.013
36.00 0
88.00 0.005
86.70 0
5 5 0.004
5 4 0.005
5 2 0.005
7 9 0.005
1-octene
Ethenel
1 -dodecene
20.2
-
2.5 0.55
42.28 0.035
43.35 0
61.56 0.03
99.43 0
4.71 0.23
6.36 0.18
8.16 0.14
10.6 0.11
1 0 . 1 0.03
7.5 0.07
10.1 0.118
18.9 0.014
19.5 0.013
10.7 0.076
Ethenel
1-octadecene
Ethenelstyrene
Ethene/2-allyl-
norbornane
23.4
43.7
42.6
0.015
0.007
0.015
0.029
0.002
-
0.12
0.12
0.11
3 5 0 Ml F.-R. 2 5
8 5 0 Ml F.-R. 2 5
6 5 0 Ml F.-R. 2 5
2 7 5 0 Ml F.-R. 2 5
1 0 5 0 Ml F.-R. 2 5
9 5 0 Ml F.-R. 2 5
3 7 B 4 0 Ml see ref. 24 2 6
3 7 B 6 0 Ml see ref. 24 2 6
2 4 B 4 0 Ml see ref. 24 2 6
3.6
7.9
0.05
0.03
0.04
0.17
0.10
0.21
2.9 0.21
6.8 0.085
0.041 19 2 5 Ml; M2 C. T. A. 1 3
0.017 28 2 5 Ml; M2 C. T. A. 1 3
2 4 3 0 Ml F.-R. 2 7
2 4 5 0 Ml F.-R. 2 7
2 4 7 0 Ml F.-R. 2 7
3 7 3 0 Ml F.-R. 2 7
3 7 5 0 Ml F.-R. 2 7
3 7 7 0 Ml F.-R. 2 7
3.2 2.6 0.150 0.065 19 2 5 Ml; M2 C. T. A. 1 3
10.3 6.4 0.111 0.022 28 2 5 Ml; M2 C. T. A. 1 3
5.93 4.58 0.130
7.95 6.60 0.109
10.08 8.85 0.098
2 6 6 0 Ml F.-R. 2 9
2 6 6 0 Ml D. A. 2 9
6 6 0 Ml F.-R. 2 9
6 6 0 Ml D. A. 2 9
2 4 6 0 Ml F.-R. 2 9
2 4 6 0 Ml D. A. 2 9
1 2 6 0 Ml F.-R. 2 9
1 2 6 0 Ml D. A. 2 9
6 2 0 Ml F.-R. 3 0
6 4 0 Ml F.-R. 3 0
6 6 0 Ml F.-R. 3 0
6 7 0 Ml F.-R. 3 0
0.034 19 2 5 Ml; M2 C. T. A. 1 5
0.024 19 4 0 Ml; M2 C. T. A. 1 5
0.022 19 6 0 Ml; M2 C. T. A. 1 5
6 B 8 5 Ml D. A. 3 1
5 B 8 5 Ml D. A. 3 1
2 6 6 0 Ml F.-R. 2 9
2 6 6 0 Ml D. A. 2 9
6 6 0 Ml F.-R. 2 9
6 6 0 Ml D. A. 2 9
3 2 0 Ml C. T. A. 3 2
3 2 2 0 Ml C. T. A. 3 2
3 2 4 0 Ml C. T. A. 3 2
3 2 6 0 Ml C. T. A. 3 2
2 4 4 0 Ml see ref. 24 2 6
2 4 6 0 Ml see ref. 24 2 6
3 2 4 0 Ml C. T. A. 3 3
2 8 4 0 Ml C. T. A. 3 3
3 0 4 0 Ml C. T. A. 3 3
3 1 4 0 Ml C. T. A. 3 3
7.2 5.0 2.9 0.057 19 2 8 Ml; M2 C. T. A. 3 4
12.0 5.7 0.3 0.036 28 2 8 Ml; M2 C. T. A. 3 4
11.2
14.7
38.45
0.015
6.3 1.6
8.4 0.4
18.58 0.085
0.044 19 2 8 Ml; M2 C. T. A. 3 4
0.035 28 2 8 Ml; M2 C. T. A. 3 4
0.041 19 6 0 Ml; M2 C. T. A. 1 5
5 4 0 Ml F.-R. 35,46
0.038 6 3 5 Ml F.-R. 3 6
0.027 6 3 5 Ml K. - T. 3 6
Monomer/
comonomer
rt r2 rll r2t r22
Copol ymeri zat i on Paramet ers II / 335
Cat./ Model Analytical
r12 cocat. Remarks
TPoly (Cl
tested met hod Refs.
Ethenel
cycl opent ene 80
120
250
300
1 . 9
2.2
Ethenel
norbomene 2.66
3.44
2.93
2.61
1 . 8 5
1 . 5
1 . 9
2.2
3.2
20
6.6
2.6
3.4
2.0
3.0
3 . 1
Ethene/norbomene
0.88
1.14
1.1
0.83
1 . 3
< 0.05 24 - 10 Ml F. - R. 39
<0.02 24 0 Ml F. - R. 39
< 0.02 24 1 0 Ml F. - R. 39
< 0 . 0 7 24 20 Ml F. - R. 39
<l 2 5 0 Ml F. - R. 40
<l 2 5 2 5 Ml F. - R. 40
n.d. 28 30 Ml F. - R. 37
n.d. 34 30 Ml F. - R. 37
n.d. 1 9 30 Ml F. - R. 37
n.d. 23 30 Ml F. - R. 37
n . d . 23 0 Ml F. - R. 37
n.d. 2 5 - 25 Ml F. - R. 38
n.d. 25 0 Ml F. - R. 38
n.d. 25 25 Ml F. - R. 38
n.d. 2 5 50 Ml F. - R. 38
n.d. 6 2 5 Ml F. - R. 38
n.d. 24 2 5 Ml F. - R. 38
<2 28 30 Ml F. - R. 40
0.06 1 9 30 Ml F. - R. 40
0.05 23 0 Ml F. - R. 40
0.05 23 30 Ml F. - R. 40
0 22 30 Ml F. - R. 40
0.05
0 . 1
0.026
0.29
0.03
1 . 2
2.2
2.2
5.2
2.2
EthenelS-phenyl-2-norbomene
7.8 0.1
7.0 0.05
Etbene/dimethanooctahydronaphthalene
7.8 0 . 1
7.0 0.05
7 . 1 0.04
Ethene/phenyldimetbanooctahydronaphtbalene
1 1 . 5 0.05
7 . 1 0.03
Ethenekrimethanododecahydroanthracene
15.6 0.06
Propene/l-octene 3 . 3 0.39
3.6 0.32
2.6 0.37
2.4 0.48
Propenelcyclopentene
40 0.001
1 5 70 Ml K.-T. 4 1
1 6 70 Ml K.-T. 4 1
1 7 70 Ml K.-T. 4 1
1 4 70 Ml K.-T. 4 1
1 9 70 Ml K.-T. 4 1
3.6 0 0 20 Cd 70 M2 C. T. A. 4 1
2.7 0 0 2 1 C 70 M2 C. T. A. 4 1
8.9 0 0 22 C 70 M2 C. T. A. 4 1
18.2 0 0 33 C 70 M2 C. T. A. 4 1
54 0 0 5 C 70 M2 C. T. A. 4 1
28 30 Ml M.-L. 43
1 9 30 Ml M.-L. 43
23 50 Ml F. - R. 40,42
1 8 50 Ml F. - R. 40,42
38 50 Ml F. - R. 40,42
28 30 Ml M.-L.
1 9 30 Ml M.-L.
23 50 Ml F. - R.
28 40 Ml D.A.
30 40 Ml D.A.
3 1 40 Ml D.A.
32 40 Ml D.A.
28 60 Ml K.-T.
43
43
40
44
44
44
44
45
High pressure copolymerization (loo- 150 MPa).
*[Monomer]/[Comonomer] ratio varied. The cited r-values hold only for a selected ratio of [Ethene]/[Propene].
Not det er mi ned.
dAltemating copolymerization, hence, r12 = r22 = 0.
References page II - 336
II / 336 COPOLYMERlZATlON PARAMETERS OF METALLOCENE-CATALYZED COPOLYMERIZATIONS
E. LIST OF CATALYSTS/ COCATALYSTS USED
1 [Cp] zTiCl2 MAO
2 [CPI 2TiMe 2 AlMe 3
3 [Cp] 2TiPh 2 MAO : AlMe 3
4 [Cp] 2Ti = CH2 AlMe 2Cl
5 MezSi[Me&pNt-Bu]TiC12 MAO
6 [CPI 2zc12 MAO
7 [CPI 2ZK12 MAO : AlMe 3
8 WPI 2ZrCl2)O MAO : AlMe 3
9 [MeCp] 2ZrCl2 MAO : AlMe 3
1 0 [C&h12Zf12 MAO : AlMe 3
11 [n-Bu-Cp] 2ZrCl2 MAO
1 2 [lnd] 2ZrCl2 MAO
13 [lnd] 2ZrBenzylz MAO
1 4 MeCH[Cp] 2ZrC12 MAO
15 Me zC[Cplnd]ZrC12 MAO
1 6 Me zC[MeCplnd]ZrC12 MAO
1 7 Me2C[3-t-BuCplndlZrC12 MAO
1 8 Ph zC[Cplnd]ZrC12 MAO
1 9 MezC[CpFlu]ZrClz MAO
20 MezC[3-MeCpFlulZrC12 MAO
2 1 Me2C[3-PropCpFlulZrC12 MAO
22 Me2C[3-t-BuCpFlulZrC12 MAO
23 Ph2C[CpFlu]ZrC1 2 MAO
24 C2H4[lnd]2ZrC12 MAO
25 CzHd[lndH4] 2ZrCl2 MAO
26 Me#i[Cp] 2ZrC12 MAO
27 Me#i[Cp]zZrCl2 MAO : AlMe 3
28 Me#i[lnd]2ZrC12 MAO
29 Modified silylbridged [lndH4] 2ZrCl2 MAO
30 MezSi[2-Melnd]2ZrCl2 MAO
3 1 Me#i[Benz(e)lnd] 2ZrCl2 MAO
32 Me #i[2-MeBenz(e)lnd] 2ZrCl2 MAO
33 Me2Si[3-t&BuCpFlu]ZrCl2 MAO
34 Ph#i[lnd]zZrClz MAO
3 5 KPI 2HfCl2 MAO
36 MezC[CpFlu]HfCl2 MAO
3 7 C2H4[lnd]2HfCl2 MAO
3 8 Ph2C[CpFlu]HfC12 MAO
(1 : 1 mixture)
(Tebbe reagent)
(1 : 1 mixture)
(1 : 1 mixture)
(1 : 1 mixture)
(1 : 1 mixture)
(1 : 1 mixture)
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Rates of Polymerization and Depolymerization,
Average Molecular Weights, and Molecular
Weight Distributions of Polymers
L. H. Peebles, Jr.
Chemistry Division, Naval Research Laboratory, Washington, DC, USA
A. Introduction II-339
B. Reference Tables for the Calculation of
Rates of Polymerization, Average Molecular
Weights, and Molecular Weight Distributions
of Polymers for Various Types of
Polymerization II-340
Table 1. Addition Polymerization with
Termination II-341
Table 2. Addition Polymerization - Living
Polymers with Partial Deactivation II-344
Table 3. Linear Condensation Polymerization
without Ring Formation II-346
Table 4. Equilibrium Polymerization II-347
Table 5. Nonlinear Polymerization Systems II-348
Table 6. Degradation of Polymers - May be
Accompanied by Crosslinking II-350
Table 7. Influence of Reactor Conditions and
Design on the Molecular Weight
Distribution II-352
C. Some Distribution Functions and Their
Properti es II-352
1. Normal Distribution Function
(Gaussian Distribution) II-353
2. Logarithmic Normal Distribution Function II-353
3. Generalized Exponential Distribution II-354
4. Poisson Distribution
II-354
D. Molecular Weight Distribution in Condensation
Polymers: The Stockmayer Distribution
Function II-354
E. Ref erences
II-356
A. INTRODUCTION
An attempt is made to present a systematic guide to the
literature dealing with rates of polymerization, average
molecular weights, and molecular weight distributions of
polymers for various types of polymerization. This chapter
is based on a review of molecular weight distributions (1) in
which many of the equations are given in detail along with
graphs showing the interrelationship among various dis-
tributions; here, we present only references to the literature.
In addition, sections have been added on the effects of
degradation and reactor design on the reaction rates and the
molecular weight distributions. Literature references
beyond (312) are those that have been added since the
third edition of Polymer Handbook.
The theoretical description of the molecular weight
distribution of a polymer and its rate of polymerization is
dependent on the assumed mechanism of polymerization
and on the mathematical simplifications used to obtain
analytical expressions. As the number of distinct reactions
is increased, such as the various transfer reactions, the
mathematical expressions can become quite complex and
unwieldy. In general, the equations for the rate of poly-
merization are the most difficult to describe, the distribution
equations are somewhat easier, and the average molecular
weights the simplest. In condensation polymerization, many
of the distribution formulas are derived by considering the
statistics or the probability of a given reaction instead of the
kinetics of the reactions. Depending on which assumptions
are made, quite different average molecular weights are
derived, despite the rigor of the derivation. The emphasis in
this section is, therefore, on the distribution functions and
their averages; the rates of polymerization are given only if
they have been explicitly derived.
This chapter is divided into several tables and sections,
each treating various types of polymerization. The Stock-
mayer distribution function for condensation polymers is
given in detail because of its general applicability and
usefulness. Some general distribution functions are given in
Section C. For all the other expressions, the reader must
refer to the original literature. Many of the simpler
functions are adequately described in textbooks of polymer
chemistry. Flory (2), Bamford et al. (3), Odian (4),
Billmeyer (5), and Kuechler (6) give extended descriptions
of many systems. Bagdasarian (7) gives an extended
discussion of methods of determining absolute values of
propagation and termination constants, the influence of
cage effects on the rate of initiation, and the influence
II / 339
II / 340 RATES OF POLYMERIZATION, AVERAGE MOLECULAR WEIGHTS, AND MOLECULAR WEIGHT DISTRIBUTIONS OF POLYMERS
of retardation, inhibition, and diffusion-controlled termina-
tion on the rate of polymerization. A review of the various
ways of deriving molecular weight distributions and the
moments of a distribution is given by Chappelear and
Simon (8).
Section B presents a series of tables describing the main
assumption or conditions imposed on the theoretical models
and references to the articles where the corresponding
equations may be found. Tables 1 and 2 present rate
equations and the distribution formulas for addition poly-
merization by a variety of mechanisms. No distinction is
made among free radical, cationic, anionic, or coordination-
type polymerization. While Table 1 treats those cases where
termination reactions predominate and where steady-state
assumptions are usually made, Table 2 treats those cases
where termination reactions either do not exist, or may be
considered as side reactions, having a minor to major
control over the molecular weight distribution. The
sequence length distributions for addition-type copolymers
are omitted. However, see Kuechler (6) for an extended
discussion of copolymerization distributions. Table 3
contains distribution formulas for linear condensation
polymers in which the polymer is assumed to be perfectly
linear and to contain no rings. Table 4 treats equilibrium
polymerization. Table 5 describes nonlinear systems. Table
6 treats those cases where polymers are degraded (or
altered) by the application of heat, light, or ionizing
radiation. In the latter case, the polymer may undergo
scission, crosslinking, or both reactions simultaneously.
Several references on crosslinking are included here but not
in Table 5. Finally, Table 7 is concerned with the influence
of reactor design on molecular weight distribution; the
kinetic equations for addition polymerization (with and
without termination) and condensation polymerization are
considered.
Section C lists a number of distribution functions and
their properties. Among them is the generalized exponential
function which is a good approximation to many real
systems (Eq. C29).
Section D presents the Stockmayer distribution function
for condensation polymerization wherein molecules of
various types of kind A react with molecules of various
types of kind B.
B. REFERENCE TABLES FOR THE CALCULATION OF
RATES OF POLYMERIZATION, AVERAGE MOLECULAR
WEIGHTS, AND MOLECULAR WEIGHT DISTRIBUTIONS
OF POLYMERS FOR VARIOUS TYPES
OF POLYMERIZATION
The following symbols are used in this chapter. R,: rate of
polymerization; Rd: rate of depolymerization; R ;: active,
growing polymer containing one monomer unit; R;E and Q;l:
active, growing polymer chains containing IZ monomer
units; P,: molecular weight distribution; ki: rate constant
for initiation; k,: rate constant for propagation; I: initiator
concentration; M: monomer concentration; M, and M,:
number-average and weight-average molecular weights,
respectively; 1 and 2 represent first and second order,
respectively. No distinction is made among free radical,
cationic, anionic, or coordination-type polymerizations.
The rate of initiation may be held constant (const)
throughout the polymerization, or it may depend on some
function of the catalyst and monomer concentrations, or it
may be instantaneous (instant), in which case only the total
number of initiating species need be known.
The rate of propagation is normally only the consump-
tion of monomer; in some cases, the rate of propagation
through terminal or pendant double bonds is also considered.
Transfer reactions may occur to initiator, momomer,
solvent, or polymer.
Termination of active species may occur by a first-order
deactivation, by second-order combination (comb) or dis-
proportionation (disprop), or not at all (living polymers).
Confusion exists over the meaning of the transfer-to-
catalyst reaction. In free radical systems, it means transfer
of the active species to the initiator by a second-order
mechanism. In ionic polymerization, it means the expulsion
of an active fragment from a growing chain by a first-order
mechanism to form dead polymer and an active initiator
fragment. The first-order mechanism is called here the
catalyst expulsion reaction (cat ex).
The nomenclature of distribution functions can be quite
confusing. In this work, the Flory distribution (Eq. C41) is
also known as the Schulz-Flory distribution, the most
probable distribution, and the exponential distribution.
The Schulz distribution (Eq. C36) is also known as the
Schulz-Zimm distribution or the generalized Poisson
distribution; at large values of k it approximates the Poisson
distribution (Eq. C48). The Pearson Type III distribution is
a variation of the Schulz distribution. If an addition polymer
is made at constant monomer concentration, no transfer
reactions occur, termination is only by second-order com-
bination, and the distribution of the polymer is described by
the Schulz distribution with k = 2. This distribution is
sometimes called the self-convolution distribution or the
convoluted exponential distribution. In a uniform distribu-
tion, all molcules have the same size - it is monodisperse.
A rectangular or box distribution has no molecules below
ra, an equal number (or weight) of molecules between Ye
and Tb, and no molecules whose size is above rb.
In Table 5, systems are treated where branching
reactions, ring formation, or gel formation may occur. See
also Table 6 for crosslinking reactions during degradation.
The symbol RAf means a monomer containing f reactive A
units. The problem of calculating the species distribution of
polyfunctional condensation polymers where branched,
cyclic, and crosslinked species can be formed is exceed-
ingly complex. Most treatments apply the restriction that
ring formation does not occur prior to the gel point, which
obviously is incorrect. The restriction is invoked because of
the transition from the pre-gel condition, where all
unreacted functional groups can react without steric
limitations to a condition containing rings in which some
of the unreacted groups are sterically unable to react with
all of the remaining unreacted groups. The problem is
further compounded because each different reacting mono-
mer will have various degrees of steric hindrance. There-
fore, a general treatment must ignore this aspect. An
examination of the Stockmayer distribution function in
Section D shows that in-depth calculations are required
even for simple oligomer species. A number of attempts
have been made to provide simpler expressions for the
number or weight of individual species and the average
TABLE 1. ADDITION POLYtiERlZATlON WITH TERMINATION
Addi t i on Pol ymeri zat i on wi t h Termi nat i on II / 341
molecular weights before and after the gel point. These
include the theory of stochastic processes (271), stochastic
graph theory (272), the theory of cascade processes which
is based on probability generating functions (151), the use
of link distribution functions (273), the recursive nature of
branching processes and elementary probability laws (274),
Monte Carlo methods (275), graph theory (276), and a
kinetic approach (277).
References
S e t Initiation Monomer Transfer
1. 1. INVARIANT MONOMER CONCENTRATION
Termination
RP Pr Mn,Mw
1.1.1 Const Const None 2 Disprop or comb 2-4 1-4 1-4
1.1.2 Const Const Monomer, solvent 2 Disprop 2,3,10-12 1-3 1-3
1.1.3 Const Const Monomer, solvent 2 Disprop and comb 3 1,3 133
1.1.4 Const, redox Const Activator 2 Comb 13 13 13
1.1.5 Const, initiation Const None 2 With catalyst; redox system 14 - 1 4
by activator
1.1.6 kiM2 Const Dimer, Monomer 2 Term 15 - 15
Initiator
1.1.7 Instant Const None 2 Term; 1 or 2 reactivation 1 6
-
1 6
1.2. VARYING MONOMER CONCENTRATION, NO TRANSFER-TO-MONOMER REACTION
1.2.1 Const Varies None 2 Comb or disprop 3
1,3 133
1.2.2 Const Varies Solvent 2 Comb and disprop 3 1,3 1,3
1.2.3 Photosensitized Varies None 2 Disprop 39 39 -
1.2.4 Const Varies None 2 Disprop and comb pseudo 1 1 7
-
with scavenger (rate of scavenger disappearance)
1.3. VARYING MONOMER CONCENTRATION, TRANSFER-TO-MONOMER REACTION OCCURS
1.3.1 Const Varies Monomer, solvent 2 Disprop or comb
1.3.2 Const Varies Monomer, solvent
kiM2
2 Disprop and comb
1.3.3 Varies Monomer 2 Comb and disprop
1.3.4 k,MI Varies Monomer, initiator 2 Disprop; degradative chain transfer
1.3.5 Instant Varies Monomer Non-steady state conditions, term by
comb or disprop
1.4. 1 TERMINATION OR DEACTIVATION, STEADY-STATE KINETICS
1.4.1 Const Const Monomer 1 Deactivation
1.4.2 kiMI Const Monomer, solvent 1 Deactivation
1.4.3 kiM2 Const Monomer 1 Deactivation
1.4.4 kiMI Varies Solvent 1 Plus solvent term
1.4.5 kiM* Varies None 1 Deactivation
1.4.6 kiMI Const None Deactivation by init. expulsion
1.5. TERMINATION BY 2 REACTION WITH MONOMER, STEADY-STATE KINETICS
1.5.1 Const Varies None 2 With monomer
1.5.2 kiMI Varies Monomer 2 With monomer
1.5.3 Const Const Monomer 2 With monomer
1.6. TWO ACTIVE ENDS PER CHAIN
1.6.1 Const Const None 2 Disprop
1.6.2 Const Const Monomer 2 Disprop
1.6.3 Const Const Monomer 2 Comb; two active chains couple
to form a chain with two active ends
1.7. SLOW EXHAUSTION OF INITIATOR, NONSTEADY-STATE KINETICS
1.7.1 kil Const None 2 Disprop* or comb
1.7.2 kil Varies None 2 Comb
*Data belong together.
3,18 1,3,18 1
-
-
1 9
334 1,3,4 1,3,4
20 - 20
313 313 313
4 134 1,4
4 1.4,21,22 1,4,21,22
4
1,4 134
4,23 134 1,4
4,23
1,4 1,4
2 1 1.21 1,21
4,23
1,4 1,4
2 3 1 1
4 1,4 1,4
3 1,3 1,3
18 18
3 1.3 1,3
25 *,26 - 1,25*,26
27
-
27
References page II - 356
II / 342 RATES OF POLYMERIZATION, AVERAGE MOLECULAR WEIGHTS, AND MOLECULAR WEIGHT DISTRIBUTIONS OF POLYMERS
TABLE 1. contcf
References
S e t Initiation Monomer Transfer Termination
RP pr M,MW
1.8. DEAD-END POLYMERIZATION, RAPID DECAY OF INITIATOR, MONOMER CONCENTRATION INVARIANT
1.8.1 kil Const Monomer, solvent 2 Disprop or comb 28
1.8.2 kiZ2 Const None 2 Disprop or comb 28
1.9. DEAD-END POLYMERIZATION, SLOW DECAY OF INITIATOR, MONOMER CONCENTRATION VARIES
1.9.1 kil Varies Monomer, solvent
1.9.2 kil Varies Monomer, solvent
1.9.3 kilM Varies None
1.9.4 Instant Varies Monomer
1.95 Redox Varies None
2 Disprop* or comb
2 Comb
1 Term, bimolecular monomer
addition. I * and R; do not terminate
1 Term, or 2 with monomer
2 Term
1.10. COPOLYMERIZATION: TWO DIFFERENT MONOMERS PRESENT
1.10.1 Const Const Monomer 2 Disprop or comb
1.10.2 Const Varies None Diffusion controlled and inversely
proportional to viscosity
1.10.3 Const Const None Rate const for term is known as
fn(conc). Comparison of cross term
parameter @
1.10.4 Const Const N o n e Alternating copolymerization
1.10.5 Varies Varies Agent Various; Monte Carlo calculations:
initiation and term influences
composition
1.11. DIFFUSION-CONTROLLED TERMINATION (see also il. 10.2 and 5.1.4)
1.11.1 Const Varies
1.11.2 kil Varies
1.11.3 Const Varies
1.11.4 kil Varies
1.115 kil Varies
1.11.6 ki Varies
1.11.7 ki Varies
1.11.8 kil or none Varies
1.11.9 Const Const
1.12. PRIMARY RADICAL TERMINATION
1.12.1 Const Varies
1.12.2 Const Const
1.13. MIXED SPECIES PROPAGATION
1.13.1 Const Varies
None or solvent*
None
None
Monomer
None
None
Monomer. solvent
Monomer, solvent
Solvent
Monomer
None or init. and
monomer *
Monomer
1.13.2 Const Const None
1.13.3 Const
*Data belong together.
Varies
2 Disprop or comb*
and diffusion controlled
2 Comb, R, =k,M,,,n >1
2 Process
2 Disprop and diffusion controlled
2 Disprop and comb, diffusion
controlled
2 Disprop, term rate for long chains
depends on entanglement density
2 Disprop, term rate for long
chains depends on entanglement
density
2 Comb. and disprop term depends
on free volume or free volume
plus entanglement, Calc. of gel point
ktcn,ml =k,(m) -. Term by comb
and disprop.
2 Comb and disprop and
primary radicals
2 Term and primary radicals
Propagation, transfer and termination
rates depend on species type, i.e.
free radical and cationic occurring
simultaneously
Zwitter-ion polymerization;
distance between ions varies as r3/,
30
30
3 1
40
4 1
1,2,3,4,10
32,33
239
314
315
-
37*
27
42
240
241
242
243
317
318
38
33,43-45
46
244
47
equilibrium between free and solvated
ions; 1 term
Bifunctional initiator, term by comb 319
-
319
1,28 1,28
1,28 1,28
-
-
1,19*
1
-
-
-
-
-
34 1,35
239 239
-
- -
316 316
1,36
-
-
-
240
241
242
243
27
-
-
-
242
243
317
-
1,38
- 44,45,15*
46
-
244 244
-
47
TABLE 1. contd
Addi t i on Pol ymeri zat i on wi t h Termi nat i on II / 343
References
S e t Initiation Monomer Transfer Termination
RP
Pr M.,Mw
1.14. EMULSION POLYMERIZATION (see also Tables 2 and 7)
1.14.1 Const
1.14.2
1.14.3
1.14.4
Const
Const
Const
1.145 Const
1.14.6 Slow and const
1.14.7 Const
1.14.8 Const
1.14.9 Varies
1.14.10 Consl
1.14.11
1.14.12
Const
Varies
1.14.13
1.14.14
Const Const None
Const Const None
Const within
particles
None
Const within
particles
Const within
particles
Const within
particles
None
None
Monomer
Const within Monomer
particles
varies outside
Const None
Const within None
particles
Const None
Varies Mi ni mi ze
Const within
particles
Monomer, agent
Const within
particles
Varies
Monomer, agent
Monomer
1.15. HETEROGENEOUS POLYMERIZATION
1.15.1 kiMI, I varies Varies Monomer
1.15.2 Instant Varies None
1.15.3 Const Const None
1.15.4 Const Const None
1. 16. INHIBITION AND RETARDATION
1.16.1 Const Varies
1.16.2 Const Const
1.16.3 Const Const
None
Inhibitor
Retarder
General theory; particles act
as independent units; 2
term within particles; number
of particles remain constant;
number of radicals per particle
General theory; Slow-term
rate within particles
48-54 - 53
55
-
55
Inst. term within particles;
number of particles varies
Normal 2 term within particles; rapid
interchange between phases of
small-sized radicals; number of
radicals per particle
56
57
Rapid exchange between phases of
small-sized radicals; term in aq
phase and in particles
58
Slow 2 comb; calcn. of number of
radicals per particle
- 59 59
Const number of particles; term by
2 comb
60 - 60
Inst term on entering a particle; const
number of particles
- 6 1
Adjust initiation and term rates while
minimizing transfer to obtain
monodisperse polymer
Instant 2 term when a free radical
enters a particle containing two
growing chains and reacts with one
of them. No term by disprop or comb
within particles
72 72 72
245 245 245
Same as case 1.14.10 but plus term by
disprop or particle by comb
Varying rate of entry, desorption of
oligometic radicals, term by comb
and disprop, Monte Carlo simulation
model
245 245 245
-
320 -
Any number of chains per particle, 1
term, 2 term by disprop or by comb.
Use of Markov chains
See 1.14.13. Copolymerization, chain
composition distribution
-
321 -
-
322 -
Polymerization in monomer rich and
monomer poor phases; 2 disprop
Term by precipitation onto growing
solid particle
62 62 62
63 - 63
2 Comb, 1 occlusion onto particle
surfaces, and primary radical term
2 Term in liquid phase, 1 radical
precipitation, propagation and 2
term at solid-liquid interface
64 - -
65 - -
2 Term, 2 addition to
inhibitor
2 Term, inhibitor
term, inhibitor coupling
2 Term, retarder
reinitiation and term
3,66,67,73 - -
68 - 6 8
69 - 69
References page II - 356
II / 344 RATES OF POLYMERIZATION, AVERAGE MOLECULAR WEIGHTS, AND MOLECULAR WEIGHT DISTRIBUTIONS OF POLYMERS
TABLE 1. contd
References
S e t Initiation Monomer Transfer Termination
RP
Pr Mn,Mw
1.16.4 Const Const Retarder
1.16.5 Const Const Retarder
1.16.6 Const Const Retarder
1.16.7 Const Varies None
1.16.8 Const Const Inhibitor
1.16.9 kil Const Inhibitor
2 Term, retarder reinitiation, term and
coupling
2 Term, rate of transfer equals rate of
reinitiation
2 Term, copolymerization of retarder
Pseudo 1 with. scavenger
2 Disprop, 2 reaction with inhibitor
2 with inhibitor or with monomer
to assess the efficiency of initiation
1.17. POLYFUNCTIONAL INITIATOR WITH VARIOUS THERMAL STABILITIES
1.17.1 kiMI Const None 2 disproportionation
On raising the
temp., other
peroxide groups
can initiate
1.18. PERIODIC MODULATION OF TERMINATION OR INITIATION
1.18.1 Const Varies None Periodic modulation of term by
disprop by addition of an inhibitor
or by magnetic or electric fields
1.18.2 Varies Varies None Periodic modulation of initiation,
term by comb and/or disprop,
ccmputer calculation
1.18.3 Varies Varies None Periodic modulation of initiation,
term by comb. Calcn. of MWD by
generating functions
3,12,70
71,74
1 0
11
1 7
75
246
- -
247
-
323 -
324 324 324
-
325 -
- -
- -
-
11
- -
-
75
- -
TABLE 2. ADDITION POLYMERIZATION - LIVING POLYMERS WITH PARTIAL DEACTIVATION
References
S e t Initiation Monomer Transfer Termination
RP fr Mn,Mw
2.1. THE POISSON DISTRIBUTION: ki = kp
2.1.1 k,MI Varies None None
2.1.2 k,Mlt Varies None None; initiator added at a constant rate
2.2. THE GOLD DISTRIBUTION: ki #kp
2.2.1 k,MI Varies None None
2.3. PARTIAL DEACTIVATION BY A 1 PROCESS OR A 2 PROCESS WITH AN IMPURITY
2.3.1 Instant Varies None 1 or2
2.3.2 Instant Varies None Rat e of t erm/ R, = const .
2.3.3 Instant initiator Varies None Rat e of t erm/ R, = const .
has two active
sites
2.3.4 Instant Varies None Rate of term independent of R,
2.3.5 Instant Varies None 1 at infinite time
2,101,102 1,2,101, 1,2,101,
102 102
1 0 3 - 1 0 3
102, 104 1,102 1,102
1 0 5 1,106 1,106
- 1,106,107 1,106,107
- 1,107 1,107
1,106
-
1,106
108,109
-
108,109
248
- -
2.3.6 Instant Const None Probability that a chain will
terminate rather than propagate
is k, jk,M
2.4. MULTIPLE PROPAGATING SPECIES: R; CAN TRANSFORM INTO Q;, ETC.
2.4.1 Instant Const None None, two propagating species 76
2.4.2 kiMI Varies None None, two propagating 1,77-79 1,77,78
species 80
76
,77-80
TABLE 2. contd
Addi t i on Pol ymeri zat i on - l i vi ng Pol ymers wi t h Part i al Deact i vat i on II / 345
References
S e t
2.4.3
2.4.4
Initiation Monomer
Instant Varies
Activated monomer Varies;
addition volume also
varies
Transfer
None
None
Termination
RP Pr M.,Mw
None, multiple propagating species 249 249 249
None; two prop constants
-
326 326
k,can increase
-
327 327
2.5. SIMULTANEOUS POLYMERIZATION AND DEPOLYMERIZATION
2.5.1 kiMI Const None None
-
1,81 1,81
2.5.2 kiMZ Varies None None 82,83 8 1 8 3
2.5.3 k,M* Varies None None 84 - -
2.6. THE k, VARIES WITH CHAIN LENGTH (see also 2.4.4, 3.3, and 3.4)
2.6.1 kiMI Varies None None
(a) all propagation constants (k,) are different
-
1,85,86 -
(b) ki : kl : k2 : k3 : ...k,, =m : (m - 1) : (m - 2) : (m - 3) : . -
1,85 -
(c) kl # k2 ... # k,= k,+l =. . . = k,
-
1,85 1,85
Cd) ki # kl # k2 = km
-
1,85 -
2.6.2 Instant, kl= k2... = k,,k,+l, et c. = 0 86 86 86 -
2.6.3 Instant, k, is a linear decreasing function of r 86 86 86
2.6.4 Const Varies None None; k, for monomer, dimer, and
-
328 328
trimer different from remaining
molecules
2.6.5 Rate constants can varv with extent of conversion: determination of rate constants from P, and the use of generating functions; termination
by monomolecular decay, disprop and/or comb:
2.7. DEACTIVATION BY TRANSFER TO MONOMER
2.7.1 kiMZ Varies Monomer
2.7.2 Instant Varies Monomer
2.7.3 Instant Varies Monomer
None
-
329 -
1,87
1,74,90
1,91
1,87 1,74,87,88
2.8. DEACTIVATION BY SLOW 1 TERMINATION
2.8.1 Instant Varies None
2.8.2 Instant Varies Monomer
2.9. DEACTIVATION BY INITIATOR EXPULSION REACTION
2.9.1 Instant Varies None
2.9.2 kiMI Varies Monomer
2.9.3 Instant Varies Monomer
2.10. DEACTIVATION BY DEGRADATIVE CHAIN TRANSFER
2.10.1 kiMI Varies Degradative transfer
to polymer
2.11. COPOLYMERIZATION
2.11.1 Instant Varies None
2.12. HETEROGENEOUS POLYMERIZATION
2.12.1 Instant Varies None
2.12.2 Instant Varies None
2.12.3 Const Const None
2.13. SPONTANEOUS POLYMERIZATION
2.13.1 Const Const None
None
None, two active ends per initiator
Slow 1
Slow l, at infinite time
None
-
1 term 67
None 250
None
-
None; diffusion of monomer through
solid polymer
2 Term with monomer; diffusion of
monomer through solid polymer
Sorption and desorption of chains from
the surface; slow 1 term which
depends on chain length
Vinyl compound and activator form
monomer; monomer both initiates
and propagates; no term
97
98
1,89,90 1,74,90
1,91,92 1,91
-
-
1 ,I4
1,74
-
250
1,93
6 7
250
9 5
96
97
98
99
100
References page II - 356
II / 346 RATES OF POLYMERIZATION, AVERAGE MOLECULAR WEIGHTS, AND MOLECULAR WEIGHT DISTRIBUTIONS OF POLYMERS
TABLE 2. contd
References
S e t Initiation Monomer Transfer Termination
RP
P, Mn,Mw
2.14. REVERSIBLE INITIATION AND REACTIVATION
2.14.1 Rev 2 with Const Monomer No termination; dead species in 251 251 251
monomer equilibrium with living species,
irreversible propagation
2.15. DEACTIVATION BY TRANSFER TO AGENT
2.15.1 kiMI Const Agent No termination. Transfer creates dead
- -
252
or const polymer and active initiator
varies varies
2.15.2 k,MI Varies Agent Numeri cal met hod for talc. of MWD
-
330 -
with mono- or polyfimctional transfer
agent. Latter leads to branching.
2.16. SLOW EQUILIBRIA
2.16.1 Varies Varies None 3-State mechanism consisting of two
- -
331
successive equilibria
2.16.2 Varies Varies None Equilibrium between dormant 332 - -
aggregated polymer and living
pol ymer
2. 17. POLYMER MICROSTRUCTURE
2.17.1 Varies Varies
2.17.2 NA NA
None
NA
None; concentration of head-to-head
and tail-to-tail, sequence length
distributions, various dyad and
triad fractions
Block copolymers
- -
334
- -
335
TABLE 3. LINEAR CONDENSATION POLYMERIZATION WITHOUT RING FORMATION
Set Conditions References
3.1
3.2
3.3
3.4
3.5
3.6
3.1
Condensation of bifunctional monomer AB; the Flory distribution. See Eq. (C41)
Bifunctional monomer AA reacting with bifunctional monomer BB; the nylon case of hexamethylene diamine and adipic acid
Deviations from the principle of equal reactivity; the substitution effect
Rate of condensation varies
3.4.1 Rate of condensation proportional to chain size
3.4.2 Condensation requires rotation into colinear orientation prior to reaction
3.4.3 The order of reaction varies with conversion, or a catalytic influence of unreacted A or B groups, or both effects
occurring simultaneously
Other simple linear condensation cases
3.5.1 AA reacting with BC. BC is an anhydride; within a given molecule, B must react before C
3.5.2 AA reacting with BC. BC is an unsymmetrical acid or glycol; B reacts only with A at a different rate from that of
C reacting with A
3.5.3 AB reacting with C and itself. B and C react only with A; C is a terminator or capping material
3.5.4 AA reacting with BB and C; the nylon case again with acetic acid as terminator
3.5.5 AA reacting with BC; A and B react with C
3.5.6 AB reacts with CC or DD kinetics
3.5.7 AA and A reacting with BB and B
Further polymerization of polymers with an initial geometric distribution
3.6.1 Further polymerization of AB when the initial distribution is geometric
3.6.2 Further polymerization of AB when the initial distribution is a superposition of two geometric distributions
3.6.3 Further polymerization of AA with BB when the initial distribution of both is geometric
Copolymerization of condensation polymers
3.7.1 AB reacting with CD; AB and CD can be hydroxy acids or similar materials
3.7.2 AA reacting with BB and CC. A reacts with B and C only and vice versa; BB and CC can be adipic and sebacic acids
3.7.3 AA and BB reacting with CC and DD; A and B react only with C and D and vice versa
3.7.4 AA reacting with BC and DD; A reacts only with B, C, and D
3.7.5 AA and DD reacting with BC; A and B react only with C and D and vice versa
3.7.6 AA reacting with BC-BC, the latter can be a dianhydride; B must react before C
1,2,110
1,24,111
1,112,253,254
1,113,114,134
255
256
1,111
1,111
1,111
1,111
1,111
1 1 5
336
1,116
1,116
1,116
1,111
111,257
1 1 1
111
111
258,259
Equilibrium Polymerization II / 347
TABLE 3. contd
S e t Conditions References
3.8 Coupled polymers
3.8.1 AB polymerized to extent of conversion cc, then coupled with CC
3.8.2 AB polymerized to extent of conversion CL, then coupled with CD. A and B can react with C or D
3.8.3 AA and BB polymerized to extent of conversion n, then coupled with an excess of CC. A and B to react completely
on coupling
3.8.4 Poisson-distribution polymer of AA coupled with BC
3.8.5 Monomer AB polymerized to extent of conversion CL, then coupled with excess CC to extent of conversion 7,
then recoupled with excess DD
3.8.6 Particularly narrow distributions via coupling reaction
I. AA and BB (great excess)+BBAABB, then remove excess BB. CC and BBAABB (great excess)+
BBAABBCCBBAABB, then remove excess BBAABB, and continue in like manner
II. AA and 2BC-CBAABC then CBAABC and 2DE-+EDCBAABCDE, etc
III. AB and CD+ABCD then ABCD and EF+ABCDEF, etc
3.8.7 Blocks of polymers of known distribution are coupled together
1,117,118
1,117
1,117
1.117
1,117
119
119
119
I. A series of Poisson-type-polymers coupled together
II. Poisson-type-polymers coupled to most probable-type polymers
III. A series of most probable-type polymers coupled together 120,118
3.9 AB reacts with CC or CD; rate of reaction of A dependent upon whether or not B has reacted 11.5
3.10 Segmented block copolymers; distribution of block sizes 260-262
3.11 Reacted sequences in homopolymers 263, 264
TABLE 4. EQUILIBRIUM POLYMERIZATION
S e t Conditions References
4.1
4.2
4.3
4.4
4.5
4.6
4.1
4.8
4.9
4.10
4.11
4.12
4.13
4.14
4.15
4.16
4.17
The most probable distribution of Flory has been derived for condensation polymerization when all reactions are
assumed to have the same probability, regardless of chain length, and whether or not exchange reactions occur:
P,+P,=P,+,-j$Pj, i<r+s
Here, Pi can be a byproduct such as water, or a polymer molecule whose size is smaller than r + S. The same distribution
results when random scission occurs to infinitely long chains. See also (265) for multifunctional monomers.
The theoretical equilibrium molecular weight distribution for the system
rM = P,
depends upon the thermodynamic definition of the final product. If the change in Gibbs free energy of formation and
polymerization is a linear function of molecular size r, then two cases can be considered:
4.2.1 The monomer is polymerized to a pure perfectly ordered state (solid); this gives the most probable distribution
4.2.2 The monomer is polymerized to a pure randomly ordered state (liquid); a completely different distribution results
If the free-energy change upon disordering of the pure polymer is independent of the molecular weight distribution, a new
distribution arises
Thermodynamics of living equilibrium polymers
Given an initial distribution, find the distribution as a function of time when chain ends react at random with all monomer units
Initiation, propagation, and termination reactions are all equilibrium reactions; an initiator is required
Initiation, propagation, and termination reactions are all equilibrium reactions; the system is self-initiating
Equilibrium initiation and equilibrium propagation with a multifunctional initiator
Equilibrium initiation and equilibrium propagation; no termination; nonequilibrium solution.
The catalyst can form an active species with any polymer molecule, and the total number of moles of the system is kept
constant (constant pressure and volume if all polymer molecules are ideal gases)
Addition polymerization, instantaneous initiation, no transfer, no termination, monomer concentration held constant, active
species in equilibrium with inactive species
Addition polymerization, rate of initiation equals ktMC, no transfer, no termination, two active species in equilibrium, monomer
concentration varies
Addition polymerization, instantaneous initiation, no transfer, no termination, active species in equilibrium with inactive species,
monomer concentration varies
Poly(phosphate) equilibria
Instantaneous initiation, polymerization and depolymerization, 1 termination
Instantaneous initiation, polymerization and depolymerization, degradative transfer to monomer
Copolymerization: bimolecular addition of one monomer, equilibrium addition of other monomer
Copolymerization: equilibrium growth with monomer A or B adding to a chain with a terminal group of either A or B. Three
cases: 2 reaction with initiator; 1 formation of active radical; 2 reaction with another monomer
Eq. C41
2,121
122
Eq. C41
1 2 3
124
1 2 5
1 2 6
1 2 7
1 2 7
128,266
129
130
77
78
77
1 3 1
132
1 3 3
230
267
References page II - 356
II / 348 RATES OF POLYMERIZATION, AVERAGE MOLECULAR WEIGHTS, AND MOLECULAR WEIGHT DISTRIBUTIONS OF POLYMERS
TABLE 4. contd
Set Conditions References
4.18 Equilibrium copolymerization of two or more comonomers
268
4.19 Polycondensation where groups have different equilibrium constants
269,270
4.20 Equilibrium copolymerization initiated by polymer chains with active sites: average mol. wts, grafting ratio, grafting efficiency,
grafting success, branching distribution, frequency of grafts
337
TABLE 5. NONLINEAR POLYMERIZATION SYSTEMS
Set Conditions References
5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
Vinyl polymerization; self-grafting
5.1.1 General case; molecular weight averages for grafted and ungrafted polymer
5.1.2 Constant rate of initiation, monomer concentration invariant, transfer to monomer and to polymer, termination by 2
disproportionation
5.1.3 Constant rate of initiation, monomer concentration varies, transfer to polymer, termination by 2 combination
5.1.4 Constant rate of initiation, monomer concentration can vary, transfer to monomer and to polymer, termination by 2
disproportionation and/or combination
5.1.5 Instantaneous initiation, monomer varies, either no transfer occurs or transfer to monomer, solvent, or polymer
is allowed; termination by coupling and varies with chain length
Vinyl polymerization; grafting onto a performed polymer whose initial distribution is either (i) of constant length or (ii) a
geometric distribution
Vinyl polymerization; all segments of the backbone chains have equal probability to be grafted
Vinyl polymerization; terminal double-bond polymerization, monomer concentration varies, transfer to monomer and to
polymer, terminal double bond polymerization
5.4.1 Termination predominantly by transfer, constant rate of initiation; batch or continuous polymerization
5.4.2 Termination by disproportionation, constant rate of initiation, includes transfer to solvent
5.4.3 Termination by combination, constant rate of initiation, amount of short and long chain branching, transfer to a
tertiary site
5.4.4 Termination by combination, initiator and monomer concentration vary, transfer to monomer and to polymer
5.4.5 Termination by combination, initiator and monomer concentration vary, transfer to monomer and to polymer,
characterization following saponification and reacetylation
Vinyl polymerization; long-chain branching.
5.5.1 constant rate of initiation, monomer concentration invariant, transfer to monomer and to polymer, termination by 2
disproportionation
5.5.2 Living polymer. Instantaneous initiation, B-hydride or B-methyl elimination to form a terminal double bond, transfer
with agent to form a saturated end
Vinyl polymerizaton; living branched polymer; polyfunctional initiator RAf; rate of initiation equals rate of propagation, no
transfer, no termination
Vinyl polymerization; R,, in a diffusion controlled gelling system; termination by disproportionation or combination, no
transfer
Vinyl polymerization; branching density as a function of conversion; branches formed by polymerization through a vinyl group
(diene polymers) or by transfer-to-polymer reaction
5.8.1 Batch polymerization
5.8.2 Continuous polymerization
Vinyl polymerization
5.9.1 Branching density as a function of conversion of (1) long-chain branching, (2) short-chain branching (backbiting),
(3) very short chain branching (radical migration)
5.9.2 Copolymerization with divinyl, no ring formation prior to gelation
5.9.3 Copolymerization with divinyl; ring formation permitted; Monte Carlo calculations for crosslinking density, weight
fraction of gel; chain-length distribution between crosslinks
5.9.4 Circuits in a network, elastically active chains
5.10a Emulsion polymerization; branch density
5. lob Emulsion polymerization; Monte Carlo calculations; can account for desorption of oligomers, chain-length dependence of
kinetic parameters, chain transfer to monomer and solvent, polymerization through terminal double bonds and long-chain
branching
5.11 Cyclopolymerization: the concentration of pendent double bonds per molecule
5.12 Gelation condition in a system when cyclopolymerization also occurs; transfer to monomer reaction occurs. Molecular weight
given
5.13 General theory of gelation for polyaddition- and polycondensation-type polymers
5.14 The general distribution function for various molecules of type A reacting with various molecules of type B; A can only react
wi t h B
342,343
282,283
144,344
345
145- 149
150
1 5 1
5.14.1 All functional groups have equal reactivity, independent of position within the molecule or the size of the molecule.
Section D
Ring formation excluded
276
278
1,3,18
1 3 5
279
280
1 8
136
1,137-139
338
338,339
340
341
1,140
355
1 4 1
142
12
1,138
143
274,281
TABLE 5. contd
Nonlinear Polymerization Systems II / 349
S e t Conditions References
5.15
5.16
5.17
5.18
5.19
5.20
5.21
5.22
5.23
5.24
5.14.2 Monomers of type RAf (fcan vary) can only react with monomers of type RB, (g can vary) where the various Bs can
have different reactivities. No ring formation
5.14.3 Monomers of type RAf and RB, where f and g can vary, the reactivity of a given B can depend on whether or not an
adjacent B on the same molecule has reacted. No ring formation
5.14.4 Monomers of type RAf and RB, where f and g can vary; no ring formation; calculation of higher distribution
moments
Crosslinking or coupling of a polymer with a known primary distribution (see also Table 6)
5.15.1 General case. No ring formation prior to gelation
5.15.2 All primary chains have the same size; no ring formation prior to gelation
5.15.3 Primary chains of the Poisson type, (Eq. C48); no ring formation prior to gelation
5.15.4 Primary chains of the Schulz type, (Eq. C36); no ring formation prior to gelation
5.15.5 Primary chains of the most probable type; ring formation allowed prior to gelation
5.15.6 Formation of star-type polymers
Homopolymer of ARB,~,. A can react only with B; the Bs may have different reactivities. Formation of rings excluded prior
to gelation
5.16.1 All B groups have the same reactivity
5.16.2 Let B groups have different reactivities
5.16.3 A controversy over the statistical approach
Copolymer of AiBf-1 and AB; A can react only with B; formation of rings excluded prior to gelation
Homopolymer of RAf; formation of rings excluded prior to gelation
5.18.1 All As equally reactive
5.18.2 Reactivity of A depends on number of As previously reacted
Various copolymers
5.19.1 Copolymer of RAf and AA; formation of rings excluded prior to gelation
5.19.2 Copolymer of RAf, AA, and BB; A can react only with B; formation of rings excluded prior to gelation; all branch
points completely reacted. See set 5.16.3 for a controversy
5.19.3 A mixture of self-condensing monomers R IA,, R~AJ,, etc., no ring formation
5.19.4 A stoichiometric mixture of RAf and RBf of the same functionality f, indistinguishable reactivity, no ring formation.
Note that different authors get different equations for M, and M,
5.19.5 A stoichiometric mixture of RAf, RA,, and RB J,, RBi ,f, g, h, i being different functionalities, indistinguishable
reactivities, no ring formation
5.19.6 A copolymer of RAf and BB; no ring formation prior to gelation
5.19.7 A copolymer of RAf, AA, and BB where B has a different reaction rate ,from B; no rings prior to gelation
5.19.8 Copolymer of RAf, AA, and BB where the As in RA/ can have different rates of reaction
Polymers of RAfB,
5.20.1 Homopoiymer of RAfB,; A can only react with B; formation of rings excluded prior to gelation
5.20.2 A mixture of monomers RAfB,, where f, g = 0, 1,2, , stoichiometry not required
Branching without gelation; copolymer of RAf and AB. A can react only with B
Gelation conditions; formation of rings excluded prior to gelation
5.22.1 AA reacting with BfC,. A can react with B and C, but with different velocities. B cannot react with C
5.22.2 AA, BB, and C reacting with DDE and FF; A, B, and C individually can react with D, E, and F, but with different
velocities
5.22.3 AAB, RC4, and GC reacting with DE and F. DE is an anhydride or similar material. D must react first and may have a
different velocity from E. A, B, C. and G may react with different velocities
284
285
346
1,152-155,
286
1,2,152,
155- 157
155,157
286
287
288
1,2,158,265,
289
1,159,160
161,162,163,
164
1,2,158
1,2,121,158,
165,166,
265,274,
277,281,
290-292
167,273,293
1,2,165
1,168,169
277,294,295
277
277,294
274,281,290
293
293
170,265
295
1,171
1,172
1,172
1,172
5.22.4 AB and CD reacting with EEF and GG. AB and CD are anhydrides or similar materials, where A must react before B and
C must react before D. A, B, C, and D may react with different velocities
5.22.5 AA and BC reacting with DDE and FG. BC is an anhydride, B reacting first, and FG is like an unsymmetrical glycol
Ring formation in linear polymers
5.23.1 Homopolymer of type AA
5.23.2 Homopolymer of type AA. Formation of catenanes
5.23.3 Homopolymer of type AB
5.23.4 Copolymer of type AABB
5.23.5 Distribution for chain fraction
5.23.6 Copolymer of AA with BC. BC can be an anhydride; within a given molecule, B must react before C; A single cyclic
1,172
1,172
1,173,174
296
1,173,175
1,173,176
12
oligomer is permitted to form
297
5.23.7 Ring-chain equilibrium constant, R, of rings, cut-off point of monomer cone below which only cyclics formed
347
Crosslinking of a polymer with a known distribution: rings are permitted prior to gelation
1 5 3
References page II - 356
II / 350 RATES OF POLYMERIZATION, AVERAGE MOLECULAR WEIGHTS, AND MOLECULAR WEIGHT DISTRIBUTIONS OF POLYMERS
TABLE 5. contd
S e t Conditions References
5.25 Gelation conditions for RAf when rings are permitted prior to gelation 1,177
5.26 Homopolymer of RAf. Ring formation permitted prior to gelation 1,178,179,
298
5.27 Copolymer of RAf and BB when rings are permitted prior to gelation 180
5.28 Gelation condition for RAf, AA, and BB when rings are permitted prior to gelation 1,181
5.29 Monte Carlo calculations on small amounts of crosslinking 299
5.30 Monte Carlo calculations for RAs, the reactivity of an A group depends on the number of previously reacted groups on that
monomer, no ring formation prior to gelation 275
5.31 Monte Carlo calculations for vinyl and divinyl copolymerization 300
5.32 Grafting of reactive polymers of the type AA, AAB, BB, and BBA where rings can form prior to gelation; M, and the gel point 348
5.33 Star type molecules prepared by anionic polymerization and different precursors (see also 5.19.1, 5.21 and 5.27) 349
TABLE 6. DEGRADATION OF POLYMERS - MAY BE ACCOMPANIED BY CROSSLINKING
References
Initial
S e t Initiation Mass distribution Transfer _ Termination
Rd p, M, Mw
6. 1. RANDOM SCISSION ONLY
6.1.1 Proportional to time Const
6.1.2 Proportional to time Const
183- 186 182- 184
183- 187 183,184,188
Arbitrary
Infinite or
uni form
Uni form
None None
None None
-
-
189 189
Uni form None
-
190
-
Uni form
None
None
None None
-
1 9 1 1 9 1
Rectangular None None
-
Flory None None
-
Schulz None None
-
Poisson
Uni form
None
None
-
Schulz None
Schulz
None
None
None
None None
301
301
Varies
Varies
Varies
Varies
Varies
Varies
Varies; monomer
radicals may
evaporate
Varies
Uni form None
Uni form Pol ymer
Schulz None
Schulz None
Schulz (k = 2) None
Schulz (k = 2) None
Flory None
1
2 Disprop
1
2 Disprop
1
2 Comb
1 or2
Disprop
193
194
1 9 3
1 9 5
196
196
197
Uni form 2 Disprop 194
-
194
Varies Schulz 2 Disprop 198
-
198
Unspecified
Polymer
None
None
Flory
Flory
Polymer
Polymer
land2
Process
1 and 2
Disprop
2 Comb
199 (all molecules must terminate)
200 (some molecules can
completely disappear)
201 2 0 1
201 - 201
6.1.3
6.1.4
6.1.5
6.1.6
6.1.7
6.1.8
Random at
all bonds
Random at
chain ends
Random at
all chains
Random
Random
Random
Const
Const
Const
Const
Const
Const
184,187
184,187
184,187,
301
187
-
184
184,188
187.301
6.1.9 Random Const
6.1 .lO Random at normal Const
and weak bonds
6.1.11 Gaussian about the Const
midpoint
6.1.12 Central Const
-
192
301
301
6.2. UNZIPPING-TYPE REACTION
1 9 3
194
193
1 9 5
196
196
-
6.2.1
6.2.2
6.2.3
6.2.4
6.2.5
6.2.6
6.2.7
1 end
1 end
1 end
1 end
1 end
1 end
1 end; various
rates of
initiation
Random scission
only
Random scission
only
1 end and
random scission
-
-
6.2.8
6.2.9
6.2.10
6.2.11 1 end and Varies
random scission
6.2.12 1 end and Varies
random scission
TABLE 6. contd
Degradation of Polymers II / 351
S e t Initiation Mass
Initial
Distribution Transfer Termination
Rd
References
p,
6.2.13 1 end and Varies Flory
random scission
6.2.14 1 end and
random scission
6.2.15 1 end and
random scission
6.2.16 1 end and
r andom
scission
6.2.17 Unzipping
reactions
Varies Uni form
Varies; units Uni form
other than
monomer may
evaporate
Varies; units
H0l.Y
other than
monomer may
evaporate
Varies various
6. 3. RANDOM SCISSION AND CROSSLINKING
6.3.1 Proportional
to time
Const Arbitrary None
6.3.2 Varies with depth
of penetration
Const Flory None
6.3.3 Proportional to
time
Const Arbitrary None
6.3.4
6.3.5
Proportional to
time
Proportional to
time
Const Arbitrary None
Const Schulz None
6.3.6 Proportional to
time
Const various Unspecified
6. 4. CROSS LINKING ONLY
6.4.1
6.4.2
6.4.3
6.4.4
6.4.5
Proportional to
time
Proportional to
time
Proportional to
time
Proportional to
time
Proportional to
time
Const Arbitrary None
Const Uni form None
Const Schulz None
Const Beasley (140) None
Const Arbitrary None
6.5. RANDOM SCISSION FOLLOWED BY UNZIPPING
Polymer
Pol ymer
Polymer
pol ymer
Various
1 and 2 Process;
comparison of
random scission,
weak link, and
transfer theories.
Compari son of
various term
mechanisms
2 Disprop
1 and 2 Disprop
or 2 comb
Various, a review
Unspecified term,
with and without
ring formation
1 and 2 Disprop
without ring
formation
End-linking
(grafting) rather
than crosslinking;
without ring
formation
End-linking; with
ring formation
Unspecified term,
without ring
formation
Various initial
distributions
Ring formation
prohibited
Ring formation
prohibited
Ring formation
prohibited
Ring formation
prohibited
Ring formation
permitted
202
- -
203
-
203
204
- -
205
-
205
206 206 206
207
-
1 5 3
208
-
302
303
209
1 5 3
208
282
302
303
210
209
211
208
1 5 3
208
302
-
210
211
208
211
28
211
29
211
-
211
29
- -
350
1 5 3
182
182,212,
213
-
1 5 3
182
182
182
1 5 3
1 5 3
182
182
1 5 3
-
153
65.1
6.5.2
Random macromolecular fragmentation to form defective groups which subsequently initiates depolymerization
Random macromolecular fragmentation to form defective groups which subsequently initiates depolymerization
with bimolecular kinetic chain termination
351
352
References page II - 356
II / 352 RATES OF POLYMERIZATION, AVERAGE MOLECULAR WEIGHTS, AND MOLECULAR WEIGHT DISTRIBUTIONS OF POLYMERS
TABLE 7. INFLUENCE OF REACTOR CONDITIONS AND DESIGN ON THE MOLECULAR WEIGHT DISTRIBUTION
Set
Conditions References
7.1 Comparison of 1 term, 2 term with monomer, 2 disprop, 2 comb, and no term for 1
and 2 self-initiation and initiation by
light in a CFSTR: R,, P, and M, are given
214
7.2 Emulsion polymerization
7.2.1 Emulsion polymerization in a CFSTR. Instantaneous 2 termination
21.5
7.2.2 Emulsion polymerization in isothermal BR; 1 init, termination with initiator, four stages of polymerization 304
7.3 Effect of inadequate stirring in a CFSTR; comparison with BR and normal CFSTR. Term. by 2 or no term. R,, P, M,s
216
7.4 Control of MWDa by use of temperature variation; term by 2 disprop or 2 comb. M,s
217
7.5 Effect of expanding drop of monomer in a catalyst solution on MWD of living polymers
218
7.6a Effect of inadequate mixing by a laminar shear model on MWD of living polymers
219
7.6b Effect of different flow lines spending different times in the reactor on the MWD of living polymers; the bimodal MWD
changes with reactor length
353
7.7 Effect of varying rate of addition of initiator and/or monomer, transfer agent, or terminator, in a BR, neglecting change
220
in volume
7.8 Effect of varying the rate of addition of an instantaneous initiator on MWD of living polymers
103,221
1.9 Effect of back mixing on MWD of living polymers prepared in BR, semi-BR, and CFSTR
222
7.10 See also Table 3, set 3.6: Further polymerization of polymers with an initial geometric distribution
7.11 Linear condensation of a multifunctional monomer in a BR
305
7.12 Living polymer, inst. initiation, no transfer, no termination in a TRn, monomer varies
306,307
7.13 Effect of mixing in a BR
308
7.14 Condensation polymerization when monomer is R times more reactive with monomer or with polymer molecules, CFSTR,
and references to BRs
309,3 10
7.15 Effect of recycling a portion of a TR; chain-stopper control
3 1 1
7.16 Production of monodisperse particles
312
7.17 Reversible polymerization with multifunctional monomers. Comparison of MWD from CFSTR with BR
354
CFSTR: Cont i nuous - f l ow, s t i r r ed t ank r eact or ; BR: bat ch r eact or ; TR: t ube r eact or ; MWD: mol ecul ar wei ght di s t r i but i on.
C. SOME DISTRIBUTION FUNCTIONS AND THEIR
PROPERTIES
The frequency function, F(r), is the fraction of molecules
of size r. Furthermore, F(r) is normalized
(Cl)
The weight fraction of molecules of size r is
W(r) = S(r)/ 2 rF(r) = r-F(r)/ i S(r) dr
(C2)
1
0
Averages of any distribution are defined by
2 rF(r)/F ripF(r) = r rF(r)dr/ [ r-F(r)dr
1 1
0 0
(C3)
The number-average degree of polymerization is defined
by
F, = 2 rF(r)/ 2 F(r) = 2 W(r)/ 2 [W(r)/r]
1 1 1 1
(Cd)
Thus, by the definitions of F(r) and W(r)
W(r) = S(r)/?,
The weight-average degree of polymerization is
w
r, = fJ rF(r)/T r-F(r) = 2 rW(r)/ f:W(r)
1 1 1 1
The z and z + 1 averages are defined by Eq. (C3) with i set
equal to 3 and 4. There is no need to restrict averages of a
distribution to positive integers - any useful average can be
defined; such as the (-5/2) average. If the intrinsic
viscosity of a polymer is related to the degree of
polymerization through the equation
M = kr , , w
where ?, is the viscosity-average degree of polymerization,
it is related to the frequency function by
7, = [$r+F(r)/$S(r)] l (C8)
As a approaches unity, P, approaches 7,. In principle, a
distribution function can be determined if sufficient
averages of the distribution can be determined. In practice,
only the number, weight, and perhaps z averages can be
found, which are insufficient to define any distribution
without making further assumptions.
The degree of polymerization is a useful concept as long
as one is describing polymers made with a single monomer
or with monomers of equal molecular weight. When
considering copolymers, one must work with the actual
molecular weight of the reacted unit. This is done in
condensation polymerization. The molecular weight dis-
tribution of addition copolymers is not included here
because of the extreme complexity of these systems.
When performing the summation of a distribution
equation to find an average of the distribution, use is
frequently made of the following sums:
cc
c
P
x-1 = l/(l - p) p < 1 (C9)
x=l
cc
c
XP
x-1 = l/(l -p)2 p < 1
x=l
c
O x2px-l = (1 +p)/(1 ,P)3 p <1
x=l
~x~p~-=~[p~x~-p~-] p < l
cc
c
&bn!/(n - i)! i! = (u + b) n is an integer
i=O
-p ain!/(n - i)! i! = na(l + ay-
i=O
2 ai*n!/(n - i)! i! = na(1 + na)(l + a)n-2
i=O
2 A-/(n - l)! = expA
i l =l
F nAn-/(n - l)! = (1 +A)expA
n=l
co
c
n2An-/(n - l)! = (1 + 3A +A*)expA
n=l
cc
c
&A-/(n - l)! = $ A2 nP-A-/@ - l)!
n=l n=l 1
1. Normal Distribution Function (Gaussian Distribution)
F(r) =
exp{-(r - F)2/202}
(27r) /*a
WO)
W(r) = (r/Y)F(r) Wl)
r=
+Drexp{-(r - 7)*/20*}
s
_
(27r) /*a
= rn
W)
-cc
~2 = +O ( r - F)*exp{-(r - F)*/2o*}
s (27r) *g
VW
W)
Some Distribution Functions and Their Properties
II / 353
Values of F(r) and si F(r) dr are found in many statistical
tables (223).
2. logarithmic Normal Distribution Function
Under the assumption that the weight distribution of the
logarithm of molecular size is normally distributed, we can
replace r in the normal distribution function by In r and ? by
In 7,
W(lnr) =
exp{-(lnr - ln~,)2/2a2}
(2n) /*CT
(W
where
cc
I
W(ln r) d(ln r) = 1
W)
1
or in the alternate form
W(r) = exp{-(lnr - 1nFm)*/2a2}
r(27r) *a
WV
where
M
s
W(r) dr = 1
0
(W
and
cm
In?, =
s
(In r) W(r) dr
(Cl9)
0
Here F,,, is the median value of the distribution, that is, one-
half of the values of r are less than r,.
O* =
1
m (lnr - ln?,)*W(r)dr (C20)
J o
F, = F, exp(-a*/2)
r, = F, exp(+0*/2)
F, = F, exp(+3a2/2)
Fi = F, exp((2i - 3)0*/2
(C21)
02)
(CW
> (CW
Note that
F, = (r, Tw) l*
F,/r, = Y,/Fw = r,+l/i-, = expg*
(C26)
The logarithmic normal distribution sometimes is given in a
generalized form (224)
W,(r) =
Fexp [-(lnr/F,)*/20*]
(24
*cTF;+~ exp{ (s + l)*g*/2}
Pm
References page II - 356
II / 354 RATES OF POLYMERIZATION, AVERAGE MOLECULAR WEIGHTS, AND MOLECULAR WEIGHT DISTRIBUTIONS OF POLYMERS
but Honig (225) has shown that
lnF, = In?, + (s-t l)(~
(CW
Thus, the normalized Lansing-Kramer function (s = 0)
(226) is identical to the normalized Wesslau function
(s = -1) (227).
The generalized logarithmic normal distribution is
skewed to large values of r, but Kotliar (237, 238) shows
that this distribution is not a good representation of a
polymer after either low- or high-molecular weight material
is removed or degradation has occurred.
3. Generalized Exponential Distribution (1,228)
Fm,k,y(r) = mykyk-[exp(-yrm)]/r(k/m)
(C29)
Wm,k,y(r) = my(k+)n k
r Iexp(-yrWW + Wml (C30)
r, = Iy(k + l)/nz]/yr(k/m)
(C31)
r, = r[(k + 2)/+@r[(k + l)/m]
cc 32)
rz = r[(k + 3)/m]/y1+r[(k + 2)/m]
(C33)
ri = r[(k+i)/m]/yl'mr[(k+i- q/m]
(C34)
and
rv = {r[(k + u + l)/m]/y+r[(k + l)/m])i/a (~35)
where a is defined by equation (C7).
The variance of a distribution g2, the usual measure of
distribution breadth for small populations, depends strongly
on the average molecular weight of the distribution:
ci2 = rn(rw - 7,)
Hence, the preferred measure of the molecular weight
distribution breadth is rw/F,.
(a) The distribution function of Schulz (9) and Zimm
(229) is obtained by setting m = 1 and requiring that k > 0.
This distribution is equivalent to the Pearson Type III
distribution
F(r) = ykrk-
kxP(-Yrww
W(r) = y(k+l)rk[exp(-yr)]/I(k + 1)
( w
WI
The distribution reduces to the most probable distribu-
tion where k =1.
The cumulative number or weight fraction of the Schulz
distribution may be computed from
r
s
bk
F1,kay(r) = ryi + k) i=.
2(-qiyirk+i
i! (k + i)
VW
0
r
J
k+l 00 (-1) iyirk+i+l
W1,k,y(r) = r$ + k) i=. i! (a + i +1) .
c
(C39)
0
(b) The Weibull (231) or Tung (232) distribution is
obtained by setting m = 1 + k and k > 0. This distribution
is usually seen in the form
W(r) dr = 1 - exp[-yr(+k)]
(C40)
0
Kotliar (233) shows that evaluation of y and k by the Tung
method can lead to erroneous values of rw/ln.
(c) The Flory distribution, as noted above, occurs when
k = m = 1, provided that lnp can be replaced by -( 1 - p),
i.e. p = 1. The Flory distribution is also written as:
F(r) =pr-(1 -p)
W(r) = rp-(1 -p)2
r, = l/(l -p)
r, =
(1 + PM1 - P)
7, = q[r(2+#a
and with the approximation In p =p - 1
r
W(r) dr Z (l/p) - [l +(1 -p)r]p-
W)
0
For high molecular weights p M 1, hence
r,:rw:rz = 1:2:3.
4. Poisson Distribution
F(r) = exp(-v) d-l/(r - l)!
W(r) = [v/(v + l)]rexp(-v) vre2/(r - l)!
F,=l+v
r, = lfv+v/(l+v)
D. MOLECULAR WEIGHT DISTRIBUTION IN
(C41)
(~42)
( w
(C44)
(C45)
VW
(C48)
w9
(C50)
Wl)
CONDENSATION POLYMERS: THE STOCKMAYER
DISTRIBUTION FUNCTION
Stockmayer (234) has presented a generalized distribution
formula for a variety of monomers containing end groups of
type A which can only react with a variety of monomers
containing end groups of type B. In the original mixture
there areAl, AZ, A3,. . . ,Ai,. . . moles of reactants bearing
respectively, fi, f2, fs, . . . ,fij . . . functional groups of type
A each, together with B 1, B2, . . . , Bj, . . . moles of reactants
of functionalities g 1, g2, . . . gj, . . . in groups of type B. all
functional groups of a given type are equally reactive and
ring formation does not occur appreciably; which obviously
is not true near the gel point. The system reacts until a
fraction ai of the A groups and a fraction ,8 of the B groups
Molecular Weight Distribution in Condensation Polymers: The Stockmayer Distribution Function II / 355
have reacted. Further If each species i has an effective molecular weight Mi,
which is lower than the original molecular weight by the
QC .fiAi =PCgjBj
term Wcfi/2, where WO is the molecular weight of the by-
i
j
product, then
Now N{m,, nj} represents the number of moles of that W=CMiAi+CBjMj
P5)
species which consists of m 1, m2, . . . , mi, . . . monomer i
j
units of the A type combined with IZ 1, IZ 2, . . . , nj units of
the B type. The number of molecules of the end of the reaction is,
K(CifiWZi - xi mi)! (Cjgjnj - Cj nj)! rri(X"i/mi!)nj(Yj"'/nj!)
Nmi nj = (CifiWZi - xi rni - Cj nj + l)! (Cj gjnj - Cj nj - xi rni + l)!
w
where neglecting byproduct,
An example will illustrate the use of Eq. (Dl).
Suppose we have the monomers acetic acid (CHsCOOH,
AI, fi = 1) and adipic acid (HOOC(CH2)4 COOH,
AZ, f2 = 2) reacting with ethylene glycol (HOCH2CH20H,
BI, gl = 2)
and glycerol (HOCH2CHOHCH20H,
B2, g2 = 3) (all hydroxyl groups of the glycerol are
considered equally reactive). What is the number of
molecules which contain exactly 1 acetic acid unit, 4
adipic acid units, 3 glycol units, and 2 glycerol units? It is
N{1,4,3,2} and
N{1,4,3,2}=K(1+8-l-4)!(6+6-3-2)!
+(1+8-l-4-3-2+1)!
+(6+6-3-2-l-4+1)!
w
where
Xl = [A$Ad [A]
x2 = [A$Aj [,i_;]
y1 = [,B12T;,,l [73>
(D4)
= [,,:;,,1[1: IO,]
K = (AI + u2)(1 - a)(1 - P)/P
N=CAi+C Bj-aCfiAi
P6)
i
i
i
The number-average molecular weight is
M, = W/N
WY
The weight-average molecular weight is
M
w
pCiMFAi+cuCjM,ZBj
xi .fiAi
Cj gj Bj
+
~P[~(fc-l)Mb2+P(gc-l)M,2+2M,Mb]
1 - QP(fc - l)(gc - 1) 1
x PCiMiAi+LYCjMjBj -
Ci .fiAi
Cj g.iBj
1
ow
where
fC= (Ff?Ai)/(FfiAi)
M, = c MifiAi
( i )/(F fiAi) (D9)
Mb = C MjgjBj
( j
Simpler expressions for M, and M, are given by Ziegel
et al. (235) for the case when only bifunctional B monomers
are present.
The gel point is
(4, = l/(fc - l)kc - 1) P 10)
Extensive computations of N{mi, nj} for the case
fl = 1, f2 = 2, f4, and g:! = 2 have appeared (236).
References page II - 356
I I / 356 RATES OF POLYMERIZATION, AVERAGE MOLECULAR WEIGHTS, AND MOLECULAR WEIGHT DISTRIBUTIONS OF POLYMERS
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Heats and Entropies of Polymerization,
Ceiling Temperatures, Equilibrium Monomer
Concentrations, and Polymerizability
of Heterocyclic Compounds*
J. Leonard
Departement de Chimie and CERSIM, Universite Laval, Quebec, Canada
A. Heats of Polymerization
Table 1. Monomers Giving Polymers
Containing Carbon Atoms Only
in the Main Chain
1 .I. With Acvclic Carbons Onlv
in the
1.1.1.
1.1.2.
Main Chain
Di enes
Monomers Giving
Polymers With or
1.I .3
1.1.4.
1.I .5.
1.2. With Aromatic or Cyclic
Without Aliphatic Side
Chains that Contain
Only C, H II-365
Monomers Giving
Polymers With Aliphatic
Side Chains that Contain
Het eroat oms II-368
Monomers Giving
Polymers With Aromatic
Side Chains that Contain
Only C, H II-371
Monomers Giving
Polymers With Aromatic
Side Chains and that
Contain Heteroatoms II-371
II-365
II-365
I I-365
II-365
Carbons in the Main Chain II-372
Table 2. Monomers Giving Polymers
Containing Heteroatoms in the
Main Chain II-373
2.1. Monomers Giving Polymers
Containing 0 in the Main
Chain, Bonded to Carbon
Onl y II-373
2.1 .l. Ethers and Acetals II-373
2.1.2. Cyclic Esters II-376
2.2.
2.3.
2.4.
2.5.
2.6.
Monomers Giving Polymers
Containing 0 in the Main
Chain, Bonded to other
Heteroatoms (S, Si, PI
Monomers Giving Polymers
Containing S in the Main
Chain, Bonded in the Chain
to Carbon Only
Monomers Giving Polymers
Containing N in the Main
Chain, Bonded in the Chain
to Carbon Only
Monomers Giving Polymers
Containing N in the Main
Chain, Bonded to other
Heteroatoms (PI
Other Monomers Giving
Polymers not Listed Above
Table 3. Copolymers
B. Entropies of Polymerization
Table 4. Monomers Giving Polymers
Containing Main Chain Carbon
Onl y
4.1. Main Chain Acyclic Carbon
Onl y
4.1 .I. Dienes
4.1.2. Monomers Giving
Polymers Without or
With Aliphatic Side
Chains that Contain
Only C, H
4.1.3. Monomers Giving
Polymers With
Aliphatic Side Chains
that Contain
Het eroat oms
*Based on the tables compiled for the third edition, by W.K. Buslield, School of Sciences Griffith University, Brisbane, Australia.
II-377
II-378
II-378
II-379
II-379
II-380
II-381
II-382
II-382
II-382
II-382
II-384
II / 363
II / 364 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
C.
4. 1. 4.
4.1.5.
4.1.6.
Monomers Giving
Polymers With Aromatic
Side Chains that
Contain Only C, H
Monomers Giving
Polymers With
Aromatic Side Chains
that Contain
Heteroatoms
Other Monomers
Giving Polymers not
Listed Above
4.2. With Aromatic or Cyclic
Carbons in the Main Chain
Table 5. Monomers Giving Polymers
Containing Heteroatoms in the
Main Chain
5.1.
5.2.
5.3.
5.4.
Monomers Giving Polymers
Containing 0 in the Main
Chain, Bonded to Carbon
Only
5.1 .l. Ethers and Acetals
5.1.2. Cyclic Esters
Monomers Giving Polymers
Containing 0 in the Main
Chain, Bonded to Other
Heteroatoms (S, Si, P)
Monomers Giving Polymers
Containing N in the Main
Chain, Bonded in the Chain
to Carbon Only
Other Monomers Giving
Polymers not Listed Above
Table 6. Copolymers
Ceiling Temperatures and Equilibrium Monomer
Concentrations
1. Equilibria involving Pure Liquid Monomers
Table 7. Monomers Giving Polymers
Containing Main Chain Acyclic
Carbon Only
Table 8. Monomers Giving Polymers
Containing Heteroatoms in the
Main Chain
8.1. Monomers Giving Polymers
Containing 0 in the Main
Chain, Bonded to Carbon
Only
8.2. Monomers Giving Polymers
Containing 0 in the Main
Chain, Bonded to Other
Heteroatoms (S, P, Si)
8.3. Monomers Giving Polymers
Containing S in the Main
II-385
II-385
II-386
II-386
II-387
II-387
II-387
II-390
II-391
II-391
II-392
II-392
II-393
II-394
II-394
II-395
II-395
II-396
D.
E.
F.
Chain, Bonded in the Chain to
Carbon Only II-396
8.4. Monomers Giving Polymers
Containing N in the Main
Chain, Bonded in the Chain to
Carbon Only
8.5. Other Monomers Giving
Polymers not Listed Above
2. Equilibria Involving Gaseous Monomers
3. Equilibria Involving Monomers in Solution
Table 9. Monomers Giving Polymers
Containing Main Chain Carbon
Only
9.1. Monomers Giving Polymers
Containing Main Chain
Acyclic Carbon Only
9.2. Monomers Giving Polymers
Containing Main Chain
Cyclic Carbon
Table 10. Monomers Giving Polymers
Containing Heteroatoms in the
Main Chain
10.1. Monomers Giving Polymers
Containing 0 in the Main
Chain, Bonded to Carbon
Only
10.2. Monomers Giving Polymers
Containing 0 in the Main
Chain, Bonded to Other
Heteroatoms (Si, P)
10.3 Monomers Giving Polymers
Containing S in the Main
Chain, Bonded in the Chain
to Carbon Only
10.4. Monomers Giving Polymers
Containing N in the Main
Chain, Bonded in the Chain
to Carbon Only
Table 11. Copolymers
11 .l. 1 : 1 Copolymers
11.2. General Copolymers
Polymerizability of 5-, 6-, and 7-Membered
Heterocyclic Ring Compounds
Table 12. S-Membered Ring Compounds
Table 13. 6-Membered Ring Compounds
Table 14. 7-Membered Ring Compounds
Table 15. Comparison of Polymerizability
of Unsubstituted 5-, 6- and
7-Membered Ring Compounds
Notes
References
II-397
II-397
II-397
II-398
II-398
II-398
II-399
II-399
II-399
I I-400
I I-400
I I-400
II-401
II-401
II-401
II-401
II-402
II-403
II-404
II-405
II-406
II-407
Heats of Polymerization II / 365
A. HEATS OF POLYMERIZATION
Symbols: The subscripts xx to AH denote the state of the monomer (first letter) and the state of the polymer (second letter), as follows:
g Gaseous state (hypothetical in case of polymer)
c Condensed amorphous state
c Crystalline or partially crystalline state
1 Liquid state
s In solution; solvent specified in the sixth column (1s denotes polymer dissolved in monomer).
For emulsion polymerization the subscript lc is used and a note added in the sixth column. In all cases where monomer or polymer is present in solution
etc., the value of AH will depend on the composition to some extent. Where the polymer is crystalline, AH will depend on the degree of crystallinity. AH
values are in kJ per mol of monomer and are generally the limiting values for high degree of polymerization n [l kcal = 4.187 kJ]. Where more than one
value is available in the literature for given states of monomer and polymer and a given method, only one value is shown in the tables. This corresponds to
one of the references indicated Ni refers to the ith note given at the end of the table.
Example: CzH4 (g)
-+ (l/n)(C2H4), (g), AH,, = -93.5kJ
Precision: generally 0.5-4.0 kJ/mol (for details see Ref. 1).
Methods of&termination: These are summarized below, using the numbering system in Ref. 1.
2 Combustion of monomer or polymer or both.
3 Reaction calorimetry.
4a Thermodynamic (van? Hoff Equat i on).
4b Semiempirical rules applied to evaluate heat of formation of polymer or monomer or both. Such rules may be found in Refs. 25,143,223,224,335.
5 Heat capacity and heat of transition (Kirchhoffs equation).
TABLE 1. MONOMERS GIVING POLYMERS CONTAINING CARBON ATOMS ONLY IN THE MAIN CHAIN
State of monomer
-mxx
Temp.
Monomer and polymer (xx)
Wmol) (Cl Method Solvent/Notes Refs.
1.1. WITH ACYCLIC CARBONS ONLY IN THE MAIN CHAIN
1.1.1. DIENES
1,3-Butadiene gg 73 2 5 4b 1 : 2 Polymerization
gg 78 25 4b 1 : 4 Polymerization
lc 73 2 5 2 Nl
Chloroprene lc 68 61.3 3
Cyclopentadiene ss 59 - 70 3 Methylene chloride
Isoprene
gg 70.5 25 4b
lc 75 2 5 2
1s 7 1 74.5 3
1s 65.5 34.6 3 NZ
1.1.2 MONOMERS GIVING POLYMERS WITH OR WITHOUT ALIPHATIC SIDE CHAINS THAT CONTAIN ONLY C, H
1.121. Olejns (listed by increasing carbon number)
Ethylene
Propene
g&t 93.5 2 5 4b
gc 108.5 25 2
s 107.5 2 5 3
gc 101.5 2 5 2
cc 1 7 3 - 173 5
cc 169 - 173 5
gc 212 1 7 3 5
gc 209 1 7 3 5
gc
212 2 5 4b
gc
209 2 5 4b
gc 211 1 2 7 5
g c 204 1 2 7 5
gl 1 9 8 227 5
Lx? 86.5 2 5 4b
&F 104 2 5 2
lc 84 2 5 4b
S C 69 - 78 3
AH~u, (Polymer) taken as 5.0
Polymer is poly( 1-butene), iso
Polymer is poly(l-butene), iso
Polymer is poly( 1-butene), iso
Polymer is poly( 1-butene), iso
Polymer is poly(l-butene), iso
Polymer is poly( 1-butene), iso
Polymer is poly(l-butene), iso
Polymer is poly(l-butene), iso
Polymer is poly( 1-butene), iso
n-Butane
1 0
1 0
45
4 1
190
1 0
46
15
47
2
23
1 8 3
2,4
385
385
385
385
385
385
385
385
385
5
3
5
6
Notes page 11-406; References page II - 407
II / 366 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 1. contd
Monomer
State of monomer -AH,
and polymer (xx) Wmol)
Temp.
(C) Method Solvent/Notes Refs.
I-Butene
gg
lc
2-Butene. cis
2-Butene. tram
Isobutene
1-Pentene
-, 4-met hyl
2-Pentene, cis
lc
lc
lc
lc
gc
gc
F
gc
gl
gg
lc
cc
cc
lc
lc
k-c
gc
gc
gc
gl
gg
lc
cc
c/c
lc
lc
gc
g c
gc
gc
gl
gc
lc
ss
S S
cc
cc
lc
lc
lc
lc
gl
gl
cc
cc
lc
lc
lc
lc
gc
gc
gc
gc
gl
gg
cc
I
YCf
lc
lc
lc
86.5 2 5 4b
83.5 2 5 4b
18 - 173 5
74 - 173 5
83 - 73 5
79 - 73 5
108 2 5 4b
1 0 3 2 5 4b
1 0 7 127 5
99 127 5
94 227 5
80 2 5 4b
15 2 5 4b
63 - 173 5
59 - 173 5
75 - 73 5
7 1 - 73 5
1 0 1 25 4b
- 96 25 4b
99 1 2 7 5
92 1 2 7 5
86 227 5
75.5 25 4b
7 1 25 4b
57 - 173 5
54 - 173 5
7 1 -73 5
67 - 7 3 5
96 25 4b
9 1 25 4b
96 1 2 7 5
89 1 2 7 5
8 3 227 5
72 25 2
48 2 5 2
53.5 2 5 ?
54 - 35 3
84 - 173 5
8 1 - 173 5
95 - 7 3 5
93 -73 5
99 2 5 2,4b
95 2 5 2,4b
117 1 2 7 5
1 1 3 227 5
82 - 173 5
79 - 173 5
93 - 7 3 5
90 -73 5
91 2 5 4b
95 2 5 4b
124 1 2 7 5
117 1 2 7 5
122 227 5
112 227 5
1 0 5 327 5
80.5 2 5 4b
75 - 173 5
72 - 173 5
87 - 73 5
8 5 - 13 5
9 1 25 2,4b
81 25 2,4b
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Low polymer
Solvent? low polymer
CH2C12, polymer swollen, N3
5
5
385
385
385
385
385
385
385
385
385
5
5
385
385
385
385
385
385
385
385
385
5
5
385
385
385
385
385
385
385
385
385
I
3,8
8
9
386
386
386
386
386
386
386
386
381
387
387
387
387
387
387
387
387
387
387
1 0
386
386
386
386
386
386
TABLE 1. contd
Heats of Polymerization II / 367
Monomer
State of monomer
and pol ymer (xx)
- A H ,
Wmol)
Temp.
(C) Method Solvent/Notes Refs.
gl
gl
-1
4-methyl lc
lc
s
g c
gc
gc
gl
2-Pentene, tram
gg
cc
cc
lc
lc
lc
lc
gl
gl
-, 4-methyl lc
lc
gc
gc
gc
gc
gl
1 -Hexene lc
1-Heptene
gg
1.1.2.2. Cycloalkanes (listed by increasing ring size)
Cyclopropane lc
-, methyl- lc
-, l,l-dimethyl- lc
Cyclobutane lc
-1 methyl- lc
-, l,l-dimethyl- lc
Cyclopentane lc
-, methyl- lc
- 1, l-dimethyl- lc
Cyclohexane lc
-,
methyl- lc
-, 1, l-dimethyl- lc
Cycloheptane lc
Cyclooctane lc
Cyclononane lc
Cyclodecane lc
Cycloundecane lc
Cyclododecane lc
Cyclotridecane lc
Cyclotetradecane lc
Cyclopentadecane lc
Cyclohexadecane lc
Cycloheptadecane lc
1.1.2.3. Cycloalkenes
Cyclobutene
Cyclopentene
11
gl
lc
c(I)c
lc
lc
c(I)c
lc
lc
lc
109 127 5 386
1 0 5 227 5 386
90 25 4b 387
88 25 4b 387
118 127 5 387
1 1 1 127 5 387
116 227 5 387
114 227 5 387
100 327 5 387
15.5 25 4b 1 0
70 - 173 5 386
68 - 173 5 386
83 - 73 5 386
8 1 - 73 5 386
87 25 2,4b 386
8 3 25 2,4b 386
106 127 5 386
1 0 3 227 5 386
86 2 5 4b 387
83 25 4b 387
1 1 5 1 2 7 5 387
1 0 7 1 2 7 5 387
1 1 3 227 5 387
1 0 3 227 5 387
97 327 5 387
83 25 4b 5
86 25 4b 5
113 25 2 11
105 25 4b 11
97.5 2 5 4b 11
1 0 5 2 5 2 1 2
100 2 5 4b 11
93.5 25 4b 11
22 25 2 1 2
1 7 2 5 4b 11
13.5 2 5 4b 11
- 3 25 2 1 2
- 9 25 4b 11
- 7.5 25 4b 11
21.5 2 5 2 1 2
34.5 2 5 2 1 2
47 25 2 1 3
48 25 2 13
45 2 5 2 13
1 4 2 5 2 13
22 25 2 13
7 25 2 13
1 2 2 5 2 1 3
8 2 5 2 1 3
8.5 2 5 2 1 3
1 2 1 2 5 2,4b cis-Polybutadiene 388
1 4 5 2 5 2,4b cis-Polybutadiene 388
17.5 25 2
N66
361
11 - 173 5 c&Pol ymer 388
1 6 -73 5 c&Pol ymer 388
1 5 2 5 2,4b cis-Polymer 388
23 - 173 5 trans-Polymer 388
1 9 - 7 3 5 trans-Polymer 388
1 8 25 2,4b trans-Polymer 388
1 8 77 5 trans-Polymer 388
Notes page 11-406; References page II-407
II / 368 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 1. contd
Monomer
State of monomer -AH, Temp.
and polymer (xx) Wmol) m
Method Solvent/Notes Refs.
Cyclopentadiene ss 59 - 173 3 Butyl chloride, N?a 3 7 1
Cyclohexene ss 1 - 65 4a Toluene, N7s 389
Cycloheptene c(III)c 1 2 - 173 5 70% rmns, 30% &-Pol ymer, Ns4 388
c(III)c 1 8 - 173 5 70% tmns, 30% &-Pol ymer, Ns4 388
c(II)c 1 8 - 73 5 70% trans, 30% &-Pol ymer, Ns4 388
c(II)c 26 - 73 5 70% rruns, 30% c&Pol ymer, Ns4 388
lc 1 8 25 2,4b 70% trans, 30% cis-Polymer 388
lc 29 25 2,4b 70% trans, 30% &-Polymer 388
11 1 7 5 1 5 70% truns, 30% &-Pol ymer 388
Cyclooctene c(II)c 1 8 - 173 5 48% t runs, 52% &-Pol ymer, N54 388
c(II)c 6 - 173 5 48% fruns, 52% &-Pol ymer, N54 388
c(I)c 27 - 73 5 48% t runs, 52% &-Pol ymer, Ns4 388
c(I)c 1 9 - 73 5 48% t runs, 52% &-Pol ymer, Ns4 388
lc 30 2 5 2,4b 48% rruns, 52% c&Polymer 388
lc 1 3 25 2,4b 48% wans, 52% c&Pol ymer 388
11 1 3 57 5 48% t runs, 52% c&Pol ymer 388
1.1.3. MONOMERS GIVING POLYMERS WITH ALIPHATIC SIDE CHAINS THAT CONTAIN HETEROATOMS
1.1.3.1. Acrylic Derivatives (listed alphabetically)
Acrolein
Acrylamide
-1
N-methylol-
-, N,N-methylene bis-
Acrylic acid
-1
n-butyl ester
-9
ethyl ester
-3 ethylhexyl ester
-, lauryl ester
-3
methyl ester
Acrylonitrile
lc
SS
ss
ss
IC
ss?
S C
S C
lc
lc
lc
ss
S C
S C
;:
ss
ss
ss
SS
ss
lc
lc
lc
lc
lc
lc
SS
ss
lc
SC
1.1.3.2. a-Substituted Acrylic Derivatives (listed alphabetically)
a-Chloroacrylic acid, methyl ester lc
a-Cyanoacrilic acid, methyl ether lc
-> ethyl ester cc
I
I
IC
lc
-, ally1 ester cc
cc
cc
lc
80 74.5
57.5 74.5
81.5 74.5
81.5 74.5
79.4 90
70.5 74.5
60 74.5
57.5 74.5
74.5 190
82.7 190
67 74.5
77.5 20
73.5 74.5
72 74.5
74.5 74.5
78 74.5
77 74.5
79 74.5
76 74.5
75.5 74.5
78 74.5
78 74.5
80.7 90
78.2 90
80.5 30
78 76.8
81.8 80
84.5 20
8 1 74.5
76.5 74.5
77.5 74.5
52.7 80
42 60
28 - 173
29 - 73
47 25
53 1 2 7
54 177
4 1 - 173
42 - 73
43 - 8
62 - 8
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
5
5
2
5
5
5
5
5
5
Hexane
Water
Water
Acetone
Benzene
Hexane
Water
Benzene
Carbon tetrachloride
Hexane
Acetone
Butanone
Benzene
Carbon tetrachloride
Hexane
Ethyl alcohol
Hexane
Benzene
15
17
1 7
17,14
332
1 7
17
1 7
332
332
1 5
36,37
1 5
15
15
17,37
1 7
17
1 7
1 7
1 7
34,37
318
318
352
21,34,37
319
36
34
17,21,38,201
17
319
354
390
390
390
390
390
391
3 9 1
3 9 1
3 9 1
TABLE 1. contd
Heats of Polymerization II / 369
Monomer
State of monomer
--AH, Temp.
and polymer (xx) Wmol) (Cl Method Solvent/Notes Refs.
-1 n-decyl ester
-, allyloxyethyl
Ethacrylic acid, methyl ester
Methacrolein
Methacrylamide
Methacrylic acid
-, benzoic acid ester
-, benzyl ester
-1 n-butyl ester
-, reti-butyl ester
-1 cyclohexyl ester
-, 2-ethoxyethyl ester
-1 ethyl ester
-, g(N-piperidyl)ethyl ester
-1 n-hexyl ester
-, 2-hydroxyethyl ester
-, 2-hydroxypropyl ester
-, isobutyl ester
-7 isopropyl ester
-9 methyl ester
-, methyl ester
deuterated
-9 n-octyl ester
lc
lc
cc
cc
lc
lc
cc
lc
lc
lc
1s
lc
ss
ss
ss
ss
lc
lc
ss
ss
ss
S C
cc
cc
cc
sl
lc
lc
1s
1s
lc
1s
lc
1s
lc
lc
1s
lc
lc
1s
lc
lc
lc
lc
IC
lc
lc
IS
cc
cc
lc
lc
ss
ss
ss
ss
cc 33 - 173 5 414
cc 35 - 73 5 414
lc 55 25 5 414
lc 51 17 3 414
lc 57 65 3 188
6 4
68
29
29
69
14
41
43
49
5 1
3 1
65. 5
56
42. 5
39. 5
35
42. 5
64. 5
66
56. 5
54
51
55
56
59
51
90
56
51. 5
60
54. 5
51
53
51. 5
62
60
59. 5
51. 5
51
58. 5
60
50
50. 5
60
60
56
55. 5
25
121
- 113
- 73
25
127
- 173
- 13
25
57
87
74. 5
74. 5
74. 5
14. 5
74. 5
14.5
25
20
25
25
74. 5
- 173
- 73
25
II
221
76. 8
74. 5
26. 9
26. 9
76. 8
26. 9
74. 5
26. 9
120
74. 5
26. 9
40
25
26. 9
25
25
14. 5
130
74. 5
2,4b
5
5
5
2,4b
5
5
5
2,4b
5
4a
3
3
3
3
3
3
2
3
3
3
3
5
5
5
23
5
3
3
3
3
3
3
3
3
4a
3
3
3
3
3
3
3
3
3
4a
3
55 25 2
57. 5 26. 9 3
34 - 173 5
36 - 73 5
55 25 5
56 71 3
54 130 4a
58. 5 14. 5 3
57. 5 14. 5 3
58. 5 74. 5 3
391
391
392
392
392
392
393
393
393
393
395
15
Water 1 7
Chl oroform 1 7
Acetone 1 7
Benzene 1 7
1 5
206
Water 36
Water 37
Dimethylformamide, NT 203,316
Methanol, N s 15
394
394
394
1,4 Dioxane 394
394
N6 39
34,31,39
1 4
1 4
39
14
34
14
40
34, 31
14
188
Emulsion (aq.) 37
14
Emulsion (aq.) 37
Emulsion (aq.) 37
34
34
42, 43, 29
11, 34, 36, 37,
41, 201, 235
206
14
414
414
414
414
o-Dichlorobenzene 42, 29
Acetonitrile 34
Tetrahydrofuran 34
Hexane 34
Notes page 11-406; References page II - 407
II / 370 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 1. contcf
Monomer
State of monomer --AH, Temp.
and polymer (xx) Wmol) (Cl
Method Solvent/Notes Refs.
-, phenyl ester
n-propyl ester
Gethacrylonitrile
1.1.3.3. Vinyl Ethers
Vinyl n-butyl ether
1.1.3.4. Vinyl Alcohol, Ketones, Halogens
Vinyl alcohol
Methyl vinyl ketone
Vinyl chloride
1.1.3.5. Vinyl Esters
Vinyl acetate
Vinyl propionate
Vinyl 2-ethylhexoate
1.1.3.6. Others (listed alphabetically)
Ally1 chloride
Ethylene, nitro
-, tetrafluoro-
Fumaric acid, diethyl ester
Itaconic acid, dimethyl ester
Maleic anhydride
Mal ei mi de
-, phenyl
a-Metbylene pentanolactone
Vinyl cyclohexane
Vinylidene chloride
N-Vinyl succinimide
lc
lc
lc
s s
lc?
1s
gc
lc
lc
lc
lc
1s
ss
s s
s s
lc
lc
1s
lc
s s
gg
gc
lc
lc
s s
1s
s s
ss
s s
s s
s s
s s
cc
cc
lc
lc
lc
lc
lc
lc
lc
lc
lc
cc
cc
lc
lc
lc
lc
gc
gc
gc
gc
1s
51.5 76.8 3
57.5 74.5 3
56.5 74.5 3
64 130 4a
Ns
Benzonitrile
39
34
15
44,29
60 50 3
N6
216
74 74.5 3
132 2 5 2
7 1 2 5 4b
111.5 2 5 2
96 74.5 3
see Acetaldehyde 1 9 5
1 7
18.19,20
1 0
AHr,, (Monomer) taken as 20 1 8
215
8 8 74.5 3 17,34,21
89.5 25 3 3 5
90 74.5 3 Acetone 1 7
86.5 74.5 3 Hexane 1 7
86 74.5 3 Benzene 1 7
86 74.5 3 17,34
88 74.5 3 34
77.5
88
9 1
74.5
20
20
3
2
3 Dimethylformamide,
tetrahydrofuran
15
214
214
155 2 5 2
172 25 2
163 f 17 25 2
65 100 3
60.5 26.9 3
59 74.5 3
67.5 74.5 3
89.5 74.5 3
88.5 74.5 3
87.5 74.5 3
37 55 4a
38.8 8 3 4a
88 - 173 5
68 - 173 5
100 - 73 5
79 - 7 3 5
1 0 5 25 2,4b
8 5 25 2,4b
1 1 1 127 5
86 127 5
60 76.8 3
75.5 25 2
73 74.5 3
67 - 173 5
56 - 173 5
77 - 13 5
66 - 73 5
8 1 25 2
70 25 2
1 0 8 25 2
97 2 5 5
107 127 5
95 1 2 7 5
54.7 97 3
o-Dichlorobenzene
Chlorobenzene
Dioxane
Acetonitrile
Dimethylformamide
DME N78. N75
DMF
22
22,23
1
235
1 4
1 5
24
24
24
24
440
315
396
396
396
396
396
396
396
396
2 1
1 8
15
397
397
397
397
397
397
391
397
397
397
384
Heats of Polymerization
TABLE 1. contd
State of monomer
-mm Temp.
Monomer and polymer (xx) Wmol) (Cl
Method Solvent/Notes
1.1.4. MONOMERS GIVING POLYMERS WITH AROMATIC SIDE CHAINS THAT CONTAIN ONLY C, H (listed alphabetically)
Acenaphthalene SS 87.8
84.8
98.5
67
67
82
43
34
58
II / 371
Refs.
Acenaphthylene
Biphenyl, p-isopropenyl-
Indene
ss
ss
ss
ss
cc
ss
ss
ss
0 3
1 8 3
26.9 3
74.5 3
74.5 3
26.9 3
60 4a
- 15 4a
- 30 3
Dichloromethane
Dichloromethane
o-Dichlorobenzene
o-Dichlorobenzene
Benzene
Toluene, N 78, N 75
Tetrahydrofuran
Methylene chloride indep. of
T [-70 to 1001
Methylene chloride
Methylene chloride
Methylene chloride
Methylene chloride
Methylene chloride
Metbylene chloride
Methylene chloride
Tetrahydrofuran
Toluene, N7s
320
320
1 4
15
15
1 4
399
1 6
190
-, 5-methyl-
-, 6-methyl-
-, 5,6-dimethyl-
-, 4,5,6,7-tetramethyl-
Naphthalene, 2-isopropenyl-
Styrene
- a-acetoxy
-, o-chloro-
-, p-chloro-
-, 2,5-dichloro-
-1 ar-ethyl-
-, a-methyl-
-,
a-methyl, p-tert-butyl-
-, 2,4,6-trimethyl-
ss
ss
ss
SS
SS
ss
ss
SS
ss
gg
lc
lc
lc
1s
1s
ss
ss
lc
lc
lc
lc
lc
lc
lc
ss
ss
ss
ss
ss
lc
58
57.5
58.5
77.5
6 5
79
75
36.5
38
74.5
70
68.5
73
73
73
66.5
26
68.5
67
69
68
35
34.5
39
33.5
47.7
1 5
1 4
29.7
70
- 50
- 60
- 7 0
- 4 0
- 4 0
- 4 0 _
- 4 0
- 5
1 0
2 5
2 5
26.9
1 2 7
25
26.9
- 6 0
64
76.8
76.8
76.8
76.8
25
- 2 0
25
- 20
22
- 10
- 10
26.9
3
3
3
3
3
3
3
4a
4a
4b
2
3
4a
2
3
3
4a
3
3
3
3
2
4a
4a
4a
4a
4a
4a
3
1 7 5
175,169
175,169
1 7 5
1 7 5
1 7 5
1 7 5
1 6
400
2 5
26
14,17,27.201.235
28,29
26
1 4
30,190
401
27
2 7
27
27
3 1
32,29
1 2 3
32,29,33,16
341
402
402
Methylene chloride
Toluene, N7s. N75
N9
Tetrahydrofuran
Cyclohexane
n-Heptane, N 7s
Toluene, N7s
Solvent and temp. not stated 3 8 1
1 4
1. 1. 5. MONOMERS GIVING POLYMERS WITH AROMATIC SIDE CHAINS AND THAT CONTAIN HETEROATOMS
2-Amino-4-alkyl/aryl-amino-6-isopropenyl-1,3,5-triazine,
R1 = H, RZ = ethyl 1s
RI = H, R2 = propyl 1s
RI = ethyl, RZ = ethyl
N-p12
R 1= propyl, R2 = prowl bN$
1s
1s
R 1= methyl, R 2 = phenyl 1s
R 1= methyl, R 2 = phenyl
NRIRz
1s
R 1 = H, R2 = p-met boxyphenyl 1s
R 1 = H, Rz = p-met hoxyphenyl 1s
2-Amino-4-(N-R. aniline)-6-isopropenyl- 1,3,5-triazine
R = n-alkyl = n-propyl lc
= n-hexyl lc
= n-octyl lc
= n-decyl lc
= n-dodecyl lc
= n-tetradecyl lc
= n-hexadecyl lc
R = alkyl = isopropyl lc
= isobutyl lc
= set-butyl lc
64.8
63.5
53.9
47.7
50.2
53.1
50.2
46.8
46 60 3 403
43 60 3 403
42 60 3 403
4 1 60 3 403
4 1 60 3 403
40 60 3 403
39 60 3 403
44 60 3 404
44 60 3 40
43 60 3 404
170 3
160 3
1 6 1 3
1 5 3 3
140 3
150 4a
160 3
160 4a
N65
N65
370
370
Nss 370
N65 370
379
379
378
378
Notes page 11-406; References page II - 407
II / 372 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 1. contd
Monomer
State of monomer
-mxx
Temp.
and polymkr (xx) (kJ/mol) ((-2 Method Solvent/Notes Refs.
= n-pentyl
= isopentyl
= 1 -methylbutyl
R = benzyl
R = chloro
R = - 4-methoxy-
R = - 4-ethoxy-
2-Anilo-4-R-6-isopropenyl-1,3,5-triazine
R = methoxy
R = ethoxy
Atropic acid, methyl ester
Atroponitrile
Benzoic acid, n-methacryloyloxy-
vinyl ester
Carbazole, N-vinyl-
2,4-Hexadiyne-1,6-di(R group)
R= -SOsCsH&Hs(p)
R = -NHCgHs(NO2)2(2,4 posn.)
R= -SOsCsH4NNCsHs(p)
R = -0CONHCH 2COOH
Oxazol e, 2-isopropenyl-
Pyridine
-, 2-isopropenyl-
-, 2-vinyl-
-, 4-vinyl-
Silane, benzyl dimethyl vinyl-
-, dimethyl phenyl vinyl-
trimethyl vinyl-
GJJrJ-Tetraethyl-4-isopropenyl-
phenylphosphonous diamide
Thiazole, 2-isopropenyl-
p-[bis(Trimethylsilyl)methyl]isopropenylbenzene
lc 44
lc 43
lc 42
lc 44
1s 11
1s 1 4
1s 1 4
1s 1 2
1s 1 2
s s 28
s s 39
lc 59
lc 84.5
SC 63.5
ss 94.9
cc 152.6
cc 11.5
cc 138
cc 130
ss 39.5
60 3 404
60 3 404
60 3 404
60 3 404
170 3 405
1 8 3 3 406
182 3 406
174 3
174 3
- 4 0 4b
50 4b
2 5 2
74.5 3
14.5 3
0 3
Toluene, N ia
Toluene, N 1s
Hexane
Dichloromethane
406
406
149
149
363
34
15
321
1 8 7 3
1 3 5 3
140 3
137 3
20 4a Tetrahydrofuran
372
373
374
375
284
ss 26 20 4a
ss 40 - 15 4a
lc 71.5 14.5 3
1s 75.5 74.5 3
S C 73.5 74.5 3
lc 78 74.5 3
ss 78 74.5 3
cc 48.2 - 7 3 2
lc 66.7 25 3
lc 67.1 77 3
lc 56.5 2 5 3
lc 65.8 2 5 3
s s 21 - 55 4a
Tetrahydrofuran
Toluene, N 7s
Benzene
Benzene, hexane
N62
N62
N62
N62
Tetrahydrofuran
284
407
1 5
1 5
15
1 7
1 7
355
366
366
362
367
408
ss 28.5 20 4a Tetrahydrofuran 284
s s 30 - 30 4a Tetrahydrofuran 409
1.2. WITH AROMATIC OR CYCLIC CARBONS IN THE MAIN CHAIN
- 11,12-Dicyano-2,6naphtoquinodimethane
11,12-bis (alkylthio)
alkyl = butyl ss 67
= s-butyl ss 59
= isopropyl s s 65
= ethyl s s 69
= methyl s s 70
- , 7,8Dicyanoquinodimethane
7,8-bis(butoxycarbonyl)- s s 26
7,8-diacetyl- s s 25
7,8-dibenzoyl- ss 22
7,8dibutoxycarbonyl- ss 26
7,8-diisobutyryl- ss 23
7,8dipropionyl- s s 24
7,8-bis(ethylthio)- s s 23
7,8-bis(phenylacetyl)- s s 2 5
7,8-bis(phenylthio)- s s 23
Norbomylene c(II)c 56
c(I)c 62
c(I)c 62
lc 65
5-Trimethylsilyl-2- cc 38
cc 40
30 4a Oligomer, benzene, N7s. Nss 410
30 4a Oligomer, benzene, N7s. Nss 410
30 4a Oligomer, benzene, Nrs, Nsa 410
30 4a Oligomer, benzene, N7s, Nsa 410
30 4a Oligomer, benzene, N7sr Nsa 410
60 4a
55 4a
5 5 4a
5 5 4a
5 5 4a
5 5 4a
60 4a
55 4a
50 4a
- 173 5
-73 5
2 5 4b
57 5
- 173 5
- 173 5
Chloroform, N7s. Nsi
Chloroform, N78, Nsi
Chloroform, N78, Nsi
Chloroform, Nrs, Nsi
Chloroform, N7s. Nsi
Chloroform, N7s, Nsi
Chloroform, N78, Nsi
Chloroform, N78, Nsr
Chloroform, N78, Nsi
55% cis/45% trunk Polymer, Ns4
55% cis/45% tran~ Polymer, N54
55% cisl45% tram Polymer, Ns4
55% cis/45% trans Polymer, Ns4
Overcooled monomer
411
412
412
412
413
413
411
413
411
415
415
415
415
416
416
TABLE 1. contd
Heats of Polymerization II / 373
State of monomer - A H, Temp.
Monomer and polymer (xx) Wmol) (C) Method Solvent/Notes Refs.
cc 39 - 13 5 416
cc 46 - 13 5 Overcooled monomer 416
lc 52 25 4b 416
IC 55 107 5 416
N-7,7-Triacyanobenzoquinonemethideimine ss 22 55 4a Toluene N ,a, N az 438
TABLE 2. MONOMERS GIVING POLYMERS CONTAINING HETEROATOMS IN THE MAIN CHAIN
State of monomer - A H, Temp.
Monomer and polymer (xx) (Wmol) CC) Method Solvent/Notes Refs.
2.1. MONOMERS GIVING POLYMERS CONTAINING 0 IN THE MAIN CHAIN, BONDED TO CARBON ONLY
2.1.1. ETHERS AND ACETALS (listed by increasing ring size of monomer)
~-RINGS (aldehydes and ketones)
Acetaldehyde lc 0 25
lc 64. 5 25
lc 62. 5 25
c' c 31 - 173
lc 3 4 - 13
lc 36 25
-, bromochlorofluoro- SC' 36. 0
-, bromodichloro- SC' 31. 2
-, bromodifluoro- SC' 43. 4
-, dibromochloro- SC' 26. 0
-, dibromofluoro- SC' 29. 0
-, dichlorofluoro- SC' 56. 2
-, difluorochloro- SC' 51. 0
-, tribromo- SC' 19. 6
-, trichloro- gc' 71+8 50
gc' 65. 5 - 50
El 51 17 - 5051
lc 381t8 50
lc 34 25
lc 34. 5 - 50
lc 20 - 50
lc 30 - 73
cc' 25 - 113
S S 14. 5 - 50
SC' 33. 5 13
SC' 39 1 0
SC 31. 8
-, trifluoro- gc 64. 5 45
lc 47 25
S C 50. 8 25
SC' 54. 9
gg - 12 25
gc 1 0 25
IC - 25 25
lc 20. 5 20
SC 35. 5 18
4,1-Dioxaoctanal
s, " 21. 5 15. 9 - 80 20
ss 16. 7 - 80
Formaldehyde gc' 66 25
gc' 55 25
Heptanal c' c' 20 - 113
c' c 1 0 - 113
4b
2
2
5
5
2,4b
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
5
4a
3
4a
4a
5
5
4a
4a
4a
4a
4a
4a
4a
4a
4b
4b
4b
3
4a
3
4a
4a
4a
2
5
5
NII
To poly(viny1 alcohol)
To poly(viny1 alcohol)
Toluene, N74
Toluene, NT4
Toluene, N 74
Toluene, N 74
Toluene, N ,4
Toluene, NT4
Toluene, N 74
Toluene, N74
Tetrahydrofuran
Pyridine
n-Heptane
Toluene, N,d
Dichloromethane
Dichloromethane
Toluene, N ,,J
n-Hexane (9 kbar), NQ
n-Hexane (1 bar, lM), Nia
N69
THF
N13
48
195
195
417
411
411
233
344
344
344
344
344
344
344
50
166
166
418
50
418
166
166
418
418
161
50
166
344
129
322
322
344
234
144, 148
48, 234
161
161
161
330
330
49, 164,
165, 132
I , 49
419
419
Notes page 11-406; References page II - 407
II / 374 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 2. contd
Monomer
State of monomer - A H , Temp.
and polymer (xx) Wmol) (Cl
Method Solvent/Notes Refs.
Hexanal
Octanal
4-Oxapentanal
Pentanal
o-Phthalaldehyde
Propanal
-, 2,2-dichloro-
-, 2-chloro, 2-methyl-
-, 2-methyl-
j-RINGS
Cyclohexene oxide
Ethylene oxide
Propylene oxide
Styrene oxide
-, 3-nitro-
t-RI NGS
Oxet ane
-, 3,3-di(chloromethyl)-
-, 3,3-dimethyl-
- 3,3-di(phenoxymethyl)-
5-RINGS
1,3-Dioxolane
cc
cc
w
lc
11
cc
cc
cc
,
L
11
lc
S C
lc
1s
lc
S C
ss
cc
cc
lc
lc
lc
lc
lc
lc
ET
lc
SS
gc
lc
ss
gc
lc
ss
ss
ss
lc
gg
gc
gc
lc
lc
gg
lc
lc
gc
lc
ss
lc
ss
s s
gg
IF
gc
lc
lc
lc
22 - 7 3 5
8 -73 5
39 2 5 3
33 2 5 3
36 97 5
8 - 173 5
7 - 173 5
1 2 - 73 5
1 0 - 7 3 5
27 25 3
28 67 5
14.7 - 7 5 4a
14.2 - 7 5 4a
19.7 - 80 4a
20.1 - 80 4a
22.7 - 7 5 4a
22.2 - 7 5 4a
22 - 7 0 4a
5 - 173 5
2 - 173 5
1 5 -73 5
1 2 -73 5
1 9 25 3
1 4 25 3
2 1 57 5
1 5 57 5
50 -65 4a
20.5 -65 4a
1 7 - 65 4a
47 - 65 4a
19.5 - 65 4a
19.5 - 65 4a
46 - 65 4a
1 6 - 6 5 4a
15.5 - 65 4a
16.5 - 6 5 4a
22 - 6 5 4a
419
419
N77 419
419
419
420
420
420
420
420
420
N69 330
THF 330
N69 329
329
N69 328
THF 528
Dichloromethane, cyclopolymer 154
Tetrahydrofuran
Tetrahydrofuran
Tetrahydrofuran
Diethyl ether
n-Pentane
421
421
421
421
421
421
421
421
172
172
172
172
172
172
166
166
167,172
166
166
97 25 2 422
104 25 4b 1 4
140 25 3 168
127.3 25 2 306
102.4 25 2 306
94.5 25 2 5 1
75.5 2 5 4b 14,52
101.5 26.9 3 1 4
1 0 1 26.9 3 1 4
81.8 25 4a
51.4 25 4a
8 1 - 9 3
84.5 26.9 3
67.5 - 9 3
83.5 26.9 3
N17
Chloromethane + chloroethane
Chloromethane + chloroethane
o-Dichlorobenzene
325
325
53
1 4
53
1 4
26 20 4b
50 25 4a
52.0 57 4a
24 100 4b
1 7 90 4a
1 5 25 4a
N60
N14
N69> N78
N17
54
292
353
1 9 8
437
292
TABLE 2. contd
Heats of Polymerization II/375
Monomer
State of monomer
-mxx
Temp.
and polymer (xx) (kJ/mol) (C)
Method Solvent/Notes Refs.
-, 4-ethyl-
-, 4,4-dimethyl-
-,
cis-4,5-dimethyl-
-3 trans-4,5-dimethyl-
-, 4-isopropyl-
-, 4-methyl-
trans-7-Oxabicyclo[4.3.0]nonane
7-Oxa-bicyclo[2.2.1]heptane,
2-alkyl-
R=H
R = exo-CH3
R = endo-CH3 R
Tetrahydrofuran
lc
IS
S S
s s
ss
ss
ss
lc
lc
lc
lc
lc
lc
lc
lc
lc
lc
gg
gg
g c
gc
lc
-, 3-methyl-
6-RINGS
m-Dioxane
p-Dioxane
Tetrahydropyran
Trioxane
T- RI NGS
1,3-Dioxepane
- 2-butyl
-, 4-methyl-
-, 2-methyl-
l-Oxa-4,5-
dithiepane LO(CH,),S,(CH,),--
lc
lc
lc
lc
lc
lc
1s
ss
1s
gg
0 20 4b
1s - 4 20 4a
gg
1.5 20 4b
SC 17.5 40 4a
SC 26.5 58 3
SC 19.5 30 3
SC 12.5 30 4a
SC 21.5 30 3
cc 6 30 3
cc 11.5 58 3
c/c 4.5 25 4a
cc 5.5 25 2
gg
19.5 20 4b
gc
53.9 25 4a
lc 13.0 25 4a
ss 1 2 75 4a
ss 13.5 60 4a
ss 1 4 0 4a
ss 1 5 - 3 0 4al3
s s 7 - 5 4a
s s 9.3 - 15 4a
ss 8.8 - 15 4a
ss 9 - 10 4a
lc 7.5 26.9 3
s s 9 26.9 3
s s 8 26.9 3
23
6.5
22
27
1 5
17.5
8
13.0
9.6
12.1
7.5
12.1
13.4
14.0
40 4a
55 4a
0 4al3
20 4a
30 4a
70 3
75 4a
- 2 4 4a
80 4b
80 4b
80 4b
80 4b
- 8 4a
44.3 25 2
49.7 25. 2
45.4 25 2
2 1 20 4b
1 2 25 4b
39.5 25 4a
47.1 50 4a
29.6 25 2
38 25 2
18.6 25 2
7.5 25 4a
12.5 50 4a
15 30 4a
25.5 25 2
23 40 4a
23 40 4a
22.6 - 6 4a
N15
Dichloromethane
Chloroethane
Benzene
Dichloromethane
Toluene, N 7s
N61
N17
N16
Diethyl ether
N78
1,2-Dichloroethane
1,ZDichloroethane
Dichloromethane
Nitrobenzene
Nitrobenzene
N18
N19
N17
Toluene, N78
Benzene
1,2-Dichloroethane, N78
Dichloromethane
1,2-Dichloroethane, N78
1,2-Dichloroethane
1,2-Dichloroethane
1,2-Dichloroethane, N78
Dioxane
Benzene
159
219
133,159,220
293
134
220
423
333
335
335
335
335
334
357
308
308
308
55
56
292
353
358
56,57
358
292
130
231
140,208
57,58,211
211
342
54,59,60
436
55,56,59
1 7 8
212
182,202
182
202
202
212
164
see 202
54
323
323
423
134,87
424
136
424
339
340
424
6 1
6 1
6 1
Notes page 11-406; References page II - 407
II / 376 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 2. contd
Monomer
State of monomer
-mm
Temp.
and polymer (xx) Wmol) 03
Method SolvenUNotes Refs.
Oxepane
8- AND LARGER RINGS
2-Butyl- 1,3,6-trioxocane
1,3-Dioxocane
Tetraoxane
1,3,6-Trioxocane
(1,3,6-Trioxocane),
n = l
n=2
n=3-8
(1,3,6,9-Tetraoxacycloundecane),
n = l
n=2
n=3
n=4-8
1,3,6,9,12-Pentaoxacyclotetradecane),
n=l
n=2
n=3-7
1,3,6,9,12,15-Hexaoxacycloheptadecane),
n=l
n=2
n=3-5
2. 1. 2. CYCLIC ESTERS
h-RINGS
f&Propiolactone
.%RINGS
y-Butyrolactone
6-RINGS
2,2-Dimethyltrimethylene carbonate
Ethylene oxalate
g c
lc
ss
gg
gc
lc
SC
cc
cc
gc
lc
ss
s s
s s
S S
s s
ss
ss
ss
s s
ss
s s
ss
ss
ss
ss
lc
lc
lc
IC
lc
lc
lc
c(II)c(II)
c(II)c
c(II)c(II)
c(II)c
lc(1)
11
cc
cc
cc
cc
cc
I
f
cc
cc
cc
cc
38.6 2 5 4a
- 1.7 2 5 4a N17
323
323
8 1 0 4a
53.5 20 4b
62.1 25 4a
18.3 25 4a
26 30 3
3.5 30 3
4 2 5 2
62.2 5 4a
12.0 2 5 4a
1 3 20 4a
22 60 4a
Toluene, N7g
N17
Nitrobenzene
N17
Toluene, N78
Benzene
425
54
324
324
202
131,202
see 202
324
324
425
1 3 4
16.7 0 4a Dichloromethane 343
4.6 0 4a Dichloromethane 343
0 0 4a Dichloromethane 343
13.4 0 4a Dichloromethane 343
3.8 0 4a Dichloromethane 343
3.8 0 4a Dichloromethane 343
0 0 4a Dichloromethane 343
11.3 5 4a Dichloromethane 343
7.5 5 4a Dichloromethane 343
0 5 4a Dichloromethane 343
10.5 - 2 4a Dichloromethane 343
2.9 - 2 4a Dichloromethane 343
0 - 2 4a Dichloromethane 343
75 2 5 3 368
82 25 3 368
80.5 25 2/4b 1 3 7
74 1 2 7 3 368
- 5 2 5 3 368
7 2 5 3 368
- 6 77 3 368
7 - 173 5
- 9 - 173 5
7 2 5 4b
- 8 2 5 4b
1 8 117 5
1 2 1 4 7 5
2 1 -173 5
6 - 173 5
2 1 - 7 3 5
6 -73 5
2 1 2 5 2
4 2 5 2
1 7 127 5
8.6 - 173 5
9.0 - 73 5
10.1 25 2
8.3 8 7 5
N54, N63, N77
N54, N63
N63. N77
N63
426
426
426
426
426
426
427
427
427
427
427
427
427
312
312
312
312
TABLE 2. contd
Heats of Polymerization II / 377
Monomer
State of monomer
-AfJxx
Temp.
and polymer (xx) - Wmol) (0 Method Solvent/Notes Refs.
Glycollide 0 0
==k
0
DL-Lactide 0
0
T
0
L-Lactide
8-Oxo-7-oxabicyclo[2,2,2]octane o
%
0
Pentanolactone
T-RINGS
a-Caprolactone
Spiroorthoester
2-R-1,4,6-trioxaspiro[4.6]
undecane
R=H
R=CH3
R=CHsBr
R=Ph
8-AND LARGER RINGS
Heptanolactone
Octanolactone
Nonanolactone
Decanolactone
Undecanolactone
Dodecanolactone
Tridecanolactone
Tetradecanolactone
Pentadecanolactone
Hexadecanolactone
lc
cc
cc
lc
cc
lc
S S
ss
cc
gc
lc
lc
lc
lc
lc
lc
lc
ss
ss
ss
ss
ss
lc
lc
lc
lc
1C
1C
lc
lc
cc
cc
lc
lc
cc
cc
1C
c(II)c
lc
20.0 142 2
34.0 25 2
10.8 25 2
31.4 277 2
8.7 25 2
27.0 127 2
2.5 40 4a
23 1 0 5 4a
20.9 25 2
90.5 25 2
34.5 25 2
27.5 25 2
10.5 25 2
9.9 77 3
1 7 25 3
3 1 25 3
13.7 77 3
1 5 40 4a
11
8
5
7
-30 to 5 4b
-50 to 5 4b
-35to-5 4 b
- 50 to - 10 4b
1 6 127 4b
1 9 127 4b
22 127 4b
24 127 4b
28 25 3
62 25 3
27 127 3
1 7 127 4b
- 2 25 3
38 25 3
6 127 3
2 1 2 7 4b
- 10 25 1
39 2 5 1
- 3 97 1
- 37 - 7 3 1
0 127 4b
Nitrobenzene, N7s
1 ,CDioxane, N 7s
N53
N53
N53
Nitrobenzene, N 7s
368
368
368
428
Dichloromethane 430
Dichloromethane 430
Dichloromethane 430
Dichlorometbane 430
N54
312
364
364
364
311
311
428
429
307
307
307
314
314
314
368
368
368
368
368
368
368
368
368
368
368
368
313
313
313
313
368
2.2. MONOMERS GIVING POLYMERS CONTAINING 0 IN THE MAIN CHAIN, BON&D TO OTHER HETEROATOMS (S, Si, P)
Cyclotrisiloxane, 1,1,3,3,5,5-hexaethyl c (III)c (II) 4.6 - 173 3 N54, N63, N77 431
c(II)c(II) 5 - 7 3 3 N54r N63. N77 431
c (1I)c - 10 - 2 3 3 N54, N63 431
c(I)c(I) 1 0 -23 3 N54, N63, N77 431
c(I)c 1 2 5 3 Ns4> N63 431
11 1 4 25 3 N63 431
1s 1 5 170 3 95% Conversion 431
-, hexametbyl lc 14.5 25 3 84
lc 23.4 77 3 N62 365
cc 2.79 25 3 N63 365
Cyclotetrasiloxane, octamethyl- 1C - 13.4 77 3 N62 365
lc - 6.4 2 5 3 N63 365
N,N-Diethylamino-
1,3,2-Dioxaphospholan, 2-methoxy- OF0 pocH,
1s - 6.3 - 20 4a N58 346
1,3,2-dioxaphosphorinane
ss 1 5 3 Dichloromethane 309
0
SS 1 4 4a 1,1,2,2-Tetrachloroethane 309
Notes page II-406; References page II - 407
II I378 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 2. contd
Monomer
State of monomer - A H , Temp.
and polymer (xx) Wmol) (C) Method Solvent/Notes Refs.
2-Oxo- 1,3,2-dioxaphosphorinane
-, 2-alkoxy-
R = methyl
R = methyl n
R = ethyl \P/
R=propyl 0 OCH3
R = trimethyl silyl
Sulfur trioxide
lc -6.28 90 4a
N59
347
1s 2.9 140 4a
ss 0.8 100 4a
SS - 1.0 100 4a
ss - 2.4 100 4a
ss - 2.7 100 4a
gc
56 1 3 4a
lc 12.5 25 4a
Diglyme or DMSO
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
348
356
356
356
356
8 6
8 6
2.3. MONOMERS GIVING POLYMERS CONTAINING S IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY (listed by
increasing ring size) (polysulfones listed under Table 3. Copolymers)
Carbon disulfide
Thiirane
-, 2,2-dimethyl-
-, cis-2,3-dimethyl-
-, truns-2,3-dimethyl-
-, 2-methyl-
Thietane
Thioacetone
Thiolane
1,2-Dithiolane S-Hz
Thiane
I I
o-Dithiane SS(CH&CH2
[5.2.2.02,6]decane s, 27
exo-3,4,5-Trithiatricyclo- , S
S
exo-3,4,5-Trithiatetracyclo-
[5.5.1.02~6.08~12]tridec-10-ene Slz
Thiepane
I I
1,2-Dithiepane SS(CH&CH2
I I
1,2-Dithiocane SS(CH&CH2
lc 23 2 5 2 179
gg
8 1 2 5 4b Nzo 69,70,71
lc 73*4 20 3 1 7 3
SC 80*4 20 3 Various solvents 1 7 3
ix 70.5 2 5 4b Nzo 69,70,7 1
gg 6 3 2 5 4b N20 69,70,71
gg 5.5 25 4b Nzo 69,70,71
gg 7 1 25 4b Nzo 69,70,7 1
gg
80 25 4b N20 69,70,7 1
1s 10.8 50-90 4a Monomer 327
gg
7.5 2 5 4b N20 64,70,7 1
ss 26.5 30 4a Ethyl alcohol 72
2%
- 2.5 2 5 4b N20 69,70,71
lc 2 26.9 3 1 4
ss 5.8 40 4a Toluene, N?s 377
ss 6.6 50 4a Toluene, N 7s 376
gg 14.5 2 5 4b N20 69,70,71
lc 10.5 26.9 3 1 4
S C 11.5 26.9 3 Dioxane 1 4
lc 1 6 26.9 3 1 4
2.4. MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY (listed by
increasing ring size)
Z-RINGS
Butylisocyanate
j-RINGS
Ethyleneimine
-, N-(P-trimethylsilylethyl)(TEI)
-> -
ZnCl2 (TEI) 2 (complex)
t-RINGS
Trimethyleneimine,
-, N-(P-trimethylsilylethyl)(TMI)
-, -3 ZnCl2 (TMI) z(complex)
.%RINGS
8-0xa-6-azabicyclo[3.2.l]octan-7-one
2-Pyrollidinone
-3
l-methyl-
Pyrrole
ss 24
-
55 4a Dimethylformamide, N 7s 432
lc 96.2 27 2 360
lc 119 27 2 360
cc 264 27 2 360
lc 115 27 2 360
cc 258 27 2 360
ss 24 38 4a
lc 4.5 7 5 2l4b
lc 3.5 43 3
lc 1 2 43 3
cc - 5.5 25 2l4b
lc 3.5 2 5 4b
ss 1 4 5 15 3
ss 104 30 3
ss 60 50 3
Dimethylsulfoxide, N 7s
Acetonitrile
Acetonitrile
Acetonitrile
433
62
1 3 5
1 3 5
6 3
64
434
434
434
TABLE 2. contd
Heats of Polymerization II / 379
Monomer
State of monomer
-mxx Temp.
and polymer (xx) Wmol) (C)
Method Solvent/Notes Refs.
6- RI NGS
2-Piperidone
-, l-methyl-
lc 9 15 2/4b 62
CC 4.5 25 2/4b 63
lc - 2 2 5 4b 64
186
75
200
250
2 5
2 5
260
240
240
240
75
7- RI NGS
a-Caprolactam lc 16.3
lc 1 6
IC 15.5
IS 16.5
cc 12.5
IC 9.5
1s 12.5
IS 1 6
IS 16.5
IS 14.5
lc 1 6
IS 11
lc 1 6
IS 16.5
1s 14.5
1s 14.5
3 310
2 62
3 65,135,138
4a 68,67,66
2 63
4b 64
4a 194
3 1 9 1
3 1 9 1
3 1 7 1
4b 62
4a 225
4b 62
4a 226
3 1 9 1
3 1 9 1
-, l-methyl
-, 3-methyl
-, 3-ethyl
-, 3-propyl
-, 4-ethyl
-, 5-methyl
-, l -met hyl 75
225
240
240
lc 22 75 4b 62
lc 22 230 3 138,207
cc 24 2 5 2 6 3
lc 16.5 2 5 4b 64
1s 22 240 3 1 7 1
1s 21.5 240 3 1 7 1
lc 10.6 186 3 310
lc 32.5 230 3 138,189
cc 23.5 2 5 2/4b 1 3 8
cc 11.5 2 5 2/4b 1 3 8
cc - 2 2 5 2/4b 1 3 8
lc - 0 230 3 138,139
IS 1 3 290 4a 139
-, l-ethyl
-, I-propyl
8-RINGS
2-Oxo-hexamethyleneimine
-, l-methyl-
-, 4-ethyl-
-, l-ethyl-
9-13-RINGS
0-Dodecalactam
2-Oxo-heptamethyleneimine
2-Oxo-octamethyleneimine
2-Oxo-nonamethyleneimine
2-Oxo-decamethyleneimine
2-Oxo-undecamethyleneimine
2.5. MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (P)
Phosphonitrile chloride
-1 cyclic trimer
-, cyclic tetramer
-, cyclic pentamer
-I
cyclic hexamer
-9 cyclic heptamer
gc 6 1
lc 6
gc 68
lc 4
FLY 79.5
3.5
gc
88
lc 1.5
gc 96.5
lc 0
2.6. OTHER MONOMERS GIVING POLYMERS NOT LISTED ABOVE
Carbon C (graphite) cc - 39.5
4,7-bis[Cyano(ethoxycarbonyl) ss 21.6
methylenel-4,7-dihydrobenzofuran
4-(2,3-Diphenyl cyclopropenyl-
idene)cyclohexa-2,5-dienone o aPh ss 21.2
1,3-Disilacyclobutane,
1,1,3,3-tetramethyl-
P h
lc 73.9
Selenium Se s 1s - 9.5
230 3 1 2 5
230 3 1 2 5
230 3 1 2 5
230 3 1 2 5
230 3 1 2 5
230 3 1 2 5
230 3 1 2 5
230 3 1 2 5
230 3 1 2 5
230 3 1 2 5
25 2 Linear polymer (carbyne) 187
60 Chloroform, N7sr NT9 435
- 15 4a
2
4a
Dichloromethane, N67 317
359
8 5
2 5
400
Notes page 11-406; References page II - 407
II / 380 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 2. contd
Monomer
State of monomer
-mxx
Temp.
and polymer (xx) (kJ/mol) (0 Method Solvent/Notes Refs.
1-Silacyclobutane, l,l-dimethyl- lc 92.7 25 2 359
lc 85.4 25 2 359
-, 1-phenyl, l-methyl- lc 91.5 25 2 359
Sulfur, Se 1s 1 0 138 2 N72 380
-, s7 IS 4 138 2 N72 380
-9 St2 IS - 1 9 160 4a N71 380
-1 SE IS - 13.5 200 4a 73,74
TABLE 3. COPOLYMERS (listed alphabetically under Monomer A) N 21
Monomer A Monomer B
State of
monomer
and pol ymer
x x
-ma.8
Temp.
Wmol) (C) Method Solvent/Notes Refs.
Acrylonitrile Methacrylic acid,
Methyl ester
Styrene
Vinyl acetate
Vinylidene chloride
Ally1 chloride Maleic anhydride
bis-(o-Aminophenyl)-2,2
dibenzymidazoleoxide Terephthalic acid
1,3-Butadiene
1 -Butene
-, 3-methyl-
2-Butene, cis Sulfur dioxide
-, trans
Cyclohexene Sulfur dioxide
Cyclopentene Sulfur dioxide
1,3-Dioxane 1,3-Dioxolane
Fumaric acid,
diethyl ester
Fumaroyl chloride
Isobutene
1-Hexadecene Sulfur dioxide
1 -Hexene
Isopropenyl acetate
Maleic acid,
diethyl ester
Maleic anhydride
-, dichloride
-, dimethylether
Styrene
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Vinyl acetate
Styrene
Styrene, a-methyl-
Sulfur dioxide
Sulfur dioxide
Maleic anhydride
Vinyl acetate
Ally1 chloride
Isopropenyl acetate
Styrene
S C
ss
ss
s s
S C
ss
cc
cc
cc
cc
cc
cc
cc
cc
cc
lc
S S
ss
lc
lc
ss
ss
s s
ss
ss
ss
s s
ss?
ss
ss
lc
lc
ss
s s
ss
S C
ss?
ss
S C
ss
ss
74
25 3
30.5 3
20 3
20 3
25 3
74.5 3
24
1 8
6.5
136
96
83.5
31.5
16.5
5.5
- 173 5
- 7 3 5
25 2
- 173 5
- 7 3 5
25 2
- 173 5
- 7 3 5
25 2
2 5 2
44.5 26.9 3
43.5 55 4a
46 3 5 4a
22 25 4a
42.5 26.9 3
43.5 25 4a
39.5 26.9 3
40.5 25 4a
38 25 4a
45 26.9 3
1 6 20 4a
78 76.8 3
80 74.5 3
71.5 74.5 3
3 1 25 2
39.5 0 4a
42 26.9 3
40 30 4a
43.5 26.9 3
74.5 76.8 3
83.5 76.8 3
74 74.5 3
14.5 76.8 3
8 1 74.5 S
82.5 74.5 3
Emulsion (aq.)
Emulsion(aq.), Nzz
Polymer + Hz0 (c)
Polymer + Hz0 (c)
Polymer + Hz0 (1)
Polymer + HCl (c)
Polymer + HCl (g)
Polymer + HCl (g)
Polymer + CHsOH (c)
Polymer + CHsOH (1)
Polymer + CHsOH (1)
Excess B
Excess B
From B-rich mixture
From A-rich mixture
Excess B
Excess B
Excess B
Excess B
Excess B
Excess B
Methylene dichloride,
N7g AHBA = - 1 1
Excess B, N22
Hexane
Excess B
N23
Chl oroform
Chl oroform
Excess B
Excess B, Nzz
Benzene
Acetonitrile
38
76
76,201
76
75
34
445
445
445
445
445
445
445
445
445
45
1 9 7
5
77
199,200
199,200
5
5
5
5
78
5
446
79
34
34
82
8 3
5
80
5
79
79
34
79
34
34
Entropies of Polymerization II / 381
TABLE 3. contd
Monomer A Monomer B
State of
monomer
and pol ymer
xx
--AH,,
Temp.
Wmol) ((3
Method Solvent/Notes Refs.
Mal ei mi de
Methacrylic acid
-, methyl ester
Propene
Styrene
-7
cc-methyl-
Sulfur dioxide
Vinyl acetate
Vinyl n-butyl ether
Vinylidene chloride
Styrene, cc-methyl-
Vinyl acetate
Vinyl n-butyl ether
Styrene
Styrene, cc-methyl-
Methacrylic acid,
methyl ester
Acrylonitrile
Methacrylic acid
Styrene
Vinyl acetate
Sulfur dioxide
Acrylonitrile
1,3-Butadiene
Fumaroyl chloride
Maleic anhydride
Mal ei mi de
Methacrylic, acid,
methyl ester
Vinyl acetate
Fumaroyl chloride
Maleic anhydride
Mal ei mi de
Butadiene
1-Butene
-, 3-methyl-
2-Butene, ci s
-, tram
Cyclohexene
Cyclopentene
1-Hexadecene
1 -Hexene
Isobutene
Propene
Acrylonitrile
Fumaric acid, diethyl ester
Maleic acid, diethyl ester
Maleic anhydride
Methacrylic acid,
methyl ester
Styrene
Maleic anhydride
Acrylonitrile
ss 12.5 74.5 3 Excess B 34
SC 84.5 76.8 3 Excess B 79
ss 90 74.5 3 Benzene 34
ss 87.5 74.5 3 Acetonitrile 34
ss 72 74.5 3 Acetonitrile 34
lc
SC
ss
lc
ss
ss
S C
ss
lc
s s
ss
ss
ss
ss
ss
ss
ss
ss
ss
I?
lc
ss
ss
ss
ss
ss
ss
ss
ss
ss
lc
lc
S C
ss
SS?
ss?
S C
ss
ss
ss
S C
42.5
80
8 1
82.5
87.5
71.5
72.5
72
44.5
43.5
92
44.5
42.5
43.5
39.5
40.5
3 8
45
42
40
43.5
3 1
39.5
42.5
78
83.5
84.5
90
2 5 2
2 5 3
30.5 3
2 5 2
24 3
24 3
26.9 3
20 3
2 5 2
14.5 3
74.5 3
74.5 3
74.5 3
24 3
3 5
74.5
74.5
74.5
26.9 3
5 5 4a
3 5 4a
2 5 4a
26.9 3
2 5 4a
26.9 3
2 5 4a
2 5 4a
26.9 3
26.9 3
30 4a
26.9 3
25 2
0 4a
26.9 3
20 3
76.8 3
76.8 3
76.8 3
24 3
3 5 3
74.5 3
25 3
Emulsion (aq.)
Excess B
Hexane
Benzene
Acetonitrile
Acetonitrile
Excess A
Excess A
Acetonitrile
Excess A
Excess A
From A-rich mixture
From B-rich mixture
Excess A
Excess A
Excess A
Excess A
Excess A
Excess A
Chl oroform
Chl oroform
Excess A
N24
Excess A
Excess A, N22
Excess A, Na2
Excess A
Benzene
Emulsion (aq.), Nza
206
3 8
76
206
8 1
8 1
5
76,201
45,
34
34
34
34
8 1
8 1
34
34
34
1 9 7
5
77
199
199
5
5
5
5
78
5
5
80
5
82
8 3
5
76
79
79
79
8 1
8 1
34
75
B. ENTROPIES OF POLYMERIZATION
Symbols: The subscripts to AS denote the state of the monomer (first letter) and the state of the polymer (second letter) as in Section A. The standard state
of the monomer is 1 atm for the gaseous state and 1M in solution, unless otherwise stated. In all cases where monomer or polymer is present in solution, the
value of AS will depend to some extent on the composition. Where the polymer is crystalline, AS will depend on the degree of crystallinity. AS values
are in (J/K) per mol of monomer and are generally the limiting values for high degree of polymerization (1 kcal = 4.187 kJ).
Notes page 11-406; References page II - 407
II / 382 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
Precision: generally 0.5-8.0 (.I/K/mol)
Methods of determination: (numbering conforms with that in Section A)
1 Third law or statistical.
4a Thermodynamic (van? Hoff Equation).
4b Semiempirical rules applied to evaluate entropy of monomer or polymer or both.
TABLE 4. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN CARBON ONLY
Monomer
State of monomer -AS& Temp.
and polymer xx (J/K/mol) (C)
Method Solvent/Notes Refs.
4.1. MAIN CHAIN ACYCLIC CARBON ONLY
4.1.1. DIBNES
1,3-Butadiene lc 89 25 1
lc 84 2 5 1 cis-1,4-Polymer
Isoprene lc 1 0 1 2 5 1
4.1.2. MONOMERS GIVING POLYMERS WITHOUT OR WITH ALIPHATIC SIDE CHAINS WHICH CONTAIN ONLY C, H
4.1.2.1. Olejlns (listed by increasing carbon number)
Ethylene
Propene
1-Butene
cc
cc
gc
gc
gg
gc
gc
gc
w
gc
gc
gc
gc
gl
gg
F
gc
lc
lc
lc
lc
lc
lc
lc
IC
gg
gc
gc
lc
lc
lc
gc
gc
2-Butene, cis
81
cc
I
Y
lc
t%
lc
gc
gc
.Y
&F
gl
66 - 173 1
59 - 173 1
338 - 73 1
331 - 7 3 1
142 2 5 4b
155 2 5 4b
1 5 8 25 1
172 25 4b
174 2 5 1
336 25 1
325 25 1
334 127 1
317 127 1
311 227 1
1 6 7 2 5 4b
1 9 1 25 1
205 25 1
1 1 3 2 5 4b
116 25 1
116 2 5 1
136 25 1
75 - 173 1
69 - 173 1
114 - 7 3 1
107 -73 1
166 25 4b
213 25 1
1 9 3 2 5 1
113 25 4b
112 25 1
1 4 1 2 5 1
204 1 2 7 1
1 8 7 127 1
182 227 1
2 1 - 173 1
1 4 - 173 1
106 - 7 3 1
99 - 7 3 1
1 6 3 25 4b
104 2 5 4b
201 2 5 1
190 25 1
196 127 1
179 127 1
172 227 1
Isotactic poly(-1-butene)
Isotactic poly(-1-butene)
Isotactic poly(-1-butene)
Isotactic poly(-1-butene)
100% Cryst. polymer
Isotactic poly(-1-butene)
Isotactic poly(-1-butene)
Isotactic poly(-1-butene)
Isotactic poly(-1-butene)
Isotactic poly(-1-butene)
Syndiotactic polymer
Isotactic polymer
Isotactic polymer
Atactic pol ymer
100% Cryst. isotactic
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
100% Cryst. isotactic
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
95,96
97
100,101
385
385
385
385
2,87
11
88- 91
11
88- 91
385
385
385
385
385
5
186
207
5
88
88,92
88,92
385
385
385
385
5
88,385
88,385
5
8 8
88
385
385
385
385
385
385
385
5
5
385
385
385
385
385
Entropies of Polymerization I I / 383
TABLE 4. contd
Monomer
State of monomer -AS& Temp.
and polymer xx (JWmol) (0
Method Solvent/Notes Refs.
-,t r a m
Isobutene
cc
cc
IC
IC
if
gc
gc
gc
gc
gl
gg
lc
lc
1 -Pentene
-, 4-methyl
cc
I
YCF
lc
lc
lc
b-l
gl
cc
c c
lc
lc
gc
lc
2-Pentene, cis
-, 4-methyl
2-Pentene, t r am
lc
gc
gc
gc
gc
gl
c c
c c
lc
lc
lc
lc
d
gl
lc
lc
s
iF
gc
gc
gl
cc
- ,4-methyl
cc
lc
lc
lc
lc
&?I
89
lc
lc
gc
gc
gc
1 7 - 173 1
1 0 - 173 1
100 - 7 3 1
9 3 - 7 3 1
159 2 5 4 b
100 2 5 4 b
195 2 5 1
194 2 5 1
193 1 2 7 1
1 7 5 1 2 7 1
170 2 2 7 1
172 2 5 4 b
112 2 5 4 b
1 2 1 2 5 1
2 4 - 173 1
2 0 - 173 1
117 - 7 3 1
113 - 7 3 1
133 2 5 1
124 2 5 1
1 9 8 127 1
190 2 2 7 1
2 8 - 173 1
2 8 - 173 1
1 1 1 - 7 3 1
1 1 1 - 7 3 1
2 1 6 2 5 1
1 3 1 2 5 1
1 3 1 2 5 1
2 1 4 1 2 7 1
2 0 0 1 2 7 1
2 0 9 227 1
1 8 8 227 1
176 327 1
2 0 - 173 1
1 6 - 173 1
114 - 7 3 1
1 1 1 - 7 3 1
129 2 5 1
120 2 5 1
1 9 5 127 1
1 8 5 2 2 7 1
134 2 5 1
134 2 5 1
2 2 0 127 1
205 127 1
215 2 2 7 1
215 2 2 7 1
183 327 1
1 8 - 173 1
1 4 - 173 1
1 1 1 - 7 3 1
102 - 7 3 1
127 2 5 1
118 2 5 1
194 1 2 7 1
186 227 1
130 2 5 1
130 2 5 1
2 1 6 127 1
2 0 2 127 1
2 1 4 2 2 7 1
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
Isotactic polymer
385
385
385
385
5
5
385
385
385
385
385
5
5
11,93
3 8 6
3 8 6
3 8 6
3 8 6
3 8 6
3 8 6
3 8 6
3 8 6
387
387
387
387
196
387
3 8 7
3 8 7
3 8 7
3 8 7
3 8 7
387
3 8 6
3 8 6
3 8 6
3 8 6
3 8 6
3 8 6
3 8 6
3 8 6
3 8 7
3 8 7
387
387
387
387
387
3 8 6
386
3 8 6
386
3 8 6
3 8 6
3 8 6
3 8 6
387
387
3 8 7
387
387
Notes page II-406; References page II - 407
II / 384 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 4. contd
Monomer
State of monomer
and polymer xx
-AS& Temp.
(J/K/mol) (C) Method Solvent/Notes Refs.
Cycloalkenes
Cyclobutene
Cyclopentene
Cyclohexene
Cycloheptene
Cyclooctene
1-Hexene
1-Heptene
gc
194 221 1 381
gl
182 321 1 387
lc 113 25 4b 5
gg
168 25 4b 5
4.1.2.2. Cycloalkanes (listed by increasing ring size)
Cyclopropane
-, methyl-
-, 1, l-dimethyl-
Cyclobutane
-, methyl-
-, l,l-dimethyl-
Cyclopentane
-, methyl-
-, l,l-dimethyl-
Cyclohexane
-3 methyl-
-, 1, l-dimethyl-
Cycloheptane
Cyclooctane
lc 69 25 4b
lc 8 5 25 4b
lc 93 25 4b
lc 55 25 4b
lc 12 25 4b
lc 15 25 4b
lc 43 25 4b
lc 64 25 4b
lc 66 25 4b
lc 11 25 4b
lc 32 25 4b
lc 36 25 4b
lc 16 25 4b
I C 3 25 4b
N25
Nz5
11
81
87
11
87
87
11
87
87
11, 87
81
87
11, 94
11. 94
11
gl
c (I)c
lc
lc
lc
c(I)c
lc
lc
lc
SS
c(III)c
c (1II)c
c(II)c
c(II)c
lc
lc
11
c(II)c
c(II)c
c (I)c
c (DC
lc
lc
11
52 25 1,4b
131 25 1,4b
11 - 173 1
54 - 73 1
52 25 1,4b
41. 2 25 1
18 - 173 1
56 - 13 1
52 25 1,4b
51 77 1
11 - 65 4b
- 7 - 173 1
6 - 113 1
31 - 13 1
56 - 73 1
37 25 4b
70 25 4b
36 51 1
1 0 - 173 1
- 25 - 173 1
49 - 13 1
8 - 73 1
63 25 1,4b
9 25 1,4b
9 57 1
cis-Polybutadiene-
cis-Polybutadiene
&-Polymer
&-Pol ymer
c&Polymer
N66
trans-Polymer
trans-Polymer
truns-Polymer
truns-Polymer
Toluene, N 7s
70% trans, 30% cis Polymer, Ns4
70% truns, 30% cis Polymer, Ns4
70% tram, 30% cis Pol ymer, N54
70% trans, 30% cis Polymer, Ns4
70% tram, 30% cis Polymer
70% tram, 30% cis Pol ymer
70% trans, 30% cis Polymer
48% trans, 52% cis Polymer, Ns4
48% tram, 52% cis Polymer, Ns4
48% tram, 52% cis Polymer, Ns4
48% tram, 52% cis Polymer, Ns4
48% tram, 52% cis Polymer
48% tram, 52% cis Polymer
48% tram, 52% cis Polymer
388
388
388
388
388
361
388
388
388
388
389
388
388
388
388
388
388
388
388
388
388
388
388
388
388
4.1.3. MONOMERS GIVING POLYMERS WITH ALIPHATIC SIDE CHAINS THAT CONTAIN HETEROATOMS
Acrylonitrile
-1 allylester
-, allylloxyethyl
lc
cc
cc
cc
lc
lc
lc
cc
lc
lc
lc
-1
n-decylester cc
cc
109
- 6
24
91
85
96
16
29
56
60
4
8
25 1 1 9 3
- 173 1 391
- 73 1 391
- 8 1 391
- 8 1 391
25 1 391
1 2 7 1 391
- 173 1 393
- 73 1 393
25 1 393
51 1 393
- 173 1 392
- 73 1 392
TABLE 4. contd
Entropies of Polymerization II/385
Monomer
State of monomer - A S ; Temp.
and polymer xx (JWmol) (C)
Method Solvent/Notes Refs.
-7
ethylester
Ethacrylic acid
-methyl ester
Ethylene, tetrafluoro-
Methacrylic acid
-,
ethyl ester
-1 methyl ester
-, methyl ester deuterated
Methacxylonitrile
a-Methylene pentanolactone
Vinylidene chloride
lc 1 4 1 25 1 392
lc 1 5 5 1 2 7 1 392
cc 3 - 173 1 390
cc 1 6 - 7 3 1 390
lc 88 25 1 390
lc 104 127 1 390
lc 1 0 7 1 7 7 1 390
1s 105 8 7 4b
gc
1 9 7 - 75.7 1
lc 112 - 75.7 1
ss 146 80 4b
lc 126 120 4a
lc 117 127 4a
cc 9 - 173 1
cc 24.1 - 7 3 1
cc 40 - 6 3 1
lc 1 0 5 25 1
lc 1 1 5 77 1
ss 130 127 4a
cc 1 0 - 173 1
cc 26 - 7 3 1
lc 110 25 1
lc 118 77 1
ss 1 5 1 127 4a
ss 108.8 8 3 4a
cc 3 1 - 173 1
cc 25 - 173 1
lc 97 -73 1
lc 9 1 - 7 3 1
lc 112 2 5 1
lc 106 2 5 1
gc
201 2 5 1
gc
1 9 5 2 5 1
gc
198 1 2 7 1
gc
1 9 1 127 1
o-Dichlorobenzene
Benzonitrile
DMF
395
98,99
98,99
316
40
42,43,102
414
414
102,103
414
414
42,49
414
414
414
414
44.29
315
397
397
213,397
397
397
397
397
397
397
397
4.1.4. MONOMERS GIVING POLYMERS WITH AROMATIC SIDE CHAINS THAT CONTAIN ONLY C, H
Acenaphtylene
Biphenyl, p-isopropenyl-
Naphthalene, 2-isopropenyl-
Styrene
s s
ss
ss
ss
gg
I C
lc
lc
lc
lc
lc
lc
-1
u-methyl-
-, u-methyl, p-rerr-butyl-
lc
s s
s s
s s
s s
ss
98
1 1 8
122
1 2 5
149
90
104
116
104
1 0 5
112
1 1 1
110
130
5 1
47
163.3
106.6
60
- 2 0
- 5
1 0
25
- 2 3
2 5
127
127
2 5
2 5
25
- 20
- 2 0
- 10
- 10
22
4a
4a
4a
4a
4b
1
1
1
4a
1
1
1
4a
4a
4a
4a
4a
4a
Toluene, N 7s
Tetrahydrofuran
Tetrahydrofuran
Toluene, N 7s
N26
Isotactic polymer
100% Cryst. isotactic
Tetrahydrofuran
n-Heptane, Nrs
Toluene, N 7s
Cyclohexane
Solvent and temp. not stated
4.1.5. MONOMERS GIVING POLYMERS WITH AROMATIC SIDE CHAINS AND THAT CONTAIN HETEROATOMS
a-Acetoxystyrene ss 8 3 64 4a Toluene, N 7s
2-Amino-4-(N-alkalino)-6-isopropenyl-1,3,5-triazine
alkyl = n-propyl 1s 117 157 4a
isopropyl 1s 114 1 5 1 4a
isobutyl 1s 114 154 4a
399
1 6
1 6
400
25
104
104
104
28
88
1 0 5
88
32
32,29,16
402
402
341
381
401
402
403
403
Notes page II-406; References page II - 407
II / 386 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 4. contd
Monomer
State of monomer -AS& Temp.
and polymer xx
(JKhol) (Cl Method Solvent/Notes Refs.
set-butyl 1s
I-methylbutyl IS
n-pentyl IS
isopentyl 1s
n-hexyl 1s
n-octyl 1s
n-decyl 1s
n-dodecyl 1s
n-tetradecyl 1s
n-hexadecyl 1s
benzyl 1s
2-Amino-4-alkyVaryl-amino-6-isopropenyl-1,3,5-triazine
Ri = H, Ra = ethyl
NH2
1s
Rt = H, Ra = propyl
N%
1s
Ri = ethyl, R2 = ethyl y N 1s
Ri = propyl, Ra = propyl
N=C
1s
Rt = methyl, Ra = phenyl
NRI R2
1s
R i = H, Ra = p-met hoxyphenyl 1s
Benzoic acid, n-methacryloyloxy- cc
cc
I
fi
Oxazole, 2-isopropenyl, 4,5dimethyl- ss
Pyridine, 2-isopropenyl- s s
Silane, benzyl dimethyl vinyl- cc
lc
lc
-, dimethyl phenyl vinyl- lc
-, trimethyl vinyl- lc
Thi azol e, 2-isopropenyl- s s
p-[bis(Trimethylsilyl)methyl]
isopropenylbenzene s s
Nfl,N,N-Tetraethyl-4-
isopropenylphenyl-phosphonous
diamide s s
112
1 1 1
114
1 1 3
112
110
109
109
1 0 5
102
1 1 3
160.5
153.8
137.5
124.6
131.7
1 1 7
- 2
5
8
8 5
96
70
0.7
83.5
107.3
127.5
109.5
69
110
1 0
4. 1. 6. OTHER MONOMERS GIVING POLYMERS NOT LISTED ABOVE
Vinylcyclohexane cc 28
I
;CF
3
95
lc 75
lc 120
lc 8 5
lc 136
lc 102
4.2. WITH AROMATIC OR CYCLIC CARBONS IN THE MAIN CHAIN
- 11,12-Dicyano-2,6-naphtoquinodimethane
11,12-bis(alkylthio)
alkyl = butyl s s 109
= set-butyl s s 109
= isopropyl s s 116
= ethyl s s 1 1 5
= methyl s s 114
-7,8-Dicyanoquinodimethane
7,8-bis(butoxycarbonyl)- ss 37
7,8-diacetyl- ss 37
7,8-dibenzoyl- ss 38
7,8-dibutoxycarbonyl- ss 37
7,8-diisobutyryl- ss 39
7,8-dipropionyl- s s 37
7,8-bis(ethylthio)- s s 37
1 4 8 4a 403
146 4a 403
150 4a 403
1 5 1 4a 403
149 4a 402
1 4 3 4a 402
140 4a 402
134 4a 402
132 4a 402
130 4a 402
1 5 7 4a 403
150 4a
1 4 5 4a
130 4a
1 2 5 4a
150 4a
160 4a
- 173 4a
- 73 4a
2 5 1,4a
227 4a
20 4a
20 4a
- 73 1
2 5 1
77 3
25 1
25 1
20 4a
Tetrahydrofuran
Tetrahydrofuran
Tetrahydrofuran
370
370
370
370
379
378
394
394
363,394
394
284
284
355
366
366
362
367
284
- 30 4a Tetrahydrofuran 409
- 5 5 4a Tetrahydrofuran 408
- 173 1 396
- 173 1 396
-73 1 396
-73 1 396
2 5 1 396
2 5 1 396
127 1 396
127 1 396
30 4a Oligomer, benzene, N7s, Nsa 410
30 4a Oligomer, benzene, N,s, Nsa 410
30 4a Oligomer, benzene, Nrs, Nsa 410
30 4a Oligomer, benzene, Nrs, Nsa 410
30 4a Oligomer, benzene, Nrs, Nsa 410
60 4a Chloroform, N7s, Nst 411
55 4a Chloroform, N7s, Nsi 412
5 5 4a Chloroform, N7s, Nsi 412
5 5 4a Chloroform, N7s, Nsi 412
5 5 4a Chloroform, Nrs, Nsi 413
5 5 4a Chloroform, N7s, Nsi 413
60 4a Chloroform, N7s. Nsi 411
TABLE 4. contd
Entropies of Polymerization II / 387
Monomer
State of monomer -AS& Temp.
and polymer xx (JIKlmol) (C) Method Solvent/Notes Refs.
7,8bis(phenylacetyl)-
7,8bis(phenylthio)-
-4,7-Dihydrobenzofuran
4,7-bis-[cyano(ethoxycarbonyl)methylene]
Norbomylene
5-trimethylsilyl-2-
N,7,7-Tricyanobenzoquinonemethideimine
ss
ss
SS
c(II)c
c (1)c
c(I)c
lc
cc
cc
cc
cc
lc
lc
ss
37
34
4 1 60 4a
5 - 173 3
50 - 7 3 3
50 25 4b
58 57 3
4 - 173 1
1 3 - 173 1
1 4 -73 1
48 -73 1
70 25 1
8 1 1 0 7 1
38 55 4a
5 5
50
4a
4a
Chloroform, NT*, Nsi
Chloroform, N7s, Nsi
413
411
Chloroform, N7s
55% cis/45% tram Pol ymer Ns4
55% cis/45% tram Pol ymer Ns4
55% cis/45% tram Pol ymer Ns4
55% cis/45% tram Pol ymer Ns4
435
415
415
415
415
416
Overcooled monomer
Overcooled monomer
Toluene, N,s, Nsi
416
416
416
416
416
438
TABLE 5. MONOMERS GIVING POLYMERS CONTAINING HETEROATOMS IN THE MAIN CHAIN
Monomer
State of monomer -AS& Temp.
and polymer xx (JIKlmol) (0 Method Solvent/Notes Refs.
5.1. MONOMERS GIVING POLYMERS CONTAINING 0 IN THE MAIN CHAIN, BONDED TO CARBON ONLY
5.1.1. ETHERS AND ACETALS (listed by increasing ring size of monomer)
Z-RINGS (aldehydes and ketones)
Acetaldehyde cc - 6 - 173 1
lc 1 4 - 73 1
lc 2 1 25 1
SC 122 4a
SC 122 4a
SC 1 3 5 4a
SC 116 4a
SC 114 4a
SC 179 4a
SC 152 4a
SC 100 4a
gc
190 f 30 50 4a
lc 95&30 50 4a
SC 134 4a
SC 117 1 3 4a
SS 52 - 5 0 4a
SC 142 1 0 4a
cc 37 - 173 1
lc 69 - 73 1
lc 80 25 1
lc 30 57 1
gc
187 45 4a
lc 97 2 5 4a
SC 1 5 5 4a
S C 142.7 2 5 4a
gc
188 2 5 4b
S C 122 1 0 4a
lc 67.4 - 80 4a
ss 77.0 - 80 4a
ix
124 2 5 1
gc
174 2 5 1
gc
169 2 5 4a
cc 25 - 173 1
cc 1 - 173 1
cc 32 - 7 3 1
-, bromochlorofluoro-
-, bromodichloro-
-, bromodifluoro-
-, dibromochloro-
-, dibromofluoro-
-, dichlorofluoro-
-, difluorochloro-
-, tribromo-
-, trichloro-
-, trichloro
-, trifluoro-
Butanal
4,7-Dioxaoctanal
Formaldehyde
Heptanal
Toluene, NT4
Toluene, N 74
Toluene, N 74
Toluene, N r4
Toluene, Nr4
Toluene, N74
Toluene, N 74
Toluene, Nr4
Toluene, Nr4
Pyridine, N z7
Tetrahydrofuran
n-Heptane
Dichloromethane
Toluene, N 74
Dichloromethane
n-Hexane [9 kbar], Nia
N69
THF
N28
417
417
417
233
344
344
344
344
344
344
344
50
50
344
50
1 6 7
1 6 6
418
418
418
418
129
322
344
322
144,148
1 6 1
330
330
141,142
106
164,165
419
419
419
Notes page 11-406; References page II - 407
II / 388 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 5. contd
Monomer
State of monomer
and polymer xx
-AS& Temp.
(JnOmol) (C) Method Solvent/Notes Refs.
Hexanal
Octanal
4-Oxapentanal
Pentanal
o-Phthalaldehyde
-, 2-chloro 2-methyl-
-, 2,2-dichloro-
-, 2-methyl-
3-RINGS
Ethylene oxide
Propylene oxide
+-RINGS
Oxetane
-, 3,3-dichloromethyl
S- RI N GS
1,3-Dioxolane
-, 4,4-dimethyl-
-, cis 4,5-dimethyl-
-, trunk 4,5-dimethyl-
-, 4-ethyl-
-, 4-isopropyl
-, 4-methyl-
7-Oxa-bicyclo[2,2,1]heptane
-, 2-endo-methyl-
I
Z(I)
lc
11
cc
cc
c/c
I
Yl
11
lc
SC
lc
1s
lc
SC
ss
cc
cc
lc
lc
lc
lc
lc
lc
SS
ss
s s
s s
s s
F
gc
gc
lc
lc
gc
gc
g c
gc
lc
lc
lc
lc
lc
lc
ss
ss
s s
s s
lc
lc
lc
lc
lc
lc
lc
lc
lc
4 -73
1 1 1 2 5
1 0 1 2 5
110 97
1 9 - 173
1 6 - 173
43 -73
41 -73
117 25
1 2 1 67
57.8 -75
65.7 -75
81.6 - 80
93.6 - 80
97.1 -75
107.6 -75
96 - 7 0
8 - 173
6 - 173
69 - 7 3
67 -73
85 25
76 2 5
90 57
77 57
90 - 65
69 - 65
74 - 6 5
78 - 65
94 - 65
1 419
1 N77 419
1 419
1 419
1 420
1 420
1 420
1 420
1 420
1 420
4a N69 330
4a THF 330
4a N69 329
4a 329
4a N69 328
4a THF 328
4a Dichloromethane 154
1 421
1 421
1 421
1 421
1 421
1 421
1 421
1 421
4a Tetrahydrofuran 172
4a Tetrahydrofuran 172
4a Tetrahydrofuran 172
4a Diethyl ether 166
4a n-Pentane 166
174 25 100% Cryst. polymer 210
189 25 Estimated for 100% tryst. polymer 210
162.7 25 4a 325
68.4 25 4a N17 325
8 3 25 1 1 0 7
205 2 5 1 177
167 2 5 1 177
139 25 4a 292
147 57 4a N@l 353
100 25 1 1 7 7
37 25 4a N17 292
67 25 1 1 7 7
63 40 4a Nl5 159
76 100 4a N14 198
1 8 90 4a N69~ N78 398
78 0 4a Dichloromethane 133,154
94 20 4a Chlorometbane 213
22 75 4a Toluene, N 78 423
59 30 4a Benzene 134
54.8 80 b4 335
55.3 80 4b 335
55.3 80 4b 335
59.4 - 2 4 4a 333
60.7 80 4b 335
53.2 - 8 4a 334
75.3 2 5 4b 308
96.2 2 5 4b 308
96.2 25 4b 308
TABLE 5. conrd
Entropi es of Pol ymeri zati on II / 389
Monomer
State of monomer -AS% Temp.
and polymer xx (JIKlmol) (C)
Method Solvent/Notes Refs.
truns-7-Oxabicyclo[4.3.0]nonane
Tetrahydrofuran
-, 3-methyl-
6-RINGS
1,3-Dioxane
Paraldehyde
Trioxane
T-RINGS
1,3-Dioxepane
-, 2-butyl
-, 2-methyl-
-, 4-methyl-
Oxepane
I-Oxa-4,5-dithiepane
8-ANDLARGER RINGS
2-Butyl- 1,3,6-trioxocane
1,3-Dioxocane
Tetraoxane
1,3,6-Trioxocane
(1,3,6-Trioxocane),
n = l
n=2
n=3
n=4
n=5
n=6
n=l
n=8
lc
5
gc
gc
gc
lc
lc
lc
lc
lc
lc
lc
IS
ss
1s
1s -23 20 4a
gc
201 25 1
gc
159 25 1
gg
64 25 1
gc
156 25 1
ss 4 1 40 4a
SC 42 2 5 4a
cc 18* 16 2 5 4a
gc
gc
gc
lc
lc
lc
ss
ss
ss
ss
ss
ss
SS
ss
gc
lc
ss
SS
gc
lc
gg
cc
5
lc
ss
s s
s s 34.3 0 4a Dichloromethane 343
ss 12.6 0 4a Dichloromethane 343
ss 36.4 0 4a Dichloromethane 343
ss 43.1 0 4a Dichloromethane 343
ss 47.7 0 4a Dichloromethane 343
s s 51.5 0 4a Dichloromethane 343
ss 54.8 0 4a Dichloromethane 343
ss 57.8 0 4a Dichloromethane 343
55.7
177
112
139
1 4 3
100
81.9
47.6
1 6
62
4 1
49
67
87
100.9
2 5 1
2 5 4a
2 5 1
50 4a
25 1
25 1
2 5 1
25 4a
25 1
50 4a
30 4a
40 4a
40 4a
- 6 4a
1 8 1 2 5 1
144 2 5 1
131.4 2 5 4a
25.1 2 5 4a
77 2 5 1
39 2 5 1
48 - 30 4a
39 60 4a
26 7 5 4a
43 0 4a
3 3 - 5 4a
37.2 - 15 4a
39 - 10 4a
38.8 - 15 4a
91.8 2 5 4a
- 12.4 2 5 4a
> 12 25 4a
1 6 1 0 4a
121.7 25 4a
10.2 25 4a
5 1 25 1
- 3 27 1
129.1 25 4a
8.0 25 4a
39 60 4a
1 3 20 4a
N61
N17
N16
Diethyl ether
N7s, Cyclic oligomer
Isotactic polymer
Syndiotactic polymer
1,2-Dichloroethane
Nitrobenzene
N17
Dichloromethane
Benzene
Toluene, N7s
1,2-Dichloroethane, N7s
1,2-Dichloroethane, N7s
1,2-Dichloroethane
l,l-Dichloromethene, N7s
1,2-Dichloroethane
N17
Benzene
Toluene, N7s
Nl7
Nl7
Benzene
Toluene, N 7s
357
140
292
1 4 0
353
140
358
358
292
140
130
231
57,58
211
342
436
184
184
141
141
1 7 8
182
164
170
170
323
323
170
170
136
134
423
424
424
340
424
339
323
323
6 1
425
324
324
1 4 2
1 3 1
324
324
134
4 2 5
Notes page 11-406; References page II - 407
II / 390 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 5. contd
Monomer
State of monomer -AS& Temp.
and polymer xx (JKhoU (Cl
Method Solvent/Notes Refs.
(1,3,6,9-Tetraoxacycloundecane) n
n = l
n=2
n=3
n=4
n=5
n=6
n=l
n=8
(1,3,6,9,12-Pentaoxacyclotetradecane) n
n = l
n=2
n=3
n=4
n=5
n=6
n=7
(1,3,6,9,12,15-Hexaoxacycloheptadecane),
n = l
n=2
n=3
n=4
n=5
ss 13.0
S S 20.1
S S 28.9
s s 48.2
s s 52.3
s s 56.9
ss 59.9
S S 62.8
4a Dichloromethane
4a Dichloromethane
4a Dichloromethane
4a Dichloromethane
4a Dichloromethane
4a Dichloromethane
4a Dichloromethane
4a Dichloromethane
343
343
343
343
343
343
343
343
ss 8.4
s s 10.0
s s 43.1
ss 49.8
S S 54.4
ss 58.2
ss 61.1
4a Dichloromethane
4a Dichloromethane
4a Dichloromethane
4a Dichloromethane
4a Dichloromethane
4a Dichloromethane
4a Dichloromethane
343
343
343
343
343
343
343
s s
ss
ss
ss
s s
8.4 - 2 4a Dichloromethane
28.1 - 2 4a Dichloromethane
44.8 - 2 4a Dichloromethane
50.7 - 2 4a Dichloromethane
54.8 - 2 4a Dichloromethane
343
343
343
343
343
5. 1. 2. CYCLIC ESTERS
a-RING.9
P-Propiolactone lc 54 25 1 368
lc 74 25 1 368
lc 5 1 127 1 368
S-RINGS
y-Butyrolactone lc 30 25 1 368
lc 65 25 1 368
lc 29 77 1 368
6 - R I NGS
2,2-Dimetyltrimethylene
carbonate c (I& (II)
c (II)c
c(II)c(II)
c(II)c
lc (I)
11
cc
cc
cc
cc
cc
,
f;
cc
cc
cc
lc
ccl
cc
lc
cc
lc
ss
ss
z
7.7 - 173 1
- 35.3 - 173 1
5.8 25 1
- 35.2 25 1
38.7 117 1
24.0 147 1
6 - 173 1
- 2 8 - 173 1
9 - 7 3 1
- 25 - 73 1
10 25 1
- 3 2 2 5 1
1 3 127 1
- 12 - 173 1
- 9 - 7 3 1
- 5 2 5 1
1 5 142 1
0.3 25 1
- 10.5 25 1
17.5 217 1
- 31.3 25 1
13.0 1 2 7 1
4 1 1 0 5 4a
25 40 4a
127.7 25 4b
76.2 25 4b
426
426
426
426
426
426
427
427
427
421
421
427
427
312
312
312
312
364
364
364
3 1 1
3 1 1
429
428
307
307
N63
N63
N63
N63
N63
N63
p-Dioxanone
Ethylene oxalate
Glycollide 0 $> o
-?
0
DL-Lactide 0
-?
0
0
L-Lactide 1,4-Dioxane, N 78
Nitrobenzene, NT8
N53
N53
TABLE 5. contd
Entropies of Polymerization I I / 391
Monomer
State of monomer -AS& Temp.
and polymer xx
(J/K/mol) (C) Method Solvent/Notes Refs.
Pentanolactone
T-RINGS
s-Caprolactone
Spiroorthoester 2-R- 1,4,6-trioxaspiro[4.6]
undecane
R=H
=CHa
= CHaBr
=Ph
8-AND LARGER RINGS
Heptanolactone
Octanolactone
Nonanolactone
Decanolactone
Undecanolactone
Dodecanolactone
Tridecanolactone
Tetradecanolactone
Pentadecanolactone
Hexadecanolactone
5.2. MONOMERS GIVING POLYMERS CONTAINING 0 IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (S, Si, P)
Cyclotrisiloxane,
1,1,3,3,5,5-hexaethyl c(III)c(II) 7 - 173 1 N54r N63. N77 431
c(II)c(II) 0 - 73 1 N54. N63. N77 431
c(II)c - 62 - 2 3 1 N54, N63 431
c(I)c(I) 9 - 2 3 1 N54r N63> N77 431
c(I)c - 2 2 2 5 1 N54r N63 431
11 25 2 5 1 N63 431
hexamethyl- lc 3.03 77 1 365
cc - 51.0 25 ,l 365
Cyclotetrasiloxane, octamethyl- lc - 190 77 1 365
lc - 194.4 2 5 1 365
N,N-Diethylamino-
1,3,2-dioxaphosphorinane on0 1s - 20.9 - 20 4a N5s 346
1,3,2-Dioxaphospholan, 2-methoxy- \p/ S S 13.5 4a 1,1,2,2-Tetrachloroethane 309
2-Oxo-1,3,2dioxaphosphorinane 0 OCHs lc - 19.3 90 4a N59 347
-, 2-alkoxy-
R = methyl 1s 11.7 140 4a Diglyme or DMSO 348
R = methyl n ss 2.5 100 4a Dichloromethane 356
R = ethyl 9 9 ss - 1.5 100 4a Dichloromethane 356
R = propyl //pOR
0
s s -4. 5 100 4a Dichloromethane 356
R = trimethyl silyl s s - 6.0 100 4a Dichloromethane 356
Sulfur trioxide
gc 178 4 1 4a 86
5.3. MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY (listed by
increasing ring size)
3-RINGS
Ethyleneimine lc 51.9 27 1 360
-, A@-trimethylsilyl ethyl)-(TEI) lc 1 1 3 27 1 360
Notes page 11-406; References page II - 407
lc
lc
lc
lc 4 2 5 1 368
lc 54 25 1 368
IC 8 77 1 368
s s
s s
s s
s s
lc 1 1 2 7 4b 368
lc - 5 127 4b 368
lc - 12 127 4b 368
lc - 18 127 4b 368
lc - 24 25 1 368
lc 69 25 1 368
lc - 2 5 1 2 7 1 368
lc - 2 5 127 4b 368
cc - 5 7 2 5 1 368
cc 50 25 1 368
lc - 26 1 2 7 1 368
lc - 25 1 2 7 4b 368
cc -41 25 1 313
cc 86 2 5 1 313
lc -23 97 1 313
c(ll)c - 109 - 73 1
N54 313
lc -21 1 2 7 4b 368
65 25 1 314
1 5 25 1 314
1 3 77 1 314
- 39.6
- 30.7
- 20.8
- 25.7
- 10
- 25
- 20
- 3 0
4a Dichloromethane, N7s 430
4a Dichlorometbane, N7s 430
4a Dichloromethane, N7s 430
4a Dichloromethane, N7s 430
II / 392 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 5. contd
Monomer
State of monomer ~ -AS& Temp.
and polymer xx
(JIKlmol) (C) Method Solvent/Notes Refs.
-,-, ZnClz(TEI)z(complex) cc 114 21 1
d-RINGS
Trimethyleneimine,
N-@I-trimethylsilyl ethyl)-(TMI) lc 83. 0 27 1
-, ZnCl z(TEI) z(complex) cc 31. 2 21 1
~-RINGS
Bicyclic oxalactam ss 12 38 4a Dimethylsulfoxide
2-Pyrrolidinone cc 3 1 25 l l 4b
6-RINGS
2-Piperidone cc 25 25 l l 4b
I - RI NGS
c-Caprolactam 1s 29 250 4a
cc - 5 25 1
-, 3-methyl- 1s 11 260 4a
-, 5-methyl- 1s 1 6 200 4a
-, I-methyl- 1s 2 1 225 4a
S-RINGS
2-Oxo-hexamethyleneimine cc - 17 25 1
N. B. Values for 9-13 rings by probably unreliable extrapolation of AS,f,t for 5-8 rings are given in Ref. 138
l3-RINGS
2-Oxo-undecamethyleneimine 1s 1 6
5.4. OTHER MONOMERS GIVING POLYMERS NOT LISTED ABOVE
4-(2,3-Diphenyl cyclopropenylidene)cyclohexa-2,5-dienone
ss 69. 4
o- ( =pa( ph
P h
1,3-Disilacyclobutane, 1,1,3,3-tetramethyl- lc 18.1
N-Phenylmaleimide ss 86
Selenium Se, 1s - 21
1-Silacyclobutane, l,l-dimethyl- lc 85. 4
l c 71.2
-, 1 -phenyl 1 -methyl- lc 57. 4
Sulfur, Se 1s 2
- , s7 1s -11
-, s8 1s - 44. 7
1s - 31
Thioacetone
30
1s 48. 9
exo-3,4,5-Trithiatricyclo- s,S
[5.2.1.02s6]decane \ ss 31.4
exo-3,4$Trithiatetracyclo- S
[5.5.1.02~6.0s~12]tridec-10-ene St: ss 29. 3
290 4a 139
- 15 4a Dichloromethane, N67 311
25 1
55 4a
200 4a
25 1
25 1
25 1
80 1
80 1
160 4a
159 4a
50- 90 4a
DME N7x
From estimated T,
N73
N73
N71
Monomer
359
440
88,111
359
359
359
380
380
- 380
13, 74, 111
321
40
50
4a Toluene, N76 377
4a Toluene, N76 376
360
360
360
433
63
63
68
63
194
225
226
63
TABLE 6. COPOLYMERS ( l i sted al phabeti cal l y under Monomer A)
State of monomer - A S& Temp.
Monomer A Monomer B and polymer, xx (J/K/mol) (C) Method SolvenUNotes Refs.
Bis-(o-aminophenyl)-2,2 Terephthalic acid cc 1 9 - 113 1 Polymer + Hz0 (c) 445
dibenzimidazoleoxide cc - 17 - 13 1 Polymer + Hz0 (c) 445
c' c - 112 25 1 Polymer + Hz0 (1) 445
TABLE 6. contd
Ceiling Temperatures and Equilibrium Monomer Concentrations II / 393
Monomer A Monomer B
State of monomer -AS& Temp.
and polymer, xx (JWmoU (a Method Solvent/Notes Refs.
1,3-Butadiene Styrene
1-Butene Sulfur dioxide
-, 3-methyl- Sulfur dioxide
2-Butene, cis Sulfur dioxide
-, trans Sulfur dioxide
Cyclopentene Sulfur dioxide
1.3 Dioxane 1,3 Dioxolane
1 -Hexadecene Sulfur dioxide
1 -Hexene Sulfur dioxide
Isobutene
Methacrylic acid
Propene
-, dichloride
-, dimethylester
Sulfur dioxide
Metbacrylic acid,
methyl ester
Sulfur dioxide
Ethylene
c c - 33 - 1 7 3 1
c c - 295 - 7 3 1
c c - 320 25 1
c c - 13 - 1 7 3 1
c/c - 108 - 7 3 1
c c - 160 25 1
lc 30 1
lc 116 25 1
ss 1 4 5 64 4a
lc 162 35 4a
lc 8 1 25 4a
ss 146 25 4a
ss 140 25 4a
ss 134 102 4a
ss 57 20 4a
ss 139 30 4a
lc 116 2 5 1
ss 1 4 5 60 4a
lc 134 0 4a
lc 1 1 7 2 5 1
S C 130 90 4a
iv
172 2 5 1
Polymer + Hcl (c) 445
Polymer + Hcl (g) 445
Polymer + HCl (g) 445
Polymer + CH 30H (c ) 445
Polymer + CHsOH (1) 445
Polymer + CHsOH (1) 445
1 0 8
109
Excess B 110
Excess B 199,200
Excess A 199,200
Excess B 5
Excess B 5
Excess B 110
Methylene dichloride, N,s, 446
ASea = -34
Chl oroform 110
109
Excess B 110
Nz3 8 3
206
Excess B
31 mol% Ain
copolymer, Nsc
109
110
222
C . CEILING TEMPERATURES AND EQUILIBRIUM MONOMER CONCENTRATIONS
Most addition polymerization reactions are exothermic and exentropic. The free energy of polymerization per monomer unit therefore becomes less
negative as the temperature is raised. At the ceiling temperature T,, the free energy of polymerization under the prevailing conditions is zero, and above
this temperature, polymerization to long-chain polymer is impossible (just as in physical aggregation a liquid cannot form a solid when the temperature is
above the melting point). The reverse phenomenon of afroor temperature is also known, e.g., for sulfur.
In general a pure liquid monomer which gives an insoluble polymer will have a single well-defined ceiling temperature, given by T, = mt,/ASt,. A
pure liquid monomer which gives a soluble polymer will have a series of ceiling temperatures corresponding to different percentage conversions of
monomer to polymer. The condition for equilibrium is then
-AG,+AG,,+AGr=O
The partial molar free energy per mol of monomer, AC t and per base mol of polymer, A& are then functions of composition and may be evaluated from
an appropriate equation for mixing of monomer and polymer, e.g., the Flory-Huggins equation. For a monomer dissolved in a solvent the situation is more
complex and the ceiling temperature at a given monomer concentration (or the equilibrium concentration of monomer at a given temperature) is dependent
on the nature of the solvent and the composition of the medium (Refs. 28,29,112,113,114,160). For the case where both monomer and polymer are in
solution the variation of T, with concentration is given to a first approximation by
T, = AH,,/(AS,, + Rln[M])
where [M] is the concentration of monomer and AH:, and ASis refer to the heat and entropy changes in an appropriate standard state. A more general
expression may be derived from the free energy condition by insertion of suitable expressions for AC t and A&. These will contain the various interaction
parameters appropriate to the polymer-monomer-solvent system.
The values of T, quoted in the table are mostly obtained from experimental values by interpolation or short extrapolation. Some unpolymerizable
monomers are included where these are structurally closely related to monomers which do polymerize and where the cause of nonpolymerization appears
to be thermodynamic. This is amplified for cyclic monomers in Section D.
Section C is divided into three sections
1 Equilibria involving pure liquid monomers (Ic, lc, 1s)
2 Equilibria involving gaseous monomers (gc, gc)
3 Equilibria involving monomers in solution (SC, SC, ss) and copolymerizations
For meaning of symbols, see Section A.
Notes page II-406; References page II - 407
II / 394 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
1 . Equilibria Involving Pure Liquid Monomers
TABLE 7. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN ACYCLIC CARBON ONLY
Monomer
State of monomer
and pol ymer
Wt. fraction
monomer at
equilibrium Notes Refs.
2-Amino-4-(N-alkylanilino)-6-isopropenyl-1,3,5-triazine
alkyl = n-propanyl lc
= n-hexanyl lc
= n-octanyl lc
= n-decanyl lc
= n-dodecanyl lc
= n-tetradecanyl lc
= n-hexadecanyl lc
= isopropyl lc
= isobutyl lc
= set-butyl lc
= n-pentyl lc
= isopentyl lc
= 1-methylbutyl lc
= benzyl lc
2-Amino-4-alkyl/aryl-amino-6-isopropenyl-1,3,5-triazine
Rt =H, Rz=etbyl 1s
R i = H, Rz = propyl 1s
R t = ethyl, Rz = ethyl
N< 2
1s
Ri =propyI, Rz = propyl y N
Rt =H, Rz Lp-methoxyphenyl N~clRz
R i = methyl R 2 = phenyl
!
2-Amino-4-(p-chloroanilino)-6-isopropenyl-1,3-5-triazine
lc
2-Amino-4-methoxy IS
-4-ethoxy 1s
6-isopropenyl-1-3,Qriazine
2-Anilo-4-methoxy 1s
-4-ethoxy 1s
6-isopropenyl-1,3,5-triazine
Atropic acid, methyl ester 1s
1-Butene lc
2-Butene, cis lc
, tram lc
-, 2-methyl- 11
-, 2,3-dimethyl- 11
a-Cyanoacrilic acid
-9 ally1 ester lc
-, n-decyl ester lc
-, allyloxyethyl lc
Cyclopentene lc
Etbacrylic acid
methyl ester
Em y lene
1s
lc
Methacrylic acid
-, benzoil acid ester lc
-> methyl ester lc
methyl ester deuterated
Gaphtalene, 2-isopropenyl
lc
1s
Pentene-1 lc
Pentene-2, cis I c
Pentene-2, tram lc
-, 4-methyl, cis lc
-, 4-met hyl , tram lc
Silane, benzyl dimethyl vinyl- lc
-, dimethyl phenyl vinyl- lc
Styrene, a-methyl- 1s
1s
1s
1 5 7
149
1 4 3
140
134
132
130
1 5 1
154
1 4 8
150
1 5 1
146
1 5 7
1 8 1
1 7 7
1 6 3
1 6 1
169
169
170
1 8 3
182
174
174
- 8
247
227
217
- 29
- 223
307
217
607
97
8 7
367
787
102
93
69
317
287
277
317
267
397
197
6 1
54
170
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Isotactic polymer, Ns7
Isotactic polymer, Ns7
Isotactic polymer, N57
Calculated, N si
Calculated, N si
149
385
385
385
1 4 3
1 4 3
N57 391
N57 392
N57
393
N66 361
N75
395
Polymer is polybutene-1-iso 385
N57
394
414
414
400
386
386
386
387
387
366
362
119
341
119
N43
N57
N57
N57
N57
N57
1 bar
6.57 kbar
402
402
402
402
402
402
402
403
403
403
403
403
403
403
370
370
370
370
379
378
404
405
405
405
405
ceiling Temperatures and Equilibrium Monomer Concentrations II / 395
TABLE 7. contcl
Monomer
State of monomer
and pol ymer
Wt. fraction
monomer at
equilibrium Notes Refs.
Vinylcyclohexane lc 561 1 N57 396
Vinylidenechloride lc 387 1 N57 397
Vinyldimethylhenzylsilane IC 397 1 N57 367
Vinyldimethylphenylsilane lc 117 1 N57 367
Vinyltrimethylsilane lc 327 1 N57 367
N.B. The following compounds are not polymer&able for thermodynamic reasons but can sometimes be copolymerized with other monomers (see Ref. 205): cc-trifluoromethyl
vinyl acetate, a-methoxystyrene, l,l-diphenylethylene, trans-crotonitrile, rrans-stilbene, rrans-1,2-di(2-pyridyl)-ethylene, rmns-1,2-dibenzoylethylene, trans-1,2-diacety-
lethylene, cc-stillbazole, methyl 2-tert-butylacrylate, I-isopropenylnaphthalene, 2,4-dimethyl-cc-methyl-styrene.
TABLE 8. MONOMERS GIVING POLYMERS CONTAINING HETEROATOMS IN THE MAIN CHAIN
Wt. fraction
State of monomer monomer at
Monomer and pol ymer equilibrium Notes Refs.
8.1. MONOMERS GIVING POLYMERS CONTAINING 0 IN THE MAIN CHAIN, BONDED TO CARBON ONLY
Acetaldehyde
-, trichloro-
-, trifluoro-
2,2-Dimethyltrimethylene carbonate
4,7-Dioxaoctanal
1,3-Dioxepane
-, 2-phenyl-
(1,3-Dioxolane) ,, n = 1
n=l-8
88
1s
IS
lc
lc
lc
1C
lc
1s
1s
1s
IS
1s
1s
1s
lc
1s
- 3 1
- 39
20
58
1 7 7
212
227
- 3 8
100
192
144
20
100
1 6 5
100
98
60
1
1
1
1
1
1
1
1
0 . 1
1
1
0.36
0.3
1
1
1
Atactic polymer (1 bar)
Isotactic polymer (1 bar)
< 10 kbar
N57
Nss
N57
N69
N22
N43
N22
N43
K, determined for
cyclic monomers
N57
N57
N57
N56
N57
N57
N56
N.57
1,3-Dioxolane, 4,4-dimethyl-
-7 cis 4,5-dimethyl-
-> truns 4,5-dimethyl-
-, 4-ethyl-
-, 4-isopropyl-
-, 4-methyl-
-, 4-phenyl-
Heptanal
Hexanal
L-Lactide
Octanal
7-Oxabicyclo[2,2,l]heptane
-, 2-exo-methyl- 0
-, 2-endo-methyl-
R
.Q
Irans-7-Oxabicyclo[4,3,0]nonane
4-Oxapentanal
1,2-Oxathiolane-2,2-dioxide
Oxepane
Oxetane
GOxo-7-oxabicyclo[2,2,2]octane
lc - 9 8 1
lc - 5 4 1
lc - 137 1
I S - 4 8 4.74 Md/l
lc - 5 4 1
lc -14 1
IS - 2 0 4.47 MdA
lc - 2 1 1
1s 20 1
lc 74 1
IC - 4 3 1
lc - 25 1
lc 640 1
lc - 19 1
lc 320 1
lc 240 1
lc 200 1
lc 1 2 1
lc - 35 1
1s - 5 9 1
1s 95 0.74
1s 41.5 1
lc - 136 1
lc 478 1
lc 180 1
N57
N57
N57
N 57, calculated
N69
N57
N57
N57
N69
N22
N32. N57
N31
N53
1 1 5
1 1 5
1 5 8
233
418
322
426
330
116
423
398
116
116,219
1 9 8
423
353
232
335
335
335
333
333
335
334
334
285
419
420
420
429
330
308
308
308
357
329
329
152
1 4 7
323
325
307
Notes page 11-406; References page II - 407
II / 396 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 8. contd
Monomer
State of monomer
and polymer
Wt. fraction
monomer at
equilibrium Notes Refs.
Pentanal lc - 4 2 1 N69 328
Propanal IS -31 1 Atactic pol ymer 1 1 5
IS - 3 9 1 Isotactic polymer 1 1 5
lc - 4 8 1 N57 421
lc - 83 1 N57 421
Spiroorthoester
2-R-1,4,6-trioxaspiro[4,6]undecane
R=H lc 172 1 N68 430
=CH3 I C 254 1 N68 430
=CHzBr lc 498 1 N68 430
=Ph I C 258 1 N68 430
Tetrahydrofuran 1s 80 1 1 bar 58,130
1s 129 1 12.5 kbar 146
-, 3-methyl 1s 4 1 342
Tri(ethylene terephthalate) 1s 297 0.014 see 174
N.B. The following compounds are not polymerizable for thermodynamic reasons but can sometimes be copolymerized with other monomers (see Ref.
205); benzaldehyde (Refs. 297-299), hexafluoroacetone, 1,1-dimethylpropanal; also numerous cyclic ethers - see Section D.
8.2. MONOMERS GIVING POLYMERS CONTAINING 0 IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (S, Si, P)
Sulfur trioxide
Sodium metaphosphate Na,(OPOa),
n=3
lc 30.4 1
0.043
86
1s 800 K, determined for cyclic
monomers, n = 3-7
300,301
n=4
n=5
Siloxanes (RtRzSiO),
RI, R,
Me, H n=3-5
1s 800 0.026
1s 800 0.008
300,301
300,301
1s 0 0.045 K, determined for cyclic
monomers, n = 4-15
176
n=6-18 IS 0 0.034 176
n = 19-00 IS 0 0.046 176
n=3-co 1s 0 0.125 176
Me, Me n=3-5 1s 110 0.100 176
n=6-18
n = 19-00
n=3-CZ
n=4-40
1s
IS
1s
1s
110
110
110
110
0.036
0.047
0.183
K, determined for cyclic
monomers, n = 4-40
K, determined for values
of n indicated
K, determined for values
of n indicated
K, determined for cyclic
monomers, n = 4-20
176
176
176
180
n=4-30 1s 1 4 5 180
Me, Et n=3-5 1s 110 0.170 176
n=6-18 1s 110 0.049
n = 19-00 1s 110 0.039
n=3-cc 1s 110 0.258
n=3-5 1s 110 0.270 K, determined for cyclic
monomers, n =4-8
176
176
176
176
n=3-8 1s 110 0.310
Me, CFs(CH2)2 n = 3-5 1s 110 0.711
176
176
n=6-18 1s 110
12 = 19-00 1s 110
n=3-cc 1s 110
Et, Et n=3 lc 247
0.089
0.027
0.827
K, determined for cyclic
monomers. n =4-20
Calculated
176
176
176
431
Me, Pr
8.3. MONOMERS GIVING POLYMERS CONTAINING S IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY
Thiacetone lc 95 1 1 4 8
1s - 5 2 1
N55
327
Thioacetophenone 1s approx. 40 1 288
N.B. Isothiocyanates (Ref. 295) are not polymerizable for thermodynamic reasons, but can be copolymerized with thiiranes; carbon disulfide (Ref. 296)
can also be copolymerized with thianes
Ceiling Temperatures and Equilibrium Monomer Concentrations II / 397
TABLE 8. contd
Monomer
State of monomer
and pol ymer
Wt. fraction
monomer at
equilibrium Notes Refs.
8.4. MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY
(s-Caprolactam). n=l IS 220
1s 225
1s 217
n=2 IS 217
n=3 1s 217
n=4 1s 217
n=5 1s 277
n= 26 1s 277
-, 3-methyl- 1s 225
-, 3-ethyl- 1s 240
-, 3-propyl- 1s 240
-, 4-ethyl- 1s 240
-I 5-methyl- 1s 172
-1 7-methyl- 1s 225
-, 7-ethyl- 1s 240
-, 7-propyl- 1s 240
2,5-Dioxopiperazine 1s 1 7 1
2-Oxo-hexamethylenimine 1s 240
-, 4-ethyl- 1s 240
-, 7-ethyl- 1s 240
-, S-propyl- 1s 240
2-Oxo-undecamethylenimine 1s 290
2-Piperidone 1s 60
2Pyrrolidone lc 76
1s 70
8.5. OTHER MONOMERS GIVING POLYMERS NOT LISTED ABOVE
Norbomene lc 777
5-trimethylsilyl-2- IC 417
Selenium Se s 1s 8 3
Sulfur S s 1s 159
1s 157
0.055
0.067
0.084
0.0078
0.0052
0.0056
0.0048
0.0076
0.086
0.1
0.1
0.35
0.18
0.107
0.1
0.1
1
0.03
0.06
0.02
0.32
1
1
1
68
192
See 181
Cyclic monomer See 181
Cyclic monomer See 181
Cyclic monomer See 181
Cyclic monomer See 181
Cyclic monomer See 181
192,194
1 9 1
1 9 1
1 7 1
225,302
226,302
191,302
191,302
From calorimetric data 437
302
1 7 1
1 7 1
302
139
1 1 8
N75 383
T, varies with the accelerator, N75 439
55% cisl45% tram polymer, Ns7 415
416
N32 8 5
N33 73,,111 .
Effect of pressure 1 4 5
N33 380
2 . Equilibria Involving Gaseous Monomers (listed alphabetically)
Monomer
State of monomer
and polymer xx
Equilibrium
pressure
(mbar) Notes Refs.
Acetaldehyde, trichloro-
-, trifluoro-
Acetone
1,3-Dioxepane
1,3-Dioxocane
1,3-Dioxolane
Ethylene, tetrafluoro-
Formaldehyde
Methacrylic acid
-1
ethyl ester
methyl ester
O;epane
Oxetane
Sulfur trioxide
Tetrahydrofuran
gc
1,3,6-Trioxocane
gc
gc
98
gc
73
gc
- 220
g c
149
! F
288
g c
87
.F
560
gc
119
@
gs
gc
g c
gc
1 7 3 1013 N35 40
164 1013 N35 43
1 3 5 1013 323
319 1013 325
27.0 312 86
0.0 40.8 86
83 1013 292
243 1013 324
1013
1013
1013
1013
1013
1 2 8
1013
50
129
Estimated, Ns6 144
323
324
292
N34 23,120
N2s 49,164,165
Notes page 11-406; References page II - 407
II / 398 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
3 . Equilibria Involving Monomers in Solution
TABLE 9. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN CARBON ONLY
State of monomer M
Monomer and polymer xx (moW Solvent/Notes R e f s .
9.1. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN ACYCLIC CARBON ONLY
Acrylonitrile
Atropic acid
-,
methyl ester
-. ethyl ester
-, n-propyl ester
-,
n-butyl ester
-, p-methyl-, methyl ester
Atroponitrile
Biphenyl, p-isopropenyl-
Cyclohexene
Cyclooctene
Isobutylene
Methacrylamide, N-butyl-
-, N-phenyl-
Methacrylic acid, methyl ester
-1 o-methyl phenyl ester
-, phenyl ester
-7 o-tert-butyl phenyl ester
-1 o-set-butylphenyl ester
-9 o-chlorophenyl ester
-, 2,6-diisopropylphenyl ester
-, 2,6-dimethyl phenyl ester
-, o-ethylphenyl ester
-, o-isopropylphenyl ester
-9 o-methoxyphenyl ester
-1 o-methoxycarbonylphenyl ester
-, o-nitrophenyl ester
-1 o-phenylphenyl ester
o-propylphenyl ester
&,6-tribromophenyl ester
2,4,6-trichlorophenyl ester
2,4,6-trimethylphenyl ester
Metbacrylonitrile
Methyl-a-p-chlorobenzylacrylate
a-Methylene pentanolactone
Methyl-a-p-methoxybenzylacrylate
Methylphenylitaconate
Naphthalene, 2-isopropenyl-
Oxazole,
-, 2-isopropenyl-4,5-dimethyl-
Pyridine, 2-isopropenyl-
Styrene
-, u, acetoxy
-, a- met hyl -
- -
1 9o-methoxy-
N,N,N,N-Tetraethyl-4-
isopropenylphenylphosphorous diamide
Thi azol e, 2-isopropenyl-
p-[Bis(Trimethylsilyl)methyl]
isopropenylbenzene
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
SS
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
SS
ss
SS
ss
ss
SS
ss
25 3x1-s Estimated from AGic, 1 9 3
- 4 0
-61
- 72
- 80
- 3 7
50
0
- 2 3
20
88
122
1 2 5
155.5
1 3 5
140
146
8 1
100
139
33
71
1 1 8
112
1 4 5
112
108
100
1 1 8
92
104
69
1 4 5
8 5
8 3
55
95
120
0
1.0
1.0
1.0
1.0
1.0
1.0
0.515
5
1.2
0.651
0.611
0.82
0.611
0.64
0.64
0.64
0.64
0.64
0.64
0.64
0.64
0.64
0.64
0.64
0.64
0.64
0.64
0.64
0.64
0.64
0.27
5
1
0.324
5
2,22
0.284
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Tetrahydrofuran
Toluene
Benzene, Nss
Supercritical COz
Ethyl benzoate
Ethyl benzoate
o-Dichlorobenzene
Ethyl benzoate
p-Xylene
Benzene or p-xylene, N,s
p-Xyl ene
Benzene or p-xylene, N 7s
Benzene or p-xylene, N?s
Benzene or p-xylene, N,s
p-Xylene
Benzene or p-xylene, N,s
Benzene or p-xylene, N,s
Benzene or p-xylene, NT5
Benzene or p-xylene, N,s
Benzene or p-xylene, N 7s
Benzene or p-xylene, N75
Benzene or p-xylene, N75
Benzene or p-xylene, N7s
Benzene or p-xylene, N75
Benzene or p-xylene, N 7s
Benzonitrile
Toluene
DMF
DMF
Toluene
Dichlorobenzene
Tetrahydrofuran
149
150
150
150
150
149
1 6
389
229,230
441
326
326
42
326
345
442
345
442
442
442
345
442
442
442
442
442
442
/
442
442
442
442
44
443
315
315
443
444
1 6
0 0.0025 Tetrahydrofuran 284
0 0.043 Tetrahydrofuran 284
150 9.1 x 10-4 Benzene 28
150 6.5 x 1O-4 Cyclohexane 28
47 1.0 Toluene 401
0 0.76 Tetrahydrofuran, Njr 16,32,33
53 1.8 n-Heptane 402
58 1.8 Toluene 402
-25 - 2 Methylene chloride 1 5 5
1 0 1.0 Tetrahydrofuran 408
0 0.010 Tetrahydrofuran 284
1.2 1.0 Tetrahydrofuran 409
TABLE 9. contd
Ceiling Temperatures and Equilibrium Monomer Concentrations II / 399
Monomer
State of monomer
and polymer xx
M
(moW
Solvent/Notes Refs.
9.2. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN CYCLIC CARBON
-, 7,8-Dycyanoquinodimethane
7,8-bis(butoxycarbony1)
7,8-Diacetyl-
7,8-Dibenzoyl-
7,8-Dibutoxycarbonyl
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
ss
93 0.014 Chloroform, N?s 411
442 1.0 Chloroform, NQ 411
87 0.018 Chloroform, Nrs 412
415 1.0 Chloroform, Nds 412
8 8 0.069 Chloroform, N75 412
301 1.0 Chloroform, N43 412
93 0.014 Chloroform, N75 412
442 1.0 Chloroform, Nds 411
79 0.014 Chloroform, N75 411
422 1.0 Chloroform, N43 411
67 0.014 Chloroform, N,s 411
481 1.1 Chloroform, N4s 411
TABLE 10. MONOMERS GIVING POLYMERS CONTAINING HETEROATOMS IN THE MAIN CHAIN
State of monomer M
Monomer and polymer xx (2)
boW
Solvent/Notes Refs.
10.1. MONOMERS GIVING POLYMERS CONTAINING 0 IN THE MAIN CHAIN, BONDED TO CARBON ONLY
Acetaldehyde
-, bromochlorofluoro-
-, bromodichloro-
-, bromodifluoro-
-, dibromochloro-
-, dibromofluoro-
-, dichlorofluoro-
-, chlorodifluoro-
-, tribromo-
-, trichloro-
-, trifluoro-
Butanal
4,7-Dioxaoctanal
1,3-Dioxepane
-, 2-butyl
-, 2-methyl-
-, 4-methyl-
(1,3-Dioxolane) n n = 1
S C
SC
SC
SC
S C
SC
S C
SC
S C
SC
SC
ss
SC
SC/
SC
SC
SC/
S C
S C
S C
S C
ss
ss
ss
ss
ss
ss
ss
ss
s s
ss
ss
ss
1s
- 80
23
- 17
48
- 4 0
- 19
52
4 1
70
63
- 7 5
11
12.5
3.5
1 8
9
8 1
9
- 18
1 2
27
- 5 6
78
27
32
-51
- 37
- 4 0
- 3 3
1
- 8
20
20
60
6
1
1
1
1
1
1
1
1
1
1
(A::,
1.0
1
1
1
1
- 2
1.0
1.0
1
1.0
1.0
1.0
1.0
1
1.0
1
1.0
1.0
2.0
1.0
2.0
1s 1 4 5 10.0
n=l-8 ss 60
Toluene, N 22
Toluene
Toluene
Toluene
Toluene
Toluene
Methyl cyclohexane
Toluene
Methyl cyclohexane
Toluene
Toluene
Tetrahydrofuran
Pyridine, N39, N4a
n-Heptane
Methyl cyclohexane
Toluene
Toluene
Dichloromethane
Toluene, isotactic polymer
n-Hexane [8 kbar], N 12
n-Hexane [lo kbar], Ni2
THF
Benzene
Dichloromethane
1,2-Dichloroethane, N57
1,2-Dichloroethane, N57
1,2-Dichloroethane
1,2-Dichloroethane, Ns7
1,2-Dichloroethane
Dichloromethane
Benzene, N4i
1,3-Dioxane, N41
Chloroethane
A few percent
dichloromethane present
A few percent
dichloromethane present
Dichloroethane, NQ
228
233
344
344
337
344
336
344
336
344
338
1 6 7
50
166
336
344
344
322
227
1 6 1
1 6 1
330
116,134
136
424
424
340
424
339
133,159
134,159
159
293
1 9 8
1 9 8
232
Notes page 11-406; References page II - 407
II / 400 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 10. contd
Monomer
State of monomer
and polymer xx
M
(moW Solvent/Notes Refs.
Formaldehyde
L-Lactide
Octanal
rrans-%Oxabicyclo[4,3,0]nonane
trans-2-Oxabicyclo[3,3,0]octane
Oxa-4,5-dithiepane
Oxepane
Pentanal
o-Phthalaldehyde
Propanal, 2-chloro-, 2-methyl-
-, 2,2-dichloro-
-, 2-methyl-
Tetrahydrofuran
Tetraoxane
Trioxane
1,3,6-Trioxocane
-, 2-Butyl-
SC 30 0.06 Dichloromethane 122
SC 25 0.004 Nitrobenzene 182
SS 284 1.0 1,4-Dioxane 429
SC - 5 9 1 THF 330
ss -51 1 Dichloromethane 357
ss 0
SS 2 5
ss 30
SC - 68
ss - 4 3
ss - 5 4
SS - 24
ss approx. 5
ss - 36.6
ss - 63
ss - 61.6
ss 25
ss 20
SC 50
SC 25
SC 25
SC 50
SC 30
SC 30
SC 30
SC 2 5
SC 2 5
ss 291
ss 330
ss 220
0.63
< 0.005
0.08
1
1.0
1.0
(ki5)
1.0
1.0
1.0
4.45
2.8
< 0.008
0.12
0.10
0.20
0.13
0.05
0.19
1.5
2.5
1.0
1.0
1.0
Dichloromethane 351
Benzene 6 1
Dichloromethane 236
THF 328
Dichloromethane, cyclopolymer 154
Tetrahydrofuran 172
Tetrahydrofuran 172
Dichloromethane, N22, Na 1 5 3
n-Pentane 166
Tetrahydrofuran 172
Diethyl ether 166
Benzene, N37, NM 231
Diethyl ether 211
1,2-Dichloroethane 1 7 8
Dichloromethane 182
Nitrobenzene 182
1,2-Dichloroethane 178
1,2-Dichloroethane 178
Benzene 178
Nitrobenzene, N45 1 7 8
Nitrobenzene, N4s 182
Dichloromethane 182
Benzene, N45 134
Toluene, N 57 425
Toluene, N 57 425
10.2. MONOMERS GIVING POLYMERS CONTAINING 0 IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (Si, P)
1,3,2-Dioxaphospholan, 2-methoxy- ss 1 5 7 0.1 1,1,2,2-Tetrachloroethane 309
1,3-Dioxepane, 4-methyl- ss - 33 1 1,2-Dichloroethane 339
-, 2-methyl- ss - 37 1 1,2-Dichloroethane 340
Siloxanes (R 1R&O) n
RI, R2
H, Me ss 0 (0.2) Toluene, N 46 176
Me, Me SS 110 0.3 Toluene, N 47 217,218
Me, Et ss 110
(0.4)
Toluene, N46 176
Me, CFdCHh ss 110
(0.9)
Cyclohexanone, N46 176
10.3. MONOMERS GIVING POLYMERS CONTAINING S IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY
1,3-Dithiolane, 2-phenylimino-4-methyl- ss 65 2.1 Benzene 290
exo-3,4,5-Trithiatetracyclo- .s
[5,5,1,02~6.0S~2]tridec-10-ene ls
m
\
ss 25 2.37 Toluene, N 76 376
exo-3,4,5-Trithiatricyclo- , I& S
ss 90 3.12 Toluene, N76 376
5.2.1.02,6]decane 7 ss 1 0 3.8 Toluene, N 76 317
S ss 70 6.0 Toluene, N 76 377
10.4. MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY
Bicyclic oxalactarn ss 60 1.0 Dimethylsulfoxide 433
n-Hexyl isocyanate S C - 22 2 Dimethylformamide 1 2 7
Pyrrole ss 17 0.017 Acetonitrile 434
N,7,7-Tricyanobenzoquinone methide imine ss 74 0.14 Toluene, N75. Nsl 438
TABLE 11. COPOLYMERS
Pol ymeri zabi l i ty of 5-, 6- and 7-Membered Het erocyci i c Ri ng Compounds I I / 401
Monomer A Monomer B
State of monomer
and pol ymer
[AlPI
(mol */I 2, Solvent/Notes Refs.
11. 1. 1: 1 COPOLYMERS
Ally1 acetate
Ally1 alcohol
Ally1 ethyl ether
Ally1 formate
1-Butene
-, 2-ethyl-
-, 3-methyl-
2-Butene, cis
-, tram
2-Butene, (50% cis)
-, 2-methyl-
Cycloheptene
Cyclohexene
1,3-Cyclooctadiene
Cyclopentene
Ethene
Ethene oxide
Formaldehyde
2-Heptene (88% cis)
I-Hexadecene
1 -Hexene
-, 2-ethyl-
Isobutene
1-Pentene
-, 2-methyl-
-, 4,4-dimethyl-
-, 2,4,4-trimethyl-
2-Pentene (50% cis)
-, 4-methyl-
4-Pentenoic acid
Propene
Propene oxide
3-Propenyl phenyl
ether
Styrene
Tetrafluoroethene
Vinyl chloride
Sulfur dioxide
lfur dioxide
LSul oxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Carbon monoxide
Carbon dioxide
Sulfur dioxide
Carbon monoxide
Carbon dioxide
Carbon monoxide
Carbon dioxide
Sulfur dioxide
Sulfur dioxide
s s
S C
SS
S C
ss
S C
SS
ss
ss
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
Sulfur dioxide
ss
ss
ss
ss
g&z
Lx
SC
&Lx
gg
tx
I23
ss
S C
ss
ss
S C
ss
ss
S C
ss
Sulfur dioxide
Sulfur dioxide
Carbon monoxide
Carbon dioxide
Carbon monoxide
Carbon dioxide
Carbon monoxide
S C
S C
gg
gg
gg
gg
gg
Carbon dioixde
gg
Carbon monoxide
kx
Carbon monoxide
gg
Carbon dioxide
kx
Carbon monoxide
kx
Carbon dioxide
88
11. 2. GENERAL COPOLYMERS
s-Caprolactam a-Caprolactam, 3-methyl- 1s
4 5
76
68
45
64
<- 80
36
46
38
34.6
<- 80
11
24
31
1 0 3
150 (- 35)
- (50)
>135
350 (- 127)
220 (- 58)
190 (- 47)
- 150 (46)
- 3 8
69
30
60
<- 80
c
6;
- 34
1 4
<- 80
8.5
<- 80
66
90
140 (- 39)
- 120 (39)
490 (- 129)
180 (- 49)
590 (- 136)
190 (- 36)
- 190 (53)
280 (- 74)
30 (- 2)
230 (- 55)
-45 (18)
225
Nzo
27
27
21
27
27
27
27
27
27
27
27
1 0
27
27
3 3
27
1.15
27
27
27
27
27
32
27
27
Excess B 110
Excess B 110
Excess B 110
Excess B 110
Excess B 110
All compositions 110
Excess B 110,199
Excess B, Nds 110
Excess B, Nbs 110
Excess B, N49 110
All compositions 110
Excess B 124
Excess B 110
Excess B (1,2 addition) 156
Excess B 110
N64 369
N64 369
Excess B 110
N64 369
N64 369
N64
369
N64 369
Excess B, N49 110
Excess B 110
Chl oroform 80
Excess B 110
All compositions 110
Excess B 110
Excess B 110
Excess B 110
Excess B 110
All compositions 110
N49
110
All compositions 110
Excess B 110
Excess B 110
N64
369
N64
369
N64
369
N64
369
N64 369
N64
369
N64 369
N64
369
N64
369
N64
369
N64
369
192,194
a Values in parentheses are for AC& in (!d/mol).
D. POLYMERIZABILITY OF 5-, 6- AND 7-MEMBERED HETEROCYCLIC RING COMPOUNDS
The free energy of polymerization is generally negative for 3-, 4-, 8-, and higher-membered ring compounds. With heterocyclic rings there is generally an
ionic mechanism available which allows these compounds to polymerize. With 5-, 6- and 7-membered ring compounds the sign of AC, and hence the
polymerizability, is critically dependent on the nature of the ring and on the extent and position of substitution. Substitution generally makes AG less
negative (more positive) and reduces polymerizability in the thermodynamic sense.
Tables 12-14 summarize the polymerizability of 5-, 6- and 7-membered rings, respectively, as a function of the nature of the ring and extent of
substitution. Table 15 provides a comparison of polymerizability of unsubstituted 5-, 6-, and 7-membered rings.
Notes page 11-406; References page II - 407
II / 402 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 12. 5-MEMBERED RING COMPOUNDS
Ring Polymerized Not pol ymeri zed Refs.
N - N
MeAOWO N51
N - N R
Mel,oAO R = Me, Ph
237
CD20
c2s3
C3N0
S
S
m
\
S
(exe)
316
1s
s\
-b
(exe)
3 7 7
N52
R = Me, Ph etc.
238,239,433
239,240
02
C3NS
C3N2
022
2 3 9
R=Me,
eC0
:p
0
S,
02 O
c3os I S,
02
0
152
1% ^ 116,133,134,
159,177.
239,241-244,
= Me, R=Me,
285-287,
P h awl 350,35 1,349,
__, ..l .., --
R,=Rz=RJ=Me
R,=R2=R,=CHzPh
2 OR, R,=Rz=CHzPh,Rz=H
R,=Rz=CHzPh,R,=H
c302
R=Me,
CH,Cl,
P h
L
398,423
0
m
0
S&JNllMe
I
P h
L-J
0 N
331
c3s2
C4N
245,246,290
0 nnnm N 00 N 00 N OS N 239,240,243
c--3
N
JxJ
0 N
A-l
0 N Me0 240,247-249
Me
Rg MeQMe.9 OQMe OGO
51,58,117,
130,140,146,
239,243,250-256,
291.303.304
c40 QD oJJ
R
R=H,R=H
l-t-
w
R=H,R=endo-Me
R=H,R=exo-Me
0
R = endo - Me, R = exe - Me
R
R = em-Me
R = em-Me
TABLE 12. contd
Pol ymeri zabi l i ty of 5-, 6- and 7-Membered Het erocycl i c Ri ng Compounds II / 403
Ring Polymerized Not polymerized Refs.
c4s
0
a::,.,.
\(truns)
0
a
357
(cis)
357
357
357
185,256
TABLE 13. L-MEMBERED RING COMPOUNDS
Ring Polymerized Not polymerized Refs.
0
C3N20 BuNKNBu 239
(0)
C3N3 239
(1
c302p
o.p.o
I
Wth
n
9 9
HP\
;I;,
3
0 R
346
347
348
c303 y----J
T-T
MeO%4e
141,178,184,257
c3s3 y---j
CdNO 2
3
0 0
C4NS
C4N2
T T J-Y
MezASAh4ez Me2SSIMe2 h4eyTSh4e, Me~S~e
148,258,259,260
02 02 02
2
185,239,240
240
Notes page 11-406; References page II - 407
II/404 HEATS AND ENTROPI ES 0~ POLYMERI ZATI ON, CEI LI NG TEMPERATURES
TABLE 13. contd
Ring Polymerized Not polymerized Refs.
c4s2
Cz.N
Si303
Me
.d;a, Q R=H,Et, P h
R
152
116,136,239,243,262,426,436
R 0
xn
0
R R 239,243,262,263,428,429
0 0 R
R=Me, Ph
4 2 7
3 8 2
246,265
118,209,239,240,243,266
153,239,243,264,226-210,283
331
185,256
431
TABLE 14. 7-MEMBERED RI NG COMPOUNDS
Ring Polymerized Not polymerized Refs.
c4os2
6 1
C5NS
2 4 0
CsN2
S02Ph
239,240
TABLE 14. contd
Polymerizability of 5-, 6- and 7-Membered Heterocyciic Ring Compounds II / 405
Ring Polymerized Not polymerized Refs.
c502
c5s2
116,136,170,241,
262,271,423,424
246
CsN
R=3-Me,4&Me,R=H,Me
5pMe,5-Et,
5 - n - pmpyl, 5-i-propyl
5 Cyclohexyl
6-Me,lmMe
R = Ph,
PhCHz
n Heptyl -
R = Me,Ph,CHzOH,
EtSCH 2
240,243,276,
277,280,305
c60
153,239,243,
281,282
c6s
256
TABLE 15. COMPARISON OF POLYMERIZABILITY (+ OR -) OF UNSUBSTITUTED 5-, 6- AND 7-MEMBERED RING COMPOUNDS
Type of ring Name of king 5Ring 6-Ring 7-Ring
1,3-C,NO
1,2-c.os
N- C,mz
oAoJ
N- C,mz
OAN'
1,3-c.o2
e=r
Cn-3
0 N
I
2-Oxazolidinone
2-Imidazolidinone
1,2-Oxathiolane-2,2-dioxide
1,3-Dioxolane
Ethylene carbonate
1,2-Dithiolane
Pynolidine
-
+
+
-
+
-
+
-
+ t
- -
+
2-Pyrrolidinone + + +
Succinimide
- -
+
Not es page 11-406; References page II - 407
II / 406 HEATS AND ENTROPIES OF POLYMERIZATION, CEILING TEMPERATURES
TABLE 15. contd
ljpe of ring Name of 5-ring S-Ring 6-Ring I-Ring
2-Pyrrolidinethione
-
+
cno
Lym3 kydrofuran ( o x o l a n e ) +
1
G-3
I
Oxolane-2-one (y-butyrolactone) +
0 0
n3
O&-k
Oxol ane-2, 5-di one(succi ni c anhydri de) -
C,S
04qF3
Thiolan-2-one (y-thiobutyrolactone)
-
a The formulae denote rings of any size. Thus in the first line 1,3C4N0 is drawn as N--C+ and represents
I
N>
oAoJ
-
+
+ +
-
+
+ +
NI
N2
N3
N4
N5
N6
N7
N9
NIO
NII
Nlz
N13
N14
N15
N16
N17
N18
N19
N20
N21
Corrected for end-group effects.
1s assumed.
Partial allowance for unreacted monomer.
Semi-empirical values for a number of other olefins
are given in Ref. 143.
Value given is for dilute solution. Values determined
for complete range of composition; maximum (14.4)
at 50 mol% monomer.
No allowance for unreacted monomer.
Strongly dependent on both monomer concentration
and temperature.
Corrected for enthalpy of glassy state.
- As,, assumed to be 120.3 J/Kmol.
Zero heat not necessarily in conflict with observed
polymerizability below - 40C. Additional loss of
free energy may be provided by the crystallization of
the polymer.
Polymer largely insoluble and remains in suspension.
After correction for species in vapour other than
formaldehyde.
In the presence of a few per cent methylene chloride.
From measurements in methylene chloride, benzene
and 1,4-dioxane.
From measurements in benzene.
From measurements on vapor-solid equilibrium.
From measurements in both methylene chloride and
nitrobenzene.
From measurements in 1,2-dichloroethane.
Value calculated by the compiler of this table from
data in Ref. cited.
Numerical values for heats of copolymerization are
listed only for those systems yielding 1 : 1 copoly-
mers. The values refer to the copolymerization of
0.5 mol of each monomer. In all other cases listed the
copolymers have a range of composition; details of
the corresponding heats of copolymerization are given
in the Ref. cited.
oAo/
E. NOTES
N22
N23
N24
N25
N26
N27
N28
N29
N30
N31
N32
N33
N34
N35
Where no solvent is specified in the seventh column,
the symbol AH,, denotes that the measured heat is for
a liquid mixture of monomers going to a solution of
copolymers. AH,, denotes the heat change for pure
liquid monomers going to condensed amorphous
polymer. (This symbolism differs from that in
Ref. 1.)
The states of monomer and/or polymer are not stated
in Ref. but are likely to be the ones given.
Value calculated from measurements on mixtures
containing excess B.
Value calculated from measurements on mixtures
containing excess A.
Value in Ref. 11 corrected using entropy of monomer
in Ref. 94.
From measurements in both benzene and cyclohex-
ane.
Standard state: mol fraction of monomer = 0.1.
After correction for species in vapor other than
formaldehyde.
Numerical values for entropies of polymerizaiton
listed are for systems yielding 1: 1 copolymers. The
values refer to the copolymerization of 0.5 mol of
each monomer. The symbolism and standard states
are the same as used for the heats of copolymerization
(see Nd.
Value of AS for the composition of polymer
indicated.
No allowance for free energy of mixing of polymer
and monomer.
Floor temperature (hypothetical for supercooled
liquid).
Floor temperature.
Calculated value. Not measurable experimentally
because of side reactions.
Small amount of vapor dissolved in the polymer:
approximately gc.
References II / 407
Ns6 Hypothetical value for acetone as a gas at 1013 mbar
pressure.
Ns7 Decreases with increasing polymer concentration
(Ref. 112,160,289).
Nss Re ognised that polymerization over WCl&tAlC12/
d
H yields an equilibrium mixture of unsaturated
cyclic rings (C sH 14) n. Species up to IZ = 15 have
been identified and higher cyclic polymers are also
likely to be present. No firm equilibrium data exist
as yet.
N 39 dT,ldP = 19 deglkbar.
N4s Value in [M] column is the mol fraction of monomer.
N4i Decreases with increasing polymer concentration in
methylene chloride, in benzene and in 1,4-dioxane
(Ref. 159).
N42 K, values determined for cyclic monomers, IZ = 1-8.
N43 Extrapolated value.
Na For equilibrium concentrations of linear oligomeric
species see Ref. 294.
N4s Note the substantial discrepancy between the two sets
of results with nitrobenzene as solvent.
N46 Value in [M] column is the volume fraction of cyclic
monomer (rings of all sizes).
Nd7 Concentration of rings, n = 13-00, taking mol.
wt. = 74 (value for it = 1); K, determined for cyclic
monomers, IZ = 3-400.
N4s Corrected for isomerization effect.
N49 Uncorrected for isomerization effect.
Nss Equilibrium concentrations of A and B lower than
expected from values for homopolymerizations.
Nsi Polymer is SCONHN(COMe)f.
N52 Polymer is $CHzCHzN(COR)f.
N53 cis and truns forms of polymer.
N54 c(I),c(II),c(III) refer to crystal forms I, II, III of
monomer.
Ns5 Standard state is lM, calculated from data in Ref.
148.
N56 Polymer dissolved in monomer; equilibrium concen-
tration in mol/L.
N57 T, calculated from A&/AS,", or AH,"/AS~s.
Nss Valid in concentration range 2.3 to 4.6M.
N5s Corrected for monomer-polymer interactions;
required temperature variable interaction parameter.
N60 Data from Ref. 292, with corrections for monomer
adsorbed in polymer.
N6i lc data from Ref. 231 combined with vaporization
data.
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N78
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Calorimetry in solution with adjustments for solution
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CN CN
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COOEt 0 _ COOEt
SR
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Activation Energies of Propagation
and Termination in Free
Radical Polymerization
T. F. Mckenna
Laboratoire de Chimie et Procedes de Polymerization, Villeurbanne, Cedex, France
A. M. Santos
Faculdade de Engenharia Qu/mica de Lorena-Faenquil, Lorena, Sao Paulo, Brazil
A. Introduction II-415
B. Tables II-416
Table 1. Dienes II-416
Table 2. Olefins II-416
Table 3. Acrylic Derivatives II-417
Table 4. Methacrylic Derivatives II-418
Table 5. Vinyl Halogens II-420
Table 6. Vinyl Ethers and Vinyl Esters II-421
Table 7. Styrene and Derivatives II-421
Table 8. Vinyl Heteroaromatics II-422
Table 9. Miscellaneous Compounds II-423
C. References I I-424
A. INTRODUCTION
The conversion of a free radical homopolymerization as a
function of time is usually expressed by the following
equation:
1 ax
2f kd
( >
OS
- -
1 --x at
= k
kt
where x is the conversion, t the time, k,, kt, and kd the
propagation, termination and initiator decomposition rate
constants, respectively, f the initiator efficiency and Z the
initiator concentration.
It is generally assumed that the temperature dependence
of free radical polymerization rate constants can be
expressed using the well-known Arrhenius equation:
k=Aeexp $
( >
where A0 is the frequency factor, R the universal gas
constant, T the absolute temperature, and E the activation of
the reaction in question. Measurement of k, and kt at
different temperatures allows one to determine values of the
activation energies of the same two reactions, E, and Et,
respectively.
If we accept this representation, then the overall
activation energy of a homopolymerization can be written
a s
Eov = E, - ;Et + ;Ed
The value of the activation energy for the initiator
decomposition reaction, Ed, can often be estimated
separately. When data are not available for E, and Et as
separate quantities, the term (EP - i Et) can be used to
model the polymerization reaction.
In the following tables, all energies are reported in terms
of kJ/mol, and any appropriate remark(s) associated with
the data are presented.
II / 415
II / 416 ACTIVATION ENERGIES OF PROPAGATION AND TERMINATION IN FREE RADICAL POLYMERIZATION
B. TABLES
TABLE 1. DIENES
Monomer
EP
E t
E, - fEt Remarks Refs.
Butadiene 10.9
38.9
24.3 & 20.9
20.5
35.7
38.9
1,3-Hexadiene 8.42
Chloroprene 40.6
Dimethyl butadiene 37.7
Isoprene 46.0
5.9
In gas phase
In emulsion
In gas phase
In gas phase
Solution polymerization in CC1 4;
temperature range: 303-333 K
For emulsion polymerization, supposing
n = 0.5
Thermal and photoinitiation; temperature
range: 278-333 K; k, measured by ESR
In emulsion
In emulsion
In emulsion
13
1 4
1 6
2 1
90
9 1
92
3 5
45
15
TABLE 2. OLEFINS
Monomer
EP
E t E, - fEt Remarks Refs.
Acetylene
Ethylene
21.4
34.3
18.4
23.9
46.4
36.8 6.22
29.7 10.0
40.0 15.2
25.1
20.8
29.7
32.5
36.9
31.4
30.3 4.2
17.6 k 0.31 15.3 f 0.26
Propene
Isoprene
30.2
23.4
41.0
1.3
33.5
- 1.59
3.13
10.0
4.19
1.05
14.2
6.44
17.8
29.7
31.0
In gas phase 2 1
In gas phase 2 1
Calculated using results of Ref. 24 3 5
In gas phase 44
High in gas phase (up to 300 NPa); pressure 73
initiated by oxygen; temperature range:
60-250C; conversion found by gravimetry
High polymerization (up to 300 MPa); pressure 82
initiated by DTBPO; temperature range:
130-165C
93
94
Activation volumes (cal/moUatm):
propagation: - 19.7, termination: 13.0
95
96
97
98
99
100
31.6
Estimation for simulation of emulsion 1 0 1
copolymerization with vinyl acetate
1 0 2
Activation volume = - 26.26 x 1O-6 m3/gmol 1 0 3
Activation volume for propagation = 1 0 4
- 0.5 cal/mol!atm
Activation volumes (cal/mol/atm): 1 0 5
propagation: - 16.8 * 0.1; termination: 9.2.
Optimized from values of industrial runs 1 0 6
In gas phase 2 1
In emulsion 15
TABLE 3. ACRYLIC DERIVATIVES
Acryl i c Deri vati ves I I / 417
Monomer
EP E t E, - fEt Remarks Refs.
Acrylamide
A
B
C
D
E
11.7f 1.2 11.7kO.8 5.8 it 1.6
16.3 f 0.8 10.9 * 0.4 10.9 f 1.3
18.8 f 1.9 10.9 It 0.4 13.4f0.3
20.5 f 0.8 7.9 * 0.4 16.9 f 1.0
25.1 f0.9 0 310.8 25.1 Zt 1.3
6.2
10.46
22 f 0.2
20 f 0.2
11.5
57.8
NJ-methylene-bis-acrylamide
9.3
Acrylic acid
23.4
21.7
14.1
-, sodium salt (1) 67.5
(2) 72.1
-, chromium salt
-, zinc salt
-, butyl ester
33.5
13.0
Solution polymerization in HzO/DMSO
mixture with potassium persulfate;
initiators: Hz0 : DMSO : (A) 100 : 0
( B) 88:12
( C) 65:35
( D) 38:62
03 0: 100
PH 1
PH 4
Compilation of data, validated for inverse
suspension polymerization
Compilation from various sources, validated
for solution polymerization
Aqueous polymerization with temperature
range: 293-313 K
Initiation with APS; temperature range:
309.5-324.5 K; solution
polymerization at pHa 4.38
Precipitation polymerization; temperature
range: 313-333 K
By PLP; temperature range: 288-328 K
Thermally induced solid state polymerization;
two methods to find E,: (1) ESR, (2) DSC;
temperature range: 60- 160 C
Polymerized with styrene-arsenic sulfide
complex initiator in DMF
Initiated with an As2S3-styrene complex in
DMSO at 363 K
68
1 1 1
112
1 1 3
1 0 7
108
109
110
87
114
1 1 5
8.8
52.3
15.5
0
73.7
8
26
116
At 20% conversion
From PLP-GPC; temperature range:
(208-266 K); bulk polymerization
From PLP; temperature range: (298-353 K);
conversion range: (lo-80%); bulk
polymerization; P = 1 bar.
38.1 109
1 1 7 14*6
E, - ET = 0 From PLP; conversion = 30% in bulk 1 1 8
polymerization
By PLP-GPC; bulk polymerization with
photoinitiators: benzoin and 2,2-
dimethoxy-2-phenylacetophenone;
temperature range: 298-303 K
119
109
9.6 f 0.56
-,
ethyl ester
-, methyl ester
4 1 12.3
29.7 22.2
19.7 - 0
31.8f2.5 20.1 * 0.8
40.7
31.8
5.9
8.5
Gamma ray induced solid state polymerization;
temperature range: 243-283 K
109
Measured by dilatometry in both benzene 120
and 1,4 dioxane (k,/kt higher in dioxane)
By ESR; temperature range: 303-333 K, 1 2 1
solution polymerization in
1,1,2-trichloroethane; initiator:
2,2-azobis(4-methoxy-2,4-
dimethylvaleronitrile) (V-70)
By ESR, assuming Ed =109.5; 121
solution polymerization in
1,1,2&ichloroethane; initiator:
2,2-azobis(4-methoxy-2,
4-dimethylvaleronitrile (V-70)
In water solvent 25
In DMF solvent 32
-, 1,3-hydroxyneopentyl ester
-3 methyl a-acetoxy ester 35.5 46.8
-1
methyl a-butoxy ester 30.5 25.1
Acrylonitrile 17.2 22.6
16.2 15.5
References page II - 424
II/ 418 ACTIVATION ENERGIES OF PROPAGATION AND TERMINATION IN FREE RADICAL POLYMERIZATION
TABLE 3. contd
Monomer
EP Et
E, - $Et Remarks Refs.
Acrylonitrile (co&d) 26.8
29.6
42.7
- 0
7.0
6.8
21.4
23.9
In DMF solvent 3 7
1 0 9
Estimated from data on solution 1 2 2
copolymerization with styrene as azeotrope
1 2 3
Polymerization in NaSCN solution with 1 2 4
Mn(C sH702)2 as free radical initiator;
temperature range: 295-313 K, value
D-Fluoroacrylic acid
-, methyl ester 9.6
estimated from overall activation energy
with Ed = 58.6 kJ/mol
Solution: acrylonitrile; initiator: AIBN;
(assume Ed = 128 kJ/mol)
7 1
TABLE 4. METHACRYLIC DERIVATIVES
Monomer
E!J Et
E, - fEt Remarks Refs.
Methacrylamide 15.5
22.1
Methacrylic acid 17.7
-,
butyl ester
-, butyl ester
-1 i-butyl ester
-. r-butyl ester
-9 chloromethyl ester
-3 cyanomethyl ester
-, dodecyl ester (lauryl ester)
-3 ethyl ester 23.2 8.9 18.0
17.4
18.4
20.4
20.9
21.8f0.27
22.9* 1.1
23.3
20.4
20.5 i 0.24
22.5 zt 0.42
21.5 iz 0.35
16.7 7.1
4.6 16.1
12.7 14.1
8.8 16.7
27.7 f 2.5
5.5
- 8.4
21.5 & 0.34
13.7
16.2
21.3 7.1
15.5
29.8
17.7
16.5
Solvent: water
By PLP; temperature range: (288-328 K);
PH 1
34
110
By PLP-GPC; 33% monomer in 1 2 5
methanol; temperature range: 293-333 K
1 0 9
Gamma ray initiation 2 7
Kinetics from calorimetry 5 5
Temperature range: 35-27C Quoted in 58
By PLP 1 3 1
By PLP-GPC; P = 1000 bars; temperature 1 4 1
range: - 10 to 60C
Temperature range: 25-55C; by PLP bulk
polymerization; photoinitiator: benzoin
1 3 5
126
By PLP-MWD; bulk polymerization;
pressure: 1 bar; photoinitiator: benzoin
1 2 7
131
By PLP-MWD; bulk polymerization;
pressure: 1 bar; photoinitiator: benzoin
Temperature range: 9-66C; by PLP with
benzoinethyl ether as free rapid initiator
Ampoule and emulsion polymerization;
AIBN initiator
1 2 7
1 2 8
7 8
Solution: acetonitrile AIBN initiator 8 7
calculated, assuming Ed of
AIBN = 128 kJ/mol from overall activation
energy; temperature range: 50-70 C
Quoted in 58
Bulk polymerization with BP0 initiator;
temperature range 60-80 C; maximum
conversion 1%
By PLP
66
131
1 3 5
By PLP-MWD; bulk polymerization; 1 3 5
photoinitiator: benzoin
Gamma ray initiation; temperature range: 5 2
- 30 to 55 C; kinetics from calorimetry
Quoted in 58
Data from bulk and solution (50% DMF);
AIBN initiator; kinetics from GLC and
gravimetty
6 3
TABLE 4. contd
Met hacryl i c Deri vat i ves II / 419
Monomer
EP Et
E, - 4Et Remarks Refs.
Methacrylic acid, ethyl ester (co&d) 27.0
22.8 zt 0.35
20.46
27.0
22.9 zt 0.46
-, hexadecyl ester 20.1
-, hexyl ester 18.0
-> methyl ester 26.4
18.4
24.3
20.9
18.8
22.4
22.8
22.6 f 2.5 Tends to 0 22.6 f 2.5
19.7 3.3 18.0
18.2 f 0.2 2.9 f 0.0 16.7 * 0.2
20.4 - 10.5 15.1
29.1
20.9 3~ 3.3 1.6~tO.4 20.1 f3.6
31.3
21.3f0.25
18.2
26.4
22.6
18.9
15.7
18.0
18.2
24.2
18.3
31.3
- 6.6 30.4
18.8
11.9
0
2.1
0-16.7
22.2
16.3
10.5
- 8.4
20.5
18.4
23.2
20.9- 12.6
13.2 11.2
13.0
23.4
11.7
3.55
0*2.5
2.93
2.9
26.9
2.94
21.1
36
-14f8
-16~t15
Quoted in 79
By PLP 1 3 1
By PLP; temperature range: 298-328 C; 1 3 5
bulk polymerization; photoinitiator: benzoin
Evaluated for emulsion polymerization 1 2 9
By PLP-GPC; bulk polymerization, 1 2 7
pressure: 1 bar; photoinitiator: benzoin
Bulk polymerization; initiator: AIBN 130
Solution polymerization in benzene; 130
initiator: AIBN
Quoted in 58
Quoted in 58
4
7
28
Termination by combination or
disproportionation
In emulsion
Gamma ray induced; temperature range:
- 25 to 55 C; used a combination of DCS
and inhibition with DPPH to find kinetic
parameters
30
47
3 1
48
Polymerization in benzene; DMDM initiator; 49
temperature range: 50-80 C
Bulk polymerization; DBPO initiator; 53
maximum conversion 25%; ESR used to find
kinetic parameters
Isothermal bulk; polymerization with AIBN 56
initiator; DCS used to follow reaction;
value found assuming Ed AIBN = 128 kJ/mol
Quoted in 58
Bulk polymerization; AIBN initiator
temperature range 15-30 C; reaction
followed by spatially intermittent
polymerization; DP lOOOO- 15000
Bulk polymerization; AIBN initiator;
1-butanethiol used as CTA; value assumes
Ed AIBN = 128 k.l/mol
Solution: benzene; AIBN initiator; kinetic
data from molecular weight data;
maximum conversion 5%
Emulsion data; particle sizes from turbidity;
potassium persulfate initiator
Solution: benzene; AIBN initiator; kinetic
parameters from intermittent illumination
Bulk polymerization
By PLP
Temperature range: 293-353 K
Suspension polymerization
Spatially intermittent polymerization/
emulsion polymerization
Solution polymerization in toluene
1 Bar; temperature range: 323-353 K,
low conversion
100 bars
1000 bars
64
65
68
72
77
8 5
131
1 3 2
1 3 3
109
156
134
164
1 3 5
136
1 3 7
138
139
140
1 4 1 22.2 f 0.3
References page II - 424
II / 420 ACTIVATION ENERGIES OF PROPAGATION AND TERMINATION IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Monomer
EP E t
E, - fE, Remarks Refs.
Metbcrylic acid, methyl ester (contd)
-, nonyl ester
-1 octyl ester
-, phenyl ester
-, o-methylphenyl ester
-3 o-ethylphenyl ester
-1 o-iso-propylphenyl ester
-, p-methylphenyl ester
-, p-ethylphenyl ester
-, p-iso-propylphenyl ester
-, p-terr-butylphenyl ester
-, ethyl cc-Benzoyloxymetbyl ester
-3
ethyl a-acetacetoxymethyl ester
-, 2-(3-chloro-3-methylcyclobutyl)-2-
hydroxyethyl ester
Methacryloyl fluoride
Methacrylonitrile
-1 n-Phenyl-a-methylene-8-lactam 22.8
22.4
22.2
23.9
22.2
17.2
15.9
48.1
29.7 f 1.5
2.9
13.0 10.9
12.1 9.7
9.2
9.6
12.2
14.4
10.6
9.3
13.2
9.5
11.5
24.55
30.68
10.4
20.9 37 .7
PLP plus GPC for bulk polymerization;
temperature range: 272-363 K
1 4 2
1 4 3
144
By PLP-GPC; bulk polymerization; 1 4 5
pressure: 1 bar; photoinitiator:
2-hydroxy-2,2-dimethylacetophenone;
temperature range: 272-363 K
By PLP-GPC; bulk polymerization; 1 4 6
pressure: 1 bar; photoinitiator: benzoin;
temperature range: 272-363 K
Quoted in 58
Quoted in 58
1 4 7
1 4 7
1 4 7
1 4 7
1 4 7
147
1 4 7
1 4 7
By ESR, assuming Ed = 129; solution 1 4 8
polymerization in benzene; initiator: AIBN
149
Polymerization in dioxane using BzzOs as
initiator
150
Solution: MEK; AIBN initiator; calculated
using Ed AIBN = 128 kI/mol;
temperature range: 50-70C
8 1
20
By PLP; solution polymerization in
benzylactone; temperature range:
283-333 K
1 5 1
Solution polymerization in n-methyl-2- 152
pyrrolidone with AIBN (calculated from
Eov assuming Ed of AIBN = 129 kI/mol)
TABLE 5. VINYL HALOGENS
Monomer
EP
E t E, - fEt Remarks Refs.
Tetrafluoroethylene 17.4 13.6 10.6
5.4 0.8 5.0
Vinyl bromide 30.0 16.3 21.8
Vinyl chloride 16.0 17.6 7.4
1 2
46
43
42
1 7
Validated for model of suspension 1 5 3
polymerization
For suspension polymerization 154
Solvent: hexane 9
Solution: N-methylpyrrolidone; AIBN used 67
as photoinitiator; most runs 5 1%
conversion
27.6 18.2
Vinylidene chloride 104 1 6 7 20.5
37.7 f 5.9 20.9f 10.5 27.2& 11.1
Styrene and Derivatives II / 421
TABLE 6. VINYL ETHERS AND VINYL ESTERS
Monomer
EP
E t E, - ;Et Remarks Refs.
Butyl vinyl ether 46.4
Vinyl acetate 18.0
30.6
1 3
1 8
1 8
39*3
19.6 zt 2.9
20.5 zt 0.39
26.4
23.5
19.7 zt 2.9
23.7
23.6
24.2
26.4
35.2
27.8
0
21.9
0
<4
0
0
11.7
14.2
0
4.0
13.4
14.2
18.0
19.6
1 3
16- 18
0
19.6 zt 2.9
N 26.4
28.1
Bulk polymerization; initiator DTBPO;
assume Ed = 51.5 kJ/mol (Ref. 82)
at given conditions; GPC data used to find
kinetic parameters
Bulk polymerization; DBPO and
cyclohexyloxyperoxide initiators;
ESR used to find kinetics
Bulk polymerization; DBPO and cyclohexyl-
oxyperoxide initiators; temperature range:
55-70 C; DSC used for kinetics;
maximum conversion 20%
Validated for emulsion copolymerization
with ethylene; temperature range:
293-323 K, pressure range: 0-34 bar
Temperature range: 293-353 K
For emulsion polymerization
Emulsion polymerization
Rotating-sector method; bulk
polymerization; photoinitiator: benzoin
By PLP-MWD; bulk polymerization;
photoinitiator: benzoin
84
1
5
6
1 8
22
38
5 3
57
1 3 1
1 3 3
102
1 5 5
109
156
1 5 7
1 5 8
159
160
1 5 5
1 6 1
TABLE 7. STYRENE AND DERIVATIVES
Monomer
EP E t
E, - fEt Remarks Refs.
Styrene 49.0
27.2 zt 4.2
26.0
32.5
31.0 & 35.0
54.0 & 59.0
25.0
73.6
29.0
37.7
29.5 zt 0.1
29.0 rk 3.0
11.7f4.2 21.3 * 6.3
8.0 22.0
9.9 27.5
2.0 24.0
In emulsion
In emulsions
In emulsions
9.2 zt 0.5
25.1
24.9 f 0.4
34.1
Gamma ray induced; bulk liquid phase
polymerization; maximum conversion 10%;
temperature range: 19-74 C
Low conversion; bulk polymerization;
ESR spectroscopy used for kinetics
Bulk photopolymerization; kinetics from
spatially intermittent polymerization
technique; temperature range: 15-36 C
DP 2400-2700
AIBN initiator; assume Ed = 128 kJ/mol;
bulk polymerization 1-butanethiol as CTA;
maximum conversion 0.4%
In emulsion; reaction followed by
dilatometry
References page II - ,424
2
3
1 0
11
1 5
1 9
29
36
42
50
5 1
64
65
70
II / 422 ACTIVATION ENERGIES OF PROPAGATION AND TERMINATION IN FREE RADICAL POLYMERIZATION
Table 7. contd
Monomer
EP Et
E, - &!I, Remarks Refs.
32.2
32.5 14.5 25.2
17.7
29.6
25.2
37.8 f 1.7
39.8
36.1
15.6
18.7
29.5
44.4
29
36.4
37.5 f 1.6
30.8
10.91
30.0
29.0
31.5
31.5
31.5
1 8
32.5
p-Bromostyrene 32.0
o-Methylstyrene 58.2
p-Methylstyrene 32.0
29.6
29.6
N-Methyl styrene 54.3
Divinylbenzene 35.5
32.3
9.5
14.2
Emulsion data; assume N = 0.5, sodium
persulfate and sodium bisulfite initiators
Bulk polymerization; AIBN initiator;
temperature range: 45- 100 C
In emulsion; sodium persulfate initiator
By ESR; temperature range: 273-403 K
Suspension polymerization; conversion less
than 0.8; temperature range: 283-353 K
Spatially intermittent
polymerization/emulsion polymerization
High conversion suspension polymerization
Emulsion polymerization; temperature
range: 318-338 K
ESR; temperature range: 323-363 K
By PLP; temperature range: 298-328 K
By PLP; temperature range: 293-353
For d, (degree of polymerization) > 4
For all chain lengths together
Bulk and diluted systems initiated by
@-acetylbenzylidene)triphenylarsonium
Measurements by rotating sector method;
initiators: AIBN (30-50 C),
BP0 (70-90 C)
Styrene
Perdeuterated styrene
PLP; temperature range: 303-363 K; in bulk
Measurments by ESR; photo and thermal
initiation; temperature range: 293-363 C
PLP; temperature range: 261-366 K;
bulk polymerization with photoinitiators:
benzoin and 2,2-dimethoxy-2-
phenylacetophenone (DMPA)
30.5
8.27
8.4
29.8
25.4
In emulsion
In emulsion
Searched by EVM
76
79
89
132
109
156
162
1 6 3
164
1 6 5
166
1 6 7
1 6 8
169
170
1 7 1
172
1 7 3
174
39
36
36
1 0 9
1 7 5
176
1 7 7
178
TABLE 8. VINYL HETEROAROMATICS
Monomer
EP E t
E, - ;E, Remarks Refs.
3-Methylene-5,5-dimethyl-2-pyrrolidone 8.2
Methylene-N-methylpyrrolidone 20.1
N-Vinylcarbazole 28.9
2-Vinylpyridine 33.5 20.9 23.0
N-Vinylpyrrolidone 29.7 6.7 26.4
(4
68.0 19.0 58.5
0%
40.0 & 2.0 13.0 33.5 f 2.0
(Cl
31.6f3.0 9.0 27.5 f 3.0
0
23.0 8.0 19.0
Solution polymerization in DMSO with
AIBN (calculated from Eov assuming
Ed of AIBN = 129 kJ/mol)
In bulk and in solution with acetonitrile;
AIBN initiator (assume Ed = 128 k.I/mol)
Low conversion
In various solvents: (A) Water
(B) L-Propanol
(C) Methanol
(D) Ethyl acetate;
1 7 9
86
42
40
4 1
6 1
rates followed by dilatometry
Table 8. contd
Miscellaneous Compounds II / 423
Monomer
E!J
Et E, - fE, Remarks Refs.
29.1 6.7
4.8
(1) 12.8
(2) 10.8
65.8fO.l
11.2
Template polymerization in DMF; AIBN 14
initiator; DSC used to follow reaction
Solution polymerization 75
In DMF; assume Ed of AIBN in
DMF = 142 kJ/mol; reaction followed by
DSC in 2 modes: (1) dynamic
(2) isothermal
Aqueous phase polymerization with 180
potassium peroxydiphosphate Ag + ;
temperature range: 293-323 K
1 8 1
Solution polymerization in n-methyl-2- 182
pyrrolidone with AIBN (calculated from
Eov assuming Ed of AIBN= 129 kJ/mol)
TABLE 9. MISCELLANEOUS COMPOUNDS
Monomer
EP Et E, - fE, Remarks Refs.
Acetaldehyde 46.0 zt 6.3
Diethyl fumarate 25.0 It 2.0
Diisopropyl fumarate
Formaldehyde
o-Methylene-y-butyrolactone
Vinylferrocene
N-Vinyl-methylacetamide 26.9
a-Ethyl, 8-hexafluoroisopropyl itaconate
Diethyl itaconate
Diisopropyl itaconate
Di-n-Butyl itaconate (DBI)
l,l-bis[(l-adamantyloxy)carbonyl]-2-vinyl-
cyclopropane
Diethylene glycol bis-ally1 carbonate (DEAC)
N-Acryloyl-2,2-dimethyl-5@-phenyl-1,
3-oxazolidine (ADPO)
16.8
8.4
20.0
18.0 57.4
29.0 30.0
21.0 24.0
28.5 66.1
53.6
29
26.5
16.3
12.1
1.9
0.5
4.35
87.1
21
Radiation induced in solid phase; calorimetry 54
used to follow reaction; temperature range:
130-150K
Bulk polymerization; AIBN initiator;
(BSSnme Ed = 128 kT/mo1) dilatometry
used to follow the reaction; temperature
range: 60-80 C
59
Assuming Ed = 129; by dilatometry; 1 8 3
bulk polymerization; initiator: AIBN
184
Quoted in 54
Solution: DMF; AIBN initiator (assume
Ed = 128 k.hOl); E, - E, N 12.1
Note nonclassical kinetics; overall
activation energy does not equal
Ed + E, - E,/2; can approximate
Et = that of styrene
80
62
Solution: methanol; AIBN initiator;
maximum conversion 10%;
temperature range: 25-75 C
Polymerization in benzene catalyzed by
dimethyl 2,2-azobisisobutyrate
Polymerization in benzene catalyzed by
dimethyl 2,2-azobisisobutyrate
(no SnC14)
(0.342 mol/l SnC14)
83
1 8 5
186
Polymerization in benzene catalysed by
dimethyl 2,2-azobisisobutyrate
Assuming Ed = 129; by ESR; solution
polymerization in benzene; initiator:
AIBN
1 8 7
1 8 8
Assuming Ed = 129.1; By ESR; 188
solution polymerization in benzene;
initiator: 2,2-azobis(isobutyrate): MAIB
Ring-opening solution homopolymerization 189
in benzene; temperature range: 323-343 K,
with AIBN (assume ED,AIBN = 123.5 kJlmo1)
Rotating sector method; Initiator: BP0 190
Assuming Ed = 124.3; temperature range: 1 9 1
323-343 C; solution polymerization
in benzene; initiator:
2,2-azobis(isobutyrate): MAIB
References page II - 424
II / 424 ACTIVATION ENERGIES OF PROPAGATION AND TERMINATION IN FREE RADICAL POLYMERIZATION
Table 9. contd
Monomer
EP Et
E, - fE, Remarks Refs.
TV-Cyclohexylmaleimide (CHMIm)
N-Acryloyl-p-aminobenzoic acid
40.9 20.1
48.3
By ESR; temperature range: 3 13-333 K; 1 9 2
solution polymerization in benzene;
initiator: AIBN
Assuming Ed = 129; solution polymerization 1 9 3
in dioxane; initiator: AIBN
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Activation Volumes of
Polymerization Reactions
G. Luft
lnstitut fur Chemische Technologie, Technische Hochschule, Darmsadt, FR Germany
Y. ogo*
Research Institute for Solvothermal Technology, Takamatsu, Takamatsu, Japan
A. Introduction
B. Activation Volumes of Some Polymerization
React i ons
C. Activation Volumes of Initiator Decomposition
D. Activation Volumes of Chain Propagation
E. Activation Volumes of Chain Termination
F. Activation Volumes of Chain Transfer
React i ons
G. Influence of Pressure on Copolymerization
Table 1. Copolymerization Parameters
Table 2. Reactivity Ratios of
Terpolymerization
Table 3. Activation Volumes
Table 4. Q, e Values
H. Ref erences
II-429
II-432
II-435
II-435
II-436
II-436
II-437
II-437
II-438
I I-439
I I-440
I I-440
A. INTRODUCTION
The activation volume is included in the pressure
dependence of the reaction rate constant (1-4):
(Al)
where k is the reaction rate constant, p is the pressure, T, the
temperature V, the volume, and Au*, the activation volume
(analogous to the activation energy). It is the difference
between the partial molar volume of the activated complex,
as formed in the transition state theory by the efficient
collision of molecules, and those of the initial reactants.
The sign of the activation volume depends on the type of
the chemical reaction. If new bonds are formed in the
transition state, the activated complex is larger than the
*Table 3. Activation Volumes.
initial species, and hence the activation volume is positive.
Inversely the activation volume is negative if bonds are
stretched and broken.
For a rough calculation of the activation volume, we can
assume that the formation of new bonds as well as
stretching occurs along the axis of a cylinder, whose
constant cross section is determined by the van der Waals
radii dmAp, dmBp, and dmCp of the atoms A, B, C:
Av* = ;N[(db, + d;&b,) + (df,,, + d,&)(&,c)]
(A21
with AAs = (0.10-0.35) dmm, An,c = (l.lO-1.35)d,nc-
dmB,c (see Refs. 2,5,6), N is the Avogadro number, dmAB,
dmnc = bond length (values, see Ref. 7), and drnBC is the
interatomic distance at the minimum of potential (sum of
van der Waals radii), dmAp, dmBp (see Ref. 8).
The stretching of the bonds in the transition state is about
0.01-0.1 nm, whereas the change in the distance dmB,g
between the unbonded atoms is usually larger (up to
0.25 nm).
If the decomposition of the activated complex causes
only small changes in the bond length or in the distance
between the atoms, its partial molar volume differs from
that of the activated complex only slightly. Hence we can
assume
Au* = Au
where Au is the excess of the partial molar volume of the
reaction products over the partial molar volumes of the
initial species.
This simplification is valid for reactions in which
products of cyclic structure are formed, as in the dimeri-
zation of cyclopentadiene, with Au* % Au = -30 cm3/mol
(9, 10).
II / 429
II / 430 ACTIVATION VOLUMES OF POLYMERIZATION REACTIONS
A second term is added to the volume change of the
reacting molecules in the transition state if a polar solvent is
involved. This term takes into account the change in the
packing density of the surrounding solvent molecules due to
the arising or disappearing of electrostatic charges between
the solvent and the reactant species. This volume change is
negative in bimolecular association and positive in unim-
olecular dissociation and tends therefore to counteract the
effect of volume change during the reaction. The activation
volume can be determined according to Eq. (Al) from rate
measurements at different pressures and constant tempera-
ture using a semilog plot of reaction rate constant versus
pressure. In this evaluation the value of (aV/ap),/V can
often be neglected, because the compressibility of fluid
reactants and compressed gases is generally small at
pressures above 100-200 MPa.
At very high pressures the increase of the reaction rate
constant at negative activation volume is retarded by the
lower mobility of the molecules due to the increased
viscosity. This effect was first measured by Hamann (11) in
an examination of the alkaline etherification of ethyl
bromide at pressures up to 4000MPa. It was also found
in the polymerization of styrene by Nicholson and Norrish
(12).
In order to obtain the reaction rate as an explicite
function of pressure, Eq. (Al) can be integrated, neglecting
the compressibility and assuming that the activation volume
does not change greatly with pressure (13):
k, = ko x exp - RT
Av*b-PO)
W)
where k, is the reaction rate constant at pressure p and ko is
the reaction rate constant at reference pressure PO.
According to Eq. (A3) the reaction rate constant in-
creases exponentially with pressure if the activation volume
is negative and decreases if AU* is positive. Eq. (A3) is
valid only in the high pressure range @ > 50MPa). At low
pressures the compressibility cannot be neglected anymore,
and the activation volume changes noticeably with pressure,
especially in the neighborhood of the critical point.
Simmons and Mason (14) studied the dimerization of
chlorotrifluoroethylene at pressures up to 10MPa. They
found that the value of the negative activation volume
decreases first with pressure and then increases rapidly. It
has a maximum at the critical point and after decreasing
again it approaches asymptotically a constant value.
The authors describe the pressure dependence of the rate
constant, taking account of the partial molar volume of the
initial reactants as well as that of the activated complex by
the use of suitable equations of state (e.g., Redlich-Kwong
or virial coefficient equations).
In order to appreciate the influence of pressure on the
reaction rate constant one can compare it with the influence
of the temperature: an increase in pressure (activation
volume Aw* = -25 cm3/mol) at a temperature of 50C
from 0.1 to 450 MPa corresponds to a temperature increase
(activation energy E = 84kJ/mol) from 50 to 105C.
Experimentally determined overall activation volumes of
some polymerization reactions are listed in Section B. The
data were determined from the dependence of the overall
rate constant of the polymerization reactions on pressure.
The values are more or less negative, hence the rate of
polymerization increases with pressure.
The overall activation volume is composed of the
activation volumes of the different polymerization steps,
initiation, or initiator decomposition, chain propagation and
chain termination:
Au* = Au; + Au;/2 - Au;/2
(A4
where Awi is the activation volume of chain propagation,
Awi is the activation volume of initiation with respect to
initiator decomposition, and Au: the activation volume of
chain termination.
The activation volumes of initiator decomposition
(values in Section C) are always positive because this
reaction is a unimolecular dissociation, in which a bond
(e.g., the O-O bond in peroxides and peresters or the N-N
bond in azo-compounds) is stretched in the transition state
and finally broken. As mentioned before, Au: depends on
the solvent. It can significantly be influenced by a change of
electrostatic charges, viscosity, and cage effects. The
activation volume of initiator decomposition is different
when induced decomposition is involved at high concen-
tration of the initiator or when the initiator decomposes in a
concerted mechanism. Au: is small for two-bond scission
initiators (15). The activation volume is higher for one-bond
scission initiator, bulky molecules, and when more bonds
brake simultaneously. The data collected in Section C were
obtained in separate measurements, observing the decrease
of the initiator concentration with time at different
pressures. The disappearance of the initiator can also be
measured during polymerization by observing the light
absorption at a characteristic waver length or using
scavenger techniques.
In the chain propagation reaction, the decrease in the
distance between the radical and the monomer molecule is
greater than the increase in length of the double bond of the
monomer. Hence the activation volumes Au; listed in
Section D are always negative. The data for Awi are
measured at high pressures by the method of the rotating
sector together with Au,, the activation volume of chain
termination.
The activation volumes Au: are also negative as shown
in Section E. Mostly the termination reactions are diffusion-
controlled. The reactant molecules undergo translational
diffusion at first to form a collision pair. It follows the
movement of the reactive sites on these molecules into a
position favorable to chemical reaction. This process has
been considered to be the rate-determining step. The
activation volume involved in this so-called segment
diffusion is observed. When chain termination is governed
by translational diffusion, the activation volume, At& for
viscous flow, is the key parameter for the evaluation of the
influence of pressure.
Introduction II / 431
The chain transfer of a radical to the monomer, to a
dead polymer, or to a modifier molecule is mostly
favored by the pressure which means that the activation
volumes should be negative, whereas the activation volume
of the intramolecular transfer (by back biting), which
initiates the formation of short side chains, can be negative
or positive. The activation volumes of these reactions are
determined from the change in short- and long-chain
branching or from the change of the average molar mass or
degree of polymerization of the formed polymers with
pressure.
Under the assumption that the monomer and the polymer
concentration do not change over a wide range and that the
temperature is kept constant, the following relation can be
derived from kinetic considerations:
Au;-Au;= RT
(A51
where VZG is the number of branches and Avt is the
activation volume of the chain transfer reaction.
Analogously, the influence of the pressure on the chain
transfer to a modifier can be described by the expression
Au; - Av;~ = RTrln(;fkp))T
= RT 8 ln( l/p - l/Pno)
aP >
W)
T
where P is the average degree of polymerization obtained in
the presence of a transfer agent and P,, is the average
degree of polymerization obtained in the absence of a
transfer agent.
Because of the mostly negative sign of the activation
volumes (listed in Section F), the radical transfer to the
modifier molecule is often slightly decreased at high
pressures.
The activation volume of degradation reactions which
can occur at high temperatures should be positive because
bond cleavage increases the volume of the activated
complex more than the formation of double bonds from
single bonds decreases it.
The difference in the activation volumes of the various
component reactions results in a different influence of the
pressure on the rate constants and leads to modified
polymers. Because of its larger negative activation volume
the chain propagation reaction is more favored by high
pressures than the termination. The chain length and
consequently the tensile strength as well as the tensile
modulus increase with pressure:
r+),= -$ [nv; -~(~AV~+AV;] (A7)
where v = chain length.
The small negative activation volume of the intramole-
cular chain transfer shows that this reaction step, which
determines the short chain branching, is less favored by
high pressures, which means that polymers with high
density and crystallinity can be synthesized at high
pressures.
Similar considerations also show that the composition of
copolymers and thus their molecular structure is influenced
by the synthesis pressure. The pressure dependence of the
copolymerization parameters ~1 and ~2, which determine
the composition of a copolymer, is expressed by the
relationship
(a1ni;ir2)T = --&Av;~~ - A$j2 - A$22 + Av;~~)
x -&(Av;~~ - Aw;~~)
where AvU;;~~, Aui22 are the activation volumes of the
propagation reaction between a monomer molecule and a
radical formed from the same monomer, and Avz12, At521
are the activation volumes of the propagation reaction
between a monomer molecule and a radical formed from
the comonomer.
Equation (A8) is valid if the composition of the initial
reaction mixture does not change appreciably with pressure.
According to Eq. (A@, an increase in pressure favors the
inclusion of monomers, which in homopolymerization
show a large negative activation volume (e.g., substituted
olefins). Values of copolymerization parameters obtained at
different pressures and activation volumes of some
copolymerization reactions are listed in Section G.
When ~1 and 1-2 should be calculated for high-pressure
copolymerization, following Alfrey and Price, the pressure
dependence of Q, e data must be taken into account. Some
values of Q and e for high pressures are collected in Section
G. The dependence of the e data of two monomers on
pressure is given by the equation
(a-;; I) T
= - & [(A$1 - A$2) +64742 - Au21)1 649)
References page II - 440
II / 432 ACTIVATION VOLUMES OF POLYMERIZATION REACTIONS
B. ACTIVATION VOLUMES (cm3/mol) OF SOME POLYMERIZATION REACTIONS
Monomer
Maximum
pressure
(MM
Temp. (C) Solvent Initiator a Au* Refs.
Acenaphthylene
Acetaldehyde
Acrylic acid anhydride
Acrylonitrile
Ally1 acetate
N-(4-Anilinophenyl)acrylamide
3,3-Bis(chloromethyl)oxetane
Butadiene
Butyl acrylate
Butyl acrylate
Butyl methacrylate
2-Cyclopropylpropene- I
Diallyl cyanamide
Diallyl phthalate
3,3-Dichloropropene-1
1,l -Dichloro-2-vinylcyclopropane
Diethyl fumarate
3,3,3-Difluorochloropropene-1
1,l -Difluoro-2-vinylcyclopropane
2,3-Dimethyl-1,3-butadiene
Ethylene
1,2-Epoxycyclohexane
n-Hexyl methacrylate
Indene
Isobutyl methacrylate
Isoprene
390 60
150 100- 200
844 - 60
844 - 7 0
844 - 7 8
400 50
200 50
850 80
100 60
200 60
300 60
500 60
1500 60
500 60
500 50
500 70
500 95
100 30
100 30
100 20
300 20
460 20
700 20
100 60
100 30
100 20
300 20
460 20
> 460 20
140 70
140 20
600 80
500 70
500 70
1000 40
1000 80
1000 20
300 60
1400 30
1000 50
1000 20
250 129
760 50-70
200 225- 235
190 80
loo-210 200-300
110- 220 190
250 130- 165
110- 550 170- 240
1 7 5 127- 197
300 135- 165
840- 1250 60
450 20
800 20
800 64
100 60
1400 20-30
1400 20-30
1400 20
1400 20
DMF
DMF
THF
Toluene BFsldiethyl ether
Benzene
Toluene
Heptane
DEE
Heptane
Benzene
Toluene
Ethyl acetate
AIBN
Diethyamine
AIBN
AIBN
BP0
AIBN
ACN
ACN
Radiation
AIBN
ACN
Radiation
AIBN
Stannic chloirde
TBPB
AIBN
AIBN
DCPC
AIBN
Stannic chlorde
DCPC
AIBN
Stannic chloride
BuLi
BuLi
DTBP
AIBN
Peroxide
DCPC
Enanthylperoxide
Methylinobutylketone
TBPO
TBPP
Oxygen
Diphenyl disulfide
DTBP
BP0
Radiation
AIBN
Oxygen
BP0
HI/I-I20
HI&I20
-5. 8
- 12.5
- 11.1
- 8.0
- 6.2
- 14
-22b
- 13.4
- 36.1
- 31.2
- 22.3
- 15.4
- 6.4
- 16
- 8.8
- 13.3
- 17.2
- 26.3
- 26.3
- 21.0
-21.2
- 5.7
- 11.4
- 25.6
- 17.4
-21
- 21.2
- 5.7
- 14.4
- 23
- 15
- 14
-9.9 to - 11.8
- 14.3
Oto8
- 14b
-3oto - 7 0
- 14
- 15
- 15
-45
- 3 6
- 4 8
- 20 to - 23
-3 t o -6
-2Oto - 2 6
- 10
-58 to -68
- 18
-18 to -22
- 22.6
- 12 to - 18
- 2 9
- 17.5
- 13
- 24
- 17.4
- 21.0
- 23.9
- 11.0
- 7.9 to 18.0
- 7.9
-9. 8
1 6
1 2 7
142
5 1
52
1 7
150
5 5
1 4 1
9 1
154
147
1 2 8
90
94,95
53
53
54
130
5 7
56
1 8
58
59
59,60
1 3 3
46,20
1 9
73
74
1 5 1
114
6 1
79
2 1
8 5
79
5 5
94
22
122
2 3
24
Activation Volumes of Some Polymerization Reactions II / 433
Monomer
Maximum
pressure
(MPa) Temp. (C) Solvent Initiatora Ad Refs.
Isopropenylcyclopropane
Itaconic acid
Maleic anhydride
Maleimide
Methyl acrylate
Methyl methacrylate
u-Methylstyrene
Octyl methacrylate
Propylene
Sodium allylsulfonate
St y r e n e
1400
1400
1400
500
500
500
500
500 20-40
100 50
180 20
210 20
400 20
700 20
200 40
300 40
100 30
300 20
550 20
100 50
100 50
100 40
100 50
100 60
100 IO
400 50
100 50
100
100
100
100
100
350
500
500
500
500
100
1600
1600
1600
800
400
400
900
208
213 25 Radiation
400 30 Radiation
100 30 ACN
200 40 Radiation
280 40 Radiation
400 40 Radiation
600 40 Radiation
300 50 AIBN
100 50 AIBN
200 60 AIBN
20
70
20
40
50
60
70
50
50
50
50
50
60
50
60
70
80
30
2 1
48
83
80-100
80
90
100
22
Dichloromethane
DMF
DMF
DMF
DMF
Methanol
Benzene
Acetone
Benzene
Benzene
Benzene
Benzene
Benzene
Butyraldehyde
Carbon
tetrachloride
Dichloroethane
Ethanol
Ethyl acetate
n-Hexane
Trichloromethane
Hz0
HI/H20
AIBN
Stannic chloride
AIBN
AIBN
AIBN
AIBN
BP0
AIBN
Radiation
Peroxide
Peroxide
ACN
Radiation
Peroxide
AIBN
Peroxide
Peroxide
Peroxide
Peroxide
AIBN
AIBN
AIBN
AIBN
Peroxide
Peroxide
Peroxide
AIBN
AIBN
AIBN
AIBN
ACN
Radiation
Radiation
Radiation
AIBN
BP0
BP0
BP0
Radiation
Radiation
- 10.8
- 23.0
- 15.0
- 23.2
- 27.4
- 30.8
- 32.3
- 4.6
-15 to -25
- 17.6
-21.4
- 22.9
- 3.6
- 12.8
- 19
- 19
- 15.6
- 21.gc
- 23.6
- 13.7
- 26.0
-21.6
- 17
- 19
-21
-23
-25
- 19
-21
- 20
- 24
- 19
- 22
- 18
- 14.5
- 13.8
- 11.8
- 10.7
- 26.3
- 25.6
- 9.6
- 9.6
- 12.2
- 14
- 9.0
- 10.8
- 12.7
-5 t o -7
- 20.5
- 18.6c
+5.8
- 20.9
- 18
- 17.1
- 17.6
- 15.8
- 50.5
- 4.3
- 29.5
-21
- 20.2
- 15
1 5 8
140
132
122
129
1 4 7
25
26
87,153
93,95
27
129
2 7
2 7
27
27
62
27
27
27
27
27
27
1 8
1 3 5
99
28
144
1 4 5
1 3 7
136
126
89
146
146
146
146
64
27
149
References page II - 440
II / 434 ACTIVATION VOLUMES OF POLYMERIZATION REACTIONS
Monomer
Maximum
pressure
WW Temp. (C) Solvent Initiator Av* Refs.
1,1,2,2-Tetrachloro-1,3-butadiene
Tetrahydrofuran
Vinyl acetate
Vinyl chloride
293 60
265 80
265 80
214 2 5
214 25
200-500 60
100 50
100 50
100
400
400
100
50
50
50
50
300 25-30
100 50
100 50
100 50
100 50
400 60
100 50
400 60
268 60
293 60
440 60
300 30
300 40
100- 600 72
1400 25-80
250-540 60
100 30
600 20
400 40
400 40
300 40
400
500
390
390
390
390
250
200
300
200
65
60
40
50
60
70
50
60
60
60
60
Emulsion
Emulsion with SDS
SDS
Emulsion with
aerosol OT
Emulsion
Emulsion with
nonionic
emulsifier
Emulsion
Acetone
Benzene
Benzene
Benzene
Butyraldehyde
Butyraldehyde
Carbon
tetrachloride
Chlorobenzene
Chl oroform
Dichloroethene
Ethanol
Ethyl acetate
Isopropyl aldehyde
Hexane
Propionaldehyde
Tetrachloroethylene
Toluene
Triethylamine
Triethylamine
Triethylamine
Triethylamine
Acetone
Butyraldehyde
Carbon
tetrachloride
Trichloroethylene
Benzaldehyde
Benzene
Benzonitrile
Toluene
AIBN
BP0
Thermal
Radiation
Radiation
AIBN
AIBN
AIBN
Peroxide
AIBN
AIBN
AIBN
HC104
AIBN
AIBN
AIBN
AIBN
AIBN
AIBN
AIBN
Peroxide
AIBN
AIBN
BP0
BPO
Thermal
BF3/diethyl et her
ACN
Radiation
AIBN
AIBN
AIBN
AIBN
BP0
BP0
BP0
BP0
LPO
AIBN
AIBN
AIBN
AIBN
- 18
- 17
- 25.8
138
- 18.7
- 17.9=
- 18.3
29
1 2 5
1 2 5
1 3 8
138
138
- 21.6
139
139
- 11.1 3 5
- 25.5 27
- 19.2 27
- 23.0 6 3
- 18 30
- 25 65
- 2 2 63
- 19.1 2 7
-20 to -25 1 5 5
-21.9 27
-21.2 27
- 19.6 27
- 24.3 27
- 6.8 1 5 7
- 19.1 27
- 15.5 157
- 16 3 1
- 17 29
- 17 29
- 1 8 32
>- 11.5 3 3
- 17.5 34
- 3 6 159
- 2 2 5 5
- 17.2 86
- 9 148
- 19 62
-21 62
- 13 36
- 10.5
- 16.7
-4. 6
- 6.8
- 8.1
- 10.4
- 18
-4. 1
- 20.5
- 12.0
- 8.2
65
1 3 1
1 4 3
124
98
1 3 1
98
98
Abbreviation: ACN: 1,l -azobiscyclohexane-I-carbonitrile; AIBN: 2,2-azobisisobutyronitrile; BP0 benzoyl peroxide; DCPC: dicyclohexyl peroxidicarbonate; DEE:
diethyl ehter; DMF: dimetbylfonnamide; DTBP: di-rerr-butyl peroxide; LFO: lauroyl peroxide; TBPB: fert-butyl perbenzoate; TBPO: terr-butyl peroctoate; THF:
tetrabydrofuran; SDS: sodium dodecylsulfate; Aerosol OT: sodium dioctyl sulfosuccinate; TBPF? rerr-butyl pervivalate.
bCalculated by other authors.
CCationic polymerization.
Activation Volumes of Initiator Decomposition and of Chain Propagation
C. ACTIVATION VOLUMES OF INITIATOR DECOMPOSITION
II / 435
Initiator Sol vent
Absolute pressure Temperature
@@a) (Cl
Activation volume Aw ;
(cm 3/mol) Refs.
AIBN
Azobis-tert-butanolate
Benzoyl peroxide
2,2-Bis(teti-butyl peroxy)butane
Decanoyl peroxide
Dicyclohexyl peroxydicarbonate
Di-n-propyl peroxydicarbonate
Dioctanoyl peroxide
Di-tert-butyl peroxide
Pentaphenylethane
tee-Amy1 perneodecanoate
tee-Amy1 perpivalate
terf-Butyl cyclohexanecarboxylate
teti-Butyl perbenzoate
tert-Butyl pemeodecanoat e
tert-Butyl perpivalate
tert-Butyl peroxy-2-ethylhexanoate
tert-Butyl phenylperacetate
l-Methyl- 1 propylpentyl perpivalate
1,1,4-Trimethylpentyl perpivalate
1,1,4-Trimethylpentyl
pemeodecanoat e
Toluene
Toluene
Octane
Acetophenone
Ally1 acetate
Carbon tetrachloride
Carbon tetrachloride
Iso-dodecane
Benzene
Iso-dodecane
Benzene
Iso-dodecane
Benzene
Iso-dodecane
Carbon tetrachloride
n-Heptane
Cyclohexane
Toluene
Toluene
Toluene
Iso-dodecane
Iso-dodecane
Cumene
Cumene
Benzene
Iso-dodecane
Iso-dodecane
n-Heptane
Benzene
Cumene
Iso-dodecane
Iso-dodecane
Iso-dodecane
0.1-150 70 13.1 37
0.1-1000 62.5 3.8b to 9.4 37
0.1-630 55 4.3 104
0.1-650 80 4.8 38
0.1-550 80 4.7 1 7
0.1-300 60 9.7 39
0.1-300 70 8.6 39
0.1-200 135- 212 22.3 8 1
0.1-300 <lOO 3 78
0.1-300 95-200 4.3 75
0.1-300 <loo 4 78
0.1-300 80-200 5.9 75
0.1-300 <loo 1 5 78
0.1-730 120 12.6 40
0.1-300 143- 230 13.4 75
0.1-730 120 13.3 40
lo-230 140- 200 10.1 77
0.1-730 120 6.7 40
0.1-730 120 5.4 40
0.1-150 60 7 37
loo-270 50 5 3 7
0.1-300 100- 200 7.0 75
0.1-300 120- 200 9.4 75
0.1-410 80 3.9 1 0 1
0.1-410 80 1 0 102
0.1-300 <lOO 7 78
0.1-300 100- 200 6.1 75
0.1-300 120- 200 6.1 8 8
0.1-200 65-105 1.6 78
0.1-300 <loo 6 78
0.1-410 80 1 103
0.1-300 120- 200 13 76
0.1-300 120- 200 1 4 76
0.1-300 100- 200 9 76
Azobisisobutyronitrile.
*Photometric analysis.
By 12 scavenger technique.
D. ACTIVATION VOLUMES OF CHAIN PROPAGATION
Monomer Sol vent Initiator
Absolute pressure
(MW
Temperature
(C)
Activation volume Au*
(cm3/mol) Refs.
Butyl acrylate
Butyl methacrylate
Ethylene
Ethylene
Methyl methacrylate
Octyl methacrylate
St y r e n e
Vinyl acetate
-
ACN 0.1-100 30
-
ACN 0.1-100 30
r-Butanol Radiation - 4 0 24
-
Diphenyl disulfide 50-175 130- 200
-
ACN 0.1-100 30
-
ACN 0.1-100 30
-
ACN 0.1-100 30
-
ACN 0.1-100 30
- 22.5 9 1
- 23.2 90
- 39 152
- 25.5 8 5
- 1 9 87
- 24.7 99
- 17.9 89
- 23.3 86
ACN: l,l-azocyclohexane-1,l -dicarbonitrile.
References page II - 440
II / 436 ACTIVATION VOLUMES OF POLYMERIZATDN REACTIONS
E. ACTIVATION VOLUMES OF CHAIN TERMINATION
Monomer Solvent
Butyl acrylate -
Butyl methacrylate -
Ethylene -
Methyl methacrylate -
Octyl methacrylate -
Styrene -
Vinyl acetate -
Absolute pressure Temperature Activation volume Au *
Initiator
(MW (Cl
(cm3/mol) Refs.
ACN 0.1-100 30 20.8 9 1
ACN 0.1-100 30 17.8 90
Diphenyl disulfide SO-175 130- 200 7 8 5
ACN 0.1-100 30 25.0 8 7
ACN 0.1-100 30 20.8 99
ACN 0.1-100 30 13.1 89
ACN 0.1-100 30 16.3 86
aACN: l,l-azocyclohexane-1,l -dicarbonitrile.
F. ACTIVATION VOLUMES OF CHAIN TRANSFER REACTIONS
Monomer Transfer agent
Absolute pressure Temperature
WW (C)
Activation volume (cm3/mol)
4,
Au; - Au;, Refs.
Acrylonitrile
3,3-Dichloropropene-1
Ethylene
Butyraldehyde
3,3-Dichloropropene-1
Acetone
Butane
Butanone
Cyclohexane
Cyclopentane
Ethanol
Ethylbenzene
Ethylene
Isopropanol
Polyethylene - intermolecular
intramolecular
Propane
Toluene
Xyl ene
Methyl methacrylate
Styrene
Vinyl acetate
Vinyl chloride
Butyraldehyde
Butyraldehyde
Carbon tetrachloride
Isobutyraldehyde
Triethylamine
Butyraldehyde
Butyraldehyde
0.1-400 50
0.1 50
136- 238 130
138- 240 130- 200
136- 238 130
136- 238 130
136- 238 130
138- 240 130- 200
198- 240 130- 200
136- 238 130
138- 240 130- 200
136- 238 130
138-240 130-200
136- 238 130
- 250 130- 255
138- 240 130- 200
136- 238 130
110- 200 100- 300
110- 200 100- 300
180- 300 175- 275
138-240 130- 200
136- 238 130
138- 240 130- 200
136- 238 130
138- 240 130- 200
138- 238 130
0.1-400 50
0.1-400 50
600 60
0.1-400 50
181- 440 60
0.1-400 50
0.1-400 50
- 24.9
- 24.5
- 21.3
- 22.9
- 19.3
-
-20.1
- 19.9
-
- 23
-21
- 22.9
- 30.7
4.7
- 33.8
-11
-2 t o -3
- 6.6
- 8
- 1.1
- 1.1
- 3.2
- 2.9
- 1.5
- 1.5
- 4.7
- 4.7
- 3.1
-3. 1
- 6.7
- 6.7
-
-6. 1
-6. 1
3
5
20- 24
-3. 1
- 3.1
4.7
4.7
7.8
7.8
- 6.6
- 15
- 6.6
- 3.2
- 3.8
62
62
4 1
I
83 j
41 I
4 1
i
4 1
I
8 3
8 3
4 1
8 3
4 1
I
83
4 1
96
8 3
4 1
82,85
82,85
83,84
83
4 1
8 3
4 1
8 3
8 3
67
63,65,68
33
68
42
67
67
Influence of Pressure on Copolymerization: Copolymerization Parameters
G . INFLUENCE OF PRESSURE ON COPOLYMERIZATION
TABLE 1. COPOLYMERIZATION PARAMETERS
II / 437
Monomer 1 Monomer 2 Solvent
Copolymerization parameters
Absolute pressure Temperature
WV (C) rt r2
Refs.
Acrylonitrile Ethyl cinnamate
Butyl acrylate
Cyclopentene
Ethyl fumarate
Methyl acrylate
a-Methylstyrene
Styrene
Vinyl acetate
Styrene
Maleic anhydride
Ethylene Vinyl acetate
Vinyl butyrate
Vinyl chloride
Vinyl formate
Vinyl isobutyrate
Vinyl pivalate
Vinyl propionate
Maleic
anhydride
Acenaphthylene
2-Ethyl- 1 -hexene
1 -Hexene
2-Methyl-2-butene
wMethylstyrene
Norbomene
Thiophene
Methyl acrylate cl-Methylstyrene
Croton aldehyde
Methyl vinyl ketone
Vinyl-2-pyridine
Benzene
-
Benzene
Isopropyl alcohol
Nsl-Dimethylformamide
tert-Butyl alcohol
fert-Butyl alcohol
rert-Butyl alcohol
tert-Butyl alcohol
terr-Butyl alcohol
rerr-Butyl alcohol
Acetic anhydride
0.1
80
280
0.1
300
0.1
300
0.1
300
0.1
300
0.1
300
0.1
300
0.1
200
400
3.5
60
5 1
102-204
3.5
3.5
3.5
3.5
60
120
3.5
34
102
204
3.5
3.5
3.5
3.5
118
0.1
288
0.1
300
0.1
200
0.1
300
0.1
300
0.1
300
0.1
320
0.1
300
0.1
600
0.1
300
0.1
300
62
62
120
60 2.4
2.8
3.9
5.5
9.20
0.65
0.76
0.05
0.04
0.02
0.05
3.10
3.50
0.20
0.17
60 0.49
0.21
0.10
0.74
0.94
0.6
0.82
62 0.80
62 0.77
62 0.92
62 0.74
62 0.79
62 0.80
62 0.696
14 0.16
0.16
0.21
0.586
0.609
0.645
0.674
0.68
0.07
0.10
70 0.15
0.11
70 0.15
0.10
0.10
0.005
70 0.005
0.03
70 0.03
0.02
0.20
0.15
0.10
0.08
20
20
0.50
0.60
0.20
0.30
62
62
62
62
62
60
70
70
50
50
50
50
0.17 6 9
0.21 6 9
0.36 6 9
0.15 105
0.10 1 0 5
0.46 1 0 5
0.43 1 0 5
0.15 1 0 5
0.10 1 0 5
0.65 105
0.53 1 0 5
0.10 1 0 5
0.05 1 0 5
0.62 1 0 5
0.50 1 0 5
0.049 100
0.041 100
0.030 100
1.51 97
1.20 97
0.95 4 1
0.99 41
1.39 116
1.485 116
1.13 116
1.50 116
1.40 1 1 7
1.37 118
1.505 120
2.7 4 1
2.1 4 1
2.0 4 1
1.29 120
1.49 120
1.49 120
1.50 120
1.26 1 1 5
0.43 43
0.32 43
0.015 106
0.011 106
0.015 106
0.010 106
0.035 106
0.025 106
0.04 106
0.03 106
0.05 106
0.03 106
0 106
0 106
0.27 105
0.23 1 0 5
0.02 1 0 5
0.02 1 0 5
1.80 1 0 5
1.20 1 0 5
1.10 1 0 5
1.05 1 0 5
References page II - 440
II / 438 ACTIVATION VOLUMES OF POLYMERIZATION REACTIONS
TABLE 1. contd
Monomer 1 Monomer 2 Solvent
Copolymerization parameters
Absolute pressure Temperature
WW (Cl r1 r2
Refs.
Methyl
methacrylate
Acenaphthylene Toluene
Styrene Acrylic acid -
Acrylonitrile Toluene
Methyl acrylate Toluene
Acrylonitrile Toluene
Diethyl fumarate Benzene
Diethyl maleate Benzene
Et hyl met hacryl at e Benzene
Met hyl met hacryl at e -
Methyl acrylate Toluene
Methylacrylate Toluene
Vinyl acetate Benzene
Vinylidene chloride -
Vinylidene chloride -
Vinyl acetate Isopropyl acetate
Vinylidene chloride -
Vinylidene
chloride
Indene
-
0.1 60 0.57 3.1 43
190
390
0.1
1 0
100
3.4
590
118
0.1
100
250
0.1
1 0
100
0.1
1 0
100
0.1
1 0
100
0.1
1 0
100
0.1
100
300
3.4
59
118
3.4
59
118
0.1
1 0
100
0.1
150
200
0.1
200
300
0.1
300
0.1
150
250
0.1
200
400
10
62
62
62
60
70
60
60
50
60
62
62
62
62
62
62
60
60
60
60
60
0.60 1.9 43
0.58 1.6 43
1.34 0.12 44
1.46 0.37 44
2.01 0.45 44
2.42 0.31 119
2.36 0.31 119
2.40 0.30 119
0.25 0.07 69
0.27 0.08 69
0.31 0.095 69
0.37 0.07 44
0.43 0.13 44
0.55 0.14 44
0.26 0.06 70
0.29 0.09 70
0.32 0.15 70
6.53 0.01 70
7.08 0.02 70
9.50 0.02 70
0.56 0.50 45
0.62 0.55 45
0.12 0.67 45
0.704 0.159 69
0.710 0.163 69
0.718 0.171 69
1.20 0.09 119
1.12 0.11 119
1.10 0.13 119
0.86 0.38 119
0.82 0.39 119
0.77 0.41 119
44 0 . 0 1 46
46 0.01 46
47 0.01 46
2.6 0.04 47
2.5 0.04 47
2.5 0.01 47
0.54-0.55 0.80-1.135 69,105
0.560 1.145 69
0.605 -0.70 0.80-1.165 69,105
0.90 0.30 1 0 5
0.60 0.35 1 0 5
0.025 3.2 47
0.025 3.1 47
0.03 3.1 47
0.475 0.205 69
0.500 0.215 69
0.525 0.225 69
TABLE 2. REACTIVITY RATIOS OF TERPOLYMERIZATIONa
Pressure (MPa) J.12 r2t rt3 r31 r23 r32
Refs.
0.1 5.5 0.15
300 3.2 0.10
aMonomers: (i) acrylonitrile; (ii) diethyl fumarate; (iii) styrene.
0.02 0.65 0.06 0.15 107,108
0.05 0.53 0.15 0.25
TABLE 3. ACTIVATION VOLUMES
Influence of Pressure on Copolymerization: Copolymerization Parameters II / 439
Monomer 1 Monomer 2 Sol vent
Absol ut e pressure Temperat ure
@IPa) ((3
Activation volume (cm3/mol)
AV Au;, -Au;, Au& - Av;, Ref s.
Acr yl oni t r i l e
Butyl acrylate
Cyc l ope nt e ne
Et hyl e ne
Ethylfumarate
Methyl acrylate
wMethylstyrene
St yr e ne
Vinyl acetate
St yr e ne
Maleic anhydride
Vinyl acetate
Et hyl e ne Vinyl acetate
Indene Acr yl oni t r i l e
Isoprene
Maleic anhydride
Me t hyl vi nyl ke t one
0.1-300
0.1-300
0.1-300
0.1-300
0.1-300
0.1-300
Benzene 0.1
- 0.1-600
2.5-60
-
Heptane
Di oxa ne
Heptane
110-190
Methyl methacrylate Heptane
Vi nyl i di e ne c hl or i de
Acr yl oni t r i l e Heptane
2-Ethyl-1-hexene
2,3-Dimethyl-2.butene
l,l-Diphenyl ethylene
1- Hexane
Cyclohexene
2-Methyl-2-butene
wMethylstyrene
Norbomene
Thi ophe ne
rrans-Stilbene
0.1-300
0.1-300
0.1-300
0.1-200
0.1-300
0.1-300
0.1-300
0.1-300
0.1-320
0.1-300
5 0
5 0
5 0
5 0
5 0
5 0
6 0 - 26.4 to - 31.4
6 0
6 2
2 4 0 - 3 6
5 0 - 17.5
5 0 - 18.0
5 0 - 24.0
5 0 -20.1
- 17.8 to 19.1 -
5 0 - 27.0
7 0 - 36
7 0 - 25
7 0 -50 to -60
7 0 - 18
7 0 - 2 3
7 0 - 2 5
7 0 - 3 5
7 0 - 2 8
7 0 - 2 6
6 0 - 25
COPOLYMERIZATION OF MALEIC ANHYDRIDE WITH MONO- AND
POLY-SUBSTITUTED OLEFINS
- 5. 0 3.7
- 1.5 - 0
- 0 3.1
- 8.5 1.9
- 1.1 6.3
0 1.0
9.3 2.7
- 11.3 11.9
0 - 4.3
0 - 3.6
2.5 - 1.0
0 0
Subst i t ut i on Comonomer Activation volume (cm3/mol)
mono-
di-(1,2)
gem-
tri-
tetra-
= CH(Pr) - 16.6
= CH(Bu) - 18.0
= CH(i-Pr) - 17.0
= CH( i - Bu) - 17.5
= CH(r-Bu) - 3 1
= CH(Ph) - 18.5
CH(Me) = CH(Et) - 19.0
CH(Me) = CH(i-Pr) - 20.0
CH(Me) = CH(t-Bu) - 3 5
CH(i-Pr) = CH(i-Pr) - 18.5
CH(Ph) = CH(Ph) - 25.0
= C(Me)(Pr) -31
= C(Me)(i-Pr) - 3 3
= ( Me) ( t - Bu) - 6 0
= C(Me)(CH gt-Bu) - 4 6
= C(Me)(Ph) - 3 5
= C(Et)(Et) - 3 4
=C(Et)(Bu) - 3 6
= (Ph)(Ph) - 50
CH(Me) = C(Me)(Me) - 25
CH(Et) = C(Me)(Me) -31
C(Me)(Me) = C(Me)(Me) - 25
107
105
105
105
105
105
100
100
97
72
4 8
4 8
4 9
4 8
71
5 0
106
106
106
106
121
106
106
106
106
106
160
Met hyl acrylate a-Methylstyrene 0.1-300 5 0 1.0 0.7 105
Croton aldehyde 0.1-300 5 0 0 0 105
Maleic anhydride - 1 8 t o - 2 5 71
Me t hyl vi nyl ke t one 0.1-300 5 0 - 1.9 1.9 105
Vinyl-2- pyridine 0.1-300 5 0 - 3.7 - 0 105
References page II - 440
II / 440 ACTIVATION VOLUMES OF POLYMERIZATION REACTIONS
TABLE 3. contd
Act i vat i on vol ume ( cm 3/mol)
Absol ut e pressure Temperat ure
Monomer 1 Monomer 2 Sol vent
WW ((3
AV* Au;, - Av;, Az~& - A;, Refs.
Met hyl Methyl acrylate 3.4-118 6 2 0.9 1.8 119
methylacrylate
styrene Diethyl fumarate -18 to -2; 71,105
Methyl acrylate - 13.8 to - 14.5 71
Methyl methacrylate - 18 to -25 71
Vi nyl - 2- pyr i di ne - 23.5 to - 26 - 2.2 0 71
TABLE 4. Q, e VALUES
Qa
e
Monomer At 0.1 MPa At 300 MPa At 0.1 MPa At 300 MPa Refs.
Acrylic acid 0.53 (0.83)b 0.45 + 0.91 (0.88p + 0.64 1 0 8
Acrylonitrile 0.53 (0.50) 0.62 + 0.90 (1.20) + 0.95 1 0 5
n-Butyl acrylate 0.40 (0.30) 0.40 + 0.35 (0.74) + 0.35 105
n-Butyl methactylate 0.62 (0.66) 0.70 - 0.08 (0.34) - 0.54 92
Crotonaldehyde 0.015 (0.02) 0.015 + 0.80 (0.84) + 0.80 1 0 5
Diethyl fumarate 0.20 (0.03) 0.25 + 1.35 (2.17) + 1.25 105,109,25
Diethyl maleate 0.03 (0.04) 0.03 + 0.62 (1.40) + 0.40 109
Ethylene 0.015 (0.013) 0.05 - 0.15 ( - 0.15) - 0.02 110
Ethyl methacrylate 0.62 (0.57) 0.66 0.00 (0.35) - 0.35 92
Indene 0.30 (0.36) 0.28 - 1.10 (- 1.03) - 1.05 111,108
Isobutylene 0.025 (0.029) 0.022 - 1.72 (- 1.06) - 1.25 112
Isopropenyl acetate 0.08 (0.02) 0.12 - 1.30 (- 0.34) - 1.60 1 0 5
Methyl acrylate 0.44 (0.44) 0.44 + 0.60 (0.60) + 0.60 1 0 5
Methyl methacrylate 0.63 (0.74) 0.63 - 0.20 (0.38) - 0.05 108,25
wMethylstyrene 1.40 (1.00) 1 . 6 5 - 1.30 (- 1.27) - 1.40 105
Methyl vinyl ketone 1.07 (0.65) 1 . 0 3 +0.95 (1.11) + 1.15 1 0 5
Propylene 0.010 (0.008) 0.015 - 1.50 ( - 2.20) - 1.05 112
Styrene 1.20 ( 1 .OO) 1 . 3 5 - 1.10 (-0.80) - 1.22 105,108,92
Vinyl acetate 0.06 (0.03) 0.05 - 0.20 ( - 0.22) - 0.35 105,108,llO
Vinyl chloride 0.0450 (0.056) 0.045 + 0.16 (0.20) +0.19 112,41
Vinyl pivalate 0.023 (-) 0.046 - 0.19 (-1 - 0.02 113
2-Vinylpyridine 1.05 (1.03) 0.95 - 0.60 ( - 0.50) - 0.50 1 0 5
Vinylidene chloride 0.27 (0.26) 0.24 + 0.42 (0.40) + 0.43 108
Reference monomer is methyl acrylate (105).
bValues in parentheses refer to the values of styrene.
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158. V. M. Zhulin, A. R. Volchek, M. G. Gonikberg, A. S.
Shashkov, S. V. Zotova, ibid., 14A, 1484 (1972).
159. V. M. Zhulin, Z. G. Makarova, N. V. Klimentova, A. P.
Suprun, A. N. Akopyan, G. P. Shakhovskoi, ibid., 24A, 2621
(1982).
160. G. Jenner, M. Kellou, Tetrahedron, 37, 1153-60 (1981).
Activation Enthalpies and Entropies of
Stereocontrol in Free Radical Polymerizations
Hans-G. Elias
Michigan Molecular Institute, 1910 West St. Andrews Rd., Midland, MI 48640, USA
A. Introduction
B. Tables
I I -445
Table 1. Ratios of Some i-ads for Different
Me c h a n i s ms II-446
Table 2. Ratios of Rate Constants for Markov
First Order Mechanisms I I-446
Table 3. AHf,i - AH& and AS$i - AS& of
Free Radical Polymerizations in
Different Solvents II-447
Table 4. Activation Enthalpy Differences
(AH: - AH:) Calculated from
Various Literature Data II-448
Table 5. Activation Entropy Differences
(ASi - AS!) Calculated from
Various Literature Data II-449
Table 6. Calculated Compensation
Temperatures To and Compensation
Enthalpies AAHA for Various
Monomers and Modes of Addition,
Assuming Markov First Order Trials I I-449
C. References II-450
A. INTRODUCTION
In free radical polymerization, the tacticity of the resulting
polymer depends on the propagation step, i.e., on stereo-
control by the propagating end. The following simple cases
exist:
(a) The last monomeric unit does not control the
stereospecificity of the propagation step. Isotactic (i) and
syndiotactic (s) additions thus exhibit the same conditional
probabilities @i = ps). The mole fractions x of the resulting
isotactic and syndiotactic diads are equal (Xi = x,). If all
steps occur at random, the four conditional probabilities for
the formation of triads are equal (pi/i = pi/s = ps,/i = p,/,),
and so are the conditional probabilities for the formation of
tetrads, pentads, etc. The resulting polymer is a true atactic
polymer. It follows that
pj = Xi = 1/2 ps =x, = 1/2
(Al)
Xii = Xis = Xsi = X,$ =
w (A9
(b) The last monomeric unit of the chain, but not the
last diad, controls the propagation step. The probabilities
for the formation of isotactic and syndiotactic diads are
thus different (pi # p,). The process is Bernoullian
(zeroth order Markov statistics) with respect to the
formation of diads. Consequently, the probability of
forming an isotactic diad at an existing isotactic diad
equals the probability of forming an isotactic diad at an
existing syndiotactic diad (pi/i = ps/i), and, by analogy,
psls =pils. It follows for the diads (6,8)
pi = Xi # 1/2
Ps = xs #I/2 (9
and for the triads
xii = p2 = x;
2 2
4s = Ps = x, (-44)
Xht = p$s + p$i = 2 XIX, = 2Xi( 1 - Xi)
W)
where xii is the mole fraction of isotactic triads and x,, is the
mole fraction of syndiotactic triads. Xht is the mole fraction
of heterotactic triads, regardless of whether formed by the
formation of an isotactic unit at a syndiotactic one
(conditional probability ps/i) or vice versa (conditional
probability pi/s).
(c) The last two monomeric units of the chain, i.e., the
last monomeric diad, regulate the stereocontrol of the
propagation step. The four conditional probabilities do
not equal each other (pi/i #pi/s # ps/i # p,/,). The mole
fractions of isotactic (Xii), syndiotactic (xss) and heterotactic
triads (xht) are thus given by (8,ll)
Xi = Xipi/i
xss = xs Psls L46)
Xht = xi pi/s + x$/i W)
This process corresponds to a Markov trial of first
order.
(d) Second order Markov statistics are present if the last
two diads (i.e., the last triad or the last three monomeric
II /445
II / 446 ACTIVATION ENTHALPIES AND ENTROPIES OF STEREOCONTROL IN FREE RADICAL POLYMERIZATIONS
units) control the propagation step. In this case
Xiii = xiiPi/i Xsss = &SPs/s ow
&is = &P i / s Xssi = xssPs/i W)
Xiss = XisPs/s &ii = XsiPi/i (AlO)
xisi = xisPs/i his = XsiPi/s (All)
In order to distinguish between Markov second order and
Markov first order mechanisms, at least tetrads must be
known.
The probability of the addition of a b diad (b = i, s) to
an existing end a (a = i, s) is given by the corresponding
rates R:
P
&a/b
lb = R,/, i- R,/b
(Al4
with a = i, s or b = i, s, in the Markov first order case, or
a = ii, is, si, ss b = ii, is, si, ss, in the Markov second order
case.
Using these definitions and assuming steady states and
the equality of instantaneous and final diad and triad
fractions, one can express ratios of all diads, triads, and
tetrads in terms of rate constants (Table 1) or ratios of rate
constants in terms of diad, triad, etc. fractions (Table 2).
The rate constants themselves can be calculated if the rate
constants of propagation are known for the corresponding
experimental conditions (1).
From the temperature dependence of the expressions
given in Table 2, differences in activation enthalpies
(AHAt - AH;) and differences in activation entropies
(AS: - ASi) can be calculated:
The quantities (AH: - AH:) and (As), - ASS) may
reflect activation parameters (2,3), conformation parameters
(4,5), or combinations thereof.
Table 3 gives the difference AAHS = AH: - AH! and
AASS = As), - AS; calculated from the temperature
dependence of diad ratios Xi/x,. In the case of Bernoulli
trials, they represent
$ $
AHi - AHs a nd AS, - AS!,
$
respectively. For first order Markov trials, they stand for
AH$ - AH;, and AS$ - ASils, respectively. In general,
$
both AAHS and AASt depend on the solvent (9,10), and
consequently on the monomer/solvent ratio (11,12), but
they are nearly independent of monomer conversion.
Table 4 gives the differences in activation enthalpies for
modes of addition other than s/i vs. i/s, and Table 5 gives
the corresponding differences in activation entropies. Only
a few of these activation parameters could be calculated
from literature data as very few triad fractions have been
reported.
For any two modes of addition, the compensation effect
between AAHS and AASS (10,12,43) for the polymeriza-
tion of a given monomer, in different solvents and/or at
different monomer/solvent ratios, can be described by
AHi -AH; = AAH; - (ASi - A&To
WV
The compensation temperature To has been found to be
independent, of the mode of addition (e.g., A = i/i vs.
B = i/s) within the limits of error (12,43). However, the
$
compensation enthalpy AAH,, depends on the mode of
addition.
B. TABLES
TABLE 1. RATIOS OF SOME i-ADS FOR DIFFERENT
MECHANISMS
Mechani sm
i-ad Ratio Bernoulli Markov 1st order Markov 2nd order
TABLE 2. RATIOS OF RATE CONSTANT FOR MARKOV FIRST
ORDER MECHANISMS
Ratios of rate constants Expressions giving ratios of rate constants
k/i &ii
ki/s
-
&
k/i
qi
&Xii 1 + (2-h/x,s)
-=
Xi&s 1 + (-%/(2Xii))
XsXis 1 + (Xis/(2Xss))
-=
k& 1 + (2.%/(&))
a From Ref. 43.
A/-/$ - A/-$ and AS& - A.$ of Free Radical Polymerizations in Different Solvents I I / 447
TABLE 3. AH& - AH;, AND ASi,i - AS$ OF FREE RADICAL POLYMERIZATIONS IN DIFFERENT SOLVENTS*
Monomer ( + additive) Vol.% Sol vent
AS!,, - As;s
(JImoUR) Remarks Refs.
Acrylonitrile
Acrylic acid, isopropyl ester
-
, methyl ester
a-Chloroacrylic acid, methyl ester
Methacrylonitrile
- , ( + 1 mol SnClJ2 mol monomer)
- , ( + 1 mol SnCWl mol monomer)
- , ( + 1 mol SnClJl mol monomer)
- , ( + 1 mol SnClJ2 mol monomer)
Methacrylic acid
-
, anhydride
- , benzyl ester
-
, s-butyl ester
-
, t-butyl ester
- , p-carboxyphenyl ester
-
, cyclohexyl ester
- , glycidyl ester
-
, cl-methylbenzyl ester
-
, methyl ester
- , - , (+ 8.7 mol ZnClz/l mol MMA)
- , - , ( + 1 mol ZnCl# mol MMA)
30
100
?
?
?
100
100
3:lb
2:lb
1:lb
1:lb
1 0
20
20
20
?
50
50
50
?
?
100
45
50
57
100
50
9.ld
9.ld
9.ld
9.ld
9.ld
9.ld
9.ld
9.ld
9.ld
9.ld
9.ld
9.ld
9.ld
9.ld
20
25
25
25
25
25
25
25
28.5
50
100
100
100
100
100
l.le
3.2e
- , - , ( + 0.04 mol ZnClz/l mol MMA) 100
- , - , ( + 1 mol ZnCla/2 mol MMA) 100
- -
, , ( + 1 mol ZnClzll mol MMA) 100
- , - , (+ 1 mol SnClJ2 mol MMA) 100
Toluene
Bulk
?
?
Toluene
Bulk
Bulk
Toluene
Toluene
Benzene
Benzene
I-Propanol
1-Propanol
2Propanol
Methanol
Benzene
Toluene
Toluene
Toluene
Dimethylfommmide
p-Cetyloxybenzoic acid
Bulk
Acetone
Dimethylformamide
Toluene
Bulk
Toluene
Acetone
Acetonitrile
Benzene
Butanone
y-Butyrolactone
Chl oroform
Dimethylformamide
Dimethyl sulfoxide
1 ,CDioxane
Methylene chloride
Pyridine
Tetrachloroethane
Tetrahydrofuran
Toluene
Paraffin
Acetone
Carbon tetrachloride
Chl oroform
Dichloroethylene
Ethanol
n-Heptane
n-Hexane
Toluene
Toluene
Bulk
Bulk
Bulk
Bulk
Bulk
Wa t e r
Ethyl acetate
Bulk
Bulk
Bulk
Bul k
3110 f 59
0
0
0
3800 f 190
250 f 50
-4lOOf71
-630f54
170563
251
2350 k 38
3980 f 92
3850 f 80
7800& 180
3140&42
13300f210
2300 f 130
3430 f 63
2090 2180
4310
0
1210f80
700 & 100
5780 f 42
8600 f 130
98OOf 110
3640 f 59
6280 zt 75
5360 f 75
3480f71
3900 zt 160
3140&88
51OOf71
3500 f 150
3350 f 96
5317 k 8
3100*67
4860 f 75
5200 f 100
39OOf 110
2810&96
2720 f 34
7030 f 75
5860f21
9380f71
6700 2~ 46
4980 k 50
5200f210
6700 z!z 29
5650 f 80
2900 & 420
62OOk 110
4480
3800 f 230
2300 f 54
3560 zt 84
2850f71
41OOf71
2700 f 190
- 130f80
-4Of 130
800 f 100
2.7 f0.19
0
- 5.9
- 5.9
2.5 f 0.59
3.0 f 0.14
- 10.8 f 0.21
-0.7*0.18
-0.1 kO.18
0.75 f 0.88
9.76 f 0.096
- 2.2 k 0.32
- 1.8 f 0.28
10.5 f 0.63
-4.1 f0.13
44.4 k 0.63
- 1.7f3.8
2.0 f 0.22
- 2.6 f 0.29
2.09
- 6.87
- 5.0 f 0.20
9.5 f 0.36
5.01to.15
14.2 f 0.042
17.5 f 0.28
2.2f0.22
10.2 3~ 0.23
7.3 zt 0.26
2.3 f 0.23
4.2 f 0.46
1.4 f 0.27
7.5 k 0.23
3.4 f 0.46
2.5 f 0.28
7.4f0.30
2.0 f 0.22
7.7 z!z 0.22
7.2 rt 0.29
4.4 f 0.33
0.8 f 0.26
1.6f0.13
9.0 k 0.23
5.36 f 0.067
16.0f0.21
8.4f0.13
3.6f0.14
3.69 f 0.059
8.50 f 0.092
3.9 f 0.26
1.3 f 1.3
9f3. 8
4.2
- 0.04 4~ 0.63
- 1.8 f0.16
3.3 f 0.24
2.2 f 0.20
5.2 & 0.2
1.13 f0.054
- 9.80 f 0.67
- 6.7 f 0.46
- 8.2 i0.33
-
-
-
-
-
-
-
-
-
(1
-
-
c
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
I R
I R
IR
I R
IR
IR
I R
(I
-
n
a
-
-
-
-
-
-
-
-
10,14
13
1 5
15
1 6
17
1 8
1 8
1 8
1 8
1 8
1 9
1 9
1 9
1 9
20
2 1
10,22
10,22
23
lo,23
lo,24
lo,25
lo,25
lo,25
lo,25
10,22
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1 2
27
9
9
9
9
9
9
9
lo,26
2 1
21
7
25
28
1 2
lo,29
10.29
lo,29
27
27
27
*In all cases, except those marked by IR (infrared) (see Remarks column), diad fractions were determined via NMR.
References page II-450
II/448 ACTIVATION ENTHALPIES AND ENTROPIES OF STEREOCONTROL IN FREE RADICAL POLYMERIZATIONS
TABLE 3. contd
Monomer ( + additive) Vol . % Solvent
AH& - AH;s
(J/mol)
ASi& - A$
(J/moUK) Remarks Ref s.
- , - , (+ 1 mol SnC14/1 mol MMA)
-
, L-menthyl ester
- , phenetyl ester
Trifluorochloroethylene
Viny1 bromide
Vinyl bromide
N-Vinyl carbazole
100
50
50
0.4
100
?
6.5
100
100
?
?
)
Bulk
Toluene
Toluene
Carbon tetrachloride
Bulk
n-Butyl acetate
o-Dichlorobenzene
Bulk
Bulk
Dimethylacetamide
Dimethylformamide
Dimethylsulfoxide
Hexamethylphosphoric
triamide
Hexane/nonane
Methylene dichloride
Toluene
Cyclohexane
Water/ethanol
Water
Bulk
Bulk
Bulk
Bulk
Acetone
Chl oroform
Dimethylformamide
Bulk
Bulk
Bulk
n-Butyl acetate
Bulk
n-Butyl acetate
4201t 13 - 14.07 z!c 0.054
960f46 0.3 z!zO.18
5600 zt 1700 4.6 zt 4.6
0 - 5.8
710 2 . 5
250 2 . 1
1930 * 54 5.3 Ito.
21401t 17 5.99 zt 0.080
1270 f 30 2.72
- 4600 * 300 -2Oztl
- 2850 f 100 - 13.5 f0.4
- 3300 * 500 - 15.4+ 1.4
- 3400 It 200 - 14.7 * 0.7
2 7
30
2 1
3 1
3 2
32
34
34
44
4 5
4 5
45
4 5
45
4 5
45
3 6
3 5
3 5
3 7
34
44
34
4 1
4 1
4 1
38
4 1
32
3 2
32
3 2
-
?
-
?
?
)
- 1500f200
- 2650 zt 100
- 3650 zt 1000
1300 & 84
5000 + 1000
1500 i 630
2900 zt 160
2260 f 50
1090 It 20
-2650&4
340 zt 25
290 zt 50
250 3~ 38
1050 zt 54
880 5 25
2830
1800
1590
880
- 10.5 f 0.7
- 11.7Ito.4
- 16.0 + 0.8
2.5 zt 0.42
18 zt4.2
2.9 z?z 2.0
6.78 h 0.067
5. 7f0. 14
1 . 9
- 6.28 i 0.04
0.21 zt 0.80
0.08 f0.16
0.5ztO.12
3.3zto.17
3.4 f 0.080
84
4.6
4.2
2 . 1
-
Viny1 chloride 1 0
33.3
33.3
100
100
100
100
50d
50d
50d
100
100
100
?
100
?
-
-
I R
- P> P-h
Viny1 formate
Viny1 trichloroacetate
a Data directly from literature, mechanistic assumptions unknown. * Sol vent / monomer mol ar r at i o.
Literature data, calculated under the assumption of Bernoulli statistics. d mol%.
mol/l. f g/ml.
TABLE 4. ACTIVATION ENTHALPY DIFFERENCE (AH: - AH;) CALCULATED FROM VARIOUS LITERATURE DATA
AH: - AH; (J/mol)
Monomer Solvent
A = i/i A = s/ i A = i/i A = i/ s A = s/ i
B = i/s B = i/i B = s/ s B = s/s B = s/s Ref s.
Glycidyl methacrylate Acetone
Bulk
Dimethylformamide
Toluene
Methanol
1-Propanol
2-Propanol
33000 i 2300
-
25000 5 1400
14000f 1500
27000&1800
- -
38000 f 2500 6500 i 750
20000f1800 3005 160
33000 i 2600 5556 i 8
-
420 f 8 0
- 1 2 4 0 zt 7 5
1 5 0 f 2 9
7100f 110 2 5
9300 i 140 2 5
580 f 33 2 5
10000 * 1000 2 5
3300f 110 19
4010f96 19
8000 + 220 19
Bulk 2800 5 120 - 130f 110 2430 * 59 -340f59 2310+54 2 9
Bulk - 13f 110 - lOOf -42588 -29529 - 140*75 2 7
Bulk -20% 160 -2lfllO -29f130 - 8 f 1 7 - 4 6 1 1 3 0 21
Ethyl acetate 2300 i 230 1800f 180 2600 f 170 370 zt 63 4480 f 54 2 9
70% ZnCl&20 700 f 240 2200f 180 14ooi 150 700 f 92 3550 f 38 2 9
Acetone 670 zt 25 - 1060f 88 -419f4 - 1060 f 92 -2150+92 41
Bulk 2850 i 84 - 1700 zt 100 650 f 25 - 1900f 130 -9OOf130 41
Chloroform 1700 i 180 - 3200 f 190 -520f46 - 300 i 190 - 3700 + 1250 41
Dimethylformamide Of 150 -250&190 - 180f200 - 180f200 - 440 f 230 41
Water 423 1 2 1 0 1 7 0 980 2500 3 5
Water/methanol 3600 f 63 - 1230 zk 54 4420 i 29 830 f 84 5600 f 140 35
Bulk 31801t46 540 f 46 2860f21 -330&29 2320 zt 25 3 9
Methacrylic acid (20 vol.%)
Methyl methacrylate/ZnCl,
9.34/0.369 (mol/mol)
2.00/1 .OO (mol/mol)
1 .OO/l .OO (mol/mol)
3.19/3.19 (mol/mol)
1.10/9.6 (mol/mol)
Vi ny1 formate
Vinyl chloride
Viny1 chloride, p, B-d2
Calculated Compensation Temperatures To and Compensation Enthalpies AAH: II / 449
TABLE 5. ACTIVATION ENTROPY DIFFERENCES (AS! - AS,, CALCULATED FROM VARIOUS LITERATURE DATA
ASf - ASf (J/mol/K)
Monomer Sol vent
A = i/i
B = i/s
A = s/i
B = i/i
A = i/i
B = s/s
A = i/s
B = s/s
A = s/i
B = s/s Refs.
Glycidyl methacrylate
Methacrylic acid (20 vol.%)
Methyl methacrylate/ZnQ
9.34/0.369 (mol/mol)
2.00/1.00 (mol/mol)
1 .OO/l .OO (mol/mol)
3.19/3.19 (mol/mol)
1.10/9.6 (mol/mol)
Vinyl formate
Vinyl chloride
Vinyl chloride, p, P-d?
Acetone
Bulk
Dimethylformamide
Toluene
Methanol
1-Propanol
2-Propanol
Bulk
Bulk
Bulk
Ethyl acetate
70% ZnClz in water
Acetone
Bulk
Chl oroform
Dimethylformamide
Water
Water/methanol
Bulk
85 f 8.8
-
-
-
54 f 4.2
321t7.1
75 * 7.5
4.0 f 0.34
- 7.0 f 0.46
-5. 2f0. 63
1.4ztO.88
3.1 zto.71
5.1 f 0.25
ll.ljIO.25
7.7 f 0.54
4.6 zt 0.46
- 1.3
11.7f0.25
8.3 * 0.17
-
125 f 8.4
72 zt 8.0
1OOf 11
- 2.9 f 0.29
- 2.8 f 0.29
- 1.7f0.38
3.9zto.71
5.2 f 0.54
-5. 6f0. 29
- 7.6 f 0.25
- 13.0 f 0.63
- 3.9 f 0.59
4.6
-4.140.21
2.1 f0.17
-
- 1.3f2.3
- 15.8 3~ 0.54
- 1.84 f 0.04
1.8 f0.17
- 8.0 h 0.38
- 6.0 f 0.46
1.8 III 0.63
- 1.5 f 0.42
- 0.75 f 0.04
2.55 f 0.080
- 1.1 f0.13
- 0.3 & 0.13
4.5
15.3 f 0.54
7.03 z!c 0.080
-
2.3 f 0.25
- 3.4 f 0.25
0.7zto.13
-2. 2f0. 17
- 1.5 f0.13
- 0.8 f 0.21
0.4hO.25
1.6f0.25
- 5.8 f 0.29
- 8.6 f 0.34
- 13.9f0.59
- 4.3 zt 0.39
3.8
3.6 f 0.34
- 1.30f0.08
10.3 zt 0.42 2 5
16.1 f0. 54 25
5.81tO.13 25
17f3.9 2 5
- 1.1 f0.13 1 9
- 0.9 * 0.38 1 9
11.1 zto.75 1 9
- 1.1 f0.13 29
- 10.8 XII 0.29 27
- 7.7 f 0.42 27
5.7 zto.13 29
3. 8zt 0. 13 29
- 9.3 f 0.29 41
-5.05~0.38 41
- 13.9 & 0.75 4 1
- 3.9 f 0.71 4 1
6.8 3 5
20.6 zt 0.54 35
4.98 f 0.08 39
TABLE 6. CALCULATED COMPENSATION TEMPERATURES To AND COMPENSATION ENTHALPIES AAH; FOR VARIOUS MONOMERS
AND MODES OF ADDITION, ASSUMING MARKOV FIRST ORDER TRIALS
Modes of addition
Monomer A B
To (K)
AAH: (Jlmol)
Acrylonitrile
Methacrylic acid, in alcohols
-
, i-butyl ester
-
, n-butyl ester
- , p-carboxyphenyl ester
- , glycidyl ester
- , hexyl ester
-
, methyl ester
-, -, (+ZnCld
- , i-propyl ester
-
, n-propyl ester
Vinyl acetate
Vinyl chloride
s/i
s/i
i/i
sli
i/i
s/i
, i/s
s/i
sli
s/i
s/i
s/i
s/i
sli
i/i
s/i
i/i
s/i
i/S
s/i
i/i
s/i
i/i
s/i
ils
s/i
s/i
s/i
s/i
i/i
Sli
i/i
s/i
i/s
i/S
iii
i/i
sls
i/S
s/s
s l s
i/S
i/S
i/s
i/S
s/s
i/S
i/s
i/i
s/s
i/s
s l s
s/s
i/S
i/i
s l s
i/S
s/s
s l s
ils
i/S
i/s
ils
i/i
s/s
i/S
1400
455
294 f 26
323&5
403 f 140
323 f 10
302 f 74
333 4123
294&3
236f4
481
345 4 15
373+11
303fll
315*49
310f20
323 zt 124
362f 15
338zt51
334 f 54
314f39
321 f9
331*24
336f21
304flO
328 f 42
230 zt 54
248 f 41
1100
283 f 25
2821t6
235 f 28
305 f 124
0
2780
6300 f 1260
-2300f510
6600 f 200
4480f21
- 180f63
4250 zt 25
3304 f 4
3576 f 8
3308
3800 zt 200
3500 f 120
3260 f 29
120f 160
2600 * 130
1440 f 84
1470 f 50
1400 f 92
4OlOIt75
1650 & 67
540 f 33
1930 k 42
2250 zt 50
243f4
2530 zt 80
3420 f 67
3300 ct 176
- 2050
820 f 130
-75-117
900 f 160
- 220 f 420
References page II-450
II / 450 ACTIVATION ENTHALPIES AND ENTROPIES OF STEREOCONTROL IN FREE RADICAL POLYMERIZATIONS
TABLE 6. contd
Modes of addition
Monomer
Vinyl formate
.
N-Vinyl carbazole
Vinyl chloroacetate
Vinyl trifluoroacetate
A B
To (K)
AAHi (J/mol)
i/s s/s 248f9 - 13*33
s/i Sk 219&10 1130*59
i/i ils 362i 23 - 1400&130
sli i/i 315 * 16 8501t80
i/i sls 323f 21 - 2OO~k25
s/i i/S 33oi 95 - 290f 42
i/s s/s 32Ozt18 97Ozt96
di sls 316f 5 14gh21
sli i/s - 243 288
sl i i l s 300 419
s/i i/S 340 167
Based on data in Tables 3-5; see also Refs. 40,43.
REFERENCES
1. H. -G. Elias, Makromol. Chem. 137, 277 (1970).
2. J. W. L. Fordham, J. Polym. Sci., 39, 321 (1959).
3. C. E. H. Bawn, W. H. Janes, A. M. North, J. Polym. Sci. C 4,
427 (1963).
4. H. Fischer, Kolloid-Z., 206, 131 (1965).
5. P. L. Luisi, R. M. Mazo, J. Polym. Sci. A-2, 7, 775 (1969).
6. F. A. Bovey, G. V. D. Tiers, J. Polym. Sci., 44, 173 (1960).
7. T. G. Fox, H. W. Schnecko, Polymer 3, 575 (1962).
8. F. A. Bovey, Polymer Conformation and Configuration,
Academic Press, New York, 1969.
9. H. Watanabe, Y. Sono, Kogyo Kagaku Zasshi, 65, 273 (1962).
10. H. -G. Elias, P. Goeldi, V. S. Kamat, Makromol. Chem., 117,
269 (1968).
11. E. L. Miller, SPE Trans., 3, 1 (1963).
12. P. Goeldi, H. -G. Elias, Makromol. Chem., 153, 81 (1972).
13. G. Svegliado, G. Talamini, G. Vidotto, J. Polym. Sci. A-l, 5,
2875 (1967).
14. H. Murano, R. Yamadera, J. Polym. Sci. B, 5, 333 (1967).
15. C. Schuerch, W. Fowells, F. P. Hood, F. A. Bovey, cited in
Ref. 36.
16. K. Matsuzaki, T. Uryu, K. Ito, Makromol. Chem., 126, 292
(1969).
17. K. Matsuzaki, T. Uryu, J. Polym. Sci. B, 4, 2.55 (1966).
18. H. Hirai, T. Ikegami, S. Makishima, J. Polym. Sci. A-l, 7,2059
(1969).
19. J. B. Lando, J. Semen, B. Farmer, Polym. Preprints, 10, 586
(1969).
20. W. L. Miller, W. S. Brey, G. B. Butler, J. Polym. Sci., 54, 329
(1961).
21. K. Yokota, Y. Ishi, Kogyo Kagaku Zasshi, 69, 1966 (1966).
22. K. Matsuzaki, A. Ishida, N. Tateno, T. Asakura, A. Hasegawa,
T. Tameda, Kogyo Kagaku Zasshi, 68, 852 (1965).
23. Y. B. Amerik, I. I. Konstantinov, B. A. Krentsel, IUPAC,
International Symposium, Macromolecular Chemistry, Tokyo,
1966, Preprint 1.1.09.
24. K. Matsuzaki, A. Ishida, N. Tateno, IUPAC, International
Symposium, Macromolecular Chemistry, Prague, 1965, Pre-
print 265.
25. Y. Iwakura, E Toda, T. Ito, K. Aoshima, Makromol. Chem.,
104, 26 (1967).
26. Y. Kato, A. Nishioka, Bull. Chem. Sot. Japan, 37, 1614
(1964).
27. S. Okuzawa, H. Hirai, S. Makishima, J. Polym. Sci. A-l, 7,
1039 (1969).
28. F. A. Bovey, J. Polym. Sci., 46, 59 (1960).
29. T. Otsu, B. Yamada, M. Imoto, J. Macromol. Chem., 1, 61
(1966).
30. H. Sobue, K. Matsuzaki, S. Nakano, J. Polym. Sci. A, 2,3339
(1964).
31. F. A. Bovey, G. V. D. Tiers, Fortschr. Hochpolym. -Forschg., 3,
139 (1963).
32. M. Uoi, M. Sumi, S. Nozakura, S. Murahashi, cited in Ref. 33.
33. S. Murahashi, in: IUPAC, International Symposium,
Makromol. Chem., 3, 435 (1967) (= Pure Appl. Chem., 15,
nos. 34 (1967)).
34. G. Talamini, G. Vidotto, Markromol. Chem., 100, 48 (1967).
35. J. Bargon, K. H. Hellwege, U. Johnsen, Makromol. Chem., 95,
187 (1966).
36. F. A. Bovey, F. D. Hood, E. W. Anderson, R. L. Komegay, J.
Phys. Chem., 71, 312 (1967).
37. H. U. Pohl, D. 0. Hummel, Makromol. Chem., 113, 203
(1968).
38. K. C. Ramey, D. C. Lini, G. Statton, J. Polym. Sci. A-l, 5,257
(1967).
39. L. Cavalli, G. C. Borsini, G. Carraro, G. Confalonieri, J.
Polym. Sci. A-l, 8, 801 (1970).
40. H. -G. Elias, P. Goeldi, Makromol. Chem., 144, 85 (1971).
41. H. -G. Elias, M. Riva, P. Goeldi, Makromol. Chem., 145, 163
(1971).
42. B. L. Johnson, H. -G. Elias, Makromol. Chem., 155, 121
(1972).
43. H. -G. Elias, P. Geoldi, B. L. Johnson, Adv. Chem. Ser., 128,
21 (1973).
44. R. E. Cais, W. L. Brown, Macromolecules, 13, 801 (1980).
45. D. R. Torrell, F. Evers, Makromol. Chem., 183, 863 (1982).
Products of Thermal Degradation of Polymers
.
John Liggat
Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland
A. Introduction I I -451
B. Tables I I -451
Table 1. Main-Chain Acyclic Carbon Polymers II-451
Table 2. Main-Chain Carbocyclic Polymers I I-464
Table 3. Main-Chain Heteroatom Polymers II-465
Table 4. Main-Chain Heterocyclic Polymers II-473
Table 5. Cellulose and Its Derivatives II-475
C. References II-475
A. INTRODUCTION
Polymer degradation is a complex phenomenon, and the
nature of the chemistry occurring during thermal decom-
position can be difficult to determine precisely. The
observed products of degradation can be the result of a
mixture of primary, secondary or even tertiary decomposi-
tion processes, and as a consequence, the distribution of
products will depend on such factors as sample thickness
and melt viscosity, in addition to the more obvious factors
such as temperature, atmosphere and the chemical structure
of the polymer itself. It is often overlooked that abnormal
structures (terminal unsaturation, head-to-head structures,
peroxide links etc.) can also markedly effect polymer
stability and product distribution.
Products are of three types. Firstly, there are the volatile
small molecules (typically of the size of monomer or
smaller) which are fairly readily separated and character-
B. TABLES
TABLE 1. MAIN-CHAIN ACYCLIC CARBON POLYMERS
ized. Secondly, there are the larger molecules that represent
fragments of the chain. These species are volatile at the
degradation temperature but condense outwith the degra-
dation zone. Generally produced as a complex spectrum of
oligomers, these fragments are more difficult to separate
and characterize in detail, particularly as internal rearrange-
ments of the backbone often occur before and during
fragmentation. In many cases, identification is limited to
key functionalities but the advent of sophisticated chroma-
tographic and mass spectrometric techniques is leading to
increasingly detailed analyses. In particular, the smaller
fragments such as dimer and trimer are in principle more
readily fully characterized than the larger fragments;
nevertheless there often remains some uncertainty, particu-
larly in relation to end groups. The most intractable product
is the third type, the residue, which is often (but not always)
insoluble, and characterization may again be limited to
identification of key functionalities.
Naturally, most of the information in the literature relates
to the easily identified low molecular weight species, and
the data in this section reflects this. In addition, most
thermal degradation studies focus on inert rather than
oxidizing environments. Following the lead of the previous
author, Norman Grassie, the vast majority of the entries
included here are concerned with products of the first two
types from purely thermal degradation processes under inert
atmospheres.
Polymer Temperature range (C) Degradation products Refs.
1.1. UNSATURATED POLYMERS
Poly(acetylene)
Poly(butadiene)
650
325- 475
20Clmin to
15% weight loss
Methane (0.87 moles relative to benzene = l), ethylene (0.47) ethane 8 2
(0.26) propylene (0.27), propane (0.047), 1,3-butadiene (0.19),
cyclopentadiene (0.086), cyclopentene (0.063), benzene (l.O),
toluene (0.18), m-xylene (0.091), p-xylene (0.015), styrene (0.041),
o-xylene (0.013) methylstyrene (O.OlO), trans-P-methylstyrene (0.01 l),
indane (0.0074) indene (0.036), methylindene (0.0072), naphthalene
(0.052), 2-methylnaphthalene (0.015), 1-methylnaphthalene (0.018)
biphenyl (0.0091), fluorene (l.O), anthracene (0.005)
14.1% of products are volatile at 25C including 1.5% of monomer 1 6
among other saturated and unsaturated hydrocarbons; 85.9% of
products are larger fragments involatile at 25C
Effect of cisltrans ratio; increasing tins content gives more cyclopentene 83
and 1,3-cyclohexadiene and less 4-vinyl-1-cyclohexene and 1,3-butadiene
II1451
II / 452 PRODUCTS OF THERMAL DEGRADATION OF POLYMERS
TABLE 1. contd
Polymer Temperature range (C) Degradation products Refs.
Poly(butadiene-co-acrylonitrile) (70/30)
25- 100 mol% butadiene
Poly(butadiene)-blend-poly(styrene)
(0-100 wt.%)
Poly(butadiene-co-sytrene) (75/25)
Poly(chloroprene)
Poly(chloroprene)-blend
poly(methy1 methacrylate)
Poly(isoprene), synthetic
97% cis-1,4; 3%, 3,4
natural rubber
gutta percha
Poly(isoprene)-bZendpoly(styrene)
(411 to 114, w/w)
chlorinated rubber
chlorinated rubber-blend-
poly(viny1 chloride)
Poly(perlIuoro-4-chloro-1,6-heptadiene)
1.2. POLY(ALKENES)
Poly(ethylene)
-9 low density
Poly(ethylene-co-carbon monoxide)
Alternating copolymer
Poly(ethylene-co-ethyl acrylate)
18 : 1 mole ratio
Poly(ethylene-co-vinyl acetate)
(12-33 mol% vinyl acetate)
(38.5% (wt.%) of ester groups)
3 10-400
350-400
Ambient to 500
327-430
377
170- 400
400-500
Ambient to 500
287-400
384
287-400
450-800
500
287-400
Ambient to 500
Ambient to 500
160- 350
320-400
335-450
Ambient to 500
264-289
500
Ambient to 500
Ambient to 500
260-290
288-425
up to 1200
14.5% of products are volatile at 25C, consisting of saturated
hydrocarbons 1 0
Main product is structurally modified chain fragments; ammonia and 98
hydrogen cyanide increasing with acrylonitrile content to
!pproximately 4% each by weight of copolymer containing
mole 75% acrylonitrile; traces of hydrogen and hydrocarbons up to CT
Volatile products as for individual polymers 84
11.8% of products are volatile at 25C; 1.9% butadiene with
other saturated and unsaturated hydrocarbons
Hydrogen chloride
HCl (90% of theoretical), ethylene, chloroprene (trace), chloroprene
dimers and other modified chain fragments
HCl (trace), methane, ethylene, propylene (trace)
Methyl methactylate, HCl, COz, CO,
methyl chloride, methanol.
lo,16
1 9
8 5
8 5
86
3.4% isoprene, 8.8% dipentene, small amounts of p-menthene. 2,16,31
In helium; methane (0.04 wt.%), ethylene (0.08), ethane (0.03) 8 7
propylene (0.15), propane (0.06) isobutylene (0.09), butenes (0.07),
methyl butene (0.09), isoprene (29) toluene (0.02) 2,3-dimethyl
cyclopentene (1.2) octene (0.05) 2,4-dimethyl cyclohexene (0.16),
m-xylene (0.33), 1-methyl-4-ethyl cyclohexene (0.18),
1,5-dimethyl-5-vinyl cyclohexene (2.5), dipentene (60), C iiH is (0.2)
c 12His (0.2) C 15H24 (3.5), Cd26 (1.8)
3.9% isoprene, 13.2% dipentene, small amounts of p-menthene 2,16,31
Dipentene main product at 45OC, optimum yields of isoprene in 32
range 675-800C e.g., 58% at 750C and 13 mbar
Monomer, dimers (1,7,7-trimethyl-2,2,1-bicyclohept-2-ene, 259
2,5,6-trimethyl 1,3,6-heptatriene, dipentene/d,l-limonene), trimers
3.0% Isoprene, 15.6% dipentene, small amounts of p-menthene 2,16,31
Styrene, isoprene, dipentene larger chain fragments of both 8 8
polymers, traces of ethylene, ethane, and propane
HCl (almost quantitative), CH4, CzH4, and H2 are minor products 8 9
formed in the later stages of reaction
HCl 90
Completely volatilized - products unknown. 49
Continuous spectrum of saturated and unsaturated hydrocarbons
from C2-Csa; lower temperature favors larger fragments
Continuous spectrum of saturated and unsaturated hydrocarbons
C L-C 15; trace of hydrogen
13,16
243
In air; CO2, H20, ethene, propene, propane, cyclopropane, butene, 9 1
butane, pentene, pentane, hexene, hexane, heptene, heptane, octene,
octane, methanol, ethanol, furan, tetrahydrofuran, formaldehyde,
acetaldehyde, propanal, acrolein, butanal, isobutanal, pentanal,
acetone, methyl vinyl ketone, methyl ethyl ketone, 2-pentanone,
2-hexanone, 2-heptanone, formic acid, acetic acid, propionic acid,
acrylic acid, butyric acid, isovaleric acid, hydroxyvaleric acid,
crotonic acid, caproic acid, butyrolactone, valerolactone
CO, H20, ethene, series of ketones with general structure 270
R-[-CO-CH2-CH2-I,-CO-R where R, R= -CHs, -CHz-CHs
or -CH=CH;,
Broad spectrum of saturated and unsaturated hydrocarbons, ethyl esters
and carboxylic acids; ethanol, ethylene, CO*, CO and small amounts
of ketene and ethyl acrylate
243
Acetic acid, ketene, CO2, ethylene, saturated and usaturated 92
hydrocarbons, chain fragment fraction containing some vinyl acetate units
Acetic acid > 99% 9 3
18.1% monomer together with methane, isobutane, and Cs and 1 6
higher saturated and unsaturated hydrocarbons
As temperature is increased the yields of fragments smaller than 28
monomer increase at the expense of larger fragments
TABLE 1. contd
Polymer Temperature range (C)
Main-Chain Acyclic Carbon Polymers II / 453
Degradation products Refs.
325
.
Poly(isopropenylcyclohexane)
345
365
300-320
400-900
Poly(isopropenylcyclohexane-co-cc-
methylstyrene) (92/8 and 33/67)
400-900
Poly(4-methyl-1-pentene) 291- 341
Poly(propylene) 328-410
400- 1200
360-400
120- 280
200-356
Poly(propylene)-blend-poly(methy1
methacrylate)
Ambient to 500
Poly(vinylcyclohexane) 335-391
360-380
Poly(chlorotrifluoro-ethylene) Ambient to 500
At 4.9% weight loss, products are isobutene (64.3%), CH4 (13.6%) 29
neopentane (10.3%); remainder C z -C iz hydrocarbons
At 15.7% weight loss, products are isobutene (78.9%) CH4 (5.9%), 29
neopentane (4.7%); remainder Cz-C iz hydrocarbons
At 46.8% weight loss, products are isobutene (81.6%), CH4 (3.9%) 29
neopentane (3.1%); remainder C 2 -C 12 hydrocarbons
Two types of t-butyl ended and two types of isopropyl ended terminal 249
monoolefins in range 2-mers to 12.mers
Methylenecyclohexane and/or methyl-1-cyclohexene, ethylcyclohexane, 94
toluene, isopropenylcyclohexane, isomer of isopropenylcyclohexane,
ethyl benzene, isopropylcyclohexadiene, pentadienylcyclohexane
(5 isomers), dicyclohexylpropane, 3-cyclohexenyl-1-cyclohexylpentadiene,
dicyclohexylhexadiene
Methylenecyclohexane and/or methyl-1-cyclohexane, benzene, toluene, 94
isopropenylcyclohexane, ethylbenzene (92/8 only), decalin (92/8 only),
cumene (33/67 only), cc-methylstyrene, styrene, (33/67 only),
pentadienylcyclohexane (92/8 only), indene and methyleneindene
(33/67 only), naphthalene, dicyclohexylhexadiene (92/8 only).
The following from the 33/67 copolymer only: 2-methylnaphthalene,
I-methylnaphthalene, biphenyl, methylstilbene, a-methylstilbene,
anthracene/phenanthrene, dihydropyrene
After 22 hours at 341C 20% residue, 71% saturated and 43
chain fragments; 9% of products volatile at 25C comprising
isobutene (56%), propane (34%) traces of monomer, and hydrocarbons
Saturated and hydrocarbons from Cz upwards, monomer yield 0.17% 1 3
As temperature is raised, yield of small fragments increases at 28
expense of large fragments
At 400C chain fragments with 7.05 wt.% of volatile products 95
comprising principally, methane 0.057 wt.%, ethane 0.13, propane 0.078,
propene 0.83, isobutene 0.16, butane 0.004, 2-methyl-1-butene 0.010,
I-pentene 0.008, pentane 1.62, 2-pentene (cis and tmns) 0.015,
2-methyl pentane 0.074, 2-methyl-1-pentene 1.19, 2,4-dimethylpentane
0.032, 2,4-di-methyl-1-pentene 0.089, 4-methylheptane 0.24,
2,4-dimethyl-1-heptene 2.20, 4,6-dimethylnonane (threo form) 0.042
(erythro form) 0.052, 2,4,6-trimethyl-l-nonene (threo form) 0.055
(erythro form) 0.066
In air; ethene, ethane, propene, propane, isobutene, butane, isobutane, 96
pentadiene, 2-methyl-1-pentene, 2,4-dimethyl-1-pentene,
5-methyl-1-heptene, dimethylbenzene, methanol, ethanol,
2-methyl-2-propene-1-01, 2-methyl furan, 2,5-dimethylfuran,
formaldehyde, acetaldehyde, acrolein, propanal, methacrolein,
2-methyl propanal, butanal, 2-vinyl crotonaldehyde, 3-methyl pentanal,
3-methyl hexanal, octanal, nonanal, decanal, ethenone, acetone,
3-buten-2-one, 2-butanone, 1-hydroxy-2-propanone,
1-cyclopropylethanone, 3-methyl-2-buten-2-one, 3-penten-2-one,
2-pentanone, 2,3-butanedione
Under 254 nm radiation; additional methane and ethylene are formed
compared with the thermal reaction
Poly(methy1 methacrylate) stabilized by blending with polypropylene;
pre-irradiation with 2537 A radiation at ambient temperature reduces
amount of methyl methacrylate formed on subsequent thermal
degradation; missing methyl methacrylate units appear in a chain
fragment fraction
97
99
Small amounts of cyclohexane, cyclohexane, methylcyclohexene, methyl 2,3
cyclohexane, vinylcyclohexene, vinylcyclohexane, ethylcyclohexane with
larger chain fragments
Cyclohexane (main product), cyclohexene, vinylcyclohexane, vinylcyclo 100
hexane oligomers, methane, ethane, ethylene, propane, propylene,
butane, butylene, hydrogen
Monomer, traces of dichlorodifluoroethene, chloropentafluoropropene,
trichlorotrifluoroethane
261
References page II - 475
II / 454 PRODUCTS OF THERMAL DEGRADATION OF POLYMERS
TABLE 1. contd
Polymer Temperature range (C) Degradation products Refs.
1.3. POLY(ACRYLICS), POLY(METHACRYLICS) .
Poly(acrylic acid) Ambient to 500
-, methyl ester 292-399
-1 ethyl ester
-9 n-propyl ester
-, isopropyl ester
-.
n-butyl ester
-, tert-butyl ester >160
-, 2-ethyl hexyl ester 300-500
-, benzyl ester 260-300
-, 1,1,.5-trihydroperfluoroamyl ester
-, 2,2,2-trichloroethyl ester
-> cr-bromo-, methyl ester
-3 a-chloro-, methyl ester
-3 a-chloro-, set-butyl ester
->
cc-cyano-, methyl ester
a-phenyl-, methyl ester
&y(acrylic acid, magnesium salt)
Poly(acrylic acid, calcium salt) Ambient to 500
Up to 980
50
300-500
50
Ambient to 500
300-500
250-500
300-500
50
-
300-315
319
110- 150
600
600
190
>180
210-280
Ambient to 500
CO, COz, HaO, CH4, acetone, ketene, ethene, propylene, 1-butene,
methyl vinyl ketone, benzene, acrylic acid, toluene, xylene, short
chain fragments such as dimer to octamer with unsaturated and
anhydride functionalities
26% of products are volatile at 25C, mainly methyl alcohol and
carbon dioxide with traces of monomer and methyl methacrylate and
Cd-Cs oxygenated compounds
(74% of products are large chain fragments involatile at 25C)
Methanol (1.9%), methyl formate (trace), methyl acetate (1.4%), methyl
acrylate (19.0%), methyl methacrylate (1.9%), saturated ester (2.1%),
dimethyl glutarate (7.5%), methyl 4-methoxycarbonyl-pent-4-enoate
(11.6%), trimethyl pentane 1,3,5-tricarboxylate (0.6%) methyl
4,6-di-methoxycarbonylhept-6-enoate (53%), saturated and tetramers
(1.0%)
Irradiated with high-pressure mercury lamp; methanol, formaldehyde,
methyl acetate, methyl formate, CO2, CO, Ha, CH4
Major products, carbon dioxide, ethylene, ethanol, and chain fragments;
minor products, ethane, ethyl acrylate, and ethyl methacrylate
Irradiated with high-pressure mercury lamp; CO, CO2, ethanol, acetalde-
hyde, ethane, ethyl formate, acetal, ethyl propionate
Ethylene, carbon dioxide, trace of ketene, ethanol (major product),
various ethyl esters (see Ref.)
Major products carbon dioxide, propene, propanol, and chain fragments;
minor products, propane, carbon monoxide, hydrogen, n-propyl acrylate,
and n-propyl methacrylate
Major products carbon dioxide, propene; minor products isopropanol
with trace carbon monoxide
Major products carbon dioxide, I-butene, butanol, and chain fragments;
minor products, butane, n-butyl acrylate, and n-butyl methacrylate
Irradiated with high-pressure mercury lamp. CO, CO:! n-butanol,
butyraldehyde, n-butene, n-butyl formate, n-butyl valerate
(after prolonged exposure)
86% isobutylene, 11% water, 3% carbon dioxide
Carbon dioxide, 2-ethyl-1-hexene, 2-ethyl-1-hexanol
Major products are benzyl alcohol, chain fragments, partially crosslinked
residue; minor products are CO2, toluene, CO, CH4, Hz
CO2, benzyl alcohol, and low polymers
Oligomers, 1.1.5~trihydroperfluoroamyl alcohol, monomer, 1,1,5-trihydro-
per8uoroamyl methacrylate
2,2,2-Trichloroethanol (so%), monomer (9%), l,l-dichloroethene,
2-chloroethanal, 2,2-dichloroethanal, 1 , 1-dichloropropane,
l,l,l-trichloroethane, 2,2,2-trichloroethylethanoate,
2,2,2-trichloroethyl chloromethanoate, 2,2,2-trichloroethylpropanoate,
2,2,2-trichloroethylmethacrylate, 2,2,2-trichloroethyl chloroethanoate,
2,2,2-trichloroethyl-2-chloroacrylate
Methylbromide, hydrogen bromide
COa, propene, methyl bromide, vinyl bromide
COa, propene, methyl chloride, monomer
set-Butyl chloride, butylene, hydrogen chloride
Yellows and some monomer formed
Monomer is the sole product
CO, CH4, CO*, acetone, ketene, ethene, propene, 1-butene, benzene,
toluene, xylene, cyclopentene, methyl ethyl ketone, diethyl ketone,
methyl-n-propyl ketone, di-n-propyl ketone, methyl vinyl ketone,
methyl isopropenyl ketone, methyl isopropyl ketone, ethyl vinyl ketone,
trace amounts of methyl-n-butyl ketone, cyclopentanone, cyclohexanone,
acrolein, ethanal and butanal, chain fragments, some monomer
CO, CH4, CO*, acetone, ketene, ethene, propene, 1-butene, benzene,
toluene, mesitylene, xylene, methyl ethyl ketone, diethyl ketone,
methyl-n-propyl ketone, methyl-n-butyl ketone, ethyl vinyl ketone,
methyl propenyl ketone (trace), ethyl propyl ketone (trace),
3-methyl-cyclopentanone, cyclohexanone (trace), cyclohexa-2-enone,
297
23
1 0 1
102
1 0 3
104
243
1 0 3
1 0 5
1 0 3
104
4
1 0 3
106
107
263
5
305
306
6
8
312
312
TABLE 1. contd
Mai n-Chai n Acycl i c Carbon Pol ymers I I / 455
Polymer Temperature range (C) Degradation products Refs.
.
Poly(acrylic acid, sodium salt)
Poly(acrylic acid, potassium salt) Ambient to 500
Poly(methy1 acrylate-co-methyl
methacrylate) (mole ratios 112/ l -2/ 1)
Poly(methy1 acrylate-co-acryloyl chloride)
6, 15, 41, 83 mol% AC
Poly(methy1 acrylate-co-2-bromoethyl
methyacrylate)
(lo-82 mol% methyl acrylate)
Poly(methy1 acrylate)-bZend-
poly((2-bromoethyl methacrylate)
(50/50, w/w)
Poly(n-butyl acrylate-co-methyl
methacrylate)
(3.9-93.4 mol% butyl acrylate)
Poly(tert-butyl acrylate-co-glycidyl
methacrylate) (34/66)
Poly(methyl-cr-chloroacrylate-
co-2,2,2-trifluoroethyl methacrylate)
(70/30)
Poly(methyl-a-chloroacrylate-co-2,2,2-
trifluoroethyl methacrylate) (70/30)
Poly(actylonitrile)
-. a-chloro
-, a-phenyl
Poly(acrylonitrile-co-2-bromoethyl
methactylate
(SO/SO, mohmol)
Poly(acrylonitrile-co-methyl
methacrylate)(l/410-1/8)
Ambient to 500
Ambient to 500
Ambient to 500
Ambient to 500
Ambient to 500
313-332
1 6 5
0-700
Ambi ent
Ambi ent
< 200
250-280
280-450
250-350
235
150- 200
Ambient to 500
Ambient to 500
Below 310
310-500
220-280
2-methyl-cyclohexanone, 1-methyl-cyclohexa-1-ene-3-one (trace),
acrolein, mesityl oxide, ethanal, propanal, butanal, chain fragments,
some monomer
CO, CH4, COz, ketene, 1-butene, propene, acetone, methyl ethyl ketone, 303
methyl isopropyl ketone, methyl-n-propyl ketone, diethyl ketone,
methyl propenyl ketone, 3-hexanone, toluene, 2-hexanone,
1,3-cyclopentadiene, cyclopentanone, 2-methyl cyclopentanone,
mesityl oxide, xylenes, benzene, propionaldehyde, acrolein, acetaldehyde,
ethene, short chain fragments, traces of monomer
CO, CH4, COz, ketene, I-butene, propene, acetone, methyl ethyl ketone, 303
methyl n-propyl ketone, l,Ccyclohexadiene, toluene,
I-methyl-1,3-cyclohexadiene, 2-hexanone, cyclopentene, l-methyl
cyclopentene, mesityl oxide, xylenes, benzene, ethene, cyclopentanone,
1,3-cyclopentadiene, diethyl ketone, short chain fragments, traces of
monomer
Monomers, COz, chain fragments larger than monomer, HZ; 108,109
more stable than poly(methy1 methacrylate); rapid decrease in
molecular weight; products of phtodegradation at 170 by 254 nm
radiation are qualitatively similar
Acrylic acid, HCl, HaO, CO, CO*, acryloyl chloride, methyl acrylate, 262
methyl acrylate chain fragments, anhydride and y-lactone structures,
chloro-methane, methyl methacrylate, methanol, 3,5-(6-chloro-2-pyrone)
and fragments thereof, Cg, Cg, C 12, C 1s fragments. Relative yields
depend upon copolymer composition
CO*, ketene, methyl bromide, acetaldehyde, methyl acrylate, methanol, 110
1,2-dibromoethane, methyl methacrylate, 2-bromoethanol,
ethyl methacrylate, CH4, CO, Hz modified chain fragments
CO*, ketene (minor), methyl bromide, vinyl bromide (minor), acetalde- 1 1 1
hyde, methanol, methyl methacrylate, methyl acrylate, 1,2-di-
bromoethane, 2-bromoethyl methacrylate
1-Butene, carbon dioxide, butanol methyl methacrylate, butyl acrylate, 112
and butyl methacrylate; small quantities of methane, ethane, propane,
butane, ethylene, propene, cis, and tram 2-butene, hydrogen, and carbon
monoxide increase with butyl acrylate content of the copolymer
Under 2537 A radiation; methyl methacrylate with smaller quantities of 1 1 3
n-butyl acrylate, n-butanol, n-butyraldehyde, hydrogen, carbon monoxide,
and methane; a chain fragment fraction increases with n-butyl acrylate
content
CO, CO2, propene, etbanal, isobutene, acrolein, ally1 alcohol 114
Gamma Radiolysis; CH4, CO, ethylene, ethane, CHsOH, CHFs, HCl, 1 1 5
CsHs, CO2, CzHsF, CHsCl, methyl formate, CHsCH#, CHF3,
CHsCFs, CH2=C(CH3)COOCH2CF3
Gamma Radiolysis; CH4, CO, ethylene, ethane, CHsOH, HCl, CsH6, 1 1 5
CO2, CHsCl, methyl formate, CHsCH2C1, CHzC12, CHCls
Colours through yellow, orange, red, and black 9
12% of products are volatile at 25C consisting of hydrogen 10,ll
cyanide, acrylonitrile, and vinyl acetonitrile; 88% of products are
involatile at room temperature
Five major volatile products are cyanogen, HCN, acrylonitrile,
acetonitrile, vinyl acetonitrile; involatile residue remains
NH3, HCN
HCN, hydrogenated acrylonitrile, dimer and trimer, acetonitrile,
methacrylonitrile
Hydrogen chloride
Hydrogen chloride and small amount of HCN at higher temperatures
High yields of monomer
Ethylene, CO 2, vinyl bromide acetaldehyde, 1,2-dibromoethane
1 2
1 1 6
1 1 7
1 1 8
119
1 1 9
1 2 0
Propane, isobutene, CO2, HCN, isocyanic acid, yellow-chain fragment
fraction
1 2 1
Only methyl methacrylate from 410/1 and 40/1 (molar ratio) copoly- 1 2 1
mers; methyl methacrylate and small amounts of acrylonitrile from
16/1 and 8/1 copolymers; rapid decrease in the molecular weight of
all copolymers
References page II - 475
II / 456 PRODUCTS OF THERMAL DEGRADATION OF POLYMERS
TABLE 1. contd
Polymer Temperature range (C) Degradation products Refs.
Poly(actylonitrile-co-methyl
vinyl ketone)
Poly(acrylonitrile-co-styrene)
(O/lOO-50/50, mol/mol)
(1.86-96.62 mol% acrylonitrile)
-
292
500
Poly(acrylonitrile-co-vinyl
acetate) (7.5 wt.% vinyl acetate)
Poly(acrylonitrile-co-methyl
acrylate-co-vinyl bromide)
(methyl acrylate, 10 wt.%; vinyl bromide,
5 wt.%)
Poly(cL-chloroacrylonitrile-co-
methyl methacrylate)
(0-50 mol% cc-chloroacrylonitrile)
260
180- 320
>150
Ambient
Poly(acrylonitrile)-blend-
poly(methy1 methacrylate)
(50150, w/w)
Poly(acryloy1 chloride)
Poly(methacrylic acid)
Up to 320
320-500
Ambient to 500
200
-1
methyl ester
900
170- 300
246-400
160 Photodegradation by 254 nm radiation gives methyl methacrylate from
410/1 to 8/1 copolymers with a 8/1 copolymer; rapid decrease in the
molecular weight of all copolymers
121
Production of water from poly(methyl vinyl ketone) accelerated by
copolymerization with acrylonitrile
Acrylonitrile causes increase in rate of chain scission; proportion of
acrylonitrile among degradation products greater than from pure
polyacrylonitrile; chain fragments increase with acrylonitrile content
of copolymer; styrene, acrylonitrile, toluene, benzene, four dimers,
and four trimers
1 2 2
1 2 3
Hydrocyanic acid, acetonitrile, acrylonitrile, propionitrile, toluene, ethyl
benzene, styrene, methane, ethylene, ethane, C 3 hydrocarbons,
but-1-ene, prop-1-ene-3nitrile, isopropylnitrile, benzene
HCN, hydrogenated acrylonitrile, dimer and trimer, acetonitrile,
methacrylonitrile, acetic acid
124
CHsBr, HBr, H20, CO*, CHsOH, NHs, HCN, hydrogenated acrylo-
nitrile, dimer and trimer, acetonitrile, methacrylonitrile, naphthyridine
fragments
1 1 7
1 1 7
Hydrogen chloride, methyl methactylate, a-chloroacrylonitrile
Under 254 nm radiation. HCl, COz, methyl chloride, methyl formate,
methanol, methyl methacrylate, CO, CH4, Hz
NHs, HCN, MMA
Chain-fragment fraction and small amounts of CO, COz, methanol,
CH4
1 2 5
126
1 2 7
Acrylic acid, HCl, H20, CO, acryloyl chloride, 3,5-(6-chloro-2-pyrone)
and fragments thereof, CS, Cg, C 12. C 1s fragments
Almost quantitative yields of H20, traces of monomer, residue of
poly(methacrylic anhydride)
CO*, propene, butenes, pentenes, pentadienes, hexene, hexadienes,
hexatrienes, benzene, toluene, heptene, heptatriene, methacrylic acid,
xylene, octatriene, octadienyne, nonatriene, hexadienoic acid,
decatriene, decatetraene, decapentaene, undecatriene, methylbenzoic
acids, trimethylbenzoic acid
262
3 3
1 2 8
100% monomer 34. 35
-3
ethyl ester
-3 n-propyl ester
->
iso-propyl ester
-3 n-butyl ester
-,
iso-butyl ester
-, set-butyl ester
-9 rert-butyl ester
-I n-amyl ester
->
iso-amyl ester
-, 1,2-dimethylpropyl ester
-, neopentyl ester
-> 3,3-dimethylbutyl ester
-,
1,3-dimethylbutyl ester
-, 2-bromoethyl ester
-, 2-sulfoethyl ester
-3 2chloroethyl ester
160
100- 400
250
245
250
250
250
170
250
250
180- 200
<180
250
250
250
250
250
250
Ambient to 500
50-600
600
600
268
As temperature is raised fragmentation increases to give complex 2
series of products and monomer yields correspondingly decreases
100% monomer under 253.7 nm radiation
Under 254 nm radiation; 100% monomer
Monomer
Monomer, ethanol, ethanoic acid
Monomer
Monomer
40% monomer and traces of 1-butene
100% monomer under 253.7 nm radiation
Monomer
Monomer and small amount of olefin by cracking of side chain
High yields of isobutylene and water, 1% monomer, trace of methacryhc
36
129
3 7
300
3 7
3 7
38
3 8
3 7
3 7
3 9
acid, residue of poly(methacrylic anhydride)
100% monomer under 253.7 nm radiation
Monomer
Monomer
Monomer and small amount of olefin by side chain cracking
Monomer
Monomer
Monomer and small amount of olefin by side chain cracking
2-Bromoethyl methacrylate (z 95%) CO2 (< 1%) vinyl bromide (< 1%)
CO, CO2, H20, SOT, ethene
CO, CO2, propene, acetaldehyde, methyl bromide, butene,
vinyl bromide, ethyl bromide, methyl methacrylate
CO*, propene, acetaldehyde, vinyl chloride, ethyl chloride, monomer
Monomer (99%) traces of acetaldehyde, methyl methacrylate,
1,2-dichloroethane, ethylene methacrylate
3 7
3 7
3 7
3 7
3 7
3 7
130
290
305
306
268
I
I
I
I
I
j
i
TABLE 1. contd
Mai n-Chai n Acycl i c Carbon Pol ymers II/457
PolymL Temperature range (C) Degradation products Refs.
Poly(methacrylic acid),
2-fluoroethyl ester
-, 2,2-dichloroethyl ester
-, 2-methoxyethyl ester
-, 2,3-dibromopropyl ester
-, 2-hydroxyethyl ester
-, 2,2,2-trifluoroethyl ester Ambi ent
-, 2,2,2-trichloroethyl ester
-, hexafluoroisopropyl ester
-, bisphenol S ester
-, ally1 ester
-, phenyl ester Ambient to 500
-, glycidyl ester Ambient to 500
-, ammonium salt
-, Li, Na, K, and Co salts
-, Mg, Ca, Sr, and Ba salts Ambient to 500
Poly[u-o-(diethylene glycol
phthalate)dimethacrylate]
Poly(methy1 methacrylate-co-alkali
(metal methacrylates) (Li, Na, K)
(0- 100 mol%)
Poly(methy1 methacrylate-co-
2-bromoethyl methacrylate)
(50/50, mol/mol)
Poly(methy1 methacrylate-
co-methacrylamide)
600
242
COs, vinyl fluoride, acetaldehyde, fluoroacetaldehyde 310
Ambient to 300
Ambient to 500
600
375-500
Monomer (90.7%), chloroacetaldehyde (8%) 1,1,2-trichloroethane (0.5%) 268
2,2-dichloroethanol, methacrylic acid (0. 1%), 2-chloroethylene
methacrylate (0.1%)
Monomer, CO s 309
Monomer, COs, CO, CH4, ethene, formaldehyde, isobutene, methyl 309
vinyl ether, methanol
600
600
240
COs, propene, acetaldehyde, methyl bromide, butene, ethyl bromide,
bromocyclopropane or 2-bromopropane
2-Hydroxyethyl methacrylate (20% at 5OOC), ethylene dimethactylate
(6%at SOOC)(main products), ethylene glycol, 3-methyl-5-hydroxy-
S-valerolactone (probably), 1,2-di-iospropenyl-oxyethane (probably),
CO, COs, methane, ethylene, ethane, propane, Hz0
Gamma radiolysis; CH4, CO, ethylene, ethane, CHsOH, CHsF, CsH6,
COs, CsHsF, methyl formate, CH3CHFOH, CHFs, CFsCHs,
CF30H, CH2=C(CH3)-COOCHsCFs
CO2, vinylidene fluoride, trifluoroacetaldehyde, trifluorethanol,
monomer
305
1 3 1
1 1 5
310
600
464
Ambient to 500
COs, propene, vinyl chloride, vinylidene chloride 306
1,1-Dichloroethene, chloroform, methyl methacrylate, methacrylic acid, 300
2,2,2+ichloroethanol, 2,2,2-trichloroethyl acrylate, 2,2,2-trichloroethyl
methacrylate, 2,2dichloroethyl methacrylate,
CHs=C(CHs)-COOCH=CCls or CHs=C(CHs)-COOCCl=CHCl
CO 2, trifluoracetaldehyde, acetaldehyde, 1, 1,1,3,3,3-hexafluoropropane, 310
hexafluoro-isopropylformate
COs, SOs, phenol, bisphenol S, hydroquinone, fragments of backbone,
benzene sulfonic acid
248
COs, CH4, CO, Hz. propene, isobutene, dimethyl ketene, acrolein,
diallyl ether, ally1 methacrylate monomer and dimer, chain fragments
including anhydride structures from side-group cyclization and an
aliphatic ketone in the vicinity of unsaturation
Monomer, some CO2
CO, COs, dimethyl ketene, isobutene, propene, acrolein, ally1 alcohol,
glycidyl methacrylate, glycidol, short chain fragments with some
unsaturation
283
314
302
Ambient to 500
Ambient to 500
Isocyanic acid, NHs, HCN, isobutene, CO2 (trace), methacrylonitrile
(trace)
132
300
400
Ambient to 500
Ethylene, butene-1, isobutene, acetylene, COs, CH4, CO, acetone, 1 3 3
isopropylaldehyde, methacrolein, butyraldehyde, methyl ethyl ketone,
benzene (trace), methyl isopropyl ketones, methyl isopropenyl ketone,
diethyl ketone, methyl n-propenyl ketone, cyclopentanone, methyl
cyclopentanone, dimethyl cyclopentanone, dimethyl cyclopentenone and
traces of toluene, di-isopropyl ketone, mesitylene, mesityl oxide
CO*, dimethyl ketene trace amounts of CO, CH4, isobutene, butene-1, 134
ethylene, acetylene, benzene toluene isobutyraldehyde, methyl ethyl
ketone, methyl isopropenyl ketone, diethyl ketone, methyl
isopropenyl ketone, di-isopropyl ketone, cyclopentanone, 2-methyl
cyclopentanone, 2,5-dimethyl-cyclopentanone,
2,5-dimethylcyclopent-3-ene-l-one, methacrolein, butyraldehyde
Monomer 194
Monomer, phthalic anhydride, diethylene glycol, CsH4, propylene, CO2 194
CO*, alkenes, CH4, CO, propanal methanol (major), acetone, 2-methyl 135
propanal, methacrolein, butanal, methyl ethyl ketone, methyl isopropyl
ketone, methyl isopropenyl ketone, methyl methacrylate (major),
methyl prop-2-enyl ketone, toluene, di-isopropyl ketone, cyclopentanone,
2-methyl cyclopentanone, 2,5-dimethyl cyclopentanone, 2.5~di-methyl
cyclopent-3-enone. Relative yields depend upon salt and copolymer
composition
Ambient to 500 Methyl methacrylate, 2-bromoethyl methacrylate, traces of vinyl bromide 130
and CO 2
up to 340 > 35 mol% methacrylamide. MMA, methanol, NHs, Hz0 146
References page II - 475
II / 458 PRODUCTS OF THERMAL DEGRADATION OF POLYMERS
TABLE 1. contd
Polymer Temperature range (C) Degradation products Refs.
Poly(methy1 methacrylate-co-
methacrylic acid)
Poly(methy1 methacrylate-co- 600
2-chloroethylmethacrylate)
22 mol% CEMA
Poly(methy1 methacrylate-
co-2,2,2-trichloroethyl
methacrylate)
24 mol% TCEMA
Poly(methy1 methacrylate-
co-methyl-E-chloroacrylate)
38 mol% MCA
Poly(methy1 methacrylate-
co-2-bromoethyl methacrylate)
22 mol% BEMA
Poly(methy1 methacrylate-
co-2,3-dibromopropyl
methacrylate)
16 mol% DBPMA
Poly(methy1 methacrylate-
co-methyl-a-bromoacrylate)
22 mol% MBA
Poly(methy1 methacrylate-
co-chlorotrifluoroethylene)
7.7 mol% MMA
77.7 and 85.7 mol% MMA
Poly(methy1 methacrylate-
co-2-sulfoethyl methacrylate)
20, 40, 60 mol% MMA
Poly(methy1 methacrylate-
co-4-vinylpyridine)
22, 35, 46, 56 mol% 4-
vinyl pyridine
Poly(methy1 methacrylate-
co-phenyl methacrylate)
9, 18, 47, 88 mol% PMA
Poly(methy1 methacrylate-
co-glycidyl methacrylate)
Poly(methy1 methacrylate
-block-t-butylaziridine)
ABA type copolymer with
MW 12000 butylaziridine
(B) and MW 16000
MMA (A)
Poly(methy1 methacrylate-co-styrene)
Poly (methyl methacrylate-co-vinyl
acetate) (5-40 mol% vinyl acetate)
> 340
<300
>300
900
600
600 CO2, propene, methyl chloride, methyl methacrylate 306
600 CO2, propene, acetaldehyde, methyl bromide, butene, vinyl bromide,
methyl methacrylate
305
600 CO, CO2, ethene, propene, methyl bromide, butene, vinyl bromide,
ethyl bromide, 1-bromopropene, 2-bromopropene, cyclopropyl
bromide, methyl methacrylate
305
600
Ambient to 500
Ambient to 500
50-600
Ambient to 500
Ambient to 500
Ambient to 500
Ambient to 600
260-340
Ambient to 500
Methacrylamide; chain fragments and small amounts of CH4, CO*, CO,
HCN, methacrylonitrile and isobutene
< 10 mol% methacrylamide. Degradation becomes progressively more
like that of PMMA
Water and methanol
Methyl methacrylate, COz, CO, CH4
(50/50 and 75125); CO2, propene, butenes, pentenes, pentadienes,
hexene, hexadienes, hexatrienes, benzene, methyl isobutyrate, methyl
methacrylate, toluene, heptene, heptatriene, methyl pentenoate,
methacrylic acid, xylene, octatriene, octadienyne, nonatriene,
hexadienoic acid, decatriene, decatetraene, decapentaene, undecatriene,
methylbenzoic acids
146
146
136
1 2 8
CO*, propene, acetaldehyde, vinyl chloride, ethyl chloride, methyl
methacrylate
306
COz, propene, vinyl chloride, vinylidene chloride, dichloroacetaldehyde,
methyl methacrylate
306
COz, acetaldehyde, methyl bromide, butene, vinyl bromide, unidentified
alkenyl bromides, methyl methacrylate
305
HCl, C02, CH3Cl, C2F3Cl (lIlOtlOmer), C3FsC1, C2FjCl3, methyl
methacrylate, chain fragments possibly with some lactonization
281
HCl, CO2, CH3C1, C2F3Cl (monomer), met hyl met hacryl at e
CO, COP, H20, SO2, ethene, methanol, methyl methaclylate
(only 60 and 80 mol% methyl methacrylate copolymers)
281
290
4-vinyl pyridine, methyl methacrylate, traces of pyridine
and 4-methyl pyridine
260
CO2, isobutene, ketene, formaldehyde, methanol, methyl methacrylate,
phenyl methacrylate, chain fragments including six-membered
anhydride ring structures. Product distribution varies with copolymer
composition with non-monomer products most pronounced at low
PMA contents
314
CH4, CO, CO2, propene, isobutene, dimethyl ketene, acrolein, ally1
alcohol, glycidol, glycidyl methyl ether, methyl methacrylate,
glycidyl methacrylate, chain fragments. Distribution varies with
copolymer composition
286
CO, CH4, CO2, ethene, propene, isobutene, aziridine, methanol,
methyl methacrylate, cc-methylstyrene, 2-phenyl-2-butene,
1-t-butylamino-2-isopropenylamino-ethane, 2-r-butylaminoethyl-ethyl-
isopropenylamine, 2-aminoethyl-2+butylaminoethyl-
isopropenylamine, oligomers - principally butylaziridine based
287
Methyl methacrylate, styrene and oligomers of styrene; formation of
oligomers of styrene strongly inhibited by presence of methyl
methacrylate units
. . ^ ^
137
Acetic acid, methyl methacrylate, methyl acetate, cham tragment tractIon,
92
ketene, CO2
TABLE 1. contd
Mai n-Chai n Acycl i c Carbon Pol ymers II / 459
Polymer Temperature range (C) Degradation products Refs.
Poly(methy1 methacrylate-co-vinyl
bromide) (6-75 mol% vinyl bromide)
Poly(2-bromoethyl methacrylate-
co-styrene) (50/50, mol/mol)
Poly(methy1 methacrylate)-bZend-
ammonium polyphosphate
Poly(methy1 methacrylate)-bZend-
poly(styrene)
Poly(methy1 methacrylate)-bZend-
poly(vinyl acetate) (lo/l-l/l, w/w)
Poly(methy1 methacrylate)-bZend-
poly(viny1 bromide) (50/50, mol/mol)
Poly(methy1 methacrylate)-blend-
poly(viny1 chloride)
Poly(methacrylamide)
Poly(methacrylonitrile)
Poly(methacrylonitrile-co-
styrene) 10 : 1 mole ratio
Poly(methacrylonitrile-
co-styrene) 1 : 1 mole ratio
Poly(methacrylonitrile-
co-styrene) 1 : 10 mole ratio
1. 4. POLY(VINYLS)
Poly(tert-butyl-N-vinyl carbamate) 185-220
Poly(chlorotrifluoroethylene) (KEL-F) 347-418
Poly( l , l-dichloro-2,2-difluoroethylene)
Poly(perfluoroheptene)
Poly(perfluoropropylene)
Poly(tetrafluoroethylene)
240
210-270
280-400
504-538
1200
600-700
Poly(trifluoroethylene)
Poly(viny1 acetate)
Poly(viny1 acetate) in presence
of zinc bromide
Poly(viny1 acetate-co-
maleic anhydride)
alternating copolymer
Poly(viny1 acetate-co-
crotonic acid)
alternating copolymer
Ambient to 500
Ambient to 500
Ambient to 450
Ambient to 500
Ambient to 500
Polymers degrade separately without interaction to give same products as 141
polymers degraded separately; copolymers and mixtures of the same
molar compositions can be distinguished by degradation behavior
Methyl metbacrylate, acetic acid, methyl acetate, methanol, COa, butene, 142
benzene, ketene
Ambient to 500 Methyl methacrylate, HBr, CO, CO2 and other unidentified products 1 4 3
Ambient to 500
up to 340
Above 340
Ambient to 500
< 200
220-270
Ambient to 500
Major products: HCl, methyl methacrylate; minor products: COz, 144,145
methyl chloride, benzene
NH3 and Hz0 146
Chain fragments (50%) in which a high proportion of amide groups have 146
been converted to cyclic imides; small amounts of COa, CH4, HCN
NHs, HCN, isobutene, COz(trace), methacrylonitrile (trace) 132
Non-volatile material, coloration through yellow, orange, and red 40
50- 100% monomer depending upon pretreatment and purity of polymer 40
Ethene, propene, isobutene, HCN, COz(from benzoyl peroxide end 277
groups), methacrylonitrile (major product), 2-cyanobutane,
2-cyanopentene, CH4
Ambient to 500
Ambient to 500
Ambient to 500
380-800
213-235
300
280-350
Ambient to 500
Ambient to 500
Ambient to 500
Methyl methacrylate, methyl bromide, methanol, CO2, methanol, HBr, 1 3 8
CO, HZ and other unidentified minor products. Relative amounts depend
upon copolymer composition
Styrene, 2-bromoethyl methacrylate, modified chain fragement fraction.
Minor products; ethylene, COz, HBr, vinyl bromide, acetaldehyde
Hz0 and NH3 from ammonium polyphosphate. Methyl methacrylate
(major product), CO, COa, methanol, dimethyl ether, hydrocarbons,
high boiling chain fragments
139
140
Ethene, isobutene, HCN, methacrylonitrile, styrene, toluene,
a-methylstyrene, B-methylstyrene, 2-phenylbutene, 4-cyano-
2,4-dimethylpentene, 4-phenyl-2-methylbutene, 3-phenyl-
2-propenenitrile, chain fragments
279
Ethene, isobutene, HCN, methacrylonitrile, styrene, toluene,
a-methylstyrene, 4-phenylbutene, 4-phenyl-2-methylbutene,
3-phenyl-2-propenenitrile, chain fragments
Ethene, isobutene, HCN, methacrylonitrile, styrene, toluene,
a-methylstyrene, B-methylstyrene, 4-phenylbutene, allylbenzene,
4-phenyl-2-methylbutene, 3-phenyl-2-propenenitrile, chain fragments
279
279
Equal amounts of CO2 and isobutylene, in yields ranging from 43 to 60% 196
25% of products volatile at 25C-monomer with traces of CsFsCl 1 4
and CsF4Clz; 72.1% of larger chain fragments involatile at 25C
20% black involatile residue; 80% monomer 22
100% monomer 49
100% monomer 49
> 95% monomer, 2-3% CaFs, no larger fragments (in vacuum) 1 4
Monomer yield drops, larger fragments appear (in vacuum) 2 3
At 6.66 mbar pressure; pure monomer; at 1013 mbar pressure, 24
15.9% monomer, 25.7% CsFs, 58.4% C4Fs
High yields of HF and products involatile at 25C 23
Quantitative yields of acetic acid 7 1
Small amounts of aromatics including benzene 7 1
Acetic acid, benzene, naphthalene, toluene, styrene, ethyl benzene, 1 4 7
propenyl benzene, propylbenzene, methylnaphthalene, ethylnaphthalene,
propenylnaphthalene, propylnaphthalene, anthracene, methylanthracene,
ethylantbracene, propylanthracene
Acetic acid produced as low as 100C 148
Acetic acid, COz, HzO, maleic anhydride, CO 240
Ethene, propene, acetic acid, COz, propanoic acid, 2-methylpropanoic
acid, butanoic acid, cyclopentanone, some unsaturated cyclic and
acyclic aliphatic ketones, some chain fragments containing
lactones
241
References page II - 475
II / 460 PRODUCTS OF THERMAL DEGRADATION OF POLYMERS
.
TABLE 1. contd
Polymer Temperature range (C) Degradation products Refs.
Poly(viny1 acetate-co-
methylvinylidene cyanide)
Alternating with lo-15
mol% VA homosequence
Poly(viny1 acetate-co-styrene)
(5-20 mol% vinyl acetate)
Poly(viny1 acetate-co-vinyl alcohol)
(50-99 mol% vinyl alcohol)
Poly(viny1 acetate-co-vinyl
chloride)
Poly(viny1 acetate-co-vinyl fluoride)
(91: 9 to 1: 89)
(80: 20 to 23 : 77)
Poly(viny1 acetate)-bZend-
poly(styrene) (l/ 1, w/w)
Poly(viny1 acetate-blend-
poly(viny1 chloride)
Poly(viny1 alcohol)
Poly(viny1 bromi de)
Poly(viny1 butyrate)
Poly(N-vinylcarbazole)
Poly(3,6-dichloro
N-vinylcarbazole)
Poly(3,6-dibromo
N-vinylcarbazole)
Poly(viny1 chloride)
Poly(viny1 chloride)-blend-
poly(cr-methylstyrene)
Poly(viny1 chloride)-bZend-
poly(styrene)
(lO/l to l/lO, w/w)
PVC 1 : 1 blend with
bisphenol A polycarbonate
285-350
Ambient to 500
0-600
Ambient to 500
180
200-500
200-500
Ambient to 500
Ambient to 500
250
240
300-325
230-410
300-500
300-500
350-500
200-300
400
600
200-800
Ambient to 1000
Ambient to 500
Ambient to 500
Ambient to 500
Ambient to 500
Vinyl acetate, acetonitrile, HCN, acetic acid, acetamide, 2-methyl-
1-aminonaphthalene, 3-cyano-3-pentene
266
Acetic acid, styrene, chain fragment fraction, ketene, CO2 92
Acetaldehyde, acetone, benzene, crotonaldehyde, acetic acid 154
Bulk polymer; hydrogen chloride and acetic acid in the proportions of 1 5 5
the monomers in the copolymer; at each end of the composition range,
incorporation of the comonomer results in a copolymer less stable than
the homopolymer; minimum stability at 40-50 mol% vinyl acetate
In tritolyl phosphate solution; similar to bulk polymer with minimum in 156
stability at 30-40 mol% vinyl acetate
Hydrogen fluoride, acetic acid, hydrocarbons 150
Hydrogen fluoride, HCl, hydrocarbons 150
Products as for individual polymers 158
Acetic acid, HCl, and traces of CO*, ketene, acetyl chloride, CO 1 5 7
and CH4
Quantitative yields of Hz0 72
Main products Hz0 and CzHsOH, with aldehydes 73
CHs-(CH=CH).-CHO and ketones CHs-(CH=CH),,-COCHs
where n = 0,1,2, etc.
I-W, ethylene, benzene, and other unidentified minor products
Butyric acid
Below 350, monomer; above 350, monomer and low-molecular
weight oligomers
Monomer (49% of total volatiles at 300C 39% at 500C) ethane,
ethene, propene, n-butane, isobutene, cis and trans but-2-ene,
1,3-butadiene, 2-methylbutadiene, trace amounts of Cs and Cg
hydrocarbons
1 4 3
74
1 7 5
244
Monomer (83% of total volatiles at 3OoC, 67% at 5OOT), ethane,
ethene, propene, n-butane, isobutene, cis and rruns but-Zene,
1,3- butadiene, 2-methylbutadiene, trace amounts of C5 and Cs
hydrocarbons
244
Monomer (48% of total volatiles at 350C 40% at 5OOC), ethane, 244
ethene, propene, n-butane, isobutene, cis and trans but-2-ene,
1,3-butadiene, 2-methylbutadiene, trace amounts of Cs and Cg
hydrocarbons
Quantitative yields of HCl 75
Saturated and unsaturated, aliphatic and aromatic hydrocarbons are 75
produced with benzene and toluene in high yield
In helium; quantitative yield of HCl, remainder residue and 76
hydrocarbons; benzene is major volatile hydrocarbons product
Aliphatic hydrocarbons, benzene (major product), toluene, ethylbenzene, 149
o-xylene, monochlorobenzene, styrene, vinyl toluene, p-dichlorobenzene,
o-dichlorobenzene, indene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene,
naphthalene, a-methylnaphthalene, l3-methylnaphthalene; effect of ZnO,
SnOz, and Al203 on the yields of products is also recorded
HCl, CO2, ethene, ethane, propane, 1-butene, 2-butene, 1-pentene, 267
cyclopentene, n-pentane, 2-metbylbutane, 1,3-pentadiene,
2-methyl- 1,3-pentadiene, complex series (60 identified) of aromatic and
polyaromatic species, including benzene, styrene, methylstyrenes,
toluene, o-xylene, m-xylene, p-xylene, biphenyl, naphthalene,
anthracene, phenanthrene, pyrene, etc. (see Ref.)
HCl, cc-methyl styrene 159
HCl, styrene
Products as for individual polymers
CO2, HCl, benzene, traces of toluene, phenol and other phenolic
compounds, bisphenol A, polycarbonate chain fragments
159
160
291
.
TABLE 1. contd
Main-Chain Acyclic Carbon Polymers II / 461
Polymer Temperature range (C) Degradation products Refs.
PVC 1 : 1 blend with
poly(dimethylsiloxane)
Poly(viny1 fluoride)
Ambient to 500
372-480
200-500
450
Poly(vinylidene chloride)
Poly(vinylidene cyanide)
Poly(vinylidene fluoride)
Poly(vinylidene fluoride-
co-chlorotrifluoroethylene)
80 mol% vinylidene fluoride
3, 10 mol% vinylidene
fluoride
Poly(vinyltrimethylsilane)
225- 275
170
>160
400-530
Ambient to 500
Ambient to 500
Ambient to 500
300-600 in argon
Poly(4-vinyl pyridine) Ambient to 500
Poly(vinylacetophenone) 380
Poly(N-acryloyl-N-
cyanoacetohydrazide)
600
1.5. POLY(VINYL KETONES), POLY(VINYL ETHERS)
Poly(methy1 isopropenyl ketone) 270-360
Ambient to 500
Poly(methy1 vinyl ketone)
Poly(trifluoroviny1 phenyl ether)
1. 6. POLY(STYRENES)
Poly(styrene)
150- 190
270-360
Ambient to 500
275-500
300-400
500- 1200
300-570
Ambient to 500
-9
(crosslinked) 346-450
-, (head-to-head) 320
500
under N2
HCl, benzene, traces of toluene, octamethylcyclotetrasiloxane,
oligomeric siloxanes
292
High yields of HF and products involatile at 25C - little carbonization 2 3
Hydrogen fluoride, C 2-C 9 fractions 1 5 0
85% wt. loss, 33 i 5% volatile products, remainder was oily green liquid; 151
Volatile products: HF (82 mol%), CH4 (5.2), CzH6 (0.6), ethylene
(0.8), acetylene (0.03), fluoroethylene (0.07), propene (0.5), CaHsF
(0.4) butane (0.06) butene (1.1) 1,Cbutadiene (0.2) 1,3-butadiene (0.7),
CdHsF (0.06), Cyclopentadiene (0.05) benzene (4.5), fluorobenzene
(0.3), toluene (l.O), CsHd(CHs)F (0.04), CeHsCzHs or CsHd(CHs)a,
and styrene (0.9) n-propylbenzene (0.2) iso-propylbenzene (0.3).
CeHs-C sHs (0.2), indene (0.3) naphthalene (0.8), fluoronaphthalene (0.3)
High yields of HCl 77
Polymer prepared in presence of oxygen; phosgene, formaldehyde, HCl 152
High yields of monomer 78
35% HF and high yields of products involatile at 25C - some 2 3
carbonization
Monomer, dimer (CdFsHs), SiF4, (from reaction of HF with glass) 265
HCl, HF, vinylidene fluoride, chlorotrifluoroethylene, dimer (ChFsH 3) 265
HCl, chlorotrifluoroethylene, dichlorodifluoroethene,
chloropentafluoropropene, trichlorotrifluoroethane, dimer (C4FsHs)
Tetramethylsilane, trimethylvinylsilane, 2-trimethylsilylpropene,
1,3-tri-methylsilylpropane, 1,3-trimethylsilylpropene,
2,4-trimethylsilylbutene- 1,2,4,6-trimethylsilylhexene- 1
Monomer, traces of pyridine and 4-methyl pyridine
CO, CH4, ethane, 4-acetyl styrene, 4-acetyl toluene, styrene, toluene,
4-vinyl acetaldehyde, a-methylstyrene, rx-methyl-4-acetylstyrene,
4-methylstyrene
Cyanoactetamide
265
1 5 3
260
307
289
Hz0
4 1
Methyl isopropenyl ketone (50%), modified chain fragments, water, 161
small amounts of CH4 and CO
Monomer under 3 13 nm radiation 42
H20, 3-methyl-2.cyclohexene-l-one and other six-membered ring ketones 44
Water, modified chain fragments, small amounts of CH4 and CO 161
Maximum of 75% volatilization-products unknown 49
40.6% monomer, 2.0% toluene, 0.1% CO, remainder dimer, trimer, 62,63
and tetramer - monomer yield increases with pressure of nitrogen - 62%
at 1013 mbar
Small hydrocarbon fragments appear (C i -Cs) - fragmentation is greater 2 8
the higher the temperature and the greater the pressure of inert gas
Pulsed pyrolysis and 40 pg of polymer. Styrene (92.4-99.8% depending 1 6 3
upon temperature), benzene, toluene, and ethyl benzene
Thin films (1000 A or less), monomer yield about 55% 1 6 4
Crosslinking with increasing quantities of divinyl or trivinyl benzene 11,64
progressively decreases the styrene yield-the yield of larger chain
fragments and the amount of carbonization also increase
Monomer, dimer, trimer, tetramer, pentamer, stilbene 1 6 5
Hydrocarbons (C 1 -Cd) (2.2 relative GC peak intensity), benzene (0.4) 1 6 6
toluene (3.3) ethylbenzene (2.0) styrene (20.4) 3-phenyl-1-propene
(1.5), I-phenylpropane (2.3) cc-methylstyrene (0.3), 1-phenylbutadiene
(1 .O), diphenylmethane (0.3), l,l-diphenylethylene (2.6),
1,2-diphenylethane (1.3), 1,2-diphenylpropane,, (0.7),
1,2-diphenyl-1-propene (0.5), 2,3-diphenyl-1-propene (2.2),
3,4-diphenyl-1-butene (0.5) 2,3-diphenylbutadiene (2.0),
1,2-diphenylethylene (6.5), 1,4-diphenylbutane (3.5)
1,4-diphenyl-1-butene (3.8) 1,4-diphenyl-1-pentene (1.3)
References page II - 475
II/ 462 PRODUCTS OF THERMAL DEGRADATION OF POLYMERS
TABLE 1. contd
Polymer Temperature range (C) Degradation products Refs.
-, (poly(diviny1 benzene))
-, (poly(triviny1 benzene))
-, u-acetoxy-
-, m-amino-
-, p-chloro-a-methyl-
-, cl-deutero-
-, bdeutero-
-, p-fluoro-a-methyl-
-, p-methoxy-a-methyl-
-, 3-methyl-
-, 4-methyl-
Poly(o-propionylstyrene)
-, u-methyl-
-, p-N,N-diethylamino-
-, m-N,N-dimethylamino-
Ambient to 600
385-450
470-500
270
340-500
320-500
Ambient
334-387
345-384
Ambi ent
Ambi ent
309-399
200-350
560
385
200-500
520- 1200
Ambient
400-900
350-500
350-500
1,3-diphenylpropadiene (2. l), 1,2-diphenylbutadiene ( 1.8),
1,4-diphenylbutadiene (1.9), 1,3,4-triphenylbutene (0.6) 1,2,5-triphenyl-
pentane (1.5) 1,2,5-triphenyl-1-pentene (4.6), 2,3,6-triphenyl-1-hexene
and 2,5,6-triphenyl-l-hexene (8.9), 1,4,5-triphenyl-1-pentene (4.4)
Styrene, 1,2-diphenylethene, 1,2-diphenylpropane, 1,4-diphenylbutane, 271
1,4-diphenyl-1-butene, 1,4-diphenylpentane, 4,5-diphenyl-1,8-octadiene,
2,3,6-triphenyl-l-hexene, 1,4,5-triphenyl-1-pentene
Volatile products include toluene, benzene, styrene, and xylene 11,64
Mixture of aliphatic and aromatic hydrocarbons 11,64
Acetic acid (99%), mixture of a-acetoxystyrene and acetophenone (1%) 1 6 7
Gaseous fraction COz, CH4, CzH6, CsHe, CsHs; liquid fraction 6 5
m-aminostyrene, m-toluidine; gum fraction mainly dimer and trimer;
crosslinked residue remains
Monomer yield rises from 41% (320C) to 61%(5OoC); minor product is 66
m-toluidine, with traces of aniline, m-ethylaniline, a-methyl-
m-aminostyrene, Hz. CO2, CH4; remainder comprises chain
fragments and residue
Gamma radiolysis: CH4 (12.9 relative mass spec. ion current), CzHe 168
(21.8), C3H6 (13.6), CsHs (10.5), C4H,a (61), HCl (4.2), CHaCl
(17.4) CsH&l (20) CzHsCl (28.1) CsHCl (3.3) CH2C12 (9.9)
CsHsCl (3.0), p-chlorostyrene (1.5), p-chloro-a-methyl styrene (12.5)
68.4% monomer, 1.5% u-deuterostyrene, 0.6% a-methylstyrene, 2,13
29.5% larger chain fragments
39.7% monomer, 1,2% toluene, 0.1% deuterotoluene, 59% larger 2,13
chain fragments
Gamma radiolysis: CH4 (0.4 relative mass spec. ion current), CsH4 1 6 8
(3.0), C3H6 W), C3H8 W3h C4H4 (3.5), C4H6 (6.01, C3H7F (W,
C4H3F (6.0), C4H9F (14.5) CsHsF (9.37), C6HsF (29),
p-fluorotoluene (23), p-fluorostyrene (6.45), p-fluoro-a-methyl
styrene (175.5) p-fluoro-isopropyl benzene (11.5)
Gamma radiolysis: CH4 (32 relative mass spec. ion current), Hz0 (26), 1 6 8
C2H4 (35), C3H4 (7.3), C3H6 Cl=), C3Hs (68.7), C4H10 WV,
CHsOH (24.2), phenol (63.8), methoxybenzene (38.6),
p-methoxytoluene (19.6)
44.4% monomer, 7.3% xylene, 48.3% larger chain fragments 3
Ratio of monomer to oligomer rises from 40% at 200C to 95% at 350C 79
C t -C4 hydrocarbons, benzene, toluene, ethylbenzene, styrene, 278
ethyltoluene, vinyltoluene, naphthalene, ethylstyrene
CO, CH4, ethane, ethene, butane, 2-propionylstyrene, 2-propionyltoluene, 313
styrene, toluene, a-methylstyrene, a-methyl-2-propionylstyrene,
various dimeric and trimeric species not fully characterized
95- 100% monomer 2 8
Fragments both larger and smaller than monomer appear in increasing 28
amounts the higher the temperature, particularly CH4, C2H4. and
C6H6 until at 1200C the monomer yield is only 33.9%
Gamma radiolysis: CH4 (1.0 relative mass spec. ion current) CzH6 (1.2), 1 6 8
C3H4 (6.7) C3H6 (1.81, C3H8 (2.71, C4H4 (2% C4H10 (9.9),
cyclopentadiene (6.1), benzene (72.8), toluene (20), styrene (50.5),
a-methyl styrene (184), isopropyl benzene (10)
Benzene, toluene, ethylbenzene, cumene, styrene, a-methyl styrene, 169
indene/phenylpropyne, methyl-1,2-dihydronaphthalene, methylene
indene, naphthalene, 2-methylnaphthalene, 1-methylnaphthalene,
biphenyl, anthracene/phenanthrene, dihydropyrene
Toluene, styrene, p-ethylstyrene, N,N-diethyl-p-toluidine, N,N-diethyl- 170
p-ethylaniline, p-N,N-diethylaminostyrene, cc-methyl-N,N-diethylamino-
styrene, 2-(p-N,N-diethylaminophenyl) butane, u-propyl-p-N,N-diethyl-
aminostyrene, N-ethyl-p-toluidine, N-ethyl-p-toluidine, N-ethyl-
p-ethylaniline, N-ethyl-p-aminostyrene and closely related compounds
m-N,N-Dimethylaminostyrene, N,N-dimethyl-m-toluidine, m-xylene, 1 7 1
styrene, N,N-dimethyl-m-ethylaniline, toluene, m-methylstyrene,
cl-methyl-m-N,N-dimethylaminostyrene, truns+Lmethyl-m-N&
dimethylaminostyrene, u-ethyl-m-N,N-dimethylaminostyrene,
N-methyl-m-toluidine, N-methyl-m-ethylaniline,
N-methyl-m-aminostyrene, oligomers of m-N,N-dimethylaminostyrene
and closely related compounds
TABLE 1. contd
Mai n-Chai n Acycl i c Carbon Pol ymers I I / 463
Polymer Temperature range (C) Degradation products Refs.
-, p-N,N-dimethylamino-
Poly(p-(2,4-dichlorobenzyl)styrene) Ambient to 500
-, p-isopropyl-a-methyl-
-, 2,3,4,5,6-pentafluoro-
a,~,IWifluoro-
Polystyrene (chain brominated
on a-position)
Poly(styrene-co-methylene)
N -CH-CH2-CH2-CH-(CH2)n N fi
i = 0134anda
, , ,
Poly(styrene-co-SOz) (1.85 : 1)
Poly(styrene-co-methacrylic acid)
18, 44 and 72 mol% MAA
Poly(styrene-co-chlorotrifluoroethylene)
7.7, 14, 20 mol% CTFE
Poly(styrene-co-glycidyl
methacrylate) 10, 23, 51, 62,
78. 86 mol% GMA
Poly(styrene-co-phenyl methacrylate)
lo-90 mol% PMA
Poly(styrene-co-1,2,2,2,-tetra-
chloroethyl acrylate) (4.7/1)
Poly(styrene-co- 1,2,2,2-tetra-
chloroethyl methacrylate) (3.8/1)
Poly(styrene-co-bis-( 1,2,2,2-tetra-
chloroethyl)fumarate) (8.9/1)
Poly(styrene-co-bis-(1,2,2,2-tetra-
chloroethyl) muconate) (7.72/1)
Poly(styrene-co-N-(2,4,6-tribromophenyl)-
maleimide) (6.4/1)
500 for
30 min
Ambient
390-446
333-382
150- 300
300-500
Ambient to 500
350 for 4 hr
200
Ambient to 500
Ambient to 500
Ambient to 500
Ambient to 500
310 and 500
3 10 and 500
310 and 500
310 and 500
310 and 500
NJ-dimethylaniline (0.2% of original polymer weight), N,N-dimethyl-
p-toluidine (2.8%) N-methylaniline (0.4%), N,N-dimethyl-p-ethylaniline
(0.4%), N-methyl-p-toluidine (0.4%), N-methyl-o-toluidine (0.4%),
p-toluidine (0.4%), N-methyl-p-ethylaniline (0.4%) p-NJV-dimethyl-
aminostyrene (36.3%), a-methyl-p-NJ-dimethylaminostyrene (0.7%)
Benzene, toluene, ethylbenzene, styrene, a-methylstyrene,
1,3-dichlorobenzene, 2,4-dichlorotoluene, monomer (major product),
complex series of halogenated and dehalogenated chain fragments
(see Ref.)
Gamma radiolysis: CH4 (8, relative mass spec. ion current), CaH4 (4.6),
C3H4 (7.21, C3H.5 (21.2), C3Hs (108), C4Hm, (57. 4)
63% of the products are volatile at 25C - contains some monomer
72% monomer, 28% larger chain fragments
HBr, trace styrene
Styrene, HBr, toluene, benzene
HBr, styrene, traces of toluene and benzene, p-bromostyrene
Benzene, toluene, ethylbenzene, styrene (major volatile product), n-pro-
pylbenzene (except with n = 2), phenylpropene, butylbenzene (except
with n = 0), phenylbutene (with n = 4 and 5 only), amylbenzene
(with n = 4 and 5 only) hexylbenzene (with n = 4 and 5 only), chain
fragment fraction (major product)
At 26.7 mbar pressure; 40% weight loss; main product is 2,4-diphenyl
thiophene; at least 11 unidentified minor products
COz, HaO, butene, isobutene, dimethyl ketene, styrene, methacrylic
acid, succinic-type 5-membered cyclic anhydrides
Chlorotrifluoroethylene, styrene, HCl, chloropentafluoropropene,
ethene, chloroethene, toluene, a-methylstyrene, dimer and trimer
structures with some unsaturation; SiF4 (from reaction of HF with
glass). Distribution of products varies with polymer composition
CO, C02, propene, isobutene, dimethyl ketene, acrolein, ally1
alcohol, toluene, styrene, cl-methylstyrene, ethylbenzene, glycidol,
glycidylmethacrylate; product distribution depends on copolymer
composition
CH4, CO, COz, propene, dimethyl ketene, toluene, styrene,
4-phenylbutene, 4-phenyl-2-methylbutene, phenyl methacrylate,
cl-methylstyrene, short chain fragments
Styrene, benzene, toluene, ethylbenzene, a-methyl styrene, diphenyl,
5,6-benzo-2-methyl-3,5-cyclohexadienone, diphenylethane,
1,3-diphenylpropane, dimers and trimers of styrene,
chloroacetaldehyde, dichloroacetaldehyde, trichloroacetaldehyde,
trichloropropanal
Styrene, benzene, toluene, allylbenzene, a-methylstyrene, indane, iso-
propenylstyrene, 5,6-benzo-2-methyl-3,5-cycle-hexadienone,
propyl-propenylbenzene, diphenylethane, 1,3-diphenylpropane, dimers
and trimers of styrene chloroacetaldehyde, dichloroacetaldehyde,
trichloroacetaldehyde, trichloropropanal, benzyl chloride,
2chloroethylstyrene, 2,2-dichloroethenyl methacrylate,
1,2,2,2-tetrachloroethyl methacrylate
Styrene, benzene, toluene, ethylbenzene, allylbenzene, cc-methylstyrene,
indane, diphenyl propylpropenylbenzene, diphenylethane,
1,3-diphenylpropane, dimers and trimers of styrene,
chloroacetaldehyde, dichloroacetaldehyde, trichloroacetaldehyde,
benzyl chloride
Styrene, benzene, toluene, ethylbenzene, a-methylstyrene, diphenyl,
propylpropenylbenzene, diphenylethane, 1,3-diphenylpropane, dimers
and trimers of styrene, chloroacetaldehyde, dichloroacetaldehyde,
trichloroacetaldehyde, trichloropropanal, benzyl chloride
Styrene, benzene, toluene, ethylbenzene, allylbenzene, a-methylstyrene,
indane, diphenylethane, 1,3-diphenylpropane, dimers and trimers of
styrene, N-(2,4,6&bromophenyl) maleimide, N-dibromophenyl
maleinimide
172
275
1 6 8
6 7
1 4
271
271
271
1 7 3
68
294
261
264
280
174
174
174
174
174
References page II - 475
II / 464 PRODUCTS OF THERMAL DEGRADATION OF POLYMERS
TABLE 1. contd
Polymer Temperature range (C) Degradation products Refs.
Poly(styrene-co-N-(pentachlorophenyl)-
maleimide) (4.9/1)
Poly(styrene) 1: 1 (w/w) blend
with bisphenol A polycarbonate
Poly(viny1 toluene-co-
divinyl benzene) lo-50% DVB
Poly(4-methoxystyrene)
1 : 1 (w/w) blend with
bisphenol A polycarbonate
310 and 500
Ambient to 500
560
Ambient to 500
Styrene, benzene, toluene, ethylbenzene, allylbenzene, a-methylstyrene, 1 7 4
indane, diphenylethane, 1,3-diphenylpropane, dimers and trimers of
styrene, pentachlorophenyl isocyanate, N-pentachlorophenyl formamide,
N-tetrachlorophenyl maleinimide, N-(pentachlorophenyl) maleimide,
methyl maleic acid pentachlorophenylimide
CO* styrene, a-methylstyrene, p-cresol, phenol, p-ethylphenol, 272
p-vinylphenol, p-isopropylphenol, polystyrene short chain fragments
with vinylidene and saturated ends, polycarbonate cyclic dimer and
chain fragments, bisphenol A
C 1 -Cd hydrocarbons, benzene, toluene, ethylbenzene, styrene, 278
ethyholuene, cc-methylstyrene, vinyltoluene, divinylbenzene,
naphthalene, ethylstyrene; distribution varies with copolymer
composition
CO*, 4-methoxystyrene, cc-methyl-4-methoxystyrene, p-cresol and other 272
phenols in small amounts, poly(4-methoxystyrene) dimer and
trimer with vinylidene and saturated ends, polycarbonate cyclic
dimer and chain fragments, bisphenol A
TABLE 2. MAIN-CHAIN CARBOCYCLIC POLYMERS
Polymer Temperature range (C) Degradation products Refs.
Poly(@,E)-
[6,2]paracyclophane-1,5-diene)
Poly(perfluoro-m-phenylene)
Poly(perfluoro-p-phenylene)
high molecular weight (15000)
low molecular weight (3700)
Poly( 1,4-phenylene)
->
2-hydroxy-
Polv( 1.4~nhenvlene ethylene)
460, 515, 620
700
700
700
250-620
300-620
420-465
Primary product is monomer; in addition, a series of secondary products 251
based on ring-opened monomer are formed by H-abstraction (see
Ref.); also detected: toluene (not 460C) and p-xylene
Volatiles comprise SiF4 (from silica vessel), CO*, with traces of CsF6 50
and CGFSH; white sublimate on vessel walls; residue contains 1%
fluorine
Volatiles comprise SiF4 (from silica vessel), CO*, with traces of 50
ChF6 and Cr,FjH; white sublimate on vessel walls; residue contains
1% fluorine
Volatiles comprise SiF4 (from silica vessel), CO*, with traces of 50
CsF6 and CeFsH; no white sublimate; residue contains 33-41%
fluorine
79% residue, 10% chain fragments, 11% volatiles comprising Hz, CH4, 5 5
H20, HCl (from catalyst)
60% residue, 24% chain fragments, 16% volatiles comprising CO, CO2 5 5
HZ, CH4
3.6% of products are volatile at 25C and consist of 2.83% xylene, 13,14,80
408-515
436-475
Poy( 1,3-phenylene-hexafluoro-
trimethylene
660 for 30 s
Poly( 1,4-phenylenemethylene) 386-416
Poly cc-(ethoxycarbonyl-vinyl)-w- 320-360 for
[4-(ethoxycarbonyl-vinyl)-phenyl] 1 h under N2
(1,4-phenylene-2,4-bis-ethoxycarbonyl-
1,3-cyclobutylene)
Et OCOCH=CH~~ +H= CHCOOEt
0.29%-toluene, 0.28% methylethyl benzene, 0.14% methylstyrene,
0.06% benzene, products involatile at 25C consist of dimeric-
octameric fragments
Mainly chain fragments (dimer-pentamer); traces of HZ, monomer
Hz, CH4, CzH4, C 2H6, toluene, p-xylylene, p-ethyltoluene, p-methyl-
bibenzyl, 1,2-di-p-tolylethane, 4,4-dimethylstilbene
CzF4 (21.6% of original weight of polymer), HF (17),
(72 F2
u1+Q$
CF, (13.9%), CsHs(CF&GjHs (lO.Z%),
CF, CF,
CsH6 (8.5%), c6H5(CF2)$6H5 (7.9%)
7.4% of products are volatile at 25C; 5.9% toluene, 1.4% benzene,
0.1% xylene
Low-molecular-weight polymer and small amount of monomer
81
176
1 7 7
13,14
1 9 5
L COOEtl n
TABLE 3. MAIN-CHAIN HETEROATOM POLYMERS
Mai n- Chai n Het eroat om Pol ymers II / 465
Polymer Temperature range (C) Degradation products Refs.
3.1. POLY(OXIDES) AND POLY(KETONES)
Poly(fluoro ethers)
a . fO-CH2-(CFa)sCHa0-CHZ&r
b . --fOCHa(CFz)sCHzO-p-CsF4&-
c . +OCH~(CFZ)~CHZO-P-C~F~-@~F~#~~
d . fOCH2(CF2)3CHa0-m-C5NFs&
Poly(oxybutylethylene)
Poly(oxy-2,5-dimethoxy-1,4-phenylene)
Poly(oxy-2,6-dimethyl-1,4-phenylene)
Poly(oxyetbylene)
Poly(oxymethylene)
Poly(oxymethyleneoxyethylene)
Poly(oxy-2-metbylphenylene)
Poly(oxy-1,3-phenylene)
Poly(oxy-1,4-phenylene)
Poly(oxy-1,4-phenylene)-
blend-polystyrene (60 : 40)
Poly(oxypropylene) atactic
isotactic
Poly(oxytetramethylene)
Poly(oxytrichloromethy1 met hyl ene)
(Poly(trichloro acetaldehyde))
510-540
CHs-(CFa)sCHa- OCH3 (46.9%) relative areas of glc traces,
CH3(CFz)3CH3(14%), CH3CF2CF2H (6.7%),
CF2=CH2 (6.7%), CF2H-CF2H (2.3%)
CF2=CH2 (17.0%), CH3(CF2)3H (16.5%),
CF2HCF2H (6.4%) CH3CF2CF2H (4.1%),
/a2\
CsFSH (9.6%), C,F,, ,CF2 (9.4%),
CF,
1 7 8
Ce,FsCHO (7.2%), CsF4HCHO (4.9%), C6FbHa (3.3%)
HF (31%) CF2=CH2 (22.0%), CH3(CF2)3H
(19.7%) CFaHCF2H (10.1%) CsF5CsF4H (5.6%),
c6F4- CF2,
,CF2 (8.1%) c@4HC6F4H (9.3%)
C,F,- CF,
HF (50%), CH3(CF2)3H (27.6%) CF2=CH2
(7.8%), CF2HCF2H (4.3%),
/CFZ\
CS~3\
,cFz (5.6%), C5NF3H2 (3.1%)
CF2
321- 365
100- 550
100- 550
400-550
Mixture of saturated and hydrocarbons (C t-C 6), aldehydes
(cl-CSh HZ, H20
41% residue, 29% fragments, 30% volatiles comprising HZ, CH4, CO,
COz, CHsOH, traces of H20, C2H6, other hydrocarbons
26% residue, 66% chain fragments, 8% volatiles comprising Ha, CH4,
H20, CO, CO2
o-Cresol, 2,6-dimethyl phenol, 2,4-dimethyl phenol,
2,4,6-trimethyl phenol, various ketones, dimers, and more
complicated structures (see Ref.), various combinations of the
monomeric skeletons
20
5 5
5 5
179
324-363 9.7% of products volatile at 25C-3.9% monomer with smaller
amounts of COa, formaldehyde, ethanol, and saturated and C t-C.1
compounds
2 5
280
222
100- 180
Diethyl ether, ethyl methyl ether, acetaldehyde, formaldehyde,
COa, CO, ethene, cyclohex-3-ene-l-one
100% Monomer
252
100% Formaldehyde; inverse relationship between molecular weight and
rate for hydroxyl terminated polymers; acetylation of terminal hydroxy
groups inhibits the reaction
27
1 8 1
314-338
250-500
300-620
550
Major volatile products CH4, CaHe, CaH4, CaHa, HCOaCaH5
p-Xylene, phenol, 2-methylphenol, 4-methylphenol, 2,4-dimethylphenol,
and a variety of more complex structures (see Ref.)
34% Residue, 53% chain fragments, 13% volatiles comprising HaO, CO,
Hz, CH4, CO2, trace of C6H6
20
180
55
Hydroquinone, phenol, benzene, diphenylether,
4,4-dihydroxydiphenylether, 4-phenoxyphenol. In addition, a broad
spectrum of phenyl and phenolic terminated oligomers with up to
10 aromatic units
255
585
300-360
As 550C plus dibenzofuran and dibenzofuran-containing oligomers
Ethylbenzene, styrene, a-methylstyrene, 2-methylphenol,
2,6-dimethylphenol, 2,4-dimethylphenol, 2,4,6-trimethylphenol,
1,3-diphenylpropane, 2,4-diphenyl-1-butene, 2,4,6-triphenyl-l-hexene,
PPO dimers
255
318
270-330
275- 355
347
12.8% of products volatile at 25C, including 4.00% acetaldehyde, 2.22%
acetone, 1.43% dipropyl ether and 0.75% propylene
20% of products volatile at 25C including 6.34% acetaldehyde, 2.39%
acetone, 2.19% dipropyl ether, and 2.22% propylene
Volatiles COmpIiSe a mixture of CH4, C2H6, CsHs, C4Hra, C2H4,
C3Hs, CH3CH0, C2HsCH0, C3H7CH0
25
25
20
Ambi ent Monomer 182
References page II - 475
II / 466 PRODUCTS OF THERMAL DEGRADATION OF POLYMERS
TABLE 3. contd
Polymer Temperature range (C) Degradation products Refs.
Poly(oxy- 1 ,Cphenylene-
carbonyl-1,4-phenylene)
(Poly(ether ketone), PEK)
Poly(oxy- 1,4-phenylene-
oxy- 1 ,Cphenylene
-carbonyl- 1 ,Cphenylene)
(Poly(ether ether ketone),
PEEK)
Poly(etherketone-co-
ethersulphone)
Moleratio 1:3,3:1, 1:l
(random), 1: 1
(alternating)
3. 2. POLY(ESTERS)
Poly(3-oxybenzoyl)
Poly(4-oxybenzoyl)
Poly(oxycarbonyl-1,3-phenylene-
hexafluoroisopropylidene-1,3-phenylene
carbonyloxy- 1,3-phenylene-hexafluoro-
isopropylidene-1,3-phenylene)
Poly(oxycarbonyl-1-chloroisopropylidene)
Poly(oxycarbonylcyclohexylidene)
Poly(oxycarbonylcyclopentylidene)
Poly(oxycarbonyl-3-pentylidene)
Poly(oxyethyleneoxyterephthaloy1)
(Poly(ethylene terephthalate))
Polyester from terephthaloyl
chloride and n = 4
polyethylene glycol
Polyester from terephthaloyl
chloride and n =22
polyethylene glycol
390, 490, 530
506
506
330
505-565
253-384
200-500
200-500
200-300
283-306
900
Ambient to 500
Ambient to 500
Low MW polymer at 490C produces benzene, phenol, benzaldehyde, 250
4-hydroxybenzaldehyde, diphenyl ether, biphenylene, benzophenone,
series of -H, -OH and -CHO terminated chain fragments containing
< 8 aromatic units and fragments containing dibenzofuran units.
High MW polymer at 530C as above. Low MW polymer at 390C
produces significant quantities of 4-hydroxy benzaldehyde and
benzophenone-4,4-diol
Phenol, dibenzofuran, benzofuran derivatives, mixtures of oligomers
mostly hydroxy terminated
315
Phenol, dibenzofuran, benzofuran derivatives, mixtures of oligomers
mostly hydroxy terminated
315
All polymers have same products with distribution varying with 250
composition. Biphenyl, hydroquinone, 4-phenoxyphenol, benzaldehyde,
4-hydroxybenzaldehyde, diphenyl sulphone, diphenylether, phenol,
benzophenone-4,4-diol. Also two series of chain fragments containing
PEK and PES units with -H, -OH and -CHO ends. Analogous fragments
with biphenyl units
Monomer, cycl i c di mer-hept amer 1 8 7
CO, CO*, phenol, p-hydroxy phenyl benzoate 1 9 7
HF (12%) cyclic structures (see Ref.) 1 7 7
HCl and a compound with a glycollidic structure
Cyclohexen-1-carboxylic acid, cyclohexanone
Cyclopenten-1-carboxylic acid, cyclopentanone, dicyclopentyl glycollide
Cis- and nuns-2-ethyl crotonic acid (major products)
Acetaldehyde major gaseous product with COz, CO, CzH4, HzO, CH4,
benzene, 2-methyl-dioxolane, terephthalic acid, and more complex
chain fragments
1 8 5
1 9 8
1 9 8
1 8 8
26
CO, CH4, COz, ethylene, acetylene, ethane, HzO, propylene, ethanal,
acetone, propanal, ethanol, benzene, toluene, ethyl benzene, styrene,
p-vinyl toluene, benzaldehyde, p-ethyl toluene, acetophenone, methyl
benzoate, vinyl benzoate, ethyl benzoate, p-methyl acetophenone,
benzoic acid, p-methyl vinyl benzoate, p-vinyl acetophenone, propyl
benzoate, p-ethyl vinyl benzoate, p-vinyl vinyl benzoate,
biphenyl, 1-hydroxy ethyl benzoate, diacetyl benzene, p-acetyl
vinyl benzoate, divinyl terephthalate, ethyl vinyl terephthalate,
ethyl vinyl terephthalate, p-acetyl benzoic acid, methyl 1 -hydroxyethyl
terephthalate, ethylene dibenzoate
192
CO, CH4, COz, ethene, ketene, acetaldehyde, 1,4-dioxane, toluene,
benzaldehyde, vinylbenzoate, divinylterephthalate, benzoic acid,
terephthaldehydic acid, terephthalic acid, hydroxyethyl methyl
terephthalate, short chain fragments
CO, CH4 (trace), COz, ethene (trace), formaldehyde, acetaldehyde,
1,3-dioxalane, ethoxyacetaldehyde, 1,4-dioxane, glycidol, diethylether,
l,Zdimethoxyethane, 2-methoxyethanol, 2-ethoxyethanol,
-CHzCHzCOCHz-(ring), HOCHzCHzOCHzCHO,
CHsOCH2CHzOCzHs, terephthalic acid, triethylene glycol,
tetraethylene glycol, chain fragments
CO, CH4 (trace), COz, ethene (trace), formaldehyde, acetaldehyde,
1,3-dioxalane, methoxyacetaldehyde, 1,4-dioxane, 7-membered cyclic
ether, methyl benzoate, ethyl benzoate, benzaldehyde,
-CHzCH$OCHz-(ring), HOCH2CHzOCH2CH0,
CHs0CHzCH20C2Hs, -(CH2CH20)zCHzCO-(ring),
CHz=CHOCH2CH20CH2CH0, HO(CHzCHz0)2CzHs,
C2Hs(OCH2CH2) sH, terephthalic acid, triethylene glycol, tetraethylene
glycol, chain fragments
298
274
274
TABLE 3. contd
Mai n- Chai n Het eroat om Pol ymers II / 467
Polymer Temperature range (C) Degradation products Refs.
Poly(oxyisophthaloyl-oxy- 1,3-phenylene) 330
Poly(oxyisophthaloyl-oxy- 1 ,Cphenylene) 330
Poly(oxy- 1 -oxohexamethylene)
Poly((o)-oxy-1-oxo-3-methyl-trimethylene)
(Poly(3-hydroxybutyrate))
Poly((~)-oxy-1-oxotetramethylene)
(Poly(4-hydroxybutyrate))
Poly(oxy-1-oxo-2-
methylethylene)
(Poly(l-lactic acid))
Poly(oxy-1-oxo-2,2-dimethyltrimethylene
(Poly(a,a-dimethyl+propiolactone))
Poly(oxy-1-oxo-trimethylene)
(Poly( P-propiolactone))
Poly(oxyterephthaloyloxy-
1,2-phenylene)
Poly(oxyterephthaloyloxy- 1,3-phenylene)
Poly(oxyterephthaloyloxy- 1,4-phenylene)
Poly(oxyterephthaloyloxy-4,4-
diphenylene)
Poly(oxytetramethyleneoxyterephthaloy1)
(Poly(butylene terephthalate))
Poly(oxydecamethylene-
oxyterephthaloyl)
Poly(oxyethyleneoxyadipoy1)
Poly(oxytetramethylene-
oxysebacoyl)
Polyester from maleic anhydride,
hexolic acid and butanediol;
mole ratio 1 : 1 : 2.2
220
Ambient to 338
250
400
600
350
320
500
250-600
180- 220
Ambient to 500
345
Ambient to 500
350
Ambient to 500
Ambient to 500
240-280
200-400
Ambient to 500
Ambient to 500
Ambient to 500
Ambient to 500
100- 440
Cyclic monomer (10 relative abundance), cyclic dimer (83.5), cyclic
trimer (24.5), benzoic acid, isophthalic acid, resorcinol and various
fragments of the main chain (see Ref.)
Cyclic dimer (17), cyclic trimer (4), m-phthalic acid (26), benzoic acid
(7.5), hydroquinone (46) and various fragments of the main chain
(see Ref.)
Monomer (c-caprolactone)
Dimer (41.2 wt.%), crotonic acid (35.3), trimer (12.5), tetramer (2.9),
iso-crotonic acid (0.9). Small amounts of CO2, propene, ketene,
acetaldehyde, and P-butyrolactone are formed at higher temperatures
due to decomposition of primary products
Crotonic acid (64.4% of original polymer), dehydrated dimer (7.2%),
dehydrated trimer ( 1.2%)
Crotonic acid (65.4% of original polymer), dehydrated dimer (8.2%),
dehydrated trimer (2.1%)
Crotonic acid (58.3% of original polymer), dehydrated dimer (9.0%),
dehydrated trimer (2.7%)
Crotonic acid (truns), dehydrated dimer (truns), dehydrated trimer and
tetramer (cisltrans not resolved)
Cyclic oligomers (y-butyrolactone and higher homologues)
CO, COa, acetaldehyde, acetone, acrylic acid, acetic acid, LX-lactide,
meso-lactide, cyclic oligomers up to nonamer, 2,3 pentanedione (?),
lactoyl lactic acid (?)
Isobutylene and CO a
Acrylic acid
COa, benzene, phenol, benzaldehyde, catechol, cyclic dimer
1 8 7
187
184
186
245
245
245
246
257
282
1 8 3
189
285
Cyclic dimer (2), cyclic trimer (0.3), terephthalic acid (0.4), benzoic acid 1 8 7
(1.5), resorcinol (20) and various fragments of the main chain (see Ref.)
COa, benzene, phenol, benzaldehyde, biphenyl, benzoic acid, 285
3-hydroxyphenylbenzoate, resorcinol, mono and di(3-hydroxyphenyl)
terephthalate, terephthalic acid, terephthaldehydic acid, short chain
fragments
Cyclic dimer (O.l), terephthalic acid (0.5), benzoic acid (6), hydroquinone 187
(40.5), and various fragments of the main chain (see Ref.)
Benzene, phenol, benzaldehyde, biphenyl, benzoquinone, 285
4-hydroxyphenylbenzoate, benzoic acid, mono and di(4-hydroxyphenyl)
terephthalate, terephthalic acid, terephthaldehydic acid, short chain
fragments
COa, benzene, phenol, benzaldehyde, biphenyl, 4-phenylphenol,
p,p-dihydroxybiphenyl, 4-hydroxybiphenylbenzoate,
di(4-hydroxybiphenyl) terephthalate
285
Butadiene, terephthalic acid, mono-3-butenyl terephthalate, and
di-3-butenyl terephthalate
190
Tetrahydrofuran, 1,3-butadiene, CO*, CO, HaO, benzoic acid, tereph- 1 9 1
thalic acid, terephthalic acid mono-3-butenyl, toluene, phenol, benzene
CO, CO 2, butadiene, tetrahydrofuran, toluene, benzene, 1,5-hexadiene, 298
dihydrofuran, 4-vinyl cyclohexene, 1,Cbutane diol, benzaldehyde,
benzoic acid, terephthaldehydic acid, terephthalic acid, mono-3-butenyl
terephthalate, cyclic dimer, short chain fragments
CO, COz, 1,9-decadiene, l,lO-decane diol, I-decene-10-01, benzoic acid, 298
terephthalic acid, mono-decenyl terephthalate
Cyclic oligomers, CO, CO*, acetaldehyde, 2-ethylacrolein 269
CO*, HaO, butadiene, tetrahydrofuran 299
Tetrahydrofuran, 1-butanol, toluene, maleic anhydride, chlorosuccinic 311
acid isomers, chlorovalerolactone isomers, hydroxypyran, allylpyran,
trichlorocylopentadiene, tetrachlorocylopentadiene,
pentachlorocylopentadiene, hexachlorocylopentadiene, phthalic anhydride,
1,4-butanediol, 1 ,Cbutanediol dibenzoate, benzoic acid,
4-cyclohexene-1,2-dicarboxylic acid anhydride, benzoic acid butenyl
ester, cyclohexadiene carboxylic acid propyl ester, hexolic anhydride,
References page II - 475
II / 468 PRODUCTS OF THERMAL DEGRADATION OF POLYMERS
TABLE 3. contd
Polymer Temperature range (C) Degradation products Refs.
Polyester from maleic anhydride,
phthalic anhydride and
butanediol; mol ratio
1 : 1 : 2.2
Unsaturated polyester resins
a. Maleic acid-phthalic acid-propylene
glycol-styrene
b. Maleic acid-tetrabromophthalic
acid-phthalic acid-propylene glycol-
styrene
c. Maleic acid-phthalic acid-
dibromoneopentyl glycol-styrene
3. 3. POLY(CARRONATES)
Poly(oxycarbonyloxy-1,3-phenylene)
Poly(oxycarbonyloxy-1,4-phenyleneisopropyl-
idene- 1,4-phenylene)
100- 440
300-800
270
300-389
200-400
290
Ambient to 500
Poly(oxycarbonyloxy- 1,4-phenylene-
isopropylidene- 1,4-phenylene-oxy-caonyl-
tetramethylene)
Poly(oxycarbonyloxy-1,3-phenylene
hexafluorotrimethylene- 1,3-phenylene)
Poly(oxycarbonyloxy-lp-phenylene-
oxycarbonyloxy-tetramethylene)
Poly(oxycarbonyloxy- 1 ,Cphenylene-
phthalidylidene-1,4-phenylene)
300
315
240
210
350
Poly(trimethylene carbonate)
Poly(neopentylene carbonate)
Poly(2-phenyl trimethylene
carbonate)
Ambient to 500
Ambient to 500
Ambient to 500
3. 4. POLY(ANHYDRIDES)
Poly(oxycarbonyl-1,3-phenylene-
hexafluorotrimethylene-1,3-phenylene-
carbonyl)
Poly(maleic anhydride-co-trans
stilbene) (alternating copolymer)
350
Ambient to 500
3.5. POLY(SULFIDES) AND POLY(SULFONES)
Poly(thioacetone) 1 4 5
Poly(thioethylene) 220-260
Poly(thio- 1,4-perfluorophenylene) 500
Poly(thiomethylene- 1,4- 250-350
phenylene-methylene)
unidentified butenyl ester, compound containing CsHCls unit,
CH3-CH=CH-CH2-0-CH3, CH3-CH=CH-CH2-0-CH=CH2,
Cl-CH=CH-0-CH2-CH3
Tetrahydrofuran, I-butanol, 3-butene-1-01, toluene, maleic anhydride,
phthalic anhydride, 1,4-butanediol, 1,4-butanediol dibenzoate, phthalic
acid butenyl ester, various esters containing butenyl, maleate and
phthalate units, CH3-CH=CH-CH2-O-CH3,
CH3-CH=CH-CH2-0-CH=CH2
Ethane (above 6OOC), propionaldehyde (above 4OOC), styrene (major
product), phthalic anhydride (major product), benzene (above (45oC),
toluene (above 5OoC), xylene (above 400C)
Styrene (major product), phthalic anhydride (major product), benzene
(above 55oC), toluene (above 450C). xylene (above 500C)
Ethane (above 5OoC), propionaldehyde (above 4ooC), styrene (major
product), phthalic anhydride (major product), benzene (above 5OOC),
toluene (above 5OOC), xylene (above 500C)
Cyclic trimer, tetramer, and pentamer, and various chain fragments
Major products: CO2, bisphenol A, minor products: CO, CH4,
4-alkyl phenols
CO, COz, CH4, phenol, diphenyl carbonate, 4-(4-hydroxyphenyl)-2-
phenyl propane
Cyclic dimer, cyclic trimer, bisphenol A, and other chain fragments
CO, CH4, CO2, H20, phenol, p-cresol, p-ethyl phenol, p-isopropyl
phenol, p-vinyl phenol, bisphenol A, cyclic dimer, chain fragments
including some ester structures
Phenol, p-cresol
CO 2, phenol, p-cresol
Cyclic monomer and dimer, and higher cyclic fragments
HF (3%), cyclic dimer
Cyclic dimer and trimer, and higher cyclic fragments
CO2, CO, 02, H20, phenol, fluorenone, diphenyl carbonate, xanthone,
anthraquinone, 2-hydroxyanthraquinone, 2-benzoxyanthraquinone,
phenolphthalein, traces of benzoxyphenol and hydroquinone
COz, Hz0 (possibly desorbed), trimethylene carbonate, cyclic oligomers
COz, monomer, oligomer
CO, CO2, Hz0 (possibly desorbed), a-methylstyrene, chain fragments
(85%, w/w)
Cyclic dimer
3 1 1
1 9 3
1 9 3
1 9 3
226
60
225
226
304
304
304
226
1 7 7
226
227
295
296
296
177
CO2, styrene, maleic anhydride; small amounts benzene, cyclohexadiene, 242
dimethylbutene, ethylcyclobutanol and 4-methoxystyrene; major products
(79%) are chain fragments, including aromatic, ketonic and unsaturated
structures
Main product is cyclic trimer [(CH3)2CS] 69
Ethylene, H#, ethanethiol 199
73% Residue; remainder, chain fragments, Hz, SiF4 (from silica vessel), 5 1
(32
Sulphur, styrene, thiobenzaldehyde, 4-methyl styrene, p-xylene,
4-ethyl toluene, HzS, 4-methyl thiobenzaldehyde, stilbene and chain
254
TABLE 3. contd
Main-Chain Heteroatom Polymers II / 469
Polymer Temperature range (C) Degradation products Refs.
650
Poly(dithiomethylene-1,4-
phenylene-methylene)
250-350
650
Poly(thio- 1,2-phenylene)
Poly(thio- 1,3-phenylene)
Poly(thio- 1,4-phenylene)
430
540
460
300-620
325-625
560
Poly(oxy- 1,4-phenylene-sulfonyl-
1,4-phenylene-oxy- 1,4-phenylene-
isopropylidene- 1,4-phenylene)
350-450
470 for 2 h
800
Poly(oxy- 1,4-phenylene-sulfonyl-
1 ,Cphenylene)
Poy(tris-(oxy-1,4-phenylene)-sulfonyl-1,4-
phenylene)
Poly(oxy-4,4-diphenylene-oxy-1,4-phenylene
sulfonyl- 1 ,Cphenylene)
Poly(oxy- 1,4-phenylene-sulfonyl- 1,4-phenylene-
oxy- 1 $phenylenemethylene- 1,4-phenylene)
Poly(sulfur dioxide-co-1-butene)
Poly(sulfur dioxide-co-l -hexene)
Poly(sulfur dioxide-co-1-octadecene)
Poly(sulfur dioxide-co-bicycloheptene)
Poly(sulfur dioxide-co-cyclopentene) 700-800
Poly(sulfur dioxide-co-cis-2-butene) 700-800
Poly(sulfur dioxide-co-methyl
methacrylate-co-1-hexene) (24.2/1)
Poly(sulfur dioxide-co-methyl
methactylate-co-bicycloheptene) (2.5/1)
700-800
700-800
470 for 2 h
550-600
800
700-800
700-800
700-800
700-800
fragments containing stilbene units, chain fragments containing polymer
repeat units with -CHzSH, -CH=S and -CHs terminal units
Toluene, ethylbenzene, p-xylene, 1,4-diethylbenzene, 4-ethyltoluene; 254
series of polycyclic aromatics containing phenanthrene and
dihydrophenanthrene
Sulphur, styrene, thiobenzaldehyde, 4-methyl styrene, p-xylene, 254
4-ethyl toluene, H#, 4-methyl thiobenzaldehyde, stilbene and chain
fragments containing stilbene units, chain fragments containing polymer
repeat units with -CHzSH, -CH=S and -CHs terminal units
Toluene, ethylbenzene, p-xylene, 1,4-diethylbenzene, 4-ethyltoluene;
series of polycyclic aromatics containing phenanthrene and
dihydrophenanthrene
Cyclic dimer (thianthrene), some cyclic trimer
Cyclic oligomers (trimer to heptamer) in decreasing yield
72% Residue; remainder chain fragments, HZ, dibenzthiophene
38% Residue, 47% chain fragments, 15% volatiles comprising mainly
H$S and HZ
Benzene, thiophenol, diphenyl, diphenylsulfide, dibenzothiophene,
chlorobenzene (from polymers with terminal chlorine atoms)
Cyclic oligomers tetramer to heptamer (pentamer dominates)
Phenol with smaller amounts of p-cresol, p-ethyl phenol, p-isopropyl-
phenyl phenol, bisphenol A, diphenyl ether, p-tolyl phenyl ether,
p-ethyl diphenyl ether, p-isopropenyl diphenyl ether, isomers of tolyl
(ethyl-phenyl)ether
In 90min at 45oC, 15% (of initial weight) of gaseous products are
formed; SO2 (76% of gaseous products), CO2 (15%), CO (4.5%),
CH4 (4.5%)
Benzene, toluene, p-xylene, isopropylbenzene, phenol (main product),
diphenyl oxide, diphenyl sulfide
SO*, benzene, toluene, styrene, phenol, methylphenol, diphenylether,
methyl diphenylether
Phenol (main product), diphenyl oxide
SO*, diphenylsulfone, phenol, diphenylether, hydroquinone,
benzenesulfonic acid, 4-hydroxybenzenesulfonic acid,
4,4-dihydroxydiphenylether, 4-phenoxyphenol; series of -H and -OH
terminated fragments up to trimer, series of compounds containing
consecutive diphenylether and dibenzofuran units, fragments containing
biphenyl units as a result of SO2 elimination; complex ring structures
with sulfonate links
254
258
258
5 1
59
200
258
201
202
203
288
203
255
SO*, benzene, phenol, diphenyl ether, dibenzofuran 288
Benzene, phenol (major product), diphenyl oxide, p-hydroxydiphenyl, or 203
p-hydroxydiphenyl oxide
Phenol (main product), diphenyl oxide 203
Benzene, toluene, p-xylene, phenol (main product), diphenyl oxide 203
Monomers 204
Monomers 204
Monomers 204
SO2, bicycloheptene, cyclopentadiene, ethylene, methyl cyclohexadiene, 204
benzene, indene, naphthalene, dihydronaphthalenes
SOz, cyclopentene, xylenes, ethylbenzene, styrene, indene, decadienes, 204
dihydronaphthalenes, tetralin, napthalene
SOz, butenes, benzene, toluene, octadienes, xylenes, styrene, indene, 204
naphthalene
SOz, hexenes, hexadienes, methyl methacrylate, toluene, naphthalene,
dodecadienes
204
SO*, ethylene cyclopentadiene, benzene, methyl methacrylate, bicyclo-
heptene, methylcyclohexa-2,4-diene, ethylbenzene, xylenes, styrene,
indene, naphthalene, dihydronaphthalenes
204
References page II - 475
II / 470 PRODUCTS OF THERMAL DEGRADATION OF POLYMERS
TABLE 3. cont ' d
Polymer Temperature range (C) Degradation products Refs.
3. 6. POLY(AMIDES)
Poly(2,5-dimethyl-l,Cpiperazinediyl-
isophthaloyl)
Poly(2,5-dimethyl-1,4-piperazinediyloxaloyl)
Poly(2,5-dimethyl- 1 ,Cpiperazinediyl-
terephthaloyl)
Poly(iminoisophthaloylimino-
1,3-phenylene) (Nomex)
Poly(iminoisophthaloylimino-
1,3-perchlorophenylene)
Poly(iminoisophthalylimino-
1,4-phenylene)
Poly(iminoisophthaloyl-co-terephthaloyl-
imino-1,4-phenylene)
Poly(imino(l-oxohexamethylene) (Nylon 6)
Poly(iminohexamethyleneiminoadipoy1)
(Nylon 66)
Poly(imino(l-oxoundecamethylene)
(Nylon 11)
Poly(imino(l-oxododecamethylene)
(Nylon 12)
Poly(iminoterephthaloylimino-
1,3-phenylene)
Poly(iminoterephthaloylimino-
1,4-phenylene) (Kevlar)
Poly(2-methylpiperazinediylterephthaloyl) 475
Poly( 1,4-piperazinediylterephthaloyl) 475
415
415
415
300- 500
300- 500
450- 550
550
300- 500
250- 620
327
310- 380
305
305
400
800
800
300- 500
300- 500
370- 450
450- 550
527
After 1 h, 5.1% residue, 73.8% chain fragments, 20.5% volatiles
comprising mainly CO, HzO, CH4, CO*, Ha, with traces of
hydrocarbons, pyrazines, pyrroles
3 0
After 1 h, 1% residue, 73.5% chain fragments, comprising mainly CO,
with traces of Hz, COz, HzO, hydrocarbons, pyrazines, pyrroles
After 1 h, 9.4% residue, 3.2% chain fragments 87.4% volatiles
comprising mainly CO, HzO, COz, CH4, NHs, with traces of
hydrocarbons, pyrazines, and pyrroles
47
4 7
Mixture of Hz, CO, COz, HzO, HCN, benzene, toluene, benzonitrile 5 7
CO2, HzO, CO 205
Benzene, HCN, toluene, benzonitrile, H2 205
CO, COz, HzO, benzene, benzonitrile, 1,3-dicyanobenzene, 319
3-cyanobenzoic acid, other trace compounds
Water (46 mol%), CO (18), CO2 (31), CH4 (1.2), HCN (1.3), and 206
smaller quantities of, NzO, NO, CHsCl, ethylene, acetylene, cyanogen,
acetonitrile, acetone, acetic acid, cyanogen chloride, propenenitrile,
benzene, toluene, benzonitrile, phenol, chlorobenzene
Mixture of Hz, CO, COa, HzO, HCN, benzene, toluene, benzonitrile 57
36% residue, 24% chain fragments, 40% volatiles comprising HZ, CO,
(332, CH4
Cyclic monomer, acetonitrile, HCN, NHs, acrylonitrile, 3-cyanopropene,
4-cyanobutadiene, 4-cyano-1-butene, 5-cyano-1,3pentadiene,
4-pentenal, 5-cyano-1-pentene, 3,5-hexadienal, 5-isocyanato-
1-pentene, linear dimer
HzO, COz, cyclopentanone, traces of saturated and hydrocarbons;
purification from water and acid polymerization catalysts increases
stability and decreases yield of CO2
HzO, COz, NHs, cyclic monomer, cyclopentanone, cyclopentylidine-
cyclopentanone, cyclopentylcyclopentanone, hexylamine,
hexamethyleneimine, hexamethylenediamine
COz, NHs, HaO, cyclic monomer, cyclopentanone,
2-cyclopentylidenecyclo pentanone, 2-cyclopentylcyclopentanone,
hexylamine, hexamethyleneimine, hexamethylenediamine,
1,2,3,5,6,7-hexahydro dicyclopenta[b,e]pyridine
Hexamethylenediamine, aminohexamethylene isocyanate,
hexamethylenediamine-monocyclopentanimine, hexamethylenediamine.
dicyclopentanimine and larger oligomers related to above;
cyclopentanone
COz, HCN, saturated and olefinic hydrocarbons Cs-C rr,
saturated and olefinic mononitriles C,H (2n+r)CN and C .H (zn-t)CN,
undecalactam, hydrocarbons and nitriles containing amide units
CO 2, HCN, saturated and olefinic hydrocarbons C s -C r 1,
saturated and olefinic mononitriles C,H (zn+r)CN and C,H (z-rCN,
dodecalactam, hydrocarbons and nitriles containing amide units
Mixture of H2, CO, COa, H20, HCN, benzene, toluene, benzonitrile
5 8
293
45, 46
207
207
247
308
308
57
Mixture of Hz, CO, COz, H20, HCN, benzene, toluene, benzonitrile 51
C02, HzO, CO 205
Benzene, HCN, toluene, benzonitrile, Hz
Cyanobenzene, dicyanobenzene, aniline, l,Cdiaminobenzene, 293
4-cyanoaniline, benzaldehyde, benzene, CO, NHs, COz, HzO,
benzamide, benzoic acid, phenylisocyanate, terephthaldehyde, benzanilide,
NH2-Ph-NH-CO-Ph, NC-Ph-NH-CO-Ph,
NH2-Ph-NH-CO-Ph-CN, Ph-NH-CO-Ph-CHO
After 1 h, 11.3% residue, 46.2% chain fragments, 42.5% volatiles 3 0
comprising mainly CO, H20, COz, CH4, NHs, Hz, with traces of
hydrocarbons, pyrazines, and pyrroles
After 1 h, 21.1% residue, 45.6% chain fragments, 33.3% volatiles 3 0
comprising mainly HzO, CO, Hz, COz, NHs, with traces of
hydrocarbons, pyrazines, and pyrroles
TABLE 3. contd
Mai n- Chai n Het eroat om Pol ymers II / 471
Polymer Temperature range (C) Degradation products Refs.
3.7. POLY(SILOXANES)
Poly(oxy-dimethylsilylene)
(Poly(dimethy1 siloxane))
Poly(oxy-methylphenylsilylene)
Poly(oxy-methyl-3,3,3-trifluoro-
propylsilylene)
Poly(oxy-phenylbutoxysilylene)
Poly(dimethy1 siloxane-co-
diphenyl siloxane)
Poly(dimethy1 siloxane-co-
phenylmethyl siloxane)
Poly(dimethyl-1,4-silphenylene)
Poly(oxy-methylphenyl-
1,4-silphenylene-silylene)
Poly(oxy-tetramethyl-
1,4-silphenylene-silylene)
Poly(oxy-tetramethyl-1,3-silphenylene-
silylene-hexafluoropropylenephenylene)
Poly(oxy-tetramethyl-1,3-silphenylene-
silylene-tetrafluoroethylenephenylene)
Poly(oxy-tetramethyl- 1,3-silphenylene-
siloxane-co-dimethylsiloxane)
Ambient to 500
410
Ambient to 500
400
615 for 30 s
430-500
Ambient to 500
Ambient to 500
400 in argon
Ambient to 500
500 in argon
Ambient to 500
615 for 30 s
615 for 30s
Ambient to 500
Poly(boron tri(dimethylsiloxane)), nonlinear 250-350
3. 8. POLY(URETHANES)
Poly(oxy-2,2-dimethyltrimethylene) 350
oxycarbonyl-N-imino- 1,4-phenylenemethylene-
1,4-phenylene-N-iminocarbonyl)
Poly(oxy- 1,4-phenyleneisopropylidene- 190
1,4-phenyleneoxycarbonylimino- 1 ,Cphenylene
methylene- 1,4-phenylene-iminocarbonyl)
Poly(oxy- 1,4-phenyleneisopropylidene-
1,4-phenylene-oxycarbonyl-N-methylimino-
1,4-phenylenemethylene- 1 ,Cphenylene-
N-methyliminocarbonyl)
Poly(oxy- 1,4-phenyleneisopropylidene- 330
1,4-phenylene-oxycarbonyl-N-methyliminohexa-
methylene-N-methyliminocarbonyl)
Poly((oxy- 1,4-phenyleneisopropylidene- 330
1,4-phenylene-oxycarbonyl-piperazine-
1,4-diyl-carbonyl)
Predominantly cyclic trimer with smaller amounts of cyclic tetramer and 208
higher cyclics; threshold degradation temperature of about 300C
reduced to 100C by 5% KOH and CH4 formed as additional product
Distribution of cyclic oligomers, n = 3 (243.9 relative mass spec. 317
intensity), n = 4 (loo), n = 5 (35.6), n = 6 (37.6), n = 7 (13.1)
n = 8 (l.l), II = 9 (0.2)
Mixture of all possible stereoisomeric cyclic trimers and tetramers with 209
small amounts of pentamer, benzene, and two more complex oligomers
Low-molecular-weight cyclic oligomers, CFz =CH-CHs, CHFs
Cyclic methyl-(3,3,3-trifluoropropyl)siloxanes, CH4, CXFs,
CFz=CH-CH3, CHz=CH-CF3
CO, Hz and hydrocarbons
Complex mixture of cyclic oligomers, which have been individually
identified, whose composition varies with the dimethyl/diphenyl ratio;
small amounts of benzene
Complex mixture of cyclic oligomers, which have been individually
identified, whose composition varies with the dimethyl/methyl phenyl
ratio; small amounts of benzene
Methane, dimethylsilane, benzene, dimethylphenylsilane,
7H3
F-H, dimethyldiphenylsilane,
CH3
Benzene, diphenylmethylsilane, triphenylmethylsilane, and higher
linear oligomers
7H3 7H3
Methane, H-y- 0- Y-H, benzene, cyclic trimer of dimethylsiloxane,
CH, CH,
and various higher chain fragments (see Ref.)
Cyclic trimer and tetramer of dimethylsiloxane and a complex mixture
of higher linear and cyclic oligomers
HF (15-Is%), methane, methyltrifluorosilane, dimethyldifluorosilane,
benzene, toluene, phenyldifluoromethane
HF (15 - 18%), methane, methyltrifluorosilane, dimethyldifluorosilane,
benzene, toluene, phenyldifluoromethane
Cyclic trimer and tetramer of dimethylsiloxane and a complex mixture
of higher linear and cyclic oligomers
Molecular weight increases; traces of cyclic products [(CH 3) zSiO] 3
and [(CHs)zSi0]4
Various fragments of the main chain (see Ref.) 231
4,4-Diphenylmethane diisocyanate, bisphenol A 231
Bisphenol A, 4,4-N-methyldiphenyl methane and linear and cyclic
fragments of the main chain (see Ref.)
Cyclic monomer and dimer, and various chain fragments 232
Cyclic dimer, bisphenol A and various chain fragments 232
70
210
211
212
213
214
215
214
216
210
210
216
15
231
References page II - 475
II / 472 PRODUCTS OF THERMAL DEGRADATION OF POLYMERS
TABLE 3. contd
Polymer Temperature range (C) Degradation products Refs.
Poly(oxy-1,3-phenylene-oxycarbonyl- 320
N-methylimino-hexamethylene-
iV-methyliminocarbonyl)
Poly(oxy-1,4-phenyleneoxycarbonyl- 325
N-methylimino- 1,4-phenylenemethylene-
1,4-phenylene-N-methyliminocarbonyl)
Poly(oxy-1,3-phenylene-oxycarbonyl- 360
piperazine- 1,4-diyl-carbonyl)
Poly(oxytetramethylene oxycarbonyl- Ambient to 500
imino- 1,4-phenylenemethylene-
1,4-phenylene-iminocarbonyl)
with 10% (w/w) ammonium Ambient to 500
polyphosphate
Poly(oxy-xylylene-oxycarbonylimino- 300
xylylene-iminocarbonyl)
Polyurethane from methylene bis- 600
(4-phenyl isocyanate) (10.5 parts) and
propoxylated trimethyl propane (100 parts)
250-350
350-500
500-650
Polyurethane from butane diol,
phenylphosphonic dichloride, and
methylene bis-(4-phenyl isocyanate)
Polyester urethane from an ethylene/
propylene glycol/adipic acid polyester,
butane diol and methyl bis-
(4-phenyl isocyanate)
Poly(urethane-co-carbonates)
650-800
Ambient to 500
Ambient to 500
330
Cyclic monomer, dimer and trimer, resorcinol 232
Cyclic dimer, 4,4-N-methyldiphenylmethane, hydroquinone, and higher 232
chain fragments (see Ref.)
Cyclic dimer and trimer, resorcinol, and various chain fragments (see
Ref.)
232
1,4-Butanediol, methylene bis-(4-phenyl isocyanate), tetrahydrofuran,
COz, HzO, butadiene, HCN, CO
228
Methylene bis-(4.phenyl isocyanate), tetrahydrofuran, HzO, aniline,
formaldehyde, CO a
229
CO*, trans-l&yclohexane-dimethanol, 4-methylene-cyclohexane-
methanol, xylylene diamine
230
Methane, CO;?, ethylene ethane, HaO, propene, propane, ethanol,
isobutene, acrolein, propanal, 2-methyl-1-butene, 2-methylpropenal,
2-butanone, benzene, dihydropyran, 2,2,4-trimethyl-1,3-dioxalane
CO*, propene, some methane and propanal
Methane, ethane, ethene, propane, propene, ethanal, propanal,
diminishing quantities of COz
234
256
256
Methane (max. rate of production at 6OOC), ethane, ethene, propene,
ethanal, propanal
256
Methane, ethane, ethene, propene, ethanal, propanal 256
COz tetrahydrofuran, dihydrofuran, aniline, p-toluidine, N-phenyl pyrro- 235
lidine, N-(p-tolyl) pyrrolidine, cyclobutylene phenylphosphonate, butane
diol, methylene bis-(Cphenyl isocyanate), 4,4-methylene dianiline
Modified chain fragments, ethylene, propylene, CO*, ethylene oxide,
propylene oxide, acetaldehyde, tetrahydrofuran, water, cyclopentanone,
ethylene, glycol, propylene glycol, adipic anhydride (trace), aniline
(trace)
Cyclic monomer, bisphenol A and higher linear and cyclic
fragments of the chain (see Ref.)
\n 1
290 Cyclic monomer, resorcinol, and various fragments of the chain
(see Ref.)
3.9. OTHER NITROGEN CONTAINING POLYMERS
Poly(t-butyl aziridine) Ambient to 500 Ethene, propane, propene, isobutane, isobutene, ethylamine,
aziridine, 1 -t-butyl-perhydro-1,4-diazine, IV-t-butyl ethylamine,
I-t-butyl-4-isopropenyl-1,2,3,4-tetrahydro- 1,4-diazine,
1,4-di-(t-butyl)-perhydro-1,4-diazine, oligomers
3. 10. PHOSPHOROUS CONTAINING POLYMERS
Poly(oxytetramethylene oxyphenyl Ambient to 550
phosphono)
Poly(oxytetramethylene oxyphenyl- Ambient to 500
phosphono) capped with phenylisocyanate)
ai?
N-C-O
Poly(bis(trifluoroethoxy)phosphazene)
Poly(diphenoxyphosphazene)
150- 400
100-400
Butadiene, tetrahydrofuran, dihydrofuran, HzO, cyclic ester of
phenylphosphonic acid and 1,4-butanediol, phenylphosphonic acid,
butane diol
Butadiene, tetrahydrofuran, dihydrofuran, HzO, cyclic ester of
phenylphosphonic acid and butanediol, phenylphosphonic acid,
butane diol, COz, aniline
Cyclic trimer, tetramer, pentamer, hexamer, and higher oligomers, 238
236
231
231
276
233
233
1 , l , l-trifluoro-2-chloroethane (due to residual chlorine in the polymer)
Cyclic tetramer, trimer and higher oligomers, chlorobenzene (due to 239
residual chlorine in the polymer), phenol, triphenylphosphate
Mai n-Chai n Heterocycl i c Pol ymers II / 413
TABLE 3. contd
Polymer Temperature range (C) Degradation products Refs.
Poly(diphenoxy-phosphazene)
(residual chlorine content: < 0.05%)
Poly(diphenoxy-phosphazene)
(residual chlorine content: 2.4%)
Poly(diphenoxy-phosphazene)
(residual chlorine content: 9.9%)
Ambient to 480
Ambient to 480
Ambient to 480
Traces of phenol, phenoxy cyclic trimer and monochlorophenoxy 316
cyclic trimer
Phenoxy cyclic trimer and tetramer, monochloropentaphenoxy cyclic 316
trimer, monochloroheptaphenoxy cyclic tetramer, dichlorohexaphenoxy
cyclic tetramers
Phenoxy cyclic trimer and tetramer, monochloropentaphenoxy cyclic 316
trimer, monochloroheptaphenoxy cyclic tetramer, dichlorohexaphenoxy
cyclic tetramers, dichlorotetraphenoxy cyclic trimers,
trichloropentaphenoxy cyclic tetramers, HCl
TABLE 4. MAIN-CHAIN HETEROCYCLIC POLYMERS
Polymer Temperature range (C) Degradation products Refs.
Phenol-formaldehyde resin
Poly( 1-methylene-2-imidazolidinone)
(Poly(ethyleneurea formaldehyde))
Poly(N-phenylmaleimide)
Poly(5,5-bibenzimidazole-2,2-diyl-
1 ,Cphenylene)
Poly(5,5-bibenzimidazole-2,2-diyl-
1,3-phenylene)
Poly(l,3,5,7-tetraoxo-2,3,6,7-tetra-
hydro-(lH,5H)-2,6-benzo[ 1,2-c :4,5-c]-
dipyrroldiyl-1,4-phenylene-carbonyl-
1 ,Cphenylene) (Poly(pyromellitimide))
Poly(l,3,5,7-tetraoxo-2,3,6,7-tetra-
hydro-(lH,SH)-2,6-benzo[l,2-c : 4,5-c]-
dipyrroldiyl- 1,4-phenylene-methylene-
1,4-phenylene) (Po1y(pyromellitimide))
Poly(l,3,5,7-tetraoxo-2,3,6,7-tetra-
hydro-(lH,SH)-2,6-benzo[ 1,2-c :4,5-c]-
dipyrroldiyl-1,4-phenylene-oxy-
1,4-phenylene) (Poly(pyromellitimide))
Poly( 1,5-diimino-3,7-dioxo-
2,3,6,7-tetrahydro-(lH,SH)-2,6-benzo
700
700
700
450-500
Hz, CO, CH4, CO2, H20, benzene, benzonitrile, chain fragments, 60%
residue
Hz, CO, CH4, CO2, H20, benzene, toluene, benzonitrile, chain
fragments, 60% residue
Hz, CO, CH4, CO2, H20, benzene, benzonitrile, phenol, chain
fragments, 60% residue
CO, COz, HCN, NHs, Hz and traces of CH4 and CsH6; NH3 is the
main product at 440C. CO increases at higher temperatures
[1,2-c : 4,5-c]dipyrroldiyl-1,3-phenylene)
Poly(l,S-diimino-3,7-dioxo- 450-500 CO, COZ HCN, NHs, Hz and traces of CHq and C6H6; NH3 is the
2,3,6,7-tetrahydro-(lH,SH)-2,6-benzo main product at 44OC, CO increases at higher temperatures
[1,2-c : 4,5-c]dipyrroldiyl-l,Cphenyleneoxy-
1 ,4-phenylene)
250-400
240
Ambient to 600
100- 400
400-700
570, 700, 1000
599-667
Volatiles comprise xylene (76%), traces of phenol, cresol, benzene 53
Formaldehyde (trace) 253
Low boiling fraction consists of NHs, CO2, HCN, CH4, CO (trace); 253
IR data also suggests presence of isocyanate, ketamine and carbodiimide
or cyanogen compounds; high boiling fraction (77% of total volatiles)
consists of chain fragments up to pentamer, including N-metbylethylene
urea, corresponding unsaturated compounds and higher homologues;
similarly, N,N-dimethyletbylene urea and homologues
Aniline, Ph-N=CH-CHa-CHs, N-phenylsuccinimide, 301
N-phenylmaleimide (trace), Ph-N=CH-CH=CH-CO-NH-Ph
Phenol, terephthalodinitrile, benzonitrile, 4,4-diaminodiphenyl, Hz, CO, 56
NHa, HCN, traces of aniline, carbonaceous residue
Hz (700 and lOOOC), NH3 (570 and 700), NzO, HCN, cyanogen (570 217
only), CH4, CzHs, ethylene, acetylene (700 and 1000). acetonitrile
(700 and lOOO), propene (570 and 700), benzene, toluene, benzonitrile
(700 only), ethylbenzene, methylbenzonitrile (700 only)
Gaseous products; Hz, NHs, HCN, and CH4; products involatile at 218
ambient temperature after approx. 50% weight loss; benzimidazole
(29.8%), benzoxazole (4.9%), 2-methylbenzimidazole (7.3%),
2-phenyl-benzimidazole (24.3%), 2-(3-methylphenyl)benzimidazole
(5.3%), 5-(3-aminophenyl)benzimidazole (9.6%)
2-(3cyanophenyl)benzimidazole (7.8%) 5,5-bibenzimidazole (4.4%)
2-phenyl-5-(3aminophenyl)-benzimidazole (4.4%),
2-phenyl-5,5-bibenzimidazole (1.9%), 2-phenyl-5-(benzoxazolo)-
benzimidazole (0.3%)
6 1
6 1
61
219
References page II - 475
II / 474 PRODUCTS OF THERMAL DEGRADATION OF POLYMERS
TABLE 4. contd
Polymer Temperature range (C) Degradation products Refs.
Poly(triazines)
jg;e,-;-cQ~
415- 505
305- 465
480-660
690-760
I
N, /,N,
$-~F-O(CP2)6-O-CF-C $
%
7
,N CF,
CH,N, N
C
t
424-550
1
CF-O(CF,),-O-CF-
&F3 CF3
Poly(perfluoropyridine)
Poly(parabanic acid)
J
600
300 COz, CO, NO
221
Poly(bismaleimides)
R=fC%, +I&-, +!H&, -@I&, -fCH&,
350-500
350-500
Poly(3-(4-octylphenyl)-
2,2-bithiophene)
800 HzS, COS, SO2, CHsSH, CS2, Ss, Ct-Cs alkanes and alkenes,
benzene, ethylbenzene, toluene, styrene, octylbenzene, thiophene,
methylthiophene, bithiophene
284
Poly(3-octylthiophene) 550- 1400 C r -Cs alkanes and alkenes, H$, CS2, benzene, toluene 284
Poly(3-octyl-2,2-bithiophene) 550- 1400 C i-Cs alkanes and alkenes, H2S, CS2, benzene, toluene 284
Poly(3-(4-octylphenyl)thiophene) 550- 1400 C 1-C s alkanes and alkenes, H& CS 2. benzene, toluene 284
CaF4, CzF,j, and smaller amounts of CsH6 and CsHs and
larger chain fragments
C2Fd with traces of CFa, CsHe, and larger chain fragments 48
Only volatile product is benzonitrile
HCN and NH3
Hz and carbonaceous residue
Pertluoroethane, perfluoromethane, perfhroroethylene,
perfluoropropane, perfluoropropylene, acetal fluoride, carbonyl fluoride
Volatiles comprise COz, CO, SiF4 (all from silica vessel); carbonaceous
residue remains
Aliphatic: C 2-C 6 fractions, maleimide (MI), succinimide (SI)
MI-CHs, SI-CH3, MI-C2HS, SI-C2H5, MI-C3H7, SI-C3H,,
MI-C4H9, SI-C4H9, MI-CsHi,, SI-CsHri, MI-(CHa)a-MI,
SI-(CH2)2-SI, MI-(CH2)6-MI, MI-(CH2)s-MI, MI-(CH2)ro-MI,
MI-(CH2) 12-MI
Benzene, toluene, aniline, SI, methylaniline, phenylisocyanate,
tolylisocyanate, and various other products (see Ref.)
Aniline, phenol, SI, anisidine, phenylisocyanate, and various other
products (see Ref.)
48
54
54
54
220
52
222
222
222
References II / 475
TABLE 5. CELLULOSE AND ITS DERIVATIVES
Polymer Temperature range (C) Degradation products Refs.
Cellulose
-, a form
Cellulose (oxidized)
Cellulose triacetate
Ethyl cellulose
250-397
Ambient to 500
330-440
180-331
250-3 10
250-900
230-320
306
Hz0 with smaller amounts of COz and CO and a tar containing 17,18
principally levoglucosan
Hz, CO, COz, HzO, furan, furancarboxyaldehyde, methylfurans, acetone, 273
hydroxypropanone, butenal, butanone, butanedione, levoglucosan
Fixed gases (not identified), pentene, acetaldehyde, furan, 162
propionaldehyde, acetone, acrolein, 2-methylfuran, butyraldehyde,
methyl ethyl ketone, benzene, 2,5dimethylfuran, methyl vinyl ketone,
2,3-butanedione, toluene, crotonaldehyde, H20, cyclopentanone,
cyclooctatetraene, acetol, pyruvaldehyde, acetic acid, furfural,
formic acid, 5-methyl-2-furfural, furfuryl alcohol, butyrolactone,
2-hydroxy-3-methyl-3-cyclopenten-2-one, phenol, o-cresol, m-cresol,
p-cresol, 2,5-dimethylphenol, 3,4-dimethylphenol, 5-hydroxymethylfurfural
Mainly Hz0 and CO2, smaller amounts of CO, formaldehyde, methanol,
acetic acid, ethanol and acetaldehyde, and very little tar
Product fraction volatile at 25C contains acetic acid, CO?, CO, CH4, 1 8
Hz, acetaldehyde and acetone; heavier fractions do not contain
levoglucosan acetate
Main products: acetic acid, water, CO, CH4, Hz, COz; minor products: 223
ketene, acetaldehyde, acetone, acetylene, ethylene, ethane, propylene,
and C4, C5 and Cg hydrocarbons
Acetic acid, acetyl derivatives of D-glucose 224
H20, CO, CO2, C2H4. C2H6, CzH50H, CHsCHO, aliphatic 224
compounds, furan derivatives
C. REFERENCES
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3. S. L. Madorsky, J. Polym. Sci., 11, 491 (1953).
4. J. R. Schaefgen, I. M. Sarasohn, J. Polym. Sci., 58, 1049
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5. C. S. Marvel, J. C. Cowan, J. Am. Chem. Sot., 61, 3156
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6. A. J. Canale, W. E. Goode, J. B. Kinsinger, J. R. Panchak,
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Radiation Chemical Yields: G Values
M. C. Senake Perera
Magnetic Resonance Facility, School of Science, Griffith University, Nathan, Qld 4111, Australia
David J. T. Hill
Department of Chemistry, University of Queensland, St Lucia, Qld 4072, Australia
A. Introduction
B. Tables of G values
Table 1. Homopolymers
1 .I. Polydienes
1.2. Polyolefins
1.3. Polyacrylates
1.4. Poly(methacrylates)
1.5. Poly(styrenes)
1.6. Poly(vinyls)
1.6.1. Acrylamides and Nitriles
1.6.2. Vinyl Monomers
1.7. Miscellaneous Polymers
.7.1. Cellulose and
Derivatives
.7.2. Poly(siloxanes)
.7.3. Poly(amino acids)
1.7.4. Polyesters
1.7.5. Polysulfones
1.7.6. Polyketones
1.7.7. Fluoropolymers
1.7.8. Others
Tabl e 2. Copolymers
2.1. Copolymers with Ethylene
2.2. Copolymers with Methyl
Methacrylate
2.3. Copolymers with Styrene
2.4. Copolymers with Sulfur
Dioxide
2.5. Other copolymers
Table 3. Polymers Blends
Table 4. Composi t es
C. Ref erences
II-481
I I -481
II-482
II-482
I I-482
II-483
I I-484
II-485
I I-486
II-486
II-486
II-487
II-487
II-487
II-487
II-488
I I-488
II-488
I I-488
II-489
II-490
II-490
II-490
II-491
II-491
II-492
II-493
II-493
II-493
A. INTRODUCTION
The G values quoted in the following tables are defined as
the radiation chemical yields of individual atomic or
molecular events for 1OOeV of energy absorbed by the
system. G(R) represents the yield of free radicals, G(X) the
yield of crosslinks, G(S) the yield of main chain scission,
and G(products) the yield of product molecules per 1OOeV
of absorbed radiation.
This table has been compiled from the polymer literature
that has been published since the third edition of the
Polymer Handbook (i.e. 1986-1997). In many cases,
the tabulated data are only representative of the total data
in the paper, and the original publication should be
consulted.
B. TABLES OF G VALUES
Notes to the Tables
General: Unless otherwise stated, the conditions applying
are y-rays, vacuum, room temperature (ambient).
Symbols/Abbreviations
+ cation radical d.b. double bond
-
anion radical t-v trans-vinylene
vat vacuum Y crosslinks
RT room temperature X crosslinks
e electron beam n neutron
II 1481
II f 482 RADIATION CHEMICAL YIELDS: G VALUES
TABLE 1. HOMOPOLYMERS
Polymer
G(R) G(X) G(S) G(products)
Radiation
conditions Comments Refs.
1.1. POLYDIENES
Polybutadiene 38.7 (d.b.) e, 263 K
0.0054 77K
9.3
1 0 5
2.1 3.3619.4
5.3
various various
Poly(2-phenyl butadiene)
Polyisoprene
NR latex
Polychloroprene
1.2. POLYOLEFINS
Squalene
Poly(butene-1)
Poly(ethylene)
4 1
7.2
0.009
0.5-0.8 1.6-2.1
various valious
various
3.0 3.9
1.0
1.09-1.39
0.63
4
1.4
15-30
0.25
1. 50- 2. 40
2.8, 5.8 (CzD4)
1. 1-2. 8 0.05-2.7
1.1
1.5
2.6/0.56 (alkyl)
0.74 G (H)
0.27 G (Y)
1.0
610 (1,2)
0.34/0.19
90
3.2
4
4.1
0.48
8-15
1.08-1.69
2.4
<0.05
0.48
0.2
112 (Vinyl)
various
various
e
77 K/RT
Air, 295 K
various
Vat, 303 K
Vat/303 K, ethyl-
ene dichloride
77K
94- 168
(d.b.1, (34, H2
various
2.8 (-Cl)
various
Vacl77, 303 K
3.0 (Hz)
13.9
(-isotactic
pentad)
7 (COOH)
9.1 (02)
-2 (t-v)
Carries
various
RT, vat
e, air
VaclO 2
300 K
Air, 300/450 K
303-373 K
He, 77 K
02, cc14
Various gases Ai r
Gamma/alpha,
77K
Vat, molten
state
3.9 (Hz)
3.5 (damage)
Excitation 64
scavenger
1, Z-PBD 138
Radical pairs, 74
isotactic
Syndiotactic 97
cis 1,4 84
98
Effect of 104
pressure
Review 186
WY) > G(X)
261
G(X) depend
on MW
G (initiation), 262
G(X) increases
G(Cy), G(db)
decreases with
Crosslinker
180
1 7 8
Radical pairs 74
Var cis content 15
Review
+ acrylate
186
248
179
235
226
89
1 0 1
1 0 7
1 7 2
116
Pressure effects 1 6 9
30
e pre-irradiated 63
5 2
1 4 7
Fibers, 1 5 1
G(S)/G(X) = 1
e, N2 1 5 5
various 70
compounds
e, NZ 8 7
Gamma/n 1 7 4
1 6 3
1 8 3
Crystalline
region units
228
270
TABLE 1. contd
Homopol ymers II / 483
Polymer
G(R) G(X) 39
G(products)
Radiation
conditions Comments Refs.
-, LDPE 2.5 (alkyl) 77K
12. 4-15. 4 (02) O2
177
96
G(S)/G(X) = 1.6 1 1 7
4.45 (butanes)
various
- 1.9 (r-v)
Alkanes
air
303 K
298-423 K
77K
2.4 0.4
1.3
2.9-3.6
2.3-4.5(alkyl)
0.3*
0.21
Various G(r-v)
various Air
0.16 (butanes)
Air
77K
77K
303 K
Alkanes
Y, c = c, (t-v)
- 9. 6 (I-V)
303 K
Air, 77 K/RT
2.4 (tmns)
0.7 (ci s)
4-5 (gas)
4.0
3.8-11.1
Various
3.6
Various
Various
0.3,0.6 *
3.110.64
9.4
;7K
Various
temperatures
various
Vacl77, 303 K
N2lair
He, e, 77K
Airlvac
02 +cc14
2.9 (H2)
2.19* + cc14
various
various
94 (-i-pentad)
Ai r
Ai r
Gamma
1 0
27
7 1
129
164
231
1 0 5
184
88
92
177
1 0
28
32
1 2 5
45
47
134
7 5
79
240
119
1 3 1
1 3 3
+I2
+ CH3SH
antioxidants
Butene- 1,
hexene- 1
Morphology
Allylic
Monolayer
crystals
Warming,
morphology
*G(X/unsat.)
77K
3.0 (total)
2.8 (alkyl)
-, LLDPE
-, HDPE
0.3, 0.43
3.7
0.76 (bulk)
1.6*
0.76 -, HDLPE 5.5
-, Chlorosulfonated
polyisobutylene
2.5
78,90,100
Various
2.1
4.8, 2.7(dPP)
186
Poly(4-methylpentene-1)
polypropylene
*G(S)/G(X) 43
52
Also 373-623 K 129
1 4 7
Also O2 158
Decreases with 159
dose
*G(S)- G(X)
1 1 8
40
244 i-Polypropylene
Various (pentad
sequences)
220 (-i-pentad) e 245
1.3. POLYACRYLATES
Poly(acrylic acid) Various gases Vaclair 170
3.6
3.49
n
t
1 8 5
189
190
233
*G(S)- S(X) 59
126
Various
Various
293-308 K
Vat
77, 300K
Gamma, aq.
0.0 0.44
0.47 0.62
1.1 Poly(acrylic anhydride)
Poly(methy1 acrylate)
HZ, CO, CO27
195- 423
CH4 etc.
References page II - 493
II / 484 RADIATION CHEMICAL YIELDS: G VALUES
TABLE 1. contd
Polymer
G(R) XV G(S) G(products)
Radiation
conditions Comments Refs.
Poly(methy1 bromoacrylate) 6.98
Poly(methy1 a-chloroacrylate) 5.1
139
1 3 3
24
62
1 7
1 3 3
6 5
22
192
238
22
22
120
246
65
22
22
192
192
9 1
176
1 2 3
1 3 3
185
189
1 9 5
1 7 6
59
59
73
57
5 1
53
65
50
1 3 1
132
135
139
152
1 6 1
176
86
1 7 3
146
1 7 1
162
17
1 4
2 3
3 3
1 8 7
1 8 8
77K
0.3-0.9
0.8
3.2-7.4
6.0
6.7*
Dose dependent
*G(S)- G(X)
0.05
77K
77K
0.29 *
0
0.14
1.28*
0.44*
2.4*
iOOK
e
e
Various
*G(S)- G(X)
Syndiotactic
*G(S)- G(X)
*G(S)- G(X)
*G(S)- G(X)
2.6
0.38*
1.1*
0.8
0.3
3.4
0.6/ 2.9
4.8
6.0
7K
e
e
300K
300 K
N2
Gamma/e
771273 K
77K
*G(S)- G(X)
*G(S)- G(X)
Syndiotactic
Syndiotactic
Aq. solution
6
various 71, 303 K
Various
1. 8-2. 9
1.9 (DMF)
1.3 (THF)
1.5
Gamma/e
Soln.
77K
77K
2. 8-4. 1 303, 343 K
Aromatic
additives
Aromatic
additives
Absorbed on
zeolite
1.3
1.31
1.9
77K
1.63. 1.09
1.4
1.5/0.33
1.2
Y7K
Gamma/n,
vat/air 206 K
Gamma/X Si wafers
Various
0.71-1.63
e/gamma,
303-383 K
Gamma/n,
vaclair
77f273 K
Vaclair, 273 K
77K
Various radicals
Bulk, alcohol
1.5*
Various
15.8 (units)
0.34 (Hz)
Air
*G(S)- G(X)
+ ethane diol
Isotactic
18.6 Vat, 363 K Isotactic
Poly(methy1 cl-cyanoacrylate) 1.6
Poly(methy1 cc-fluoroacrylate) 1.0
1.4. POLY (METHACRYLATES)
Poly(benzy1 methacrylate)
0
Poly(t-butyl methacrylate)
Poly(cyclohexy1 methacrylate)
Poly(glycidy1 methacrylate)
Poly(hexafluoroisopropy1 methacrylate)
Poly(hexy1 methacrylate)
Poly(isobuty1 methactylate)
Poly(2-methyl heptyl methacrylate)
Poly(methacrylic acid)
9.2
0.1
0.5
0.2
0.04
Poly(methacrylic anhydride)
Poly(methy1 methacrylate)
l.l-1.5(+)
0.7-0.9( - )
0.5, 1.5($)
0.58
1.42
1.9f4.1
1.04/1.11
1.9, 4.4
1.5
0.22,0.46,1.08 Various Deep UV, e,
X-ray
TABLE 1. contd
Homopol ymers I I / 485
Pol ymer
G(R) G(X) G(S)
G(products)
Radiation
conditions Comments Refs.
Poly(ethy1 methacrylate)
Poly(n-butyl methacrylate)
Poly(2-hydroxyethyl methacrylate)
Poly(pheny1 methacrylate)
1.5. POLY(STYRENES)
Poly(a-methyl styrene)
Poly(p-methyl styrene)
Poly(styrene)
1.5
1.1
1.7
1.7
1.6
0.99, 0.4
0.77
5.1 (soln.)
0.89
(amorphous
solid)
0.48 (crystalline
solid)
1.21 (333 K)
0.89 (303 K)
0.46 (195 K)
G(damage) = 8.8
Poly( 1-naphthyl methacrylate)
1.0
0.14
Poly(2-naphthyl methacrylate)
Poly(2,2,2-trichloroethyl methacrylate)
0.14
0.19
0.03 3.7
3.7
0 1.7
0.4 1.3
1.2, 1.7
0.44
0.3
0.33
0.78
0
0.105, 0.05
0.1
0.45-7.9
0.022
0.17
0. 035- 0. 042 0.010-0.051 0.032 (HZ) 303-373 K
0.043 0.0009 303 K
0. 043- 0. 027
0.048, 0.021
0.05
0.03/0.2
0.043
0.02
0.29
0.4kqO.89, 0.97,
1.13
0.022
1.09, 2.12
0. 086- 0. 074
0.2*
0.27, 0.07
0.02/0.2
0.00086
3.9
0.1
300 K
N2, RT
Vat
N2
Vat
Air, RT
Gamma/e,
298-416 K
300K
300 K
77, 300K
e
Gamma/e,
77- 373 K
273-319K
303, 353, 373,
383, 393 K
77, 298 K
Gamma/e,
77- 373 K
303 K
Air
303-423 K
77K
Air
77K
Isotactic 190
Syndiotactic 192
222
Protons, gamma 223
e, gamma 224
Cs + , O5 + ions 225
238
i -PMMA 249
Morphology 258
effects,
racemization
264
Benzene 1
solution
238
238
1 7 5
Dioxane
solution
Syndiotactic
Syndiotactic
11
192
192
1 9 3
238
1 3 1
38
Benzene 2 5
solution
+ Depolymeriza- 194
tion
1 9 7
38
Emulsion 48
polymerization
Sheet 56
absorbed on 58
silica gel
60
Includes lit. 6 1
review
67
*G(S)- G(X) 73
Various doses 130
132
Gamma/n, 1 3 5
vaclair, 206 K
Sheet 136
0 2 +cc14 1 4 7
373-623 K
Ai r 1 5 7
References page II - 493
.
II / 486 RADIATION CHEMICAL YIELDS: G VALUES
TABLE 1. contd
Polymer G(R) G(X) G(S) G(products)
Radiation
conditions Comments Refs.
0.0009
1.8
0.5
1. 6. POLY(VINYLS)
1.6.1. ACRYLAMIDES AND NITRILES
Poly(acrylamide)
Poly(methacrylamide) 1.2* *G(S)-G(X) 1 4 1
Poly(acrylonitrile) 3. 7-4. 1 303 K Absorbed on 5 3
zeolite
5
198
200
Various sources 1 9 5
255
Poly(methacrylonitrile)
Poly(u-chloroacrylonitrile) 1.4
1.6.2. VINYL MONOMERS
Poly(t-butyl crotonate)
Poly(t-butyl vinyl ether)
Poly(ethy1 vinyl ether)
Poly(isobuty1 vinyl ether)
Poly(isopropy1 vinyl ether)
0.88
0.15-3.0
2.8, 4.2
2.2. 2.8
0.077
0.094
various
0.018, 0.15 0.06, 0.07
0.0174
0.0425
0. 014- 0. 05
0.03-0.05
6.7-15.2
0.05
various
0. 03- 0. 05
2.5
5
1.3310.62
0.59
0.66
0.055
0.0027
various
0.0012
0.033 (Hz)
0.105
24.7-30.4
G(degradation)
0.01
Various
0.03 (Hz)
Hz, CH4,
C2Hzr C3H4.
C6H6
various
(-02)
Various
hydrogen
0.04
0.4510.52 various
0.0
0.4-3.3
3.3 gamma
3. 6 X
0.5 Ne
0.4 4r
2.7 *
1. 1-7. 2
3.2
2.1-3.3*
3.1-3.3
3.3*
0.59
3.6, 10.3
0.36, 0.50
0.39, 1.73
0.86, 1.50
77K
313K
Gamma/n,
vaclair
77K
Gamma/n/alpha,
air
77K
Gamma/e,
77- 373 K
Abs of air
Various dose
rates
Ion beam
Vat, various
t emp.
Air/Ha0
e, 02
Aq. soln, 304K
Vaclair,
77- 393 K
77, 300K
77, 300K
Absence of 02
77K
Vaclair
Radical pairs
1 6 1
74
81
8 5
98
112
Warming 1 9
6
7
33
38
Various sources
+ Crosslinking
agents
Deuterium subs
1 9 5
196
228
234
Variable temp.
dose rate
Tacticity,
crystallinity
effect
Gamma, X-ray,
Ne, Ar
250
257
255
Aq. soln.
Hydrogel
149
1 0 3
108
167
1 3 3
*G(S)- G(X) 59
Solution + bulk 99
1 4 5
*G(S)- G(X) 5 9
62
*G(S)- G(X) 1 7
273, 348 K
273, 348 K Liquid
273, 348 K
273, 348 K
54
1 2 2
1 2 2
1 2 2
1 2 2
.
TABLE 1. contd
Homopolymers II / 487
Polymer
G(R) G(X) G(S) G(products)
Radiation
conditions Comments Refs.
Poly(methy1 vinyl ether)
Poly(tetrafluoroethylene)
Poly(viny1 acetate) 2. 4-4. 1
Poly(viny1 alcohol)
Poly(viny1 bromi de)
Poly(viny1 butyral)
Poly(viny1 carbazole)
Poly(viny1 chloride)
0.7 (holes)
1.7
Poly(viny1 imidazole)
Poly(viny1 pyrrolidone)
3.3
1.7. MISCELLANEOUS POLYMERS
1.7.1. CELLULOSE AND DERIVATIVES
Cellulose
Cellulose acetate
1.7.2. POLY(SIL0XANE.S)
Poly(oxydimethy1 diphenylsilylene)
Poly(oxydimethy1 silylene)
Various
Poly(methy1 phenyl silane) 0.01-0.21
Poly(cyclohexy1 methyl silane) 1 1. 8-17. 4
Poly(dimethy1 siloxane) 1.7
Silicon containing poly(acetylene) 0.3-2.3
1.7.3. POLY (AMINO ACIDS)
Poly(alanine)
Poly(glycine)
Poly(tyrosine)
Poly(valine)
2.9
3.6
2.2
< 0.4
0.31, 0.64
0.5
1.08
1.02
0.71
0.35 0.6
2.36
10- 11 20-115
10-54
0. 41- 0. 75
0.01-1.32
273, 348 K
02+CC14K
243-273 K
0.9-2.4 gel dose Absence o f 02
02
Air
N2
39-55(HBr)
e, N2
;7K
Air
various Vat/O 2
7.7 (HCl) Vat/O 2
(d.b.)
17(HCl) e, Nzlvac
0.24 (Hz) VaclO 2
8 (HCl)
2.8-3.5 (Py +)
O-l.2 (Phenyl+)
3.0 (-Cl)
%
77K
13- 186
7.1
CO, CHO, COOH Vaclair 1 1 1
Vaclair Post irrad. 26
Air Hz0 incr. G(S) 156
122
Also 373-623 K 147
2 1
1 9 5
236
Solution 9
241
168
1 6 5
Under pressure 1 1 3
1 1 5
119
THF soln. 8,44
+ additives
154
160
G(cation) 247
273 K
G(X) Increases 263
with crosslinker
269
+ Crosslinker 256
Aq. soln. 1 2
+ Warming 1 3
various 205
solutions
various
2.48
18.5/120
2.7
3.0
2.8
Various Various various
Liq. 94
N2, 303 K Also blends with 1 4 3
PS
Ai r Effect of 104
pressure
76
80
Liquid 82
186
G(X) increases 265
with crosslinker
LET 230
dependence
Dose 232
dependence
243
Effect of various 252
pendent groups
3.8-7.0 Various 95
Various 128
3.0-3.3 Various 95
0.12 Various 95
0.04-0.12 (NHs) Air/Nz/NzO Aq. soln. 102
Various 95
References page II - 493
II / 488 RADIATION CHEMICAL YIELDS: G VALUES
TABLE 1. contd
Polymer
G(R) G(X) 34
G(products)
Radiation
conditions Comments Refs.
1.7.4. POLYESTERS
Poly(hydroxybutyrate)
Poly(L-lactic acid)
Poly(~, L lactic acid)
2.0, 1.5
2. 37- 1. 23
2.4, 1.2
1.65 Air
77, 300K
77, 300K
77, 300K
Poly(glycolic acid) 1.72, 1.47 77, 300K
1.7.5. POLYSULFONES
Bis-A-PSF
Hydroquinone PSF
Biphenol PSF
Bis-S-PSF
PES (Polyethersulfone)
1.7.6. POLYKETONES
PEEK
PEEKK
PEEK- Me
PEEKK-Me
PEK-Ar
1.7.7. FLUOROPOLYMERS
Fluoro elastomers
Poly(perfluoroethers)
Poly(tetrafluoroethylene)
0.13
0.13
0.57
0.19
0.14
0.56
0.084
0.084
0.51
0.128
0.24
0.11
0.004
0.001
1 .Oe20 spin/kG
0.11
0.12
0.004
0.001
1.1 e20 spin/kG
0.28
0.009
0.001
0.37
0.012
0.001
0.42
0.039
0.005
various
0.13-1.34 0.11-0.67 Various gases
0.14 (SO2)
0.145 (SOZ)
0.136 (SOz)
0.14 (SO2)
0.14 (502)
0.063 (SO2)
0.06 (SO2)
0.6 (SOP)
0.198 (SO2)
0.243 (SO2)
Various temp
0.00054 gases
Vat, 77 K
Vat, 300K
Air, 300K
77K
Vat, 77 K
Vat, 300K
Air, 300 K
77K
Vat, 77 K
Vat, 300K
Air, 300 K
Vat, 77 K
Vat, 300K
Air, 300 K
Vat, 77 K
Vat, 300K
Air, 300K
various various
G(S)
2.15
various Various
Various gases e, argon 9 K
G(decomposition) e
=0.2-1.2
G(wt. loss),
G(w)
Pressure and
temp. effect
on G(S) and
G(X)
Pressure and
temp. effects
on G(S) and
G(X)
1 9 1
201
203
201
274
203
274
207
208
211
207
208
211
207
208
211
207
207
209
211
212
209
211
209
209
209
Review 186
202
Structure, temp. 259
effects
260
As polymerized 237
sintered, low
crystalline
Dose rate 267
effects on G(S)
6.0
TABLE 1. contd
Homopol ymers II / 489
Polymer
GO-0 G(X) G(S) G(products)
Radiation
conditions Comments Refs.
0.3 at 373
0.57 at 473
0.89 at 573
1.33 at 673
2.07 at 773
Poly(viny1 fluoride) 0.22
Poly(vinylidene fluoride) 0.37
0.46-0.78 0.38-0.86
0.6-0.78 0.29
1.7.8. OTHERS
Aromatic polymers
Alkyl aromatic poly amides
various
Aryloxyphosphazenes
-[(R-Ph-O)z-PN],-
-biphenol 0.6, 0.19
-his phenol 0.6, 0.22
-hydroquinone 0.6, 0.35
Poly(bis(phenoxy)phosphazene)
Poly(bis(4-methyl-phenoxy)phosphazene)
Poly(bis(4-t-butyl-phenoxy)phosphazene)
Poly(bis(4-cumyl-phenoxy)phosphazene)
Poly(l-(r-butoxycarbonylthio)ethylene) 3.39
Poly(r-butyl isopropenyl ketone)
Poly(butylene), 1,4-disubstituted(urethane side
chain)
Poly(epoxide)(Araldite) 0.59
Poly(ether imide) (Ultem) 0.01
Hyaluronic acid
Poly(l-mercapto ethylene) 2.65
Poly(oxadiazole-2,5-diyl-1,4-phenylene-
phthalidylidene-1,4-phenylene)
Poly(oxycarbonyl- 1, I-dimethyl-2-
isopropylidene-ethylene)
Poly(oxycarboxyethylene)
Poly(oxyethylene)
5
Poly(oxyethyleneoxyterephthaloy1)
Poly(oxymethylene)
Poly(oxy- 1,4-phenylenesulfonyl- 1,4-phenelene
oxy-1,4-phenylene-isopropylidene-1,4-
phenylene)
Poly(oxy-l,Cphenylenesulfony-1,4-phenylene)
Poly(oxysebacoyloxy- 1,4-phenylene)
isopropylidene- 1,4-phenylene)
various Various
0.22 (R = Me) 0.26
2.12 (R=Et) 0.26
0.9 0.7
3.5 2.0
0.1 0.1
0.2 0.2
1.5
0.33
0.139 0.00528
various
1.9
0.4-11 14.5, 40.5
2.6
36
57-144
0.023
8
0.05 0.012
Poly(phenylene oxide) 5.7e20 spin!kG
0.6, 0.33
Poly(phenylene sulfide) 0.16, 0.04
Poly(thiophenylene) 0.015/0.067 0.030/0.15
Poly(thiopropylene) 0.0014
0.07 (Polyvinyl)
0.11 (Polyvinyl)
1-4 (HF) 293 K
Various gases
77, 300 K
77, 300K
77, 300K
77K
77K
77K
5.0-6.7 (02)
2.0 (H202)
o-o.1
(peroxide)
Vaclair
77K
N2 air
e, 02 air
200K
Various
320 (HCHO) 423 K
0.04 gas 300-423 K
0.04 gas 300-423 K 1 5 3
Air 68
0.08 H2
0.015 CH4
0.03H2
77K 211
77, 300K 206
77, 300K
vaclair
77K
+ Dose effect s 271
+ Crosslinker
46
46
49
254
204,211
WW.V) 251
Reduces with
increase in
methylene
110
110
210
210
210
273
273
273
273
Warming 1 3
142
93
36
114
pH dependence 253
Warming 1 9
39
50
Aq. soln.
Dose rate
dependence
Al so e
3 5
1 0 3
8 3
5 5
29
37
1 5 3
206
109
Radical pairs 74
References page II - 493
II / 490 RADIATION CHEMICAL YIELDS: G VALUES
TABLE 2. COPOLYMERS
Copolymers G(R) C(X) G(S) G(products)
Radiation
conditions Comments Refs.
2.1. COPOLYMERS WITH ETHYLENE
Poly(ethylene-co-1-butene)
Poly(ethylene-co-ethyl acrylate)
Poly(ethylene-co-hexene)
Poly(ethylene-co-propylene)
2.92
Various
Butyl rubber
Halogenated butyl rubber
2.3 (total)
0.19 (allyl)
3.1-4.0
2.53-3.2
0.43, 0.83 0.11, 0.35
0.69
1.1
0.913.2
0.26
1.2
0.33
3.2
0.16
Various Various
O-O.6 3.9-6.09
Dose Dose
dependent dependent
2.2. COPOLYMER WITH METHYL METHACRYLATE
Poly(methy1 methacrylate-co-
bromomethyl methacrylate)
Poly(methy1 methacrylate-co-
chlorotrifluoroethylene)
0.2-1.4 0. 06-0. 1
Poly(methy1 methacrylate-co-
dichlorostyrene)
Poly(methy1 methacrylate-co-dimethyl
itaconate)
Poly(methy1 methacrylate-co-
hexafluoroisopropyl methacrylate)
Poly(methy1 methacrylate-co-
hexyl methacrylate)
Poly(methy1 methacrylate-co-
methacrylic acid)
Poly(methy1 methacrylate-co-meth-
acrylic acid-styrene)
Poly(methy1 methacrylate-co-meth-
acrylic acid-co-cumyl phenyl
methacrylate)
Poly(methy1 methacrylate-co-
methacrylic acid-co-2-naphthyl
methacrylate)
Poly(methy1 methacrylate-co-
methacrylic acid)
Poly(methy1 methacrylate-co-2
naphthyl methacrylate)
Poly(methy1 methacrylate-co-
methacrylonitrile, vinylidene
chloride, methyl-a-chloroacrylate,
a-chloronitrile ter polymers)
Poly(methy1 methacrylate-co-methyl
bromoacrylate)
1.3
0.4
0. 53- 0. 87
3.6
22
1.8, 2.06
2.9
1.2
273 K
77K 20% MAA
238
1.6 238
0.06
2.0 238
1.06 238
1.9-3.1 1 4 5
2.0 0.41 4.16
0. 7- 1
2.1
2.1
3.2-3.5 *
1.0*
2. 0-3. 1
1.09
Various
various
various
Various
303-423 K
e, air
303-423 K
303 K
various
Various
various
8.6-11.0 (02)
5(COOH)
Air
303-423 K
Ai r
Air
Air
Various gases, 293-298
02
various Various
0.07-0.62 gel
dose
Various chain 77-398 K
ends
Various gases 77K
77K
77K
+ Additives
+ Additives
23%, 36%
Propylene
+ Additives
+ Additives
2.0 GPa
+ variation
In terpolymer
1 0
1 2 5
89
1 2 5
1 0
1 2 7
70
1 2 5
1 0
96
1 0 1
116
104
1 6
182
Review 186
various sources 195
Chloro and
bromo
139
50
*G(S)- G(X)
*G(S)- G(X)
139
219
220
65
137
1 7
59
65
137
1 4 6
1 3 3
238
TABLE 2. contd
C o p o l y me r s II / 491
Copolymer
G(R) cm G(S) G(products)
Radiation
conditions Comments Refs.
Poly(methy1 methacrylate-co-methyl- 3.1
a-chloroacrylate)
Poly(methy1 methacrylate-co-methyl-
a-chloroacrylate)
Poly(methy1 methacrylate-co-methyl-
2-chloroacrylate)
Poly(methy1 methacrylate-co-methyl-
a-chloroacrylonitrile)
Poly(methy1 methacrylate-co-methyl- 5.9
wcyanoacrylate)
Poly(methy1 methacrylate-co-methyl-
a-fluoroacrylate)
Poly(methy1 methaqlate-co-methyl
fluoroacrylate)
Poly(methy1 methacrylate-co-
3-oximino-2-butanone methacrylate)
Poly(methy1 methacrylate-co-
tribromophenyl methacrylate)
Poly(methy1 methacrylate-co-
trichloroethyl-alpha-chloroacrylate)
Poly(methy1 methacrylate-co-
trichlorophenyl methacrylate)
Poly(methy1 methacrylate-co-
trifluoroethylene methacrylate)
Poly(methy1 methacrylate-co-
vinylidene chloride)
Poly(methy1 methacrylate-co-
vinylidene fluoride)
0.06
6.6
o-o.44
0.07-0.19
3.8
0.05-0.7
3.1
2.8*
1. 0-2. 2
2.4
> 0.55
0.38-2.2
1. 4-2. 4
Poly(glycidy1 methacrylate-co-ethyl
methactylate)
Poly(glycidy1 methacrylate-co-ethyl 6.5
acrylate)
1. 35-8. 5
0.4-4.4
1.9
2. 8-3. 4
1.6
1.6
1.51-5.5
2.3. COPOLYMERS WITH STYRENE
Poly(styrene-co-acrylates)
Poly(styrene-co-acrylonitrile) 0.077
0.4-2.8 77 K 0.04-0.59
0.14-4.2 300 K
Poly(styrene-co-butadiene) 4.3133
0.3-3.0
various
various
0.055
0.0-0.09
2.8117
Poly(styrene-co-cyanoacrylates)
Poly(styrene-co-1-mercaptoethylene)
Poly(styrene-co-methyl acrylate)
Various
0. 04- 0. 38
various
2. 18- 2. 47
CO, CH4,
CO* etc.
0.40-2.76 77 K
0.14-1.39 300K
Poly(styrene-co-methyl methacrylate) 0.18 0.83 (gases)
Poly(styrene-co-methacrylonitrile) 0.31-2.16
Poly(styrene-co-butyl vinyl ketone)
Poly(styrene-co-methyl isopropyl ketone)
2.4. COPOYMERS WITH SULFUR DIOXIDE
Poly( 1-butene-co-sulfur dioxide) Various gases
1 2
Poly(2-butene-co-sulfur dioxide)
Poly(cyclohexene-co-sulfur dioxide)
Poly(4,4-dimethylpentene-co-sulfur dioxide)
Various gases
Various gases
Various gases
77K 14% MCA
77K
77K
77K
*G(S)- G(X)
14% CAN
20% MCA
Various
Air
Also TPBM
77K
*G(S)- G(X)
77K
Various
compositions
246
1 3 3
24
1 7
1 3 3
1 3 3
6 5
1 3 7
69
72
140
72
6 5
1 7
137
65
246
73
34
Vat
Air
313K
77K
77K
Various
temperatures
Vat
Various 215,221
compositions
Effect of 104
pressure
3
Block 98
copolymers
73
1 9
12- 80% s t y 126
77 WR),
300 W(gas)
various 216
compositions
51% sty 132
e
e
various 199
compositions
239
239
273-423 K 31,124,150
e 1 3 1
273-423 K 31,124
273-423 K 31,124
273-423 K 31,124
References page II - 493
II / 492 RADIATION CHEMICAL YIELDS: G VALUES
TABLE 2. contd
Copol ymer G(R) G(X) G(S)
G(products)
Radiation
conditions Comments Refs.
Poly(ethylene-co-sulfur dioxide)
Poly(hexene-l-co-sulfur dioxide)
Poly(isohutene-co-sulfur dioxide)
Poly(3-methyl-1-butene-co-sulfur
dioxide)
Poly(propylene-co-sulfur dioxide)
1.8
2.2
2. 5. OTHER COPOLYMERS
Poly(buty1 methacrylate-co-1-naphthyl
methacrylate)
Poly(glutamic acid-co-tyrosine)
Poly(glycolic acid-co-l-lactic acid)
Poly(glycidy1 methacrylate-co-
3-chlorostyrene)
Poly(hydroxy butyrate-co-valerate)
2. 23- 2. 36
1.49-1.53
1.0
various
Poly(methacrylonitrile-co-methyl-
2-chloroacrylate)
Poly(N-vinylpyrrolidone-co-r-butyl- 3.01
s-vinyl thiocarbonate)
Poly(acrylonitrile-co-butadiene)
Poly(acrylonitrile-co-chloroprene)
Poly(tetrafluoroethylene-co-
hexafluoropropylene)
Poly(tetrafluoroethylene-co-propylene)
Poly(viny1 chloride-co-ethylglycodi-
methacrylate)
Poly(vinylidene chloride-co-dimetbyl
itaconate)
Poly(vinylidene chloride-co-hexafluoro-
propylene)
Tetrafluoroethylene, perlluoro methyl
vinyl ether copolymer 2: 1
Various gases
Various gases
Various gases
Various gases
Various gases
0.14
0.03-0s o-o.5
0.42
3.0-0.5
201150
3.3
1.3
1.16
2.1-3.4
3.2-43.
Various gases
1 ,Cester
3.5 (Gas)
0.42
2.3-2.1
0. 6-5. 2 (HF)
30 (d.b.)
1.2
0.93 (CF4)
0.31 (COF2)
0.055 (CO2)
0.14 (CF3 OCF3)
1.43 (total gas)
0.34 (acid
fluoride)
0.9 New chain ends
1 (-CF2-CF3)
0.09 (-CFr-0-CFs)
0.5 (CFz-COOH)
0.2(-CF = CF2)
Polysulphone-polydimetbyl siloxane various
block copolymer
273-423 K
273-423 K
273-423 K
273-423 K
273-423 K
124
31,124
31,124
Poly(31,124, 150
31, 124, 150
300K
77K
300 K
Benzene soln. 1
various 214
compositions
various 203
compositions
144
17, 263, 273, Different 217
303 K compositions
e, gamma 218
77K
Air
*G(S)- G(X) 1 7
+ Warming 1 3
104
119
106
N2
240 C
Emulsion 1 2 1
polymer + H 20
116
266
8
VaclairlH 2 0
e
*G(S)- G(X) 17
+ Additives 166
229
268
Dose and 272
molecular
weight effects
TABLE 3. POLYMERS BLENDS
Polymers Blends and Composites II / 493
Polymer Blends G(X) G(S)
Comments Refs.
Poly(methy1 methacrylate)/
Poly( 1-naphthyl(methacrylate)
Poly(methy1 methacrylate)/
Poly(styrene-co-acrylonitrile)
Poly(methy1 methacrylate)/styrene-
acrylonitrile
Poly(methy1 methacrylate)/Acrylonitrile
0.025
0.041
0.034
0.02
0.008
0. 042
0. 036
0. 009
0.01
0.14 Benzene 1
0.051 50% PMMA 1 6 1
0. 027 SAN 100 242
0. 15 85
0. 21 50
0. 23 15
0. 14 ACN 100 242
0. 25 85
0. 34 50
0. 88 15
TABLE 4. COMPOSITES
Polymer Composites G(products)
Radiation
conditions Refs.
Glass-DGEBA-DDM H2, CO, 32 77 K, RT 227
Color-DGEBA-DDM Hz, CO, COz
77 K, RT 227
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,.
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~

.
_
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_
_

._
-
_
SECTION III
PHYSICAL PROPERTIES OF
MONOMERS AND SOLVENTS
n
Physical Properties of Monomers
Daniel R. Bloch
Lakeshore Research, 5536 W. Branch Trail, Racine, WI 53402, USA
A. Introduction
B. Tables of Physical Properties
Tabl e 1. Acetylenes
Table 2. Acid Dichlorides
Table 3. Acroleins
Table 4. Acrylamides/Methacrylamides
4.1. Acrylamides
4.2. Methacrylamide
Table 5. Acrylates/Methacrylates
5.1. Acrylate, Acids/Esters
5.2. Methacrylate, Acids/Esters
Tabl e 6. Alcohols
6.1. Alkanediols
6.2. Ether Diols
Table 7. Ally1 Functional
Table 8. Amines, Difunctional
Tabl e 9. Anhydrides
9.1. Monoanhydrides
9.2. Dianhydrides
Table 10. Butadi enes
Tabl e
Tabl e
Table
Table
Table
Tabl e
1
10.1. 1,2-Butadienes
10.2. 1,3-Butadienes
1. Butenes
11 .I. 1 -Butenes
11.2. 2-Butenes
2. Epoxi des
12.1. Monoepoxides
12.2. Diepoxides
3. Ethylene Halides
4. Fumar i c, Aci ds/ Est er s
5. l socyanat es
6. Lact ams
Tabl e 17. Lactones
Table 18. Maleic, Acids/Esters
Tabl e 19. Propenes
Tabl e 20. St yrenes
Table 21. Vinyl Functional
21.1. Aryl
2 1.2. Esters
21.3. Ethers
Ill-l
Ill-4
Ill-4
Ill-4
Ill-4
Ill-4
Ill-4
Ill-6
Ill-8
Ill-8
Ill-l 2
Ill-l 6
Ill-l 6
Ill-l 8
Ill-l 8
Ill-20
Ill-20
Ill-20
Ill-24
Ill-24
Ill-24
Ill-24
Ill-26
Ill-26
Ill-26
Ill-26
Ill-26
Ill-28
Ill-28
Ill-30
Ill-30
Ill-32
Ill-32
Ill-32
Ill-32
Ill-34
Ill-36
Ill-36
Ill-36
Ill-38
21.4. N-substituted
21.5. Sulfonates
Ill-38
Ill-40
A. INTRODUCTION
This chapter contains some of the principal properties of the
more common monomers. The monomers are arranged
alphabetically, in groups, with derivatives listed alphabeti-
cally within the groups. Compounds are listed under their
most commonly used names in polymer chemistry. There-
fore, some names are not in agreement with the nomencla-
ture rules of the International Union of Pure and Applied
Chemistry.
Data are taken from a variety of published literature,
including the 3rd edition of the Polymer Handbook,
The Brandon Worldwide Monomer Reference Guide and
Sourcebook, the Aldrich Catalog Handbook of Fine
Chemicals, and Polysciences Monomers/Polymers,
Scientific Polymer Products, TCI America, Lancaster
and Janssen Chemica catalogs. Where a range is reported
in the literature, the average value is used here for melting
points and boiling points. No attempt was made to verify
the reported values experimentally.
Linear structures are given for most monomers. Mole-
cular formulas are provided when linear structures cannot
be unambiguously drawn.
Molecular weight is calculated based on the International
Atomic Weight values.
Boiling point is given in degrees Celsius (C), at
760mmHg, unless indicated otherwise by the value in
mmHg following a slash (/).
Melting point is given in degrees Celsius (C), at
760mmHg, unless indicated otherwise by the value in
mmHg following a slash (/).
Refractive index is given at 20C unless indicated
otherwise by the temperature in Celsius following a slash
(4.
Density is relative to water at 4C and measured at 20C
unless otherwise indicated by the value following a slash
(4.
Flash point was determined by the closed-cup method,
using a Setaflash apparatus.
III / 1
III / 2 PHYSICAL PROPERTIES OF MONOMERS
RTECS# is the reference to the Registry of Toxic Effects
of Chemical Substances.
R&S is the reference found in the Sigma-Aldrich
Library of Regulatory & Safety Data, available from
Aldrich Chemical Company.
ET-NMR is the reference to spectra in the Aldrich
Library of 13C and H ET-NMR Spectra, available from
the Aldrich Chemical Company.
ET-IR is the reference to spectra in the Aldrich Library
of IT-IR Spectra, available from the Aldrich Chemical
Company.
Merck Index is the reference to The Merck Index,
Merck & Co., Inc., Whitehouse Station, NJ.
Beilstein is the reference to Beilsteins Handbuch
der Organischen Chemie, Springer-Verlag, New York,
NY.
Fieser is the reference to L. F. Fieser and M. Fieser,
Reagents for Organic Synthesis, John Wiley, New York,
NY.
Abbreviations: (d) decomposes; (s) sublimes; (aq)
aqueous.
III f 4 PHYSICAL PROPERTIES OF MONOMERS
B. TABLES OF PHYSICAL PROPERTIES
TABLE 1. ACETYLENES
Formula RC = CR CAS
Registry Boiling Melting
Name R R Number Mol. wt. poi nt (C) point (C)
Acetylene -H -H 74- 86- 2 26. 04 - 82 - 84( s)
-, Chloro -Cl -H 60. 48 - 32 - 126
-, Dichloro- -Cl -Cl 94. 93 - 66
- , Diphenyl-
-CsHs -CsHs
501- 65- 5 178. 23 60 170/ 19
- 9 Phenyl- -CsHs -H 102.14 1 4 3
TABLE 2. ACID DICHLORIDES
Formul a ClC(O)RC(O)Cl CAS
Registry Boiling Melting
Name R Number Mol. wt. poi nt (C) point (C)
Adipoyl -(CH2)4- 111-50-2 183.03 10612
Azelaoyl
-(CH2)7-
123-98-8 255.12 166/18
Diethylmanoyl -C(CH2CH3)2- 54505- 72- 5 197. 06 198
Dodecanedioyl -CH2)10- 4834- 98- 4 267. 20 140/0.5
Glutaryl -(CH2)3- 2873- 74- 7 169. 01 217
lsophthaloyl -Cf,H4- 99- 63- 8 203. 02 276 43
Malonyl -CH2- 1663-67-8 140.95 54119
Methylpimeloyl -(CH2)2CHI(CH3)(CH2)2- 44987- 62- 4 197. 06 I18/10
Oxalyl -co-co- 79- 37- 8 126. 93 61 - 8
Phthaloyl -CeH4- 88- 95- 9 203. 02 270 12
Pimeloyl -CH2)5- 142-79-0 197.06 113/5
Sebacoyl
-(CH2)8-
111-19-3 239.14 168/12 - 2. 5
Suberoyl
-(CH2)6-
10027-07-3 211.09 162/15
Succinyl -W2)2- 543- 20- 4 154. 98 190 16
Terephthaloyl -CcjH4- 100-20-9 203. 02 266 80
Thionyl ClC(S)Cl 7719-09-7 118.97 79 - 105
TABLE 3. ACROLEINS
Formula HC(O)CR = CHR CAS
Registry Boiling Melting
Name R R Number Mol. wt. poi nt (C) poi nt (C)
Acrolein -H -H 107-02-8 56. 06 53 - 87
-, 2-Chloro- -Cl -H 90.51 40130
- ,
2-Methyl- -CH3 - H 78- 85- 3 70. 09 68 -81
-, 3-Methyl-,
trans-(Crotonaldehyde) -H -CH3 123-73-9 70. 09 104
-, 2-Chloro-3-methyl- -Cl -CH3 104.54 1 4 8
TABLE 4. ACRYLAMIDES/METHACRYLAMlDES
CAS Registry Boiling Melting
Name R R Number Mol. wt. poi nt (C) poi nt (CT)
4.1. ACRYLAMIDES H2C=CHC(0)NRR
Acrylamide -H -H 79- 06- 1 71.08 125125
-> Acetyl-, N- -C(0)CH3 - H 1432- 45- 7 113.12 1 2 9
-, Adamant yl -, N-
-CIO& -H 19026-83-6 205. 30 155
-, Allyl-, N- -CH2CH=CH2 -H 2555-13-7 111.14 120/19
-, Benzyl -, N- -CH&jH5 -H 13304-62-6 161.20 70
- ,
Butoxymethyl-, N- -CH20(CH2)3CH3 -H 1852-16-0 157.21 12510.3 - 9
-, tert-Butyl-, N-
-WH3)3
-H 107-58-4 127.19 1 2 8
-> Cyclohexyl-, N-
-C6Hll
-H 3066- 72- 6 153. 23 113
-, Cystamine-bis-, N,N- -CH2CH2SSCH2CH2- -H 60984- 57- 8 260. 38 123
-, Diacetone-, N- -C(CH3)2CH2C(0)CH3 -H 2873- 97- 4 169. 23 9310. 1 55
- . Diallyl-, N,N- -CH2CH=CH2 -CH2CH=CH2 3085- 68- 5 151.21 10813
-, Di-n-butyl-, N,N-
-(CHdKH3 -(=2)3CH3
2274-13-7 183.29 9711
Acetyl enes, Aci d Di chl ori des, Acrol ei ns, Acryl ami des Methacryl ami des III /5
Densi ty
(at 20C)
Refractive
index (at 20C)
Flash
point (C)
RTECS
Number R and S FT-NMR FT.IR Merck Beilstein Fi eser
1. 000 A09600000 1,ll
0. 990 1(2),27111 1(3), 533A 1(2),946B 11,9428 5, 656 1, 335
0. 929 1. 548
Densi ty Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number
1.259 1. 4700
1.143 1. 4680
1.145 1. 4590
1.069 1. 4680
1.324 1. 4720
>llO
>llO
7 4
>llO
107
180
4 7
>llO
None
>llO
>llO
>llO
>llO
7 7
180
None
1.449 1.4650
1.217 1.4720
1.455 1.4290
1.409 1.5684
1.205 1.4690
1.121 1.4680
1.172 1.4680
1.407 1.4680
1.631 1.5190
NT2625000
KI2950000
WN4900000
wz1797000
XM5 150000
RandS FT-NMR FT-IR Merck Beilstein Fi eser
l(l), 8675 1(1),741A 2, 653
1(1),869C 2, 709
l(l),8676 1(1),1211B l( 1),74OB 2, 687
1(1),869E 1(1)1212C 2(4),2127
l( 1),8671 1(1),1212A l( 1),74OD 2, 634
1(2),1981H 1(2),352A 9, 834
1(1),867F 1(1),1211A 1(1),740A 2(1),252 12, 291
1(1),867K 1(1),1212B 1(1),741B
1(1),867D l( 1),739C 11,6867 2, 542 17, 241
1(2),1981G 1(2),351D 11,7439 9, 805 14, 263
1(1),869A 1(1),741C 2, 671
1(1),869D 1(1),742B 2, 719
1(1),869B 1(1),741D 2, 694
1(1),867H 1(1),1211C l( 1),74OC 11,8844 2, 613
1(2),19811 1(2),352B 9, 844
1(2),3197F 1(2),1227B 11,9278 13,297
Densi ty
(at 20C)
Refractive
index (at 20C)
Flash
point (C)
RTECS
Number R and S FT-NMR FT-IR Merck Beilstein Fieser
0. 839 1. 4025 - 19 AS105000 1(1),515A 1(1),733B 1(1),470D 11,122 1,725 10,2
1. 199 1. 463
0. 847 1. 4160 - 16 022625000 1(1),515B 1(1),733C 1(1),471A 1(3),2981
0. 846 1.4365 9 GP9625000 1(1),515G 1(1),472C 11,2599 1, 728
1. 478
Density
(at 20C)
Refractive
index (at 20C)
Flash
poi nt (C)
RTECS
Number R and S FT-NMR FT-IR Merck Beilstein Fi eser
1.122 AS3325000 1(1),877K 1(1),1221A 1(1),749B 11,123 2, 400
0. 9790 1.4620 >llO AS3450000
, AS3460000 4(4),664
>llO AS3475000 l(l),8871 1(1),1236A l( 1),75OC 11,2943
III / 6 PHYSICAL PROPERTIES OF MONOMERS
TABLE 4. contd
Name R R
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
-, Diethyl-, N,N-
-, 1,2-Dihydroxyethylene-
bis-,N,N
-, Diisopropyl-, N,N-
-, 4,CDimethoxybutyl-, N-
-, Dimethyl-, N,N-
-, 3-(Dimethylamino)-
propyl-, N-
-1 l , l-Dimethyl-2-
sulfoethyl-, N-(AMPS)
-, Diphenylmethyl-,N-
-, Ethylenebis-,N,N-
-, Ethylhexyl-,N-
-, 2-Glycolic acid, N-
-, 2-Glycolic acid
methyl ester, N-
-, Hexamethylenebis-, -
N,N
-, rert-Hexyl-, N-
-, Hydroxymethyl-,
N- (solution)
-, Isobomyl-, N-
-, Isobutoxymethyl-, N-
-, Isopropyl-, N-
-, Isopropylidenebis-,
N,N-
-, 3-Methoxypropyl-, N-
-, Methyl-, N-
-, Methylenebis-, N,N-
-, (1-Methoxy)
-, (Methoxy)-
acetoxymethyl-, N-
-, Morpholinoethyl-, N-
-, 1-Naphthyl-, N-
-, Octadecyl-, N-
-, Octamethylenebis-,
N,N-
-, rert-Octyl-, N-
-1 Phthalamidomethyl-, N-
-, 2,2,2-Trichloro-l-
hydroxyethyl-, N-
-, Tri(hydroxymethyl)-
methyl-, N
-, 1,1,3-Trimethylbutyl-, N-
-, Trimethylenebis-, N,N-
-, Triphenylmethyl-, N-
-CHzCHa -CH2CH3 2675-94-7 127.19
-CH(OH)CH(OH)- -H 868-63-3 200.19
93119
156(d)
-CWHh -CH(CHdz 44975-46-4 155.24 54 jo.4
-WzhWOCWz -H 38486-53-2 187.24 13510.7
-CH3 -CH3 2680-03-7 99.13 82121
-4CHzhNCH3)z -H 3845-76-9 156.23 117/2
1 8
-C(CH3)2CH2S03H -H 15214-89-8 207.25 195(d)
-CH(%Hsh
-CH2CH2-
-CH2CH(CH#H3)
(CHdKH3
-CH(OH)C(O)OH
-CH(OH)C(0)OCH3
-H 10254-08-7 237.30
-H 2956-58-3 168.20
-H 91625-16-0 183.30
140
-H 6737-24-2 163.13
-H 77402-03-0 173.17
1 7 8
12310.5
95
-md6- -H 7150-41-6 224.28
-CH&H2C(CH3)s -H 51330-07-5 155.24
-CH20H -H 924-42-5 101.11
74
1 3 5
100
-C 1oH 17
-CH20CH2CH(CH&
-CWHd2
-WH3)2-
-H
-H
-H
-H
17159-04-5
16669-59-3
2210-25-5
207.31
157.21
113.16
182.22
1 3 5
1 0 8
9012 6 1
210
-(CH2)3OCH3 -H 107374-86-7 143.19
-CH3 -H 1187-59-3 85.11
-CH2- -H 110-26-9 154.17
9910.3
106/4
-C(OCH3)C(0)OCH3 -H 77402-03-0 173.17 73
-CH2CH2NC4Hs0 -H 5117-12-4 141.17
-C 10H7
-H 22302-62-1 197.24
-(CH2)17CH3
-H 1506-54-3 323.56
-W2)1- -H 2945-02-0 252.35
158150 >llO
1 3 8
75
1 3 8
-CH2NCsH402
-CH(OH)CCls
-H
-H
-H
4223-03-4
80500-94-3
183.29
230.22
218.47
-C(CH20H)3 -H 13880-05-2 175.18
-H 25269-93-6 169.27
-H 4887-13-2 182.22
-H 102548-89-0 313.40
125125
58
190
170
139
55
112
204
4.2. METHACRYLAMIDES H2C=C(CH3)C(0)NRR
Methacrylamide
-, Acetyl-, N-
-, Acetylphenyl-, N-
-, Allyl-, N-
-, 3-Aminopropyl-, N-,
hydrochloride
-, Benzyl -, N-
-, Bis(diethylaminoethyl)-,
NJ+
-, Butoxymethyl-, N-
-H
-C(0)CH3
-CdbC(O)CH3
-CH2CH=CH2
-(CH2)3NH2.HCl
-CHZC~H~
-CHZCH~N(CH~CH&
-CH20(CH&CH3
-H 79-39-0 85.11
-H 44810-87-9 127.14
-H 58813-69-7 203.24
-H 2186-33-6 125.17
-H 72607-53-5 178.66
-H
-CH2CH2N-
(CH2CH3h
-H
-, tert-Butyl-, N-
-, 2-Cyanoethyl-, N-
-, 2-Cyanoethyl-, N-,
methyl-, N
-WH3)3 -H
-CH2CH2CN -H
-CH2CH2CN -CH3
3219-55-4 175.23
76392-05-7 183.28
5153-77-5
28384-61-4
6554-73-0
24854-94-2
171.24
142.20
138.17
152.20
215
7611.2
9012.2
12210.4
105fO.3
1 6 3
113/1
109
1 3 8
1 3 8
124
82
60
46
46
AcrylamidedMethacrylamides III 17
Densi ty Refractive Flash RTECS
(at 20C) index (at 20C) poi nt (C) Number R and S FT-NMR FT-IR Merck Beilstein Fi eser
0.962 1.4730 7 1 AU3230000
0.949 1.4820 >llO
160 1(1),1065K 1(1),1438C
AI8967330
1.074 1.4130 None
0.970 1.4610 7 9
AS3600000
AS3630000
AS3675000
AS3678000 l(l),8835
AI8967330 1(1),913D
1.122 1.5120 >llO 27(4),278
1.10 UC6475000 1(1),877L 1(1),1221B l( 1),749C 2(2),399
1(1),885K l( 1),1233C
l(l),8931 1(1),1244C 1(3),784B 4(3),130
4(4), 1268
1(1),883K 4(3),526
1(1),915E 1(1),1276B 1(1),781A
1(1),913D l( 1),1272B
1(1),885J 1(1),75OA 2(4),1472
4(4),517
1(1),123OC 1(1),749D
1(1),1272B
l( 1),883M 1(1),1231B
1.4702
0.96 1.46 122
1.4755
III / 8 PHYSICAL PROPERTIES OF MONOMERS
TABLE 4. contd
Name R R
CAS Registry Boiling Melting
Number Mol. wt. point (C) poi nt (C)
-, Cyclohexyl-, N-
-, Diallyl-, N,N-
-, Dibenzyl-, N,N-
-1 Dibutyl-, N,N-
-, 3-Di(butyl)aminopropyl-, N-
-, Diethyl-, N,N-
-, 3-(Diethylamino)propyl-, N-
-, Diisopropyl-, N,N-
-, 2,2-Dimethoxyethyl-, N-
-, Dimethyl-, N,N-
-, 2-(Dimethylamino)ethyl-, N-
-, 3-(Dimethylamino)propyl-,
N -
-1 Dodecyl-, N-
-, Ethylenebis-, N,N-
-, 2-Ethylhexyl-, N-
- , 2-Hydroxyethyl-, N-
-, Hydroxymetbyl-, N-
-, 4-Hydroxyphenyl-, N-
-, Isobutoxymethyl-, N-
- , Isopropyl-, N-
-, Methoxymetbyl-, N-
-, Methyl-, N-
-, Methylenebis-, N,N-
-, Methyl-, N-, Phenyl-, N-
-, Met hyl -, N-, 2,2-dimethoxy-
ethyl-, N-
-, 3-(N-morpholino)propyl-, N-
-, 2-(2-Oxo-l-imidazolidinyl)-
ethyl-, N-
-, Phenyl-, N-
-, Phenyl-, N-, Phenylethyl-, N-
-, 3-(Trifluoromethyl)phenyl-,
N -
-, 3-(Trimethylammonium)-
propyl-, chloride,
N- (eq. solution)
-C6Hll -H
-CHaCH=CHz -CH2CH=CH2
-C&C&I5 -CH&&
-(CHz)3CH3 -(CHz)sCHs
-(CHzhNW-b),CH,h
-H
-CH2CH3 -CH2CH3
-(CW~NCH~CH~)Z -H
-CWCHh -WCHd2
-CH2CH(OCH3)2 -H
-CH3 -CH3
-CH2CH2N(CH3)2 -H
-(CW3WCH3)2
-H
-(CWIICH~
-H
-CH2CH2- -H
-CHzCH(CHzCH3)(CH2)3CH3 -H
-CH2CH20H -H
-CHzOH -H
-CsH&H -H
-CHz0CH(CH3)2 -H
-CWCHh
-H
-CHaOCHs -H
-CH3 -H
-CHa- -H
-CH3
-CsHs
-CH3 -CH2CH(OCH3)2
-O-bhNWbO
- H 55937-58-1 212.30 150/0.08
-CHaCH2C3H5N20 - H 3089- 19-8 197.24 100
-CsHs
-H 1611-83-2 161.20 84
-CsH5 -cH2cH&jH5 76392-02-4 266.37 63
-C&&F3 -H 783-05-1 229.20 95
-(CHz)sN(CHs)s HCl -H 51410-72-1 220.74 - 22.5
2918-67-4
13169-99-8
57625-30-6
22240-86-4
76392-03-5
5441-99-6
51745-62-1
95984-11-5
6976-91-6
13081-44-2
5205-93-6
1191-39-5
6117-25-5
5238-56-2
923-02-4
19243-95-9
4548-27-0
13749-61-6
3644-12-0
3887-02-3
2359-15-1
2918-73-2
95984-81-9
167.25
197.32
265.36
197.32
253.41
141.21
197.30
169.27
173.21
113.16
156.34
170.26
253.43
196.25
197.32
129.16
115.13
177.20
171.24
127.19
129.16
99.13
182.22
238.31
187.24
50/1.1
U/O.8
12510.13
8217
134/10
66110
8711.8
13412
145/0.08
110/0.3
14711.2
cu. 100
127/5
112/115
80.03
8813.5
8812
7212
102
4 1
47
27
170
- 3 7
154
90
164
50
TABLE 5. ACRYLATES/METHACRYLATES
Name R
CAS Registry Boiling Melting
Number Mol. wt. poi nt (C) point (C)
5.1. ACRYLATE, ACIDS/ESTERS H2C = CHC(O)OR
Acid
Ally1 ester
Anhydride
Benzyl ester
4-Biphenylyl ester
Bisphenol A ethoxylate diester
Bisphenol A diglycidyl
ether diester
2-Bromo-
3-Bromo-, cis-
2-Bromo-, ethyl ester
2-Bromoethyl ester
2-Bromomethyl-
2-Bromometbyl-, ethyl ester
2-Bromomethyl-, methyl ester
1,3-Butylene diester
1,4-Butylene diester
2-Butylene- 1,4 diester
-H 79-10-7 72.06
-CH2CH=CH2 999-55-3 112.13
-C(O)CH=CHa 205 1-76-5 126.11
-CH~C~HS 2495-35-4 162.19
--C6H&sH5
13026-23-8 226.27
(-(CH2CH20C6H4)2C(CH3)2 64401-02-1 424
(-CH2CH(OH)CH20C6H&C(CH3)2 4687-94-9 484.55
HaC=CBrC(O)OH
BrCH=CHC(O)OH
HzC=CBrC(0)OCH2CH3
-CHzCHzBr
H$=C(CHaBr)C(O)OH
H2C=C(CHzBr)C(O)OCH2CHs
H2C=C(CH2Br)C(O)OCHs
-CH2CH2CH(CH3)-
-(CH2)4-
-CH2CH=CHCH2-
10443-65-9
1609-92-3
4519-46-4
4823-47-6
72707-66-5
17435-72-2
4224-69-5
19485-03-1
1070-70-8
150.97 63
150.96 63
164.99 72/78
179.03 5215
164.99 70
193.05 86120
179.02 36/1.3
198.22 7310.1
198.22 83/0.3
127. 16 60123
139 1 3
123
97135
110/8
224
Acrylates/Methacrylates III 19
Densi ty Refractive Flash RTECS
(at 20C) index (at 2OC) point (C) Number R and S FT-NMR FT-IR Merck Beilstein Fi eser
1.4731
1.4600
1.4744
0.940 1.4790 140
1 so02
1.100 1.4300 >llO UC6380000
0.97 1.46 107
s11225000
1.4707
0.97 1.4740
1.110 1.4560 >llO
1.053 1.427
4(3),276
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT-IR Merck Beilstein Fieser
1.051
0.880
1.0573
1.146 1.5450
1.180 1.5570
1.4774
1. 388 1.478
1.489 1.490
1.030 1.4500
1. 051 1.4560
0.9344 1.4422
1.4202
1.4320
1.4487
1.5143
1.4770
54
AS4375000 1(1),547A 1(1),776A 1(1),498B 11,124 2,397
8 2,400
1 0 1
>llO
>llO
78
93
>llO
l(l),5638 2,402
l(l),5631 2(4),1486
1(1),563K 1(1),806C 1(1),516C
AS4900000 1(1),745J 1(1),1031C 1(3),696D
AS5250000
uD3130000 2(4),170
III/l0 PHYSICAL PROPERTIES OF MONOMERS
TABLE 5. contd
Acrylates/Methacrylates
Name R
CAS Registry Boiling Melting
Number Mol. wt. point (C) poi nt (C)
2-(2-Butoxyethoxy)ethyl ester -CH2CH20CH2CH20(CH&CH3
2-Butoxyethyl ester -CH2CH20(CH&CH3
n-Butyl ester
-V-bMX
s-Butyl ester -CH(CH3)CH2CH3
t-Butyl ester
-WH3)3
2-Chloro- H2C=CClC(0)OH
2-Chloro-, butyl ester H2C=CCl(0)O(CH2)3CH3
2-Chloro-, ethyl ester H2C=CClC(0)OCH2CH3
2-Chloro-, methyl ester H2C=CCIC(0)OCH3
3-Chloro-, cis- Cl CH=CHC(O)OH
3-Chloro-, truns- Cl CH=CHC(O)OH
2-Chloroethyl ester -CHZCH2Cl
Cinnamyl ester -CH2CH=CHC&&
Crotyl ester -CH2CH=CHCH3
2-Cyano-, butyl ester H2C=C(CN)C(0)O(CH2)3CH3
2-Cyano-, ethyl ester H~C=C(CN)C(O)OCH~CHJ
2-Cyano-, isobutyl ester H,C=C(CN)C(0)OCH2CH(CHs)2
2-Cyanoethyl ester -CH2CH2CN
Cyclohexyl ester
46Hll
Cyclopentyl ester -Cd-b
n-Decyl ester
-(CHd&H3
2,3-Dibromopropyl ester -CHzCHBrCHzBr
2,3-Dichloropropyl ester -CH2CHClCH2Cl
Dicyclopentenyl ester 410H13
Dicyclopentenyloxyethyl ester -CH2CH20CloH13
2-(Diethylamino)ethyl ester -CH2CH2N(CH2CH3)2
3-(Diethylamino)propyl ester -CHzhWH2CW2
Di(ethylene glycol) diester -CH2CH20CH2CH2-
Dihydrodicyclopentadienyl ester -C10H15
2,3-Dihydroxypropyl ester -CH2CH(OH)CH20H
2-(Dimethylamino) ethyl ester -CH2CH2N(CH3)2
3-(Dimethylamino) neopentyl -CHzC(CH&CH2N(CHj)2
ester
3Qimethylamino) propyl ester -(CH2)3N(CH3)2
Dipentaerythritol pentaester (-CH2)3CCH20CH2C(CH20H)(CH2-)2
Di(propy1ene glycol) diester -CH2CH(CH3)0CH2CH(CH3)-
Di(trimethylolpropane) tetraester ((-CH&C(CH2CH3)CH&O
Dodecyl ester
-CW~ICH~
lH,lH,llH-Eicosafluoro- -CH2(CF2)gCHF2
undecylester
2-(2-Ethoxyethoxy)ethyl ester -(CH2CH20)2CH2CH3
2-Ethoxyethyl ester -CH#ZH20CH2CH3
Ethyl ester -CH2CH3
Ethylene diester -CH2CH2-
2-Ethylhexyl ester -CH2CH(CH2CH3)(CH2)3CH3
Fmfuryl ester -CH2C4H30
Glycidyl ester -CH2CH(-0-)CH2
Glycerol propoxylate triester -CH(CH3)CH20CH(CH20CH2CH(CH3)-)2
lH,lH,2H,2H-Heptadecafluoro- -CH#ZH2(CF&ZF3
decyl ester
lH,lH-Heptafluorobutyl ester -CH2CF2CF2CF3
Heptyl ester -(CHd&&
Hexadecyl ester
-(CH2)15CH3
2,2,3,4,4,4-Hexafluorobutyl ester -CH2CF$HFCF3
IH-Hexafluoroisoporpyl ester
-CWCF3h
Hexanediol diester -(CH2)6-
n-Hexyl ester -(CWsCH3
4-Hydroxybutyl ester
-(C&hOH
2-Hydroxyethyl ester -CH2CH20H
2-Hydroxy-3-phenoxypropyl -CH2CH(OH)CH#C6H5
ester
2-Hydroxypropyl ester -CH2CH(OH)CH3
Isobomyl ester -CloHl8
Isobutyl ester -CH2CH(CH3)2
125 1-90-3
141-32-2
2998-08-5
1663-39-4
26952-44-3
13401-85-9
687-46-7
80-63-7
1609-93-4
2345-61-1
2206-89-5
103123
63/2
1 4 5
59125
30125
176(d)
100/42
41120
52/50
- 6 4
60
6 1
84
23916-33-8
6606-65- 1
7085-85-0
1069-55-2
106-71-8
3066-71-5
16868-13-6
2156-96-9
19660-16-3
24910-84-7
33791-58-1
65983-31-5
2426-54-2
4074-88-8
12542-30-2
10095-20-2
2439-35-2
20166-73-8
232.28
172.22
128.17
128.17
128.17
106.5 1
162.62
134.56
120.54
106.51
106.51
134.57
188.23
126.16
153.18
125.13
153.18
125.13
154.21
282.38
212.34
271.94
183.04
202.25
248.32
171.27
185.27
214.22
204.27
146.15
143.19
181.24
64/20
10512
38/10
9216
9015
8114
10318
1 8 3
145/0.08
185150
105/6
5810.5
10514
lOOJO.
171.27
44/0.1
162
119/5
115/0.1
64112
5311.4
- 17
- 17
<-60
- 4 0
<-60
18526-07-3 157.22
60506-81-2 524.53
85136-76-1 242.27
94108-97-1 466.53
2156-97-0 240.39
4998-38-3 586.17
1 6 7
9510.5
120/1
115/1 49
7328-17-8 188.23
lO6-74- 1 144.17
140-88-5 100.12
2274-11-5 170.16
103-11-7 184.28
10525-17-4 152.15
106-90-1 128.13
52408-84- 1 428
27905-45-9 518.10
250
65/16
99
6712
217
92116
115178
- 7 2
- 9 0
loo/4
424-64-6 254.11
2499-58-3 170.25
13402-02-3 296.50
54052-90-3 236.11
2160-89-6 222.09
13048-33-4 226.28
2499-95-8 156.23
2478-10-6 144.17
818-61-1 116.11
16969-10-1 222.24
1211743
5611
170115
48112
84
295
190
9510.1
90112
- 4 5
- 101
999-61-1 130.15 77115 - 9 2
5888-33-5 208.30 275 - 15
106-63-8 128.19 132 -61
Acrylates/Methacrylates III /ll
Densi ty Refractive Fl ash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT-IR Merck Beilstein Fieser -
0.9821 1.4394
0.9497 1.4323
0.894 1.4180
0.8114 1.4140
0.8850 1.4108
9 0
3 9
17
UD3150000
1. 1404 1.4384
1. 189 1.4420 3 3
AS5960000
1. 1404 1.4384
1.0495 1.5660
0.986
1. 069
1 /a420 9 9
108
1.0690 1.4433 124 AT15OOOOO
0.975 1.4673 2 9 AS7350000
0. 8781 1.440
1.7803 1.5520
1.2603 1.4765
227
1.085 1.5010
0.9250 1.443
0.9180 1.441
1.118 1.4630
1.08 1.509
9 9
6 8
> 110
AS8225000
AS9450000
0.943 1.4380 5 8
0.90 1.439 7 5
AS8578000 1(1),771G 1(1),1073C 1(3),734A
0.928
1.1915
1.4400 6 8
115
1.101
0.884
1.4488
1.4790
1.4450
> 110
> 110
1. 016
0.9819
0.924
1. 090
0. 8859
1.1125
1.099
1.064
1.4390
1.4282
1.4060
1.4610
1.4360
1.4800
1.4490
1.4610
1.3380
102
6 5
15
100
7 9
7 6
AS9800000
AT0700000
AT0350000
AT0855000
AS9275000
1.418 1.3301
0. 8846 1.4311
0. 8620 1.4470
1. 398 1.352
1. 330 1.3190
1.010 1.4562
0. 8882 1.4280
1. 039 1.4520
1. 011 1.4502
1.160 1.5280
31 2(4), 1464
5 9
1 0
> 110
6 8
> 110
9 8
8 9
AT143OooO
AT1450000
AT1750000
1. 05 1.4448 6 5
0. 986 1.4760 9 3
0. 8896 1.4140 3 3 AT2100000 2(3),1227
1(1),719E 1(1),974A 1(1),642A 11,1539 2(2),388
1(1),719F l( 1),974B 1(3),674D 2(3),1228
1(1),563F 1(1),805C 1(1),516A 2,400
l( 1),563G 1(1),806A 1(1),516B 2,400
1(1),719D 1(1),973C
l( 1),727M
1(1),719G 1(1),974C
1(1),1088C
1(1),745C 1(1),1029B
1(1),729E 1(1),639B
l( 1),753L 1(1),1044C 1(3),72OC
l(l),7535 1(1),1044A 1(3),720B
3(3),543
4(3),649
2(3),1230
2(3),1232
2(3),1232
1(1),638C 11,3715 2,399 6, 251
1(3),675B 2(4), 1496
1(3),675A 2(3),1229
17(3), 1005
2(3),1228
2(4),1470
2(4), 1496
1(1),719H
HI/12 PHYSICAL PROPERTIES OF MONOMERS
TABLE 5. contd
Name R
Isodecyl ester
-(C&hCWCHdz
Isooctyl ester
-(CHz)5CWHdz
Isopropoxyethyl ester -CH#ZH20CH(CH3)z
Isopropyl ester -WCHh
Methallyl ester -CHzC(CHs)=CH2
2-(2-Methoxyethoxy) ethyl ester -CH2CHzOCH2CHzOCH3
2-Methoxyethyl ester -CH2CH20CHs
Methyl ester -CHs
2-Methylbutyl ester -CH2CH(CH3)CH2CH3
2-(N-Motpholino)ethyl ester -CHzCHzNC4Hs0
1-Naphthyl ester -C 10H7
2-Naphthyl ester
-C 10H7
Neopentyl ester
-CHFXH3)3
Neopentyl glycol diester -CHzC(CH&CHz-
No n y l e s t e r
-(CHdsCH3
Octadecyl ester -(CH2)17CH3
lH,lH,SH-Octafluoropentyl ester -CH2(CF&CF2H
n-Octyl ester
-(CHhCH3
lH,lH-Pentadecafluorooctyl ester-CHz(CF&CFs
Pentaerythritol tetraester (-CW4C
Penterythrltol triester (-CHz)3CCH20H
Pentaerythritol stearate diester (-CH2)2C(CH20H)CH20C(O)(CH2)1
2,2,3,3,3-Pentafluoropropyl ester -CHzCF2CFs
1 ,SPentanediol diester
-(CH2)5-
n-Pentyl ester
-(CHdKH3
2-Phenoxyethyl ester -CH2CH20C6H5
Phenyl ester
-C6H5
1,4-Phenylene diester -&$H4-
1 ,CPhenylene di(acrylic acid) CsH4(CH=CHC(O)OH)2
2-Phenylethyl ester -CH$H&,&
Trimethyl 2-phosphonoacrylate (CHsO)zP(O)C(C(O)OCHs)=CHz
Propargyl ester -CH2C E CH
n-Propyl ester -CH2CH2CH3
1,2-Propylene glycol diester -CH2CH(CH3)-
1,3Propylene glycol diester
-(CH2)3-
Tetradecyl ester
-(CHdnCH3
Tetra(ethylene glycol) diester -(CH2CHz0)3CH2CHz-
2,2,3,3-Tetrafluoropropyl ester -CH2CF2CF2H
Tetrahydrofurfuryl ester -t&H90
S,S-Thiodi-1,4-phenylene dithiol -SC6H4g%jH4S-
diester
2,3,3-Trichloro- ClCHz=CClC(O)OH
Tridecyl ester
-(CHdlzCH3
Tri(ethylene glycol) diester -(CH2CHzO)zCH&H-
2,2,2-Trifluoroethyl ester -CHzCFs
l,l,l-Tri(2-hydroxyethoxy- (-CH2CHzOCH&CCHzCHs
methyl)propane triester
Tri(2-hydroxyethyl) isocyanurate (-CH2CH2)sCsNsOs
triester
3,5,5-Trimethylcyclohexyl ester -CsHs(CHs)s
3,.5,5-Trimethylhexyl ester -(CH&CH(CHs)CH2C(CHs)s
Trimethylolpropane triester (-CH&CCHzCHs
Trimethylolpropane ethoxylate ((-CHzCHz0),CHz)3CCH2CH3
triester
Tri(propylene glycol) diester (-CH&Hs)CHzO)#ZHzCH(CH+
Vinyl ester -CH=CHz
5. 2. METHACRYLATE, ACIDS/ESTERS (H2C=C(CH3)C(0)OR)
Acid - H 79-41-4 86.09 1 6 3
2-(Acetoacetoxy)ethyl ester -CH2CHzC(0)OCH2C(O)CH3 21282-97-3 214.22 274
Ally1 ester -CH2CH=CH2 96-05-9 126.16 60143
Anhydride -C(0)C(CH3)=CH2 760-93-0 1 5 4 . 1 7 200
2-( 1 -Aziridinyl)ethyl ester -CH2CH(-NH-)CHz 6498-81-3 155.20 1 9 0
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
6CH3
1330-61-6
29590-42-9
212.34
1 8 4 . 2 5
1 5 9 . 2 1
114.14
126.16
174.20
130.14
86.09
142.20
1 8 5 . 2
198.22
198.22
142.24
212.25
1 9 8 . 3 1
324.55
286.12
184.28
454.13
352.34
298.30
510.72
204.10
212.25
142.20
1 9 2 . 2 1
148.16
218.21
218.21
176.22
194.13
1 1 0 . 1 1
114.14
184.19
184.19
268.44
302.33
1 8 6 . 1 1
156.18
386.56
121/10
125120
82119
51/103
70150
8614.6
56112
8 0
63127
67/0.2
21211
13810.4
3113
10515
7610.2
16013
88/41
5710.05
6515
- 1 0 0
689-12-3
818-67-7
7328-18-9
3121-61-7
96-33-3 - 7 5
19727-38-9
20069-66-3
52684-34-1
4513-36-4
2223-82-7
4813-57-4
376-84- 1
2499-59-4
307-98-2
4986-89-4
3524-68-3
92092-01-8
356-86-5
36840-85-4
2998-23-4
48145-04-6
937-41-7
6729-79-9
16323-43-6
3530-36-7
55168-74-6
10477-47-1
925-60-0
3 2
>315
18
15
30
50/100
9410.3
4717
103/0.6
87112
8 8
>300
10415
91/0.1
1 3 8
25151-33-1
21643-42-5
17831-71-9
7383-71-3
2399-48-6
129283-82-5
43140
6310.3
1 2 2 1 0 . 5
13810.4
>120/0.3
1 3 2
8719
2257-35-4 175.40
3076-04-8 254.41
1680-21-3 258.30
407-47-6 154.09
28961-43-5 428.48
~-60
64
72
150/10
12510.2
92
1 5 7
40220-08-4 423.38 97
86178-38-3 196.29 4010.1
2664-55-3 1 9 8 . 3 1 58/0.8
15625-89-5 296.32 316
28961-43-5 ca. 428 1 5 7
- 3 4
42978-66-5 300 >120/1
2177-18-6 98.10 9 1
<-20
1 6
- 2 0
Acrylates/Methacrylates III 113
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT.IR Merck Beilstein Fieser
0.875
0.880
0.9549
0.8932
0.9285
1.0421
1.012
0.956
0.8883
1.0711
1.4420 1 0 6 AT2190000
1.4370 80 UD3391000
1.4258
1.4060
1.4372
1.4392
1.4272
1.4020
1.4800
1.4728
60 KL6000000 2(3),1232
7 AT2800000 1(1),719C 1(1),973B 1(1),638B 11,5935 3,638B 17,183
0.859
1.030
0.875
0.800
1.4530
1.4375
> 37
1 2 3 AS8925000
1.3467
1.4350
1.3279
1.4870
1.4840
190
70
0.8810
1. 63
1.190
1.180
1.018
1.32
0.8920
1.104
1 7 0
>llO UD3370000 l(l),7531 1(1),639C
1.3363
1.4551
1.4240
1.5180 >llO KM0700000 6(3),572
1.249
0.9078
1.4540
1(2),1775F 1(2),1050A 1(2),179B
1 0 5 1(1),1109B 1(1),1489B
0.8700
1.110
1.317
1.063
1.4130
1.4470
1.4529
1.4468
1.4638
1.3629
1.4580
>llO AS8100000 1(1),759E 1(1),1053B 1(1),639A
45 1(1),745A
>llO
1.099
1.216
1.110
1.4609
1.3506
1.4710
6 3
1 2 l( 1),743M 1(1),1028C 1(3),696C
>llO KM2890000 1(1),999C
0.9292 1.455 8 8
0.875 1.4370 8 9 UD3643625
1.100 1.4736 >llO AT4810000 1(1),729F 1(1),64OA
1.110 1.4720 86 KM2890000 1(1),999C
1.030 1.4500 AT4690000 1(1),729A l( 1),638D
0.942 1.4320 2
1.015 1.432
1.122 1.4560
0.934 1.4360
1. 035 1.454
2(4),1468
9,914
4(4),3638
17(3),1104
17(3),1104
2(4),1462
2(3),1230
76 022975000 1(1),547B 1(1),776B 1(1),499C 11,5849 2,421
1 0 6 1(1),791E 1(1),1107C
34 UD3483000 1(1),721E 1(1),977A 1(1),641B 2(3),1290
8 3 025700000 1(1),831C 1(1),117OC 2(3),1293
6(3),1481
III / 14 PHYSICAL PROPERTIES OF MONOMERS
TABLE 5. contd
Name R
Benzyl ester -CH&&
Bisphenol A diester -C&C(CfhhC6H4-
Bisphenol A tetraethoxylate ((-CH~CH~O)ZC~H~)~C(CH~)~
diester
2-Bromoethyl ester -CHzCHzBr
1,3-Butylene diester -CH2CH2CH(CH3)-
1,4-Butylene diester -(CH2)4-
2-Butoxyethyl ester -CH2CH20(CH&CHs
n-Butyl ester -(CHhCH3
s-Butyl ester -CH(CH3)CH2CH3
tert-Butyl ester
-WH3)3
N-rert-Butyl-2-aminoethyl ester -CH+ZH2NHC(CHs)s
2-Chloro-2-hydroxypropyl ester -CH2C(OH)ClCHs
2Chloroethyl ester -CH2CH2C1
Chloromethyl ester -CH2CI
Cinnamyl ester -CHzCH=CHC6H5
Chloride CH,=C(CH,)C(O)Cl
2-Cyanoethyl ester -CH2CH2CN
1,4-Cyclohexanediol diester
-CsH10-
Cyclohexyl ester
-C6Hll
Decanediol diester -(CWlo-
Decyl ester -(CHzMX
2,3-Dibromopropyl ester -CHzCHBrCH2Br
2-(Dibutylamino)ethyl ester -(CH~)~N(CH~CH~CH~CH~)Z
Dicyclopentenyl ester -C1oH13
Dicyclopentenyloxyethyl ester -C12H170
2-(Diethylamino) ethyl ester -WW2WH2CHd2
3-(Dimethylamino) propyl ester -(CH2)sN(CHs)z
Di(ethylene glycol) diester -CH2CH20CH2CH2-
3,4-Dihydroxybutyl ester -CH2CH2CH(OH)CH20H
2,3-Dihydroxypropyl ester -CHzCH(OH)CH20H
2-(Dimethylamino) ethyl ester -CH2CH2N(CH3)2
Diurethane diester (isomers)
CdbN208
1 H, 1 H,7H-Dodecafluoroheptyl -CHz(CF2)sCF2H
ester
Dodecanediol diester
-(=2)12-
Dodecyl ester
-(CHdllCH3
2,3-Epithiopropyl ester -CH2CH(-S-)CH2
2,3-Epoxybutyl ester -CH2CH(-0-)CHCH3
3,4-Epoxybutyl ester -CH2CHzCH(-0-)CH2
2,3-Epoxyopropyl ester -CH2CH(-0-)CH2
4-Ethoxybutyl ester -(CH&OCH2CHs
2-Ethoxyethyl ester -CHzCH20CH2CHs
Ethyl ester -CH2CH3
Ethyl 2-bromomethyl- ester CH2=C(CHzBr)C(O)OCH2CHs
2-Ethylbutyl ester -CH2CH(CHzCHs)CH2CH3
1,2-Ethylene diester -CH2CH2-
2-Ethylhexyl ester -CH2CH(CH2CH3)(CH2)sCH3
2-(Ethylthio)ethyl ester -CHzCHzSCHzCHs
Ethyl 2-(trimethoxysilylmethyl-) CHz=C(CH2Si(OCHs)s)C(O)OCH2CHa
ester
Furfuryl ester -CH2C4H30
Glycerol diester -CH2CH(OH)CHz-
Glycerol triester -CH(CH2-)2
Glycidyl ester -CH(-0-)CH2
lH,lH,2H,2H-Heptadeca- -(CHddCFd7CF3
fluorodecyl ester
lH,lH-Heptafluorobutyl ester -CH2(CFd2CF3
Heptyl ester -(CHd&H3
1,6-Hexanediol diester
-(CH2)6-
2,2,3,4,4,4-Hexafluorobutyl ester -CHzCFzCHFCFs
lH-Hexafluoroisopropyl ester
-CWFh
Hexyl ester
-Wd5CH3
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
2495-37-6 176.22
3253-39-2 364.44
41637-38-1 452.55
232
ca. 540
4513-56-8 193.05
1189-08-8 226.28
2082-81-7 226.28
13532-94-0 186.25
97-88-1 142.20
2998-18-7 142.20
585-07-9 142.20
3775-90-4 185.27
13159-52-9 178.62
1888-94-4 148.60
27550-73-8 146.57
31736-34-2 202.25
920-46-7 104.54
4513-53-5 139.16
38479-34-4 252.31
101-43-9 168.24
6701-13-9 310.44
3179-47-3 226.36
3066-70-4 285.96
2397-75-3 241.38
31621-69-9 218.30
68586-19-6 262.35
105-16-8 185.28
17577-32-1 199.30
2358-84-1 242.27
62180-57-8 174.20
5919-74-4 160.17
2867-47-2 157.22
72869-86-4 470.57
2261-99-6 400.17
4712.7
290
13314
9013
1 6 1
1 4 6
1 3 2
loo/12
95/2
5917.5
54120
14113
9 5
99/2
6914
17012
327
7210.03
lOO/l
137113
150/10
80/10
10511.5
13412
llOJO.25
140/0.6
1 8 7
200
107123
72829-09-5 338.49
142-90-5 252.42
3139-91-1 158.22
68212-07-7 156.18
55750-22-6 156.18
106-91-2 142.16
76392-24-0 186.25
2370-63-0 158.20
97-63-2 114.15
17435-72-2 193.05
5138-86-3 170.25
97-90-5 198.22
688-84-6 198.31
14216-25-2 174.26
74976-84-4 186.33
14214
5911.4
4510.25
55/0.8
1 8 9
85123
92135
1 1 8
3810.8
74116
240
218
102/15
71110
3454-28-2 166.18 8115
1830-78-0 228.25 12011
52408-84-1 296.3 150/0.1
106-91-2 142.16 1 8 9
1996-88-9 532.20 12014
13695-31-3 268.13 1 3 4
5459-37-0 184.28 104114
6606-59-3 254.33 >315
36405-47-7 250.14 1 5 8
3063-94-3 236.11 99
142-09-6 170.25 88/14
7 3
50
-44
<-60
-30
0.95
- 7
<-75
- 4 0
<- 18
AcrylatedMethacrylates III 115
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT-IR Merck Beilstein Fieser
1.040
1.120
1.5120
1(2),1931F 1(2),1296C 1(2),316B
1.5320
1 0 7
>llO
1.010
1.023
0.939
0.894
0.875
0.914
1.190
1.4520
1.4565
1.4335
1.4230
1.4195
1.4150
1.4420
1.4750
130
1 1 3
9 3
5 0
1(1),729D
1(1),721A
1(1),999A 1(1),639D
1(1),975C 1(1),641A
5 0
7 1
1 5 0
023675000
023675500
023500000
1.4434
1.070 1.4420
1.4459
3 0 2 5 7 9 1 0 0 0 1(1),857B 1(1),732C 2(3),1293
0.9626
0.875
1.459
1.4577
1.443
8 2
8 2
1 0 1
1.050
1.064
0.922
1.4474
1.4990
1.4970
1.4442
>llO
z-l10
8 5
1.082 1.4580 6 6
0.933
1.110
1.4400
1.485
7 0
>150
0 2 4 2 0 0 0 0 0 1(1),771H 1(1),1074A 1(1),675C 4(3),649
1.46
0.868 1.4450 >llO 0 2 4 3 0 0 0 0 0 1(1),721D 1(1),976C 1(3),678B 2(3),1290
1.038
1.042
1.4422
1.4472
1.4490
1.4223
1.4290
1.4130
1.4790
7 6 0 2 4 3 7 5 0 0 0
0.964
0.917
1.398
7 1
1 5
8 7
0 2 4 5 5 0 0 0 0
1(1),781F 1(1),1089A 1(1),668D
1(1),759C 1(1),1052C 1(3),723C
1(1),719J 1(1),975B 1(1),640D
1.051 1.4540 8 6 0 2 4 4 0 0 0 0 0
0.885 1.4380 9 2 024630000
1(1),998B
1(1),976B
1(1),642D
0.897 1.4380 5 9
1(1),729B
1(1),721C
1(2),2985A 1(3),686B
1.078 1.4820 9 0
1.120 1.4720 >115
1.042 1.4490 7 6 oZ4375000 1(1),781F 1(1),1089A 1(1),668D
1.345 1.3410 3 7
0.995 1.4580 150
1.348 1.3610 5 7
1. 302 1.3310 1 4
0.885 1.432 6 3
1(1),745F 1(1),103OB
l( 1),745E 1(1),1030A
2(4),1534
2(3),1292
2(3),1286
2(4),1582
4(4),1509
2(4),1533
6CW5
6(3),1942
4(3),676
2(3),1292
2(3),1291
2,423
2(3),1292
2(3),1289
17(3),1248
III / 16 PHYSICAL PROPERTIES OF MONOMERS
TABLE 5. contd
Name R
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
4-Hydroxybutyl ester -(CHzhOH
2-Hydroxyethyl ester -CHaCHaOH
3-(5Hydroxypentyloxy)- -CH2CH2C(0)O(CH2)s0H
3-oxopropyl ester
3-Hydroxypropyl ester
-KHzhOH
Isobomyl ester
-c lOH8
Isobutyl ester -CHZCH(CH~)~
2-Isocyanatoethyl ester -CHsCH;?NCO
Isodecyl ester
-0bhCWCW2
Isopropyl ester
-CHCHh
Methallyl ester -CH2C(CH3)=CH2
2-(2-Methoxyethoxy) ethyl ester -(CHaCHaO)aCHs
2-Methoxyethyl ester -CH2CH20CH3
Methyl ester -CH3
2-Methyl-2-nitropropyl ester -CHaC(CH3)(N02)CH3
2-(Methylthio) ethyl ester -CHzCHaSCHs
Methyl 2-bromomethyl ester CH2=C(CH2Br)C(0)OCH3
Methyl 2-(l-hydroxyethyl-)ester CH$Z(CH(OH)CHs)C(O)OCHs
2-N-Morpholinoethyl ester -CHaCHsNC4Hs0
Neopentylglycol diester -CH2C(CH3)$H2-
Nona(ethylene glycol) diester -(CH2CH2o)&H$IX2-
Nona(propylene glycol) diester -(CH(CHs)CH20)8CH(CHs)CH2-
Nonyl ester
-(CHdsCH3
4-Nonylphenyl ester
-CsH4(CHd&&
Octadecyl ester -(CH2) 17CH3
n-Octyl ester -(CHW%
Pentabromophenyl ester -C.&5
Pentachlorophenyl ester -C&T5
lH,lH-Pentafluorooctyl ester
-CH2(CFd&F3
Pentaerythritol tetraester C(CH2-14
2,2,3,3,3-Pentafloropropyl ester -CHaCFaCFs
Pentyl ester -(CHa)&Hs
2-Phenoxyethyl ester -CH2CH20C&
Phenyl ester
-C6H5
2-Phenylethyl ester -CH2CH2C&
n-Propyl ester -CH2CH2CH3
1,2Propylene diester -CH2CH(CH3)-
1,3-Propylene diester -@-f2)3-
2-Sulfoethyl ester -CHaCH$!ZOsH
3-Sulfopropyl ester, potassium -(CH&SOsK
salt
Tetra(ethylene glycol) diester -CHaCH2(0CH2CH&-
2,2,3,3-Tetrafluoropropyl ester -CH2CF2CF2H
Trimethylsilyl ester -Si(CHs)s
2-(Trimethylsilyloxy)ethyl ester -CHaCHaOSi(CHs)s
3-(Trimethylsilyloxy)propyl ester -(CHa)sOSi(CHs)s
3-(Tris(trimethylsilyloxy)silyl)
-(CH2)3Si(OSi(CH3)3)3
propyl ester
Vinyl ester -CH=CH2
997-46-6 158.20 105/0.01
868-77-9 130.14 250
85099-IO- 1 244.29
276-09-3
7534-94-3
97-86-9
30674-80-7
29964-84-9
4655-34-9
8 16-74-0
45103-58-0
6976-93-8
80-62-6
2177-42-6
14216-23-0
4224-69-5
18020-65-0
2997-88-8
1985-5 1-9
25852-47-5
25852-49-7
2696-43-7
76391-98-5
32360-05-7
2157-01-9
18967-31-2
16184-61-5
3934-23-4
3253-41-6
45115-53-5
2849-98-1
1059.5-06-9
2177-70-0
3683-12-3
2210-28-8
1188-09-6
10595-80-9
31098-21-2
109-17-1
45102-52-1
13688-56-7
17407-09-9
2530-85-0
17096-07-0
4245-37-8
144.17
222.33
142.20
155.17
226.36
128.17
140.18
188.22
144.17
100.12
187.20
160.24
179.02
130.14
199.25
240.30
550
560
212.33
288.43
338.58
198.31
556.69
334.41
468.16
408.45
218.12
156.23
206.24
162.19
190.24
128.17
212.25
212.25
194.21
246.33
90/9
245
1 5 5
2 1 1
126110
1 2 5
1 5 7
67/l
66/16
100
10214
3810.06
36/1.3
91120
80/0.08
112/1.2
>200/ 1
125/0.03
19516
105/4
6715
55/110
73117
1 8 3
115/10
119/11
1 4 0
68/1
68/l
(4
300.37 220
200.14 1 2 4
158.28 51120
202.33 6510.9
248.35 190
422.82 113/0.2
112.13 111
- 12
-48
-51
-45
-41
-48
1 9
1 3 2
8 7
66
295(d)
TABLE 6. ALCOHOLS
Name
Formula HOROH
R
CAS
Registry
Number Mol. wt.
Boiling Melting
point (C) point (C)
6. 1. ALKANEDIOLS
1,2-Butane -CH(C2H5)CH2- 584-03-2 90.12 1911747
1,3-Butane -CH(CHs)CH2CH2- 107-88-0 90.12 203
1 ,CButane -(CH2)4- 110-63-4 90.12 230 16
l,lO-Decane -W-h)lo- 112-47-0 174.28 17018 7 3
1,12-Dodecane -(CHZ)IZ- 5675-51-4 202.34 189/12 8 2
1,2-Ethylene -W2)2- 107-21-1 62.07 1 9 7 - 13
Alcohols III 117
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT-IR Merck Beilstein Fieser
1.073 1.4520 97 024725000
1.080 1.4360 >llO
1(1),753M 1(1),1045A 1(1),665B
1.066
0.9830
0.886
1.096
0.878
0.8847
1.4470
1.4770
1.420
1.4430
1.4122
96
1 0 7
4 1 024900000
97
>llO 025000000
1(1),721B 1(1),976A 1(3),677C 2(3),1287
1.020 1.4397 >llO
0.993 1.4310 6 5
0.936 1.4140 1 0 025075000
1.087 1.450 >llO
1.040 1.4800 8 8
1.489 1.4900 78 AS4900000
1.071 1.4520 4 3
l(l),7191 1(1),975A 1(1),64OC 11,5849 2(2),398
2(3),1288
l(l),7455 1(1),1031C
1.003
1.099
1.010
1.099
0.864
1.4530
1.4660
1.4520
1.4660
1.5020
1.4510
1.4373
1 1 7
>llO
>llO
>llO
>llO
1 9 6
2(4),1535
2(3),1290
1.5732 1.3482
96
>lOo
6
1.0687 100
0.98
0.9022
1.5130
1.5184
1.508
1.4450
1.4450
1 2 2
1.3245 1.4772
1(1),1065F 1(1),1438B 1(1),890D
1.080 1.4630 8 2 oz4oooooo
1.250 1.3730 50
0.890 1.4147 3 2
0.928 1.4280 76
1.045 1.4310 92 UC0230000
0.918 1.4190 >llO
1(1),745B 1(1),1029A
1(2),2985B 1(3),686C
1(2),2985C 1(3),687A
1(2),2985D 1(3),687B
2(4),1531
1(2),1116C
0.933 1.4360 1 3 2(3),1290
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT-IR Merck Beilstein Fieser
1.006 1.4380 9 3 EK0380000 1(1),141A 1(1),196C 1(1),130B 1,477
1. 005 1.4400 1 2 1 EK0440000 1(1),139L 1(1),195C 1(1),130D 11,1566 1,477
1. 017 1.4450 >llO EK0525000 1(1),139K 1(1),195B 1(1),130A 1,478
HD84337 13 1(1),143N 1(1),205C 1(1),136D 11,2842 1(2),560
1(1),145A 1(1),206B 1(1),137A 1(2),562
1.113 1.4310 >llO KW2975000 1(1),139A 1(1),127D 11,3755 1,465 15,156
III/18 PHYSICAL PROPERTIES OF MONOMERS
TABLE 6. contcf
Name
Formula HOROH
R
CAS
Registry
Number Mol. wt.
Boiling
point (C)
Melting
point (C)
1,7-Heptane
1,16-Hexadiene
1,6-Hexane
1,7-Heptane
1,16-Hexadiene
1,9-Nonane
1,8-Octane
1,5-Pentane
1,2Propane
1,3-Propane
1,14-Tetradecane
6.2. ETHER DIOLS
Di(ethylene glycol) -CHzCH20CHzCH2- 111-46-6 106.12
Di(propylene glycol) -CH(CHs)CH20CH(CH3)CH2- 110-98-5 134.18
Hexa(ethylene glycol) -CH2CH2(OCH2CH2)s- 2615-15-8 282.34
Penta(ethylene glycol) -CH2CH2(0CH2CH2)4- 4792-15-8 238.28
Tetra(ethylene glycol) -CHzCHz(OCHsCHz)s- 112-60-7 194.23
Tri(ethylene glycol) -CH2CHz(OCHzCH2)2- 112-27-6 150.17
Tri(propylene glycol) -CH(CH3)CH2(0CH(CH3)CH2)2- 24800-44-0 192.26
-(CH2)7-
-(CH2)16-
-(cH2)6-
-(CH2)7-
-@-I21 16-
-CHdg-
-W-f2h-
-(CH2)5-
-CH(CH3)CH2-
629-30- 1 132.20
23079-20-1 258.45
629-11-8 118.18
629-30- 1 132.20
23079-20-1 258.45
3937-56-2 160.26
629-41-4 146.23
111-29-5 104.15
57-55-6 76.10
504-63-2 76.10
19812-64-7 230.39
259
19813
250
259
19813
177/15
172120
242
1 8 7
214
245 - 10
21714
18412
314
285
273
18
92
42
18
92
48
60
- 6 0
-27
8 8
6
- 6
- 7
TABLE 7. ALLY1 FUNCTIONAL
Name
Formula C&=CHCH2R
R
CAS
Registry
Number Mol. wt.
Boiling
point (C)
Melting
point (C)
Acetate -OC(0)CH3
-Acetic acid -CH2C(0)OH
Acetoacetate -OC(0)CH2C(O)CH3
Alcohol -OH
-, 2-Bromo- HzC=CBrCH20H
-, 2-Chloro- HzC=CC1CH20H
-, 3-Methyl(croty1 alcohol) CH3CH=CHCH20H
-Amine -NH2
-N-Aniline -NC&
-4-Anisole -C&oCH3
-Benzene
-CsH5
Benzyl ether -oCH2C&
Bromide -Br
Butyl ether
-WJ-bWH3
Butyrate -OC(0)CH2CH2CH3
Chloride -CI
Chloroacetate -OC(0)CH2CI
Chloroformate -OC(O)Cl
Cyanide -CN
Cyanoacetate -OC(0)CH2CN
Diallyl amine -NH-
2,3-Dibromide Hz=CBrCHsBr
2,3-Dichloride H2C=CClCH2CI
Ether -O-
Ethyl ether -OCH2CH3
Fluoride -F
Formate -OC(O)H
Glycidyl ether -0-CH2CH(-0-)CH2
Iodide -I
Isocyanate -NC0
Isopropyl ether -OCH(CH3)s
4-(2-Methoxyphenol) -C,&(oCH3)oH
Methyl ether -0CH3
-2-Phenol -C,&oH
591-87-7
591-80-0
1118-84-9
107-18-6
5976-47-6
6117-91-5
107-11-9
589-09-3
140-67-0
300-57-2
14593-43-2
106-95-6
3739-64-8
205 1-78-7
107-05-1
2916-14-5
2937-50-0
109-75-1
13361-32-5
124-02-7
513-31-5
557-40-4
557-31-3
818-92-8
106-92-3
556-569
1476-23-9
97-53-0
627-40-7
1745-81-9
100.12
100.12
142.16
58.08
136.98
92.53
72.12
57.10
133.19
148.21
118.18
148.21
120.98
114.19
128.17
76.09
134.56
120.54
67.09
125.13
97.16
199.88
110.97
98.15
86.13
60.07
86.09
114.14
167.98
83.09
100.16
164.20
72.11
134.18
104
84112 -22
1941737
97 - 129
1 5 2
134
1 2 2
5 3 - 88
219
215
1 5 6
204
70 -119
44115
4 5 - 134
1641265
1 0 9
1 1 8
110/20
1 1 2 -88
141
94
9 5
66
- 10
84
1 5 4
1 0 3
8 8
8 4
154 -11
46
220
Ally1 Funct i onal III 119
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT-IR Merck Beilstein Fieser
0. 95 1
0 . 9 5 1
0.994 1.4500 1 2 9
1.036 1.4320 1 0 7
1.053 1.4400 79
1.118 1.4460 1 4 3 ID5950000 1(1),225D 1(1),341B 1(1),223B 11,3109 1,468
1.023 1.4410 1 3 8 UB8785000 1(1),225E 1(1),341C 1(1),226A 1(2),537
1.127 1.4640 >llO MM3670000 1(1),229B 1(1),347A 1(1),227A 1,468
1.126 1.4620 >llO RZ2670000 l( 1),227K l( 1),346B 1(1),226D 1,468
1.125 1.4590 1 7 7 xc21OOOOO l( 1),227H 1(1),346A 1(1),226C 1,468
1.125 1.4550 166 YE4550000 l( 1),227D 1(1),345A 1(1),226B 11,9585 1,468
1.021 1.4440 >llO YK6825000 l( 1),227F l( 1),345B
1.4550
1.4550
>llO
1 0 2
>llO
>llO
MI9804000 l(l),1435
l( 1),145E
MO2100000 1(1),143D
MI9804000 l(l),1435
1(1),145E
1(1),143M
1(1),143K
SA0480000 l(l),1411
TY2000000 1(1),139C
TY2010000 1(1),139B
1(1),145C
1(1),204B
l( 1),202B
l( 1),204B
1(1),205B
1(1),204C
1(1),199A
1(1),192C
1(1),192B
1(1),207A
1(1),135C
1(1),137D
1(1),134B
1(1),135C
1(1),137D
1(1),136B
1(1),135D
1(1),132B
1(1),128B
1(1),128A
1,489
11,461O 1,484
1,489
1,489
1,493
1,490
11,7073 1,481
11,7868 1,472
11,9629 1,475
1(2),564
Density
(at 20C)
Refractive
index (at 20C)
1.4040
1.4283
1.4390
1.4120
1 . 5
1.4590
1.4270
1.4205
1.5630
1.5210
1.5100
1.5070
1.4690
1.4060
1.4140
1.4135
1.4460
1.4220
1.4050
1.4430
1.4405
1.5470
1.4603
1.4160
1.3880
Flash
point (C)
7
8 9
7 5
22
RTECS
Number R and S FT-NMR FT-IR Merck Beilstein Fieser
-
0.928
0.981
1.037
0.854
1.6
1.162
0.845
0.761
0.982
0.965
0.892
0.959
1.398
0.783
0.902
0.939
1.159
1.136
0.834
1.065
0.787
1.934
1. 211
0.803
0.760
AF1760000
SB2800000
BA5075000
1(1),715C 1(1),963C 1(1),633B 2,136
1(1),547H 1(1),778A 1(1),499B 2,425
1(1),787A 1(1),687C 1(1),1098A 1(1),687C 19(3),1203
1(1),147A 1(1),207B 1(1),138B 11, 284 1,436
54
3 7
- 2 9
89
8 1
3 3
76
- 2
1 4
4 1
- 2 9
6 1
3 1
2 3
>llO
1 6
8 1
UD4725000
EM9275000
BA5425000
BZ8225000
CY2275000
1(1),183D
1(1),147C
1(1),347A
1(1),1383K
1(1),1243C
1(1),1139E
1(1),208A 1(1),138C 11,2604
1(1),518C 1(1),322B 11,285
1(2),454B 1(1),1191A
1(2),208B 1(1),1053B 11,3657
1(2),24B 1(1),946B
uc7090000
ES5775000
uc7350000
l(l),951 1(1),135A
1(1),219G 1(1),333B
1(1),717N 1(1),970B
l( 1),95E 1(1),133C
LQ5775000 1(1),863B
EM8050000 1(1),991F
AG3690000 1(1),1013F
UC6650000 l(l),3473
UC8200000 l(l),lOlK
1(1),1206B
1(1),1358C
1(1),1391B
1(1),520A
1(1),93D 11,286
1(1),637B
1(1),93C 11,287
1(1),737A
1(1),843A 11, 288
1,439
1,442
4,205
12,170
6,751
5,484
6(3),1459
1,201
1(3),1882
2,272
1,198
2,198
3,12 13,2
2,408
1(1),322C 11,2951
1(1),99C 11,3009
1(1),212D 11, 290
1(1),212C 11, 291
4,208
1,201
- 7
- 21
KN7525000 1(1),219H 1(1),333C
1(1),219E 1(1),332C
1,438
1,438
0.9460
0.962
1.837
0.940
0.7764
1.066
0.978
1.028
1.4330
1.5540
1.4170
1.3946
1.5410
1.5200
1.5450
57 RR0875000 1(1),251C
1 8 VDO450000 1(1),95J
4 3 NQ8175000 1(1),1023E
>llO
6 3
8 8
SJ4375000 1(1),1283E
SJ3850000 1(1),1265H
1(1),374A
1(1),1404A
1(2),278A
1(2),245B
1(1),233D
1(1),94A 11,292
1(1),872A
1,202
4,214
1(1),1091A 11,3855 6.961
1(1),107OD 6,572
III/20 PHYSICAL PROPERTIES OF MONOMERS
TABLE 7. contd
Formul a CHz=CHCH2R CAS
Registry Boiling Melting
Name R Number Mol. wt. point (CT) point (C)
Phenyl ether -OCsHs 1746-13-0 134.18 1 9 2
4-Chloro- -0CjH4Cl 168.63 107112
2,4,6-Tribromo- -0CsHaBrs 3278-89-5 370.88 7 5
Phenyl sulfone -S(OmC6H5 16212-05-8 182.24 111/0.5
Propyl -CH2CH2CH3 1471-03-0 100.16 9 1
-Succinic anhydride -C4H303 7539-12-0 140.1 260 6
Sulfide -S- 592-88-1 114.21 1 3 8
2-Tolyl ether -oC&CHj 148.21 81/2
3-Tolyl ether -oC&CHj 148.21 213
4-Tolyl ether -oC6H&H3 148.21 91/10
-Urea -NHC(O)NHz 557-11-9 100.12 8 5
TABLE 8. AMINES, DIFUNCTIONAL
Name
Butane-
Decane-
Dodecane-
Ethylene-
Heptane-
Hexane-
Nonane-
Oct ane-
Pentane-
1,2-Phenylene-
1,3-Phenylene-
1,4-Phenylene-
Propane-
Formul a H2NRNH2
R
-(CH2)4-
-KH2)10-
-V2)12-
-W2)2-
-(CH2)7-
-(CH2)6-
-(CH2)9-
- & = 2 ) 8 -
-(CH2)5-
-CsH4-
-C,j&-
-CsH4-
-(CH2)3-
CAS
Registry Boiling Melting
Number Mol. wt. Point( C) Pointr C)
110-60-1 88.15 1 5 9 2 7
646-25-3 172.32 140112 62
2783-17-7 200.37 70
107-15-3 60.10 1 1 8 8.5
646-19-5 130.24 224 2 8
124-09-4 116.21 204 43
646-24-2 158.29 2581756 3 7
373-44-4 144.26 225 5 1
462-94-2 102.18 1 7 9
95-54-5 108.14 257 1 0 4
108-45-2 108.14 283 6 5
106-50-3 108.14 267 144
109-76-2 74.13 1 4 0 - 1 2
TABLE 9. ANHYDRIDES
Name Formula
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
9.1. MONOANHYDRIDES
Acetoxysuccinic
S-Acetylmercaptosuccinic
Aconitic, cis-
Acrylic (see Acrylates)
Allylsuccinic
4-Amino- 1 &naphthalic
1,2,4-Benzenetricarboxylic
(trimellitic)
Bicyclo[2.2.2.]oct-5-ene-
2,3-dicarboxylic, endo-
Bromomaleic
4-Bromo, 1,8-naphthalic
3-(tert-Butyldimethylsilyloxy)-
glutaric
4-rerr-Butylphthalic
IV-Carboxybenzyloxy-L-aspartic
Cantharidin
5-Chloroisotoic
4-Chloro- 1 ,8-naphthalic
Citraconic
Cyclohexane-1,2-dicarboxylic,
cis-
C1oH1003 24327-08-0 178.19 1 4 5
C4HBr03 5926-51-2 176.96 215
Cd-bBrO3 21563-29-1 277.08 218
CllH2oWi 91424-40-7 244.37 8 0
C12H1203
C12HllN05
ClOH1204
CsH4C1N03
C12H5C103
C5H403
GH1003
79814-40-7 158.11 56
6953-60-2 174.18 8 3
6318-55-4 156.10 7 5
7539-12-0 140.1
6492-86-0 213.20
552-30-7 192.13
32703-79-0 204.23 73
4515-23-5 249.23 1 2 3
56-25-7 196.20 216
4743-17-3 197.58
3W4
4053-08-1 232.63 208
616-02-4 112.08 213 7
13149-00-3 154.17 158117 3 3
260 6
1 6 7
Amines(difunctional) and Anhydrides III 121
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT.NMR FT-IR Merck Beilstein Fieser
0. 978 1. 5200 63 DA8575000 1(1),1241M 1(2),207A 1(1),1052B 6, 144 11,14
1. 5348
6, 205
1. 189 1. 5480 >llO WR24OOOOO 1(2),2185B 1(2),158OA 6, 299
0. 767 1. 3990 - 5 1(1),219F 1(1),333A 1(3),2780 1, 438
0. 887 1. 4889 4 6 BC4900000 l(l),2875 1(1),432C 1(1),269C 11, 295 1, 440
0. 950 1. 5179
0. 9564 1. 5179
0. 970 1. 5168
YR7875000 1(1),939M 1(1),1308B 1(1),8OOD 11, 296 4, 209
Density Refractive Flash RTECS
(at 20C) Index(At 20C) Point(W) Number R and S FT-NMR FT-IR Merck Beiistein Fieser
0. 877 1. 4569 52
155
0. 899 1. 4565 3 4
8 8
81
>llO
165
0. 873 1. 4582 63
>llO
0. 888 1. 4565 34
EJ68OOOOO
HD7175000
JR22OOOOO
KH8575000
MO1 180000
RG8841500
SA0200000
SS7875000
ss77004lOO
SS8050000
TX6825000
1(1),309G
l(l),3111
l(l),3115
1(1),309A
1(1),311E
1(1),311B
1(1),311H
1(1),311F
l(1,309K
1(1),1429A
1(1),1431C
1(1),1433D
1(1),309D
1(1),465A
1(1),469B
1(1),469C
1(1),463B
1(1),468A
l( 1),467A
1(1),469A
1(1),468B
1(2),536B
1(2),539A
1(2),542C
1(1),464A
1(1),291D 11,7964 4, 264
1(1),293D 4, 273
l( 1),294A 4, 273
1(1),289C 11,3752 4, 230 4, 231
1(1),293A 4, 271
1(1),292C 11,4614 4, 269
1(1),293C 4, 272
1(1),293B 4, 271
l(1,292B 11,1608 4, 266
1(1),1235C 11,7255 13,6 8, 393
1(1),1239A 11,7254 3,33
1(1),1242B 11,7256 13,61
1(1),290A 4, 261
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number RandS FT-NMR FT-IR Merck Beilstein Fieser
1. 163
1. 905
I
1. 247
i
1. 4710
DC2050000
>llO
RN8575000
QL6127295
101 GE6825000
>llO
1(1),837E 1(1),1179B
1(1),837D
1(2),1961B
1(2),1959G 1(2),1329C
1(1),835N l(l),1 178B
1(1),839A 1(1),1182B
1(2),1961A 1(2),1330B
1(2),2987F 1(3),692A
1(2),1957H 1(2),332C
1(2),1959N 1(2),335D
1(1),837J 1(1),1181A 1(1),718D
1(1),835G 1(1),1175C 1(1),715D
1(1),715C
1(2),336A
1,(2),334A 11,9617
1(1),717D
1(1),719C
18(2),1128
18, 463
18(2),469
18, 468
17, 435
17, 523
19, 161
27, 265
17, 522
17, 440
III / 22 PHYSICAL PROPERTIES OF MONOMERS
TABLE 9. contd
Name Formula
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
Cyclohexane-1,2-dicarboxylic,
trans-
Diacetyl-L-tartaric
3,5-Diacetyltetrahydropyran-
2,4,6-trione
Dichloromaleic
3,6-Dichlorophthalic
4,5-Dichlorophthalic
3,6-Difluorophthalic
Diglycolic
2,2-Dimethylglutaric
3,3-Dimethylglutaric
2,3-Dimethylmaleic
2,2-Dimethylsuccinic
Diphenic
2,3-Diphenylmaleic
2-Dodecen- 1 -ylsuccinic
3,6-Epoxy-1,2,3,6-tetra-
hydrophthalic, exo-
3-Ethyl-3-methylglutaric
3Fluorophthalic
4Fluorophthalic
2-Formamidosuccinic
Glutaric
1 4 5 6 7 7-Hexachloro-5- , 3, 19
norbomene-
2,3-dicarboxylic
Hexafluoroglutaric
Hexahydro-4-methylphthalic
Homophthalic
3-Hydroxyphthalic
Isatoic
Isobutenylsuccinic
Itaconic
Maleic
3-Methylglutaric
N-Methylisatoic
Methyl-5-norbomene-
2,3-dicarboxylic
4-Methylphthalic
Methylsuccinic
1,8-Naphthalic
3-Nitro- 1 ,8-naphthalic
4-Nitro-1,8-naphthalic
3-Nitrophthalic
4-Nitrophthalic
5-Norbomene-endo-
2,3-dicarboxylic,
cis-
Octadecylsuccinic
2-Octen-1-ylsuccinic
3-Oxabicyclo[3.1.0] hexane-
2,4-dione
2,5-Oxazolidenedione
2-Phenylglutaric
Phenylmaleic
1-Phenyl-2,3-naphthalene-
dicarboxylic
Phenylsuccinic
Phthalic
N-Phthaloylglutamic
1-Propenyloxymethylmaleic
Pyrazinedicarboxylic
C22H3803
C12H1803
C5H403
C3HWh
C11H1003
26680-54-6
5617-74-3
350.55 25114 62
210.27 168/10 1 0
112.08 lOOf 60
c lOH603
C18H1003
2185-00-4 101.06
2959-96-8 190.20
36122-35-7 176.16
1985-37-1 247.28
ClOH803 1131-15-3 176.17
C8H403 85-44-9 148.12
CdbNOs 3343-28-0 259.22
C7H1004
130221-78-2 158.16
CsH2N203
4744-50-7 150.09
14166-21-3 154.17 146
6283-74-5 216.15 131
33524-89-9 212.16 154
1122-17-4 166.95
4466-59-5 217.01
942-06-3 217.01
652-40-4 184.10
4480-83-5 116.07
2938-48-9 142.16
4160-82-1 142.16
766-39-2 126.11
17347-61-4 128.13
6050-13-1 224.22
4808-48-4 250.26
19780-11-1 266.38
6118-51-0 166.13
6970-57-6 156.18
652-39- 1 166.11
3 19-03-9 116.11
33605-73-1 143.10
108-55-4 114.10
115-27-5 370.83
376-68-1 222.04
19438-60-9 168.19
703-59-3 162.14
37418-88-5 164.12
118-48-9 163.13
18908-20-8 157.17
2170-03-8 112.09
108-31-6 98.06
4166-53-4 128.13
10328-92-4 117.16
25134-21-8 178.19
19438-61-0 162.14
4100-80-5 114.10
81-84-5 198.18
3027-38-1 243.17
34087-02-0 343.17
641-70-3 193.11
5466-84-2 193.11
129-64-6 164.16
240
175/60
181/25
223
219
18015
185120
72
146114
114/12
202
181/25
295
239
218/13
191/12
284
2 5 1
1 8 8
1 8 6
219
92
36
1 2 4
94
30
225
1 6 0
42
118(d)
1 5 9
79
1 4 5
56
237
141
200
233(d)
64
7 1
52
4 5
9 1
34
268
248(d)
228
1 6 4
1 1 8
166
120(d)
97
121
259
54
1 3 2
1 9 9
210(d)
Amines(difunctional) and Anhydri des III 123
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT-IR Merck Beilstein Fieser
l( 1),835H 1(1),1176A 1(1),716A 17,452
1(1),837F l(l),1 179c
1(1),839L 1(1),1174A
18,162
17(4),6841
ON4025000
1(1),839B
1(2),1959B
1(2),1959C
1(2),1959A
1(1),841C
l( 1),839G
1(1),839H
1(1),837K
1(1),835C
1(2),1959L
1(2),1957C
l( 1),835K
1(1),837B
1(1),457D
1(1),719D
1(2),1328B
1(2),1328C
1(2),1328A
1(1),1183C
1(1),1184A
1(1),1181B
l(l),1 175A
1(1),722A
1(1),720D
1(1),721A
1(1),719A
1(2),335B
1(1),717A
17,434 5,195
17,483
17,483
17(5),11,259
19,153
17,418
17,419
17,445
17,417
17,526
17,532
1(1),1177A
1(1),1179A 19(2),181
l(l),8391 1(1),1184B 1(1),721B 17(1),231
17(5),11,259
18(11),5,548
MA3850000 1(1),839E 1(1),1183A 1(1),720B
RB9080000 1(1),839C 1(1),1182C 1(1),720A 11,2084
17,411
1(1),839K
l(l),8351
1(2),1957E
1(2),1959F
1(2),1957F
1(1),835E
1(1),835J
l(l),8371
l( 1),839F
1(2),1957G
l(l),8350
1(1),1184C
l(l),1 176B
17(4),5814
1(2),1329B
1(1),716B
1(2),331D
T13300000
DM3 100000
ON3675000
1(1),1175B
1(1),1176C
1(1),118OC
1(1),1183B
1(2),332A
DM3 140000
RB9100000 1(1),1178C
1(1),716D
1(1),718C 11,5586
1(1),72OC
1(2),332B
1(1),718C
17,489
18,94
27,264
17(4),5927
17,442
17,432
17,415
27,265
17(2),461
QK5350000
QK5370000
T13328000
DT5600000
1(2),1957M
l( 1),835B
1(2),1959M
1(2),1961C
1(2),1961D
1(2),1959H
1(2),19591
1(1),835M
1(2),1327B
1(1),1174C 1(1),715B
1(2),335C
1(2),133OC
1(2),1330A
1(1),1177C
1(2),334B
1(2),334C
1(1),717C 11,1801
17,492
17,414
17,521
17,523
17,524
17,486
17,486
17(2),461
1.135 1 0 8
1 7 7
>llO
1.654 1.3240
1.162 1.4770
11,254
5,422
1.713
1.232 1.5060
1.220
1.055
1.000 1.4694 >llO
1(1),835F 17,442
l( 1),907M 27,245
1(2),1957D 1(2),331C 17,494
17.510
I
17,492
TI3150000 1(2),1957J 1(2),1327A 1(2),332D 11,7346 17,469 1,882
MA3900000 1(2),2017M 1(2)1391A 21(3),5370
>llO
2 7 . 6 8 1
1.100 1.4610
III/24 PHYSICAL PROPERTIES OF MONOMERS
TABLE 9. contd
Name Formula
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
2,3Pyridenedicarboxylic
GH3NOs
3,4Pyridinedicarboxylic
C7HWh
Succinic
C4H403
4-Sulfo-1,8-naphthalic c 12H606S
Tetrabromophthalic
C8Br403
Tetrachlorophthalic
GC1403
Tetrafluorophthalic
CEF403
1,2,3,6-Tetrahydrophthalic, cis- CsHsOs
3,4,5,6-Tetrahydrophthalic CEH803
3,3-Tetramethyleneglutaric
CgHdh
Tetrapropenylsuccinic (isomers) C tsHzs03
Trimellitic CgH3C104
2-(Triphenylphosphoranylidene)- CzzHtrOsP
succinic
9. 2. DIANHYDRIDES
Benzene-1,2,4,5-tetracarboxylic CtaHzOs
Benzophenone-
C17H607
3,3,4,4-tetracarboxylic
Bicyclo[2.2.2.]oct-7-ene-
ClZH806
2,3,5,6-tetracarboxylic
Biphenylene-3,3,4,4- c 16H606
tetracarboxylic
Cyclobutanetetracarboxylic CEH406
Cyclopentane-1,2,3,4- Cd606
tetracarboxylic, cis,cis-
Diethylenetriaminepentaacetic Cl4HwN308
Ethylenediaminetetraacetic
CloHnNz06
4,4-(Hexafluoroisopropylidene) CisHsF&
diphthalic
Naphthalene-1,4,5,8-tetra-
c 14H406
carboxylic
Perylene-3,4,9, IO-tetracarboxylic Cz4HsOs
Tetrahydrofuran-2,3,4,5tetra-
CEH407
carhoxylic
699-98-9 149.11
4664-08-8 149.11
108-30-5 100.07
71501-16-1 316.34
632-79-1 463.72
117-08-8 285.90
652- 12-0 220.08
935-79-5 152.15
2426-02-0 152.15
5662-95-3 168.19
26544-38-7 266.38
1204-28-0 210.57
906-65-0 360.35
89-32-7 218.12 397 283
2421-28-5 322.23 220
1719-83-1 248.19 >300
2420-87-3 294.22 300
4415-87-6 196.11 >300
6053-68-5 210.14 225(d)
23911-26-4 357.32 1 8 3
23911-25-3 256.22 190(d)
1107-00-2 444.25 244
81-30-1 268.18 >300
128-69-8 392.32 >300
25774-69-0 212.11 223
1 3 8
76
1 2 6 1 1 9
3 7 1
186/15
15013
275
256
9 5
98
72
6 5
67
167(d)
TABLE 10. BUTADIENES
Name Formula
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
10.1. 1,2-BUTADIENES
1,2-Butadiene H2C=C=CHCH3 590-19-2 54.09 11 - 1 3 6
-, 4-Bromo- HzC=C=CHCHzBr 133.00 110
-, 4Chloro- H2C=C=CHCHzCl 88.54 8 8
-, 4-Hydroxy- H2C=C=CHCH20H 70.09 1 2 7
-, 4-Iodo- HzC=C=CHCH21 179.99 1 3 0
-, 3-Methyl- HzC=C=C(CH3)2 598-25-4 68.12 4 1 - 1 4 8
10.2. 1,3-BUTADIENES
1,3-Butadiene HzC=CHCH=CHz 106-99-0 54.09 - 4 - 109
-, 2-Bromo- H2C=CBrCH=CH2 133.00 421165
-, 1-Chloro- HCC1=CHCH=CH2 88.54 6 8
-, 1-Chloro-2-methyl- HCCl=C(CH3)CH=CH2 102.57 1 0 7
-, I-Chloro-3-Methyl- HCCl=CHC(CH3)=CHz 102.57 100
-, 2-Chloro- H2C=CClCH=CH2 126-99-8 88.54 59
-, 2-Chloro-3-methyl- HzC=CClC(CH3)=CH2 102.57 9 3
-, 1,2-Dichloro- HCCl=CClCH=CH2 122.98 631105
-, 2,3-Dichloro- H2C=CClCCl = CH2 122.98 9 8
Butadienes III 125
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT-IR Merck
1. 005 1. 4790
WNO875OOO
TI3350000
TI3450000
GW5775000
>llO WN1300000
DB93OOOCO 1(2),1959K 1(2),335A
162 1(21),1957L 1(2),333B
QK3695000 1(2),1961F 1(2),336B 19, 196
1(2),2547K
1(2),2547L
1(1),835A
1(2),2203F
1(2),1959E
1(2),1959D
l( 1),835L
1(1),837M
1(1),839J
1(2),1981E
1(1),837H 1(1),118OB 1(1),716C
1(1),837Ci 1(1),118OA
1(1),841B
1(1),841A
1(2),1957N
1(1),1185A
1(2),1327C
1(2),19616 1(2),336C
1(3),336A
1(3),336B
l(l),1 174B
1(2),1329A
l(l),1 177B
1(1),1182A
1(2),1353B 1(2),351B
1(2),168OC 1(2),55OD
1(2),795B
l(lX715A 1 1
1(2),5OlD
1(2),333D
1(2),333C
1(1),717B
1(1),719B
1(1),721C
,884l
Bei l s t ei n Fieser
27,261
27,261
17, 407 4, 468
17, 485
17, 484 15, 300
17(5),11,260
17, 462
17, 461
17, 237
17(5),11,105
19, 196
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT.IR Merck Beilstein Fieser
0. 652 1.4205/1.3 1(4),975
1. 4255 1. 5248
0. 9891 1. 4775
0. 9164 1. 4759
1. 7129 1. 5709
0. 694 1. 4190 -23 1(1),27B 1(1),35C 1(1),3OC 1, 252
0.650/- 6
1. 42921 - 2 5 EI9275000 1(1),27D 1(1),36B 11,150o 1, 249
1. 397 1. 4988
0. 961 1. 4709
0. 9710 1. 4792
0. 9543 1. 4719
0. 9583 1.4583 EI9625000
0. 9593 1.4686
1. 1991 1.4960
1. 1829 1.4890
III / 26 PHYSICAL PROPERTIES OF MONOMERS
TABLE 10. contd
Name Formula
-, 2,3-Dimethyl- H2C=C(CH3)C(CH3)=CH2
-, 2-Fluoro- H2C=CFCH=CH2
-, Hexachloro- cc12=cc1cc1= cc12
-, Hexafluoro- CF2=CFCF=CF2
-, 2-Iodo- H2C=CICH=CH2
-, 2-Methyl- H2C=C(CH3)CH=CH2
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
513-81-5 82.15 6 8 - 7 6
72.08 1 2
87-68-3 260.76 215 - 20
685-63-2 162.03 7 - 132
179.99 1 1 2
78-79-5 68.12 34 - 146
TABLE 11. BUTENES
Name Formula
11.1. 1.BUTENES
1-Butene H2C=CHCH2CH3
-, 4-Bromo- HzC=CHCH#H2Br
-, 2,3-Dimethyl- H2C=C(CH3)CH(CH3)2
-, 3,3-Dimethyl- HzC=CHC(CH~)~CH~
-, 2-Methyl- H2C=C(CH3)CH2CH3
-, 3-Methyl- H2C=CHCH2(CH3)2
11.2. 2-BUTENES
2-Butene, cis- CH3CH=CHCH3
2-Butene, truns- CH3CH=CHCH3
1,4-Dihydroxy-, cis- HzC(OH)CH = CHCH2(0H)
2,3-Dimethyl- (CH3)2C = C(CH3)2
2-Methyl- (CH3)2C=CHCH3
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
106-98-9 56.11 - 6 - 185
5162-44-7 1 3 5 . 0 1 99
563-78-0 84.16 56 - 158
558-37-2 84.16 4 1 - 1 1 5
563-46-2 70.14 3 1 - 137
563-45-1 70.14 20 - 168
590-18-1 56.11 4 - 139
624-64-6 56.11 1 - 105
6117-80-2 8 8 . 1 1 131/12 7
563-79- 1 84.16 7 3 - 7 5
513-35-9 70.14 36 - 134
TABLE 12. EPOXIDES
Name Formula
12.1. MONOEPOXIDES CH2(-0-)CHR
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
Allylglycidyl ether -CH20CH2CH=CH2 106-92-3 114.14
2-Biphenylyl glycidyl ether -CH2oC6H&& 7144-65-2 266.28
n-Butyl glycidyl ether -CH20(CH&ZH3 2426-08-6 130.19
t-Butyl glycidyl ether -CHZOC(CH~)~ 7665-72-7 130.19
4-t-Butylphenyl glycidyl ether -CH2oc&C(CH3)3 3101-60-8 206.29
4-Chlorophenyl glycidyl ether -t-&oC6H&l 2212-05-7 184.62
Cyclohexene oxide
C6HlOO 286-20-4 98.15
Cyclooctene oxide
Cd140 286-62-4 126.20
Cyclopentene oxide
W-W 285-67-6 84.12
Epibromohydrin -CHzBr 3132-64-7 136.98
Epichlorohydrin -CHICI 106-89-8 92.53
Epifluorohydrin -CH2F 503-09-3 76.07
1,2-Epoxybutane, truns- CH3CH(-0-)CHCH3 21490-63-1 72.11
1,2-Epoxydecane
-W%hCH3
2404-44-6 156.27
1,2-Epoxydodecane -WWKH3 2855-19-8 184.32
1,2-Epoxyhexadecane
-(CH2)13CH3
7320-37-8 240.43
1,2-Epoxyhexane
-(CHhCH3 1436-34-6 100.16
2,3-Epoxynorbomane, exe- C7H100 3 146-39-2 110.16
1,2-Epoxyoctadecane
-(CWI&H~ 7390-8 1-0 268.49
2,3-Epoxypropyl benzene -CH2C& 4436-24-2 134.18
N-(2,3-Epoxypropyl)phthalimide -CH2NCgH402 5455-98-1 203.20
1,2-Epoxytetradecane
-(CJ&)llCH3 3234-28-4 212.38
Ethylene oxide - H 75-21-8 44.05
2-Ethylhexyl glycidyl ether -CH20CH2CH(CH2CH3)(CH2)3CH3 2461-15-6 186.30
Furfuryl glycidyl ether -CH20CH2C4H30 5380-87-0 154.17
Glycidol -CH20H 556-52-5 74.08
1 5 4
120/0.1
1 6 5
151
16614
1 2 9
5515
1 0 2
1 3 5
1 1 6
8 5
54
94115
124115
176112
1 1 9
13710.5
99117
95110.4
1 0 . 7
6110.3
103/11
61115
3 1
32
54
- 4 0
- 57
2 1
1 2 3
34
99
- 1 1 1
Butenes and Epoxi des III 127
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT.NMR FT-IR Merck Beilstein Fieser
0.726 1.4390 - 2 2 l( 1),27F 1(1),37A 1(1),32A 11,3228 1(3),991 1,276
0.843 1.400
1.665 1.5550 None E.J0700000 1(1),105H 1(1),150A 1(1),102A 1,250 10,195
1.553/- 2 0 1.378/- 2 0
1.5616
1.4220 1.4220 - 5 4 NT4037000 1(1),27E 1(1),36C 1(1),3OD 11,5087 1,252
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT.IR Merck Beilstein Fieser
1.3962 1(1),15C 11,1513 1,203
1.330 1.4625 9 l( 1),97E 1(1),136C 1(1),94B l(l),84
0.684 1.3890 - 1 8 l(l),231 1(1),31B 1(1),22A 1(3),816
0.653 1.3760 - 2 9 1(1),23B 1(1),29B 1(1),25B 1,217
0.650 1.3780 <- 35 1(1),23G 1(1),3OC 1(1),21B 1,211
0.62710 1.3640 - 5 7 1(1),23A 1(1),29A 1(1),21C 1,213
1.3931/- 2 5 3 7 1(1),19A 11,1514 1,205
1.3848/- 2 5 1(1),19B 11,1514 1,205
1.070 1.4780 1 2 6 EM4970000 1(1),153A 1(1),221A 1(1),146C 1(2),567
0.708 1.4120 - 17 1(1),25H 1(1),35B 1(1),25A 11,644 1,218
0.662 1.3870 - 4 6 1(1),25D 1(1),34A 1(1),21D 11,644 1,211
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT-IR Merck Beilstein Fieser
0.962 1.4330
0.910
0.917
1.038
0.970
1.4190
1.4170
1.5150
1.5450
1.4520
0.964 1.4340
1.601 1.4820
1.183 1.4380
1.067 1.3680
0.804 1.3730
0.840 1.4290
0.844 1.4360
0.846 1.4460
0.831 1.4060
1.020 1.5230
0.845 1.4408
0.89114 1.3597/7
0.891 1.4340
1.122 1.4810
1.117 1.4330
5 7
5 6
4 3
102
1 0 7
2 7
5 6
1 0
5 6
3 4
4
- 2 7
7 8
1 0 5
9 3
1 6
1 0
>llO
8 2
>llO
9 7
1 0 2
8 1
RR0875000
TX42OOON
RR0475000
TX4250000
TX5600000
RN7 175000
RN8935000
TX41 15000
TX4900000
TZ3325000
EK3855000
JR2450000
ML9450000
MO3630000
RB7 176000
DA0178000
TI4950000
KX2450000
TZ330OCOO
LU1423000
uB4375000
1(1),251C
1(1),1253D
1(1),249K
1(1),251A
1(1),1253A
1(1),1253B
1(1),251L
1(1),251M
1(1),251K
l( 1),247L
l( 1),2471
1(1),247H
1(1),245F
1(1),245J
l( 1),245K
1(1),247A
1(1),245H
1(1),253D
1(1),247B
1(1),1251D
1(2),2083B
1(1),245L
l( 1),245A
l(l), 251B
1 (2),2319J
l( 1),249B
1(1),374A
1(2),225A
1(1),373A
1(1),373B
1(2),224A
1(2),224B
1(1),376C
1(1),377A
1(1),376B
1(1),370B
1(1),369B
1(1),369A
1(1),364C
1(1),365C
1(1),366A
1(1),366C
1(1),378B
1(1),367A
1(2),22OC
1(2),1461C
1(1),366B
1(1),373C
1(3),17C
1(1),37OC
1(1),233D
1(1),1065C
1(1),232C
1(1),1065B
1(1),1064D
1(1),235A
1(1),235B
1(1),234D
1(1),232A
1(1),231D 11,3563
1(1),231C
l( 1),229B
1(1),230A
1(1),230B
1(1),230D
1(1),229A
1(1),235D
1(1),231B
1(2),408A
1(2),23OC
11,3758
1(1),232D
1(1),232B 11,4385
17(3),988
17(3),988
17,21
17,21
17,21
17,6 5,290
17(3),49
17,18
17(3),136
17,20
17,86
17(3),140
17,5 1
17(3),139
17,4 8,150
17(5),347
17,104
III / 28 PHYSICAL PROPERTIES OF MONOMERS
I
TABLE 12. contd
I
Name Formula
CAS Registry Boiling Melting
I
Number Mol. wt. point (C) point (C)
3-Glycidoxypropyl trimethoxy- -CH20(CH2)3Si(OCH3)3
silane
(R)-(-)-Glycidyl Butyrate -CH20C(0)CH2CH2CH3
Glycidyl isopropyl ether -CH20CH(CHj)2
Glycidyl methacrylate (see Methacrylates)
Glycidyltrimetbylammonium -CH2N(CH3)&l
chloride, (70% aq. solution)
Hexafluoropropylene oxide FzC(-0-)CFCF3
4-Methoxyphenyl glycidyl ether -CH20CsH40CH3
a-Pinene oxide
ClOH160
Propylene oxide -CH3
Styrene oxide
-CsHs
Tetracyanoethylene oxide WW-O-)WN)2
1,1,2,2-Tetrafluoroethyl glycidyl -CHzOCF2CHF2
ether
Vinylethylene oxide -CH=CH*
12.2. DIEPOXIDES CH2(-0-)CHRCH(-0-)CH,
Bis(3,4-epoxycyclohexylmethyl) C6H&O-)CH~0C(0)(CH2)4C(O)OCH2C6H~(-O-)
adipate
1,3-Butadiene diepoxide CH2(-0-)CHCH(-0-)CH2
1,4-Butanediol diglycidol ether -CH20(CH2)40CH2-
1,2,5,6-Diepoxycyclooctane
CEH1202
1,2,7&Diepoxyoctane
-(CH2)4-
3,4-Epoxycyclohexylmethyl C6H9(-O-)CH20C(O)C6H9(-0-)
3,4-epoxycyclohexane-
carboxylate
Ethylene glycol digycidyl ether -CH20(CH2)20CH2-
2530-83-8 236.34 12012
60456-26-0 144.17 90119
4016-14-2 116.16 131
3033-77-0 151.54
428.59- 1 166.02
2211-94-1 180.20
1686-14-2 152.24
75-56-9 58.08
96-09-3 120.15
3 189-43-3 144.09
85567-21-1 174.10
-42
46
102150
34 -112
1 9 4 -37
1 4 3
930-22-3 70.09 6 5
3130-19-6 366.46
1464-53-5 86.09 57125 3
2425-79-8 202.25 158/11
27035-39-8 140.18 7010.4
2426-07-5 142.20 240
2386-87-0 252.31 -37
2224-15-9 174.20 11214.5
TABLE 13. ETHYLENE HALIDES
CAS Registry Boiling Melting
Name Formula Number Mol. wt. point (C) point (C)
Ethylene H2C=CH2 74-85- 1 28.05 - 104 - 169
-, Bromo- (vinyl bromide) BrCH=CHz 593-60-2 106.96 161750 - 139
-, Chloro- (vinyl chloride) ClCH=CH2 75-01-4 62.50 - 13.4 - 154
-, I-Chloro-l-fluoro- ClCF=CH2 84.48 -24 - 169
-, Chlorotrifluoro- ClCF=CF2 79-38-9 116.47 - 29 - 157
-, 1,1-Dibromo- (vinylidene Br2C=CH2 185.86 92
bromide)
-, 1,2-Dibromo-, cis- BrCH=CHBr 185.86 1 1 2 -53
1,2-Dibromo-, rrans- BrCH=CHBr 185.86 1 0 8 - 6
-, l,l-Dichloro- (vinylidene C12C=CH2 75-35-4 96.94 3 1 - 122
chloride)
-, 1,2-Dichloro-, cis- ClCH=CHCl 156-59-2 96.94 60 - 80
-, 1,2-Dichloro-, truns- ClCH=CHCl 156-60-5 96.94 48 -50
-, Tetrabromo- Br2C=CBr2 343.66 226 56
-, Tetrachloro- c12c=cc12 127-18-4 165.83 121 - 22
-, Tetrafluoro- F2C=CF2 116-14-3 100.02 -76 - 142
- Tetraiodo-
, 12c=c12 5 13-92-8 531.64 1 9 2
-, Tribromo- Br$=CHBr 264.76 1 6 3
-, Trichloro- C12C=CHCl 79-01-6 131.39 8 7 - 85
Ethyl ene Hal i des III 129
Density
(at 20C)
Refractive
index (at 20C)
Flash
point (C)
RTECS
Number R and S FT-NMR FT. IR Merck Beilstein Fieser
1.070 1.4290 >llO VV4025000 1(2),2973B 1(3),667C 1(2),1113D
1.018 1.4280 8 5
0.924 1.4100 3 3 TZ3500000
1(1),781E 1(1),1088B
l(l),2495 1(1),372C
17(5),3,34
1(3),306A 17(3),988
18,583
17(3),20
1(1),1065A
1(1),237A 5, 152
1(1),228B 11,7869 17,6
1(1),1063C 17,49
18(5),7,215
1.129 1.4780 >llO BQ3480000 1(1),616B
TZ3400000
DA0176000
TK4565000
TZ2975000
CZ9625000
l( 1),249A
1(1),1253C
1(1),253B
1(1),245B
1(1),1251A
1(1),1003F
>llO
6 6
- 3 5
7 9
1(2),224C
1(1),377C
1(1),363B
1(2),219C
1(1),1376C
0.964 1.4690
0.830 1.3660
1.054 1.5350
1.380 1.3490 5 1
. 0.870 1.4170 - 5 0 EM7350000 1(1),247D 1(1),367C 1(1),233A 17(1),13 4,53
1.149 1.4930 >llO MO1880550
1(1),251E 1(1),374B 1(1),234A 11,3621 19,14
l(l),2511 1(1),375C 1(1),234C
1(1),253E 1(1),378C 1(1),235C
1(1),251F 1(1),374C 1(1),234B
1.113 1.4340 4 6 EJ8400000
1.100 1.4610 >llO EJ5100000
1.138 1.4690 1 0 5 GX9627000
0.997 1.4450 9 8 RG9450000
1.170 1.4980 1 1 8 RN7750000
1.118 1.4630 >llO KH5780000 1(1),251G 1(1),375A 17(3),997
Density
(at 20C)
Refractive
index (at 20C)
Flash
point (C)
RTECS
Number R and S FT-NMR FT. IR Merck Beilstein Fieser
KU5340000 1(1),15A 1(3),17C 11,3748 1,180
1.517 1.4350 None KU8400000 1(1),95B 1(1),133A 1(1),93A 1,188
0.911 1.3700 - 61 KU9625000 1(1),95A 11,9898 1,186 1,1274
KVO525000 l(l),1031 WW6
2.178
2.2464 1.5428
2.2308 1.550
1.213 1.4254 -9 KV9275000 l(l),lOlB 1(1),142B 1(1),98B 11,990O 1, 186
1.284 1.4481 6 KV9420000 l(l),lOlD 1(1),143A 1(1),98A 11,86 1, 188 14, 127
1. 257 1. 4456 6 KV9400000 l(l),lOlE 1(1),134B 1(1),79D 11,86 1, 188 12, 175
1. 623 1.5060 None KX385OOOO l(l),1035 l(l),lOlC 11,9126 1, 187
1.1507/- 4 0
2.983 KX4125000 1(1),103K 11,9151 1, 195
2.708 1.6045/16
1.463 1.4760 None KX4550000 1(1),103G 1(1),147C l(l),lOlB 11,9552 1,187 11,552
III/30 PHYSICAL PROPERTIES OF MONOMERS
TABLE 14. FUMARATE ACIDS/ESTERS
Name
Formula ROC(O)CH=CHC(O)OR
R
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
Acid -H
2-Bromo- HOC(O)CBr=CHC(O)OH
2-Chloro- HOC(O)CCl=CHC(O)OH
2-Chloro-, diethyl ester CH3CH20C(0)CCl=CHC(O)OCHZCH3
2-Chloro-, dimethyl ester CH30C(0)CCl=CHC(O)OCH3
Di-n-amyl ester
-Wb).KH3
Diethyl ester -CH2CH3
Diisoamyl ester -CH2CH2CH(CH3)2
Diisobutyl ester -CH2CH(CH3)2
Diisopropyl ester
-WCHh
2,3-Dimethyl- HOC(O)C(CH3)=C(CH3)C(O)OH
Dimethyl ester -CH3
Dinitrile- (fumaronitrile) NCCH=CHCN
Diphenyl ester -CsHs
Di-n-propyl ester -CHzCH#ZHj
2-Methyl- (mesaconic acid) HOC(0)C(CH3) = CHC(O)OH
2-Methyl-, diethyl ester CH3CH20C(0)C(CH3)=CHC(O)CHZCH3
110-17-8 116.07
194.98
150.52
206.63
178.57
256.33
623-91-6 172.18
256.33
228.29
200.24
144.13
624-49-7 144.13
764-42-1 78.07
268.27
200.24
498-24-8 130.10
2W4
136/19
224
16217
217
166/11
170/160
226
299(s)
1 8 6
1 9 3
2
1 9 2
186
219114
11015
205(d)
186.21
2 4 1
1 0 3
96
1 6 2
204
229
2-Methyl-, dimethyl ester CH,0C(0)C(CH3)=CHC(O)OCH3 158.16 204
TABLE 15. ISOCYANATES
Name
Formula OCNRNCO
R
CAS
Registry
Number Mol. wt.
Boiling Melting
point (C) point (C)
1,3-Benzene diisocyanate -CsH4-
1,4-Benzene diisocyanate -C,5H4-
1,3-Bis(isopropy1)benzene
-C(CHd2C&C(CHsh-
u,u-diisocyanate
1,4-Bis(isopropyl)benzene
-C(CHd2CdbC(CHd2-
a,a-diisocyanate
1,4-Butene diisocyanate
-(CH2)4-
a-Chlorotoluene -C&(C&Cl)-
2,cdiisocyanate
1,4-Cyclohexylene diisocyanate, -C6Hio-
trans-
1,12-Dodecane diisocyanate
-WH2)12-
1,6-Hexane diisocyanate
-(CH2)6-
Isopherone diisocyanate -CloH~a-
(isomers)
4,4-Methylenebis(cyclohexy1
-(C~HIO)CH~(C~HIO)-
isocyanate) (isomers)
4,4-Methylenebis(2,6-di-
-C~H~(CH~CH~)ZCH~C~H~(CH~CH~)~-
ethylphenyl
isocyanate)
4,4-Methylenebis(phenyliso- -C&CH&H4-
cyanate)
2-Methylpentane 1,5-diisocyanate-CH+ZH(CH3)(CH2)3-
1,8-Octane diisocyanate
-P32h-
2,CToluene diisocyanate
-CsHdCH+
123-61-5 160.13
104-49-4 160.13
2778-42-9 244.30
2778-41-8 244.30
4538-37-8 140.14
51979-57-8 208.60
7517-76-2 166.18 60
13879-35-1 252.36 16813
822-06-0 168.20 255
4098-71-9 222.29 158/15
5124-30-1
105442-35-1
101-68-8 250.26 20015 43
34813-62-2 168.20
10124-86-4 196.25
584-84-9 174.16
262.35
362.48
121125 50
260 98
157110 - 10
15013 72
102/14
153/11
56
156115
120/10 2 1
Fumarate Acids/Esters and lsocyanates III 131
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT-IR Merck Beilstein Fieser
LS9625000 1(1),553A 1(1),787B 1(1),502D 11,420O 2,737 5,319
1. 4571 1.1880
1.290
0.9681
1.052
0.9655
0.9760
1.4496
1.4410 94 EM5950000 1(1),725M 1(1),993C 1(1),645A 2,742
1.4479
1.4432
EM6125000 1(1),725L 1(1),993B l( 1),644D 2, 741
1. 4349 LT23OOOOO 1(1),993A 1(1),136OB 1(1),844A 2(1),302 0.9416
1.0129
1.466
1.4439
0x5075000 1(1),553C 1(1),788A 1(1),503B 11,5806 2,763
1.0453 1.4488
1.0914 1.4512
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT-IR Merck Beilstein Fieser
>llO NR0150000
>llO CZ6150000
1 5 3 CY 8480000
1(2),2165G 1(3),1432D 13,50
1(2),2165H 13, 105
>93
1 0 6 1(1),1023F 1(1),1404B 4(3),578
>llO 1(2),2169H 1(2),1572A 13(4),245
GU9642500 1(1),1025A 1(1),1406A 13(3),12
MO1740000
NQ9370000
1(1),1023H 1(1),1405A
1(1),1023G 1(1),1404C
1(1),1023J 1(1),1405C
4(3),624
1(1),871A 4(2),7 11
1.105
1.362 1.5960
1.4590 >llO
1.4520 140
1.4840 >llO
1.4970 >llO NQ9250000 1(1),1025B
0.940
1.040
1.049
1.066 13(4),33
1(2),2169K 1(2),1572C
1.180 >llO NQ9350000
1.049 1.4550 >llO
1.007 1.4550 >llO
1.214 1.5680 >llO CZ630000
1(2),2163D
l(l),10231
1(2),2169F
13(3),461
4(3),614
1(2),478B 11,9456 13,138 1,117
1(1),1405B
III / 32 PHYSICAL PROPERTIES OF MONOMERS
TABLE 16. LACTAMS
CAS Registry
Name
Boiling Melting
Formula Number Mol. wt. poitit (C) point (C)
y-Butyrolactam (2-pyrrolidinone) -C(0)(CH2)3NH- 616-45-5 8 5 . 1 1 245 24
E-Caprolactam -C(O)(CH&NH- 105-60-2 113.16 137110 69
12-Dodecanolactam -C(WC&)I~NH- 947-04-6 197.32 151
7-Heptanolactam -C(o)(CH&NH- 673-66-5 127.19 149/10 3 6
P-Propiolactam -C(0)CH2CH2NH- 930-21-2 71.08
&Valerolactam
106115 7 5
-C(0)(CH2)4NH- 675-20-7 99.13 256 39
TABLE 17. LACTONES
CAS Registry
Name
Boiling Melting
Formula Number Mol. wt. point (C) point (C)
y-Butyrolactone
-WWH2)3O- 96-48-0 86.09 204 - 4 5
E-Caprolactone
-WWH2M3- 502-44-3 114.14 97115
/3-Propiolactone
-WWCHd,O- 57-57-8 72.06 1 6 2
&Valerolactone
- 33
-C(O)(CH2)40- 542-28-9 100.12 5910.5
TABLE 18. MALEATE ACIDS/ESTERS
Formul a ROC(O)CH=CIIC(O)OR CAS
Registry
Name
Boiling Melting
R Number Mol. wt. point (C) point (C)
Acid - H 110-16-7 116.07 141
2-Chloro- HOC(O)CCl=CHC(O)OH 150.52 1 1 0
2-Chloro-, diethyl ester CH3CH20C(0)CCl=CHC(O)OCH2CH3 206.63 235
2-Chloro-, dimethyl ester CH30C(0)CCl=CHC(O)OCH3 178.57 1 0 7
Diallyl ester -CH2CH=CH2 999-21-3 196.20 1 IO/4 - 4 7
Di-n-amyl ester
-KHd4CH3 256.33 161/10
Di-n-butyl ester
-(CHd3CH3 105-76-0 228.29 2 8 1
2,3-Dichloro- HOC(O)CCl=CClC(O)OH 184.97 120
Diethyl ester -CH2CH3 141-05-9 172.18 225 - 10
2,3-Dihydroxy- HOC(O)C(OH)=C(OH)C(O)OH 148.07 1 5 5
Diisoamyl ester -CHzCH$H(CH& 156.33
Dimethyl ester
157113
-CH3 624-48-6 144.13 204
Diphenyl ester -CsHs 268.27 226115 9 3
Di-n-propyl ester -CH2CH2CH3 200.24 126112
2-Methyl-, ck- (citraconic acid) HOC(O)C(CH3)=CHC(O)OH 498-23-7 130.10 90
2-Methyl-, diethyl ester, cis- CH3CH20C(0)C(CH3)=CHC(O)OCHzCH3 1 8 6 . 2 1 230
2-Methyl-, dimethyl ester, cis- CH30C(0)C(CH3)=CHC(O)OCH3 158.16 2 1 1
TABLE 19. PROPENES
CAS Registry
Name
Boiling
Formula
Melting
Number Mol. wt. point (C) point (C)
Propene H2C=CHCH3 115-07-1 42.08 - 4 8 - 185
-, I-Bromo-, ck- BrCH=CHCH3 590-13-6 120.98 58
-, 1-Bromo-, trans- BrCH=CHCH3 590-15-8 120.98 64
-, 2-Bromo- H2C=CBrCH3 557-93-7 120.98 48 - 125
-, 1Chloro-, cis- ClCH=CHCH3 76.53 3 3 - 1 3 5
-, 1-Chloro-, trms- ClCH=CHCH3 76.53 3 7
-, 2-Chloro-
- 9 9
H2C=CClCH3 557-98-2 76.53 2 2 . 5 - 139
-, I-Chloro-2-methyl- ClCH=C(CH& 513-37-1 90.55 6 8
(isocrotyl chloride)
-, 3-Chloro-Zmethyl- H2C=C(CH3)CH2Cl 563-47-3 90.55 7 1 - 80
(methallyl chloride)
-, l,l-Dichloro- C12C=CHCH3 563-58-6 110.97 76
Lactams, Lactones, Maleate Aci ds/ Esters and Propenes III 133
Density
(at 20C)
Refractive
index (at 20C)
Flash
point (C)
RTECS
Number R and S FT-NMR FT-IR Merck Beilstein Fieser
1.120 1.4870 >llO UY5715000 1(1),923B 1(1),1285B 1(1),788D 11,8027 21,236
CM3675000 l( 1),927G 1(1),1293B 1(1),792B 11,1762 21(2),216
CL6940000 l( 1),929A 1(1),1296A 1(1),794A
>llO CN4810000 1(1),927M 1(1),1295B 1(1),793C 21,242
1(1),923A 1(1),1285A 21(3),3141
>llO TOO1 10000 1(1),927E 1(1),1292C 1(1),791D 21,238
Density
(at 20C)
Refractive
index (at 20C)
Flash
point (C)
RTECS
Number R and S FT-NMR FT-IR Merck Beilstein Fieser
1.120 1.4360 9 8 Lu3500000 1(1),803J 1(1),1127A 1(1),697D 11,1596 17,234 1,101
1.030 1.4630 1 0 9 MO8400000 1(1),819E 1(1),1161C 1(1),699B 17(2),290
1.146 1.4120 7 0 RQ7350000 l( 1),803A 11,7832 17(1),130 1,957
1.079 1.4580 100 1(1),815A 1(1),1152A 1(1),704D 17,235
Density
(at 20C)
Refractive
index (at 20C)
Flash
point (C)
RTECS
Number R and S FT-NMR FT-IR Merck Beilstein Fieser
1.590 OM9625000 l(l),5510 1(1),787A 1(1),503A 11,5585 2,748
1.1741
1.277
1.073 1.4690 z-l10 ON0700000 1(1),725K 1(1),993A 2(3),1926
0.9741 1.4475
0.988 1.4452 >llO ON0875000 l(l),7255 1(1),992C 2(3),1925
1.064 1.4410 93 ON1225000 l(l),7251 1(1),992B 1(1),644C 11,3113 2,751
0.9714 1.4459
1.152 1.4410 9 1 EM6300000 1(1),725H 1(1),992A 1(1),644B 2,751
1.0245 1.4433
GE6650000 1(1),553B 1(1),787C 1(1),503C 11,2323 2,768
1.0491 1.4468
1.9491 1.4473
Density
(at 20C)
Refractive
index (at 20C)
Flash
point (C)
RTECS
Number R and S FT-NMR FT-IR Merck Beilstein Fieser
1.423
1.408
1.362
0.9347
0 . 9 3 5 1
0.899
0.920
1.4545
1.4530
1.436
1.4055
1.4054
1.3939
1.4225
0.917 1.4278 - 12 UC8050000
UC6740000 1(1),15B 11,7862 1,196
- 3 4 l( 1),95F 1(1),134A 1(3),710
- 15 l( 1),95C 1(4),754 4,236
4 UC7085000 1(1),95H 1(1),134C 1(1),96B 1,200
- 3 4 UC7200000 1(1),95D
- 1 UC8045000 l( 1),971
1(1),97J
1(1),133B l( 1),96A 1,198
1(1),137C 1(1),97A 11,2147 1,209
1(1),138A 1(1),96D 11,2148 1,209
1(1),144A 1(3),138D 1,199 1.169 1.4450 0 UC8290000 l(l),lOlG
III/ 34 PHYSICAL PROPERTIES OF MONOMERS
TABLE 19. contd
Name Formula
-, 1,2-Dichloro- ClCH=CClCHs
-, Hexafluoro- F2C=CFCFs
-, 2-Methyl- (isobutylene) H2C=C(CH3)2
-, 1,1,2-Trichloro- C12C=CClCHs
-, 1,1,3-Trichloro- C12C=CHCH2Cl
-, 1,2,3-Trichloro- ClCH=CClCH2Cl
-, 3,3,3-Trichloro- H2C=CHCC1s
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
110.97 77
116-15-4 150.02 - 28 - 153
115-11-7 56.11 - 7 - 140
145.42 1 1 8
145.42 131
145.42 1 4 2
145.42 1 1 4
TABLE20. STYRENES
Name
Formula CHz=CHR
R
CAS
Registry
Number Mol. wt.
Boiling Melting
point (C) poi nt (C)
Styrene
-, 4-Acetoxy-
-, 2-Amino-
-, 4-Amino-
-, 4-Benzyloxy-3-methoxy-
-, 3,5-Bis(trifluoromethyl)-
a-Bromo-
P-Bromo-
-, 2-Bromo-
-, 3-Bromo-
-, 4-Bromo-
-, 4-rert-Butyl-
-, 4-Carboxy-
wChloro-
B-Chloro-
-, 2-Chloro-
-, 3-Chloro-
-, 3-Chloromethyl
(3-vinylbenzyl chloride)
-, 4-Chloro-
-, 4-Chloromethyl-
-, 4-Chloro-wMethyl-
-, 2-Cyano-
-, 3-Cyano-
-, 4-Cyano-
-, 2,5-Dichloro-
-, 2,6-Dichloro-
-, 3,4-Dichloro-
-9 a$-Difluoro-
-, 1,2-Difluoro-
-, 2,6-Difluoro-
-, 1,3-Diisopropenyl benzene
-, 3,4-Dimethoxy-
-3 a,2-dimethyl-
-, 2,4-Dimethyl-
-, 2,5-Dimethyl-
-, Divinyl-, (isomers)
-, 4-Ethoxy-
-, 2-Ethyl-
-, 4-Ethyl-
-, 3-Iodo-
-, 2-Fluoro-
-, 3-Fluoro-
-, 4-Fluoro-
-, 2-Hydroxy-
-, 3-Hydroxy-
-, 4-Hydroxy-
-, 4-Isopropyl-
46H5
-C6H@C(o)CHj
-C&NH2
-C,jH4NH2
-Cr,Hs(OCHs)OCHzCsHs
--Cdb(CFd2
H2C=CBrC&
HCBr=CHCbHs
-CeHABr
-C,jHdBr
-CbHhBr
-CdbC(CHd3
-C&+Co2H
H2C=CClC&
HCCI=CHC6H5
-CsH4Cl
-C,5H4Cl
-C&CH#
-CsH4Cl
-C&&H2Cl
H2C=C(CH&$L+CI
-C&&N
-C&jCN
-C&4CN
-Cf,H3C12
-q5H3C12
-C,5H3C12
HCF=CFC,jHs
-Cdbh
-C6H#z
Cd-h(C(CHd=CHh
-Cdh(OCH3)2
H2C=C(CH3)C&CH3
-C6HdCH&
-CsHdCHh
C&(CH=CH2)2
-C.&@CH2CH3
-C6H&H2CH3
-C&CH2CH3
-C&I
-C,&F
-C&F
--C&F
-C.&OH
-C&OH
-C&OH
-Cd%H(CHd2
100- 42- 5
2628- 16- 2
3867- 18- 3
1520- 21- 4
55708- 65- 1
349- 59- 7
98- 81- 7
103- 64- 0
2039- 88- 5
2039- 86- 3
2039- 82- 9
1746- 23- 2
1075- 49- 6
2039- 87- 4
2039- 85- 2
57458- 41- 0
1073- 67- 2
1592- 20- 7
1712- 70- 5
5338- 96- 5
3435- 51- 6
1123-84-8
28469- 92- 3
2039- 83- 0
366- 37- 0
3748- 13- 8
6380- 23- 0
26444- 18- 8
2234- 20- 0
2039- 89- 6
1321- 74- 0
5459- 40- 5
7564- 63- 8
3454- 07- 7
394- 46- 7
350- 51- 6
405- 99- 2
2055- 40- 5
104. 15
162. 19
119.18
119.18
240. 30
240. 15
183. 05
183. 05
183. 05
183. 05
183. 05
160. 26
148. 16
138. 60
138. 60
138. 60
138. 60
152. 62
138. 60
152. 62
152. 62
129. 16
129. 16
129. 16
173. 04
173. 04
173. 04
140. 03
140. 03
140. 03
158. 25
164. 20
132. 21
132. 21
132. 21
130. 19
148. 21
132. 21
132. 21
233. 05
122. 14
122. 14
122. 14
120. 15
120. 15
120. 15
146. 22
1 4 5
260
104/ 8
249
51
60120
6914
111/20
210
7413
212
219
199
199
188
6216
229
192
229
53/ 0. 15
8312. 6
9213
7413
88/ 8
7613
88/ 60
90145
59151
231
120/ 10
54111
70/ 11
71110
5911
191
193
67115
3014
30114
108/ 15
115
204
- 30
7
23
7
- 44
7
- 53
4. 5
- 37
143
- 23
- 63
- 16
- 15
- 64
- 35
- 127
- 50
73
29
73. 5
- 45
Styrenes III 135
Density Refractive Flash RTECS
(at 20C) index (at 20C) poi nt (C) Number R and S FT-NMR FT-IR Merck Beilstein Fieser
1.1818 1.4471
UD03.50000 1(1),105A 1(3),143C 1(3),697
UD0890000 l( 1),23F 1(3),28B 11,5024 1,207
1.382 1.4827
1.403 1.4950 48 UD1928500 1(1),103H 1(1),148A 1(3),142A 1(3),707
1.414 1.5020
1.369 1.4827
Density Refractive
(at 20C) index (at 20C)
,Flash
Pqht (C)
RTECS
Number R and S FT-NMR FT-IR Merck Beilstein Fieser
0.9059
1.060
1.608
1.014
1.5470 3 1 WL3675000 1(1),1139A 1(2),23A 1(1),945B 11,883O 5,474
1.5380 8 7 SL3784000 1(2),1927F 1(2),1287C 6(3),2387
1.6267
1.334 1.4250
1.410 1.5880
1.427 1.6070
1.460 1.5927
1.406 1.5891
1.400 1.5940
0.875 1.5260
>I10
1 2 2
8 7
1 0 2
8 5
67
7 5
80
WL3840000
WL3850000
1(1),1237M 1(2),197C
1(1),1213A 1(2),155A
1(1),1203F
1(1),1203H 1(2),136C
1(1),1203L 1(2),138A
1(1),1205D 1(2),139C
l( 1),1205H 1(2),141A
1(2),1789D 1(2),1076A
12,1187
1(1),1053A
5(4),1386
5,477
1(1),1017B 5,477
1(1),1018A 5(3),1176
1(3),195B 5(3),1176
1(1),1019C 5(2),367
5(3),1254
1(2),194D 9(3),2755
1.1016/18
1.1095/15
1.080
1.090
1.074
1.5612
1.5648
1.5648
1.5613
58
62
1 0 5
WL4160000 1(1),1203K 1(2),137C 1(1),1017D
1(1),1205C 1(2),139B 1(1),1018C
1.155
1.083
1.065
1.5662
1.5740
1.5550
1.5756
1.5630
1.575
60
1 0 4
74
1(1),1205F 1(2),14OB
1(1),1205G 1(2),14OC
1(1),1019B 5(2),367
1(1),1018D
1.083 104
1.267 1.5740 7 1 1(1),1205J 1(2),141C 1(1),1019D
1.5061
1.130
0.925
1.109
0.894
0.906
0.904
0.914
0.990
0.8955
0.8925
1.4990
1.5570
1.5710
1.5150
1.5390
1.5391
1.5470
1.5498
1.5351
1.5376
1.6390
1.5200
1.5175
1.5156
1.5783127
1.5804131
30
9 1
>llO
43
60
6 3
64
87
CY8535000
l(l),12051 1(2),141B
1(1),1139L 1(2),26B
1(1),1243D 1(2),208C
1(1),947C
1(1),1053D
WL4450000
WL4460000
cz9370000
1(1),1141D 1(2),27C
l(l),1 141E 1(2),28A
1(1),1141B
1(1),1243A 1(3),984B 6,561
1.025
1.025
1.024
1.0609/18
1.0468/35
3 5 1(1),1203J 1(2),137B
29 1(1),1205B 1(2),139A
26 1(1),1205E 1(2),140A
1(1),1081B
1(1),1019A
0.885 1.5289
6,954
5,491
5,491
5(3),1171
5(3),1171
III / 36 PHYSICAL PROPERTIES OF MONOMERS
TABLE 20. contd
Formula CH2 =CHR CAS
Registry Boiling Melting
Name R Number Mol. wt. point (C) point (C)
-, 2-Methoxy- -&-H4oC& 612-15-7 134.18 6 1 . 3 29
-, 3-Methoxy- -C,&oCH3 626-20-0 134.18 14412
-, 4-Methoxy- -C&&CH3 637-69-4 134.18 204
-, 2-Metboxy-Chydroxy- -CsHsOCHs(OH) 7786-61-0 150.18 224
W- Met hyl - H2C=C(CH3)CsH5 98-83-9 118.18 1 6 7 - 24
-, 2-Methyl- -CsH4CH3 611-15-4 118.18 171 - 6 9
-, 3-Methyl- -C,jH&H3 100-80-1 118.18 170 - 82
-, 4-Methyl- -C,&CHj 622-97-9 118.18 1 7 2 - 3 4
-, P-Nitro- HC(N02)=CHC6H5 149.15 250 5 8
-, 2-Nitro- -C&N& 1 4 9 . 1 5 13
-, 3-Nitro- -C,&No2 586-39-0 1 4 9 . 1 5 9013.5 - 5
-, 4-Nitro- -C&&o2 100-13-0 1 4 9 . 1 5 120/10 2 5
-, Pentabromo- -C&r5 53097-59-9 498.66 1 8 8
-, Pentafluoro- -CsFs 653-34-9 194.10 139
-,4-Phenoxy- -C6H&C& 4973-29-9 1 9 6 . 2 5 7 1
-, 4-Phenyl- -C6H&ds 2350-89-2 1 8 0 . 2 5 120
-, 4-Sulfonic acid, sodium salt -C6H4BQsNa 2695-37-6 206.20 225
-, 2-Trifluoromethyl- -C&CF3 395-45-9 172.15 61140
-, 3-Trifluoromethyl- -C&&F3 402-24-4 172.15 55112
-, 4-Trifluoromethyl- -C,&CF3 402-50-6 1 7 2 . 1 5 65140
-, 2,4,6-Trimethyl- -Cdb(CH& 769-25-5 146.24 209
TABLE 21. VINYL FUNCTIONAL
Name Formula
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
21.1. ARYL H*C=CHR
9-Anthracene -C14H9
Benzene (see Styrene)
2-Naphthalene -C10H7
2Pyridine -C5H4N
3Pyridine -CsH4N
4Pyridine -CsHdN
2-Quinoline -Cg&N
21.2. ESTERS H2C=CHOC(0)R
Acetate
Acrylate (see Acrylates)
Ally1 adipate
Benzoate
Bromoacetate
4-tert-Butyl benzoate
Butyrate
Carbonate
Chloroacetate
2-Chlorobenzoate
Chloroformate
Cinnamate
Crotonate
Decanoate
Dodecanoate
2-Ethylhexanoate
Formate
2-Furoate
Hexadecanoate (palmitate)
Hexanoate (caproate)
Maleate
-CH3
2444-68-0
827-54-3
100-69-6
1121-55-7
100-43-6
772-03-2
108-05-4
-(CH2)4C(0)OCH2CH=CH2
--C6H5
-CHzBr
-CdhC(CHd3
-(CHdzCH3
-OCH=CH2
-CH2C1
-CeH4Cl
- Cl
-cH=cHcsH~
-CH2CH=CHCH3
-(CHzM%
-(CWIOCH~
-CH(CHzCHs)(CHz)sCH3
- H
-C4H30
-W2)14CH3
-(CHd4CH3
-CH=CHC(O)OCH=CHz
56860-96-9
769-78-8
5309-70-6
15484-80-7
123-20-6
872-36-6
2549-51-1
15721-27-4
5 130-24-5
3098-92-8
14861-06-4
4704-3 1-8
2146-71-6
94-04-2
692-45-5
1917-10-8
693-38-9
3050-69-9
204.27 62110
1 5 4 . 2 1
105.14
105.14
105.14
155.20
6 5
6 1
80129
68115
63115
7110.5
86.09 72 - 9 3
212.25
148.16
165.0
204.27
114.14
86.05
120.54
1 8 2 . 6 1
1 0 6 . 5 1
174.20
1 1 2 . 1 3
1 9 8 . 3 1
226.36
1 7 0 . 2 5
72.06
138.12
282.47
142.20
1 6 8 . 1 5
13519
203
50110
111/2
1 1 6
1 6 2
1 3 4
22
681735
12517
1 3 3
146150
140/10
128/20
46
182/10
16512
160/10
94110
- 9 0
1 4
24
Vinyl Functional III 137
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number RandS FT-NMR FT-IR Merck Beilstein Fieser
72 l(l),12410 1(2),207C 1(1),1052C 6,561
>llO SL8205000 6(3),4981
45 WL5075300 l(l),1 139B 1(2),2437C l( 1),945C 5,484
58 WL5075900 1(1),1139K 1(1),947A 5( 1),233
52 WL5075800 1(1),1139M 1(2),26C 1(3),869B 5,485
45 WL5076000 1(1),1139N 1(2),27A l( 1),947B 5,485
1.0049 1.5388
0.9999 1.5540
0.994 1.5620
1.110 1.5820
0.909 1.5380
0.917 1.544
0.890 1.5408
0.897 1.5412
5.478 1.070 1.5840
1.6016
1 0 7 1(1),1555D 1(2),687C 1(1),1334D
WL547oooo
1(1),1205N 1(1),102OB
1(1),1205K 1(2),142A 1(1),102OA
l(l),1 145G 1(2),35B 1(1),951D
1(2),22071 1(2),1598C
1(1),1207C 1(2),143A
1(1),1207K 1(2),138C
1(1),1209F 1(2),148A
l(l),1 141G 1(3),871A
1.406 1.4455 34
42 5(4),1367
5(3),1197
5(4),1369
5,500
1.175 1.4700
1.161 1.4655
1.165 1.4660
0.906 1.5320 7 5
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT.NMR FT-IR Merck Beilstein Fieser
l(l),11531 1(2),51A
1(1),1151G 1(2),46A
1(2),2495G 1(3),242C
1(2),2499B 1(3),248B
0.975
0.975
1.340
1.5490
1.5530
1.5500
47
52
1 2 8
UUlO40000
uu1045000
1(1),963B
1(1),959C
1(2),734A
1(2),738D
1(2),853D
20,256
20(2),170
20,425
0.934 1.3950 - 6 AK0875000 1(1),715A 1(1),963A 1(1),632D 11,9896 WW 12,565
1.070 1.5290 82 DI1050000
1(2),1903L 1(2),1248C
9(1),65
9(4),1885
2(4),792
FG3325000 l( 1),697E 1(1),933A l(l),mA
13,342
1.4100 - 4 1(1),863A 1(1),1206A
GQ585OC-00 1(1),721H 1(1),978C
1(1),736D
1(1),642B
3(3),28
2(3),1263
2(3),843
MO7875000
LRO525000
1(1),719A 1(1),793A 1(1),637C 2(4),1005
1(1),1206A 1(1),736C 3(3),28
8,530
8.530
0.999
0.9022
1.355
1.19
1.22
1.253
1. 07
0.940
0.886
0.8639
0.875
0 . 9 6 5 1
0.8602
0.8837
1.5180
1.411
1.4210
1.4440
>llO
20
72
1.4480
1.4350
1.4387
1.4256
1.4757
27
104
136
65
1.4444
1.4159
III/38 PHYSICAL PROPERTIES OF MONOMERS
TABLE 21. contd
Name Formula
CAS Registry Boiling Melting
Number Mol. wt. point (C) point (C)
Maleate, monoester -CH=CHC(O)OH
Metbacrylate (see Methacrylates)
Neodecanoate
-C9H19
Nonate
-4CHzhCH3
Octadecanoate (stearate) -(CHz)l6CH3
9-Octadecenoate (oleate) -(CH2)7CH=CH(CH2)7CHs
Octanoate -(CHd&H3
Pentafluoropropionate -CF2CF3
Pentanoate
-(CHhCH3
Pivalate -WH3)3
Propionate -CHzCH3
Sebacate -(CHz)sC(0)OCH=CH2
Succinate -CHzCH2C(0)OCH=CH2
Tetradecanoate (myristate) -KH2)12CH3
Thioacetate H2C=CHSC(0)CH3
Trichloroacetate -cc13
Trifluoroacetate -CF3
LTrifluoromethyl acetate HzC=C(CFs)OC(0)CH3
Trithiocarbonate H2C=CHSC(S)SCH=CH2
Undecanoate
-(CHhCH3
Versatate
-WHddCHd5CH3
21.3. ETHERS H2C=CHOR
Ally1
Butoxyethyl
n-Butyl
2-Butyl
rerr-Butyl
1-Chloroethyl
2-Chloroethyl
Cyclohexyl
1,2-Dichloroethyl
Di(ethylene glycol)
Divinyl
Dodecyl
Ethyl
2-Ethylhexyl
Glycidyl
Hexachlorodivinyl
Hexadecyl
4-Hydroxybutyl
2-Hydroxyethyl
Isoamyl
Isobutyl
Isooctyl
Isopropyl
2-(2-Methoxyethoxy)ethyl
2-Methoxyethyl
Methyl
Octadecyl
Perfluoropropyl
Phenyl
1-Phenylethyl
Propyl
-CH2CH=CH2
-CH2CH20(CHz)sCHs
-(CHhCH3
-CH(CH2CH3)CH3
-WH3)3
-CHC1CH3
-CH2CH2Cl
-CsH11
-CHClCH2Cl
-CHzCH20CHzCH20H
-CH=CH2
-(CHz)llCH3
-CH2CH3
-CHzCH(CH2CH3)(CH2)3CH3
-CHzCH(-0-)CH2
(c12c=cc1)20
-W2)15CH3
-(CHzhOH
-CH2CH20H
-CHZCH~CH(CH~)~
-CHZCH(CH~)~
-(CHd5CJWH3)2
-CWCW2
-(CHzCHz0)2CH3
-CH2CH20CH3
-CH3
-(CHd17Cfb
FzC=CFOCF2CF2CF3
-C6H5
-CH(c&)CHj
-CHzCH2CH3
21. 4. N-SUBSTITUTED H2C=CHR
-Caprolactam -NC6Hloo 2235-00-9 139.20
-Carbazole
-NCnHs 1484-13-5 193.25
-Formamide -NHC(O)H 13162-05-5 71.08
-Phthalimide -NC&& 3485-84-5 173.17
-Pyrolidone -NC&o 88-12-0 111.14
-N-Methylacetamide -N(CHs)C(0)CH3 3 195-78-6 99.10
19896-47-0 1 4 2 . 1 1 80/1
51000-52-3
6280-03-1
111-63-7
3896-58-0
818-44-0
5873-43-8
3377-92-2
105-38-4
10355-50-7
13416-90-5
5809-91-6
10340-63-3
7062-87-5
433-28-3
2247-91-8
930-35-8
49863-74-3
3917-15-5
4223-11-4
111-34-2
4181-12-8
926-02-3
110-75-8
110-75-8
2182-55-0
929-37-3
109-93-3
765-14-0
109-92-2
103-44-6
3678-15-7
822-28-6
17832-28-9
764-48-7
109-53-5
37769-62-3
926-65-8
26256-87- 1
1663-35-0
107-25-5
930-02-9
1623-05-8
766-94-9
6230-62-2
764-47-6
1 9 8 . 3 1
184.28
310.51
308.49
170.25
190.08
128.17
1 2 8 . 1 7
100.12
254.33
170.16
254.41
102.15
1 8 9 . 4 3
140.06
154.09
134.24
212.33
1 9 8 . 3 1
216
133150
18112
1 4 5
7917
581560
1 3 2
1 1 2
9 5
14213
5013
15213
1 1 5
3815
42
8 6
12518
6011
84.12 6 7
1 4 4 . 2 1 70120
100.16 94
100.16 8 7
100.16 7 5
106.55 1 0 9
106.55 1 0 9
126.20 147
141.00 1 2 8
132.16 1 9 6
70.09 2 8
212.38 1 1 8
72.11 3 3
156.27 1 7 7
100.12 1 3 9
276.76 210
268.47 17315
116.16 1 8 9
8 8 . 1 1 1 4 3
114.19 1 1 2
100.16 8 2
156.27 1 7 5
86.13 8 3
190.24 242
1 0 2 . 1 3 1 0 8
58.08 5
296.54 17815
266.04 36
1 2 0 . 1 5 1 5 4
1 4 8 . 2 1 2 1 1
86.13 6 5
128121
15413
210
1 6 6 - 36
32
36
- 8 1
15
48
- 92
- 7 0
- 109
- 101
- 12
- 1 1 6
- 85
1 6
- 3 3
- 1 1 2
- 140
- 83
- 123
2 7
- 5 0
36
6 5
- 16
8 5
Vi nyl Funct i onal III 139
Density Refractive Flash RTECS
(at 20C) index (at 20C) point (C) Number R and S FT-NMR FT-IR Merck Beilstein Fieser
2(3),1290
2(4),1045 0.882
0.8689
0.904
1(1),719B
0.8719
1.4360 8 3
1.4291
>llO
>llO
1.4256
0.866 1.4050 1 0
0.9173 1.4030 6 UF857.5000 2(3),532
0.87
1.203 1.3170
1.212 1.3410
- 31
2
>llO
l( 1),745G 1(1),1030c 1(3),704B
1(1),697F 1(1),933B
0.8
0.866
0.774
<20
4 6
- 9
KH7175000
KN5950000 1(1),219C 1(1),332B 1(1),213D
0.762
1.048
1.048
0.891
1.197
0.986
0.773
0.817
0.754
0.816
1.006
1.654
1.4109
1.4220
1.410
1.4558
I .3980
1.4380
1.4380
1.4540
1.4558/17
1.4480
1.3989
1.4382
1.3770
1.4280
1.4326
- 17
1 6
1 6
3 5
KN6300000 1(1),221C 1(1),336A 1(1),213B 11,2139
KN6300000 1(1),221C 1(1),336A 1(1),213B 11,2139
8 3
- 3 0
>llO
- 4 5
5 2
3 5
KM5495500
KOO710000
KOO175000
1(1),219B 1(1),332A 1(1),212B
0.939 1.4440
0.982 1.4360
0.7826 1.4072
0.7645 1.3950
8 5
4 8 KM5495000
- 13 KO1300000 1(1),219D 1(3),278A 1(3),1862
0.7534
0.990
0.8967
0.7511/0
0.821
1. 53
1.3840
1.4390
1.4072
1.3730/0
1.440
- 3 2
1 7
- 5 6
1 7 7
KO2300000
RG0300000
1(1),219A 1(3),277C
1.5226
1.3908 - 26 1(3),1859
1.029 1 0 1
1.014 1.4940 1 0 2
FE6350000 1(2),2425E 1(3),161C
1.040 1.5120 9 4 UY6107000 1(1),923K 1(1),1288A 1(1),790B
0.9600 1.4835 6 0 AC6475000 1(1),891K 1(1),1242C 1(1),759C
2(4),466
19(3),1598
1(4),2387
1(3),1863
1(2),473
1(2),473
6(3,18
1(4),2398
1(4),2398
1,433 11,235
1(3),1864
17(5),8,12
1(4),25 18
1(2),520
1(3),1857 1,697
1(4),2057
2(3),3207
20(2),282
21( 1),363
4(3),442
III / 40 PHYSICAL PROPERTIES OF MONOMERS
TABLE 21. contd
CAS Registry Boiling Melting
Name Formula Number Mol. wt. point (C) point (C)
21. 5. SULFONATES H2C=CHS03R
Ethylene sulfonic acid 108.10 100/0.5
n-Amy1 ester $H~)KH, 178.23 131/17
n-Butyl ester
-(CHzWH3
164.21 117/15
Ethyl ester -CH2CH3 136.16 7615
n-Hexyl ester
-(CHz)5CH3
192.26 146115
Isoamyl ester -(CW2CWCHs)2 178.23 124115
Isobutyl ester -CH#ZH(CH& 164.21 7815
Isopropyl ester -WChh 152.20 7014
Methyl ester -CH, 122.13 91115
Phenyl ester -CsH5 1562-34-1 184.21 4512
n-Propyl ester -CH2CH2CH3 152.20 110/18
Vi nyl Funct i onal III 141
Density
(at 20C)
Refractive
index (at 20C)
Flash
point (C)
RTECS
Number R and S FT-NMR FT-IR Merck Beilstein Fieser
1.4003 1.4493
1.087 1.4412
1.122 1.4416
1.183 1. 431
1.050 1.4430
1.082 1.4415
1.190 1.426
1.132 1.4321
1.248 1.4316
1.165 1.426 >llO 1(2),2219A 1(2),1605A 1(3),1437A 6(3),65 1 13,241
1.156 1.4368
Isorefractive and Isopycnic Solvent Pairs
Hans-G. El ias
Michigan Molecular Institute, 1910 West St. Andrews Rd., Midland, MI 48640, USA
A. INTRODUCTION
Isorefractive solvents are solvents having the same
refractive index, and isopycnic solvents are those that have
the same density.
The determination of molar masses by non-colligative
methods such as light scattering and ultracentrifugation
will lead only to apparent molar masses if solvent mixtures
are used whose components are not isorefractive. The
observed increases or decreases of these apparent molar
masses depend in sign and magnitude on both the
preferential solvation and the refractive index increment
of solvent 2 in solvent 1 at a fixed polymer concentration.
The effect disappears if isorefractive solvent pairs are
used.
A similar effect may be observed in ultracentrifugal
experiments with non-isopycnic solvent pairs. To suppress
these effects, isopycnic-isorefractive solvent pairs should be
used. A table of isorefractive and isopycnic solvent pairs
was prepared (for 25C), starting with 392 commonly used
solvents. A solvent pair was classified as isorefractive and
isopycnic if the components had differences no greater than
50.002 in refractive index and &O.O15g/ml in density.
The miscibility of the components was not checked.
B. TABLE OF ISOREFRACTIVE AND ISOPYCNIC SOLVENT PAIRS
Refractive index Density (g/ml)
Solvent 1 Solvent 2 1 2 1 2
Acetone
Ethyl formate
Ethanol
2,ZDimethylbutane
2-Methylpentane
2, 3-Dimethylbutane
n-Hexane
Isopropyl acetate
2-Butanone
Butyraldehyde
n-Propyl ether
2,4-Dimethylpentane
Acetaldehyde diethyl acetal
n-Propyl acetate
Butyronitrile
Ethyl propionate
2-Methylhexane
Ett. 101 1.357 1.359 0.788 0.786
Methyl acetate 1.358 1.360 0.916 0.935
Propi oni t ri l e 1.359 1.363 0.786 0.777
2-Methylpentane 1.366 1.369 0.644 0.649
n-Hexane 1.369 1.372 0.649 0.655
2,3-Dimethylbutane 1.369 1.372 0.649 0.657
3-Methylpentane 1.369 1.374 0.649 0.660
n-Hexane 1.372 1.372 0.657 0.655
3-Methylpentane 1.372 1.374 0.657 0.660
3-Methylpentane 1.372 1.374 0.655 0.660
2-Chloropropane 1.375 1.376 0.868 0.865
Butyraldehyde 1.377 1.378 0.801 0.799
But yroni t ri l e 1.378 1.382 0.799 0.786
n-Butyl ethyl ether 1.379 1.380 0.753 0.746
2-Methylhexane 1.379 1.382 0.799 0.786
n-Butyl ethyl ether 1.379 1.380 0.753 0.746
Et hyl propi onat e 1.382 1.382 0.883 0.888
Isobutyl formate 1.382 1.383 0.883 0.881
1-Chloropropane 1.382 1.386 0.883 0.890
tSutano1 1.382 1.385 0.786 0.781
Isobutyl formate 1.382 1.383 0.888 0.881
1-Chloropropane 1.382 1.386 0.888 0.890
n-Heptane 1.382 1.385 0.674 0.680
3-Methylhexane 1.382 1.386 0.674 0.683
III 143
III/44 ISOREFRACTIVE AND ISOPYCNIC SOLVENT PAIRS
Refractive index Density (g/ml)
Solvent 1 Solvent 2 1 2 1 2
n-Propanol
Isobutyl formate
Diethylamine
n-Heptane
3-Methylhexane
1-Chloropropane
3-Methyl-Zbutanone
n-Propylamine
2,3,3-Trimethylbutane
sButy1 acetate
n-Butyl formate
Isobutyl acetate
2,2,4-Trimethylpentane
Diisopropylamine
2-Pentanone
3-Pentanone
Methyl butyrate
2-Chloro-2-methyl-propane
n-Butyl acetate
4-Methyl-2-pentanone
2-Methyl-1-propanol
Octane
2-Butanol
2-Hexanone
3-Methyl-2-butanone 1.383 1.386 0.806 0.807
2-Pentanone 1.383 1.387 0.806 0.804
1-Chloropropane 1.383 1.386 0.881 0.890
s-Butyl acetate 1.383 1.387 0.881 0.868
n-Butylformate 1.383 1.387 0.881 0.888
n-Propylamine 1.384 1.386 0.702 0.713
3-Methylhexane 1.385 1.386 0.680 0.683
2,3,3-Trimethylbutane 1.385 1.387 0.680 0.686
2,2,4-Trimethylpentane 1.385 1.389 0.680 0.687
2, 3-Dimethylpentane 1.385 1.389 0.680 0.691
2,3,3-Trimethylbutane 1.386 1.387 0.683 0.686
2, 4-Trimethylpentane 1.386 1.389 0.683 0.687
2,3-Dimethylpentane 1.386 1.389 0.683 0.691
Butyl formate 1.386 1.387 0.890 0.888
2-Pentanone 1.386 1.390 0.807 0.802
3-Pentanone 1.386 1.390 0.807 0.810
Diisopropylamine 1.386 1.390 0.713 0.712
s-Butylamine 1.386 1.390 0.713 0.720
2,2,4-Trimethylpentane 1.387 1.389 0.686 0.683
2,3-Dimethylpentane 1.387 1.389 0.686 0.691
Methyl butyrate 1.387 1.391 0.868 0.875
n-Dodecane 1.387 1.391 0.888 0.775
Methyl butyrate 1.388 1.391 0.871 0.875
n-Butyl acetate 1.388 1.392 0.871 0.877
2, 3-Dimethylpentane 1.389 1.389 0.687 0.691
s-Butylamine 1.390 1.390 0.712 0.720
3-Pentanone 1.390 1.390 0.802 0.810
4-Methyl-2-pentanone 1.390 1.394 0.802 0.797
2-Methyl- 1 -propanol 1.390 1.394 0.802 0.798
4-Methyl-Zpentanone 1.390 1.394 0.810 0.797
%-Methyl- 1 -propanol 1.390 1.394 0.810 0.798
n-Butyl acetate 1.391 1.392 0.875 0.877
2-Chlorobutane 1.391 1.395 0.875 0.868
2-Chlorobutane 1.392 1.395 0.872 0.868
2-Chlorobutane 1.392 1.395 0.877 0.868
2-Methyl-1-propanol 1.394 1.394 0.797 0.798
Valeronitrile 1.394 1.395 0.797 0.795
2-Butanol 1.394 1.395 0.797 0.803
2-Hexanone 1.394 1.395 0.797 0.810
1 -Butanol 1.394 1.397 0.797 0.812
Methacrylonitrile 1.394 1.398 0.797 0.795
3-Methyl-2-pentanone 1.394 1.398 0.797 0.808
Valeronitrile 1.394 1.395 0.798 0.795
2-Butanol 1.394 1.395 0.798 0.803
2-Hexanone 1.394 1.395 0.798 0.810
But anol 1.394 1.397 0.798 0.812
Methacrylonitrile 1.394 1.398 0.798 0.795
3-Methyl-2-pentanone 1.394 1.398 0.798 0.808
2,2,5Trimethylhexane 1.395 1.397 0.698 0.703
But anol 1.395 1.397 0.803 0.812
Methacrylonitrile 1.395 1.398 0.803 0.795
3-MethyL2pentanone 1.395 1.398 0.803 0.808
2,4-Dimethyl-3-pentanone 1.395 1.399 0.803 0.805
But anol 1.395 1.397 0.810 0.812
lsorefractive and lsopycnic Solvent Pairs III / 45
Refractive index Density (g/ml)
Solvent 1 Solvent 2 1 2 1 2
Valeronitrile
2-Hexanone
Isobutylamine
2-Chlorobutane
Butyric acid
n-Butanol
1-Chloro-2-methyl-propane
2,5,5-Trimethylhexane
Methyl methacrylate
Methacrylonitrile
3-Methyl-Zpentanone
Triethylamine
n-Butylamine
Isobutyl n-butyrate
1-Nitropropane
Amy1 acetate
n-Dodecane
1-Chlorobutane
2,2,3-Trimethylpentane
Isovaleric acid
Dipropylamine
n-Nonane
Isoamylacetate
2-Pentanol
2-Methoxybutanol
3-Methyl- 1 -butanol
Methacrylonitrile 1.395
3-Methyl-Zpentanone 1.395
2,4-Dimethyl-3-pentanone 1.395
Methacrylonitrile 1.395
3-Methyl-Zpentanone 1.395
2,4-Dimethyl-3-pentanone 1.395
3-Methyl-Zpentanone 1.395
Triethylamine 1.395
n-Butylamine 1.395
Isobutyl n-butyrate 1.395
2-Methoxyethanol 1.396
3-Methyl-2-pentanone 1.397
2,4-Dimethyl-3-pentanone 1.397
Isobutyl n-Butyrate 1.397
Amy1 acetate 1.397
1-Chlorobutane 1.397
2,2,3-Trimethylpentane 1.397
3-Methyl-Zpentanone 1.398
2,4-Dimethyl-3-pentanone 1.398
2-Methyl-2-butanol 1.398
2,4-Dimethyl-4-pentanone 1.398
n-Butylamine 1.399
2,2,3-Trimethylpentane 1.399
n-Nonane 1.399
Dipropylamine 1.399
n-Dodecane 1.399
n-Amy1 acetate 1.399
Isoamyl acetate 1.399
1-Chlorobutane 1.399
Propionic anhydride 1.399
1 -Chlorobutane 1.400
Tetrahydrofuran 1.400
Dipropylamine 1.400
Cyclopentane 1.400
Tetrahydrofuran 1.400
n-Nonane 1.401
2-Ethoxyethanol 1.402
Valerie acid 1.402
Cyclopentane 1.403
Methylcyclopentane 1.403
2,2,4-Trimethyl-l-pentene 1.403
Tributyl borate 1.403
2-Methyl- 1 -butanol 1.404
3-Methyl- 1 -butanol 1.404
4-Heptanone 1.404
2-Heptanone 1.404
3-Methyl-1-butanol 1.404
Caproni t ri l e 1.404
4-Heptanone 1.404
2-Heptanone 1.404
Pentanol 1.404
3-Methyl-2-butanol 1.404
Caproni t ri l e 1.404
4-Heptanone 1.404
1.398
1.398
1.399
1.398
1.398
1.399
1.398
1.399
1.399
1.399
1.400
1.398
1.399
1.399
1.400
1.400
1.401
1.398
1.399
1.404
1.399
1.399
1.401
1.401
1.401
1.400
1.400
1.403
1.401
1.400
1.400
1.404
1.403
1.404
1.404
1.403
1.405
1.406
1.404
1.407
1.407
1.407
1.404
1.404
1.405
1.406
1.404
1.405
1.405
1.406
1.408
1.408
1.405
1.405
0.810 0.795
0.810 0.808
0.810 0.805
0.795 0.795
0.795 0.808
0.795 0.805
0.810 0.808
0.729 0.723
0.729 0.736
0.868 0.860
0.955 0.960
0.812 0.808
0.812 0.805
0.872 0.860
0.872 0.871
0.872 0.881
0.703 0.712
0.795 0.808
0.795 0.805
0.795 0.805
0.808 0.805
0.723 0.736
0.723 0.712
0.723 0.714
0.723 0.736
0.736 0.746
0.860 0.871
0.860 0.868
8.860 0.875
0.995 1.007
0.871 0.881
0.871 0.885
0.746 0.736
0.746 0.740
0.871 0.885
0.712 0.714
0.923 0.926
0.923 0.936
0.736 0.740
0.736 0.744
0.714 0.712
0.868 0.854
0.804 0.805
0.804 0.805
0.804 0.813
0.804 0.811
0.805 0.805
0.805 0.801
0.805 0.813
0.805 0.811
0.805 0.810
0.805 0.815
0.805 0.801
0.805 0.813
III/46 ISOREFRACTIVE AND ISOPYCNIC SOLVENT PAIRS
Refractive index Density (g/ml)
Solvent 1 Solvent 2 1 2 1 2
Cyclopentane
Caproni t ri l e
4-Heptanone
2-Ethoxyethanol
2-Heptanone
2-Pentanol
2,2,4-Trimethyl- 1 -pentene
Tributyl borate
1 -Pentanol
3-Methyl-2-butanol
4-Methyl-Zpentanol
3-Isopropyl-2-pentanone
2-Methyl- 1-butanol
Isoamyl isovalerate
Amy1 ether
2,4-Dimethyldioxane
2-Heptanone 1.404 1.406 0.805 0.811
Pentanol 1.404 1.408 0.805 0.810
3-Methyl-2-butanol 1.404 1.408 0.805 0.815
Methylcyclopentane 1.404 1.407 0.740 0.744
4-Heptanone 1.405 1.405 0.801 0.813
2-Heptanone 1.405 1.406 0.801 0.811
2-Pentanol 1.405 1.407 0.801 0.804
1 -Pentanol 1.405 1.408 0.801 0.810
3-Methyl-Zbutanol 1.405 1.408 0.801 0.815
4-Methyl-2-pentanol 1.405 1.409 0.801 0.802
3-Isopropyl-2-pentanone 1.405 1.409 0.801 0.808
2-Methyl- 1-butanol 1.405 1.409 0.801 0.815
2-Heptanone 1.405 1.406 0.813 0.811
1 -Pentanol 1.405 1.408 0.813 0.810
3-Methyl-Zbutanol 1.405 1.408 0.813 0.815
4-Methyl-2-pentanol 1.405 1.409 0.813 0.802
3-Isopropyl-2-pentanone 1.405 1.409 0.813 0.808
2-Methyl- 1-butanol 1.405 1.409 0.813 0.815
Valeric acid 1.405 1.406 0.926 0.936
1-Pentanol 1.406 1.408 0.811 0.810
3-Methyl-Zbutanol 1.406 1.408 0.811 0.802
4-Methyl-Zpentanol 1.406 1.409 0.811 0.802
3-Isopropyl-2-pentanone 1.406 1.409 0.811 0.808
2-Ethoxyethanol 1.406 1.409 0.811 0.815
2-Methyl- 1-butanol 1.406 1.409 0.811 0.815
Amy1 ether 1.406 1.410 0.811 0.799
1 -Pentanol 1.407 1.408 0.804 0.810
3-Methyl-Zbutanol 1.407 1.408 0.804 0.815
4-Methyl-2-pentanol 1.407 1.409 0.804 0.802
3-Isopropyl-2-pentanone 1.407 1.409 0.804 0.808
%-Methyl- 1-butanol 1.407 1.409 0.804 0.815
Amy1 ether 1.407 1.410 0.804 0.799
n-Decane 1.407 1.409 0.712 0.726
Isoamyl isovalerate 1.407 1.410 0.854 0.853
Ally1 alcohol 1.407 1.411 0.854 0.847
3-Methyl-Zbutanol 1.408 1.408 0.810 0.815
4-Methyl-2-pentanol 1.408 1.409 0.810 0.802
3-Isopropyl-2-pentanone 1.408 1.409 0.810 0.808
2-Methyl- 1 -butanol 1.408 1.409 0.810 0.815
Amy1 ether 1.408 1.410 0.810 0.799
4-Methyl-2-pentanol 1.408 1.409 0.815 0.802
3-Isopropyl-2-pentanone 1.408 1.409 0.815 0.808
2-Methyl-1-butanol 1.408 1.409 0.815 0.815
Amy1 ether 1.408 1.410 0.815 0.799
3-Isopropyl-2-pentanone 1.409 1.409 0.802 0.808
2-Methyl- 1-butanol 1.409 1.409 0.802 0.815
Amy1 ether 1.409 1.410 0.802 0.799
2-Methyl- 1-butanol 1.409 1.409 0.808 0.815
Amy1 ether 1.409 1.410 0.808 0.799
Amy1 ether 1.409 1.410 0.815 0.799
Ally1 alcohol 1.410 1.411 0.853 0.847
2-Octanone 1.410 1.414 0.799 0.814
Ally1 chloride 1.412 1.413 0.935 0.932
Caproic acid 1.412 1.415 0.935 0.923
lsorefractive and lsopycnic Solvent Pairs III / 47
Refractive index Density (g/ml)
Solvent 1 Solvent 2 1 2 1 2
Diethyl malonate
Ally1 chloride
2-Octanone
3-Octanone
3-Methyl-Zheptanone
1 -Hexanol
2-Pentanol
Dibutylamine
Capryl oni t ri l e
2-Heptanol
Allylamine
3-Methyl-2-pentanol
2-Ethyl- 1-butanol
Methylcyclohexane
1-Heptanol
3-Isopropyl-2-heptanone
3-Chloro-Zmethyl-1-propene
Captylic acid
1 -0ctanol
1-Chlorooctane
2-Methyl-7-ethylnonane
Butyrolactone
4-n-PropylJ-ethyldioxane
2-Methyl-7-ethyl-4-undecanone
6-Ethyl-3-octanol
Chloro-t-butanol
N-Methylmorpholine
Ethyl cyanoacetate 1.412 1.415 1.051 1.056
Capric acid 1.413 1.415 0.932 0.923
3-Methyl-Zheptanone 1.414 1.415 0.814 0.818
1 -Hexanol 1.414 1.416 0.814 0.814
2-Pentanol 1.414 1.416 0.814 0.826
Caprylnitrile. 1.414 1.418 0.814 0.810 -
2-Heptanol 1.414 1.418 0.814 0.818
3-Methyl-2-heptanone 1.414 1.415 0.830 0.818
2-Pentanol 1.414 1.416 0.830 0.826
1 -Hexanol 1.415 1.416 0.818 0.814
2-Pentanol 1.415 1.416 0.818 0.826
Capryl oni t ri l e 1.415 1.418 0.818 0.810
2-Heptanol 1.415 1.418 0.818 0.818
2-Pentanol 1.416 1.416 0.814 0.826
Capryl oni t ri l e 1.416 1.418 0.814 0.810
2-Heptanol 1.416 1.418 0.814 0.818
3-Methyl-Zpentanol 1.416 1.420 0.814 0.823
2-Ethyl-l -butanol 1.416 1.420 0.814 0.829
2-Heptanol 1.416 1.418 0.826 0.818
3-Methyl-2-pentanol 1.416 1.418 0.816 0.818
2-Ethyl- 1-butanol 1.416 1.420 0.826 0.829
Allylamine 1.416 1.419 0.756 0.758
2-Heptanol 1.418 1.418 0.810 0.818
3-Methyl-2-pentanol 1.418 1.420 0.810 0.823
1-Heptanol 1.418 1.422 0.810 0.818
2-Methyl-2-pentanol 1.418 1.420 0.818 0.823
2-Ethyl- 1-butanol 1.418 1.420 0.818 0.829
1-Heptanol 1.418 1.422 0.818 0.818
3-Isopropyl-2-heptanone 1.418 1.423 0.818 0.815
Methylcyclohexane 1.419 1.421 0.758 0.765
2-Ethyl-1-butanol 1.420 1.420 0.823 0.829
1-Heptanol 1.420 1.422 0.823 0.818
3-Isopropyl-2-heptanone 1.420 1.423 0.815 0.815
1-Heptanol 1.420 1.420 0.829 0.818
3-Isopropyl-2-heptanone 1.420 1.423 0.829 0.815
Cyclohexane 1.421 1.424 0.765 0.774
3-Isopropyl-2-heptanone 1.422 1.423 0.818 0.815
1 -0ctanol 1.423 1.427 0.815 0.821
3-Methyl-2-pentanone 1.423 1.427 0.815 0.824
Caprylic acid 1.425 1.426 0.917 0.905
N-Methylalaninenitrile 1.426 1.429 0.905 0.895
3-Methyl-2-pentanol 1.427 1.427 0.821 0.824
1-Chloro-2-ethylhexane 1.428 1.430 0.867 0.872
2-Methyl-7-ethyl-4-undecanone 1.433 1.435 0.830 0.832
Chloro-t-butanol 1.434 1.436 1.051 1.059
1,3Propanediol 1.434 1.438 1.051 1.049
Diethyl maleate 1.434 1.438 1.051 1.064
N-methylmorpholine 1.435 1.436 0.927 0.924
2-Methyl-7-ethyl-4-nonanol 1.435 1.438 0.832 0.829
6-Ethyl-2-nonanol 1.435 1.438 0.832 0.836
5-Ethyl-2-nonanol 1.435 1.438 0.832 0.830
1,3Propanediol 1.436 1.438 1.059 1.049
Diethyl maleate 1.436 1.438 1.059 1.064
Dibutyl sebacate 1.436 1.440 0.924 0.932
III / 48 ISOREFRACTIVE AND ISOPYCNIC SOLVENT PAIRS
Refractive index Density (g/ml)
Solvent 1 Solvent 2 1 2 1 2
2-Methyl-7-ethyl-4-nonanol
5-Ethyl-2-nonanol
1,3-Propanediol
Methyl salicylate
6-Ethyl-3-octanol
Butanethiol
6-Ethyl-3-decanol
1-Chlorododecane (technical)
2-Methyl-7-ethyl-4-undecanol
Mesityl oxide
Butyl stearate
Ethyl sulfide
1,3-Butanediol sulfite
1,2-Dichloroethane
1 -Chlorotetradecane
Diethylene glycol
2-Butyloctyl-3aminopropyl ether
Formamide
2-Methylmorpholine
Dipropylene glycol monoethyl ether
1-Amino-2-methyl-2-pentanol
3-MethylJ-ethyl-2,4-heptanediol
2Propylcyclohexanone
5-Ethyl-2-nonanol 1.438 1.438 0.829 0.830
6-Ethyl-3-octanol 1.438 1.438 0.829 0.836
Butanethiol 1.438 1.440 0.829 0.837
7-Methyl-7-ethyl-4-undecanol 1.438 1.442 0.829 0.829
Ethyl sulfide 1.438 1.442 0.829 0.831
6-Ethyl-3-decanol 1.438 1.441 0.829 0.838
6-Ethyl-3-octanol 1.438 1.438 0.830 0.836
Butanethiol 1.438 1.440 0.830 0.837
2-Methyl-7-ethyl-4-undecanol 1.438 1.442 0.830 0.829
Ethyl sulfide 1.438 1.442 0.830 0.831
6-Ethyl-3-decanol 1.438 1.441 0.830 0.838
Diethyl maleate 1.438 1.438 1.049 1.064
2-Methyl-7-ethyl- 1 -undecanol 1.438 1.442 0.836 0.829
Ethyl sulfide 1.438 1.442 0.836 0.831
Butanethiol 1.438 1.442 0.836 0.837
6-Ethyl-3-decanol 1.438 1.441 0.836 0.838
6-Ethyl-3-decanol 1.440 1.441 0.837 0.838
2-Methyl-7-ethyl-4-undecanol 1.440 1.442 0.837 0.829
Ethyl sulfide 1.440 1.442 0.837 0.831
Mesityl oxide 1.440 1.442 0.837 0.850
2-Methyl-7-ethyl-4-undecanol 1.441 1.442 0.838 0.829
Ethyl sulfide 1.441 1.442 0.838 0.831
Mesityl oxide 1.441 1.442 0.838 0.850
Mesityl oxide 1.441 1.442 0.862 0.850
Butyl stearate 1.441 1.442 0.862 0.854
I-Chlorotetradecane 1.441 1.445 0.862 0.858
Ethyl sulfide 1.442 1.442 0.829 0.831
2-Butyloctyl-3aminopropyl ether 1.442 1.446 0.829 0.842
Butyl stearate 1.442 1.442 0.850 0.854
1-Chlorotetradecane 1.442 1.445 0.850 0.858
2-Butyloctyl-3aminopropyl ether 1.442 1.446 0.850 0.842
1 -Chlorotetradecane 1.442 1.445 0.850 0.858
2-Butyloctyl-3-aminopropyl ether 1.442 1.446 0.854 0.842
2-Butyloctyl-3aminopropyl ether 1.442 1.446 0.831 0.842
1 ,ZDichloroethane 1.444 1.444 1.231 1.245
tram- 1 ,ZDichloroethylene 1.444 1.444 1.231 1.257
tram- 1 ,ZDichloroethylene 1.444 1.444 1.231 1.257
2-Butyloctyl-3aminopropyl ether 1.445 1.446 0.857 0.842
1-Chlorohexadecane 1.445 1.448 0.857 0.859
Formamide 1.445 1.446 1.128 1.129
Ethylene glycol diglycidyl ether 1.445 1.447 1.128 1.134
3-Lauroxy- 1 - p r o p y l a mi n e 1.446 1.447 0.842 0.840
Ethylene glycol diglycidyl ether 1.446 1.447 1.129 1.134
Cyclohexanone 1.446 1.448 0.95 1 0.943
I-Amino-2-propanol 1.446 1.448 0.951 0.961
Tetrahydrofurfuryl alcohol 1.446 1.450 1.043 1.050
2-Butylcyclohexanone 1.449 1.453 1.050 1.047
2Propylcyclohexanone 1.452 1.452 0.922 0.923
4-Methylcyclohexanone 1.452 1.454 0.922 0.908
2,2-Dimethyl-2,2-dipropyldiethanolamine 1.452 1.456 0.922 0.922
4-Methylcyclohexanol 1.452 1.454 0.923 0.908
3-Methylcyclohexanol 1.452 1.455 0.923 0.913
2,2-Dimethyl-2,2-dipropyldiethanolamine 1.452 1.456 0.923 0.922
1 ,&Cineole 1.452 1.456 0.923 0.921
lsorefractive and lsopycnic Solvent Pairs III / 49
Refractive index Density (g/ml)
Solvent 1 Solvent 2 1 2 1 2
4-Methylcyclohexanol
3-Methylcyclohexanol
Cyclohexylamine
1-Chloroeicosane (technical)
Oleic acid
1,1,2,2-Tetramethyldiethanolamine
Carbon tetrachloride
2-( b-Ethyl)butylcyclohexanone
N-(n-Butyl)diethanolamine
2-Butylcyclohexanol
N-P-Oxypropylmorpholine
Fluorobenzene
o-a-Pinene
m-Fluorotoluene
1 -a-Pinene
p-Fluorotoluene
N-(2-Hydroxyethyl)-2-hydrobutylamine
2-Allyloxy-2-hydroxypropylamine
cis-Decahydronaphthalene
1-Methoxy-1-butene-3-yn
n-Dodecyl-4-t-butylphenyl ether
Butylbenzene
p-Cymene
Isopropylbenzene
2,2-Dimethyl-2,2-dipropyldiethanolamine
2,2-Dimethyl-2,2-dipropyldiethanolamine
1 -Chloroeicosane
Oleic acid
2-(P-Ethyl)butylcyclohexanone
2-Butylcyclohexanol
2-( b-Ethyl)hexylcyclohexanone
1 -Aminopropanol
N-(n-Butyl)diethanolamine
4,5-Dichloro-1,3-dioxolane-2-one
2,4-(bis)a-Phenylethyl)phenylmethyl ether
2-(P-Ethyl)hexylcyclohexanone
Cyclohexanol
2-(P-Ethyl)hexylcyclohexanone
2-Ethylcyclohexanol
Fluorobenzene
N-(2-Hydroxyethyl)-2-hydroxybutyl amine
1 -a-Pinene
truns-Decahydronaphthalene
p-Fluorotoluene
trans-Decahydronaphthalene
o-Fluorotoluene
N-(2-Hydroxyethyl)-2-hydropropylamine
2-Allyloxy-2-hydroxypropylamine
Di(2-Hydroxybutyl)ethanolamine
Di(2-Hydroxypropyl)ethanolamine
Di(2-Hydroxybutyl)ethanolamine
1-Methoxy-1-butene-3-yn
n-Dodecyl-4-t-butylphenyl ether
n-Dodecylphenyl ether
n-Dodecyl-4-methylphenyl ether
n-Dodecylphenyl ether
n-Dodecyl-4-methylphenyl ether
n-Dodecylphenyl ether
Dioctylbenzene (90% p ; 10% m)
p-Cymene
Isopropylbenzene
t-Butylbenzene (80% p, 15% m, 5% o)
n-Propylbenzene
s-Butylbenzene
Hexyl-m-xylene
t-Butylbenzene
1.454
1.455
1.456
1.459
1.459
1.459
1.459
1.459
1.459
1.459
1.461
1.461
1.461
1.462
1.462
1.462
1.463
1.464
1.464
1.465
1.465
1.467
1.467
1.467
1.467
1.467
1.469
1.479
1.479
1.479
1.479
1.480
1.480
1.482
1.487
1.487
1.487
1.487
1.487
1.487
1.487
1.487
Isopropylethylbenzene (35% p, 60% m, 5% o) 1.487
Isopropylbenzene 1.488
t-Butylcumene (80% p, 15% m, 5% o) 1.488
n-Propylbenzene 1.488
s-Butylbenzene 1.488
Hexyl-m-xylene (mainly 1,3,5) 1.488
t-Butylbenzene 1.488
Isopropylethylbenzene (35% p, 60% m, 5% o) 1.488
t-Butyltoluene 1.488
Hexylcumene (90% p, 5% m, 5% o) 1.488
Octyltoluene (96% p, 2% m, 2% o) 1.488
t-Butylcumene (80% p, 15% m, 5% o) 1.489
1.456 0.908 0.922
1.456 0.913 0.922
1.459 0.862 0.872
1.459 0.872 0.887 _
1.461 0.887 0.892
1.462 0.887 0.898
1.463 0.887 0.892
1.459 0.973 0.965
1.461 0.973 0.965
1.461 1.584 1.591
1.462 0.892 0.898
1.463 0.892 0.892
1.465 0.965 0.968
1.463 0.898 0.892
1.463 0.898 0.908
1.463 1.013 1.020
1.467 1.020 1.027
1.465 0.855 0.855
1.468 0.855 0.867
1.467 0.994 0.995
1.468 0.855 0.867
1.468 0.994 0.995
1.468 1.027 1.042
1.469 1.027 1.017
1.469 1.027 1.018
1.469 1.027 1.042
1.469 1.017 1.018
1.480 0.893 0.902
1.482 0.893 0.881
1.482 0.893 0.891
1.483 0.893 0.889
1.482 0.902 0.891
1.483 0.902 0.889
1.482 0.881 0.891
1.487 0.856 0.856
1.488 0.856 0.853
1.489 0.856 0.857
1.490 0.856 0.856
1.490 0.856 0.856
1.490 0.856 0.856
1.490 0.856 0.860
1.490 0.856 0.862
1.491 0.856 0.856
1.489 0.853 0.857
1.490 0.853 0.856
1.490 0.853 0.858
1.490 0.853 0.858
1.490 0.853 0.860
1.490 0.853 0.862
1.491 0.853 0.856
1.491 0.853 0.858
1.492 0.853 0.863
1.492 0.853 0.866
1.490 0.857 0.856
III / 50 SOREFRACTIVE AND ISOPYCNIC SOLVENT PAIRS
Refractive index Density (g/ml)
Solvent 1 Solvent 2 1 2 1 2
n-Propylbenzene 1.489
s-Butylbenzene 1.489
Hexyl-m-xylene (mainly 1,3,5) 1.489
t-Butylbenzene 1.489
Isopropylethylbenzene
(35%p, 60% m, 5% o) 1.489
t-Butylbenzene (80% p, 15% m, 5% o) 1.489
tButylcumene (80% p, 15% m, 5% o) n-Propylbenzene 1.490
s-Butylbenzene 1.490
Hexyl-m-xylene (mainly 1,3,5) 1.490
tButylbenzene 1.490
Isopropylethylbenzene
(35%p,60% m,5% o) 1.490
t-Butyltoluene (80% p, 15% rn, 5% o) 1.490
Hexylcumene (90% p, 5% m, 5% o) 1.490
Octyltoluene (96% p, 2% m, 2% o) 1.490
Octylcumene (90% p, 4% m, 6% o) 1.490
Dihexylbenzene 1.490
p-Xylene 1.490
1,3-Diethylbenzene 1.490
t-Butyl-m-xylene (mainly 1,3,5) 1.490
Ethylbenzene 1.490
Octylethylbenzene (80-90% p, 10% m) 1.490
Isopropyl-m-xylene (mainly 1,3,5) 1.490
Toluene 1.490
nPropylbenzene s-Butylbenzene 1.490
Hexyl-m-xylene (mainly 1,3,5) 1.490
t-Butylbenzene 1.490
Isopropylethylbenzene (35% p, 60% m, 5% o) 1.490
t-Butyltoluene (80% p, 15% m, 5% p) 1.490
Hexylcumene (90% p, 5% m, 5% o) 1.490
Octyltoluene (96% p, 2% m 2% o) 1.490
Octylcumene (90% p, 4% m 6% o) 1.490
Dihexylbenzene 1.490
p-Xylene 1.490
1,3-Diethylbenzene 1.490
t-Butyl-m-xylene (mainly 1,3,5) 1.490
Ethylbenzene 1.490
Octylethylbenzene (80-90% p, 10% m) 1.490
Isopropyl-m-xylene (mainly 1,3,5) 1.490
Toluene 1.490
s-Butylbenzene Hexyl-m-xylene (mainly 1,3,5) 1.490
t-Butylbenzene 1.490
Isopropylethylbenzene (35% p, 60% m, 5% o) 1.490
t-Butyltoluene (80% p, 15% m, 5% o) 1.490
Hexylcumene (90% p, 5% m, 5% o) 1.490
Octyltoluene (96% p, 2% m, 2% o) 1.490
Octylcumene (90% p, 4% m, 6% o) 1.490
Dihexylbenzene 1.490
p-Xylene 1.490
1,3-Diethylbenzene 1.490
t-Butyl-m-xylene (mainly 1,3,5) 1.490
Ethylbenzene 1.490
Octylethylbenzene (80-90% p, 10% m) 1.490
1.490 0.857 0.858
1.490 0.857 0.858
1.490 0.857 0.860
1.490 0.857 0.862
1.491 0.857 0.856
1.491 0.857 0.858
1.490 0.856 0.858
1.490 0.856 0.858
1.490 0.856 0.860
1.490 0.856 0.862
1.491 0.856 0.856
1.491 0.856 0.858
1.492 0.856 0.863
1.492 0.856 0.866
1.492 0.856 0.869
1.492 0.856 0.870
1.493 0.856 0.857
1.493 0.856 0.860
1.493 0.856 0.862
1.493 0.856 0.863
1.493 0.856 0.866
1.494 0.856 0.860
1.494 0.856 0.862
1.490 0.858 0.858
1.490 0.858 0.860
1.490 0.858 0.862
1.491 0.858 0.856
1.491 0.858 0.858
1.492 0.858 0.863
1.492 0.858 0.866
1.492 0.858 0.869
1.492 0.858 0.870
1.493 0.858 0.857
1.493 0.858 0.860
1.493 0.858 0.862
1.493 0.858 0.863
1.493 0.858 0.866
1.494 0.858 0.860
1.494 0.858 0.862
1.490 0.858 0.860
1.490 0.858 0.862
1.491 0.858 0.856
1.491 0.858 0.858
1.492 0.858 0.863
1.492 0.858 0.866
1.492 0.858 0.869
1.492 0.858 0.870
1.493 0.858 0.857
1.493 0.858 0.860
1.493 0.858 0.862
1.493 0.858 0.863
1.493 0.858 0.866
lsorefractive and lsopycnic Solvent Pairs III / 51
Refractive index Density (g/ml)
Solvent 1 Solvent 2 1 2 1 2
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
Hexyl-m-xylene (mainly 1,3,5) t-Butylbenzene
Isopropylethylbenzene (35% p, 60% m, 5% o)
t-Butyltoluene (80% p, 15% m, 5% o)
Hexylcumene (90% p, 5% m, 5% o)
Octyltoluene (96% p, 2% m, 2% o)
Octylcumene (90% p, 4% m, 6% o)
Dihexylbenzene
p-Xylene
1,3-Diethylbenzene
t-Butyl-m-xylene (mainly 1,3,5)
Ethylbenzene
t-Butylbenzene
Octylethylbenzene (80-90% p, 10% m)
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
Isopropylethylbenzene (35% p, 60% m, 5% o)
t-Butyltoluene (80% p, 15% m, 5% o)
Hexylcumene (90% p, 5% m, 5% o)
Octyltoluene (96% p, 2% m, 2% o)
Octylcumene (90% p, 4% m, 6% o)
Dihexylbenzene
p-Xylene
1,3-Diethylbenzene
t-Butyl-m-xylene (mainly 1,3,5)
Ethylbenzene
Octylethylbenzene (80-90% p, 10% m)
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
Isopropylethylbenzene (35% p, 60% m) Hexylcumene (90% p, 5% m, 5% 0)
Octyltoluene (96% p, 2% m, 2% o)
Octylcumene (90% p, 4% m, 6% o)
Dihexylbenzene
p-Xylene
1,3-Diethylbenzene
t-Butyl-m-xylene (mainly 1,3,5)
Ethylbenzene
Octylethylbenzene (80-90% p, 10% m)
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
t-Butyltoluene (85% p, 10% m)
t-Butylethylbenzene (70% p, 25% m, 5% o)
m-Xylene
Hexylethylbenzene
Hexylcumene (90% p, 5% m, 5% o)
Octyltoluene (96% p, 2% m, 2% o)
Octylcumene (90% p, 4% m, 6% o)
Dihexylbenzene
p-Xylene
1,3-Diethylbenzene
tButyl-m-xylene (mainly 1,3,5)
Ethylbenzene
Octylethylbenzene (80-90% p, 10% m)
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.490
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.491
1.494
1.494
1.490
1 .491
.491
.492
.492
.492
.492
1.493
1.493
1.493
1.493
1.493
1.494
1.494
1.491
1.491
1.492
1.492
1.492
1.492
1.493
1.493
1.493
1.493
1.493
1.494
1.494
1.492
1.492
1.492
1.492
1.493
1.493
1.493
1.493
1.493
1.494
1.494
1.495
1.495
1.495
1.492
1.492
1.492
1.492
1.493
1.493
1.493
1.493
1.493
1.494
1.494
0.858 0.860
0.858 0 . 8 6 2
0.860 0.862
0.860 0.856
0.860 0.858
0.860 0.863
0.860 0.866
0.860 0.869
0.860 0.870
0.860 0.857
0.860 0.860
0.860 0.862
0.860 0.863
0.860 0.866
0.860 0.860
0.860 0.862
0.862 0.856
0.862 0.858
0.862 0.863
0.862 0.866
0.862 0.869
0.862 0.870
0.862 0.857
0.862 0.860
0.862 0.862
0.862 0.863
0.862 0.866
0.862 0.860
0.862 0.862
0.858 0.863
0.858 0.866
0.858 0.869
0.858 0.870
0.858 0.857
0.858 0.860
0.858 0.862
0.858 0.863
0.858 0.866
0.858 0.860
0.858 0.862
0.858 0.854
0.858 0.860
0.858 0.868
0.858 0.863
0.856 0.866
0.856 0.869
0.856 0.870
0.856 0.857
0.856 0.860
0.856 0.862
0.856 0.863
0.856 0.866
0.856 0.860
0.856 0.862
III / 52 ISOREFRACTIVE AND ISOPYCNIC SOLVENT PAIRS
Refractive index Density (g/ml)
Solvent 1 Solvent 2 1 2 1 2
t-Butylethylbenzene (70% p, 25% m, 5% o)
m-Xylene
1 -Phenyl- 1 -hydroxyphenyl ether
Hexylcumene (90% p, 5% m)
Hexylethylbenzene(70% p, 25% m, 5% o)
1,3-Dimotpholyl-2-propanol
Octyltoluene (96% p, 2% m, 2% o)
Octylcumene (90% p, 4% m, 6% o)
Dihexylbenzene
p-Xylene
1,3-Diethylbenzene
t-Butyl-m-xylene (mainly 1,3,5)
Ethylbenzene
Octylethylbenzene (80-90% p, 10% m)
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
t-Butylethylbenzene (70% p. 25% m, 5% o)
m-Xylene
Dihexylbenzene (85% p, 10% m)
Hexylethylbenzene (70% p, 25% m, 5% o)
1 ,CDiethylbenzene
Isopropylbenzene
Octylcumene (90% p, 4% m, 6% 0)
p-Xylene
1,3-Diethylbenzene
t-Butyl-m-xylene (mainly 1,3,5)
Ethylbenzene
Octylethylbenzene (80-90% p, 10% m)
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
m-Xylene
Octyltoluene (96% p, 2% m)
Hexylethylbenzene (70% p, 25% m, 5% o)
1,4-Diethylbenzene
Isopropylbenzene
Octylcumene (90% p, 4% m, 6% o)
Dihexylbenzene (85% p, 10% m, 5% o)
p-Xylene
t-Butyl-m-xylene (mainly 1,3,5)
Ethylbenzene
Octylethylbenzene (80-90% p, 10% m)
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
t-Butylethylbenzene (70% p, 25% m, 5% o)
m-Xyl ene
Octylcumene (90% p, 4% m, 6% o)
Hexylethylbenzene (70% p, 25% m, 5% o)
1 ,CDiethylbenzene
Isopropylbenzene
p-Xylene
1,3-Diethylbenzene
t-Butyl-m-xylene (mainly 1,3,5)
Ethylbenzene
Octylethylbenzene (80-90% p, 10% m)
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
t-Butylethylbenzene (70% p, 25% m, 5% o)
m-Xylene
Hexylethylbenzene (70% p, 25% m, 5% o)
1.491 1.495 0.856 0.854
1.491 1.495 0.856 0.860
1.491 1.495 0.856 0.868
1.491 1.493 1.081 1.094
1.492 1.492 0.863 0.866
1.492 1.492 0.863 0.869
1.492 1.492 0.863 0.870
1.492 1.493 0.863 0.857
1.492 1.493 0.863 0.860
1.492 1.493 0.863 0.862
1.492 1.493 0.863 0.863
1.492 1.493 0.863 0.866
1.492 1.494 0.863 0.860
1.492 1.494 0.863 0.862
1.492 1.495 0.863 0.854
1.492 1.495 0.863 0.860
1.492 1.495 0.863 0.868
1.492 1.496 0.863 0.858
1.492 1.498 0.863 0.857
1.492 1.492 0.870 0.869
1.492 1.493 0.870 0.857
1.492 1.493 0.870 0.860
1.492 1.493 0.870 0.862
1.492 1.493 0.870 0.863
1.492 1.493 0.870 0.866
1.492 1.494 0.870 0.860
1.492 1.494 0.870 0.862
1.492 1.495 0.870 0.860
1.492 1.495 0.870 0.868
1.492 1.496 0.870 0.858
1.492 1.498 0.870 0.857
1.492 1.492 0.866 0.869
1.492 1.492 0.866 0.870
1.492 1.493 0.866 0.857
1.492 1.493 0.866 0.862
1.492 1.493 0.866 0.863
1.492 1.493 0.866 0.866
1.492 1.494 0.866 0.860
1.492 1.494 0.866 0.862
1.492 1.495 0.866 0.854
1.492 1.495 0.866 0.860
1.492 1.495 0.866 0.868
1.492 1.496 0.866 0.858
1.492 1.498 0.866 0.857
1.492 1.493 0.866 0.857
1.492 1.493 0.866 0.860
1.492 1.493 0.866 0.862
1.492 1.493 0.866 0.863
1.492 1.493 0.866 0.866
1.492 1.494 0.866 0.860
1.492 1.494 0.866 0.862
1.492 1.495 0.866 0.854
1.492 1.495 0.866 0.860
1.492 1.495 0.866 0.868
lsorefractive and lsopycnic Solvent Pairs III / 53
Refractive index Density (g/ml)
Solvent 1 Solvent 2 1 2 1 2
p-Xylene
1 ,CDiethylbenzene
Isopropylbenzene
1,3-Diethylbenzene
t-Butyl-m-xylene (mainly 1,3,5)
Ethylbenzene
Octylethylbenzene (80-90% p, 10% m)
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
t-Butylethylbenzene (70% p, 25% m, 5% o)
m-Xylene
Hexylethylbenzene (70% p, 25% m, 5% o)
1 ,CDiethylbenzene
Mesitylene
1,3-Diethylbenzene
Isopropylbenzene
t-Butyl-m-xylene (mainly 1,3,5)
Ethylbenzene
Octyltoluene (96% p, 2% m, 2% o)
Octylethylbenzene (80-90% p, 10% m)
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
t-Butylethylbenzene (70% p, 25% m, 5% o)
m-Xylene
1 ,CDiethylbenzene
Mesitylene
t-Butyl-m-xylene (mainly 1,3,5)
Hexyltoluene (70% p, 25% m, 5% o)
Isopropylbenzene
Etbylbenzene
Octylethylbenzene (80-90% p, 10% m)
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
t-Butylethylbenzene (70% p, 25% m, 5% o)
m-Xylene
Hexylethylbenzene (70% p, 25% m, 5% o)
1,4-Diethylbenzene
Mesitylene
Hexyltoluene (70% p, 25% m, 5% o)
Isopropylbenzene
Etbylbenzene Octylethylbenzene (80-90% p, 10% m)
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
t-Butyletbylbenzene (70% p, 25% m, 5% o)
m-Xylene
Hexyletbylbenzene (70% p, 25% m, 5% o)
1 ,CDiethylbenzene
Mesitylene
Hexyltoluene (70% p, 25% m, 5% o)
Isopropylbenzene
Octylethylbenzene (80-90% p, 10% m) Isopropyl-m-xylene (mainly 1,3,5)
Toluene
t-Butylethylbenzene (70% p, 25% m, 5% o)
m-Xylene
Hexylethylbenzene (70% p, 25% m, 5% o)
1,6Diethylbenzene
Mesitylene
1.492 1.496 0.866 0.858
1.492 1.498 0.866 0.857
1.493 1.493 0.857 0.860
1.493 1.493 0.857 0.862
1.493 1.493 0.857 0.863
1.493 1.493 0.857 0.866
1.493 1.494 0.857 0.860
1.493 1.494 0.857 0.862
1.493 1.495 0.857 0.854
1.493 1.495 0.857 0.860
1.493 1.495 0.857 0.868
1.493 1.496 0.857 0.858
1.493 1.497 0.857 0.861
1.493 1.498 0.857 0.857
1.493 1.493 0.860 0.862
1.493 1.493 0.860 0.863
1.493 1.493 0.860 0.866
1.493 1.493 0.860 0.866
1.493 1.494 0.860 0.860
1.493 1.494 0.860 0.862
1.493 1.495 0.860 0.854
1.493 1.495 0.860 0.860
1.493 1.496 0.860 0.858
1.493 1.497 0.860 0.861
1.493 1.497 0.860 0.870
1.493 1.498 0.860 0.860
1.493 1.493 0.862 0.863
1.493 1.493 0.862 0.866
1.493 1.494 0.862 0.860
1.493 1.494 0.862 0.862
1.493 1.495 0.862 0.854
1.493 1.495 0.862 0.860
1.493 1.495 0.862 0.868
1.493 1.496 0.862 0.858
1.493 1.497 0.862 0.861
1.493 1.497 0.862 0.870
1.493 1.498 0.862 0.857
1.493 1.493 0.863 0.866
1.493 1.494 0.863 0.860
1.493 1.494 0.863 0.862
1.493 1.495 0.863 0.854
1.493 1.495 0.863 0.860
1.493 1.495 0.863 0.868
1.493 1.496 0.863 0.858
1.493 1.497 0.863 0.861
1.493 1.497 0.863 0.870
1.493 1.498 0.863 0.857
1.493 1.494 0.866 0.860
1.493 1.494 0.866 0.862
1.493 I .495 0.866 0.854
1.493 1.495 0.866 0.860
1.493 1.495 0.866 0.868
1.493 1.496 0.866 0.858
1.493 1.497 0.866 0.861
III I54 ISOREFRACTIVE AND ISOPYCNIC SOLVENT PAIRS
Refractive index Density (g/ml)
Solvent 1 Solvent 2 1 2 1 2
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
t-Butylethylbenzene (70% p, 25% m)
m-Xylene
Hexylethylbenzene (70% p, 25% m)
1 ,CDiethylbenzene
Mesitylene
Hexyltoluene (70% p, 25% m)
Benzene
Mesitylene
1 ,2-Diethylbenzene
/3-Picoline
Phenet ol e
Cyclohexylcumene (50% p, 20% m)
Benzyl acetate
Hexyltoluene (70% p, 25% m, 5% o)
Isopropylbenzene
Toluene
t-Butylethylbenzene (70% p, 25% m, 5% o)
m-Xylene
Hexylethylbenzene (70% p, 25% m, 5% o)
1 ,CDiethylbenzene
Mesitylene
Hexyltoluene (70% p, 25% m, 5% o)
Benzene
t-Butylethylbenzene (70% p, 25% m, 5% o)
m-Xylene
Hexylethylbenzene (70% p, 25% m, 5% o)
1,4-Diethylbenzene
Mesitylene
Hexyltoluene (70% p, 25% m, 5% o)
Benzene
m-Xylene
1 ,CDiethylbenzene
Mesitylene
Hexylethylbenzene (70% p, 25% m, 5% o)
1 ,CDiethylbenzene
Mesitylene
Benzene
1,4-Diethylbenzene
Mesitylene
Hexyltoluene (70% p, 25% m, 5% o)
Benzene
Mesitylene
Hexyltoluene (70% p. 25% m, 5% o)
Ethylbenzene
Benzene
1 ,ZDiethylbenzene
Mesitylene
1,2-Diethylbenzene
1 ,ZDiethylbenzene
o-Xylene
Phenet ol e
Pyridine
Cyclohexylethylbenzene
(60% p, 20% m, 20% o)
Chloro-t-butylbenzene
Cyclohexylethylbenzene (60% p, 20% m) Cyclohexyltoluene
2-Furfurol Thiophene
Benzyl alcohol m-Cresol
m-Cresol Benzaldehyde
m-Toluidine o-Toluidine
1.493 1.497 0.866 0.870
1.493 1.498 0.866 0.857
1.494 1.494 0.860 0.862
1.494 1.495 0.860 0.854
1.494 1.495 0.860 0.860
1.494 1:495 0.860 0.868
1.494 1.496 0.860 0.858
1.494 1.497 0.860 0.861
1.494 1.497 0.860 0.870
1.494 1.498 0.860 0.874
1.494 1.495 0.862 0.854
1.494 1.495 0.862 0.860
1.494 1.495 0.862 0.868
1.494 1.496 0.862 0.858
1.494 1.497 0.862 0.861
1.494 1.497 0.862 0.870
1.494 1.498 0.862 0.874
1.495 1.495 0.854 0.860
1.495 1.496 0.854 0.858
1.495 1.497 0.854 0.861
1.495 1.495 0.860 0.868
1.495 1.496 0.860 0.858
1.495 1.497 0.860 0.861
1.495 1.498 0.860 0.874
1.495 1.496 0.868 0.858
1.495 1.497 0.868 0.861
1.495 1.497 0.868 0.870
1.495 1.498 0.868 0.874
1.496 1.497 0.858 0.861
1.496 1.498 0.858 0.870
1.497 1.497 0.861 0.870
1.497 1.498 0.870 0.874
1.497 1.501 0.870 0.876
1.498 1.498 0.874 0.874
1.498 1.501 0.874 0.876
1.498 1.501 0.874 0.876
1.501 1.503 0.867 0.876
1.504 1.505 0.953 0.961
1.505 1.507 0.961 0.978
1.516 1.520 0.917 0.923
1.518 1.521 1.051 1.039
1.520 1.523 0.923 0.923
1.524 1.526 1.057 1.059
1.538 1.542 1.041 1.037
1.542 1.544 1.037 1.041
1.566 1.570 0.985 0.994
Refractive Indices of Common Solvents
Hans-G. Elias
Michigan Molecular Institute, 1910 West St. Andrews Rd., Midland, MI 48640, USA
A. INTRODUCTION
Measurements which depend on the difference in refractive
index between the polymer and the solvent will, in general,
give greater accuracy as the refractive index increment
between polymer and solvent is increased. The magnitude
of the increment may be either positive or negative.
Systems involving refractive index increments are those
of light scattering and ultracentrifugation when either
schlieren or interference optics is used. A table of
commonly used solvents, arranged according to increasing
refractive index, will be useful in practical work with many
different polymers. Data at 25C D-line.
B. TABLE OF REFRACTIVE INDICES OF COMMON
SOLVENTS
Solvents Refractive index
Trifluoroacetic acid 1.283
Trifluoroethanol 1.290
Octafluoro- 1 -pentanol 1.316
Dodecafluoro- 1 -heptanol 1.316
Methanol 1.326
Acetonitrile 1.342
Ethyl ether 1.352
Acet one 1.357
Ethyl formate 1.358
Ethanol 1.359
Methyl acetate 1.360
Propionitrile 1.363
2,2-Dimethylbutane 1.366
Isopropyl ether 1.367
2-Methylpentane 1.369
Formic acid 1.369
Ethyl acetate 1.370
Acetic acid 1.370
Propionaldehyde 1.371
n-Hexane 1.372
2,3-Dimethylbutane 1.372
3-Methylpentane 1.374
2-Propanol 1.375
Isopropyl acetate 1.375
Propyl formate 1.375
Solvents
2-Chloropropane
2-Butanone
Butyraldehyde
2,4-Dimethylpentane
Propyl ether
Acetaldehyde diethyl acetal
Butyl ethyl ether
Nitromethane
Trifluoropropanol
2-Methylhexane
Butyronitrile
Propyl acetate
Ethyl propionate
2-Methyl-2-propanol
Propanol
Isobutyl formate
Diethyl carbonate
Heptane
t-Butanol
Propionic acid
3-Methylhexane
Propylamine
3-Methyl-Zbutanone
1-Chloropropane
2,2,3-Trimethylbutane
s-Butyl acetate
Butyl formate
Isobutyl acetate
2,2,4-Trimethylpentane
2,3-Dimethylpentane
Acetic anhydride
Diisopropylamine
2-Butylamine
2-Pentanone
3-Pentanone
Nitroethane
Methyl n-butyrate
Butyl acetate
2-Nitropropane
4-Methyl-2-propanone
2-Methyl- 1 -propanol
Oct ane
Refractive index
1.376
1.377
1.378
1.379
1.379
1.379
1.380
1.380
1.381
1.382
1.382
1.382
1.382
1.383
1.383
1.383
1.383
1.385
1.385
1.385
1.386
1.386
1.386
1.386
1.387
1.387
1.387
1.388
1.389
1.389
1.389
1.390
1.390
1.390
1.390
1.390
1.391
1.392
1.392
1.394
1.394
1.395
III / 55
III/ 56 REFRACTIVE INDICES OF COMMON SOLVENTS
Solvents Refractive index Solvents
Isobutylamine
Valeronitrile
2-Butanol
2-Hexanone
2-Chlorobutane
Butyric acid
2,2,5Trimethylhexane
Dibutyl ether
Butanol
Acrolein
1-Chloro-2-methylpropane
Methacrylonitrile
3-Methyl-2-pentanone
Triethylamine
Butylamine
2,4-Dimethyl-3-pentanone
Isobutyl n-butyrate
1 -Nitropropane
Dodecane
Amy1 acetate
1-Chlorobutane
2-Methoxyethanol
Propionic anhydride
2,2,3-Trimethylpentane
1-Chlorobutane
B-Methoxypropionitrile
Isovaleric acid
Nonane
Dipropylamine
Isoamyl acetate
Cycl opent ane
2-Methyl-2-butanol
3-Methyl-1-butanol
Tetrahydrofuran
Capronitrile
4-Heptanone
2-Ethoxyethanol
2-Heptanone
Valerie acid
Diisobutylene
Methylcyclopentane
Isoamyl ether
2-Pentanol
Tributyl borate
Pentanol
3-Methyl-2-butanol
Diethyl oxalate
Decane
4-Methyl-2-pentanol
3-Isopropyl-2-pentanone
2-Methyl- 1-butanol
Butyric anhydride
Amy1 ether
Isoamyl isovalerate
1-Chloropentane
Ally1 alcohol
1.395 2,4-Dimethyldioxane 1.412
1.395 Ethyl lactate 1.412
1.395 Diethyl malonate 1.412
1.395 3-Chloropropene 1.413
1.395 Ethylene glycol diacetate 1.413
1.396 2-Octanone 1.414
1.397 3-Octanone 1.414
1.397 3-Methyl-Zheptanone 1.415
1.397 Caproic acid 1.415
1.397 4-Methyldioxane 1.415
1.397 1,2Propylene glycol monobutyl ether 1.415
1.398 Ethyl cyanoacetate 1.415
1.398 Dibutylamine 1.416
1.399 Hexanol 1.416
1.399 2-Pentanol 1.416
1.399 1,l -Dichloroethane 1.416
1.399 Heptachlorodiethyl ether 1.416
1.399 3-Methoxypropylamine 1.417
1.400 Caprylonitrile 1.418
1.400 2-Heptanol 1.418
1.400 Allylamine 1.419
1.400 1 ,ZPropylene glycol carbonate 1.419
1.400 2-Heptanol 1.420
1.401 3-Methyl-Zpentanol 1.420
1.401 2-Ethyl- 1 -butanol 1.420
1.401 1-Chloro-2-methyl-1-propene 1.420
1.402 1,6Dioxane 1.420
1.403 Methylcyclopropane 1.421
1.403 4-Hydroxy-4-methyl-2-pentanone 1.421
1.403 Heptanol 1.422
1.404 3-Isopropyl-2-heptanone 1.423
1.404 Cyclohexane 1.424
1.404 2-Bromopropane 1.424
1.404 3-Chloro-Zmethyl- 1-propene 1.425
1.405 Caprylic acid 1.426
1.405 Ethylene carbonate 1.426
1.405 Oct anol 1.427
1.406 3-Methyl-2-heptanol 1.427
1.406 NJ-Dimethylformamide 1.427
1.407 Sulfuric acid 1.427
1.407 1-Chlorooctane 1.428
1.405 Triisobutylene 1.429
1.407 N-Methylalaninenitrile 1.429
1.407 1 ,ZEthanediol 1.429
1.408 l-Chloro-2-ethylhexane 1.430
1.408 Ethylcyclohexane 1.431
1.408 1,2-Propanediol 1.431
1.409 1-Bromopropane 1.431
1.409 2-Methyl-7-ethyl-4-nonanone 1.433
1.409 Ethylene glycol monoallyl ether 1.434
1.409 Butyrolactone 1.434
1.409 2-Methyl-7-ethyl-undecanone 1.435
1.410 1,2-Dichloroisobutane 1.435
1.410 1 ,ZPropylene glycol sulfite 1.435
1.410 N-Methylmorpholine 1.436
1.411 Chloro-t-butanol 1.436
Refractive index
/
.
Refractive Indices of Common Solvents III / 57
Solvents Refractive index Solvents Refractive index
Epichlorohydrin
Triethylene glycol monobutyl ether
2-Methyl-7-ethyl-4-nonanol
SEthyl-Znonanol
6-Ethyl-3-octanol
1,3-Propanediol
Diethyl maleate
Butanethiol
Dibutyl sebacate
2-Chloroethanol
6-Ethyl-3-decanol
1 -Chlorododecane
3-Methyl-2,4-pentanediol
Dimethyl maleate
2-Methyl-7-ethyl-4-undecanol
Ethyl sulfide
Mesityl oxide
Butyl stearate
Cyclohexene
Lauryl glycidyl ether
Dibutyl maleate
1,3-Butylene glycol sulfite
1,2-Dichloroethane
Glycol sulfite
Chl oroform
1-Chlorotetradecane
Diethylene glycol
cis- 1 ,ZDichloroethylene
2-Butyloctyl-3-aminopropyl ether
2-Methylmorpholine
Formamide
3-Lauryl- 1 -hydroxypropylamine
Ethylene glycol diglycidyl ether
1 -Chlorohexanedecane
Cyclohexanone
1-Amino-2-propanol
Diethylene glycol
mono-P-hydroxyisopropyl ether
1-Amino-2-methyl-2-pentanol
Tetrahydrofurfuryl alcohol
2-Propylcyclohexanone
2-Aminoethanol
1,4-Butanediol glycidyl ether
4-Chloro-1,3-dioxolane-2-one
1-Chlorooctadecane
2-Butylcyclohexanone
Ethylenediamine
2-( P-Methyl)propylcyclohexanone
4-Methylcyclohexanol
3-Methylcyclohexanol
Bis(2-chloroethyl) ether
Cyclohexyl methacrylate
1,8-Cineole
2,2-Dimethyl-2,2-dipropyl
diethanolamine
1,3-Butanediol glycidyl ether
1.436
1.437
1.438
1.438
1.438
.438
.438
.440
.440
.440
.441
.441
1
1
1
1.441
1.441
1.442
1.442
1.442
1.442
1.443
1.443
1.444
1.444
1.444
1.444
1.444
1.445
1.445
1.445
1.446
1.446
1.446
1.447
1.447
1.448
1.448
1.448
1.448
1.449
1.450
1.452
1.452
1.452
1.452
1.453
1.453
1.454
1.454
1.454
1.455
1.455
1.456
1.456
1.456
1.456
1-Chloroeicosane
Oleic acid
( 1,1,2,2-Tetramethyl) diethanolamine
3-Aminopropanol
Carbon tetrachloride
3-Methyl-5-ethyl-2,4-heptanediol
2-( P-Ethyl)butylcyclohexanone
2-Methylcyclohexanol
N-(n-Butyl)diethanolamine
4,5-Dichloro-1,3-dioxolane-Zone
2-Butylcyclohexanol
N- P-Hydroxypropylmorpholine
2-( P-Ethyl)hexylcyclohexanone
2-Ethylcyclohexanol
Fluorobenzene
o-a-Pinene
L-a-Pinene
Cyclohexanol
m-Fluorotoluene
p-Fluorotoluene
N-(2-Hydroxyethyl)-2-
hydroxybutylamine
4-Chloromethyl-1,3-dioxolane-2-one
truns-Decahydronaphthalene
o-Fluorotoluene
N-(2-Hydroxyethyl)-2-
hydroxypropylamine
3-Allyloxy-2-hydroxypropylamine
Di(2-hydroxybutyl)ethanolamine
Di(2-hydroxypropyl)ethanolamine
n-Limonene
2-(a-Hydroxybutyl)cyclohexanol
1,2,3-Trichloroisobutane
Decahydronapht hal ene
1,2,3Propanetriol
Trichloroethylene
N-(P-Hydroxyethyl)morpholine
Dimethyl sulfoxide
cis-Decahydronaphthalene
2-(a-Hydroxyethyl)cyclohexanol
1-Methoxy-1-butene-3-yn
2-Butylidenecyclohexanone
N-( P-Chloroallyl)morpholine
n-Dodecyl-4-t-butyl phenyl ether
n-Dodecyl phenyl ether
n-Dodecyl 4-methylphenyl ether
N-Hydroxyethyl- 1,3-propanediamine
Morpholyl N-(ethylhydroxy)ethylamine
2-Ethylidenecyclohexanone
Butylbenzene
Dioctylbenzene (90% p. 10% m)
p-Cymene
Isopropylbenzene
Furfuryl alcohol
t-Butylcumene (80% p, 15% m, 5% o)
n-Propyl benzene
1.459
1.459
1.459
1.459
1.459
1.459
1.461
1.461
1.461
1.462
1.462
1.462
1.463
1.463
1.463
1.464
1.465
1.465
1.465
1.467
1.467
1.467
1.468
1.468
1.468
1.469
1.469
1.469
1.471
1.473
1.473
1.474
1.475
1.474
1.476
1.476
1.479
1.479
1.480
1.481
1.481
1.482
1.482
1.483
1.483
1.485
1.486
1.487
1.487
1.488
1.489
1.489
1.490
1.490
III / 58 REFRACTIVE INDICES OF COMMON SOLVENTS
Solvents Refractive index Solvents Refractive index
s-Butylbenzene
Hexyl-m-xylene (mainly 1,3,5)
t-Butylbenzene
Dibutyl phthalate
Isopropylethylbenzene
(35% p, 60% m, 5% o)
t-Butyltoluene (85% p, 10% m, 5% o)
1 -Phenyl- 1 -hydroxyphenyl ethane
Hexylcumene (90% p, 5% m, 5% o)
Octyltoluene (96% p, 2% m, 2% o)
Octylcumene (90% p, 4% m, 6% o)
Dihexylbenzene
(85% p, 10% m, 5% 0)
p-Xylene
1,3-Diethylbenzene
t-Butyl-m-xylene (mainly 1,3,5)
Ethylbenzene
Octylethylbenzene
(80-90% p, 10% m)
1,3-Dimorpholyl-2-propanol
1,1,2,2-Tetrachloroethane
Isopropyl-m-xylene (mainly 1,3,5)
Toluene
Benzyl ethyl ether
t-Butylethylbenzene
(70% p, 25% m, 5% o)
m-Xylene
Hexylethylbenzene
(70% p, 25% m, 5% o)
1 ,bDiethylbenzene
2,3-Dichlorodioxane
Mesitylene
Hexyltoluene (90% p, 5% m, 5% o)
2-Iodopropane
Benzene
Propyl benzoate
a-Picoline
1 ,ZDiethylbenzene
Pentachloroethane
1 -1odopropane
o-Xylene
Ethyl benzoate
P-Picoline
Tetrachloroethylene
Phenetole
Pyridine
Iodoethane
Phenyl methallyl ether
Anisole
1.490
1.490
1.490
1.490
1.491
1.491
1.491
1.492
1.492
1.493
1.492
1.493
1.493
1.493
1.493
1.493
1.493
1.493
1.494
1.494
1.494
1.495
1.495
1.495
1.496
1.496
1.497
1.497
1.497
1.498
1.498
1.499
1.501
1.501
1.502
1.503
1.503
1.504
1.504
1.505
1.507
1.512
1.514
1.515
Methyl benzoate
Cyclohexylcumene
(60% p, 25% m, 15% o)
Diallyl phthalate
Benzyl acetate
Cyclohexylethylbenzene
(70% p, 20% m, 20% 0)
2-Methyl-4-t-butylphenol
Phenyl acetonitrile
(Chloro-t-butyl)benzene
Methyl salicylate
Cyclohexyltoluene
(50% p, 20% m, 30% 0)
Chlorobenzene
Furfural
Octachlorodiethyl ether
Benzonitrile
Thiophene
Nonachlorodiethyl ether
Iodomet hane
4-Phenyldioxane
3-Phenyl- 1 -propanol
Acet ophenone
Benzyl alcohol
1,2-Dibromoethane
1,2,3,4-Tetrahydronaphthalene
m-Cresol
B,P-Di(butylxanthogenic acid)
diethylester
m-Dichlorobenzene
Benzaldehyde
Styrene
Nitrobenzene
o-Dichlorobenzene
Bromobenzene
o-Nitroanisole
m-Toluidine
Benzyl benzoate
o-Toluidine
1 -Methoxyphenyl- 1 -phenylethane
Aniline
o-Chloroaniline
Bromoform
Thiophenol
2,4-Bis(a-phenylethyl)phenylmethyl
ether
Carbon disulfide
1,1,2,2-Tetrabromoethane
Methylene iodide
1.515
1.516
1.517
1.518
1.520
1.521
1.521
1.521
1.522
1.523
1.523
1.524
1.525
1.526
1.526
1.529
1.530
1.530
1.532
1.532
1.538
1.538
1.539
1.542
1.543
1.544
1.544
1.545
1.550
1.551
1.557
1.560
1.566
1.568
1.570
1.571
1.583
1.586
1.587
1.588
1.590
1.628
1.633
1.749
Physical Constants of the Most Common
Solvents for Polymers
Daniel R. Bloch
Lakeshore Research, Racine, WI, USA
Values given here have been taken a variety of reference sodium D line. Boiling points are given at 760 mmHg
books. Where a range was given, the melting and boiling unless indicated otherwise by the pressure in mmHg
points given here are average values. Flash point was following a slash (/). Viscosity is reported at 20C unless
determined by the closed cup method, using a Setaflash indicated at another temperature in Celsius following a
apparatus. The refractive index is reported relative to the slash (/).
Compound
CAS Formul a Melting Boiling pt. Density Viscosity at Refractive Flash pt.
Number wt. Pt. (C) (C) (at 20C) 20C (cps) index (at 20C) (C)
Acetic acid 64- 19- 7
Acetic anhydride 108- 24- 7
Acetone 67-64- 1
Acetonitrile 75-05-8
n-Amy1 acetate 628- 63- 7
Aniline 62- 53- 3
Anisole 100- 66- 3
Benzene 71- 43- 2
Benzonitrile 100- 47- 0
Benzyl acetate 140- 11- 4
Benzyl alcohol 100- 51- 6
Biphenyl 92- 52- 4
Bromoform 75- 25- 2
n-Butanol 71- 36- 3
n-Butyl acetate 123- 86- 4
y-Butyrolactone 96- 48- 0
Carbon disulfide 75-15-0
Carbon tetrachloride 56- 23- 5
Chlorobenzene 108- 90- 7
2-Chloroethanol 107- 07- 3
Chloroform 67- 66- 3
2-Chlorophenol 95- 57- 8
m-Cresol 108- 39- 4
Cyclohexane 110- 82- 7
Cyclohexanol 108- 93- 0
Cyclohexanone 10%94- 1
Cyclohexyl acetate 622- 45- 7
Cyclopentanol 96- 41- 3
cis-Decahydronaphthalene 493- 01- 6
Diacetone alcohol 123- 42- 2
Di-n-amyl ether 693- 65- 2
1,2-Dichlorobenzene 95- 50- 1
Di-2-chlorodiethylether 111- 44- 4
1,2-Dichloroethylene, cis & ~rans 540- 59- 0
Dichloromethane/methylene chloride 75-09-2
1,3,-Dichloro-2,4,6-trifluorobenzene 2368-53-8
Diethyl ether 60- 29- 7
60.05 1 7
102.09 - 7 3
58.08 - 9 4
41.05 - 4 8
130.19 - 7 1
93.13 - 6
108.14 - 3 7
78.11 6
103.12 - 13
150.18 - 5 1
108.14 - 1 5
154.21 7 1
252.75 8.3
74.12 - 9 0
116.16 - 7 8
86.09 - 4 5
76.14 - 111
153.82 - 2 3
112.56 - 4 5
80.51 - 8 9
119.38 - 6 3
128.56 8
108.14 9
84.16 7
100.16 2 2
98.15 - 4 7
142.2
86.13 - 1 9
138.25 - 4 3
116.16
158.29 - 6 9
147 - 17
143.01 - 4 7
96.94 - 5 7
84.93 - 9 7
200.98
74.12 - 1 1 6
1 1 8 1.049
140 1.082
5 6 0.790
8 2 0.786
1 4 8 0.876
184 1.022
154 0.995
8 0 0.874
1 9 1 1.010
2 0 6 1.040
205 1.045
255 0.992
1 5 1 2.894
118 0.810
1 2 5 0.882
205 1.120
4 6 1.266
7 7 1.594
132 1.107
129 1.201
6 1 1.492
176 1.241
203 1.034
8 1 0.779
1 6 1 0.948
1 5 5 0.947
1 7 3 0.966
140 0.949
193 0.896
166 0.931
1 8 8 0.785
180 1.306
66115 1.220
48-60 1.265
4 0 1.325
162 1.599
34.6 0.708
1. 21
0.324
0.52
5.8
2.948
5.8
0.969
0.568
20.8
0.979
2.543115
1.4230
1.4870
1.26
1.3716 4 0
1.3900 5 4
1.3588 - 1 7
1.3440 5
1.4026 3 6
1.5860 7 0
1.5160 5 1
1.5010 - 1 1
1.5280 7 1
1.5020 102
1.5400 9 3
1.5960
1.3990
1.3940
1.4360
1.6270
1.4600
1.5240
1.4410
1.4460
1.5580
1.5400
1.4260
1.4650
1.4500
1.4390
1.4530
1.4750
3 5
9 8
- 3 3
2 3
6 0
1.4119
1.5510
1.4560
1.4470
1.4240
6 3
8 6
- 1 8
6 7
4 6
5 7
5 1
5 7
6 1
5 7
6 5
5 5
6
1.3530
7 6
- 4 0
III I59
III j 60 PHYSICAL CONSTANTS OF THE MOST COMMON SOLVENTS FOR POLYMERS
Compound
CAS Formula Melting Boiling pt. Densi ty Viscosity at Refractive Flash pt. .
Number wt.
pt. (C) (C) (at 20C) 20C (cps) index (at 20C) (Cl
Di(ethylene glycol) 111-46-6
Di(ethylene glycol mono-n-butyl 112-34-5
ether
Di(ethylene glycol) monoethyl ether 111-90-0
Diisobutyl ketone 108-83-8
Diisopropyl ketone 565-80-0
1,2-Dimethoxyethanelethylene 110-71-4
glycol dimethyl ether
NJ-Dimethylacetamide 127-19-5
NJ-Dimethylformamide 68-12-2
Dimethylsulfoxide 67-68-5
1,4-Dioxane 123-91-1
Diphenyl ether 101-84-8
Di(propylene glycol) 110-98-5
Di(propylene glycol) monomethyl 34590-94-8
ether
Ethanol
Ethyl acetate
Ethylene glycol diacetate
Ethylene carbonate
Ethylene dichloride
Ethylene gylcol
Ethylene glycol mono-n-butyl ether
Ethylene glycol diacetate
Ethylene glycol diethyl ether
Ethylene glycol dimethyl ether
Ethylene glycol monoethyl ether
Ethylhexyl acetate
(S)-(-)-Ethyl lactate
Formaldehyde, 37% solution
Formamide
Formic acid, 96%
Furfurol
Glycerine
n-Heptane
Hexachloroethane
Hexafluorobenzene
Hexamethylphosphoric triamide
Hexane
Isobutanol
Isobutyl isobutyrate
Isobutyric acid
Isophorone
Isopropanol
Isopropyl acetate
Isopropylamine
Mesitylene
Mesityl oxide
Methanol
2-Methoxyethanol
Methyl acetate
Methyl ethyl ketone
Methyl isoamyl ketone
Methyl isobutyl ketone
Methyl propyl ketone
N-Methylpyrrolidone
Morpholine
Nitrobenzene
Nitromethane
n-Octane
n-Pentanol
Perfluoroacetone
Perfluorotributylamine
Phenol
1,4-Phenylenediamine
64-17-5 46.07
141-78-6 88.11
111-55-7 146.14
96-49- 1 88.06
107-06-2 98.96
107-21-1 62.07
111-76-2 118.18
111-55-7 146.14
629-14-1 118.18
110-71-4 90.12
110-80-5 90.12
103-09-3 172.27
687-47-8 118.13
50-00-0 30.03
75-12-7 45.04
64-18-6 46.03
98-00-0 98.1
56-81-5 92.09
142-82-5 100.21
67-72- 1 236.74
392-56-3 186.05
680-3 1-9 179.2
110-54-3 86.18
78-83-1 74.12
97-85-8 144.21
79-3 1-2 88.11
78-59-1 138.21
67-63-0 60.1
108-21-4 102.13
75-31-0 59.11
108-67-8 120.2
141-79-7 98.15
67-56-1 32.04
109-86-4 76.1
79-20-9 74.08
78-93-3 72.11
110-12-3 114.19
108-10-1 100.16
107-87-9 86.13
872-50-4 99.13
110-91-8 87.12
98-95-3 123.11
75-52-5 61.04
111-65-9 114.23
71-41-0 88.15
684-16-2 166.02
3 11-89-7 671.1
108-95-2 94.11
106-50-3 108.14
106.12 - 10 245 1.118 1.4460 1 4 3
162.23 - 6 8 231 0.967 1.4320 100
134.18
142.24
114.19
90.12
- 4 6
- 80
- 5 8
202 0.999 1.4270 96
169 0.806 1.4113 49
124 0.806 1.4000 1 5
8 5 0.867 1.3790 0
87.12
73.1
78.13
88.11
170.21
134.18
148.2
- 20
-61
1 8
1 2
28
166 0.937 1.4380 70
1 5 3 0.944 1.4310 57
189 1.101 1.4790 95
102 1.034 1.26 1.4220 1 2
259 1.073 1.5790 >llO
230 1.023 1.4410 1 3 7
90112 0.938 1.4220 74
- 130
- 84
-41
39
- 3 5
- 13
- 75
-41
- 7 4
- 5 8
- 9 0
1.2 1.3600
0.455 1.3720
1.4150
- 26
- 15
3
8
- 2 9
20
-91
1 9 3
4
7
- 95
- 108
-81
- 4 7
- 8
- 89
- 73
- 101
- 4 5
- 5 3
- 98
- 85
- 98
- 87
78
77
1 8 7
2441740
8 3
1 9 7
1711743
187
1 2 1
8 5
1 3 5
200
154
97
210
1 0 1
170
182120
98
1.4450
1.4310
1.4190
1.4150
1.3923
1.3790
1.4070
1.4130
1.3765
1.4470
1.3704
1.4860
1.4740
1.3870
8
- 3
82
160
1 5
>llO
60
82
20
0
44
77
28
56
154
68
65
160
- 1
- 80
- 7 8
- 24
- 7
6
- 29
- 57
- 7 8
- 129
80
2321740
69
108
1 4 8
154
214
82
89
34
1 6 3
129
6 5
1 2 5
58
80
1 4 5
1 1 8
110
82/10
129
211
1 0 1
1 2 7
1 3 8
- 26
1 7 8
182
267
0.785
0.902
1.128
1.321
1.256
1.113
0.903
1.128
0.842
0.867
0.930
0.870
1.042
1.083
1.134
1.220
1.135
1.261
0.684
2.091
1.612
1.030
0.659
0.803
0.855
0.950
0.923
0.785
0.872
0.694
0.864
0.858
0.791
0.965
0.932
0.805
0.888
0.801
0.802
1.033
0.999
1.196
1.127
0.703
0.811
1.3770 1 0
1.4580 1 0 5
0.326 1.3750 - 23
1.3960 27
1.3980 37
1.3930 5 5
1.4760 84
1.3770 11
1.3770 1 6
1.3746 - 3 2
1.4990 44
1.4450 30
1.3290 11
1.4020 46
1.3610 - 9
0.423115 1.3970 3
1.4070 4 1
1.3960 1 3
1.3900 7
1.4700 86
1.4540 3 5
1.5510 8 7
1.3820 3 5
2.256 1.3980 1 5
1.4090 48
4 1
144
1.883
1.071 1.5425
None
79
Physical Constants of the Most Common Solvents for Polymers III / 61
Compound
CAS Formula Melting Boiling pt. Density Viscosity at Refractive Flash pt.
Number wt. pt. (0 (Cl
(at 20C) 20C (cps) index (at 20C) (C)
Piperazine
n-Propanol
Propyl acetate
Propylene carbonate
Propylene glycol
Propylene glycol mono-n-butyl
ether
Propylene glycol monomethyl
ether
Propylene glycol mono-n-propyl
ether
Propylene glycol mono-r-butyl
ether
Pyridine
1,1,2,2-Tetrachloroethane
Tetrachloroethylene
Tetrahydrofuran
Tetrahydrofurfnryl alcohol
Tetrahydronaphthaleneketralin
Tetramethylene sulfone
Tetramethylurea
Toluene
l,l,l-Trichloroethane
Trichloroethylene
Tricresyl phosphate
Trifluoroacetic acid
Water
o-Xylene
p-Xyl ene
110-85-0
71-23-8
109-60-4
108-32-7
57-55-6
107-98-2 90.12 - 9 7 119 0.922 1.4030 3 3
1569-01-3 118.18 140- 160 0.885 1.4110 48
57018-52-7 132.20 144 0.874 1.4130 44
110-86-1 79.1 - 4 2 1 1 5 0.978
79-34-5 167.85 -45 1 4 7 1.586
127-18-4 165.83 - 22 1 2 1 1.623
109-99-9 72.11 - 108 66 0.889
97-99-4 102.13 - 80 178 1.054
119-64-2 132.21 - 35 207 0.973
126-33-0 120.17 21 285 1.261
632-22-4 116.16 - 1 177 0.971
108-88-3 92.14 - 9 3 1 1 1 0.865
71-55-6 133.41 - 3 5 7 5 1.338
79-01-6 131.39 - 85 8 7 1.463
1330-78-5 368.37 265/10 1.143
76-05-1 114.02 - 15 72 1.480
7732-18-5 18.02 0 100 0.998
95-47-6 106.17 - 24 144 0.870
106-42-3 106.17 1 3 138 0.866
86.14 109 146
60.1 - 127 97
102.13 - 9 5 102
102.09 - 5 5 240
76.1 - 6 0 1 8 7
132.2 72120
0.804 2.256 1.3840
0.888 1.3840
1.189 1.4210
1.036 1.4320
0.885 1.4160
1.5100
1.4935
1.5060
0.486 1.4070
1.4520
1.5410
1.4840
1.4506
0.59 1.4960
1.4366
1.4760
1.5550
1.005 1.3329
1.5050
0.648 1.4950
109
1 5
1 2
132
1 0 7
58
20
None
None
- 17
83
77
165
6 5
4
None
None
>llO
None
None
32
27
SECTION IV
PHYSICAL DATA OF OLIGOMERS
-
-
-
_
_
_

.
_
_
-
_
_
-
-
-

~
.
-
-
-
-

-
-
_

.
_
-
.-
_
_
_
-
.
-
_
-
-
Physical Data of Oligomers
M. Rothe
Lehrstuhl Organische Chemie II, University at Ulm, Ulm, FR Germany
A. Introduction
B. Oligomers Containing Main Chain Acyclic
Carbon Only
Table 1. Oligofolefins)
1 .I. Oligofmethylenes) and
Oligofethylenes)
1. 2. Oligofperfluoromethylenes)
and Oligo(perfluoroethylenes)
1. 3. Oligofisobutenes)
1. 4. Oligofl -alkenylenes)
Ref erences
Tabl e 2. Oligo(dienes)
2.1. Oligomers of 1,3-Butadiene
2.2. Oligomers of lsoprene
2.3. Oligomers of 1,3-Butadiene
Derivatives
2 . 4 . 1,4-Oligofalkadienes)
2.5. Oligomers of Cyclopentadiene
and 1,3-Cyclohexadiene
2.6. Oligomers of Allene
Ref erences
Table 3. Oligofacetylenes)
3.1. Linear Oligomers of
Acetylene
3.2. Polyenyne Oligomers
3.3. Oligomeric a-o-Diynes
3. 4. Oligofalkynes)
3. 5. Cycl i c Oligo(alkynes)
3.6. Pericyclynes
Ref erences
Table 4. Oligomers with Aliphatic Side
Chains which in Addition Contain
Het eroat oms
4.1. Oligomeric Acrylic
Derivatives
4.2. Oligomeric Methacrylic
Derivatives
4.3. Oligomers of 8-Alkyl
Substituted Vinyl Derivatives
4.4. Oligo(vinyl) Derivatives
Ref erences
Table 5. Oligofstyrenes)
Ref erences
IV-2
IV-3
IV-3
IV-3
IV-6
IV-8
IV-9
IV-9
IV-I 4
IV-I 4
IV-1 5
IV-l 6
IV-l 6
IV-1 7
IV-I 7
IV-l 8
IV-I 9
IV-1 9
IV-20
IV-20
IV-20
IV-20
I V-21
I V-21
IV-22
IV-22
IV-24
IV-26
IV-27
IV-28
IV-30
IV-32
C. Oligomers Contaning Heteroatoms in the
Main Chain
Table 6. Oligomers Containing 0 in the
,
Main Chain
6.1. Oligo(ethers.1 and
Oligo(acetals)
Ref erences
6 . 2 . Oligofcarbonates)
Ref erences
6 . 3 . Oligofesters)
Ref erences
6 . 4 . Oligo(urethanes)
Ref erences
Table 7. Oligo(sulfides) and Oligofselenides)
7. 1. Cycl i c Oligofthiomethylenes)
and OligofSelenomethylenes)
7. 2. Cycl i c Oligofthioalkylenes)
7.3. Substituted
Cyclicfthioethylenes)
7.4. Cyclic Co-Oligomers of
Formaldehyde and
Thioformaldehyde
7. 5. Cycl i c Oligofethersulfides)
7.6. Thiacyclophanes
Ref erences
Table 8. Oligomers Containing N in the
Main Chain
8. 1. Oligofamides)
Ref erences
8 . 2 . Oligo(peptides)
Ref erences
8 . 3 . Oligo(imines)
Ref erences
8. 4. Oligo(ureas)
Ref erences
D. Carbon Chain Oligomers Containing Main
Chain Cyclic Units
Table 9. Oligocyclopentylenes
Table 10. Oligo(spiranes)
Table 11. Oligofxylylenes)
11 .I. Linear Oligo(xylenes)
11.2. Cyclic Oligo(xylylenes)
Table 12. Oligofstilbenes)
IV-33
IV-33
IV-33
IV-43
IV-47
IV-47
IV-48
IV-56
IV-58
I V-61
IV-62
IV-62
IV-62
IV-62
IV-62
IV-63
IV-63
IV-63
IV-64
IV-64
IV-70
IV-72
IV-84
IV-88
IV-89
IV-89
IV-90
IV-90
IV-90
IV-90
IV-90
IV-90
IV-90
I V-91
IV/l
IV/2 PHYSICAL DATA OF OLICOMERS
Table 13. Oligofbenzyls) I V-91
Table 14. Oigo(2,5-dimethyl-benzyls) I V-91
Table 15. Oligo(2,3,5,6-tetramethyl benzyls) I V-91
Table 16. Oligofpphenylene oxides) I V-91
Table 17. Oligofpphenylene sulfides) I V-91
Table 18. Oligofpphenoxy phenylmethanes) I V-91
Table 19. Oligofdiphenylmethanes) I V-91
Ref erences I V-91
Table 20. Phenol-Formaldehyde and Related
Oligomers IV-92
20.1. Linear Phenol-Formaldehyde
Oligomers IV-92
20.2. Oligomeric Phenol Alcohols IV-93
20.3. Cyclic Phenol-Formaldehyde
01 i gomers IV-94
20.4. Branched Phenol-
Formaldehyde Oligomers IV-94
20.5. Hydroquinone Oligomers IV-95
Ref erences IV-95
Table 21. Oligofphenylenes) IV-96
21 .l. o-Oligofphenylenes) IV-96
21.2. m-Oligofphenylenes) IV-96
21.3. pOligo(phenylenes) IV-97
21.4. Oligofpquinones) IV-98
Ref erences IV-98
E. Oligomers Containing Heterocyclic Rings
in the Main Chain IV-99
Table 22. Heterocyclic Oligomers IV-99
22.1 Oligoffuran) Derivatives IV-99
22.2. Oligofthiophene) Derivatives IV-l 00
22.3. Oligofpyrrole) Derivatives IV-I 00
22.4. Oligofpyridine) Derivatives IV-1 00
22.5. Cyclic Oligofheterocyclics) IV-1 01
Ref erences IV-1 01
Table 23. Oligofsaccharides) IV-1 02
23.1. Oligomeric Pentoses IV-1 02
23.2. Oligomeric Hexoses IV-1 02
23.3. Oligomeric Amino Sugars IV-I 03
Ref erences IV-1 04
A. INTRODUCTION
Oligomers are defined as the low members of the
polymeric-homologous series with molecular weights up
to about 1000-2000. They are easily obtained by step-
wise synthesis from suitably protected monomer derivatives
or by separation from the polymers. As monodisperse
oligomers are low molecular compounds of defined
molecular weights, they represent ideal model substances
for the polymers. By physical studies of a complete series
of oligomers, substantial knowledge is gained of the
relation between chain length and physical properties. In
this way certain physical data of the polymers could be
explained for the first time. In chemical aspects, oligomers
must, on principle, have the same properties as the related
polymers; they are, however, much more accessible to all
studies, owing to their strictly defined and comparatively
simpler structure.
Homologous oligomers differ sufficiently in their
physical properties - due to their low molecular weight -
so that they can be separated into individual chemicals.
They can therefore be used for elucidating the structure of
polymers and, in close relation, for the investigation of the
mechanisms of polymerization. Oligomers are intermedi-
ates in polycondensation and polyaddition reactions and
are present in more or less significant amounts in the
polymers, due to equilibria between different chains, and
between chains and rings. Therefore important conclusions
on the structure of the related high polymers can be drawn
from isolation and structure determination of oligomers,
along with a comparison of the chemical properties of
polymers and oligomers. In this way clear evidence can be
obtained as regards the type of linkage between the
monomer units in the polymer as well as the structure of
unknown endgroups. Finally, unequivocal evidence on the
mechanism of polymer formation is to be expected from the
behavior of oligomers under the conditions of the
polyreaction.
The following tables give the physical properties of the
most important, linear, cyclic, and branched monodisperse
oligomers which are significant for polymer chemistry.
Derivatives and co-oligomers (such as co-oligo-peptides,
-saccharides, and -nucleotides) as well as organosilicon and
inorganic oligomers are not included, nor are any low
polymers which have not been proved to be strictly mono-
disperse. Only those literature references are cited that
indicate the best methods of synthesis and the most im-
portant physical properties of the oligomers concerned
(including spectroscopic and conformational data which
could not be mentioned in detail in the tables).
In the last few decades several reviews on linear and
cyclic oligomers have appeared. A small list is giving
below.
1. H. Zahn, G. B. Gleitsmann, Angew. Chem., 68, 229 (1956);
Angew. Chem., Int. Ed. Engl., 2, 410 (1963).
2. M. Rothe, Makromol. Chem., 35, 183 (1960).
3. M. Rothe, I. Rothe, in: J. Bra&up, H. Immergut (Eds.),
Polymer Handbook, 3rd Ed., Wiley, New York, 1989.
4. J. A. Semlyen, Cyclic Polymers, Elsevier, London, 1986.
5. S. Penczek, S. Slomkowski, Compr. Polym. Sci., 3, 725
(1989).
6. I? Maravigna, G. Montaudo, Compr. Polym. Sci., 5,63 (1989).
7. V. Percec, C. Pugh, 0. Nuyken, S. D. Pask, Compr. Polym.
Sci., 6, 281 (1989).
8. C. V. Uglea, I. I. Negulescu, Synthesis and Characterization
of Oligomers, CRC Press, Boca Raton, 1991.
9. M. Rothe, in: E. W. Fischer, R. C. Schulz, H. Sillescu (Eds.),
Chemistry and Physics of Macromolecules, VCH,
Weinheim, 199 1.
10. K. Hatada, K. Ute, N. Miyatake, Prog. Polym. Sci., 19, 1067
(1994).
11. J. M. Tour, Trends Polym. Sci., 2, 332 (1994).
Oligomers Cont ai ni ng Mai n Chai n Acycl i c Carbon Onl y IV/3
B. OLICOMERS CONTAINING MAIN CHAIN ACYCLIC CARBON ONLY
TABLE 1. OLICO(OLEFINS)
1.1. OLIGO(METHYLENES) AND OLIGO(ETHYLENES)
1.1.1. n-ALKANES H[CH2],H
n Mol. wt . m.p. (C) b.p. ( C/mbar) d4 (g/cm3)/C Refs.
1 16.0 - 182.6 - 161.6/1013 0.4240/- 1 6 4
2 30.1 - 183.3 - 88.5/1013 0.5462189
3 44.1 - 187.1 - 42.211013 0.5824/- 45
4 58.1 - 138.4 - 0.5/1013 0.6011/0
5 72.2 - 129.7 36.1/1013 0.6263120
6 86.2 - 94.0 68.7/1013 0.6594120
7 100.2 - 90.5 98.4/1013 0.6838/20
8 114.2 - 56.8 125.5/1013 0.7026120
9 128.3 - 53.5 150.8/1013 0.1177/20
1 0 142.3 - 29.1 174.1/1013 0.7301/20
1 1 156.3 - 25.6 195.9/1013 0.7402120
1 2 170.3 - 9.7 216.3/1013 0.7481/ 20
1 3 184.4 - 6.0 235.5/1013 0.7563120
1 4 198.4 5.5 253.611013 0.7627120
1 5 212.4 10.1 210.7/1013 0.7684120
1 6 226.4 1 8 . 1 287.1/1013 0.1733/20
1 7 240.5 22.1 302.6/1013 0.7767122
1 8 254.5 28.2 317.4/1013 0.7768128
1 9 268.5 32.0 331.6/1013 0.7776132
2 0 282.6 36.7 345.1/1013
2 1 296.6 40.4 215120
2 2 310.6 44.4 222-225120
2 3 324.6 47.4 234120
2 4 338.7 51.1 243120
2 5 352.1 5 4 259120
2 6 366.7 57.0 262120
2 7 380.7 60.0 270120
2 8 394.8 61.6 279-281120
2 9 408.8 64.0 286120
3 0 422.8 66.0 304120
3 1 436.9 67.9 302120
3 2 450.9 70.4 310120
0.1550/ 70
0.7583/70
0.1631/70
0.1641/70
0.1657/70
0.7693170
0.7704170
0.1732/70
0.7750/70
0.7755170
0.7195/70
0.7678/100
0.7645/100
3 3 464.9 71.3
3 4 478.9 72.9
3 5 493.0 74.7
3 6 507.0 76.1
331120 0.74361135
298.414 0.7783190
3 7 531.0 71.2
3 8 535.0 79.2
3 9 549.1 80.5
4 0 563.1 81.5
4 1 577.1 81.7
4 2 591.2 82.9
4 3 605.2 85.5
4 4 619.2 86.4
150/10-4
33214 0.7812190
0.7514/135
4 5 633.2 87.2
4 6 647.2 88.0
4 8 675.3 88.5-89
5 0 703.4 92.1 420-422120
5 2 731.4 94.0
21,22,75,84,88,93
21,75,84,88,93
21,22,75,84,88,93
21,22,75,84,88,112,178,192
3,7,13,21,22,30,75,84,88,93,112,178,192,195
3,5,7,21,22,30,75,78,84,88,93,112,178,192,195
3,5,7,13,21,22,30,75,84,88,93,112,178,192
3,5,7,13,21,22,30,78,84,87,88,93,112,178,192,195
1,5,7,13,21,22,30,84,87,88,93,111,112,178,192
L,3,5,7,18,21,22,30,84,87,88,93,111,112,178,192,195
1,3,7,13,21,22,30,77,83,84,87,88,93,111,112
1,7,17,21,22,30,79,84,87,88,93,111,112,178,185,192
1,7,13,21,30,77,83,84,87,88,93,112,205,206
1,7,17,21,30,84,87,88,93,111,112
1,3,7,21,30,77,83,84,87,88,93,112
1,7,11,15,16,19,21,30,78,84,87,88,93,111,112,192
1,3,7,13,14,21,30,75,77,83,84,88,93,111,112,193
l-3,7,11,14,15,17,19,21,30,75,84,88,93,111
1,3,4,7,14,15,19,21,77,83,84,88,93,97,111,121,
198,221,235
1,3-7,11,14,15,17-19,21,22,79,82,88,91,93,107,
110,111,198
1,3,4,10,14,15,19,21,77,83,86,88,93,111,118,
194,198,232
1,3,4,7,11,14,21,78,83,88,91,93,97,111,115,121,198
1,3,4,10,14,21,77,83,86,88,93,121,198
1,3,4,11,14,17,21,83,86,88,91,93,99,182,198,202,204
1,3-5,14,21,77,83,88,93,118,193,198,232
l-4,7,11,14,21,83,85,88,93,198
l-4,8,14,21,77,83,85,88,93,118,198
1,4,11,13-15,17,19,21,83,85,86,88,90,93,99,100,
111,198
1,3,4,11,14,21,77,83,85,88,91,93,118,198
l-4,6,7,11,14,18,21,82,83,85,86,88,93,110,198
l-4,8,77,83,85,86
1,2,4,11,15,16,19,20,83,85,91,95,97,99,109,111,
115,185,198
1,4,5,77,83,91,109,116,119,198,207
l-4,7,11,77,83,85,86,198
147 8 10,15,19,77,79,83,85,86,88,91,95,118 11, ,
1,2,4,7,10,13-15,19,77,78,83,85,86,88,90,91
107,109,111,185,191,193,194,198,207,211,221,
223,232,233
75,109,198
75,77,83,198
12,75,77,83
6,7,10,17,18,21,75,77,82,83,86,93,99,110,198
7 5
7 6
10,22,77,83,86
3,11,15,19,77,79,80,83,89,91,95,107,110,111,115,
116,118,205
109
77,80,83,91,100,198
100,109,202,204
6,7,11,15,18,21,77,80,82,83,90,93,110,116,
188,193,198
77,80,83,90
I V/ 4 PHiSlCAL DATA OF OLIGOMERS
1.1.1. contd
n Mol. wt. m.p. (C) b.p. ( Urnbar) dd (g/cm3)/C Refs.
54 759.5 95.0
56 787.6 95.5-96
60 843.6 99.1
6 1 857.6 100.3
62 871.7 100.5
64 899.7 102.1
6 5 913.7 102.1
66 927.8 103.6
67 941.8 104.1
69 969.9 104.7
70 983.9 105.3
72 1012.0 103- 105
80 1124.2 108.0
82 1152.2 110.1
94 1320.6 113.8
96
98
100
102
104
120
122
140
144
150
160
162
168
192
194
1 9 8
210
216
240
242
246
258
288
294
384
390
1348.6
1404.7
1432.8
1460.8
1685.3
1965.8
2021.9
2106.1
2246.4
2358.5
2695.2
2779.4
2947.7
3029.8
3368.5
3396.6
3450.6
3621.0
4039.8
4126.0
5386.4
5470.5
110- 112
113- 114
115.2
115.5-116.5
115-115.5
119.2
116- 117
121.0
1 2 1
123-123.5
122.2
121-121.5
121.9
127.5
126.9
127.0
127.4
128.4
120-121
128- 130
128.8
128.8
130.4
131.3
132
2,7,77,80,83,90
106,204
250/10-4 6,7,18,21,77,80,82,83,90,93,104,109,110,187,188,
190,193,198
1 0 9
2,7,77,80,83,90,116
0.76541135 2,7,13,22,77,79,80,83,90
109
9,77,80,83,90
9,77,80,83,90
109
300/10-4 6,7,18,21,77,80,82,83,90,93,100,110,116
100,202
18,82,104,109
20,77,80,81,83,89,110,188
0.7831115 15,19,20,77,79,80,83,100,103,107,110,
116-118,188,204
100,202
229
18,22,77,80-83,93,104,110,185
105,108,183,203
106,203,204
82,98,104,200,202
229
82
98,200,202
105,108,183,203,227,248
104,108
229
98,114,177,189,199,200,202,221
98,186,189,200-202,225
224,229
105,108,183,184,197,203,224-227,229,248
224,229
98,200,202,225
189,199
229
105,108,181,183,184,203,224-227,229,249
224,229
98,200,202
108,183,203,224,225,229,248
98,200
105,108,183,203,229,248
Conformation, chain folding: Refs. 108,178 (n = 2-10,12), 179 (n = 9%44), 181,183,184,193,194,202,205-208,211,226,227,248.
Crystal l i zati on: Refs. 168,177-179,181,183,184,188-190,194,197,199-202,211,224-227,248.
Thermal behavi or, phase transi ti ons, DSC: Refs. 88,98,107,107,109,119,181,184,186-191,193,197-204,217,221,224-226,246.
NMR: Refs. 95,97 (n = 19,22,32), 99 (n = 6,8,10,14,18,24,28), 100,179,187,191,205,206,221,229,246.
IR, Raman: Refs. 98,108,116,119,178,182,192-194,200,202,232,248.
X-ray: Refs. 100,107,109,112,119,183,184,187,190,191,198,206,223,224,226,233.
El ectron di f f racti on: Refs. 187,188.
MS: Ref. 195.
GPC: Ref. 185.
1.1.2. CYCLOALKANES [[CHQ
n Mol. wt. m.p. (C) b.p. (Wmbar) dq (g/cm3)PC Refs.
3 42.1 - 127.5 - 32.8/1013 0.688/- 40 23,24,93,94,178
4 56.1 - 90 12.5/1013 0.7038/0 25,93,94,178,232
5 70.1 -93.9 49.3/1013 0.7457120 26,93,94,178,183,195
6 84.2 6.6 80.7/1013 0.7784120 27-29,93,94,99,111,178,183,195
7 98.2 - 8.0 118.5/1013 0.8098/20 29,31,93,94,178,195
8 112.2 13.5 149/1000 0.8349/20 32-34,93,94,99,178,195,208
Ol i gomers Cont ai ni ng Mai n Chai n Acycl i c Carbon Onl y IV/S
1.1.2. contd
It Mol. wt. m.p. (C) b.p. (Wmbar) dq (g/cm3)/C Refs.
9 126.2 9.7 69119 0.8534120
1 0 140.3 9.5 69116 0.8575120
1 1 154.3 - 7. 3 91/16 0.8591/20
1 2 168.3 60.6 0.861120
1 3 182.4 24.4
1 4 196.4 56.2
1.5 210.4 63.4
1 6 224.4 60.5
1 7 238.5 6 5
1 8 252.5 72-73
1 9 266.5 8 0
2 0 280.5 61-62
2 1 294.6 64-65
2 2 308.6 46.8
2 3 322.6 53-54
2 4 336.6 48.8
128127 0.861120
131/15 0.8259179
147116 0.8240/78
170-171127 0.819179
0.8200177
0.8201176
17710.5
17710.1
222-22810.8
0.8174175
0.8259164
2 5 350.7 53-54
2 6 364.7 44-46
2 7 378.7 47-48
2 8 392.8 47-48
2 9 406.8 54.5-55.5
3 0 420.8 57-58
3 2 448.9 65.5-66.5
3 4 476.9 66-67
3 6 505.0 70.0
218-219/0.7 0.8120178
213-21410.3
21511.5
23010.3
230-24010.4
0.8243158
0.8232164
0.8233169
0.8261170
0.8229176
3 7 519.0
4 0 561.1
4 2 589.2
4 4 617.2
4 5 631.2
4 6 645.2
4 8 673.3
5 0 701.4
5 4 757.5
6 0 841.6
6 4 897.7
7 2 1009.9
65-66
76-77
75-76
82-82.5
80-81
83.5-85
89.2
87-88
90-91
96.5
107.0
13C-NMR
103.5-104.5
8 0
8 4
9 6
100
104
120
1 2 8
144
160
168
192
2 0 0
2 8 8
1122.2
1178.3
1346.6
1402.7
13C-NMR
108.8
116.0
1683.2
1795.5
2019.9
2294.3
2356.5
2693.2
2805.4
4039.8
120.8
124.3
129.8
29,34,93,94,178,208
29,35,36,93,94,99,178,180,208
29,37,93,94,99,208
29,38,39,40,93,94,99,101,111,114,178,180,196,
208,214,215,217,232
29,34,38,40,93,94,99,196,208,217
17,29,38,40,41,93,94,99,180,196,208-210,214,
217,218,220
29,38,40,44,93,94,99,196,208,217
16,38,40-42,93,94,99,111,169,180,196,208,209,
212,214,217,220
40,43,44,93,94
17,40-42,45,93,94,99
40,93,94,99
18,40,41,93,94,99,111
41,94,99,102
38,40,43,48,94,96,99,220
46,48,94,99
38,40,41,45,48,94-99,100,101,111,114,169,196,
202,210,211,213-217,219,228,235,246
47,94
38,40,43,48,94,99,210
41,94,102
38,41,48,94,97,99,102,111,219,222
38,94,99
18,41,42,45,48,90,93,94,99,102
41,48,94,97,99,102,111,169,222
48,92,94,113
41,45,94,97,99,100,101,102,111,114,115,120,196,
211,214,215,217,228,248,256
9 9
18,41,93,97,99,102,111,115,216,219,222,248,256
42,102
99,100
41,102
2 2 2
97,98,100,101,111,114,115,120,196,198,200,
202,207,211,213,217,230,235,248,256
1 8
41,102
101,120,211,247
97,111,115,234,248,256
98,100,101,120,196,198,200,202,207,211,213,
216,217,228,230,231,235
97,111,115,248,256
1 0 1
96,98,100,120,196,198,202,216,217,230,231,235
228
248,256
211,228
219,248,256
98,100,198,200,202,230
219,248,256
1 7 7
9 8
228,248,256
98,100,202,230
Conformation, chain folding: Refs: 94,97,113,178 (n = 3-10,12), 179 (n = 3-96). 180,187,202,207-209,211-213,215-217,219,220,228,230,231,234,235,246,248.
Crystal l i zati on: Refs. 178,179,217,230,234,248.
Thermal behavi or, phase transi ti on, DSC: Refs. 96,101,179,196,209,216-221,230,246.
NMR: Refs. 95,97,99 (n = 6,8,10-16,18-24,26,28-30,32,36,37,40,44), 100 (n = 24,26,44,48,72,96), 111,114,115,179 (n = 3-96), 180,189,214-219,234,246,248,256.
IR, Raman: Refs. 92,96,178,179,200,202,209,220,235.
X-ray: Refs. 113,120,179,202,210,211,215,216,218,223,230,256.
Electron diffraction: Refs. 230, 231.
WC: Ref. 211.
I V/ 6 PHYSICAL DATA OF OLIGOMERS
1.2. OLIGO(PERFLUOROMETHYLENES) AND OLIGO (PERFLUOROETHYLENES)
1.2.1. PERFLUORO-n-ALKANES F[CF2],F
n Mol. wt. m.p. (C) b.p. (Wmbar) dd (g/cm3)/C Refs.
1 88.0 - 183.6 - 128/1005 1.619/- 129 22,49,63,64,125,130,179
2 138.0 - 96.6 - 78.311013 1.590/- 7 8 49,50,63,64,125,130,154,179
3 188.0 - 147.7 - 36.711013 22,51,52,64,125,130,131,179
4 238.0 - 129.2 - 2.211013 22,52-54,64,125,126,129,132,139,144,179,241
5 288.1 - 125.4 29.211013 1.620/20 22,52,54-56,124,129
6 338.1 90.7 57.211013 1.6995120 22,52,57,58,124-126,134,144,175,179
7 388.1 93.3 82.211013 1.7333120 22,52,56,59,125,128,134,144,175,179
8 438.1 - 19.0 103.3/1013 1.776125 22,52,59,125,134,144,175,179
9 488.1 - 16 125.3/1013 1.799125 22,52,59,127
10 538.1 36 144.2/1013 1.770145 22,52,59,127
11 588.1 57 161/1013 1.745170 22,52,59
12 638.1 75.3 178/1013 1.670/113.5 22,52,59,127,175,179,250,251
14 738.1 IR, Raman spectr. 124,127,133,179,240,249
16 838.2 129.0 232/1013 54,59,127,175
18 938.2 IR, Raman spectr. 124,127,133
20 1038.2 164.7 IR, Raman spectr. 124,127,133,175,179,243-245,249,252
24 1238.2 192.0 IR, Raman speck 175,242,243,245
1.2.2. PERFLUORO-CYCLOALKANES r[CH&l
n Mol. wt. m.p. (C) b.p. (C/mbar) Refs.
3 150.0 - 80 - 31.5/1013 60,61
4 200.0 - 38.7 - 211013 61,63,144
5 250.0 10.3 22.5/1013 51,54-56,61,64
6 300.0 58.2 51 (subl.) 51,56,59,64,65,144
7 350.0 - 37 76.211013 51,59
8 400.0 -55 101.5/1013 5 9
9 450.0 -56 124.6/1013 5 9
10 500.0 -44 146.5/1013 5 9
1.2.3. c(,o-DISUBSTITUTED PERFLUORO-n-ALKANES X-[CF2],-X
x n Mol. wt. m.p. (C) b.p. (Wmbar) Refs.
CH3S
H 1 52.0 - 51.6/1013
2 102.0 - 20/1013 144,145
3 152.0 lo-11/1013 146
4 202.0 43.5/1013 135-137,144
5 252.1 66.5/1013 136
6 302.1 88.5-89.5/1013 135-137,144
7 352.1 104.2/1013 136,137
8 402.1 130.6/1013 136,137
10 502.1 42-43 153-154/1013 135-137
2 194.2 67-70153 135
4 294.2 80-83127 135
6 394.3 81-84/5 135
8 494.3 102- 106/5 135
10 594.3 90-9411 135
12 694.3 118-122/1 135
CHsS02 2 258.4 1 2 5 1 3 5
4 358.4 1 5 1 1 3 5
6 458.5 168 1 3 5
8 558.5 1 7 1 1 3 5
10 658.5 187 1 3 5
CH3CO0 4 318.1 115-116/133 1 3 5
6 418.1 121-123167 1 3 5
8 518.1 126-127133 1 3 5
10 618.2 144146133 1 3 5
HOCHs 2 164.1 1 3 5
4 264.1 1 3 5
81-82
6 9 135-136/36
Ol i gomers Cont ai ni ng Mai n Chai n Acycl i c Carbon Onl y IV/7
1.2.3. contd
x n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
I 2 353.8 113/1013 2 3 6
4 453.8 149/1013 2 3 6
6 553.8 186/1013 2 3 6
8 653.8 22211013 2 3 6
1 0 753.8 25811013 2 3 6
1.2.4. a,o-DISUBSTITUTED PERFLUORO-n-ALKANES WITH DIFFERENT ENDGROUPS X-[CF2].-Y
x Y n Mol. wt. m.p. b.p. (Urnbar) diO (g/cm3) Refs.
H Cl 2 136.5 - 10/1013 6 1
3 186.5 21/1013 1.556 6 1
4 236.5 50/1013 1.607 6 1
5 286.5 7711013 1.661 6 1
6 336.5 100/1013 1.719 6 1
7 386.5 122.5/1013 1.738 6 1
8 436.5 144.5/1013 1.778 6 1
9 486.5 162.5/1013 6 1
1 0 536.5 4 6 162.5/1013 6 1
1 1 586.5 5 2 17711013 6 1
1 2 636.5 7 8 202/1013 6 1
1 3 686.5 8 7 213/1013 6 1
1 4 736.5 9 5 227-22811013 6 1
H F 2 120.0 - 48.5/1013 240,252
3 170.0 - 16/986 2 4 0
4 220.0 141986 2 4 0
5 270.0 461986 2 4 0
7 370.0 941986 2 4 0
1 2 620.0 7 2 250,25 1
(CFdzCF I 4 495.9 139/1026 237
6 596.0 189/1008 237
1.2.5. SEMIFLUORINATED n-ALKANES F-[CF21m-[CH2],-H
m n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
1
6
7
8
1 0
1 0
1 0
1 0
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1
1 2
7
8
8
1 0
1 2
2
4
6
8
1 0
1 2
1 4
1 6
1 8
2 0
84.0
488.3
468.3
532.3
540.3
632.4
660.4
688.4
648.2
676.2
704.3
732.4
760.4
788.4
816.5
844.5
872.6
800.6
-
- 13.0
27.0
3 5
53.0
6 4
6 5
71.0
76.0
8 4
8 8
9 2
9 1
9 3
9 4
9 7
100
46.711013 155,176
138,176
255
138,176
251
138,176
138,176,251,255
138,176,251
138,176,250,251,255
138,176,250,251,255
138,176,250,251,255
138,176,251
138,176,251
138,176,250,251,255
138,176,251
138,176,251
138,176,251
138,176,250,251,255
1.2.6. ANIONIC OLIGOMERS OF PERFLUORO-n-ALKENES (MAJOR OLIGOMERS, cisltruns MIXTURES)
n Compound Mol. wt. b.p. (Wmbar)
CF2 = CF2 (Refs. 238,239,243):
4 CF3CF2-C(CF3)=C(CF3)-CFTCF3 400.1 95-96/1013
5 (CF3CF2)2(CF3)C-C(CF3)=CF(CF3) 500.1 135-138/1012
WI8
PHYSICAL DATA OF OLIGOMERS
1.2.6. contd
n Compound
6 (CF3CF2)2(CF3)C-C-CF(CFzCF3),
I I
CF2
Mol. wt. b.p. (Wmbar)
600.1 SO-165/1013
CFs-CF=CFz (Refs. 253,254,257):
2 (CF3)2CF-CF=CF-CF3
(CF3)*C=CF-CF2-CF3
3 (CF3)2C=C(CF2-CF3-CF(CF3)2
[(CF3) 2CF] 2C=CF-CF3
(CF3)2CF-CF=C(CF3)-CF2-CFz-CF3
1.2.7. PERFLUORO-l-ALKENEB F-[CF2],-CF=CR2
300.1 46-48.5/1013
46-48.511013
450.1 114.8/1013
llO-115/1013
llO-115/1013
n Mol. wt. b.p. at N 983 mbar (C)
1 150.0 , - 2 9
2 200.0 1
3 250.0 28-29
5 350.0 8 1
7 450.1 123
Conformation; Crystallization: Refs. 126,179,242,243-245,251.
Phase transition, DSC: Refs. 55,125,138,175,176,179,242,244,245,249,251.
NMR: Refs. 134,179,250,251.
X-ray: Refs. 65,138,175,176,179,244,245.
I R, Raman: Refs. 125-127,133,138,175,176,241,242,245,249,250,255.
MS: Ref. 56.
e
1.2571
1.2782
1.2868
Refs.
240
240
240
240
240
1.3. OLIGO(ISOBUTENES)
Compound m.p. (C)
MONOMER (mol. wt. 56.1)
Isobutene CH z=C(CH 3) 2
DIMERS (mol. wt. 112.2; Refs. 66-70,72,74,122,141,143,147,148,150-152,153)
2,4,4-Trimethyl-l-pentene
CH2=C-CH2C(CH3)3
AH3
- 93.6
b.p. (C/l013 mbar)
- 6
101.4
df (g/cm31
0.7150
2,4,4-Trimethyl-2-pentene
CH3-C=CH-C(CH3)3
AH3
3,4,4-Trimethyl-2-pentene
CH3- CH= C- C(CH3)3
a3
2,3,4-Trimethyl-2-pentene
P%C= y- CHPW2
CH3
2,3,4-Trimethyl-l-pentene
CH2=C-CH(CH3)2
I I
a3CH3
2,3,3-Trimethyl-l-pentene
CHFC-C(CH~)~-CH~-CH~
CH3
1,1,3-Trimethyl-cyclopentane
, CH2- CH2
(cH3)2c, 1
CH2- CH- CH3
- 106.5 104.9 0.7212
112.3 0.7392
- 113.4 116.3 0.7434
108 0.729
- 6 9 108.4 0.7352
105.0 0.7481
References
ml9
1.3. contd
Compound m.p. (C)
TRIMERS (mol. wt. 168.3, Refs. 71,73,74,123,140,142,143,147-149,151,152)
l,l-Dineopentylethylene
CH2=C[CH2WH3)212
2,2,4,6,6-Pentamethyl-3-heptene
(CH3)3C- CH= C- CH2- C(CH3)3
CH3
TETRAMERS (mol. wt. 224.4; Refs. 74,141-143,147,151,152)
2,2,6,6,8,8-Hexamethyl-4-methylene-nonane
(CH3)3C-CHz-F;-CH2-C(CH&-CH~-C(CH3)3
CH2
2,2,4,6,6,8,8-Heptamethyl-4-nonene
(CH3)3C- Hz-T= CH-C(CH3)2-CH2-C(CH3)3
CH3
b.p. (C/l013 mbar)
178.0/1013
13C-NMR
106-107/11
13C-NMR
13C-NMR
die (g/cm3)
0.7599
1. 4. OLIGO(l-ALKENYLENES)
x n Configuration Mol. wt. m.p. (C) b.p. ( Urnbar) ng Refs.
2 2 cisltrans 108.2 - 7 0 150.8/1002
3 cisltrans 162.3 104115
4 cisltrans 216.3 8%91/0.07
5 cisltrans 270.4 105-110/0.07
6 cisltrans 324.5 162/0.1
n =4-13 cisltrans GC Refs. 161,166
n =4-7,10,11 cisltrans H-, 13C-NMR Ref. 161
3 2 cis 136.2 21-23
4 2 cis 164.3 0 51/0.5 (cisltrans)
3 cisltrans 246.4 11210.5
4 cis 328.6 25-27
5 2 cis 192.3 4 6 48/0.001 (cisltrans)
3 cisltrans 288.5 116/0.001
6 2 cis 220.4 18.5 89/0.07 (cisltrans)
3 cisltrans 330.6
n=2-8 (cisltrans): GPC, b.p., nr, IR, UV, MS Refs. 158-160
130/0.07
7 2 cis 248.4 38.5 12210.4 (cisltrans)
8 2 cis 276.5 38-39 123-124/0.2 (cisltrans)
1 0 1 cisltrans 166.3 100/0.11
2 cisltrans 332.6 54-55 150/0.09
transltrans IR: 970 cm-
translcis 970, 725 cm-
cislcis 725 cm-
3 cisltrans 498.3 22010.12
4 cisltrans 665.2 25510.12
n = 2-14: MS Refs. 167,168
n=2-9: GPC Ref. 160
1 3 n = 2-7: MS Ref. 166
163,170-172
164,173,174
161,164
161,164
1 6 1
1.4972 162
1.4971 40,157,162
1 5 7
4 0
40,157
1 5 7
40,157,158
157,158
40,157
40,157
156
156-158,160
156
156
156
156
156
REFERENCES
1. F. Krafft, Chem. Ber., 15, 1687, 1711 (1882); 19, 2218
(1886); 40, 4479 (1907).
2. A. Gascard, Ann. Chim. (Paris) (9), 15, 332 (1921).
3. A. Mueller, Proc. Roy. Sot. (London) A, 120, 437 (1928);
127, 417 (1930); 138, 514 (1932).
4. J. H. Hildebrand, A. Wachter, J. Am. Chem. Sot., 51, 2487
(1929).
5. G. S. Parks, H. M. Huffmann, S. B. Thomas, J. Am. Chem.
Sot., 52, 1032 (1930).
6. W. H. Carothers, J. W. Hill, J. E. Kirby, R. A. Jacobsen, J.
Am. Chem. Sot., 52, 5279 (1930).
7. W. E. K. van A. M. J. Chem. Gramer, Bibber, King, Sot.,
1533 (1931).
8. H. F. Chem. Ber., 68, 707 Staudinger, Staiger, (1935).
IV/l0 PHYSICAL DATA OF OLICOMERS
9. F. Francis, A. M. King, J. A. V. Willis, J. Chem. Sot., 999
(1937)
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IV/14 PHYSICAL DATA OF OLIGOMERS
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TABLE 2. OLICO(DIENES)
2.1. OLIGOMERS OF 1,3-BUTADIENE
252. D. S. Young, N. Fukuhara, L. A. Bigelow, J. Am. Chem.
Sot., 62, 1171 (1940).
253. W. Brunskill, W. T. Flowers, R. Gregory, R. N. Haszeldine. J.
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Chem., 9, 94 (1977).
Oligomers n Mol. wt. m.p. (C) b.p. (Wmbar) ?lDPC Refs.
LINEAR DIMERS 2 1 0 8 . 2
3-Methyl-1-truns-4,6-heptatriene
CH*=CH-CH(CH3)-CH=CH-CH=CH*
1,3,6-Octatriene
CH*=CH-CH=CH-CH2-CH=CH-CH3
1,3,7-Octatriene
CH*=CH-CH=CH-CH2-CHz-CH=CHz
tram
cis
2,4,6-Octatriene (cisltmns)
CH3-CH=CH-CH=CH-CH=CH-CH3
all-tram
A 3,3-Octahydro-diphenyl 3 162.3
Vinylcyclopolyenes r [(CH$H= CHCH&CH(CHCH$CH$
4-Vinyl-1-cyclohexene 2 1 0 8 . 2
(x= 1)
17-Vinyl-all-tram-1,5,9,13-cyclo- 5 270.4
octadecatetraene
(x = 4)
21-Vinyl-all-trans-1,5,9,13,17- 6 3 2 4 . 5
cyclodocosapentaene (X = 5)
1,2-Divinyl-cyclobutane 2 1 0 8 . 2
cis -
PI
-
t ram
4-
CYCLOPOLYENES r [CHz- CH= CH- CH21nl
1,5-Cyclooctadiene 2 1 0 8 . 2
cis,cis
tmns,trans
1,5,9Xyclododecatriene 3 162.3
trans,trans,trans
cis,trans,trans
cis,cis,trans
All-truns-1,5,9,13-cyclohexadecatetraene 4 216.4
All-trans- 1,5,9,13,17-cycloeicosapentaene 5 270.4
All-trans.1,5,9,13,17,21-cyclotetracosahexaene 6 3 2 4 . 5
117/1013 1.4657120 13,14,33,35,36,38
129/1013 1.4743120 3 3 . 3 6
124-125/1013
115-117/1013
65-66153
5 2 . 5 147-148/1019
230-232/1013
129-130/1013 1.4642120 l-7,34-37,44,48,49
- 13611.3 1.5093/20 3 7
N 17011.3 1.5098/20 3 7
38/51 1.4563 1,8,48,49
112-113/1013 1.4451/20 8,44,48,49
- 70. 1 150.8/1002 1 . 4 9 3 6 1 2 0
- 6 2 1.4933120
3 4 237.511013 1.5005/20
- 16.8 241.5/1013 1.5078/20
-9to-8 24411013 1.5129/20
19-20 -9711 1.507/20
N 14211 1.5133/20
-17611 1.5133/20
1 . 4 6 8 6 1 2 0
1 . 4 5 9 4 1 2 0
1.5131/27
31,32,35,36,39
3 9
3 9
34,40,41
34,40,41
42,43
1,3-10,35-37
1,48,9
4
5-7,10-12,35-37
5-7,12,45,46
5,6,12,45-47
6,12,46
3 7
3 7
3 7
2. 2. OLIGOMERS OF ISOPRENE
Oligo(dienes) IV/15
Oligomers n Mol. wt. b.p. (Urnbar) Il~/C Refs.
LINEAR OLIGOMERS
2,7-Dimethyl-1-trans-3,7-octatriene
CH2=C(CH3)-CH=CH-CH2-CH2-C(CH3)=CH2
2,6-Dimethyl-1,3,6-Octatriene
CH2=C(CH3)-CH=CH-CH2-C(CH3)=CH-CH3
2,7-Dimethyl-1-trans-3,6-octatriene
CH2=C(CH3)-CH=CH-CH2-CH=C(CH3)-CHj
2,6-Dimethyl-1-trans-3,7-octatriene
CH2=C(CH3)-CH=CH-CH2-CH(CH3)-CH=CH2
3-Methyl-6-methylene-1,7-octadiene
CH2=CH-C(CH3)-(CH2)2-C(=CH2)-CH=CH2
2,6,10-Trimethyl-1-trans-3,5,10-dodecatetraene
CH2=C(CH3)-CH=CH-CH=C(CH3)-(CH2)3-C(CH3)=CH-CH3
7,1l-Dimethyl-3-methylene-l-trans-6,1l-dodecatriene (p-famesene)
CH2=C(CH3)-(CH2)3-C(CH3)=CH-(CH2)2-C(=CH~)-CH=CH2
2,6,10,14-Tetramethyl-l-truns-3,6,10,14-hexadecapentaene
CH2=C(CH3)CH=CH-[CH2C(CH3)=CHCH2]3=H
CYCLIC OLIGOMERS
trans-1,2-Dimethyl-1,2-divinylcyclobutane
/
&
/
truns-1-Isopropenyl-2-methyl-2-vinylcyclobutane
/
+
/
trans-1,2-Diisopropenylcyclobutane
4-Isbpropenyl-1-methyl-1-cyclohexene (dipentene) (D,L)
\
I
/
6-Isopropenyl-3-methyl-1-cyclohexene (diprene) (D,L)
\A
C
2,4-Dimethyl-4-vinyl-I-cyclohexene
1,4-Dimethyl-Cvinyl- 1-cyclohexene
cis,cis 1,5-Dimethyl-1,5-cyclooctadiene
cis,cis 2,5-Dimethyl-1,5-cyclooctadiene
2 136.3 134.5-1351992 1.4541127 49
136.3
136.3
136.3
136.3
136.3
204.3
204.3
272.5
176/1013 1.4721125 50,5 1
57-58116 1.4794 6,30,52,27
54113 1.4786120 11,29,30
167/1013 1.4704125 50
161/1013 1.4570125 50
7811.3 1.4963120 53
7011.3 1.4786120 5 3
160/1.3 1.5013/20 5 3
2 136.3 152.5-1531992 1.4591127 49
2 136.3 155.1-155.41987 1.4585129 49
2 136.3 17811013 1.4727118 15- 17,
55,62,71
2 136.3 173-175/1000 1.4735120 15,16,
59,71
2 136.3 162/1000 1.4654120 11,29,30,
49,55,
58-60,71
2 136.3 160.5-161.5/988 1.4658128 11,17,30,
49,53,55,
57-59,71
2 136.3 182.41988 1.4863128 49,54,
56-59,71
2 136.3 182.5-1841992 1.4870127 49,54,
56-59,71
IV/16 PHYSICAL DATA OF OLICOMERS
2.2. contd
Oligomers n Mol. wt. b.p. (Wmbar) n OPC Refs.
1,5,10-Trimethyl-cis,trans,trans-1,5,9-cyclododeca~ene 3 204.3 138111 1.5120 6 1
2. 3. OLIGOMERS OF l&BUTADIENE DERIVATIVES
Monomer Oligomers n Mol. wt. m.p. (C) b.p. (Wmbar) lZ#C Refs.
2-Chloro-1.3-butadiene
2,3-Dichloro-1,3-butadiene
Hexafluoro-1,3-butadiene
C l
3,4,7,8-Tetrachloro-1,5-cyclooctadiene
Cyclic dimer
2-Cyano-1,3-butadiene 4-Vinyl- 1,4-dicyano- 1 eyclohexene
NC
I-Phenyl-1,3-butadiene 3-Phenyl-4-trans-styryl-1-cyclohexene
2-Phenyl-1,3-butadiene l,CDiphenyl-4-vinyl-I-cyclohexene
1,3-Diphenyl-1,3-butadiene 1,3,4-Triphenyl-4-trans-styry-I-cyclohexene
I-Chloro-4-(wchloro-vinyl)-1-cyclohexene
0
C(Cl)= CH2
Cl \
1,6-Dichloro-1,Scyclooctadiene
C l
CsHs
CH= CHC,jHs
CSHS
177.1 5311.2 1.5 135 125 63-66
177.1 13.8 6410.33 1 . 5 3 3 9 1 2 5 9,63-66
246.0 98-99 140- 146/4.8 6 3
324.1 40 so/1013 20,21
1 5 8 . 2 55-56 llO-112/1.3 69
260.4 189-191/3 6 7
260.4 6 0 220-222111 6 8
412.3 137-138 IS,19
2.4. 1,4-OLIGO(ALKADIENES) CH3CH2-[CH2-CX=CH-CH21,-CH2CH3
x n Configuration Mol. wt. b.p. (Wmbar) n&T Refs.
H 1 cis 112.2 121.7/985 1.4136120 87
trans 1 2 1 . 4 1 9 8 5 1.4116/20 8 7
2 All-& 166.3 90-91123 1.4455123 85
All-trans 87-88/23 1 . 4 4 1 5 1 2 4 85
3 All-cis 220.4 120-12512 1.4638/19 8 6
CH3 1 1 2 6 . 2 138-140/1013 1.4224120 7 5
2 194.3 9217 1.4540/20 7 5
3 2 6 2 . 5 98/0.3 1.4729120 7 5
4 330.6 140/0.2 1.4878/16 15
2.5. OLIGOMERS OF CYCLOPENTADIENE AND 1,3-CYCLOHEXADIENE
Oligo(dienes) Iv/17
Oligomers n Mol. wt. m.p. (C) b.p. (Urnbar) IlLJT Refs.
Dicyclopentadiene 2 1 3 2 . 2 8 4
3 2 163/1021 22,23,49,10,14
exo 1
endo 4
170/1017 1.5070/25 49,70,72
Tricyclopentadiene 3 198.3 6 8 251/1021 22,23,14,84
Tetracyclopentadiene 4 264.4 2 0 7 34411021 22,23,74,84
truns-Tricyclo[5,3,0,0*$3$decadiene 2 132.2 170-172/1013 1.5080/25 49,70
Dicyclohexadiene 2 160.3 22911013 22,13,74
2.6. OLIGOMERS OF ALLENE
Oligomers n Mol. wt. m.p. (C) b.p. (Urnbar) ?l#T Refs.
DIMERS 2 80.1
l$Dimethylene-cyclobutane 7411013 1.4690/20 24-27,77,81,82
<
1,3-Dimethylene-cyclobutane 69/1013 1 . 4 4 8 5 1 2 0 77-80
3 1 2 0 . 2
1,2,4-Trimethylene-cyclohexane 68-69/80 1 . 4 9 1 9 1 2 5 76,ll ,
1,3,5-Trimethylene-cyclohexane 33.5-35 68-69/80 1 . 4 9 1 9 1 2 5 16
71
17
UV, H-NMR, MS
IR, UV, H-NMR, MS
3-Methylenebicyclo-[4,2,0]-octa-1(6)-ene
a
1.5-(or 1,6-)-Dimethylenespiro-[3,3]heptane
TETRAMERS 4
2,6- + 2,7-Dimethylenebicyclo-[4,4,0]-dec-9,10-ene (fi-tetramer)
160.3
107-108/17 1 . 5 2 4 8 1 2 5 24,25,28,60,83
IV/l8 PHYSICAL DATA OF OLIGOMERS
2 . 6 . contd
Oligomers n Mol. wt. m.p. (C) b.p. (CYmbar) I8 DPC Refs.
1,3,5,7-Tetramethylene cyclooctane 6014.7 1 . 5 1 0 2 1 2 5 7 6
PENTAMERS 5 200.4
6-Methylene-3,4,7,8-tetrahydrospiro[2- and 3-methylenel-cyclobutane-1,2(1 H,5H)-naphthalene + 7-methylene-3,4,5,6-tetrahydrospiro[2- and
3-methylenelcyclobutane-1,2-(1 H$H)-naphthalene 7310.03 1.5307/20 24,88
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Japan, 39, 2425 (1966).
57.
58.
59.
S. Watanabe, K. Suga, H. Vikuchi, Austr. J. Chem., 3,385 (1970).
L. I. Zakharkin, G. G. Zhigareva, Izv. Akad. Nauk SSSR, 168,
(1964); Bull. Akad. Sci. USSR, 149 (1964).
J. L. Binder, K. C. Eberly, G. E. P. Smith, Jr., J. Polym. Sci., 38,
229 (1959).
60. S. Lebedev, Zh. Russ. Fiz.-Khim. Obshch., 45, 1249 (1913);
C. 1914 I, 1406; J. W. Lebedew, A. A. Ivanov, ibid., 48,997
(1916); C. 1923 I, 1539.
61. Y. Tanaka, H. Sato, Y. Nakafutami, H. Iwasaki, T. Taketomi,
Polym. J., 14, 713 (1982).
62. G. S. Whitby, R. N. Crozier, Can. J. Res., 6, 203 (1932).
63. R. E. Foster, R. S. Schreiber, J. Am. Chem. Sot., 70,2303 (1948).
64. J. G. T. Brown, J. D. Rose, J. L. Simonsen, J. Chem. Sot., 10
(1944).
65.
Oligo(acetylenes) IV/19
A. C. Cope, W. R. Schmitz, J. Am. Chem. Sot., 72, 3056
(1950).
66.
67.
68.
69.
70.
A. L. Klebanskii, M. M. Denisova, Zh. Obshch. Khim. SSSR,
17, 703 (1947); Chem. Abstr. 42, 1215~ (1948).
K. Alder, J. Haydn, W. Vogt, Chem. Ber., 86, 1302 (1953);
C. Liebermann, C. N. Riiber, Chem. Ber., 35, 2696 (1902).
K. Alder, J. Haydn, Ann. Chem., 570, 201 (1950).
C. S. Marvel, N. 0. Brace, J. Am. Chem. Sot., 71, 37 (1949).
N. J. Turro, G. S. Hammond, J. Am. Chem. Sot., 84, 2841
(1962).
71.
72.
73.
74.
75.
76.
I. N. Nazarov, A. I. Kuznetsova, N. V. Kuznetsov, Zh. Obshch.
Khim. SSSR, 25,291 (1955); J. Gen. Chem., 25,307 (1955).
P D. Bartlett, I. S. Goldstem, J. Am. Chem. Sot., 69, 2553
(1947); I? D. Bartlett, A. Schneider, J. Am. Chem. Sot., 68,6
(1946); H. A. Bruson, T. W. Riener, J. Am. Chem. Sot., 67,
723, 1178 (1945), 68, 8 (1946).
K. Alder, G. Stein, Ann. Chem., 496, 197 (1932).
K. Alder, G. Stein, Chem. Ber., 67, 613 (1934).
C. Pinazzi, D. Reyx, Bull. Sot. Chim. France, 3930 (1972).
R. E. Benson, R. V. Lindsey, Jr., J. Am. Chem. Sot., 81,4247
(1959).
77.
78.
79.
B. Weinstein, A. H. Fenselau, J. Chem. Sot. C, 368 (1967).
F. F. Caserio, Jr., S. H. Parker, R. Piccolini, J. D. Roberts, J.
Am. Chem. Sot., 80, 5507 (1958).
J. K. Williams, W. H. Sharkey, J. Am. Chem. Sot., 81,4269
(1959).
80.
81.
Y. M. Slobodin, A. l? Khitrov, Zh. Obshch. Khim., 33, 153
(1963); J. Gen. Chem. USSR, 33, 146 (1963).
A. T. Blomquist, J. A. Verdol, J. Am. Chem. Sot., 77, 1806
(1955).
82.
83.
84.
85.
Y. M. Slobodin, A. P. Khitrov, Zh. Obshch. Khim., 33, 2819
(1963); J. Gen. Chem. USSR, 33, 2745 (1963).
B. Weinstein, A. H. Fenselau, J. Org. Chem., 32,2278 (1967).
H. Staudinger, A. Rheiner, Helv. Chim. Acta, 7, 23 (1924).
C. Pinazzi, D. Reyx, G. Levesque, C. R., Ser. C, 270, 2120
(1970).
86.
87.
C. Pinazzi, D. Reyx, C. R. Ser. C, 274, 252 (1972).
K. N. Campbell, L. T. Eby, J. Am. Chem. Sot., 63, 2683
(1941).
88. B. Weinstein, A. H. Fenselau, J. Org. Chem., 32,2988 (1967).
TABLE 3. OLICO(ACETYLENES)
3.1. LINEAR OLIGOMERS OF ACETYLENE
Vinylacetylene
CH2=CH-C= CH
Divinylacetylene
CH2=CH-C-C-CH=CH2
1,3-Hexadiene-5-yne cisltrans
CH2=CH-CH=CH-C= CH
1,3,7-Octatriene-5-yne
CH2=CH-CH=CH-C- C-CH=CH2
(E)-: GC; H-, 13C-NMR; Ref. 7
(Z)-: GC; H-, 13C-NMR; Ref. 7
n Mol. wt. b.p. (Urnbar) d (g/cm3)/C
2 5 2 . 1 5/1009 0.705/0
3 7 8 . 1 84%85/1013 0.772120
3 7 8 . 1 81-82/1013 0.780/28
4 105. 1 10127 0.830/20
6
1. 5055
1.4900
1.5834
Refs.
12
1-3
1,2,4-6,25
1,2,7
IV/20 PHYSICAL DATA OF OLIGOMERS
3.2. POLYENYNE OLIGOMERS (CH3)3C-[C=C-CH=CH],-C~C-C(CH3)3
n Mol. wt. m.p. (C) Refs.
1 188.3 69-72 26
2 238.4 118-120 26
3 288.4 155-156 26
5 388.5 220 d 26
7 488.6 204 d 26
3.3. OLIGOMERIC a,w-DIYNES H[C = C-(CH2)x-C = C] .H
x n Mol. wt. m.p. (C) b.p. (Urnbar) nDPC Refs.
1 1 64.1
2 126. 1
3 188.2
2 1 78. 1
2 154.2
4 30.4
3 1 92. 1
2 182. 3
4 362.5
4 1 106.2
2 210.3
4 418.6
5 1 120.2
2 238.4
6 1 134.2
2 266.4
4 530.8
-2oto-19
65-66
103-104
99-100
167-168 d
- 84.8
--5
60-61
21-22
93-94
- 27.3
21-22
30-31
59-61
63-64/1013
87.5-88.5/1011
111.5/1013
llO-111/0.9
93-951253
119-120/0.1
162/1013
68-71/18
8
839
8
1.4381/23 1 0
11-14
11,12
1.4423/20 1 5
11,12
11,12
1.4521/18 1 6
1.5205/23 11,17
11,17
1.4490/20 1 5
1.5119/26 11.12
1 8
11,12
11,12
3.4. OLIGO(ALKYNES) H[C - C-(CH2)J n-C - CH
x n Mol. wt. m.p. (C) b.p. (Urnbar) PlDlC Refs.
1 1 64. 1
2 102. 1
3 140.2
4 178.2
6 254.3
1 78. 1
2 130.2
1 106.2
2 186.2
3 266.4
7 586.9
8 667.0
5 1 120. 2
2 214.3
3 308.5
6 1 134.2
2 242.4
-21 to - 19
21-21.5
44-45
73-74
112-113.5
46
- 3
1 9
3 6
5 5
- 27.3
8
3 3
2 4
63-6411013
1.4833 122
87.5-88.5/1011
61-6313
93-951253
111/1.3
16710.4
162/1013
113/1.1
170/0.1
68-71/18
13110.3
1.4381123
1.4521/18
1.4775125
1.4918125
1.4490/20
1.4791126
1.4806/25
8
8
8
8
8
1 0
1 9
1 6
9
9
9
9
1 5
9
9
1 8
9
3.5. CYCLIC OLIGO(ALKYNES) r[(CEC),-(CH&]q
X
Y
n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
1 4 2 160.2 3 9 8710.3 9,20,21
4 320.5 7 1 21510.3 9,20
5 2 188. 3 1 0 0 loo-110/0.001 9,20
6 2 216.4 - 3.5 1 lo- 120/0.001 2 0
7 2 244.4 9 7 160- 180/4 2 0
8 2 272.5 38-39 145-147/0.01 2 0
9 2 300.5 106. 5 198-202/0.001 2 0
Ref erences IV/21
3. 5. contd
x
Y
n Mol. wt. m.p. (C) b.p. (Wmbar) Refs.
2 2 3 228. 3 175- 180 d 14
4 304. 4 170- 180 d 14
5 380. 5 165 d 14
6 456. 6 - 180 d 14
7 532. 6 - 180 d 14
3 2 180. 2 115-120 (expl.) 11. 12
3 270. 4 174- 175 13
4 360. 5 213- 214 13, 22
4 2 208. 3 163 12,13,17,20,22
3 312. 4 173- 174 13, 22
4 416. 6 154- 155 13, 22
5 520. 7 155- 157 13. 22
5 2 236. 3 212 l l - 13, 20, 22
3 354. 5 125- 126 13. 22 -
4 472. 7 135- 136 13, 22
5 590. 9 144- 145 13, 22
6 709. 0 144- 145 13. 22
6 2 264. 4 82 12, 20, 22
3 396. 6 135- 136 22
4 528. 8 152- 154 22
7 2 292. 4 171 20
8 2 320. 5 85 20, 22
9 2 348. 5 142 20
10 1 188.3 18 23
2 376. 6 101-102 23
3 5 2 284. 4 >200 20
3. 6. PEFUCYCLYNES [C=C- C(CH&
n Mol. wt.
5 330.5
6 396.6
7 462.1
8 528.8
m.p. (C) Refs.
201-202 24
249-250 24
173-174 24
189-190 24
REFERENCES
1. J. A. Nieuwland, W. S. Calcott, F. B. Downing, A. S. Carter, J. 12. F. Sondheimer, Y. Amiel, R. Wolovsky, J. Am. Chem. Sot., 79,
Am. Chem. Sot., 53, 4197 (1931). 6263 (1957).
2. K. K. Georgieff, W. T. Cave, K. G. Blaikie, J. Am. Chem. Sot., 13. F. Sondheimer, Y. Amiel, R. Wolovsky, J. Am. Chem. Sot., 79,
76, 5494 (1954). 4247 (1957).
3. R. Lespieau, Guillemonat, Koll.-Z., 63, 84 (1933).
4. D. A. Ben-Efraim, F. Sondheimer, Tetrahedron, 25, 2837
(1969).
14. F. Sondheimer, R. Wolovsky, J. Am. Chem. Sot., 84, 260
(1962).
5. J. H. Van Boom, L. Brandsma, J. F. Arens, Rec. Trav. Chim.
Pay-Bas, 85, 952 (1966).
6. F. Sondheimer, D. A. Ben-Efraim, Y. Gaoni, J. Am. Chem.
Sot., 83, 1682 (1961).
7. H. Hopf, L. Eisenhuth, V. Lehne, L. Ernst, Chem. Ber., 119,
1105 (1986).
8. D. A. Ben-Efraim, F. Sondheimer, Tetrahedron, 25, 2823
(1969).
9. J. H. Wotiz, R. F. Adams, C. G. Parsons, J. Am. Chem. Sot.,
83, 373 (1961).
10. R. A. Raphael, F. Sondheimer, J. Chem. Sot., 120 (1950).
11. Y. Amiel, F. Sondheimer, R. Wolovsky, Proc. Chem. Sot.,
1957, p. 22.
15. A. L. Henne, K. W. Greenlee, J. Am. Chem. Sot., 67, 484
(1945); R. Lespieau, Joumaud, Compt. Rend., 188, 1410
(1929).
16. H. Bader, L. C. Cross, I. M. Heilbom, E. R. H. Jones, J. Chem.
SOL, 619 (1949).
17. F. Sondheimer, Y. Amiel, J. Am. Chem. Sot., 79,5817 (1957).
18. W. M. Lauer, W. J. Gensler, J. Am. Chem. Sot., 67, 1171
(1945).
19. F. Sondheimer, Y. Gaoni, J. Am. Chem. Sot., 84,352O (1962).
20. J. Dale, A. J. Hubert, G. S. D., King, J. Chem. Sot., 73, (1963).
21. D. J. Cram, N. L. Allinger, J. Am. Chem. Sot., 78, 2518
(1956).
22. F. Sondheimer, Y. Amiel, R. Wolovsky, J. Am. Chem. Sot., 81,
4600 (1959).
IV/22 PHYSICAL DATA OF OLICOMERS
23. G. Egl i nt on, A. R. GaIbraith, J. Chem. Sot., 889 ( 1959) ; Chem 25. A. L. Klebanskii, U. A. Dranitzina, I. M. Dobromilskaya,
& Ind., 737 (1956). Compt . Rend. Acad. Sci . USSR, 2, 229 (1935); Chem, Abst r. ,
24. L. T. Scott, G. J. DeCicco, J. L. Hyun, G. Reinhardt, J. Am.
29, 6205 (1935).
Chem. Sot., 105, 7760 (1983); 107, 6546 (1985). 26. F. Wudl, S. F? Bitler, J. Am. Chem. Sot., 108, 4685 (1986).
TABLE 4. OLIGOMERS WITH ALIPHATIC SIDE CHAINS WHICH IN ADDITION CONTAIN HETEROATOMS
4.1. OLIGOMERIC ACRYLIC DERIVATIVES
4.1.1. OLIGO(ACRYLIC ACIDS)
4.1.1.1. H[CH2CH(COOH)].CH3
n Mol. wt. Configuration m.p. (C) b.p. ( Urnbar) Refs.
1 8 8 . 1
2 160.2
3 232.2
lsotactic (meso)
Syndiotactic (racemic)
Isotactic (meso)
Heterotactic (racemic)
Syndiotactic (meso)
- 4 6 153/1012
1 2 8 l-3,ll
1 4 1 l-3,ll
167.5-170.0 3,78
160.0-163.0 3,78
153.5-154.5 3,78
4.1.1.2. (CH,),C(COOH)-[CH2CH(COOH)].-C(COOH)(CH3)2
n Mol. wt. m.p. (C) Refs.
1 246.3 30-35 4
2 318.3 70-80a 4
3 390.4 181-183 4
4 462.5 80-82 5
ap-Nitrobenzyl ester.
4.1.2. OLIGO (ACRYLATES)
4.1.2.1. H[CH2CH(COOH)].CH3
n Mol. wt. Configuration b.p. (Urnbar) nJC Refs.
1 1 0 2 . 1
2 188.2
3 274.3
Isotactic (meso)
Syndiotactic (racemic)
Isotactic (meso)
Heterotactic (racemic)
Syndiotactic (meso)
91.51990 1.3838/20 6
6410.9 1.4258 3,6,101
NMR 3
163115 1.4440 3,6,78
160/15 1.4420 3,6,78
156115 1.4407 3,6,78
4.1.2.2. Anionic Oligomers RO[CH2CH(COOR)] .H
R n Mol. wt. b.p. (Wmbar)
CH3 1 1 1 8 . 1 55-56127
CH3 2 204.2 9011
C2H5 1 146.2 75-77127
C2H5 2 246.3 8210.15
ng
1 . 4 3 3
1.446
Refs.
7
7
7,42,56
7,42,56,62
4.1.2.3. Unsaturated Oligomers
Oligomers R n Mol. wt. b.p. (Urnbar) ng Refs.
Dialkyl-A-dihydromuconate (tram) CH3 2 1 7 2 . 2 86-88/1.3 1 . 4 4 9 7 42,44,58,60,61,63
ROOC-CH=CH-CH2CH2COOR C2Hs 2 200.2 80-84/1.3 5 8
Dialky-A 3-dihydromuconate CH3 2 1 7 2 . 2 74-7511.3 42,58,60,63
ROOC-CH2-CH=CH-CH2COOR C2H5 2 200.2 107-108/1.3 58,63
Dialkyl-a-methyleneglutarate oligomers CH3 1 1 7 2 . 2 5910.3 7,8,42,44,62
Ol i gomeri c Acryl i c Deri vati ves Iv/23
4.1.2.3. contd
Oligomers R n Mol. wt. b.p. (Wmbar) Fzg Refs.
CH2=C(COOR)-[CHzCH(COOR)].H 2 258.2 120/0.9 8
3 344.3 166-168/0.4 8
4 430.4 180/0.03 8
CZHS
1 200.2 52-5310.2 1.0392 42,52,56,62
4.1.3. ANIONIC OLIGOMERS OF ACRYLAMIDE CHz=CHCO-[NHCH&H2CO],NNH2
n Mol. wt. m.p. (C) Refs.
1 142.2 149-150 110-112
2 213.2 179-181 112
4.1.4. OLIGO(ACRYLONITRILES)
4.1.4.1. H[CH2CH(CN)].H
n Mol. wt. b.p. (Wmbar) TtDPC Refs.
1 55.1 97.1/1013 1.3689/15
2 108.1 116-118/6.5 1.4320125 9,45
3 161.2 195-196/3.5 1.4609120 9,10,45
4.1.4.2. H[CH2CH(CN)].CH3
na Mol. wt. m.p. (C) b.p. (Urnbar) dylC (g/cm3) nLJC Refs.
1 69.1 - 71.5 107-108/1013 0.773 1.3720/20 31
2 122.2 8.8b 10613 0.905 1 1.4191/60 10,11,38,54,80
55c 9413 0.8940 1.4155/60 10,11,38,54,80
3 175.2 37-39b 10,38,53
53-54d 10,53
80-81e 10,53
4 228.3 130-132s 1 0
158 1 0
a n = 2-5 (diastereomers): C-NMR, Ref. 35.
b Isotactic (mew).
Syndiotactic (racemic).
d Heterotactic (racemic).
* Syndiotactic (meso).
f Two stereoisomers.
4.1.4.3. H[CH(CN)CH2] ,,CH2CN
n Mol. wt. b.p. (Urnbar) ItDPC Refs.
1 94.1 287.411013 1.4341/20
2 147.2 85/0.01 1.4644125 9,12
3 200.2 9510.01 9,12
4.1.4.4. 1,2-Dicyanocyclobutanes
n Configuration Mol. wt. m.p. (C) b.p. ( Urnbar)
e
Refs.
1 cisltrans 106.1 13,42,43,66,81
cis 67-67.5 190120 1.4628 13,14,79
tram 30.5131.5 160120 13,14,79
Iv/24 PHYSICAL DATA OF OLICOMERS
4.1.4.5. Unsaturated Oligomers
Oligomers 0 n Mol. wt. m.p. (C) b.p. (Urnbar) llg Refs.
2,3-Dihydromuconitrile
NCCHsCH=CHCHsCN
1 ,CDicyano- I-butene
CN-CH=CH-CH2CH2CN
cis
tram
2-Methyleneglutaronitrile
CHs=C(CN)-CHzCHzCN (cisltrans)
2,4,6-Tricyano-1-hexene
CHa=C(CN)-CH2CH(CN)-CH2CH2CN
1,1,4,4-Tetracyanoethyl-1,4-dicyano-2-butene
(NCCH;?CH2)2C(CN)-CH=CH-C(CN)(CH2CH2CN)2
1,4-Dicyano-1,3-butadiene
NC- CH=CH- CH=CH- CH
cis,cis
trans,trans
2 106.1 16 14,15,82
2 106.1 42,46,49,67
-19 to -17 99.5-102.5/0.5 1 . 4 6 1 1 49,50,83
-13 to - 12 84.5-86.510.5 1 . 4 6 4 6 49,50
2 106.1 - 9.6 6510.13 1 . 4 5 5 0 42,44-48,52
3 1 5 9 . 2 152-16412.5 1 . 4 1 6 2 42,45
6 318.4 240 14,45,46
2 104.1 425 1
128- 129 8 3
159-161 91
4.2. OLIGOMERIC METHACRYLIC DERIVATIVES
4.2.1. OLIGO(METHACRYLIC ACIDS)
4.2.1.1. H[CH&CH,)(COOH)],-C(COOH)(CHs)z
n Mol. wt. m.p. (C) Refs.
2 260.3 Oil 1 9
3 346.4 45-48 18,19
4 432.5 56-59 1 9
4.2.1.2. Anionic Oligo(methacrylic acids)
n Mol. wt. m.p. (C) Refs.
CHsO-[CH2C(CH3)(COOH)]aH
2 204.2 82 1 7
3 290.3 160 1 7
4.2.2. OLIGO(METHACRYLATES)
4.2.2.1. Anionic Oligo(methacrylates) RO-[CH~C(CHJ)(COOOR)] .H
R R ?I Mol. wt. b.p. (Urnbar) d20/(g/cm3) C
2 0
no
Refs.
CH30 CH30 1
2
3
4
6
1 3 2 . 2 14711013
2 3 2 . 3 241/1013
332.4 116/0.1
432.5 190/0.1
632.8
n =2-10: GPC Ref. 36
2 1 6 . 3 59-61/0.13
3 5 8 . 5 128-130/0.13
500.7 186-90/0.13
642.9 246-25010.4
0.7949
1 . 0 5 4 0
1 . 1 0 4 5
1.12
1.565
1.4053
1 . 4 3 7 8
1 . 4 5 6 7
1.4681
17,36,41,73
17,36,41
17,36,41
17
17
n-CdHsO n-&H90 1
2
3
4
0.8970 1 . 4 2 1 3 14
0.9436 1 . 4 4 0 0 7 4
0.9736 1 . 4 5 0 8 7 4
0.9909 1 . 4 5 7 4 7 4
lsotactic and syndiotactic oligomers (CHj)sC-~CHZC(CH~)COGCH~].-H, n = 2-100 (mol. wt. 158.2-10070.0): HPLC, GPC, SFC; DSC (Ts. T,), X-ray (n = 2-5).
NMR, MS; Ref s. 114- 1 2 4 .
Reviews: Refs. 114,115.
Properties of specific oligomers: n (isotactic and syndiotactic, resp.) = 2-8,13,14,16,19,21,22-25,27-29,31,36,41,44,45,50,58,80,1~.
m.p. (C), (isotactic oligomers): n = 28: 98.5, n = 31: 104.5, n = 36: 109.6, n = 41: 117.3, n = 44: 124.3; Ref . 116.
i
4.2.2.2. Unsaturated Oligomers CH2=C(COOCH3)-[CH2-X-(COOCH3)1.-CH3
Ol i gomeri c Met hacryl i c Deri vat i ves I V / 2 5
X n Mol. wt. b.p. (Urnbar) Refs.
CHzCH
C(CH3)
1 188.2
2 276.3
1 188.2
10714
17314
1.4445
1.4588
IR, MS, H-NMR
16,20,42,59,65,77
16,20,42,59,65,77
Ref. 65,ll
Ref. 75
n = 2-4: 2D-COSY-NMR
4.2.2.3. Cyclic Oligomers
Oligomers R n Configuration Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
1,2-Dimethylcyclobutane- 1,2-dicarboxylates
&&H3 $&
..CO:CH3 CH3
CH3 2 cis 200.2 IR, MS, H-NMR 6 5
tram IR, MS, H-NMR 6 5
2,4,6-Trimethyl-6-methoxy-methyl-cyclohexanone-2,4-dic~boxylate
0 CH, 3
II
Hz6 \ i&
H3C
hO,CH,
1,3,3,5-Tetramethylcyclohexane-2-one-1,5-dicarboxylate CH3 3
H3C\ COOCH3
A
cis
tram
H3C
2 6 8 . 3 1 2 2 1 0 . 1 3 17,36
2 7 0 . 1 128-138/3 64,72
128-138/3 64,72 52-54
6-endo 2 6 8 . 3 117-119
6-exo Oi l
4,6,7-Trimethyl-3-oxo-7-propyl-2-oxabicyclo-[2,2,2]octane-6-c~boxylate
0
CH3 3
(C3H7)
CH3 CH3
l-Ethyl-4,6,7-trimethyl-3-oxo-7-propyl-2-oxa-bicyclo[2,2,2]octane-6-c~boxylate
CH3 4 6-exo 296.4 IR, MS, H-NMR
64
6 4
6 4
4.2.3. OLIGO(METHACRYLOYL CHLORIDES)
Oligomers n
2-Chloro-2,5-dimethylcyclopentanone-5-carboxylic chloride
0 2
H3C
?Y
COCl
Cl, CH3
2,5-Dimethyl-A*-cyclopentenone-5-carboxylic acid chloride
0 2
H3C
COCl
CH3
Mol. wt. b.p. (Urnbar) Refs.
209.1 ill-117/23 40
209.1 ill-117/23 40
IV/26 PHYSICAL DATA OF OLICOMERS
/
1
4.2.4. ANIONIC OLIGOMERS OF METHACRYLAMIDE CH,=C(CH,)CO-[NHCH2CH(CH3)CO].NH2
n Mol. wt. m.p. (C)
1 170.2 118-120
2 255.3 155-158
3 340.4 195
4-9: GPC, MS, Ref. 84 n =
Refs.
84
84
84
4.2.5. OLIGO(METHACRYLONITRILES)
4.2.5.1. Anionic Oligo(methacryZonitriZes) CH~O[CHZC(CH~)CN] .H
II Mol. wt. b.p. (Urnbar) ll#C Refs.
1 99.1 160.6/1013
2
1.4038/20 1 1 3
166.2 9210.7 1.438 21,34
3 233.3 16510.7 1.464 21,34
4 300.4 23510.7 1.478 21,34
5 367.5 30%30510.7 1.488 21,34
4.2.5.2. I,2-Dicyano-1,2-dimethyl-cyclobutunes r[CH$(CH,)(CN)-C(CH$(CN)CH&
n Configuration Mol. wt. m.p. (C) b.p. (Wmbar) Refs.
2 cis 134.2 107-108 170133 16,66,89
2 trans 134.2 90.3 120133 16,66,89
4.2.5.3. Unsaturated Oligomers
Oligomers
a-Methylene-&methyladiponitrile
CH$H(CN)-CH+ZH2C(CN)=CH2
5-Cyano-8-methyl-2-methylene-nonanedinitrile
CHs=C(CN)-[CH2CH2CH(CN)12=CH3
n Mol. wt.
2 1 3 4 . 2
3 2 0 1 . 3
m.p. (C)
47-49
b.p. (Wmbar) ng Refs.
148133 1 . 4 5 0 2 16,42,89
19411.3 1 . 4 7 2 0 16
4.3. OLIGOMERS OF fi-ALKYL-SUBSTITUTED VINYL DERIVATIVES
4.3.1. OLI GO( ESTERS)
Monomer R Oligomers n Mol. wt. b.p. (C/mbar) ng Refs.
CHjCH=CHCOOR
n-C3H+ZH=CHCOOR
i-C3H$H=CHCOOR
CH3
C2H5
CH3
CH3
CH3
2-methyl-3-pentene-
1,3-dicarboxylate (cisltrans)
CH$H=C(COOR)-
CH(CH3)CH 2COOR
2-Methyl-4-pentene-
1,3-dicarboxylate (cisltruns)
CHz=CH-CH(COOR)-
CH(CH$H2COOR
2-n-Fropyl-3-heptene-
1,3-dicarboxylate
CjH7XH=C(COOR)-
CH(CH2COOR)-C3H,
2-Isopropyl-5-methyl-
4-hexene-1,3-dicarboxylate
(CH3)2C=CH-CH(COOR)-
CH(CH 2COOR)-CH(CH 3) z
2 200.2 70-80/96 42,55,68,70,71
2 2 2 8 . 3 8410.75 1 . 4 5 1 2 42,55,56,69
2 200.2 90-110/13 42,70,7 1
2 252.3 lOO- 102/4 5 5
2 2 5 2 . 3 90-9313 5 5
4. 3. 2. OLIGG(CRGTONONITRILES)
Oligo(vinyl) Derivatives Iv/27
Oligomers n Mol. wt. b.p. (Wmbar) ng Refs.
1,3-Dicyano-2-methyl-3-pentene (cis/?rurw)
CHsCH=C(CN)-CH(CHs)CH$ZN
1,3,5-Tricyano-2,4,6&imethylcyclohexane
r [CWV- CWWlq
1,3,5-Tricyano-2,4-dimethyl&heptene
CHsCH=C(CN)-CH(CHs)CH(CN)-CH(CHs)CH2CN
2 134. 2 81- 83/ 0. 3 1 . 4 7 3 0 42, 52, 55- 51
3 201. 3 152- 15510. 3 1. 4950 42, Sl
3 150-160/0.13 42. 52
4. 4. OLIGO(VINYL) DERIVATIVES
4.4.1. OLIGO(VINYL ALCOHOLS) AND OLIGO(VINYL ACETATES) H[CH $HOR] .CH 3
R n Configuration Mol. wt. m.p. (C) b.p. (Wmbar)
e
Refs.
H
COCH 3
2 Isotactic (meso)
Syndiotactic (racemic)
3 Isotactic (meso)
Heterotactic (racemic)
Syndiotactic (meso)
2 Isotactic (meso)
Syndiotactic (racemic)
Mixture
3 Isotactic
Heterotactic
Syndiotactic
Mixture
104.1
48- 49
148. 2 61
87. 5- 88
188. 2
214. 3
21- 22
32. 5- 33. 5
1314
1414
12011. 3
12011. 3
20/ 1013 1. 4172
201/1013 1. 4142
103- lOI/ 1. 4170
116-117.510.7 1 . 4 3 4 2
115-116/0.7 1 . 4 3 1 9
112-114/0.5 1.4297
120-122/0.7 1 . 4 3 2 0
1. 4321
1. 4378
80, 86, 87
80, 86, 87
84, 85
84, 85
84, 85
86, 88, 97
86, 88, 97
96
84, 88
84
84. 88
84, 96
4.4.2. OLIGO(VINYL CHLORIDES) H[CHzCHCL] ,$H3 a
n Configuration Mol. wt. b.p. (Wmbar)
nDm
Refs.
26 Isotactic (meso) 1 4 1 . 0 40116 1 . 4 4 0 9 80, 90- 95, 97
Syndiotactic (racemic) 36116 1 . 4 3 9 0 80, 90- 95, 97
Mixture 140-141/1013 1 . 4 4 0 9 95
3b Isotactic 203. 5 102. 5120 1 . 4 1 2 2 89, 94, 95
Heterotactic 103.5120 1 . 4 7 0 4 89, 94, 95
Syndiotactic 104.5120 1 . 4 6 8 6 89, 94, 95
Mixture 102.5- 104.5 1 . 4 6 9 9 89
a Oligomers (CHs)sC-[CHsCHCl] n-H, n = 1,2,3 (three-; erythro-), 4 (ribo-; xylo-; arabino-; lyxo-): HPLC, 13C-NMR, Ref. 39.
b 2,4-Dibromopentanes and 2.4.6~tribromoheptanes: Kerr Effekt, Ref. 98.
4.4.3. OLIGG(VINYL ALDEHYDES) AND OLIGG(VINYL KETONES)
Monomer Oligomers n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
Acrolein 2-Formyl-2,3dihydropyran 2 112.1 145-148/1013 22- 25
CH2=CHCH0 0
0 CHO
3-Formyl-5,6-dihydropyran 2 112.1 77-78116 26, 27
0 \ CHO
0
a-Methylacrolein 2-Formyl-2.5~dimethyl-2,3dihydropyran 2 140. 2 - 15 166/ mO 24, 28
CH2=C(CHs)CH0
a3
T-l
CHO
0 CH3
a-Ethylacrolein 2-Formyl-2,5-diethyl-2,3dihydropyran 2 168. 2 195/1013 24
CH2=C(CH2H5)CH0
W-Q
IV/28 PHYSICAL DATA OF OLICOMERS
4.43. contd
Monomer Oligomers n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
Methyl vinyl ketone 2-Methyl-6-acetyl-5.6.dihydropyran 2 128.2 68117 2 9
CH*=CH-CO-CHs
/cl
CH3 0 COCH3
3-Methylene-2,6-heptanedione 2 1 4 0 . 2 5-7 91-9211 4 6
CHsCOC(=CH2)CH2CH2COCH3
2-Methyl-1-butene-(3)-one 2,6-Dimethyl-3,7-dioxo-1-octene 2 168.2 83-85/23 30,99, loo
CH2=C(CH3)COCHs CH3COCH(CHs)CH2CH2COC(CH3)=CH2
Phenyl vinyl ketone 2,4-Dibenzoylpentane 2 280.4 H-NMR 99,100
CHz=CH-CO-CGHs CHsCH(COC6Hs)CH2CH(COC~Hs)CH3
Isotactic (meso) 64-65 100/1.3 99,100
Syndiotactic (racemic) 62-63 15511.3 99,100
4.4.4. OLIGOMERIC N-VINYL DERIVATIVES
Monomer Oligomers n Mol. wt. m.p. (C) Ref.
N-Vinyl-pyrrolidone 1,3-Bis-[N-pyrrolidone-(2).yl]-1-butene
CH= CH- CH- CH3
2 2 1 2 . 3 75 31
4.4.5. OLIGO(VINYL PYRIDINES)
Monomer Oligomers n Conf i gurat i on Mol. wt. b. p. (Urnbar) Ref s.
2-Vinylpyridine
4-Vinylpyridine
H[cHz-cH(~j(:Hl i :i:::% :::;:; 2 2 6 . 3
331.4
4 Isotactic (meso) 436.6
n = 2-7: LC, H-, 13C-NMR Refs. 108,109
sym-Tri(4-pyridyl)-cyclohexane 3 3 1 5 . 4
106-108/0.33
L C , G C , H-, 13C-NMR ;:;;&:::$;
LC GC H- 13C-NMR 3 3 9 104,103,107,109
m. p. ( C) : 2 2 8 . 5 32,33
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No. Monomer Oligomers n Mol. wt. m.p. (C) b.p. (Urnbar)
e
Refs.
Styrene 3-Methyl-1-phenylindane 2 2 0 8 . 3 9 . 5 168-169/21 1 . 5 8 1 0 1-5
(2 stereoisomers) 2 5 . 5 157116 1 . 5 8 0 9
CH3
5. 1. contd
Oiigo(styrenes) Iv/ 31
No. Monomer Oligomers n Mol. wt. m.p. (C) b.p. (TImbar)
4f
Refs.
1,3-Diphenyl-1-butene
CH3- CH- CH= CH
1,4-Diphenyl- 1 -butene
1,2-Diphenylcyclobutane
a-Methylstyrene 1,3,3-Trimethyl-1-phenylindane
4-Methyl-2,4-diphenyl-2-pentene
a-Methyl-p-methoxystyrene
a-Methyl-p-aminostyrene 1,3,3-Trimethyl-4,6-diamino- 2
phenylindane
lkHz
RN0 C(CHWH= ,GNH,
CH3
2
a-Methyl-p-carboxystyrene 1,3,3-Trimethyl-l-phenylindane- 2
4,6-dicarboxylic acid
HOOC
a-p-Dimethylstyrene
COOH
1,3,3,4,6-Pentamethyl- 2
1-phenylindane
2 0 8 . 3 181-182127 1 . 5 9 3 0 l-3,6,23
134-13511
2 0 8 . 3 124/1013 6,23
2 0 8 . 3 1.5913 7
236.4 5 3 158-160/13 8-10
236.4 5 2 166-167120 1.5728 8,11,12
296.4 237-240124 1.5703
266.4 93-94
9,13
9
266.4 1 7 3
348.4 297
264.4 40 142-144/1.1 9,15,16
9,14
9,14
IV/32 PHYSICAL DATA OF OLICOMERS
5. 1. contd
No. Monomer Oligomers n Mol. wt. m.p. (C) b.p. (Urnbar)
e
Refs.
a-Ethylstyrene 1,3-Diethyl-3-methyl-
1-phenylindane
2
3,5-Diphenyl-5-methyl-2-heptene 2 264.4 133-135/1.6 1.54345/25 17
u-m-Dimethylstyrene 1,3,3,3,7-Pentamethyl-
I-phenylindane
2
p-Bromostyrene cis-1,3-Di@-bromophenyl)-I-butene 2 3 6 6 . 1 67-68 1 8 . 1 9
Br eCH= CHCH(CH3) CBr
1,2,3,4-Tetraphenylcyclobutane 2
C6HS
C6H5
1,2-Diphenyl-l-p-tolyethane 2
CH3
264.4 104-106/0.4 1 S642 17
264.4 5 7 9
272.4 42-43 2 0
3 6 0 . 5 164-165 20-22
REFERENCES
1. P. E. Spoerri, M. J. Rosen, J. Am. Chem. Sot., 72, 4918
(1950).
2. M. J. Rosen, J. Org. Chem., 18, 1701 (1953).
3. B. B. Corson, J. Dorsky, J. E. Nickels, W. M. Kutz, H. I.
Thayer, J. Org. Chem., 19, 17 (1954).
4. M. J. Rosen, Org. Syn. Coll. Vol. IV, 665 (1963).
5. R. Stoemer, H. Kootz, Chem. Ber., 61, 2330 (1928).
6. R. Fittig, E. Erdmann, Ann. Chem., 216, 179 (1883);
H. Stobbe, G. Posnjak, Ann. Chem., 371, 287 (1909).
7. I. S. Bengelsdorf, J. Org. Chem., 25, 1468 (1960).
8. E. Bergmann, H. Taubadel, H. Weiss, Chem. Ber., 64, 1493
(1931).
9. J. C. Petropoulos, J. J. Fisher, J. Am. Chem. Sot., 80, 1938
(1958).
10. L. M. Adams, R. J. Lee, F. T. Wadsworth, J. Org. Chem., 24,
1186 (1959).
11. F. S. Dainton, R. H. Tomlinson, J. Chem. Sot., 151 (1953).
12. J. M. Van der Zanden, Th. R. Rix, Rec. Trav. Chim., 75, 1343
(1956).
13. J. M. Van der Zanden, Th. R. Rix, Rec. Trav. Chim., 75, 1166
(1956).
14. J. V. Braun, E. Anton, W. Haensel, G. Werner, Ann. Chem.,
472, 1 (1929).
15. M. Tiffeneau, Ann. Chim. Phys., 10, p. 145, p. 197 (1907).
16. V. N. Ipatieff, H. Pines, R. C. Oldberg, J. Am. Chem. Sot., 70,
2123 (1948).
17. C. G. Overberger, E. M. Pearce, D. Thanner, J. Am. Chem.
Sot., SO, 1761 (1958).
18. G. L. Goemer, J. W. Pearce, J. Am. Chem. Sot., 73,2304 (195 1).
19. J. Hukki, Acta Chem. Stand., 3, 279 (1949).
20. D. S. Bra&man, P. H. Plesch, J. Chem. Sot., 3563 (1958);
Chem. Ind., 255 (1955).
21. M. Pailer, U. Mueller, Monatsh. Chem., 79, 615 (1948).
22. J. D. Fulton, J. D. Dunitz, Nature (London), 160, 161 (1947).
Oligo(oxyethylenes) Iv/33
C . OLICOMERS CONTAINING HETEROATOMS IN THE MAIN CHAIN
TABLE 6. OLICOMERS CONTAINING 0 IN THE MAIN CHAIN
6.1. OLIGO(ETHERS) AND OLIGO(ACETALS)
6.1.1. OLIGO(OXYETHYLENES)
6.1.1.1. Linear Oligo(oxyethylenes) H[OCH2CH2],0H
nn Mol. wt. m.p. (C) b.p. (Urnbar) (g/d dzO n?PC Refs.
1 6 2 . 1
2 106. 1
3 150.2
4 194.2
5 238.3
6 282.3
7 326.4
8 370.4
9 414.5
1 0 458.6
1 2 546.6
1 4 634.7
1 5 678.8
1 6 722.9
1 8 811.0
2 0 899. 1
2 5 1119. 3
2 7 1207. 5
3 0 1321.6
3 5 1559.8
3 6 1604.0
4 5 2000.4
5 4 2396.9
-
- 12.6
- 6
- 4.3
- 3
2 to 0
9
17. 8-18. 8
19. 7-21. 8
30.0
25. 8-28. 3
36. 5-38. 5
29.5
40.0
49. 5-505
35.0
44.4
47.0
44. 6-44. 8
46.4
5 0 . 1
43. 0-43. 4
53.0
54.2
197.8/1013
245/1013
122-123/0.1
155-15610.8
173-174/0.8
175-177/0.07
230-23210.9
206-209/0.02
186-192/0.001
210/0.1
246-257/0.001
1.1136/20 1.4324
1.120/20 1.4479
1.1274115 1. 4573
1.127120 1. 4611
1.4629
1.127/20 1.4640
1. 4653
1.1278/20 1.4660
23-26,55,119,149,209
23-26,55,57,119,129,149,209
23-25,26,55,57,119,129,149,209
23-27,55,57,70,119,120,129,149,209
25-27,55,57,68,71,119,149,209
23-28,55,68-70,119,120,209,215
25,26,55,57,69,71,119,219
27,120,215,219
37,50,52-54,56,59,219
27,51,54,71,219
219
2 5
37,50-54,59
219
25,37,211
51,54
51,53,54,59
3 7
25,54
51,53,54,59
3 7
37,54
212
Q n = 1-27: HPLC, Refs. 72-74; n = 1-45: GPC, Ref. 220; n = 6,8,9,10,15,16,18,25,35,54: IR, Raman, NMR, MS, DSC, Ref. 211,212,214,215,219,224.
6.1.1.2. Oligo(oxyethylene) Monoalkyl Ethers R-[OCH2CH2] .-OH
R n* Mol. wt. m.p. (C) b.p. (Urnbar) ng Refs.
CH3
C2H5
n-C3H7
n-CdH9
n-C6H13
1 7 6 . 1
2 120. 1
3 164.2
5 252.3
6 296.4
7 341.4
8 385.5
9 429.5
1 0 473.6
1 1 518.1
1 8 825.0
1 9 0 . 1
2 134.2
3 178.2
4 222.3
1 148.2
2 192.3
3 236.3
1 118.2
2 162.2
3 206.3
1 146.2
2 190.3
3 234.3
4 278.4
- 85.1 124/1009
194.2/1013
245.311013
110/0.013
125/0.013
150/0.007
165/0.007
13-14 185/0.003
18-18. 5 218-220/0.013
2 2 236-238/0.013
24-25
135/1013
196/1013
248/1013
284/1013
152-153/1012
215.8/1023
148-150/23
171/1013
-68.1 112-114/15
278/1013
1.4024
1.4260
1. 4075
1. 4273
1.4380
1.4499
1.4133
1.4196
-50.1
- 36.9
- 30.3
- 15.0
26,124,125,127-129,177,196
1 2 7
1 8 0
1 7 8
1 7 8
1 7 8
1 7 8
1 7 8
1 7 8
1 7 8
2 4
24,125-129,176,177,196
126,129
1 2 6
1 2 9
128,129,175-177,196
1 7 5
1 7 5
24,125,129,176,177,194,196
1 9 4
2 0 6
1 0 2
1 0 2
1 0 2
1 0 2
Iv/34 PHYSICAL DATA OF OLICOMERS
6.1.1.1. contd
n Mol. wt. m.p. (C) b.p. (Wmbar) Wcm3) dzo n$PC Refs.
n-C9H19
n-C nHz5
n-c 16H33
CsH.+=z
(C6H5)3C
C6H5
5 322. 4
6 366. 5
9 498. 6
4 320. 5
8 496. 7
1 186. 3
2 230. 4
3 274. 4
4 318. 5
5 362. 5
6 406. 6
7 550. 8
8 594. 8
9 638. 9
10 683. 0
11 727. 0
12 771. 1
9 638. 9
12 771. 1
3 240. 3
4 284. 3
5 328. 4
6 372. 4
8 460. 6
9 504. 6
3 392. 4
4 436. 5
5 480. 6
6 524. 6
1 138. 2
2 182. 2
3 226. 3
4 270. 3
5 314. 4
- 3. 3
1. 2
13. 0
22. 7
20. 2
18. 6
17. 0
20. 0
22. 8
25. 4
28. 5
32. 3
33. 5
40.0
40. 3
42. 0
40. 5
43. 5
180- 18210. 5 NMR, MS
14qo. 13 1. 4456
MS/ o. 13 1. 4485
17810. 13 1. 4510
188/ 0. 07 1. 4531
21210. 07 1. 4548
23310. 13 1. 4560
236- 240/ 0. 15 1. 4576
166- 169/ 0. 5
120. 5112
163. 0/ 11
190. 5111
181/ 0. 3
21810. 5
1. 503
1. 501
1. 499
1. 493
1. 488
1. 483
1. 540
1. 544
1. 549
1. 561
1. 5370
1. 5230
1. 5144
1. 5075
1. 5030
102
102
102
225
225
70, 207
70, 207
70, 207
70, 207
70, 207
70, 207
207
207
207
207
207
207
56
56
75, 175
75
75
75
75
75
75
75
75
75
109
109
109
109
109
On =4, 6, 8, 12, 16 wi th R=n- C9H 19 and n- C15Hsl : Raman spectr. , Ref . 213.
6. 1. 1. 3. Ol i go( oxyethyl ene) Di al kyl Ethers H( CH2) , - [ OCH2CH2] , - O( CH2) xH
n x Mol. wt. m.p. (C) b.p. (Wmbar) IZJT Refs.
1
2
3
4
5
6
7
9
1 90. 1
2 118. 2
3 145. 7
4 174. 2
1 134. 2
2 162. 2
3 190. 2
4 218. 3
1 178. 8
2 206. 3
1 222. 3
2 250. 3
4 306. 4
1 266. 3
2 294. 4
1 310. 4
2 338. 4
4 394. 5
1 354. 4
1 442. 5
2 470. 6
3 498. 6
4 526. 7
6 582. 8
16. 0
21. 5
12. 7
11. 7
13. 0
84/ 1013
124/ 1013
159- 1601965
204/ 1013
161/ 1013
189/ 1013
2191983
250/ 1013
216/ 1013
118/ 13
148/ 19
159115
192113
149- 151/ 3. 3
17414
13510. 1
125/ 0. 01
15510. 4
205- 20714
1. 3797120
1. 3922120
1. 4183120
1. 4143120
1. 4025/ 25
1. 4265120
1. 4233120
1. 4371120
1. 4332120
1. 4384120
1. 4471120
1. 4454120
1. 4509120
130, 131, 133, 134, 195
24, 131, 132, 135
131, 175
24, 131, 132
24, 26, 134, 179, 195
8, 24, 135, 179
179
24, 179
134
135
8, 24, 134
24, 135
24
134. 136. 166
135
24, 134
24, 135
24
134
52, 58, 59
58, 59
58
58
58
/
Oligo(oxyethylenes) I v / 35
6.1.1.3. contd
n X Mol . wt . m.p. (C) b. p. (Urnbar) IloFT Refs.
8 638.8 1 9 . 5
1 0 695.0 28.5
1 2 751.1 37.0
1 6 863.3 49.5
1 8 919.4 54.0
2 1 1003.8 62.0
2 6 1143.8 69.0
1 5 1 706.8 28.7
2 734.9 3 5 . 1
3 762.9 30.8
4 791.0 31.3
5 819.0 32.0
6 847.1 32.2
I 875.2 33.7
8 903.2 35.3
9 931.2 38.4
1 0 959.3 39.5
1 1 987.4 42.5
1 2 1015.4 45.5
1 3 1043. 5 47.3
1 4 1071.6 50.0
1 5 1099.6 51.7
1 6 1127.6 54.4
1 7 1155.7 57.6
1 8 1183.7 59.0
2 1 1267.9 6 2
2 6 1408.2 6 8
3 0 1520.4 7 1
2 5 4 1231.5 43.5
1 5 1540. 1 55.5
3 0 1960.9 72.7
4 5 1 2028.4 51.3
1 0 2280.9 52.8
1 3 2365.0 5 6 . 1
1 5 2449.2 5 7 . 1
1 8 2505.3 61.2
2 1 2589.4 64.3
3 0 2841.9 6 6
Ramall
5 8
58.63
58,63,64
58,63,64
58,63
5 8
58.63
52.59.60
59.60.224
60,63
60,63
60,63
60,63
60,63
60,63
60,63
60,63
60,63
60,63
60,63,64,67
60,63,64,67
60,63,64,67
60,63,64,67
60.63.64.67
60,63,64,67
60,62,65
6 2
6 2
6 6
6 6
6 6
6 1
6 1
6 1
6 1
6 1
6 1
6 6
n = 2-45, x = 1: GPC, Ref.: 220; a-alkyl (CHj, Cs H 19, Cl5 Hsl), co-methoxy oligo(oxyethylenes), n = 4-12,15,16,25: Ref. 214, n = 15, x = 5,6,7: micelliation and
surface properties, Ref. 221.
6.1.1.4. Amino Derivatives of OZigo(oxyethylenes) a,o-Diamines RNH-CH$H2-[OCH2CH2] .-NHR
R n Mol. wt. b. p. (Urnbar) nJ25C Refs.
H 1 94.2 48-50/1.3 7 6
2 148.2 77-7810.3 7 6
3 192. 3 115/0.3 1.4637 76.77
4 236.3 133-13410.2 1.4647 7 7
5 280.4 175-17710.07 1.4668 7 7
CH3 3 220.3 97-9810.2 1. 4511 7 7
4 264.4 131-133/0.2 1.4549 7 7
5 308.4 146- 148/0.07 1.4562 7 7
aN-Gligoethylene mono- and dialkylamines RIR2N(CH2CH20),H; RI, RZ=C4H9 and R, =~PC,~H~~, Rz =H; n = 1-6; GC; Ref. 88
6.1.1.5. Cyclic Oligo(oxyethylenes) r[OCH$I?H&,1
Ila Mol. wt. m.p. (C) b.p. (Urnbar) dq (gkm3)PC Refs.
1 44.1 - 111. 3 10.7/1013 1.892216 2 9
2 8 8 . 1 1 1 . 8 101.3/1013 1.0336/20 30,85-87,92,102,145
3 132.2 0 168-172/1013 78,79,102
4 176.2 1 7 106/13 1.109125 31,40,79-81,86,102,145,216
5 220.3 Oil 15211.7 1.113/20 31,39,79,81,83,102,145,216
I V / 3 6 PHYSICAL DATA OF OLIGOMERS
6.1.1.5. c ontd
na Mol. wt. m.p. (C) b.p. (Urnbar) dd (g/cm3)/C Refs.
6 2 6 4 . 3 39.5-40.5 80/0.013 39,41,79,81-83,102,145,216
7 308.4 Oi l 39,84,145,216
8 352.4 19 39,84,145
9 396.9 Oi l 2 1 7
10 441 .o 35.5-36.8 217,219
11 4 8 5 . 1 Oi l 217
12 529.2 36.5-38.5 217,219
13 5 7 3 . 3 Oi l 217
1 4 617.4 28.5-31 2 1 7
15 6 6 1 . 5 38-41.5 2 1 7
1 6 705.6 49.5-50.5 217,219
17 749.7 44-47 2 1 7
18 793.8 47-50 2 1 7
19 837.9 51-53.5 217
2 0 882.0 46-50.5 217
n = 2.4-8; GC, MS; Ref. 145; n = 4-20: IR, NMR, MS, Refs. 216,217,219.
6.1.1.6. Oligomers of Substituted Ethylene Oxides
Epoxide Oligomers n Mol. wt. m.p. (C) b.p. (Wmbar) n#T Refs.
Oxirane
(Ethylene oxide)
Crown ethers r[OCH$H2],1
2-Methyl-1,3-dioxolane
2-Methyl-1,3,6-trioxocane
r[OCH(CH3)-(OCH2CH&
Methyloxirane
(Propylene oxide)
Dimers
cis- + truns-2,5-Dimethyl-1,4-dioxane
trans-
cis- + frans-2,6-Dimethyl-1.4~dioxane
cis- + trans-2-Ethyl-4-methyl-1,3-dioxolane
cis-
trans-
r[OCH(C2HS)-OCH2CH(CH3)j-l
Higher Oligomers
rPCW%)CWn~
Ethyloxirane r PCWHOWHdq
(1,2-Butene oxide)
2,3-Dimethyl oxirane
(2,3-Butene oxide)
cis- Monomer
I
Dimers
2,cis-3,trans-5,cis-6-
Tetramethyl-1,4-dioxane*
2,cis-4,trans-5-Trimethyl-
2-ethyl- 1,3-dioxane *
0 r
11
0 i
Trimers
1-8
2 88.1
cf. Tab. 1.1.1.5
110-112
82-83/1013 1.3970/20
3 132.2 110/13
2 116.2 117-130/1013 80,90,92,93
GC, MS, H-NMR, IR 8 9 , 1 1 4
- 4 . 5 121.5/1000 1 . 4 1 4 7 1 2 2 1 1 2 , 1 1 3
127.7-129/1001 1.4169/20
GC, MS, H-NMR, IR
8 9 , 1 1 9
GC, MS, H-NMR, IR 8 9
1.4029/24 1 1 5
1.4044/24 115
4 2 3 2 . 3
5 290.4
4 288.4
9 3 61-65/0.009 1 . 4 4 5 3 1 2 3
77-83/0.009 1 . 4 4 5 3 1 2 3
n = 4-6: GPC, Ref. 91
99-101/0.13 1 . 4 5 0 3 1 2 3
n = 4-6: GPC, Ref. 91
49,89-93
90-92
90-92
1 72.1 59.9-60.41996 1.3826120 1 1 6
2 1 4 4 . 2 94,95
3 2 1 6 . 3 GPC, H-NMR
4 2 8 8 . 4 GPC, H-NMR
GC, H-NMR
GC, H-NMR
85-87,92,
110-112
70,150
94,95
94,95
9 5
9 5
Oligo(oxyethylenes) IV/37
6.1.1.6. contd
Epoxide Oligomers n Mol. wt. m.p. (C) b.p. (Urnbar) nDPc Refs.
cis-, trans-
2,2-Dimethyloxirane
(Isobutene oxide)
(R)-terr, Butyloxirane
Methyleneoxirane
(Epoxyallene)
Epichlorohydrin
n-Propoxymethyl-
oxirane (n-Propyl
glycidyl ether)
Phenyloxirane
(Styrene oxide)
2,cis-3,trans-5-cis-6-
Tetramethyl- 1 ,Cdioxane b
T&+&q
2,&-4,cis-5-Trimethyl-
2-ethyl- 1,3-dioxolane b
0 r
rJ 0 i
2,rrans-4,rrans-5-Trimethyl-
2-ethyl- 1,3-dioxolane b
2,trans~3,cis-5-tram&
Tetramethyl- 1,4-dioxane
0+O
kc
2,traw3,trans-5,cis-6-
Tet r amet hyl - 1 ,Cdioxane
z+
Dimers
2,5-Tetramethyl- 1 ,Cdioxane
r PWHMklq
2-Isopropyl-4,4-dimethyl-
1,3-dioxolane
r PCWCfV%h~ WC%Wb
2,4,6-Triisopropyl-1,3,5-trioxane
rWWCWH3hllnl
rPCH{W%WH21q
2R, 5R, 8R, llR-
r [OC(=CH2Pd1
r [OCH(CH2Cl)CH2],1
cis-
tr ans-
2R, 5R, 8S, llS-
Z-Benzyl-4-phenyl-1,3-dioxolane
r WH(CH2Cd-k~ ocH(c6%)%1-]
2,5-Diphenyl-1,4-dioxane
cis-
I rans-
r PCW&P%lnl
1 72.1
2 1 4 4 . 2
53.6-54.11996 1 . 3 7 3 6 1 2 0 1 1 6
94,95
GC, H-NMR 94,95
GC, H-NMR 94,95
2 GC, H-NMR 94.95.114
39.5-40.0
2 1 4 4 . 2
3 2 1 6 . 3
4 400.6
4 224.2
2 1 8 5 . 0
4 3 7 0 . 1
2 2 3 2 . 3
2 2 4 0 . 3
2 2 4 0 . 3
GC, H-NMR 9 4 . 9 5
GC, H-NMR 94,95,114,117
140/1013
135/1013
96
96
96
6 4 96
1 6 8 . 0 92.97
[c@=50,8(c=l.l,CsHl2)
120-122 146-147/1007 1.4880/20 9 8 , 1 1 8
60/0.2 (subl.) 92,100,103-105
65-66 67-7510.7 99
109-110 99
136-136.5 190-20511 90,92,98,100,101,
1 0 3 , 1 0 4
n = 2-6: GPC, Refs. 100,103,104
88/0.6 1.4330/30 91
n = 2-5: GPC, Ref. 91
37-40 150-151/1 43,106
1 5 2 92,106,107
121-122 42,43
1 7 7 42-44
2,4,6-Tribenzyl-1,3,5-trioxane
r [OCH(CH2C&)Iq
3 360.4 GFC, NMR 1 0 6
3n = 2-5: GFC, MS, 1 0 6
a St er eoi somer s.
b The letters r and i indicate retention and inversion at the carbon, respectively.
IV/38 PHYSICAL DATA OF OLICOMERS
6.1.1.7. Oligo(oxyethylenes) Contuining Spirune Residues r [OCH&A)CHz-(OCH2CH&]q
A n x Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
0 1 1 144.2
2 188.2
3 232.3
I 408.3
2 1 288.3 I
2 316.4
3 464.5
I 816.6
OCH(CsHS)O 1 2 294.1
2 2 588.3
3 2 882.4
Oil
163-165
86-87
52-53
42-43
Oil
9 9
86-87
91-99113 1 8 2
MS, H-NMR 182,183
97-98/0.008 1 8 2
182-183/0.004 1 8 2
1 8 2
182-183
1 8 2
1 8 2
MS, H-NMR 1 8 3
1 8 3
1 8 3
6.1.1.8. Benzo Crown Ethersa
Position of
phenolic groups x n Mol. wt. m.p. (C) b.p. (C) Refs.
O- 1
2
3
4
9
P
3
4
5
2
3
4
272.3 208.5
408.4 190- 192
544.6 150-152
180. 2 67-69
360.4 164.0
224.2 44-45. 0
448.5 113-114
268.3 19-19.5
536.3 106. 8
977.1 ~26
448.5 95. 5-96. 5
536.6 93. 5-94
624.7 67-68
380-384/1025
1 0 2
41,188
41,188
4 1
41,102,188,189
4 1
41,102,188,189
4 1
41,188
41,188
187,190
187,190
187,190
Ref. 187.
6.1.2. OLIGO(OXYPOLYMETHYLENES)
6.1.2.1. Linear Oligomers R-[O(CH2),],-R
R R x n Mol. wt. m.p. (C) b.p. (Urnbar) ?Z*lC Refs.
H OH 4 1
2
3
4
5
6
7
8
9
1 4
5 1
2
3
7
6 1
3
1 0 1
3
H Cl 4 1
2
3
4
9 0 . 1 2 0 . 1 85/0.01
162.2 3 108/0.01
234.4 1 0 . 1 151/0.01
306.4 1 8 183/0.01
378.5 3 7 226/0.01
450.6 3 1 253/0.01
522.7 4 2
594.8 3 4
667.0 4 1
1027. 5 3 8
104.2 - 18 137-138/16
190. 3 16-18 141-14210.7
216.4 29.5 188-190/1
620.9 36-38
118.2 4 3 13212
318.5 5 6 209-210/1
174. 3 72-15 175-176119
486.8 8 0 290-300/ 1
n = 3, x = 3-6: X-ray, IR, Raman Spectr., DSC
108.6 Sl-82/19
180. 7 87/0.01
252.8 132/0.01
324.9 160/0.01
1.4460/20
1.4544126
1.4484160
1.4494120
1.4570/25
1.4495/60
1.4538/60
1 0 8
33,222
3 3
1.4538/60 33,222
1.4518/60 3 3
1 3 7
108,120,137
33,120,137,222,223
1 3 7
1 3 7
1 3 7
1 3 7
1 3 7
1 3 7
1 3 7
137,138
1 3 7
1 3 7
1 3 7
6.1.2.1. contd
Oligo(oxypolymethylenes) IV/39
R R x n Mol. wt. m.p. (C) b.p. ( Urnbar) tZDPC Refs.
C,jH5NHCO OCONHC6HS 4 1 328.4 1 8 0 1 3 7
2 400.5 1 1 9 1 3 7
3 472.6 7 4 1 3 7
4 544.7 5 4 1 3 7
5 616.8 4 8 1 3 7
6 688.9 4 7 1 3 7
n = 2-7: HPLC, MS; Ref. 146
CH3 OCH3 4 n = 2-8: GC,MS; Ref . 139
6.1.2.2. Oligo(oxypolymethylene) Ethers H(CH&-[O(CH2),J .-H
x n Mol. wt. m.p. (C) b.p. (C/mbar) d&km3)/C I$ Refs.
3 2 160.3 180/1013
3 218.3 240-250/1013
4 2 202.3 234-236/1013
3 274.4 13712
4 346.6 190/1
5 2 244.4 120/03
3 330.6 160/0.4
4 416.7 200/0.3
6 2 286.5 130/0.5
3 386.7 184/0.8
0.836120 1.4090
0.843120 1.4226
0.878/20 1. 4357
0.895/20 1. 4393
0.843120 1. 4318
0.870/20 1.4416
0.890/20 1. 4471
0.842120 1.4379
0.867120 1. 445
3 3
3 3
24,32,33
32,33
32,33
3 3
3 3
3 3
3 3
3 3
4 486.8 20.5 26012 0.879120 1. 451 3 3
1 0 2 454.8 4 0 23310.4 0.819/60 1.4370/60 3 3
3 611.1 5 0 310-330/3 0.834160 1.4416160 3 3
4 767.4 5 9 0.850/60 1.4457160 3 3
6.1.2.3. Cyclic Oligomers
Oligomers n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
r [O(CH2)31nl 1 5 8 . 1 4 7 1 4 0
4 232.3 7 0 38,92,140,141,143
rl = 3-8: GC, MS; Refs. 140,141,143
8 6 . 1
344.5 157
n = 3- 9: GLC, MS; Ref s. 140, 143
114.2
456.7 138
465.1 122
r 1 WW41q
2 144.2 183-185 60113 147,148
n = 2-9: GC, MS; Refs. 139
79-80/1013 142,143
38,92,140,143
139-141/1013 1 4 2
1 4 4
34.92
6.1.2.4. Oligomers of Catechol Poly(methylene ethers)
x
rto O(CH2)xlq
n Mol. wt. m.p. (C) b.p. ( Urnbar) dm
4 e
Refs.
1 1 122. 1 - 18 172-173/1013 1.0640 1.5423 198,199,208-211
2 244.2 261.6-262.6 1 9 8
2 1 136. 1 212-214/1009 1.180 208,210
2 272.3 208-209 4 1
3 1 150.2 14-15 120127 1. 1343 1.5396 199-203,210
2 300.3 150-152 41,202
5 1 178.2 Oil 9513 1. 0847 1.5346 199-201
2 356.4 185.5-187.5 2 0 1
IV/40 PHYSICAL DATA OF OLIGOMERS
6.1.2.4. contd
x n Mol. wt. m.p. (C) b.p. (Wmbar) d*O
4
I I F Refs.
6 1 192.2 38 104/ 1. 3 200, 204
2 384. 5 140-141 200-201/0.11 41,204
3 516. 1 112 204
7 1 206. 3 17- 18 156113 1. 0638 200
2 412. 5 158- 159 205
1 0 2 248. 4 Oil 179113 1.0342 200
2 496. 7 137- 138. 5 41
6. 1. 3. OLIGO(FOFUvL4LDEHYDE) DERIVATIVES
6.1.3.1. Oligo(oxymethyZene) Dihydrutes H[OCH2],OH
n Mol. wt. m.p. (C) Refs.
4 138.1 95-105 d 172
8 258. 1 115-120 d
12
6.1.3.2. Oligo(oxymethylene) Diacetates CH$O-[OCH2].-OCOCH3
n Mol. wt. m.p. (C) b.p. (Urnbar) d (g/cm3)PC nD/c Refs.
1 132. 1 - 23 39- 40/ 0. 13 1. 128/ 24 1.4025124 2- 4
2 162. 1 - 13 60- 6210. 13 1. 158/ 24 1. 4124124 3, 4
3 192. 2 - 3 8410. 13 1. 179/ 24 1. 4185/ 24 3
4 222. 2 7 102-W/O.13 1.195124 1.233 124 2. 3
5 252. 2 17 124-126/0.13 1.204124 1.4258124 3
8 342. 3 32- 34 1. 216136 1.4291136 23
9 372. 3 40- 43 1. 353115 3
1 0 402. 4 63. 1- 66. 2 3, 218
1 1 432. 4 11. 2- 73. 7 3, 218
12 462. 4 79. 9- 82. 5 2, 3, 218
14 522. 5 84- 86 3
15 552. 5 90. 5- 92 1. 364/ 15 3
16 582. 5 93- 95 2.3
17 612. 6 98. 5- 99. 5 1. 370115 3
19 612. 6 107- 109 1. 390/ 15 3
20 702. 6 111-112 2, 23
22 162. 7 116-118 1. 465 3
6. 1. 3. 3. Oligo(oxymethyZene) Dimethyl Ethers CH3-[OCHz] .-OCH,
n Mol. wt. m.p. (C) b.p. (Urnbar) d (g/cm3)/C Refs.
1 76.1 104.8 45.511013 0. 8538/ 20 5, 8, 12, 15
2 106. 1 - 69. 7 105.0/1013 0. 9597125 5,13-15,197
3 136. 2 - 42. 5 155.9/1013 1.0242125 5,197
4 166. 2 - 9. 8 201.8/1013 1.0671125 5,197
5 196. 2 18. 3 242. 311013 1. 1003/ 25 5, 197
6 226. 3 31- 34 3
8 286. 4 49- 51 3
1 0 346. 4 63. 1- 66. 2 3, 218
1 1 376. 4 11. 2- 13. 1 3, 218
12 406. 5 79. 9- 82. 5 3, 218
13 436. 5 89- 91 3
14 466. 5 101-104 3
15 496. 5 109-111 3
6.1.3.4. OZigo(oxymethyZene) Dipropyl Ethers C3H7-[OCH2]n-OC3H7
Ol i gomers of Al dehydes IV/41
C3H7 n Mol . wt . m. p. (C) b. p. (Urnbar) d/T (g/cm3) nJ T Refs.
n- 1 132.2 137.5/1013 0.83325125 1.3913125 6-9
2 162.2 61115 0.89725125 1.4004/25 69
3 192.2 97115 0.94325125 1.4086/23 699
4 222.3 - 15 to - 13 0.99025125 1.4137126 6
5 252.3 8-8. 56 1.01424/25 1.4181/26 6
i- 1 132.2 117-119/1013 0.8242/20 1.3864/20 8.10
2 162.2 39.5-41131 0.8897/20 1.3971/20 1 0
3 192.2 68.2-68.5/4 0.9348/20 1.4035/20 1 0
4 222.3 93.5-94.514 0.9751120 1.4117/20 1 0
5 252.3 120-123/4 1.0275120 1.4235120 1 0
6 282.3 23. 4-24. 3 159-16315 1.101/26 1.4467126 1 0
6.1.3.5. Oligo(oqmethyZene) Diallyl Ethers CHz=CHCHz-[OCHz] .-OCHzCH-CH2
n Mol . wt . m. p. (C) b. p. (Urnbar) n&T Refs.
1 128.2 138-139/1013 1.4226121 6. 11
2 158.2 75-16.5120 0.946 1.4280/25 6
3 188.2 58.5-6410.4 0.992 1.4320125 6
4 218.2 - 4.3 82-8710.4 1. 027 1.4350125 6
5 248.3 1 5 . 5 105-107/0.4 1.059 1.4371125 6
6 278.3 22.5 144-155/0.5 1.079 1.4411125 6
6.1.3.6. Cyclic OZigo(oxymethyZenes) r [OCH&-
n Mol . wt . m.p. (C) b. p. (Urnbar) d (g/cm 3, Refs.
3 9 0 . 1 67-68 114.5/1013 1. 39 16-18,31,46-48,121,122
4 120. 1 1 1 4 1. 435 17-19,31,46-48,122,123
5 150.2 6 1 1.480 31,45-47
6 180.2 72.5 1.440 4 7
1 5 450.4 68-70 3 1
6.1.4. OLIGOMERS OF HIGHER ALDEHYDES
Al debyde Oligomers n Mol . wt . m.p. (C) b. p. (Urnbar) Refs.
CHx-CHO
CsHs-CHO
r [OCWWI~
r [OCH(C&s)h-
3 132. 3 1 2 . 6 125/1013 2 0
4 176.2 246.2 112- 115 ( Subl . ) 20,21
3 318.4 175-176 7511013 3 5
444.5 284-285 3 6
6.1 S. HIGHER CYCLIC OLIGO(ACETALS)
6.1.5.1. Oligomers of I ,3-Dioxacycloalkanes rOCH2-O(CH2),]q
x n Mol . wt . m. p. (C) b.p. (Urnbar) dd (g/cm3)/C ?lDlC Refs.
2 1 74.1 - 95.3
2 148.2 6 7
5 370.4 2 8
7511013 1.0595/20 1.4002/20 1 5 1
152-155
1 5 2
n = 2-5: NMR, Ref. 1 5 2
n = 2-9: GC, MS, Refs. 153-155
IV/42 PHYSICAL DATA OF OLICOMERS
6.1.5.1. contd
x It Mol. wt. m.p. (C) b.p. (Urnbar) dd (g/cm3)PC n&T Refs.
4 1 102. 1 117/1009 1.003/20 1.4308/20 22,147,156-158
2 204.3 90-92 1 5 7
5 1 116.2 40-44115 22,169-171
2 232.3 56-58 22,152,169
6 2 260.4 71-72 2 2
8 1 158.2 - 63 196/1013 0.985/25 1.4564125 159,160,162
2 316.5 8 2 159,160
9 2 344.5 68-69 2 2
1 0 2 372.6 93-94 2 2
1 4 2 484.8 103.5-104 2 2
6.1.5.2. Oligomers of Poly(oxacycloalkanes) rOCH2-(0CH$H&]~
x n Mol. wt. m.p. (C) b.p. (Urnbar) nDlC Refs.
2 1 118. 1
2 236.3
3 354.4
4 472.5
5 590.7
6 708.8
3 1 162.2
2 324.4
3 486.5
4 648.7
5 810.9
6 973.1
7 1135.3
8 1297.5
4 1
2
3
4
5
6
5 1
2
3
4
5
6
6 1
206.2
412.5
618.7
824.9
250.3
500.6
750.9
1001. 1
294.3
157/1013
59. 9-60. 3
Oil
34. 7-35. 2
Oil
39. 7-40. 1
n = 1-9: GPC, Ref. 168
2 7 5610.5
88. 0-88. 6 85 (subl.)
2 7
56.5
1 9
38. 3-39. 5
2 3
28.5
n = 1-8: GPC, H-NMR, 13C-NMR, Refs. 163,164,168
23.5 90/0.3
44. 0-44. 6
1 6
5 4
2 7
3 0
n = 1-4: GPC, Ref. 168
- 6.5 142- 14410.3
79. 1-79. 5
3 4
6 3
3 2
4 8
142-14410.3
n = 1-7: GPC, Ref. 168
1. 4421 151,158,168,170
152,168,171
152,168
152,168
1 6 8
1 6 8
1.4541/30 22,159,161,164,166-168
159,161,164,165,168,214
159,164,165,168,214
159,164,165,168,214
159,164,165,168,214
159,164,168,214
159,164,214
1 6 4
1.4616125 161,162,166-168
167,168,214
167.168.214
168,214
214
214
1.4642/20 166-168
168,214
168,214
168,214
214
214
1 6 6
6.1.5.3. Oligomers of Substituted 1,3-Dioxacycloalkanes r OCRTOCHZ-X-(CH&,,
R x II Mol. wt. m.p. (C) b.p. (Timbar) d4 (g/cm3)PC IZLJT Refs.
CH3
H
H
CHpCH2
CH=CH
1 130.2
2 260.4
1 100. 1
2 200.2
1 154.2
2 308.4
145.7/146.8
- 55.2
1 1 7
n = 2-6:
1
234
73-741139
1281979
HP-GPC
30/0.03
1.067120 1.4570/20
1.4932124
1 8 1
1 8 1
173,174
174,184,185
Ref. 174
160, 186
1 8 6
References Iv/43
6.1.5.4. Oligomers of 7,9-Dioxabicyclo[4,3,O]nonane
Q
rP T-Uq
Monomer Configuration n Mol. wt. m.p. (C) b.p. (CT) Refs.
4
,CHz cis 1 128.2 52.0112 1 9 1
0
2 256.3 142-143 191,192
tram 1 128. 2 51.0/27 1 9 1
2 256.3 107-109 191,192
6.1.5.5. Oligomers of Substituted PoZy(oxacycloaZkanes) r[OCH(CH$-(OCH$H&]q
x n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
2 1 132.2 3211.3 1 7 2
2 264.3 36-31 1 7 2
3 1 176.2 6010.3 1 7 2
2 352.4 61-62 1 7 2
4 1 220.3 8210.2 1 7 2
2 440.5 33-34 1 7 2
5 1 264.3 120/0.13 1 7 2
2 528.6 52-53. 5 1 7 2
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Iv/46 PHYSICAL DATA OF OLICOMERS
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6 . 2 . OLIGO(CARBONATES)
6.2.1. CYCLIC OLIGO(DIOL CARBONATES) r[O(CHd,* CO],+
x n Mol. wt. m.p. (C) Refs.
4 2 232.2 175-176 1,2,9
5 2 260.3 117-118 2,V
6 2 288.3 128-129 2,8,9
7 2 316.4 97-98 23
8 1 172.2 21.5-23 29
8 2 344.5 116-117 2,8,9
9 1 186.3 35-35 23
9 2 372.5 95-95.5 23
1 0 1 200.3 10-11 23
1 0 2 400.6 105-106
2,W
1 1 1 214.3 40-41
23
1 1 2 428.6 97-97.5 25
1 2 1 228.3 11-12
23
1 2 2 456.7 93-95 2,U-J
Oligo(carbonates) IV/47
6.2.2. CYCLIC OLIGO(CARBONATES) OF DI- AND
TRI-ETHYLENE GLYCOL r[O(CH2CH2O),-CO]q
X n Mol. wt. m.p. (C) Refs.
2 2 264.2 139-140 8
2 3 396.3 165-167 8
3 1 176.2 39-40 8
3 2 352.4 120-121 8
6.2.3. CYCLIC OLIGO@,p-BISPHENOL CARBONATES)
L &$-&j [O
A
RI R2
R2 k2
n Mol. wt. m.p. (C) Refs.
WH3)z H H 3 762.9 335-340 6,7,9,10
H H 4 1017. 1 3 7 5 3,4,9,10
CH3 H 4 1129.4 301-303 3,9
Cl Cl 4 1568.2 420 3,9
s H H 4 977.1 320-322 399
6.2.4. CYCLIC OLIGO(o,o-BISPHENOL CARBONATES)
R It Mol. wt. m.p. (C) Refs.
CH3 1 254.3 144-146 7
2 508.6 276-279 5-7
Cl 2 295.1 365-368 5
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Iv/48 PHYSICAL DATA OF OLICOMERS
6. 3. OLIGO(ESTERS)
6.3.1. OLIGO(ESTERS) OF HYDROXY ACI DS
6.3.1.1. Oligo(esters) of Aliphatic Hydmxy Acids
6. 3. 1. 1. 1. OLIGO(WHYDROXY ACID) METHYL ESTERS
H[OCHRCO] .0CH3
R n Mol. wt. b.p. (Urnbar) Refs.
C H 3 1 104.1 58- 59139
2 176. 2 79- 8013 53
CHWHd2 1 132. 2 81- 82160 51
2 232. 3 106. 5- 107/ 1 51
CWH3) z 3 332. 4 151- 153/ 1 51
4 432. 5 197- 199. 5/ 1 51
5 532. 6 207- 212 51
6. 3. 1. 1. 3. CYCLIC OLIGO(ESTERS) OF WHYDROXY ACIDS r[OCHRCO]q
6. 3. 1. 1. 2. ACETYL OLIGO(WHYDROXY ACID) METHYL ESTERS
CH3CO-[OCHRCO],OCH3
R it Mol. wt. b.p. (Urnbar) [{a}]:: Cont. Refs.
C H 3 1 146.1 67-68117 - 47. 3 1. 410 48, 53
2 218. 2 87- 8810. 7 - 65. 6 1. 98" 53
3 290. 3 144- 146/ 1 - 81. 8 1. 53a 53
CWCH3) 2 1 174. 2 89- 89. 5 - 30. 9 1. 7gb 51
CWCHd2 2 274. 3 101- 101. 5 - 43. 8 1. 146 51
3 374. 4 153- 154 - 49. 0 1. 216 51
4 474. 5 186- 188 - 53. 6 1. 14b 51
5 574. 6 230- 232 - 60. 8 0. 866 51
%I CH*C12.
bin CHCl 3.
R ConfIg. n Mol. wt. m.p. (C) b.p. (Urnbar) HaHr, Refs.
H 2 116.1 86- 87 169116 1, 2, 100, 101
5 290. 2 230 102
6 348. 2 215 102
CH3 L 2 144. 1 98. 7 150133 - 280a 3. 4
D L 2 144. 1 128 256 2- 1
WCHd2 L 2 200. 2 152- 153 - 256' 103
DL 2 200. 2 134- 135 103
CHzCWCH3) z L 2 228. 3 169- 170 - 226b 103
D L 2 228. 3 138- 140 103
nc=0.58, ChH,j, 18C.
by= 1, CHC13, 25C.
6.3.1.1.4. OLIGO((R)-P-HYDROXYBUTYRIC ACIDS) H[OCH(CH3)CH2CO] ,OH
n Mol. wt. m.p. (C)
HaHF
(c = 1, CH#& rl (nm) Method Refs.
2 190. 2
3 216. 3
4 362. 4
5 448. 5
6 534. 5
7 620. 6
8 706. 7
12 1051. 1
16 1395. 5
24 2084. 2
32 2172. 9
64 5527. 9
128 11037. 8
- 19. 7 (H20); 389
NMR, MS
49 - 52. 9, 365
65
81
89
100-101 11.7; 365
128-129 - 7. 7; 365
134. 3
155- 156. 5
154. 3 3. 8; 365
161. 3 7. 1; 365
I R, NMR, MS
NMR, MS
NMR, MS
I R, NMR, MS
I R, NMR, MS
NMR
I R, NMR, MS
I R, NMR, MS
NMR, MS
149, 150
149
63,64,73,144,149
64,73,144,149
64, 73
64, 73
64,73,144,151
1 4 4
1 4 4
1 4 4
1 4 4
1 4 4
1 4 4
6. 3. 1. 1. 5. OLIGO@-HYDROXYPIVALIC ACIDS) H[OCH2C(CH3)2CO] .OH
n Mol. wt. m.p. [Cl Refs.
1 118. 1 123- 124 50
2 218. 2 71. 5- 72. 5 50
3 318. 4 67- 68 50
4 418. 5 111. 5- 112. 5 50
5 518. 6 119.5-120.5 50
6 618. 7 138- 139 50
6. 3. 1. 1. 6. OLIGO( @-HYDROXYPIVALIC ACID) ISOBUTYL ESTERS
H[OCH2C-(CH3)2CO]nOCH2CH(CH3)2
n Mol. wt. m.p. (C) b.p. (Clmbar) Refs.
2 274. 4 115- 117/ 0. 7 49
3 374. 5 175- 17711 49
4 474. 6 75. 5- 76 49
5 574. 7 97- 98 49
6 674. 8 120. 5- 121. 5 49
7 774. 9 134- 135 49
Oligo(esters) of Hydroxy Acids IV/49
6.3.1.1.7. CYCLI C OLIGO(ESTERS) OF 6-HYDROXYTETRAHYDROPYRAN-2-CARBOXYLIC ACI D
Config. n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
RS 1 128.1 18-20 64- 6515 79, 82, 105
2 256. 2 160 76, 79, 80, 82- 84
4 512. 5 155 76, 79, 80, 82, 83, 85
5 640. 7 175 76, 79, 80, 82, 83, 86
R 1 128.1 + 142 81,83,87
4 512. 5 115 - 189 76, 78, 82- 84, 87
5 640. 7 125 - 136 76, 81- 83, 86, 87
I
I
6.3.1 .1.8. CYCLIC OLIGO(ESTERS) OF O-HYDROXY ACIDS r[O(CH,),CO]q
I
xa na Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
I 2 1 72.1 511133
3 216. 2 56- 58 104
I
4 288. 3 116- 120 104
I 5 350. 3 80- 85 104
6 432. 4 133- 135 104
/ 7 504. 5 84- 86 104
5 1 114.1 5 140-106/13 8-lo,91
2 228. 3 112-113 130/0.2 8,9,65,66,69,77,91-95
3 342. 4 25010. 3 9, 65, 66, 72, 91- 95
6 1 128.2 80-82/15 10
2 256. 3 45 13510. 3 9, 69
I 3 384. 5 20210. 3 9
7 1 142.2 72-73115 10,91
I 2 284. 4 93 15210. 2 9, 69, 91
8 1 156.2 31-31.5 86-87/13 9-11
2 312. 5 57- 58 158/ 0. 04 9, 10, 69, 77
3 468. 7 20 240/ 0. 1 9 I
9 1 170. 3 6. 4 100/ 13 9- 12, 77
2 340. 5 97 19210. 4 9, 12- 14, 69, 77
1 3 510. 8 29 27010. 4 9
10 1 184.3 3 116/13 9-12,77,91
I 2 368. 6 74 9, 12, 69, 77, 91
1 1 1 198.3 2 130/ 13 10,11,15,77,91
2 396. 6 104 9,69,77,91
12 1 212.3 27. 5 143113 9-12,16,77,91
2 424. 7 84 9, 14, 77, 91
13 1 226. 4 33- 33. 7 165120 9, 11, 16, 77
I 2 452. 7 107 9, 12, 77
14 1 240. 4 37- 37. 5 169113 9-11,16,77,91
2 480. 7 90- 91 9, 15, 69, 76, 77, 88, 91
, 15 1 254. 4 35. 5- 36. 5 188/ 20 9,11,16,77
2 / 508. 8 111 16 1 268. 4 42- 43 194120 9,11,16 9, 69, 77
2 536. 9 97 9
17 1 282. 5 37 14310. 3 9
2 564. 9 114 9
22 1 348. 6 36 17510. 3 9
2 697. 2 105 9
a~ =10, n =2.7 (sharp fractions): GPC, NMR, MS, Ref. 154.
6.3.1.1.9. CYCLIC OLIGOESTERS OF (R)-P-HYDROXYBUTYRIC ACID r[OCH(CH3)CH#J]A
n Mol. wt. m.p. (C) [a]? (c = 1, CHCI3) Methods Refs.
2 172. 2 124. 5- 125 - 91. 7 IR, NMR, MS, X-ray 146
3 258. 3 110-110.5 - 33. 9 IR, NMR, MS, X-ray 144,145,148,151
4 344. 4 178- 178. 5 15. 4 IR, NMR, MS, X-ray 144,151
5 430. 5 102. 5- 103. 5 6. 7 IR, NMR, MS, X-ray 144,151,152
6 516. 6 112-113.5 11.1 IR, NMR, MS, X-ray 144,151,152
IV/SO PHYSICAL DATA OF OLICOMERS
6.3.1.1.9. contd
n Mol. wt. m.p. (C) [a]$l (c = 1, CHCIJ) Methods Refs.
7 602.6 118-119.2 - 1.0 IR, NMR, MS, X-ray 144,151,152
8 688.7 84-85 3 . 1 NMR, X-ray 144, 151
9 774.8 92. 5-93 0.8 IR, NMR, MS 144, 151
1 0 860.9 89. 5-90. 5 + 0.5 IR, NMR, MS 144, 151
1 2 1033. 1 98-99 6.5 (CH2C12) IR, NMR, MS 1 4 4
1 6 1377. 5 122-123 1 . 3 (CH2C12) IR, NMR, MS 1 4 4
3 2 2754.9 NMR, MS 1 4 4
6.3.1.1.10. CYCLIC OLIGESTERS OF (R)-3-HYDROXYPENTANOIC ACID r[OCH(C,Hs)CH2CO$
n Mol. wt. m.p. (C) [a]: (c = 1 CHCIJ)
,
Refs.
3 300.4 98. 5-99. 0 - 19.4 1 4 7
4 400.5 36. 0-36. 6 34.0 1 4 7
5 500.6 110.5-111 1 9 . 8 1 4 7
6 600.7 97. 5-98. 5 1 9 . 6 1 4 7
7 700.8 54. 0-54. 5 1 3 . 2 1 4 7
8 801.0 1 5 . 3 1 4 7
9 901.1 1 4 . 5 1 4 7
1 0 1001.2 13.9 1 4 7
1 1 1101. 3 1 3 . 8 1 4 7
1 2 1201.4 1 3 . 2 1 4 7
6.3.1.2. Oligo(esters) of Aromatic Hydroxy Acids
6.3.1.2.1. LINEAR OLIGO(ESTERS) OF SALICYLIC ACIDS H
R3 R4 RS
Mol. wt. m.p. (C) Refs.
H H H H 2 258.2 148-149 17-19
3 378.3 150-152 1 3 0
4 498.4 177-183 1 3 0
H Me H H 2 286.3 1 6 2 2 0
H H Me H 2 286.3 128-129 2 0
6.3.1.2.2. CYCLIC OLIGO(ESTERS) OF SALICYLIC ACIDS
R3 R4 R5 R6
n Mol. wt. m.p. (C) Refs.
H
Me
H
H
Me
CHMez
H
H
Me
H
H
H
H
H
H
Me
H
H
H
H
H
H
Me
Me
2 240.2 234 17,19,132,135
3 360.3 200 17,21,132,135
4 480.4 298-300 17,132,135,141
6 720.7 3 7 5 1 7
2 268.3 240 20-23.135
3 402.4 264-265 22,13.5,139
4 536.5 299-300 22,135,141
2 268.3 255 20,22,23,135
3 402.4 207-207.5 22,135,139
4 536.5 3 0 5 2 2
2 268.3 235-235.5 20,22,23,135
3 402.4 244.5-245 22,135
4 536.5 3 4 7 21,22
2 296.3 211-212 1 3 7
3 444.5 2 5 5 137, 138
2 352.4 209 24,139,142
3 528.7 217 24,133,134,136,138,142
6.3.1.2.2. c ont d
Oligo(esters) of Di ol s and Di carboxyl i c Aci ds IV/51
R3 R4 R5 R6
n Mol. wt. m.p. (C) Refs.
Me H H CHMez 2 352.4 176-178 137,139
3 528.7 247 136-138.140
4 704.8 3 2 3 1 3 7
CMe3 H H Me 2 380.5 2 3 8 1 3 7
H CHMe2 H Me 2 352.4 1 3 6 1 3 7
3 528.7 1 9 1 1 3 7
P h H H H 4 784.8 360 1 3 7
6.3.1.2.3. CYCLIC OLIGO(ESTERS) OF THIOSALICYLIC ACIDS
R3 R4 R5 R6
II Mol. wt. m.p. (C) Refs.
H
Me
H
H
Me
CHMe 2
H
H
Me
H
H
H
H
H
H
Me
Me
Me
2 272.3 182-183 25,26,131,141,143
3 408.5 257-258 25,131
4 544.7 288-290 2 5
2 300.0 245-250 131,136
3 450.0 300-302 131,136
4 600.1 320 1 3 1
2 300.0 155-157 1 3 1
3 450.0 250-255 1 3 1
2 300.0 1 5 5 131,136
3 450.0 >300 131,136
2 328. 1 2 3 5 1 3 1
3 492.1 >300 1 3 1
2 384.1 203 1 3 1
6.3.1.2.4. LINEAR OLIGO(ESTERS) OF p-(P-HYDROXY)-ETHOXYBENZOIC ACID H[OCH2CH2
+ COInOR
n Mol. wt. m.p. (C) Refs.
R=H 1 182.2 1 7 7 2 7
2 346.3 1 6 5 2 7
3 510.5 1 8 3 2 7
4 674.7 1 9 2 2 7
R= -CH2CH20H 1 226.2 7 7 2 8
2 390.4 1 1 4 2 8
3 554.6 1 3 6 2 8
4 718.7 1 5 6 2 8
6.3.1.2.5. LINEAR OLIGO(ESTERS) OF 2,5-HYDROXYMETHYLFURAN CARBOXYLIC ACID HIOCHz
n = 1-5: GPC, HPLC, H-NMR; Ref. 67,68.
CO],0CH3
6.3.1.2.6. CYCLIC OLIGO(ESTERS) OF 2,5-HYDROXYMETHYLFURAN CARBOXYLIC ACID H[OCH2 CO],0CH3
n = 3-5: GPC, MS, H-NMR, 13C-NMR; Ref. 67,68.
6.3.2. OLIGO(ESTERS) OF DIOLS AND DICARBOXYLIC ACIDS
6.3.2.1. Aliphatic Oligo(esters)
6.3.2.1.1. CYCLIC OLIGO(ALKYLENE SUCCINATES) r [O(CH&O-CO(CH.&CO],l
x n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
2 2 288.3 1 3 1 29,30,89,108,116,118
3 1 158.2 8 2 90-9213 29,108,118,128
2 316.3 1 3 8 29,108,118,129
4 1 172.2 4 2 95-9613 29,108,118,128
2 344.4 1 2 1 29,108,118
IV/52 PHYSICAL DATA OF OLIGOMERS
6.3.2.1.1. contd
x n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
5 1 186.2 1 9 88-8911 29,108,118,128
2 312.4 8 7 29,108,118
6 1 200.2 - 15 108-110/3 29,108,118,128
2 400.5 1 1 0 29,108,118
I 1 214.3 4 9 116-118/1-3 29,108,118
2 428.5 8 6 29,108,118
8 1 228.3 7 1 29,108,118
2 456.6 1 0 9 29,108,118
1 0 1 256.3 6 0 130-132/1 29,108,118,128
2 512.7 1 0 9 15,29,108
6.3.2.1.2. CYCLIC OLIGO(ALKYLENE ADIPATES) 6.3.2.1.5. CYCLIC OLIGO(THIOESTERS) OF DICARBOXYLIC ACIDS
~[OCH2-X-CH20-CO(CH2)4CO],q
r[~(~~~)~~-~~(~H~),~~l~
X n Mol. wt. m.p. (C) Refs. x
Y
n Mol. wt. m.p. (C) Refs.
C(CH3)z 2 428.5 127-128 41
(CHdz 2 400.4 57 106
(CH2)3 2 428.5 82-84 1 1 5
(CH2)8
n = 1-5 (sharp fractions): GPC, NMR 156
6.3.2.1.3. CYCLIC OLIGO(ALKYLENE SEBACATES)
r[~(~H~X~~~(~~2)~~~1~
x n Mol. wt. m.p. (C) Refs.
2 1 228.3 4 2 15,29
2 456.6 8 1 15.29
3 1 242.3 1 4 29,31
2 484.6 113-113.5 15,29,31
8 1 312.5 6 8 6 9
6.3.2.1.4. CYCLIC OLIGO(ETHYLENE DICARBOXYLATES)
~[O(CH~)~O-CO(CHZ),COI;;
x n Mol. wt. m.p. (C) Refs.
1 2 260.2 160 109
2 2 288.3 1 3 1 29,30,116,118
3 2 316.3 144 106,107
4 2 344.4 5 6 1 0 7
5 2 372.4 147 106,107
6 2 400.5 5 4 1 0 7
7 1 214.3 5 2 15,29
2 428.5 1 4 7 15,29,106-108
8 1 228.3 4 2 15,29
2 456.6 8 1 15,29,106-108
9 1 242.3 3 5 1 5
2 484.6 1 4 3 1 5
1 0 1 256.3 1 8 2 9
2 512.7 9 6 15,29
1 1 1 270.4 - 8 2 9
2 540.7 145-146 15,29
1 2 2 568.8 102-103 15,108
2 1
3
4
5
5
3 3
4
4
324.5 144 1 0 9
380.5 140-145 110,111
408.4 97- 105 1 1 1
218.2 75-78 1 1 1
436.4 125-129 110
408.4 97-102 1 1 1
218.2 115-117 1 1 1
436.4 108-110 1 1 1
6.3.2.1.6. CYCLIC OLIGO(CYCLOHEXYLENE DICARBOXYLATES)
Q
H
rP
0 - CO(CH,),CO],7
X Mol. wt. Config. m.p. (C) Config. m.p. (C) Refs.
1 368.4 t r am 233-235 cis 189-191 112,113
3 424.5 220-222 144-146 112,113
5 480.6 210-212 143-145 112,113
7 536.7 160-162 134-136 112,113
8 564.8 145-148 93-95 112,113
6.3.2.1.7. CYCLIC OLIGO(ESTERS) OF OXALIC ACID
r [OCH2-X- CH20- COCO],J
x Mol. wt. m.p. (C) Refs.
CH2 260.2 185-187 108,125
CH20CH2 320.2 162.5-164 62,108,115
(CHzOCHd2 408.3 68-72 62,108
Oligo(esters) of Diols and Dicarboxylic Acids I v/ 53
6.3.2.2.3. CYCLIC OLIGO(O-XYLYLENE DICARBOXYLATES)
CH20- CO(CH2)&O]q
6.3.2.1.8. CYCLIC OLIGO(ESTERS) OF D IGLYCOLIC A CID
TO-X-O-COCH20CH$ZO]q
x Mol. wt. m.p. (C) Refs.
CH2CH2 320.3 185-187 114,129
CH(CH3)-CH(CH3) 376.4 128-130 114
(CHd20CHd2 408.4 125-126 129
-
x Mol. wt. m.p. (C) Refs.
320.3 233-235 117
348.4 215-218 1 1 7
376.5 217 1 1 7
404.5 1 7 3 117
432.6 144 1 1 7
460.6 1 2 1 1 1 7
488.7 134 117
516.7 119 117
544.8 1 3 5 117
428.4 276-278 114
428.4 265-268 114
.
416.3 208-209 114
6.3.2.2.4. CYCLI C OLIGO(ETHYLENEI SOPHTHALATES)
r[OCH$H20-CO
6. 3. 2. 1. 9. CYCLI C OLIGO(TETRAETHYLENE GLYCOL SUCCI NATE )
n = 1: X-ray, NMR, MS; n = 2-8: (sharp fractions): GPC, NMR, MS,
Refs. 160-162.
n Mol. wt. m.p. (C) Refs.
2 384.4 3 3 0 34,90
6.3.2.2. Aromatic Oligo(esters)
6. 3. 2. 2. 1. CYCLI C OLIGO(ALKYLENEPHTHALATES)
flO(CH,),O- CO COll
6.3.2.2.5. OLIGO(ETHYLENE TEREPHTHALATES)
6. 3. 2. 2. 5. 1. OLI GOMERI C HYDROXY ACI DS
CO],OH
II Mol. wt. m.p. (C) Refs.
n R Mol. wt. m.p. (C) Refs.
2 1 192.2 60-62 118,119
1 3 ; 412.4 384.3 1 9 8 1 9 3 90,108,118-120 108,120
4 1 220.2 106 108,120
I 2 440.5 140 108,120
5 1 234.3 101-102 108,119,120
2 468.5 139 108,120
6 1 248.3 64-65 108,119,120
I 2 496.6 6 6 108,120
7 2 524.6 163 108,120
8 2 552.7 64-65 108,120
9 2 580.7 140-141 108,120
/ 1 0 2 608.8 78-79 108,120
1 1 2 636.8 138-139 108,120
1 2 2 664.9 8 4 108,120
3
1 210.2 1 7 8 3 5
2 402.4 200-205 3 6
3 594.6 219-223 3 6
6.3.2.2.5.2. OLIG~MERIC DIOLS
CO],0CH2CH20H
n Mol. wt. m.p. (C) Refs.
1 254.2 109-110 35,36,59,74,75
2 446.4 173-174 35,36,74,75
3 638.6 200-205 35,36,74,75
4 830.8 213-216 35,36,74
5 1023.0 218-220 3 6
6.3.2.2.2. CYCLIC OLIGO(O-PHENYLENE DICARBOXYLATES)
!
I
rP O- CO(CH2)zCOl21
6.3.2.2.5.3. OLIG~MERIC D ICARBOXYLIC A CIDS
CO-[OCH2CH2WC0 CO],OH
n Mol. wt. m.p. (C) Refs.
x Mol. wt. m.p. (C) Refs.
1 358.3 >360 36-38
2 550.5 284-286 33,36-38
3 742.7 274-276 33,37,38
4 934.9 252-255 3 8
5 1127.1 233-236 3 8
3 412.4 238-240 122
5 468.5 145-147 122
I 524.6 110-112 122
8 552.7 108-110 122
IV/54 PHYSICAL DATA OF OLICOMERS
6.3.2.2.5.4. OLIGOMERIC DICARBOXYLATES 6.3.2.2.5.5. CYCLIC OLIGO(ESTERS)
CO-[OCH2CH20-CO CO],,0CH3
n Mol. wt. m.p. (C) Refs.
1 386.3 168-170 35,52,74
2 578.5 194-198 35,52,74
3 770.7 215-217 52,74
4 962.8 231-232 5 2
5 1155.0 242-243 5 2
6 1347.1 248-249 5 2
7 1539.3 250-252 5 2
8 1731.5 251-253 5 2
9 1923.7 253-254 5 2
1 0 2115.8 254-256 5 2
n Mol. wt. m.p. (C) Refs.
2 384.0. 225 32,33,46,57,75,90,159
3 576.5 321 33,39,40,43,44,46,57,58,
60,61,70,75,90,163-165
4 768.7 3 2 6 33,40,43,46,57,58,61,75,166
5 960.9 2 6 4 33,40,46,57,58,61,75
6 1152.7 3 0 6 33,46,58,61,75
7 1344.8 238-240 33,61,75
n = 3-13 (sharp fractions): GPC, MS, NMR, Ref. 158
6.3.2.2.6. CYCLIC OLIGO(ESTERS)OF DI- AND TRI-ETHYLENE GLYCOLS r[OCH,YCH,0-~~-~-~~-~~~,~~~2~-~~-~-~~]l
X Y 2 Mol. wt. m.p. (C) Refs.
CHzOCH2 428.4 173-179 40,43,57,90
CHzOCH1 CHzOCH2 472.4 2 2 3 45.90.115
(CHzOCHdz W20CHd2 560.5 1 3 0 9 0
CH20CH2 CHzOCH2 472.4 168-170 1 1 5
(CH20CHd2 (CHzOCHd2 560.5 108-111 1 1 5
c- [aCHlCH,-- (OCH2CH2C- COO CO)] n = 3-7 (sharp fractions): GPC, MS, NMR, Ref. 158 n
6.3.2.2.7. CYCLIC OLIGO(ESTERS) OF TETRAETHYLENE GLYCOL
Mol. wt.
I
m.p. (C) Refs.
1 324.3 98-99 126
2 648.7 9 6 90,126,127
6.3.2.2.8. CYCLIC OLIGO(ALKYLENE TEREPHTHALATES)
r,OCH,-x-CH20-COoCO]2,
XR na Mol. wt. m.p. (C) Refs.
KHz) 412.4 251 9 0
(CH2)3 2 440.4 2 0 8 9 0
(CH2)4 2 454.5 149 9 0
C(CH3)2 2 234.3 2 8 4 9 0
268.3 3 8 4 9 0
X = (CH 2) 8, n = 2-5 (sharp fractions): GPC, NMR, MS 157.
6.3.2.2.9. OLIGO(BUTYLENE TEREPHTHALATES)
6.3.2.2.9.1. OLIGOMERIC DIOLS
CO],0(CH2)40H
n Mol. wt. m.p. (C) Refs. n Mol. wt. m.p. (C) Refs.
1 310.3 7 2 96-99
2 530.6 138 43,96-99
3 750.8 1 7 5 96-99
5 1191.1 1 9 3 96-99
7 1630.5 2 0 2 97-99
6.3.2.2.9.2. OLIGOMERIC DICARBOXYLIC ACIDS
HOOCe CO[O(CH2)40- COG CO],OH
n Mol. wt. m.p. (C) Refs.
1 386.4 2 9 0 43,96-98
2 606.6 2 6 6 96-98
3 826.8 2 5 4 97,98
4 1047.0 2 4 7 97,98
6 1487.5 235 97,98
6.3.2.2.9.3. OLIGOMERIC DICARBOXYLIC ACID DIBENZYL ESTERS
CgHsCHz- 0- CO[O(CH&W COG CO],O- CH2C6HS
n Mol. wt.
1 566.6
2 786.8
3 1007.1
4 1227.3
6 1667.8
8 2108.2
1 0 2548.7
6.3.2.2.9.4. CYCLIC OLIGO(ESTERS)
r [O(CH2)40- coo~~l,z,
m.p. (C) Refs.
139 96-98
1 6 8 96-98
1 7 8 97,98
1 8 7 97,98
199 97,98
205 97,98
208 97,98
440.5 199 54-56,90,96,159
660.7 171.5 55,56,96
880.9 251 43,55,56,96
1101.2 207 9 6
n = 2-9 (sharp fractions): GPC, MS, X-ray (n = 2), Ref. 155
Oligo(esters) of Dials and Di carboxyl i c Aci ds IV/55
6.3.2.2.10. OLIGO(l.4-CYCLOHEXYLENEDIMETHYLENE 6.3.2.2.10.3. CYCLIC OLIGO(ESTERS)
TEREPHTHALATES)
6.3.2.2.10.1. OLIGOMERIC HYDROXY ACIDS
CO],OH
r[OCHz
++Hp-COGCO],
n Config. Mol. wt . m.p. (C) Refs.
Config. Mol . wt. (CT) Refs. 2 tram 548.7 2 9 9 9 0
n
0 m.p.
3 tram 823.0 385 41,42,90
1 t r am 292.3 175-178 4 1
6.3.2.2.10.2. OLIGOMERIC DICARBOXYLIC ACIDS
- 0
H CO],OH
n Config. Mol. wt. m.p. (C) Refs.
1 truns 440.4 >310 4 1
1 cis 440.4 > 300 4 1
6.1.3.2.2.11. OLIGOMERIC 4,4'-ISOPROPYLIDENEDIPHENOL (BISPHENOL A) TEREPHTHALATES
R~[O~C(CH~)~~O-CO~COI,,RI
RI R2
n Mol. wt. m.p. (C) Refs.
CsHsCHz
H
CeH&Hz
H
H
CsH5CHz
O-WH3)3 1 522.6
2 881.0
3 1239.4
4 1597.7
5 1956. 1
O-WH3)3 1 432.5
2 790.9
3 1149.2
4 1513.6
5 1866.0
OH 1 466.4
2 824.9
3 1183. 3
4 1541.6
5 1900.0
OH 1 376.4
OH 2 734.8
3 913.1
4 1451.5
O(CHd 1oBr 1 685.7
2 1044. 1
3 1402. 5
WHhoBr 1 826.0
2 1184.4
3 1542.8
A 1 1071. 3
2 1788. 1
Bb 1 1211.6
O-CW313 1 798.8
2 1157.5
O(CHd l&r 1 962.8
1 2 0
1 9 7
2 6 5
3 0 7
-
1 4 7
1 6 0
280
297
314
2 1 3
280
300
3 0 5
3 1 5
1 9 3
2 7 5
292
305
6 3
1 3 4
232
8 8
1 3 0
236
1 3 2
1 7 0
8 3
1 1 7
1 7 7
4 7
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
123,124
C = Br(CH&O-CO co.
IV/56 PHYSICAL DATA OF OLIGOMERS
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6. 4. OLICO(URETHANES)
6.4.1. OLIGO(ALKYLENE URETHANES)
6.4.1.1. Oligo(ethyZene urethanes) R-[OCH2CH2NHCO],-OCH3
R n Mol. wt. m.p. (C) b.p. (C/mbar) Re f s .
CH3C0 2
3
4
5
6
H 1
2
3
4
5
6
248.2 69-70
335.3 98-99
422.4 138.5-139.5
509.5 164-165
596.6 174-176
683.6 185-186
119.1 - 0
206.2 62-63
293.3 101.5-102.5
380.4 129-130
467.4 152-153
554.5 168.5-169.5
1 5
1 5
1 5
1 5
1 5
1 5
116-117/3 1 5
1 5
1 5
1 5
1 5
Oligo(urethanes) I V/ 5 9
6.4.1.2. Oligol(3-merhyl)erhylene urethanes] R-[OCH2CH(CH3)NHCO],-OCH3
R n Mol. wt. m.p. (C) b.p. (Wmbar)
[aID
c (o/c), EtOH Refs.
CH$O 1 175.2 109- 110/4 - 23.2 1. 39 1 1
2 276.3 93-98 - 30.2 0.32 1 1
3 377.4 113-117 -31.8 0.77 1 1
4 478.5 143- 147 - 30.9 1. 14 1 1
5 579.6 153-154 - 30.6 0.42 1 1
6 680.7 1 6 7 1 1
7 781.8 1 7 3 1 1
H 1 133.2 NJ-110/3 - 15.8 2.8 11,16
2 234.3 60-64 1 1
3 335.4 86-87 1 1
4 436.5 120-122 1 1
5 537.6 135-137 1 1
6 638.7 152-153 1 1
6.4.1.3. Oligo[(3-isopropyl)ethylene urethanes] CHJCO OCH$XNHCO -OCH3
[ kH3)Il,
n Mol. wt. m.p. (C) b.p. (Wmbar)
b]D
c (%), EtOH Refs.
1 203.2 117.5-118/1 - 22.2 0.79 1 0
2 332.4 111.5-112.5 - 33.5 2.0 1 0
3 461.6 142-143 - 28.4 2 . 1 1 0
4 590.7 156.5-158 - 4.2 1 . 9 1 0
6.4.1.4. Oligo[(3-isobutyl)ethylene urethanes] R OCH,CHNHCO
1 &H,CH(CH,), ]yocH3
R n Mol. wt. m.p. (C) b.p. (C/mbar)
[aI;
c (%), EtOH Refs.
CH3C0 1 217.3 128-129/1 9
2 360.5 73-74 -41.7 2.0 9,14
3 503.6 97-98 - 42.9 1.0 9,14
4 646.8 136-138 -41.5 1 . 4 9,14
5 790.0 149-150 - 38.5 2.0 9,13
6 933.2 162-164 - 35.9 1 . 0 9,13
7 1076.4 168-169 - 30.5 2.2 9,13
8 1219.5 180-181 1 2
9 1362.7 185.5-186.5 1 2
H 1 175.3 119-121/1 - 34.1 2.6 1 4
2 Oil - 47.2 2.3 1 4
3 Oil - 45.0 0.99 1 4
6.4.1.5. Oligo [(3-benzyl)ethylene urethanes] R OCH$HNHCO -OCH3
1 ~2Ws]n
R n Mol. wt. m.p. (C)
b]D
c (o/o), EtOH Refs.
CH3C0 2 428.5 104.5-106.5 - 17.9 1 . 2 11,14
3 605.7 138-139 - 18.1 0. 71 11,14
4 782.9 149-150 1 1
H 1 209.2 51. 5-53 - 25.9 0.72 11.14
2 386.4 130-131 - 27.8 0.77 11,14
3 563.6 153-154 1 1
I V/ 60 PHYSICAL DATA OF OLICOMERS
6.4.1.6. Oligo(trimethylene urethanes)
R n Mol. wt. m.p. (C) Refs.
CHjCO 2 276.3 57.5-58.5 1 8
3 377.4 95-97 1 8
4 478.5 118.5-120 1 8
5 579.6 133.5-135 1 8
H 1 133.2 Oil 1 8
2 234.3 Oil 1 8
3 335.4 76.5-79 1 8
4 436.5 106.5-108.5 1 8
5 537.6 126-128 1 8
6.4.2. OLIGO(URETHANES) OF DIISOCYANATES AND GLYCOLS
6.4.2.1. Oligo(urethanes) of Diisocyanates and 1,4-Butanediol
6.4.2.1.1. DIOL OLIGO(URETHANES)
H[O(CH2)40-CO-NH-X-NH-CO].-O(CH2)40H
6.4.1.7. Oligo(pentamethylene urethanes)
R-[O(CH2)5NHCO]n-OCH3
R n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
CH3C0 2 332.4 63.7 1,18-21
3 461.6 98.7 1,18-21
4 590.7 109.2 1,18-21
5 719.9 124.7 1,18-21
6 849. 0 131. 2 1,18-21
7 978.2 138.2 1,18-21
8 1107.4 143.2 1,18-21
9 1236.6 150.2 1,18-21
10 1365.7 155.2 1,18-21
H 1 161.2 131-134/0.3 1,18-20
2 290.4 75.2 1.18-20
3 419.5 100.2 1,18-20
4 548.7 112.2 1,18-20
5 677.8 116.2 1,18-20
6 807.0 125.2 1,18-20
7 936.2 135.2 1,18-20
8 1065.3 141.2 1,18-20
x n Mol. wt. m.p. (C) Refs.
KHZ)6 1
n
-P-Q-
OCH3 OCH3
L
3
4
5
6
7
9
1
2
3
7
1 5
1
2
3
4
5
348.4 103-105 2,3,5,6
606.8 1 4 6 US
865. 1 162-163 23
1123.4 169-170 23
1381.7 171-173 23
1640.0 173-174 23
1898. 3 175-176 2,3
2414.9 177-179 23
476.5 133. 5 23
862.9 127-128 23
1249.4 164- 166 233
2795.0 190-195 23
5886.3 210-215 23
404.4 1 1 5 2 2
710.7 1 2 2 2 2
1021.0 1 2 0 2 2
1331.3 1 3 6 2 2
1641.6 1 3 3 2 2
6.4.2.1.2. DIAMINE OLIGO(URETHANES)
H[NR-X-NR-CO-O(CH, ), o-COl, -NR-X-NHR
x R n Mol. wt. m.p. (C) Refs.
W2);:
-NzN-
Dihydrobromides.
H 1 536.4 228 5
2 794.7 226 5
3 1053.0 2 1 8 5
4 1311.4 212 5
1 314. 4 97-98 2 3
2 542.6 126. 5 2 3
3 770.9 147-148 2 3
4 999.2 1 6 9 2 3
References IV/61
6.4.2.1.3. ALKOXYACYLAMINE OLIGO(URETHANES)
RO[CO~~CHz+NHCO--(CH3101,CONH~CH2~NHCOOCHJ
R n Mol. wt. m.p. (C) Refs.
CH3 0
1
2
3
C2H5 0
1
2
3
CsH17 0
1
2
3
C1sH37 0
2
3
314.3 181. 7 2 4
654.7 185.2 2 4
995.1 201.6 2 4
1335. 5 176.9 2 4
328.3 125. 3 2 4
668.7 187.6 2 4
1009. 1 208 2 4
1449. 5 182. 5 2 4
412.5 1 1 4 2 4
752.9 183. 3 2 4
1093. 3 208.2 2 4
1433.7 1 8 5 2 4
552.7 123. 8 2 4
893. 1 166.2 2 4
1233. 5 192.4 2 4
1573.9 1 9 9 2 4
6.4.2.1.4. CYCLIC OLIGO(URETHANES) r[NR-X-NR-CO-O-Y-O-CO],1
R x Y n Mol. wt. m.p. (C) Refs.
H (CH2)6 (CHd4 1 258.3 1 6 4 467
2 516.6 1 9 8 623
CH3 CHzWHdzCHz 2 764.9 254-255 2 5
6.4.2.2. Oligo(urethanes) of Hexamethylene Diisocyanate and Diglycols
6.4.2.2.1. DIOL OLIGO(URETHANES)
HO[(CH&X(CH&O-CO-NH(CH&NH-CO-O],-
(CHdzWCHdzOH
x n Mol. wt. m.p. (C) Refs.
0 1 380.4 68-69
22
2 654.8 103-104 2
3 929.1 123-125 22
4 1203.4 120-123 2
5 1478.7 123-124
23
7 2026.3 122-124
23
1.5 4221.0 119-123
23
s 1 412.6 105-106 2
3 993.4 132-134 2
7 2155.5 133-135 2
REFERENCES
1. Y. Iwakura, K. Hayashi, K. Iwata, Makromol. Chem., 89,214 7. 0. Bayer, Ann. Chem., 549,286 (1941); Angew. Chem., 59A,
(1965). 257 (1947).
2. W. Kern, H. Kalsch, K. J. Rauterkus, H. Sutter, Makromol.
Chem., 44-46, 78 (1961).
3. W. Kern, Angew. Chem., 71, 585 (1959).
4. W. Kern, K. J. Rauterkus, W. Weber, Makromol. Chem., 43,
98 (1961).
5. H. Zahn, M. Dominik, Makromol. Chem., 44-46,290 (1961).
6. H. Zahn, M. Dominik, Chem. Bet, 94, 125 (1961).
8. W. Kern, K. J. Rauterkus, W. Weber, W. Heitz, Makromol.
Chem., 57, 241 (1962).
9. K. Iwata, Y. Iwakura, K. Hayashi, Makromol. Chem., 112,242
(1968).
10. K. Iwata, Y. Iwakura, K. Hayashi, Makromol. Chem., 116,250
(1968).
11. K. Iwata, Y. Iwakura, Makromol. Chem., 135, 165 (1970).
6.4.2.2.2. CYCLIC OLIGO(URETHANES)
r[(CH&X(CH&@CONH(CH&NH-CO-O],1
x n Mol. wt. m.p. (C) Refs.
0 1 274.3 138 4,17
2 548.6 170 1 7
3 722.9 131-133 1 7
4 1097.2 151-153 1 7
5 1371.5 136 1 7
6 1645.8 145-148 1 7
7 1920.1 134 1 7
S 1 290.4 128 4
.
IV/62 PHYSICAL DATA OF OLICOMERS
12. K. Iwata, Y. Iwakura, Makromol. Chem., 134, 321 (1970).
13. Y. Iwakura, K. Hayashi, K. Iwata, Makromol. Chem., 108,296
(1967).
14. Y. Iwakura, K. Hayashi, K. Iwata, Makromol. Chem., 93,274
(1966).
15. Y. Iwakura, K. Hayashi, K. Iwata, Makromol. Chem., 95,217
(1966).
16. Y. Iwakura, K. Hayashi, K. Iwata, Makromol. Chem., 104,46
(1967).
17. W. Heitz, H. Hoecker, W. Kern, H. Ullner, Makromol. Chem.,
150,73 (1971).
18. J. N. Hay. Makromol. Chem., 178, 1601 (1977).
TABLE 7. OLIGO(SULFIDES) AND OLICO(SELENIDES) 7.2. CYCLIC OLIGO(THIOALKYLENES) r[S(CH,),]q
7.1. CYCLIC OLIGO(THIOMETHYLENES) AND OLIGO(SELE-
NOMETHYLENES) r[XCH,]q
x n Mol. wt. m.p. (C) b.p. (Wmbar) Refs.
2 2 120.2
3 180.4
4 240.5
5 300.6
6 360.7
3 2 148.3
3 222.4
4 296.6
6 444.9
4 2 176.3
4 4 352.7
6 529.0
5 2 204.3
4 408.6
6 612.8
6 2 232.5
4 464.9
6 697.4
10 2 344.7
16 2 513.0
112-113
8 4
224-225
97.5-99
91-93
199-200/1013 43-45
22,24,27
23,25,26,30
2 5
25,28,29
86-8711 25,29,42
23,30
25,29,30,42
2 5
2 5
2 5
2 5
25,26
2 5
2 5
21,25
2 5
2 5
21,26
2 6
X n Mol. wt. m.p. (C) Refs.
S 2 92.2 105-106 1 1
3 138.3 215-218 l-7,15,16,20
4 184.4 49-50 15 >, 6 , 8 113,18,20
5 230.5 123-125 6,9,13,14,19,20
S 6 276.5 221-229 1 2
Se 3 279.0 226-228 1,17
4 372.0 80-81 1
19. H. Tagawa, E. Wada, K. Iwata, K. Hayashi, Y. Iwakura, Rep.
Prog. Polym. Phys. Japan., 10, 211 (1967).
20. H. Tagawa, E. Wada, T. Sakurai, Makromol. Chem., 154,215
(1972).
21. M. Nagura, H. Tagawa, E. Wada, Makromol. Chem., 165,325
(1973).
22. B. Fu, C. Feger, W. J. MacKnight, N. S. Schneider, Polymer,
20, 889 (1985).
23. L. L. Harrell, Jr., Macromolecules, 2, 607 (1969).
24. Y. Camberlin, J. P. Pascault, J. M. Letoffe, P. Claudy, J. Polym.
Sci., Polym. Chem. Ed., 20, 383 (1982).
25. S. Foti, P. Maravigna, G. Montaudo, Macromolecules, 15,883
(1982).
87-88
57.5-59
29-30
94-95.5
31-32
67-10
81-82.5
33-33.5
36.5-38
8 2
30-32
56-59.5
48-49
75-77
7. 3. SUBSTITUTED CYCLIC OLIGO(THIOETHYLENES) r[S-CR1R2-CHR&q
RI RZ R3 n Mol. wt. m.p. (C) Refs.
CH3 H H 4 296.6
5 370.7
C2H5 4 352.7
(CHdzCH 4 408.8
C6H5 2 272.4
CH3 CH3
H 2 176. 3
CH3 H CH3 4 352.6
H 2 280.5
32,33
Oil 32.33
3 3
3 3
33,34
3 3
155-180 33,35
(MN
3 3
7.4. CYCLIC CO-OLIGOMERS OF FORMALDEHYDE AND
THIOFORMALDEHYDE r[OCH2-(SCH&.j-l
x Mol. wt.
4 214.4
5 260.5
m.p. (C)
106-108
163-165
Refs.
6,lO
6,lO
Oligo(sulfides) IV/63
7.5. CYCLIC OLIGO(ETHER SULFIDES) r[(SCH~CH~)x-(OCH~CH&]n~
x
Y
n Mol. wt. m.p. (C) b.p. (Wmbar) Refs.
1 1 1 104.2
1 2 208.3
2 1 148.2
2 2 296.5
3 1 192. 3
3 2 384.6
4 1 236.3
5 1 280.4
2 1 1 164. 3
1 2 328.6
1 3 492.9
2 1 208.3
3 1 252.4
4 1 296.4
3 1 1 224.4
2 1 268.5
3 1 312.5
4 1 356.6
4 1 1 284.5
2 1 328.6
- 17
22. 5-23
90-91
Liquid
5 0
1 2 3
20-24
51-52
54-56
89-90
43-44
147/1007
40-48/0.2
go-9511
123-124/0.1
164-170/0.1
62-6410.1
134-136/0.1
34-3610.1
200-206/3
Liquid
93-95
1 2 5
45,46
26,36
30,3 1
26,31,36
31,36
26,36
30,31
30,31
30,31
28,29
2 8
3 1
29-31
30,31
30,31
30,3 1
30,31
30,31
30,3 1
3 1
7. 6. THIACYCLOPHANES
r[--Cl%
CH2-S-1,
x n Mol. wt. m.p. (C) Refs.
CH 2 212.4 122-123 30,37,39
3 408.7 124-125 37,39
4 544.9 161-162 3 9
N 2 274.4 220-222 30,37,38,41
3 411.6 18. 5-188 30,37,40,41
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
M. Russo, L. Mortillaro, L. Credali, C. De Checchi, J. Polym. 16.
Sci. A-l, 4, 248 (1966).
17.
A. W. V. Hofmann, Ann. Chem., 145, 357 (1868).
E. Baumann, Chem. Ber., 23, 60 (1890).
R. W. Bonst, E. W. Constable, Org. Syn. Coll. Vol. II, 610.
M. Schmidt, K. Blaettner, Angew. Chem., 71, 407 (1959).
L. Credali, M. Russo, Polymer, 8, 469 (1967).
E. Gipstein, E. Wellisch, 0. J. Sweeting, J. Polym. Sci. B, 1,
237 (1963).
18.
19.
20.
M. Russo, L. Mortillaro, C. De Checchi, G. Valle, M. Mammi,
J. Polym. Sci. B, 3, 501 (1965).
M. Russo, L. Mortillaro, L. Credali, C. De Checchi, J. Polym.
Sci. B, 3, 455 (1965).
21.
22.
23.
24.
M. Russo, L. Mortillaro, L. Credali, C. De Checchi, J. Chem.
Sot. C, 428 (1966).
25.
E. Block, E. R. Corey, R. E. Penn, T. L. Renken, P. F. Sherwin,
J. Am. Chem. Sot., 98, 5715 (1976).
E. Weissflog, Phosph. Sulf., 12, 141 (1982).
M. Schmidt, K. Blaettner, P. Kochendoerfer, H. Ruf,
Z. Naturforsch., 21b, 622 (1966).
H. Schmidt, E. Weissflog, Z. Anorg. Allg. Chem., 406, 271
(1974).
26.
27.
28.
J. Lal, J. Org. Chem., 26, 971 (1961).
29.
B. G. Maura, L. Tulli, Ann. Chim., Roma, 55, 892 (1965).
L. Mortillaro, L. Credali, M. Russo, C. De Chjecchi, Polym.
Lett., 3, 581 (1965).
G. W. Frank, P. J. Degen, Acta Cryst. B, 29, 1815 (1973).
G. Valle, A. Piazzesi, A. de1 Pra, Cryst. Struct. Commun., 1,
289 (1972).
M. E. Peach, E. Weissflog, N. Pelz, Org. Mass Spectr., 10,781
(1975).
H. Stetter, W. Wirth, Ann. Chem., 631, 144 (1960).
D. Sellmann, L. Zapf, Angew. Chem., 96, 799 (1984).
W. Rosen, D. M. Busch, Inorg. Chem., 9, 262 (1970).
D. Gerber, P. Chongsawangvirod, A. K. Leung, L. A. Ochry-
mowycz, J. Org. Chem., 42, 2644 (1977).
L. A. Ochrymowycz, C.-P Mak, J. D. Michna, J. Org. Chem.,
39, 2079 (1974).
J. Buter, R. M. Kellogg, J. Chem. Sot., Chem. Commun., 466
(1980); J. Buter, R. M. Kellogg, J. Org. Chem., 46,4481(1981).
W. N. Setzer, C. A. Ogle, G. S. Wilson, R. S. Glass, Inorg.
Chem., 22, 266 (1983); R. S. Glass, G. S. Wilson, W. N.
Setzer, J. Am. Chem. Sot., 102, 5068 (1980).
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Austr. J. Chem., 24, 1401 (1971).
J. R. Meadow, E. E. Reid, J. Am. Sot., 56, 2177 (1934).
IV/64 PHYSICAL DATA OF OLICOMERS
30. J. S. Bradshaw, J. Y. K. Hui, J. Heterocycl. Chem., 11, 649
(1974).
31. J. S. Bradshaw, J. Y. K. Hui, B. L. Baymore, R. M. Izatt,
J. J. Christensen, J. Heterocycl. Chem., 10, 1 (1973);
J. S. Bradshaw, J. Y. K. Hui, J. Y. Chan, B. L. Haymore,
J. J. Christensen, R. M. Izatt, J. Heterocycl. Chem., 11, 45
(1974).
32. J. L. Lambert, D. van Ooteghem, E. J. Goethals, J. Polym. Sci.
A-l, 9, 3055 (1971).
33. E. J. Goethals, Adv. Polym. Sci., 23, 103 (1977).
34. A. Noshay, C. C. Price, J. Polym. Sci., 54, 533 (1961).
35. W. van Craeynest, E. J. Goethals, Eur. Polym. J., 12,859.9 (1976).
36. J. R. Dann, P. P. Chiesa, J. W. Gates, J. Org. Chem., 26, 1991
(1961).
TABLE 8. OLICOMERS CONTAINING N IN THE MAIN CHAIN
8. 1. OLIGO(AMIDES)
8.1.1. OLIGO(AMIDES) OF ~-AMINO ACIDS (NYLON 3)
8.1.1.1. Linear Oligo(amides) of P-Alunine H[NH(CHz)zCO].OH
n Mol. wt. m.p. Cd) CT) Refs.
1 89. 1 206 1
2 160. 2 212 2, 4, 96
3 231. 2 >25. 5 3, 4, 96
4 302. 3 >260 4, 96
5 373. 4 >310 5
6 444. 5 >320 5
8.1.1.2. Cyclic Oligo(amides) of P-Alanine r[ NH( CH2) 2CO] , l
n Mol. wt.
1 71. 1 74- 74. 5 6, 104, 113
2 142. 2 298- 299 4, 8, 9, 72, 84, 114, 116
3 213. 2 >360 4, 10, 84, 88, 93, 101, 114, 116
4 284. 3 353 4, 10, 84, 114, 116
5 355. 4 327 84, 114, 116
6 426. 5 360 114, 116
I 497. 6 341 114, 116
8 568. 8 >360 114, 116
9 639. 7 349 114, 116
10 710. 8 >350 116
11 781. 8 >350 116
m.p WI Refs.
8.1.1.3. Linear Oligo(amides) of C-Methyl-@Alanines
H[NHCHRiCHR2CO],0H
Rl R2 n Mol. wt. m.p. (C) Refs.
CH3 H 1 103. 1 188- 189 102
3 273. 3 240- 241 92
37. F. Vogtle, F. Ley, Chem. Ber., 116, 3000 (1983).
38. F. Viigtle, L. Schunder, Chem. Bet, 102, 2677 (1969).
39. R. H. Mitchell, V. Boekelheide, J. Am. Chem. Sot., 96, 1547
(1974); V. Boekelheide, J. L. Mondt, Tetrahedron Lett., 1203
(1970).
40. K. Galuszko, Rocz. Chem., 49, 1597 (1975).
41. H. J. J.-B. Martel, M. Rasmussen, Tetrahedron Lett., 3843
(1971).
42. B. V. Gorewit, W. K. Musker, J. Coord. Chem., 5,67 (1976).
43. R. G. Gillis, A. B. Lacey, Org. Synth., Coll. Vol. IV, 396 (1963).
44. V. Meyer, Chem. Ber., 19, 3259 (1886).
45. J. D. A. Johnson, J. Chem. Sot., 1530 (1933).
46. H. T. Clarke, J. Chem. Sot., 101, 1806 (1912).
8.1.1.4. Cyclic Oligo(amides) of C-Methyl-@Alanines
r[NHCHRtCHR$O]q
Rl R2 n
Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
CH3 H 1 85.1 100/13 104,105
3 255. 3 300 91
H CH3 1 85. 1 98- 99120 104
2 170. 2 255 84
3 255. 3 >350 84, 85, 87
4 340. 4 >350 84
5 425. 5 >350 84
6 510. 6 >350 84
7 595. 7 330- 335 84
8 680. 8 338- 340 84
9 765. 9 327- 330 84
10 851.0 330 84
11 936. 0 325 84
8.1.1.5. Linear Oligo(amides) of C-Dimethyl-P-Alanines
H[NHC(R~)ZC(R~)~COI.OH
RI R2
n Mol. wt. m.p. (C) Refs.
H CH3 1 117. 1 239 106
3 315. 4 209- 212 94
6 612. 8 207. 5- 210. 5 94
CH3 H 1 117. 1 217 103
3 315. 4 182- 184 95
8.1.1.6. Cyclic Oligo(amides) of C- Di methyl - f i - Al ani nes
r[NHC(Rl)zC(Rz)2COl~1
RI R2 n Mol. wt. m.p. (C) b.p. (Wmbar) Refs.
H CH3 1 99.1 70-7311.1 107
3 297. 4 255- 259. 5 84, 91
4 396. 5 270 84
5 495. 7 257 84
6 594. 8 310 84, 91
7 693. 9 290 84
8 793. 1 256 84
9 892. 3 315 84
10 991.3 252 84
11 1090. 5 315 84
12 1189. 6 245 84
CH3H 1 99. 1 16- 17 112/ 20 104, 105
3 297. 4 257- 258 91
Oligo(amides) IV/65
8.1.2. OLIGO(AMIDES) OF y-AMINOBUTYRIC ACID (NYLON 4) 8.1.3. OLIGO(AMIDES) OF-&AMINOVALERIC ACID (NYLON 5)
8.1.2.1. Linear OZigo(amides) H[NH(CHz) $01 .OH 8.1.3.1. Linear Oligo(amides) H[NH(CH2)4COlnOH
n Mol. wt . m.p. (C) Refs. n Mol. wt. m.p. (C) Refs.
1 103. 1 204- 205 1 1
2 188. 2 186 4,7,12
3 273. 4 198- 199 4
4 358. 4 202- 203 4
6 528. 6 196- 198 133
8 698. 8 206- 208 133
1 0 869. 0 199- 203 133
1 2 1039. 3 208 133
1 6 1379. 6 207- 209 133
20 1719. 4 206- 208 133
8.1.2.2. Cyclic Oligo(amides) r[NH(CH&CO]q
n Mol. wt. m.p. (C) Refs.
1 85.1 24 13, 14
2 170.2 283 4, 10, 70, 71, 73
3 255. 3 242- 243 4, l O
4 340. 4 255 4, 10, 70
6 510. 6 303 10, 135
8 680. 9 298 135
1 0 851. 1 312 135
1 2 1021. 3 301 135
1 4 1191. 5 >355 135
8.1.2.3. Anionic Oligo(amides)
CGHsCO-[NH(CH&CO],-N,
o=h,(cH2)3
n Mol. wt. m.p. (C) Refs.
0 189. 2 92. 5 15
1 274. 3 121 16
8.1.2.4. Cari oni c Oligo(amides)
R+-[NH(CH&CO],-N,
cl-
1,(CH2)3
o = c
R n Mol. wt. m.p. (C) Refs.
H2
1 206. 5 181 71, 89, 118
Hz
/f-c- (cH2)3 11 0 188. 7 156 89, 119
N H 1 273. 5 162 89
8.1.2.5. Amidino-Oligo(aminobutyric Acids)
(n12~~~-[NH(cH2)3col,oLI
n Mol. wt. m.p. (C) Refs.
1 170.2 175-177 89, 118, 121
2 255. 3 175 89
3 340. 4 162- 163 89
1 117.2 160-162 1 7
2 216. 3 178 18
3 315. 4 184- 185. 5 18
4 414. 5 196. 5- 198. 5 18
8.1.3.2. Cyclic Oligo(amides) r[NH(CH&CO],l
n Mol. wt. m.p. (C) Refs.
1 98.1 39- 40 14, 17, 19
2 198. 3 295- 296 8, 18
3 297. 4 329- 331 18
4 396. 5 266- 267 18
8.1.3.3. Cationic Oligo(amides)
R+-[NH(CH,),CO],N,
cl-
1,(CH2)4
o = c
R n Mol. wt. m.p. (C) Refs.
Hz 1 234. 5 114 89
, c - 0 216. 5 93- 94 89
(cH2)4 /I
NH 1 315.5 1 3 8 89
8.1.3.4. Amidino-Oligo(aminovaleric Acids)
,C-[NH(CH2)&O],0H
(CH2)4 11
N
n Mol. wt. m.p. (C) Refs.
1 198.3 166-168 89,118
2 297. 4 92- 94 89
3 396. 5 112 89
8.1.4. OLIGO(AMIDES) OF E-AMINOCAPROIC ACID (NYLON 6)
8.1.4.1. Linear OZigo(amides) H[NH(CH2)5CO] .OH
n Mol. wt. m.p. (C) Refs.
1 131. 2 206- 208 20, 21
2 244. 3 204- 205 22- 24, 136
3 357. 3 208- 209 23- 25, 69, 136
4 470. 6 220- 221 23, 24, 36
5 583. 8 214- 215 23, 69, 136
6 697. 0 212- 214 23, 24, 136
7 810. 1 210- 211 23, 69, 136
8 923. 3 210- 211 23
9 1036. 5 208- 211 26, 69
1 0 1149.6 212- 213 26
1 1 1262.8 209- 212 26, 69
1 2 1375.9 211- 213 26
1 3 1489.1 210- 211 69
1 4 1602.3 207- 208 136
1 5 1715.3 207- 208 69
1 7 1941.5 209- 211 69
I v/ 66 PHYSICAL DATA OF OLIGOMERS
8.1.4.1. contd
n Mol. wt. m.p. (C) Refs.
1 8 2054.9 206-209 136
2 1 2394.5 212-213 6 9
2 2 2507.5 209-211 136
2 5 2847.0 212-213.5 6 9
2 6 2960.2 209-211 136
3 0 3412.8 210-213 136
3 4 3865.5 211-214 136
3 8 4318.1 214-217 136
8.1.4.2. Oligo(aminocaproic Amides)
H;[NH(CH&CO],-NHR CL-
R n Mol. wt. m.p. (C) Refs.
n-C4H9 1 222.8 1 4 3 122
2 335.9 176 122
3 449.1 189 122
CH&Hs 1 256.8 164.5 122
2 369.9 179 122
3 483.1 194-195 122
8.1.4.3. Amidino-Oligo(aminocaproic Acids)
,C-[NH(CH2)sCO]n-OH
P2)5 II
N
n Mol. wt. m.p. (C) Refs.
1 226.3 168 120,128
2 339.5 120 120
3 452.6 154 120
8.1.4.4. Amidino-Oligo(aminocaproic Amides)
,c----WWWsCOln--NHR
(CH2)s II
N
R II Mol. wt. m.p. (C) Refs.
n-C4H9 0 168.3 5 3 122
1 281.4 129 122
2 394.6 148-150 122
CH2CsHs 0 202.3 76-78 122
1 315.5 1 3 5 122
2 428.6 157 122
8.1.4.5. Anionic Oligo(amides)
CH3CO-[NH(CH2)SCO]n-N,
O=&,(CH2)s
n Mol. wt. b.p. (Urnbar)
e G
Refs.
0 155.2 123121 1.4898 3 2
1 268.5 1.4992 0.76 3 3
2 381.5 0.67 3 3
3 494.7 0.58 3 3
PC: solvent, tetrahydrofuran/cyclohexane/water (186: 14: 10).
8.1.4.6. Cationic Oligo(amides)
R+-[NH(CH2)sCO]n-N,
cl-
I ,(CH2)5
o = c
R n Mol. wt. m.p. (C) Refs.
Hz 1 262.8 112 120
2 375.9 Oil 120
3 489.1 Oil 120
CH2IQ ,c-
cl 244.8 137 89,120
1 357.9 106-108 120
8.1.4.7. End-group Protected Oligo(amides)
C2HSCO-[NH(CH2)sCO]n-NHCsH7
n Mol. wt. m.p. (C) Refs.
1 228.3 106 31,112
2 341.5 149 31,112
3 454.7 172 31,112
4 567.8 1 8 1 3 1
5 681.0 187 31,112
6 794.2 1 9 1 31,112
7 907.3 197 31,112
8 1020.5 2 0 0 31,112
9 1133.6 201 31,112
1 0 1246.8 201 31,112
1 1 1360.0 2 0 4 3 1
1 2 1473.1 2 0 2 31,112
1 3 1586.3 2 0 0 3 1
1 4 1699.3 205 3 1
1 5 1812.6 2 0 6 3 1
1 6 1925.8 2 0 6 3 1
8.1.4.8. Cyclic Oligo(amides) r@H(CH&CO],~
RF
no Mol. wt. m.p. (C) TCWb EAWC Refs.
113.2 69.5 0.56 0.88 14,17,27,78
226.3 348 0.48 0.81 4,24,28,29,45,78,98,110,111,112,148
339.5 244 0.34 0.77 4,24,28,29,45,78,98,111,112,147
452.6 256-257 0.25 0.69 4,24,28,29,45,78,98,111,112
565.8 254 0.16 0.59 4,24,29,78,98,111,112
678.9 260 0.10 0.49 4,24,29,60,98,111,112
792.1 243 0.08 0.40 29,30,60,98,111
905.3 254 0.04 29,30,60,98,111
1018.4 245 0.02 29,30,68,138
Oligo(amides) IV/67
8.1.4.8. contd
na Mol. wt. m.p. (C) TCW EAWC Refs.
1 0 1131.8 257 117,137
1 1 1244.8 249 1 3 8
1 2 1357.9 262 117,137
1 3 1471. 1 249 1 3 8
1 4 1584.3 263 117,137
1 5 1697.4 256 1 3 8
1 6 1810.6 2 6 1 117,137
1 8 2036.9 2 6 3 117,137
2 0 2263.2 259 117,137
2 1 2376.4 248 1 3 8
2 2 2489.5 250 117,137
2 4 2715.9 252 117,137
2 5 2829.0 249 1 3 8
2 6 2942.2 246 1 3 7
2 7 3055.3 244 1 3 8
2 8 3168.5 247 1 3 7
3 0 3394.8 2 5 5 117,137
3 2 3621.2 248 1 3 7
3 3 3734.3 2 3 1 1 3 8
3 4 3847.5 2 3 1 1 3 7
3 6 4073.8 228 1 3 7
3 8 4300.1 230 1 3 7
4 0 4526.4 235 1 3 7
4 8 5431.7 234 1 3 8
5 0 5658.1 229 1 3 8
5 5 6223.9 226 1 3 8
5 6 6337.0 229 1 3 8
6 0 6789.7 227 1 3 8
6 4 7242.3 226 1 3 8
7 0 7921.3 2 2 5 1 3 8
7 2 8 147. 6 2 2 5 1 3 8
8 0 9052.9 224 1 3 8
9 0 10184.5 222 1 3 8
1 0 0 11316. 1 2 2 1 1 3 8
a n = 2-40: HPLC (trifluoroethanol/water mixtures), Ref. 117; n = 2- 18: FD-MS, Ref. 117; n = 2-100: HPLC (trifluoroe.thanol/water, gradient elution, Ref. 138.
b PC, TLC: solvent, tetrahydrofuran/cyclohexane/water (186 : 14 : 10).
PC, TLC: solvent, ethyl acetate/acetone/water (10 : 10 : 2). Refs. 29,134.
8.1.5. OLIGG(AMIDES) OF HIGHER o-AMINO ACIDS
(NYLON 7-12)
8.1.5.1. Linear Oligo(amides) H[NH(CH2)JZO],,OH
x n Mol. wt. m.p. (C) Refs.
6 1 145.2 195 34,35
2 272.4 205-208 3 6
7 1 159.2 188 4,37
2 300.4 191-192 4,38
8 1 173.3 184 4,34
2 328.5 184-186 4
1 0 1 201.3 186-187 34,38,39
2 384.6 189-190 4,40,140
3 567.9 183-184 5,40,115,140
4 751.2 177-179 40,63,115
5 934.5 177-178 6 3
1 0 1850.8 181-182 63,67
1 1 1 215.3 186-187 4 1
2 412.6 192-193 3 1
8.1.5.2. Cyclic Oligo(amides) r[NH(CH&CO],1
n n Mol. wt. m.p. (C) Refs.
6 1 127.2 29-30 14,17,42
2 254.4 236-237 4,lO
3 381.6 259-261 8 9
6 4 508.8 215-216 8 9
5 636.0 2 3 6 8 9
6 763.2 244-245 8 9
8 1017.5 258-259 8 9
1 0 1271.9 262-263 8 9
7 1 141.2 72-73 13,14,34,42
2 282.4 277 4,10,76,77
3 423.6 217 8 9
4 564.8 2 1 9 82,89
5 706.0 215 8 9
6 847.2 215 8 9
8 1 155.3 138-139 14,42
2 310.5 201 4,lO
9 1 169.3 162 14,42
2 338.4 2 3 8 10,144
IV/68 PHYSICAL DATA OF OLIGOMERS
8.1.5.2. contd
x n Mol. wt. m.p. (C) Refs.
1 0 1 183.3 1 5 5 42,43,15
2 366.6 188-189 4,10,44,75,98
1 0 4 741.2 203 140
5 926.6 2 0 4 140
6 1111.9 2 1 7 140
I 1297.2 205 140
8 1482.5 221 140
9 1667.8 201 140
3 549.9 184 44,60,75,98
1 1 1 197.3 1 5 5 13,14,42,75
2 394.6 2 1 2 60,61,75,98,115
3 531.9 1 7 5 31,75
1 4 2 478.8 182 139
8.1.6. OLlGO(AMIDES) OF AROMATIC AMINO ACIDS
8.1.6.1. Linear Oligo(amides) of o-Aminobenzoic Acid
n Mol. wt. m.p. (C) Refs.
1 137.1 146 46-48
2 256.3 203-204 46,123,124,131
3 375.4 2 5 6 46,131
4 494.5 d 4 6
8.1.6.2. Cyclic Oligo(amides) of odminobenzoic Acids
Rl RZ n Mol. wt. m.p. (C) Refs.
H H 2 238.2 335-337 47,125-128,131
CH3 H 2 266.3 2 0 7 41
3 399.2 >320 1 3 1
4 532.2 >300 130
C6HSCH2 H 2 418.2 158-159 1 3 1
3 621.3 260-263 1 3 1
CH3 3 669.3 260-263 129
CH3 CH3 3 441.2 >300 1 2 9
8.1.6.3. Cyclic Oligo(amides) of m-Aminobenzoic Acids
~[RN~CJ,
R n Mol. wt. m.p. (C) Ref.
CH3 3 399.2 >320 132
8.1.6.4. Linear Oligo(amides) of p-Aminobenzoic Acid
H [NH+,,],
R n Mol. wt. m.p. (C) Refs.
H 2 256.1 216 8 6
3 315.4 2310 8 6
CZHS 2 284.1 176 8 6
3 403.2 > 266 8 6
4 522.2 >330 8 6
8.1.6.5. Cyclic Oligo(amides) of 4.Amiko-2,3-dihydroquinoline-
3-Carboxylic Acid
R n Mol. wt. m.p. (C) Ref.
n-C3H, 4 857.0 1 9 8 91
CHZC~HT 4 1049.2 2 0 6 91
8.1.7. CYCLIC DIAMIDES OF ALIPHATIC DICARBOXYLIC ACIDS
AND DIAMINES r[NH(CH2)xNp CO(CH&CO],l
x n Mol. wt. m.p. (C) Refs.
6
7
8
9
1 0
1 1
1 2
1 142.2 201 142
1 170.2 2 3 8 49,50,74,139
1 198.3 3 0 4 49,51,139
1 226.3 337 49,139
2 452.6 2 3 4 1 4 3
3 679.0 2 4 6 1 4 3
4 905.3 2 4 4 1 4 3
1 254.3 238 49,51,139
1 282.4 267 49,139
1 310.5 2 0 9 8,49,139,146
1 338.5 228 49,139,147
1 366.6 1 9 5 8,49,139
1 394.6 2 0 6 139
1 422.7 186 1 3 9
8.1.8. OLIGO(AMIDES) OF ADIPIC ACID AND HEXAMETHYLENE
DIAMINE (NYLON 6.6)
8.1.8.1. Linear Oligo(amides) H[NH(CH2)6NH-CO(CH2)4CO].OH
n Mol. wt. m.p. (C) Refs.
1 244.3 1 9 3 52,53
2 410.1 221-222 52,53,63
3 696.9 246-248 52,53,63
4 923.3 247-249 31,63,65
5 1149.5 247-250 31,63,65
1 0 2281.1 250-255 6 3
8.1.8.2. End-Group Protected Oligo(amides)
8.1.8.2.1. OLIGOMERIC DICARBOXYLIC ACID DIPROPYLAMIDES
C3H7NH-CO(CH2)4CO-[NH(CH2)6NH-CO(CH2)4CO].-NHC3H7
n Mol . wt . m.p. (C) Refs.
1 454.7 229-230 64
2 681.0 239-242 64
3 907.3 248-250 64
4 1133.6 257-260 64
5 1359.9 258- 261 64
8.1.8.2.2. OLIGOMERIC DIPROPIONYL DIAMINES
C2H5CO-[NH(CH2)6NH-CO(CH2)4CO].-NH(CH2)6NH-COC2H5
n Mol. wt. m.p. (C) Refs.
1 454.7 202-203 64
2 681.0 226-228 64
3 907.3 229- 231 64
Oligo(amides) IV/69
8.1.8.3. Oligomeric Diamines
H:[NH(CH2)6NH-CO(CH&CO],,-NH(CH2)6NH; 2C1-
It Mol . wt . m. p. (C) Refs.
1 415.4 248-250 6 5
2 641.7 249- 251 6 5
3 868.0 252-254 6 5
4 1094.4 251-254 6 5
5 1320.7 252- 255 65
8.1.8.4. Oligomeric Dicarboxylic Acids
HOOC(CH2)&0-[NH(CH&NH-CO(CH2)4CO].OH
n Mol. wt. m. p. (C) Refs.
1 372.4 188- 189 56
2 598.7 200-205 56,57
3 825.0 210- 211 56
4 1051.3 214-219 3 1
8. I .8.5. Cyclic OZigo(amides) r [NH(CH&NH- CO(CH&CO]q
no Mol . wt . m. p. (C) TCWb EAW= Refs.
1 226.3 254
2 452.6 243-244
3 678.9 235
4 905.3 273
5 1131.6 279
6 1357.9 279
7 1584.3 291
8 1810.6 282
9 2036.9 280
10 2263.2 280
12 2715.9 280
1 4 3168.5 292
1 6 3621.2 284
1 8 4073.8 275
2 0 4526.4 270
an = 1-20: HPLC (trifluoroethauol/water, gradient elution), Ref. 149.
b PC, TLC: solvent: tetrahydrofuran/cyclohexane/water (186:14: 10).
c PC, TLC: solvent: ethyl acetate/acetone/water .(lO: 10: 2).
0.47 0.51 51,53-55,62,80,81,90,98,108
0.28 0.38 53-55,62,80,81,90,98,109
0.13 0.23 53,55,62,98
0.06 0.16 53,60,62,98
1 4 9
1 4 9
1 4 9
1 4 9
1 4 9
1 4 9
1 4 9
149
149
1 4 9
1 4 9
8. 1. 9. OLIGO(AMIDES) OF SEBACIC ACID AND HEXAMETHY- 8.1.9.3. Oligomeric Diamines
LENEDIAMINE (NYLON 6.10) H[NH(CH2)6NH-CO(CH2)&O]n-NH(CH2)6NH2
8.1.9.1. Linear Oligo(amides) H[NH(CH2)6NH-CO(CH2)&O].OH
n Mol. wt. m.p. (C) Refs.
n Mol . wt . m.p. (C) Refs.
1 300.4 187- 188 58
2 582.8 196- 199 63,67
3 865.3 208-210 63,67
8.1.9.2. Cyclic OZigo(amides) r[NH(CH2)6NH-CO(CH2)&0],1
1 398.6 129-131 57,58
2 681.1 177-179 58
3 963.5 203-210 58
8.1.9.4. Oligomeric Dicarboxylic Acids
HOOC(CH2)sCO-[NH(CH2)6NH-CO(CH2)&O].0H
n Mol . wt . m. p. (C) Refs. n Mol . wt . m.p. (C) Refs.
1 282.4 232 51,98,145 1 494.6 156- 159 57,58
2 564.8 222 58,60,98,145 2 767.1 182- 184 57,58
3 847.3 221 1 4 5 3 1049.5 181-185 58
Iv/70 PHYSICAL DATA OF OLICOMERS
8.1.10. OLIGO(AMIDES) OF DECANE DICARBOXYLIC ACID AND
p,p-DIAMINO-DICYCLOHEXYLMETHANE (QIANA TYPE)
y[NH++CH2++NH-CO(CHz)&W],
n Mol. wt.
1 404.6
Config. m.p. (C) Refs.
tram-tram 310-314 8 3
cis-tram 269-272 8 3
cis-cis 254-257 8 3
8.1.11. OLIGO(AMIDES) OF OXALIC ACID AND HEXAMETHYLE-
NEDIAMINE r [NH(CH&NH- COCO],l
n Mol. wt. m.p. (C) Refs.
1 170.2 2 3 2 6 6
2 340.4 303 6 6
3 510.6 345 6 6
8.1.13. OLIGO(AMIDES) OF N,N-DIALKYLETHYLENEDIAMINE
AND DICARBOXYLIC ACIDS
8.1.13.1. Aliphatic Dicarboxylic Acids
rNRCH2CH,NR- CO(CH&CO],l
R x n Mol. wt. m.p. (C) Refs.
C6HsCHz 3 2 672.8 231-234 7 9
5 2 729.0 199-201 7 9
7 2 785.1 199-204 7 9
8.1.13.2. Terephthalic Acid rNRCH2CH2NR- COG CO],7
R n Mol. wt. m.p. (C) Refs.
CH3 3 654.8 114-123 9 9
CsHsCHz 3 1111.4 255-257 100
4 1481.8 143-145 100
6 2222.8 140-144 100
8.1.12. OLIGO(AMIDES) OF TEREPHTHALIC ACID AND
PENTAMETHYLENEDIAMINE [NH(CH&NW COG CO],
8.1.13.3. Pyridine-2.5Dicarboxylic Acid
rNRCH2CH2NR- CO+ CO],1
n Mol. wt. m.p. (C) Refs.
2 464.3 4 0 7 5 9
R n Mol. wt. m.p. (C) Refs.
CH3 3 663.8 123-129 9 9
4 885.0 132-136 9 9
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(1968).
86. H. Bredereck, H. v. Schuh, Chem. Ber., 81, 715 (1948).
87. L. Trossarelli, M. Guaita, A. Priola, Makromol. Chem., 109,
253 (1967).
88. G. Camino, L. Costa, L. Trossarelli, J. Polym. Sci., Polym.
Chem. Ed., 18, 377 (1980).
89. M. Rothe, Ch. Seltenreich, R. HoBbach, H. Emmett, unpub-
lished data.
90. L. E. Alexander, J. Polym. Sci., Polym. Lett. Ed., 10, 759
(1972).
91. J. Lowbridge, E. Mtetwa, R. J. Ridge, C. N. C. Drey, J.
Chem. Sot., Perkin Trans. I, 155, (1986).
92. C. N. C. Drey, E. Mtetwa, J. Chem. Sot., Perkin Trans. I,
1587 (1982).
93. D. N. White, C. Morrow, P. J. Cox, C. N. C. Drey, J.
Lowbridge, J. Chem. Sot., Perkin Trans. II, 239 (1982).
94. C. N. C. Drey, R. J. Ridge, J. Chem. Sot., Perkin Trans. I,
2468 (1981).
95. C. N. C. Drey, J. Lowbridge, R. J. Ridge, J. Chem. Sot.,
Perkin Trans. I, 2001 (1973).
96. W. Ried, K. Marquardt, Ann. Chem., 642, 141 (1961).
97. H. Berenbold, W.-H. Gtindel, Ann. Chem., 532 (1978).
98. G. Heidemann, Encycl. Polym. Sci. Technol., 9,485 (1968).
99. F. Voegtle, W. M. Mtiller, Angew. Chem., 96, 711 (1984).
100. F. Behm, W. Simon, W. M. Mtiller, F. Voegtle, Helv. Chim.
Acta, 68, 940 (1985); F. Voegtle, H. Puff, E. Friedrichs, W.
M. Miller, J. Chem. Sot., Chem. Commun., 1398 (1982).
101. J. L. Van Winkle, J. D. McClure, P. H. Williams, J. Org.
Chem., 31, 3300 (1966).
102. L. Birkofer, I. Starch, Chem. Ber., 86, 749 (1953).
103. M. D. Slimmer, Chem. Ber., 35, 400 (1902).
104. L. Birkofer, J. Schramm, Ann. Chem., 2195 (1975).
105. R. Graf, Ann. Chem., 661, 111 (1963).
106. D. H. Johnson, J. Chem. Sot. C, 126 (1968).
107. E. Testa, L. Fontanella, Ann. Chem., 625, 95 (1959).
108. M. G. Northolt, L. E. Alexander, J. Phys. Chem., 72,2838
(1968).
109. M. G. Northolt, Acta Cryst. B, 26, 240 (1970).
110. M. G. Northolt, L. E. Alexander, Acta Cryst. B, 27, 523
(1971).
111. G. Heidemann, H.-J. Nettelbeck, Faserforsch. Textiltechn.,
18, 183 (1967).
IV/ 72 PHYSICAL DATA OF OLICOMERS
112. H. Halbotb, J. Polym. Sci. C, 729 (1969); H. Halbotb,
G. Rehage, Faserforsch. Textiltechn., 18, 177 (1967).
113. M. Rothe, A. Haberle, unpublished data.
114. M. Rothe, F. Wehowsky, unpublished data.
115. M. Rothe, W. Fischer, unpublished data.
116. M. Rothe, D. Mtihlhausen, unpublished data.
117. M. Rothe, M. Lohmtiller, G. Schmidtberg, unpublished data.
118. M. Rotbe, W. Helmling, unpublished data.
119. H. Bredereck, K. Bredereck, Chem. Ber., 94, 2278 (1961).
120. M. Rothe, M. Schlipf, unpublished data.
121. M. Rothe, D. Jacob, unpublished data.
122. M. Rothe, W. Mtiller, unpublished data.
123. R. P. Staiger, E. B. Miller, J. Org. Chem., 24, 1214 (1959).
124. S. Petersen, E. Tietze, Ann. Chem., 623, 166 (1959).
125. N. S. Dokunikhin, L. A. Galva, J. D. Kraft, Dokl. Akad.
Nauk SSSR, 81, 1073 (1951).
126. F. C. Cooper, M. W. Partridge, J. Chem. Sot., 3429 (1954).
127. H. N. Rydon, N. H. P. Smith, D. Williams, J. Chem. Sot.,
1900 (1957).
128. D. J. Williams, J. Chem. Sot., Chem. Commun., 170 (1977).
129. S. J. Edge, W. D. Ollis, J. S. Stephanatou, J. F. Stoddart,
J. Chem. Sot., Perkin Trans. I, 1701 (1982); S. J. Edge.
W. D. Ollis, J. S. Stephanatou, J. F. Stoddart, D. J. Williams,
K. A. Woode, Tetrahedron Lett., 2229 (1981).
130. A. Hoorfar, W. D. Ollis, J. F. Stoddart, D. J. Williams,
Tetrahedron Lett., 4211 (1980); A. Hoorfar, W. D. Ollis,
J. F. Stoddart, J. Chem. Sot., Perkin Trans. I, 1721 (1982).
13 1. A. Hoorfar, W. D. Oills, J. A. Price, J. S. Stephanatou,
J. F. Stoddart, J. Chem. Sot., Perkin Trans. I, 1649 (1982);
W. D. Ollis, J. S. Stephanatou, J. F. Stoddart, A. G. Ferrige,
8.2. OLIGO(PEPTIDES)
8.2.1. OLIGO(PEPTIDES) OF GLYCINE
8.2.1.1. Linear OZigo(peptides) H[NHCHzCO] ,,OH
II Mol. wt. m.p. (C) Refs.
1 75.1 233-236 1
2 132.1 210-215 2,7,75
3 189.2 235 3,4,75
4 246.2 240 4,5,75
5 303.3 270 4,5,75,78
6 360.3 >256 d 6
8.2.1.2. Cyclic Oligo(peptides) r[NHCWOl,1
n Mol. wt. m.p. (C) Refs.
2 114.1 309 2,7,79,131,174,177,184
4 228.2 340 8,9,77,79,80,191,205,206
5 285.3 > 330 9,77-80,136
6 342.3 >360 4,8,10,11,77,79,80,131
7 399.4 > 280 77,79,131
8 456.4 > 350 77,79,131,205
9 513.5 290 77,79,131
1 0 570.5 290 77,79,131
1 1 627.6 300 77,79,131
Angew. Chem., 88, 223 (1976); W. D. Ollis, J. A. Price,
J. S. Stephanatou, J. F. Stoddart, Angew. Chem., 87, 169
(1975).
132. F. E. Elhadi, W. D. Ollis, J. F. Stoddart, D. J. Williams,
K. A. Woode, Tetrahedron Lett., 4215 (1980); F. E. Elhadi,
W. D. Ollis, J. F. Stoddart, J. Chem. Sot., Perkin Trans. I,
1727 (1982).
133. M. Rothe, E. Bigdeli, unpublished data.
134. M. Rothe, Makromol. Chem., 35, 183 (1960).
135. M. Rotbe, G. Ries, unpublished data.
136. M. Rotbe, M. Schilling, unpublished data.
137. M. Rothe, M. Lohmiiller, U. Breuksch, G. Schmidtberg,
Angew. Chem., 106, 2047 (1994); Angew. Chem., Int. Ed.
Engl., 33, 1960 (1994).
138. M. Rotbe, T. Mohr, B. Trnka, R. Berginski, unpublished
data.
139. M. Rothe, E. W. Reinold, unpublished data.
140. M. Rothe, H. Ritsche-Thoma, unpublished data.
141. M. Rothe, E. Gatter, unpublished data.
142. M. Rotbe, K. Steiner, W. Knobloch, unpublished data.
143. M. Rothe, K. Kitzelmann, unpublished data.
144. M. Rothe, N. Griiner, unpublished data.
145. M. Rothe, M. Gehrmann, unpublished data.
146. H. P GroBmann, J. Schwede, B. Heise, V. Rauschenberger,
E. W. Reinold, M. Rothe, Polymer Bull., 32, 653 (1994).
147. J. Dybal, B. Schneider, D. Doskocilova, J. Baldrian, H.
Pavlikovi, J. Kvarda, I. Prokopova, Polymer, 38,2483 (1997).
148. G. Di Silvestro, P. Sozzani, S. Bruckner, L. Malpezzi, C.
Guaita, Makromol. Chem., 188, 2745 (1987).
149. M. Rothe, G. Dangel, G. Ries, unpublished data.
8. 2. 2. OLIGO(PEFTIDES) OF SARCOSI NE
8.2.2. I . Linear OZigo(peptides) H[N(CH 3)CH zCO] .OH
n Mol. wt. m.p. (C) Refs.
1 89.1 211-213 1
2 160.2 190-191 13,17,21
8.2.2.2. Cyclic Oligo(peptides) r[N(CH3)CH2COlq
n Mol. wt. m.p. (C) Refs.
2 142.2
3 213.3
4 284.4
5 355.5
6 426.5
7 497.7
8 568.7
9 639.8
1 0 711.0
1 2 853.0
1 4 7
221
> 350
255
315
296
338
> 320
>320
13,27,51,61,177,187,191,204
51,191,192,197
51,166,191-195,198
51,191-193,199
17,51,163,166,191,193,200
51,191,193,201
51,191,193,196,202
17,163
193,203
17,163
8.2.3. OLIGO(PEPTIDES) OF L-ALANINE
8.2.3.1. Linear OZigo(peptides) H[NHCH(CH3)CO] ,,OH
Oligo(peptides) IV/73
Specific rotation
n Mol. wt.
1 8 9 . 1
2 160.2
3 231.3
4 302.3
5 313.4
6 444.5
I 515.6
m.p. (C)
298
251-263
269-272
> 320
> 320
> 320
[aID ((2 c (o/o)
Sol vent
+ 1 4 . 5 2 5 1 0 6.0 N HCI
- 38.5 21 0.9 0.2 N HCl
- 85.7 21 0.6 0.2 N HCl
- 131.0 21 0.6 0.2 N HCl
- 150.0 21 0.5 0.2 N HCl
- 167.0 2 7 0.3 0.2 N HCl
Refs.
1
6,12,15,73,85,138,139
14,15,73,85,138.139
15,16,73,85,138,139
15,16,85,138
15,16,85,138
1 5
8.2.3.2. Endgrozq Protected OZigo(peptides) R-[NHCH(CH3)CO] n -R
R R
Specific rotation
n Mol. wt. m.p. (C) [aIF c (%)
Solvent Refs.
-
BOC OMe 2 214.3 110-111 - 71. 8
3 345.4 193-194 -84.8a
4 416.5 >240 d - 84.0
5 487.6 >240 d - 83.1
6 558.6 >240 d -82.0a
7 629.1 >240 d - 79.5
Zb OEt 2 322.4 1 1 6 -51.1
3 393.4 1 9 2 - 73.0
4 464.5 251-253 -95.1
5 535.6 250 - 107.1
6 606.7 ~275 d - 119.3
I 677.8 >275 d - 125.4
1 0 891.0 >250 d - 136.9
MO 2 363.4 135-136 - 35.4
3 434.5 198-200 - 62.5
4 505.6 270-271 - 78.0
5 516.1 >275 d - 92.0
6 647.1 >275 d - 102.5
I 718.8 >275 d - 108.1
8 789.9 >275 d - 1171.1
9 861.0 >275 d - 121.6
MEEA OEt 3 419.5 138-140 - 70.7
4 490.6 240-241 - 89.2
5 561.6 >250 d - 98.5
6 632.1 >250 d - 108.2
7 703.8 >250 d - 119.0
MO 3 460.5 110-111 - 49.9
5 602.7 250 d - 87.5
6 673.8 >275 d - 94.5
7 744.9 >275 d - 102.3
8 816.0 >275 d - 104.4
9 887.1 >275 d - 110.2
0.5
0.5
0.5
0.5
0.25
0.25
0.2
0.47
0.48
0.46
0.45
0.45
0.45
0.44
0.20
0.55
0.49
0.20
0.45
0.50
0.44
0.40
0. 21
0.23
0.25
0.22
HFIP 86,95,102,103
HFIP 86,87,95,102,103
HFIP 86,87,95,102,103
HFIP 86,87,95,102,103
HFIP 86,87,102,103
HFIP 86,87,102,103
TFE 81-83
TFE 14,81-83
TFE 8 1
TFE 81-83
TFE 8 1
TFE 8 1
TFE 82.83
TFE 8 1
TFE 8 1
TFE 8 1
TFE 8 1
TFE 8 1
TFE 8 1
TFE 8 1
TFE! 8 1
TFE 8 1
TFE 8 1
TFE 8 1
TFE 8 1
TFE 8 1
TFE 81,84
TFE 81,84
TFE 81,84
TFE 81,84
TFE 81,84
TFE 81,84
a t = 22C.
bZ-, CcH&Hz-OCO-; BOC-, (CH3)3C-OCO-; MEEA-, CH30CH2CH20CH2CH20CH~CO-; -OMe, -CH3; -OEt, -OCZH5;
-MO, O - -N-; TFE, trifluorethanol; HFIP, Hexafluoroisopropanol.
8.2.3.3. Cyclic Oligo(peptides) r[NHCH(CH3)COm
Specific rotation
I I Mol. wt. m.p. (C)
[ aI D ( "C) c ( %)
Solvent Refs.
2 142.2 2 9 7 - 29.6 2 0 1 . 9 Hz0 6,79,174,183-185
4 284.3 250 - 68 2 2 0.5 DMF 134,135,195,206
6 426.5 >310 - 210.4 2 0 0.02 Hz0 136,137
IV/74 PHYSICAL DATA OF OLICOMERS
8.2.3.3. contd
Specific rotation
n Mol. wt. m.p. (C)
[alo (C) c (%)
Solvent Refs.
I 497.6 302 - 60.5 2 0 2.1 Hz0 7 9
8 568.6 3 3 1 - 62.1 2 0 1 . 4 Hz0 7 9
9 639.7 3 2 1 -97.1 2 0 1 H20 7 9
1 0 710.8 3 6 8 - 102.7 2 0 0 . 1 Hz0 7 9
1 1 781.8 289 - 133.0 2 0 0.002 H20 7 9
8.2.4. OLIGO(PEPT1DE.S) OF a-AMINOISOBUTYRIC ACID
CsH5CH20CO-[NHC(CH3)zCO],--OX
x n Mol. wt. m.p. (C) Refs.
WH313 1 293.4 60-1 88,90,91,94
2 318.5 134 90,91,94
3 463.6 166.5-167.5 88,91-94
4 558.1 178 88,89,91-94
5 633.8 2 3 6 88,89,91-94
6 718.9 215-218 88,91
I 804.0 229-230 9 1
8 889.1 241-248 9 1
9 974.2 262-263 9 1
CO4313 10 1059.3 257-258 9 1
1 1 1144.4 271-212 9 1
1 2 1229.5 > 300 9 1
1 231.2 88-89 90,151,152
2 322.4 161-162.5 1 5 1
3 407.5 205 -206 88,92
4 482.5 243-244 88,92
5 511.1 254-256 88,92
6 662.8 243-245 8 8
8.2.5. OLIGO(PEPTIDES) OF HYDROPHOBIC AMINO ACIDS (wAMINOBUTYRIC ACIDS, NORVALINE, VALINE, NORELEUCINE, LEUCINE,
ISOLEUCINE, CYCLOHEXYLALANINE, PHENYLALANINE, TRIYPTOPHAN)
8.2.5.1. Linear Oligo(peptides) H[NHCHRCO] .OH
Specific rotation
R n Mol. wt.
[aID (Cl c (%) Sol vent Refs.
L-Val 1 117.2
-CWCW2
2 216.3
3 315.4
L-Leu 1 131.2
-CH2CH(CH3)2 2 244.3
3 357.5
4 470.7
L-Ile 1 131.2
-CH(CH3)CH2CH3 2 244.3
+ 28. 8 2 0
+ 10. 8 2 5
-41.8 2 1
+ 13. 9 2 5
- 13.7 2 3
-51.4 2 0
- 90.0 2 0
+ 40. 6 2 0
+ 17.1 2 5
3.4
2.0
2.7
9 . 1
1 . 0
3 . 1
1.6
1
1
1 eq. HCl
6NHCl 1
H20
18,19
1 N Cl 1 9
4. 5 N HCl 1
1 N NaOH 18,22-24,74
1 N NaOH 2 6
1 N NaOH 2 6
6NHCl 1
H2O-t 2 0
8.2.5.2. Endgroup Protected OZigo(peptides) (CH3)3COCO-[NHCHRCO].-OCH3
Specific rotation
R n Mol. wt. m.p. (C) [aIT Sol vent Refs.
L-Abu 2 302.3 108-109 - 5.95 HFIPa 9 5
-CH2CH3 3 387.5 126-127 - 10.84 HFIPa 9 5
4 472.6 228-229 - 16.72 HFIPa 9 5
5 557.7 > 250 - 20.44 HFIP 9 5
8.2.5.2. contd
Oligo(peptides) IV/75
Specific rotation
R n Mol. wt. m.p. (C)
MT
Solvent Refs.
L-Nva
-CH2CH2CH3
L-Val
-CWX) 2
L-Me
-CH2CH2CH2CH3
L-IAI
-CH2CH(CH3)2
L-Ile
-CH(CH3)CH2CHj
D - d e
-CH(CH3)CH2CH3
L-Cha
-CH2 H
- 0
L-Phe
-CH2
43
6 642.8 >250
I 727.8 >250
2 330.4 95-96
3 429.5 119-120
4 528.7 207-208
5 627.8 220
6 726.9 220
7 826.1 220
2 330.4 166-167
3 429.5 170-171
4 528.7 247-248
5 627.8 > 260
6 726.9 > 260
7 826.1 ~-260
2 358.5 63-64
3 471.6 146- 147
4 584.8 214-215
5 698.0 > 240
6 811.1 > 240
7 924.3 > 240
2 358.5 141-142
3 471.6 158-1. 59
4 584.8 208-209
5 698.0 > 250
6 811.1 > 250
7 924.3 > 250
2 358.5 158-159
3 471.6 193-194
4 584.8 245
5 698.0 >250 d
6 811.1 >250 d
7 924.3 >240 d
8 1037.5 >240 d
2 358.5 133-134
3 471.6 175-176
4 584.8 2 4 5
5 698.0 >250 d
6 811.1 >250 d
7 924.3 >250 d
2 438.6 117-118
3 591.8 171-172
4 745.1 203-204
5 898.3 > 240
6 1051. 5 > 240
I 1204.7 > 240
2 426.5 121-122
3 573 .I 173-114
- 23.12
- 27.21
HFIPa
HFIP
9 5
9 5
98,102,103,105,113,153
- 48.3 TFEb
- 40.8 HFAb
- 76.7 TFEb
- 77.4 HFA*
-91.0 TFE*
- 107.5 HFA*
- 103.6 TFEb
- 126.2 HFA*
- 94.3 TFE*
193.0 HFAb
+37.8 TFEb
- 144.5 HFA*
- 3.88 HFIPC
-6.51 HFIP
- 6.42 HFIPC
- 7.74 HFIPC
- 7.26 HFIPC
-7.51 HFIPC
- 46.9 HFAd
-75.1 HFAd
- 92.6 HFAd
- 101.0 HFAd
- 111.1 HFAd
- 120.0 HFAd
- 44.0 TFEe
- 67.6 TFEC
- 83.4 TFEe
- 87.8 TFE
- 93.9 TFEe
+ 13. 9 TFEe
+ 24. 6 TFEP
+30.1 TFEf
+ 39. 9 HFIP8
+48.1 TFEf
+ 58.3 HFIPg
+ 58.3 TFEf
+ 13. 5 HFIPg
+ 55. 0 TFEf
+ 94. 8 HFIPg
+55.3 TFEf
+ 101. 8 HFIPg
+ 109. 4 HFIPg
- 43.3 HFIPh
-54.1 HFIPh
- 57.7 HFIPk
-61.2 HFIPk
- 65.6 HFIPh
- 66.9 HFIPh
0.00 TFE
- 8.7 DMF
- 15.3 TFE
- 14.9 DMF
95,97,98,102,103,105,113,153
95,97,98,102,103,105,113,153
95,97,98,102,103,153
97-99,102,103,153
97,98,102,103,153
96,102,103,112,113,115
96,102,103,112,113,115
1 5 3
96,102,103,112,113,115
1 5 3
96,102,103,112,115,153
96,102,103,153
96,102,103,112,153
95,106
95,106
95,106
95,106
1 0 6
1 0 6
100,102,104,111
100,102,104,111,153
100,102,104,111,153
100,102,104,111,153
100,102,104,111,153
100,102,104,111,153
56-58,101,102,112,115,116
56-58,101,102,112,115,116
56,57,101,102,112,115,116
56,57,101,102,112,115,116
56,57,101,102,112,115,116
56,101,102
56,101
115,116
115,116
115,116
115,116
115,116
1 1 5
110,111,115
110, 111
110, 111
110,111,114
110, 111
110, 111
102,107-109,111,112
102,107-109,111,112
IV/76 PHYSICAL DATA OF OLICOMERS
8.2.5.2. contd
Specific rotation
R n Mol. wt. m.p. (C)
blT
Solvent Refs.
4 720.8 196-197 - 22.2 T F E i 102,107-109,111,112
- 16.1 DMF
5 868.0 213-214 - 28.3 TFE 102,107-109,111,112
- 19.2 DMF
6 1 0 1 5 . 2 223-226 - 25.0 T F E i 102,108,109,111
- 21. 1 DMF
7 1162.3 > 235 - 22.1 DMF 102,108,109,111
8 1 3 0 9 . 5 >235 1 0 8 , 1 0 9
9 1 4 5 6 . 7 >235 1 0 8 , 1 0 9
X = 546 nm; T = 20C; c = 5 x 10m4 M; c@(n/180) rad x cm/g]; HFIP = hexafluoroisopropanol.
b X = 589 nm; T = 25C; c = 3 x 10m3 M (n = 2-6), 3 x 10d4 M (n = 7); TFE = trifluoroethanol; HFA = hexafluoroacetone sesquihydrate.
X = 589 nm; T = 22C; c = 10 m3 M; HFIP = hexafluoroisopropanol.
d X = 589 nm; T = 25C; c = 3 x 10m3 M; HFA = hexafluoroacetone sesquihydrate.
X = 589 nm; T = 25C; c = 0.025-0.2%; TFE = trifluoroethanol.
f X = 589 nm; T = 25C; c = 0.6%; TFE = trifluoroethanol.
8 X = 589nm; T = 21C; c = 0.1%; hexafluoroacetone sesquihydrate.
h X = 589 am; T = 20C; c = O.l-0.2%; HFIP = hexafluoroisopropanol.
X = 589 nm; T in TFE = 23C in DMF = 18C; c = 0.2%; TFE = trifluoroethanol.
8.2.5.3. Endgroup Protected Oligo(peptides) of Tryptophan X-[NHCHRCO] ,,-OCH3
Specific rotation
R x n Mol. wt. m.p. (C) bl:: c (%I
Solvent Refs.
-,,,,-lfg) z ; 5 3 8 . 5 7 2 1 . 8 85-95 196 - 13 1 MeOH 208, 225 208
W3)zPS 1 2 7 6 . 3 108-109 - 2.4 1.0 MeOH 1 4 0
2 428.4 153-154 - 47.6 0 . 5 MeOH 1 4 0
3 580.6 - 66.8 0 . 5 MeOH 1 4 0
4 732.7 - 65.6 0 . 5 MeOH 1 4 0
5 884.9 151-154 - 65.0 0 . 5 MeOH 1 4 0
LI Z- = Benzyl oxycar bonyl - .
8.2.5.4. Cyclic Oligo(peptides) r[NHCHRC%i
Specific rotation
R n Mol. wt. m.p. (C) [aID (Cl c (%I Solvent Refs.
L-Val
-CWCHdz
L-Leu
L-Ile
-CH(CH3)CH2CH3
L-Phe
-CH2
L-Trp
2 2 2 6 . 3 2 7 7 - 46.0 2 0 0 . 8 C H 3COOH
198.3 269-271 - 77.5 18-22 1.0 CH3COOH 207
565.8
2 2 6 . 3
5 6 5 . 8
294.4
735.9
1 4 7 1 . 8
372.4
>300
308
3 5 7
315-316
250-254
2 5 1 . 5
- 7 1 15 1.0 EtOH
- 60.0 18-22 1.0 C H 3COOH
- 100 25-28
- 124.3 2 5
- 142 2 0
- 14.7 2 0
0 . 2
1.0
0 . 4
C H &OOH
DMF
MeOH
C H $OOH
22,25,177,184,185,
1 8 8 , 2 0 7
1 3 2
1 3 1 , 2 0 7
131
177,184,185,188
7 8
131
2 3 0 , 2 3 2
Oligofpeptides) I V/77
I
8.2.5.5. Endgroup Protected Oligo(Dipeptides) R[NHCHR,CO-NHCHR2CO].-R
Specific rotation
/
R R
Ri R2
n Mol. wt. m.p. (C) [al; c (%I
Solvent Refs.
- Boca OMe D-Val L-Val 1 300.4 110. 7 23.7
L-CH(CH s) 2 D-CH(CHs) 2 2 528.7 209.6 - 17.8
3 727.0 232.7 -21.0
4 925.2 261.1 - 8.9
6 1321.8 d - 6.2
8 1718.3 d - 11.4
Npsa OEt L-Leu L-Ala 2 567.6 110-111 - 66.5
-CH2CH(CH3)2 -CH3 3 751.8 203-205 - 96.9
4 936.0 257- 260 d - 101.3
5 1120.2 >270 d - 84.6
6 8 1 3 0 4 . 4 1 6 7 2 . 8 >270 >270 d d
-
- 52.6 50.0
LI Boc- = ferr. butyloxycarbonyl-; Nps. = o-nitrophenylsulfenyl-; HPIP = hexafluoroisopropanol; TPB = trifluoroethanol.
1. 02 CHCls 118
1.00 CHCl 3 118
1. 02 CHCl s 118
1. 00 CHCl 3 117,118
1. 12 CHCl s 118
1. 05 CHCl 3 118
2.0 HPIP/TPE (1: 2) 119
2.0 HFIP/TFE ( 1: 2) 119
2.0 HPIP/TPE ( 1: 2) 119
2.0 HPIP/TPE ( 1: 2) 119
2 . 0 2 . 0 HPIP/TFE (1: 2) 119 119 HPIP/TPE (1: 2)
8.2.6. OLIGO(PEPTIDES) OF L-AND D-PROLINE
I n
8.2.6.1. Linear Oligo(all-L-peptides) H[N-CHCO],OH
I
I
n Mol. wt. m.p. (C) EF-Valuesa tKl:b
Refs.
1 115.2 220-222 1. 00 - 87 1
2 212.3 144 145 0.84 - 175 52,62,69,70,150,171-173
3 309.4 1 2 2 0.72 - 220 53,62,69,70,150,171-173
4 406.5 1 7 0 0.60 - 293 62,69,70,150,171-173
5 503.6 1 8 9 0.52 1. 00 - 338 62,69,70,150,172,173
! t
600.7 209 0.91 - 376
697.8 228 0.77 - 394 62,69,70,150,172,173 62,69,70,150
8 794.9 >280 0.72 - 412 62,69,70,150
9 892.0 > 280 0.66 - 435 62,69,150
1 0 989.1 >300 0.60 1.00 - 456 62,69,70,150
1 1 1086.2 >300 0.92 - 466 62,69,70,150
i ;; 1183. 3 >300 0.83 - 472 62,69,70,150
1280.4 >300 0.75 1.00 - 480 69,70
I 1 4 1377.5 > 300 0.70 0.94 -491 6 9
1 5 1474.6 > 300 0.64 0.90 - 496 62,69,70
1 6 1571.7 >300 0.86 - 499 69,70
1 7 1668.8 >300 1 .oo 0. 81 - 505 6 9
I 1 8 1765.9 > 300 0.95 - 509 69,70
1 9 1863.0 >300 0.90 - 513 6 9
2 0 1960. 1 > 300 0.84 - 520 69,70
2 1 2057.3 > 300 -521 7 0
2 2 2154.5 >300 1 0 0 - 523 7 0
I 2 5 2445.7 > 300 0.93 1 .oo - 526 7 0
2 8 2737.0 >300 0.92 1.00 - 528 7 0
1 3 0 293 1. 3 > 300 0.95 - 530 7 0
/ 3 1 3028.5 > 300 0.93 1. 00 - 532 7 0
3 4 3320.1 >300 1. 00 0.93- 530 7 0
3 7 3611.4 >300 0.93 1 .oo - 528 7 0
4 0 3902.7 > 300 0.94 - 532 7 0
/
a Paper electrophoresis; buffer; HCOOH/CH sCOOH/H 20 ( 1: 1 : 3). 1000-5000 V, 40- 115 mA, 40-240 mi n .
I
/
c(%)=1,H20.
8.2.6.2. Endgmup Protected Oligo(peptides)
n
8.2.6.2.1. tert-BUTYLOXYCARBONYL OLIGO(ALL-L-PROLINES) (CH&COCO-[N-CHCO],-OH
n Mol. wt. m.p. (C) blffb
Refs.
1 215.3 137-138 0.84 - 1 0 5 62,72,169,179
2 312.4 191-193 0.68 - 153. 5 62,150,167,179,181
3 409.5 219-220 0.60 - 1 7 3 62,150,167,179
4 506.6 1 7 8 0.53 - 1 9 4 62,150,167
IV/78 PHYSICAL DATA OF OLICOMERS
8.2.6.2.1. contd
n Mol. wt. m.p. (C)
Mi
Refs.
5 603.7 2 2 5 0.47 - 220 62,150,167
6 700.8 247 0.41 - 239 62,150,167
7 797.9 267 0.37 - 247 62,150
8 894.0 5 280 0.33 - 256 62,150
9 991.1 > 280 0.29 - 265 62,150
1 0 1088.2 >280 0.25 - 212 62,150
1 1 1185. 3 >300 0.23 - 269 62,150
1 2 1282.4 >300 0.22 - 277 62,150
1 5 1573.7 > 300 0.22 -291 62,150
a TLC: solvent, n-butanol/acetone/acetic acid/ammonia, 1:4/water (9 : 3 : 2 : 2 : 4).
by (%)=l, CHC13.
n
8.2.6.2.2. tert-AMYLOXYCARBONYL OLIGO(ALL-L-PROLINES) CsH1lOCO-[N-CHCO]fi-OH
Specific rotation
n Mol. wt. m.p. (C)
[alo (Cl c (%I Sol vent Refs.
1 229.3 94-95. 5 - 47.2 2 1 1 . 7 EtOH 63-68,170,179
2 326.4 157-159 - 113 2 5 2.0 EtOH 64-68.179
3 423.5 200-201.5 - 170 2 5 2.2 EtOH 64-68,179,182
4 520.6 207.5-208.5 - 227 2 4 2 . 1 EtOH 64-68
5 617.7 224.5-226 - 248 2 4 2.3 EtOH 64-68
6 714.8 240-242 -291 2 4 2 . 1 EtOH 64-68
8 908.0 280 - 318 2 2 0.9 EtOH 64-68
8.2.6.2.3. tert-BUTYLOXYCARBONYL D,L-OLIGO(DIPROLINES)
R n
(CH$COCO -[N- CHCO-N- CHCO],- OH
n Mol. wt.
1 312.4
2 506.6
3 700.8
a c (% ) = 1, DMF.
m.p. (C)
2 0 4
188-189
220-221
[aliti
Refs.
-70.1 158,165
- 38.8 158
- 32.4 158,159
8.2.6.2.4. tert-BUTYLOXYCARBONYL OLIGO(D,L-DIPROLINE)
BENZYL ESTERS
n n
(CH,),COCO-[N-CHCO-N-CHCO],OCH,C,H,
n Mol. wt. m.p. (C)
[aliti
Refs.
2 612.7 64-66 - 24.0 164
3 806.9 157-160 - 23.2 164
4 1001.2 146-148 - 20.4 164
a c (%) = 1, DMF.
8.2.6.3. Cyclic Oligo(peptides)
n
8.2.6.3.1. CYCLIC OLIGO(ALL-L-PROLINES) r[N-CHCO],l
n Mol. wt. m.p. (C)
[dD (C) c (%I
Solvent Refs.
2 194.2 1 4 6 - 151.6 1 9 0.5 Hz0 54,55,180,185
3 291.3 3 5 8 +48.5 2 5 0.48 CHjOH 53,154-157,162,163,168,176,189,190
n n
8.2.6.3.2. CYCLIC OLIGO(L,D-DIPROLINES) [N-CHCO-N-CHCO],
L D
n Mol. wt. m.p. (C) Refs.
1 194.2 194-199 158,180,185,186
2 388.4 >300 d 1 5 8
3 582.6 >310 d 158, 159
4 776.8 >250 d 158
6 1165.2 >280 d 158
9 1747.8 >250 d 1 5 8
1 2 2330.4 >250 d 1 5 8
Oligo(peptides) IV/79
n n n
8. 2. 6. 3. 3. CYCLI C OLICO(D,L,L-TRIPROLINES) [N-CHCO-[N-CHCO-N-CHCO],
D L L
Specific rotation
n Mol. wt. m.p. (C)
c (So)
Sol vent Refs.
1 291.2 181-184 + 70. 7 1 Hz0 159-163
2 582.3 304 - 60.9 1 Hz0 159-163
3 873.5 230 d - 114.5 1 Hz0 159-163
4 1164.6 250 d - 72.0 1 Hz0 159-163
5 1455.8 250 d - 101.8 0.5 Hz0 159-163
8.2.7. OLIGO(PEPTIDES) OF L-AZETIDINE-2-CARBOXYLIC ACID
8.2.7.1. Cyclic OZigo(peptides) r [NqHCO],l
n Mol. wt. m.p. (C) [a]z8a Refs.
2 166.2 207-212 + 8. 2 1 7 5
3 249.3 334-340 + 20.8 1 7 5
6 498.5 339-350 - 352.0 1 7 5
c (%) = 0.5, H 20
8.2.8. OLIGO(PEPT1DE.S) OF L-HYDROXY AND L-MERCAPTO AMINO ACIDS
8.2.8.1. Linear OZigo(peptides) H[NHCHRCO] .OH
Specific rotation
n Mol. wt. m.p. (C)
((2 c (%I
Solvent Refs.
L-Ser
-CH20H
L-Tyr
-CHZC~H~OH
L-cys
-CH2SH1.5 HCl
L-Met
-CHzCH#CHj
1 105. 1
2 192.2
1 181.2
2 344.4 285-288
3 507.6 181-182
1 121. 1
2 224.2
1 149.2
2 280.4 229-23 1
3 411.6 219-220
+ 14.5 2 5 9.3
+ 14. 2 2 5 7
- 7.3 2 5 4
+ 30.1 1 9 4
+7.6 2 6 1 2
+35 2 2 1
+23.4 2 0 5
+ 27. 0 2 4 2
- 70.0 1 6 1
N HCl 1
N HCl 28,35,139
6. 1 N HCl 1
H20+ 1 eq. HCl 29-31
3 1
N HCl 1
0. 2 N HCl 3 7
3NHCl 1
Hz0 32-34
H20 3 3
I 8.2.8.2. Endgroup Protected Oligo(peptides) (CH3) 3COCO- [NHCHRCO] n -0CH 3
I
Specific rotation
1 R n Mol. wt. m.p. (C) [aID c (%I
Solvent Refs.
L-Cys(Me) 2
-CHzSCH3 3
4
5
6
7
L-Met 2
-CH#H2SCH3 3
4
5
6
7
a HFIP = hexafluoroisopropanol.
366.5 94-95 102,121,122,133
483.7 104- 105 102,121,122,133
600.8 191-192 102,121,122,133
718.0 211-212 102,121,122,133
835.2 > 220 102,121,122,133
952.3 > 220 102,121,122,133
394.5 66-67 - 29.6 0.003 M HFIPa 102,123,124,127-129
525.8 92-96 - 37.6 0.003 M HFIP 102,123,124,127-129
656.9 191-194 -41.4 0.03 M HFIP 102,123,124,127-129
788.1 236 d - 48.1 0.003 M HFIP 102,123,124,127-129
919.3 245 d - 50.3 0.03 M HFIP 102,123,124,126 -129
1050.5 > 275 - 54.8 0.03 M HFIP 102,123-129
IV/80 PHYSICAL DATA OF OLICOMERS
8.2.8.3. Fonnyl-Oligo(L-Methionines) HCO-[NHCHRCO].-OH
Specific rotation
R n Mol. wt. m.p. (C)
[aID c (%o)
Solvent a Refs.
L-Met 2 308.4 125-126 - 44. 8 0 . 5 HFIP 1 3 0
-CH2CH#CH3 3 439.6 176-177 - 56.7 0 . 5 HFIP 1 3 0
4 570.8 195-196 - 67.2 0 . 5 HFlP 1 3 0
5 702.0 216-217 - 63.3 0 . 5 HFIP 1 3 0
6 833.2 230-231 d - 81.8 0 . 5 HFIP 1 3 0
8.2.8.4. Cyclic Oligo(peptides) r[NHCHRCO],,
Specific rotation
R n Mol. wt. m.p. (C) [aID (C)
Solvent a Refs.
-CHzOH 2 1 7 4 . 2 247 6 7 . 5 2 5 2 . 2 Hz0 35,174,183
-CHZC~H~OH 2 326.4 277-280 - 223.8 20 2 . 4 NaOH 36,174
8.2.8.5. Oligo(peptides) of Cystine CyS = -NHCHCO-
[ AHZS- ]
Specific rotation
R n m.p. (C)
b]D (Cl Solvent a Refs.
H-Cy&Cy&-OH 2 2 2 . 3 - 2 9 2 5 1 N HCl 3 8
H--CyS-cyS-oH 444.6 - 58.7 2 6 1 N HCl 37.38
H- Cy S - Cy S - OH
HFIP = hexafluoroisopropanol.
8.2.9. OLIGO(PEPTIDES) OF ACIDIC AMINO ACIDS
8.2.9.1. IX- and w-Oligo(peptides) of L-Aspartic Acid and L-Glutamic Acid H[NH-X-CO],OH
Specific rotation
X n Mol. wt.
[aID (C)
Solvent Refs.
ASP
-YHCHz-
COOH
Glu
-CH-
~H~CH,COOH
Glu
-~HCH*CH2-
COOH
2 248.2 + 1 8 . 5
3 3 6 3 . 3 + 6.0
4 478.3 + 1 6 . 1
5 593.4 +6.1
6 7 0 8 . 5 + 8.7
1 147.1 +31.2
2 2 7 6 . 3 + 18.2
3 405.4 - 7.2
2 2 7 6 . 3 +4.2
3 405.4 - 7 . 2
4 5 3 4 . 5 - 16.0
5 663.6 - 14.8
6 792.7 - 17.2
7 9 2 1 . 8 - 19.1
20 2 0 . 5 N HCl 76
20 2 0 . 5 N HCl 76
20 1 0 . 5 N HCl 76
20 1 0 . 5 N HCl 7 6
2 0 2 0 . 5 N HCl 7 6
2 2 . 4 1 6NHCl 1
2 4 1-2 0 . 5 N HCl 42-44
19 1.4
Hz0
4 5
24 1-2 0 . 5 N HCl 43,44,46,47,59,178
20 2 0 . 5 N HCl 48,59,178
2 4 1-2 0 . 5 N HCl 59,178
2 0 1-5 0 . 5 N HCl 5 9
20 1-5 0 . 5 N HCl 5 9
20 1-5 0 . 5 N HCl 59,71
8.2.9.2. y-Oligo(peptides) of D-Gkmic Acid Esters H[NH-X-CO].-OC(CHs)j
Oligo(peptides) IV/81 .
Specific rotation
X
D-Gill
-YHCH2CH2-
COOC(CH&
n Mol. wt.
3 6 2 9 . 8
4 5 1000.2 815.0
6 1 1 8 5 . 4
m.p. (C)
81- 84
125-127.5 126-131
>58
ME
+ 17. 9
+
+
2 2 . 3 2 7 . 6
+ 2 9 . 4
c (%I
3
3 3
3
Solvent
MeOH
MeOH MeOH
MeOH
Refs.
5 9
5 9
5 9
5 9
8.2.9.3. cc-OZigo(peptides) of y-Unsubstituted L-Glutamic Acid Derivatives CHjCO-[NHCH(CH2CH2COOH)CO] .-NHC~HS
Specific rotation
na Mol. wt. [aIF c (%I
Solvent Ref.
1 216.2 - 2 3 1 Hz0 226
2 345.4 - 36 1 Hz0 226
3 474.3 - 49. 5 1 Hz0 226
n = 2-12: ion-exchange chromatography, IR, CD, MS, pK val ues, Refs. 227,228.
8.2.9.4. cc-Oligo(peptides) of Benzyloxycarbonyl L-Aspartic Acid and L-Glutamic Acid Ethyl Esters
CgH~CH~0CO-[NHCHRCO]n-1-NHCHRCOOC2H5
Specific rotation
R R n Mol. wt. m.p. (C) big c (%I
Solvent0 Refs.
ASP
-CH2COOCH3 -CH~COOC~HS
cilu
-CH2CH2COOCH3 -CH2CH&OOC2H5
Gl U
-CH2CH2COOC2HS -CH~CH~COOC~HS
a DCA, dichloroacetic acid; TFE, trifluoroethanol,
2 452.5 SO-81 + 17. 9 3. 1 DCA 49,146
3 581.6 127-128 - 1.01 3. 1 DCA 49,146
4 7 1 0 . 7 143-144 - 13. 1 1. 1 DCA 49,146
5 8 3 9 . 8 161-163 - 19. 1 0. 1 DCA 49,146
6 968.9 175-178 - 26.6 0 . 7 DCA 49
8 1 2 2 7 . 2 207 d - 35. 1 0 . 5 DCA 49,141,146
1 1 1 6 1 4 . 5 224 d - 42.9 0 . 4 5 DCA 49,146
1 4 2001.9 233 d - 46.0 0 . 3 DCA 49,146
2 4 8 0 . 5 8 6 - 12.4 2 DCA 50,141,146
3 623.6 1 2 4 - 18.0 2 DCA 50,146
4 7 6 6 . 8 1 3 9 - 21. 3 2 DCA 50,141,146
5 910.0 200 - 22. 1 2 DCA 50,141,146
6 1053.1 250 - 26. 7 2 DCA 50,146
7 1 1 9 6 . 3 259 - 28. 7 2 DCA 50,141,146
9 1 4 8 2 . 5 d - 32.6 2 DCA 50,146
1 1 1 7 6 8 . 8 d - 35.6 2 DCA 50,146
2 4 9 4 . 5 104-105 - 17.9 T F E 43,120,142-145
3 651.7 127-128 - 27. 1 2 T F E 43,120,142-145
4 8 0 8 . 9 137-139 - 30.9 T F E 142- 145
5 966.0 177-178.5 - 26. 5 T F E 142-145
7 1 2 8 0 . 4 > 2 3 5 - 20. 9 1 T F E 142-144
8 1437.5 > 2 3 5 - 16. 5 TFE 142,143,145
9 1 5 9 4 . 7 >235 - 7. 6 1 T F E 142,143,145
8.2.9.5. o-Oligo(peptides) of Benzyloqcarbonyl L-Aspartic Acid and L- and D-Glutamic Acid o-A&y1 Esters CsH5CH20CO-[NH-X-CO].-OR
Specific rotation
X R n Mol. wt. m.p. (C)
b]D ((2 c (%I
Solvent a Refs.
~-Asp WH3)3 2 5 5 0 . 7 70- 72 - 23.0 2 5 1 DMF 16
-YHCH2- 4 3 7 2 1 . 9 8 9 3 . 1 93-95 97-99 -22.1 - 19.3 2 5 2 5 1 1 D M F D M F 76
COOC(CH,),
76
5 1064.3 121-123 - 18. 7 2 5 1 DMF 76
6 1 2 3 5 . 4 157-162 - 20. 0 2 5 1 DMF 7 6
.
IV/ 82 PHYSICAL DATA OF OLICOMERS
8.2.9.5. contd
Specific rotation
X R n Mol. wt. m.p. (C) b]D (Cl c (%I
Solvent Refs.
L-Glu CH3
2 452.5 97-98 - 25.2 2 0 5 DMF 5 9
- YHCHzCH2-
3 595.5 135-137 - 26.1 2 0 5 DMF 5 9
4 738.6 135-139 - 28.2 2 0 5
COOCH3
DMF 5 9
5 881.7 175-179 -30.1 2 0 5 DMF 5 9
6 1024.8 195-198 -31.5 2 0 5 DMF 5 9
7 1153.9 206-213 - 32.8 2 0 5 DMF 5 9
D-C&I CCH3)3 2 578.7 88. 5-91 + 27. 4 2 5 3 MeOH 5 9
-fICH2CH2-
3 763.9 77. 5-81. 5 + 30. 6 2 5 3 MeOH 5 9
4 949.1 95-97 + 34. 5 2 5 3
COOC(CH3)3
MeOH 5 9
5 1134. 3 99- 102 +36.1 2 5 3 MeOH 5 9
6 1319.6 73-77 + 42. 4 2 5 3 MeOH 5 9
7 1504.8 74-78 + 42. 9 2 5 3 MeOH 5 9
L-Glu
WH3)3 2
578.7 83-84 - 25.4 2 2 1 MeOH 7 1
-YHCH2CH2-
3 763.9 7 9 - 30.2 2 1 1 MeOH 7 1
4 949.1 87-89 - 33.2 2 2 1
COOCP3)3
MeOH 7 1
5 1134.3 102- 103.5 - 36.8 2 3 1 MeOH 7 1
6 1319.6 123-125 - 39.9 22.5 1 MeOH 7 1
7 1504.8 130-132 - 43.7 2 1 1 MeOH 7 1
8.2.9.6. cc-Oligo(peptides) of Ace@ L-Ghtamic Acid Esters CH3CO-[NHCH(CH2CH2COOC~H5)CO],OC2H~
Specific rotation
n Mol. wt. m.p. (C)
[al: c (%)
Sol vent Ref.
2 402.4 94-95 -29.1 0. 5-1. 5 TFE 1 4 2
3 559.6 150-151 -31.2 0. 5-1. 5 TFE 1 4 2
4 716.8 1 7 1 - 39.3 0. 5-1. 5 TFE 1 4 2
5 873.9 > 230 - 34.9 0. 5-1. 5 TFE 1 4 2
8 1345.5 >230 - 17.3 0. 5-1. 5 TFE 1 4 2
a TFE, Trifluoroethanol
8.2.9.7. wOZigo(peptides) of a-NitrophenylsulfenyZ L-Glutamic Acid Amides and Esters Nps-[NHCH(CH2CH2COOCH2CgH5)CO] .-R
Specific rotation
R n Mol. wt. m.p. (C) [aID ((3 c(%o)
Sol vent Ref.
NHC2H5 1 417.5 92-93 1 4 7
2 636.7 147- 148 1 4 7
4 1075.2 180-182 1 4 7
6 1513.6 233-234 1 4 8
OcH2c6H5 2 699.7 65-67 - 40.0 2 0 1 . 0 CHC13 1 4 9
4 1138. 1 114-115 - 26.2 2 2 1 . 0 CHCl 3 1 4 9
8 2014.9 198-205 - 8.2 2 5 0.9 CHC13 1 4 9
1 2 2891.7 236-238 +7.1 2 6 0.5 CHCl 3 1 4 9
Nps = o-Nitrophenylsulfenyl.
8.2.9.8. Cycle-y-Oligo(peptides) of Glutamic Acid
riNH,,,,,CCW
Specific rotation
R n Mol. wt. m.p. (C) b]D (C) c (So)
Solvent Ref.
H 2 258.2 189-192 + 14.0 2 2 0.5 0. 1 N HCl 6 0
3 387.3 235-238 + 90. 0 2 2 0.5 0. 1 N HCl 6 0
4 516.5 232-236 + 38.5 2 2 0.45 0.1 N HCl 6 0
WH3)3
2 370.4 220-222 + 23. 0 2 3 1 DMF 6 0
3 555.7 203-206 - 52.5 2 3 1 DMF 6 0
4 740.9 230-232 - 38.0 2 3 0.5 DMF 6 0
.
Oligo(peptides) IV/83
8.2.10. OLIGO(PEPTIDES) OF BASIC L-AMINO ACIDS (LYSINE, ORNITHINE, ARGININE, HISTIDINE)
8.2.10.1. Linear Oligo(peptides) H[NHCHRCO],OH
Specific rotation
R la Mol. wt.
RF~ [a]D (C) c (%I
Solvent Refs.
LYS 1 146.2 0.24 + 25. 7 2 5 1 . 6 6NHCl
-(CH2)4m2 2 274.4 0.17 + 5. 6 2 5 2 6NHCl
3 402.6 0.12 - 2.2 2 4 2 0.5 N HCl
4 530.7 0.09
5 658.9 0.06
n = 2-20: Ion-exchange chromatography, Refs. 209-212; n = 2-22; ORD, pK values, Ref. 209; n = 2-5: CD, Ref. 217.
Lys(Boc) b 1 246.3 237-255 +4.7 2 6 0.88 2NNHj
-(CH*)&H-Boc 2 474.6 1 8 8 + 16. 4 2 0 1 MeOH
3 702.9 185-187 f7.4 2 0 1 MeOH
4% 2 330.4 224-226a + 1780c,d 1 . 4 N HCl
-(CHz)3-NHCNH2 3 486.6 227-232 + 1540Cld 3.9 N HCl
II 4 642.7 238-241 b + 1030~d 1 . 8 N HCl
NH
1
39,40
40,41
4 0
4 0
219
213,214
214
216
1 2 6
216
a TLC in n-butanol/acetic acid/water/pyridine (30: 6 : 24 : 20).
b Boc = ten butyloxycarbonyl-.
As flavianates.
dX=224nm
8.2.10.2. Endgroup Protected Oligo(peptides) X-[NHCHRCO],-Y
Specific rotation
R X Y n Mol. wt. m.p. (C) [aI 2. rl (nm) (C) c (%) Solvent Refs.
Lys(Boc) b Z
-(CH2)4NH-Boc
Z
Z
Z
Boc
WCH3)3
Boc OH
H
LYScab
Boc
-(CH2)4NH-Z
LYS(Z) Boc
-(CH2)4NH-Z
Om(Boc) Z
-(CH2)3NI-Boc
Om(Boc)
Arg(NW Z
-(CH&-NHtNH2
N-NO2
OCH3
WCH3)3
NHCH3
OH
Suco
OcHzcsHs
OH
OCH3
OCH3
1 394.5 Oil
2 622.8 97-98
4 1079.4 1 2 1
8 2192.6 >260
2 664.8 82-84
4 1121.4 143-145
2 721.8 1 2 9
4 1078.3 1 7 4
8 1991.5 > 260
1 6 3817.7 > 260
1 380.4 Oil
2 790.0 1 1 2
3 837.0 1 0 7
7 1773.2 268
3 802.0 1 1 4
4 1031.0 92-95
n = 1,5-8,10,20: TLC, IR, CD
2 732.8 8 0
3 995.1 1 4 0
4 1257.4 156- 158
5 1519.7 1 7 0
7 2044.3 245-248
2 642.7 97-105
4 1167. 3 124- 127
8 2216.5 1235-140
1 380.4 7 1
2 594.7 1 2 5
3 809.0 1 4 7
4 1023.2 1 5 2
5 1237.5 165-171
1 367.4 153-153.5
3 769.7 133-136
4 970.9 139- 140
- 10.6
- 5.5
- 15.3
- 16.4
- 10.4
- 15.5
- 14.4
- 16.6
- 18.0
- 14.6
- 2.4
-3.1
- 12.2
- 19.0
- 5.5
- 15.4
589 2 6 1 . 9 Acetone 219
589 20 2.1 Acetone 218-220
589 2 2 2 . 1 CH3COOH 220
589 22 2.1 CH3COOH 220
578 22 1 DMF 2 1 3
578 20 1 DMF 2 1 3
589 2 2 CH ,COOH 220
589 2 2 CH,COOH 220
589 2 2 CHjCOOH 220
589 2 2 CH3COOH 220
589 26 2.0 Acetone 219
578 22 1 CH&OOH 2 1 3
589 20 1 MeOH 214
578 22 1 DMF 2 1 3
578 22 1 DMF 2 1 3
589 20 1 MeOH 214
- 14.0 578 1
-16.2 578 1
- 15.7 578 1
- 16.7 578 1
- 13.9 578 1
- 14.4 589 2 7 1. 08
- 15.1 589 2 0 1. 34
- 13.7 589 2 0 1 . 1
- 17.8 589 20 1
-5.1 589 2 5 1. 05
DMF 2 1 3
DMF 213
DMF 213
DMF 2 1 3
DMF 2 1 3
2 1 5
2 1 5
2 1 5
90% AcOHb 2 2 1
90% AcOH 221,222
90% AcOH 222
MeOH 221,222
DMF 222
216
216
216
IV/84 PHYSICAL DATA OF OLICOMERS
8.2.10.2. contd
Specific rotation
R X Y n Mol. wt. m.p. (C)
[aI i
rl (nm) (C) c (%) Solvent Refs.
His(n-Born) b BOc OCH3 3 9 0 4 . 1 67- 69 - 15. 5 589 2 0 0 . 4 9 MeOH 2 2 3
-Cl&-> 4 5 1 1 6 1 . 4 1 4 1 8 . 7 78-81 93-97 - -21.2 22.3 5 8 9 5 8 9 2 0 2 0 0 . 4 9 0 . 4 8 MeOH MeOH 2 2 3 2 2 3
6 1 6 7 6 . 0
CH,0CH,C6H,
117-122 - 23. 3 589 2 0 0 . 5 2 MeOH 2 2 3
7 1 9 3 3 . 3 155-163 - 23.2 589 2 0 0 . 5 2 MeOH 2 2 3
a Suco =p-oxymethylbenzylcholestan-3-f-y1 succinate.
* Z- = Benzyloxycarbonyl-; Boc- = ferf butyloxycarbonyl-; z-Born- = N(x)-benzyloxymethyl-; AcOH = acetic acid.
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4
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lymers, 17,2385 (1978); J.-P Meraldi, E. R. Blout, R. Boni,
A. S. Verdini, ibid., 17, 2401 (1978).
176. J. Vicar, P. Malon, A. Trka, J. Smolikova, J. Fric, K. Blaha,
Coll. Czech. Chem. Commun., 42, 2701 (1977).
i
177. K. Blaha, J. Fric, Coll. Czech. Chem. Commun., 35, 619
(1970); K. Bliha, J. Smolikova, A. Vitek, ibid., 31, 4296
(1966); K. Bliha, Z. Samek, ibid., 32, 3780 (1967).
/I
, 178. H.-J. Burkhardt, H. K. Mitchell, Arch. Biochem. Biophys.,
#
94, 32 (1961).
179. E. Benedetti, A. Bavoso, B. Di Blasio, V. Pavone, C. Pedone,
I
C. Toniolo, G. M. Bonora, Biopolymers, 22, 305 (1983).
180. I. Vicar, J. Smolikova, K. Blaha, Coll. Czech. Chem. Com-
mun., 37,406O (1972); J. Z. Siemion, Ann. Chem., 748, 88
I
(1971).
! 181. M. E. Kamwaya, 0. Oster, H. Bradaczek, Acta Cryst. B, 37,
j
1564 (1981).
182. G. Kartha, T. Ashida, M. Kakudo, Acta Cryst. B, 30, 1861
(1974).
183. H. Brockmann, H. Musso, Chem. Ber., 89, 241 (1956).
184. W. Pickenhagen, P. Dietrich, B. Keil, J. Polonski, F. Non-
I
aille, E. Lederer, Helv. Chim. Acta, 58, 1078 (1975).
185. C. Eguchi, A. Kakuta, Bull. Chem. Sot. Japan, 47, 2277
I
(1974).
186. P. E. Young, V. Madison, E. R. Blout, J. Am. Chem. Sot., 48,
5365 (1976).
!
187. T. Sugihara, Y. Imanishi, T. Higashimura, Biopolymers, 12,
2823 (1973).
188. D. E. Nitecki, B. Halpern, J. W. Westley, J. Org. Chem., 33,
864 (1968).
I
189. M. Rothe, I. Rothe, T. Toth, K.-D. Steffen, in: H. C. Beyer-
man, A. van de Linde, W. Maassen van den Brink (Eds.),
I
Peptides 1966, Proc. 8th Eur. Peptide Symp., North-
Holland Publ. Co., Amsterdam, 1967, p. 8.
190. M. Rothe, R. Theyson, D. Miihlhausen, F. Eisenbeiss,
W. Schindler, in: J. Meienhofer (Ed.), Chemistry and
/
1
Biology of Peptides, Proc. 3rd Amer. Peptide Symp.,
Ann Arbor Sci. Publ., Ann Arbor, 1972, p. 51.
191. K. Titlestad, Acta Chem. Stand. B, 29, 153 (1975).
192. J. Dale, K. Titlestad, Acta Chem. Stand. B, 29, 353 (1975).
193. J. Dale, P. Groth, K. Titlestad, Acta Chem. Stand. B, 31,523
(1977).
194. J. Dale, K. Titlestad, J. Chem. Sot., Chem. Commun., 1403
(1970).
195. J. Dale, K. Titlestad, J. Chem. Sot., Chem. Commun., 255
(1972).
196. K. Titlestad, P. Groth, J. Dale, M. Y. Ali, J. Chem. Sot.,
Chem. Commun., 346 (1973).
197. P. Groth, Acta. Stand. A, 30, 838 (1976).
198. P. Groth, Acta. Stand. 24, 780 (1970).
199. P Grotb, Acta. Scand. 27, 3419 (1973); K. Titlestad, P
Groth, J. Dale, J. Chem. Sot., Chem. Commun., 646 (1973).
200. P Groth, Acta. Stand. A, 31, 232 (1977).
201. P Groth, Acta. Stand. A, 29, 38 (1975).
202. P. Groth, Acta. Stand. 27, 3217 (1973).
203. P. Grotb, Acta. Stand. A, 30, 840 (1976).
204. P. Groth, Acta. Stand. 23, 3155 (1969).
205. J. Dale, K. Titlestad, Tetrahedron Lett., 379 (1978).
206. K. Titlestad, Acta Chem. Stand. B, 31, 641 (1977).
207. K. Suzuki, Y. Sasaki, N. Endo, Y. Mihara, Chem. Pharm.
Bull., 29, 233 (1981).
208. H. Eckstein, Ann. Chem., 2145 (1976).
209. A. Yaron, M. C. Otey, H. A. Sober, E. Katchalski, S. Ehrlich-
Rogozinski, A. Berger, Biopolymers, 11, 607 (1972);
A. Yaron, E. Katchalski, A. Berger, G. D. Fasman, H. A.
Sober, Biopolymers, 10, 1107 (1971).
210. J. W. Stewart, M. A. Stahmann, J. Chromatogr., 9, 233
(1962); in: M. A. Stahmann (Ed.), Polyamino Acids,
Polypeptides, and Proteins, The University of Wisconsin
Press, Madison, 1962, p. 95; H. A. Sober, in: M. A. Stah-
mann (Ed.), Polyamino Acis, Polypeptides, and Proteins,
The University of Wisconsin Press, Madison, 1962, p. 105.
211. 0. Grahl-Nielsen, G. L. Trisch, Biochemistry, 8, 187 (1969).
212. N. Yu. Kozhevnikova, G. P. Vlasov, Zh. Obshch, Khim., 49,
924 (1979); J. Gen. Chem. USSR, 49, 800 (1979).
213. E. Schnabel, Hoppe-Seylers Z. Physiol. Chem., 357, 1365
(1976).
214. G. P. Vlasov, V. R. Glushenkova, T. N. Prokopyuk, Zh.
Obshch. Khim., 41, 430 (1971); J. Gen. Chem. USSR, 41,
422 (1971).
215. L. B. Nadezhdina, T. A. Komogorova, G. P. Vlasov, Zh.
Obshch, Khim., 51, 214 (1981); J. Gen. Chem. USSR, 51,
187 (1981).
216. H. Ito, I. Ichikizaki, T. Ando, Int. J. Protein Res., 1, 59
(1970).
217. W. L. Mattice, W. H. Harrison, III, Biopolymers, 14, 2025
(1975).
218. H. Yajima, K. Kawasaki, H. Minami, H. Kawatani,
N. Mizokami, Y. Kiso, F. Tamura, Chem. Pharm. Bull.,
18, 1394 (1970).
219. R. Schwyzer, W. Rittel, Helv. Chim. Acta, 44, 159
(1961).
220. I. GCczy, Acta Chim. Acad. Sci. Hung., 115, 345 (1984); H.
A. Van der Schee, G. I. Tesser, unpublished data.
221. G. I. Tesser, J. T. Buis, Rec. Trav. Chim. Pays-Bas, 90, 444
(1971).
Iv/88 PHYSICAL DATA OF OLICOMERS
222. F. Marchiori, G. Borin, B. Filippi, V. Moretto, G. M. Bonora,
C. Toniolo, Int. J. Peptide Protein Res., 14, 143 (1979);
F. Marchiori, G. Borin, D. Stivanello, V. Moreto, G. Chessa,
Hoppe-Seylers Z. Physiol. Chem., 363, 1483 (1982).
223. G. M. Bonora, C. Toniolo, J. H. Jones, K. N. Rajasekharan,
Int. J. Peptide Protein Res., 27, 1 (1986); K. N. Rajshe-
kharan, J. H. Jones, G. M. Bonora, C. Toniolo, Int. J. Peptide
Protein Res., 26, 605 (1985).
224. C. Toniolo, G. M. Bonora, I. F. Liischer, C. H. Schneider, Int.
J. Peptide Protein Res., 23, 47 (1984).
225. M. Wilchek, A. Patchomik, J. Org. Chem., 28, 1874 (1963).
226. M. Rinaudo, A. Domard, G. Spach, Biopolymers, 12, 2199
(1973); M. Rinaudo, A. Domard, ibid., 12, 2211 (1973).
227. M. Rinaudo, A. Domard, Biopolymers, 14, 2035 (1975); J.
Am. Chem. Sot., 98,636O (1976).
228. C. Bosso, A. Domard, F. M. Devienne, R. Combarieu,
Spectros. Int. J., 3, 81 (1984).
229. R. Guamaccia, G. P. Lorenzi, V. Rizzo, P. L. Luisi, Biopo-
lymers, 14,2329 (1975); P. L. Luisi, V. Rizzo, G. P. Lorenzi,
B. Straub, U. Suter, R. Guamaccia, ibid., 14, 2347 (1975).
230. R. Deslauriers, Z. Gronka, K. Schaumburg, T. Shiba,
R. Walter, J. Am. Chem. Sot., 97, 5093 (1975).
231. N. Go, H. A. Scheraga, Macromolecules, 6, 525 (1973).
232. H. Edelhoch, R. E. Lippoldt, M. Wilchek, J. Biol. Chem.,
243,4799 (1968); H. Edelhoch, R. S. Bernstein, M. Wilchek,
ibid., 243, 5985 (1968).
8. 3. OLIGO(IMINES)
8.3.1. LINEAR OLIGO(IMINES)
8.3.1.1. Linear OZigo(ethyZene imines) H[NHCH2CH2] nNH2
n Mol. wt. m.p. (C) b.p. (Urnbar)
4: Wm3)
ng Refs.
1 60. 1 11. 0 116.5/1013 0.8994 1.4536 12
2 103. 1 207.1/1013 0.9586 1.4810 1-3
3 146.2 12. 0 277.911013 0.9839 1. 4951 1-4
4 189.2 333/1013 0.9994 1. 5015 1-3
7 318.5 109-llO/ll
1.5132 2.5
9 404.7 199-200/1
1. 5161 23
8.3.1.2. Linear Oligo(alkylene imines) R-[NH(CH2)6NH(CHz) lo] ,,-R
R R n Mol. wt. m.p. (C) Ref.
H OH 1 272.5
2 526.9
3 781.4
KHz) loOH OH 1 428.8
2 683.2
3 937.7
H NH(CHd6NHz 1 370.7
2 625.1
, 3 879.6
64-67
70-72
85-86
99- 100
90-93
80-84
70-72
86-88
81-85
8.3.2. CYCLIC OLIGO(IMINES) r[NH(CH&],l
x n Mol. wt. m.p. (C) b.p. (Urnbar) d4 (g/cm3)PC Refs.
2 1 43. 1
2 86. 1
4 172. 3
3 1 57. 1
2 114.2
4 1 71. 1
2 142.2
5 1 85.2
2 170.3
6 1 99.2
2 198.2
3 297.5
4 396.7
5 495.9
6 595.1
1 0 4
3 5
14-15
- 9
7 2
42
59-60
45
67-68
55-56/1013
145-146/1013
110/10-4
6311013
186-188/1013
88/1013
95116
106/1013
108-110/16
138/1013
0.8321124 2,738
83
1 0
0.8436/20 1 1
8,11-13
0.852Oj22.5 1 4
0.9020/18 8,13
0.8606/20 1 4
0.9195/13 8
0.8864/21 8,15,16
13,17,18
1 7
1 7
1 7
1 7
I
!
1
I
I
I
I
I
I
i
8.3.2. contd
Oligo(ureas) I V/89
x n Mol. wt. m.p. (C) b.p. (Urnbar) d4 (g/cm3)/T Refs.
I 1 113. 1 - 33 162/1013 0.8895/20 16.19
2 226.2 2 6 0.9012/30 1 9
8 1 127.2 90/32 0.9021/21 1 6
2 254.5 5 5 2 0
9 1 141. 3 0.8982/21 1 6
2 282.5 3 8 1 9
1 3 1 197.4 50-51 1 6
2 394.7 5 2 2 1
REFERENCES
1. A. L. Wilson, Ind. Eng. Chem., 27, 870 (1935).
2. G. D. Jones, A. Langsjoen, M. M. Ch. Neumann, J. Zomlefer,
J. Org. Chem., 9, 125 (1944).
3. H. B. Jonassen, T. B. Crumpler, T. D. OBrien, J. Am. Chem.
Sot., 67, 1709 (1945).
4. F. G. Mann, J. Chem. Sot., 461 (1934).
5. G. S. Whitby, N. Wellman, V. W. Floutz, L. H. Stephens, Ind.
Eng. Chem., 42, 445 (1950).
6. H. Zahn, G. B. Gleitsmann, Makromol. Chem., 63, 129
(1963).
7. C. F. H. Allen, F. W. Spangler, E. R. Webster, Org. Syn., 30,38
(1950).
8. J. v. Braun, G. Blessing, F. Zobel, Chem. Ber., 57, 185 (1924).
9. A. Ladenburg, J. Abel, Chem. Ber., 21, 758 (1888).
10. H. Stetter, K.-H. Mayer, Chem. Ber., 94, 1410 (1961).
11. C. C. Howard, W. Marckwald, Chem. Ber., 32, 2031, 2038
(1899).
12. E. L. Buhle, A. M. Moore, F. Y. Wiselogle, J. Am. Chem. Sot.,
65, 29 (1943).
13.
14.
15.
16.
H. Stetter, J. Marx, Ann. Chem., 607, 59 (1958); H. Stetter,
H. Spangenberger, Chem. Ber., 91, 1982 (1958).
T. S. Stevens, In E. R. Rodd (Ed.), Chemistry of Carbon
Compounds, Vol. IV, Part A, 1st ed., Elsevier, Amsterdam,
1953, p. 61; N. Campbell, ibid., p. 570.
K. Ziegler, Ph. Orth, Chem. Bet, 66, 1867 (1933).
L. Ruzicka, M. Kobelt, 0. Haefliger, V. Prelog, Helv. Chim.
Acta, 32, 544 (1944).
17. H. Zahn, H. Spoor, Chem. Ber., 89, 1296 (1956); 92, 1375
(1959).
18.
19.
20.
21.
M. A. Th. Rogers, Nature (London), 177, 128 (1956).
A. Mueller, E. Srepel, E. Funder-Fritzsche, F. Dither,
Monatsh. Chem., 83, 386 (1952).
A. Mueller, L. Kindlmann, Chem. Ber., 74, 416 (1941).
A. Mueller, Chem. Ber., 67, 295 (1934).
8.4. OLI GO(UREAS)
8.4.1. OLIGO(METHYLENE UREAS) H[NHCONHCH 2] .NHCONH 2
8.4.4. CYCLIC OLIGO(UREAS)
rlN(CH1)CO--N(CH?)~CH2~ In1
n Mol. wt. m.p. (C)
1 132.1 218 d
2 204.2 221
3 276.3 231-233
5 420.5 236 d
8.4.2. OLIGO(METHYLENE THIOUREAS)
H[NHCSNHCH 2] .NHCSNH 2
Refs.
12
1
12
2
n Mol. wt. m.p. (C) Refs.
2 504.6 300-301
r[N(CH3)CON(CH,k(CH&-N(CH,)CON(CH,
1 422.6 157-158 5
2 845.1 180-181 5
zn Mol. wt. m.p. (C) Refs.
1 164.3 198 d
3,4
2 252.4 210 d 3
3 340.5 215 d 3
3.4.3. OLIGO(METHYLOL THIOUREAS) R[NHCSNHCH2],0H
8.4.5. OLIGO(CARBONYLPIPERAZINES)
R n Mol. wt. m.p. (C) Refs.
n Mol. wt. m.p. (C) Refs.
H 1 106.2 104-105
3,4
0 196.3 42-43 67
2 194.3 190-192 d 3 1 308.4 1 7 7 7,8
CH20H 1 136.2 9 2 3
2 420.5 261 7
2 224.3 132
3,4
3 532.7 337 7
I V/ 9 0 PHYSICAL DATA OF OLICOMERS
REFERENCES
1. A. A. Wanscheidt, S. K. Naumova, J. P. Melnikowa, Zh. 5. S. Foti, P Maravigna, G. Montaudo, Macromolecules, 15, 883
Obshch. Khim., 10, 1968 (1940); through Chem. Zentralbl., (1982).
II, 184 (1941).
6. B. Kuhn, Chem. Ber., 33, 2900 (1900).
2. H. Kadowaki, Bull. Chem. Sot. Japan, 11, 248 (1936).
7. R. Schwalm, W. Heitz, Makromol. Chem., 187, 1415
3. H. J. Becher, F. Griffel, Chem. Ber., 91, 691 (1958). (1986).
4. H. Staudinger, K. Wagner, Makromol. Chem., 12, 168 (1954). 8. D. E. Rivett, J. F. K. Wilshire, Aust. J. Chem., 19, 869 (1966).
D. CARBON CHAIN OLICOMERS CONTAINING MAIN CHAIN CYCLIC UNITS
TABLE 9. OLIGO(CYCLOPENTYLENES) H
w-l
H
n
n Mol. wt. m.p. (C) b.p. (Urnbar)
df (g/cm)
Refs.
1 7 0 . 1 - 93.9 42.311013 0.7510
2 138. 3 190/1013 0.8646 12
3 206.3 293-29411013 0.9177 12
4 274.5 369-370/1013 0.9564 12
6 410.7 143- 146 23510.13 1
TABLE 10. OLIGO(SPIRANES) R
WR
R n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
CH2 5 216.3 78/0.4 3
W2)2 3 244.4 8410.07 3
5 324.5 6 1 3
7 406.6 107-108 3
(CHd3 3 272.5 52.5 120- 122/0.07 3
5 352.6 79.5 3
7 432.7 103-104 3
9 512.8 138-140 3
TABLE 11. OLIGO(XYLYLENES)
11.1. LINEAR OLIGO(XYLYLENES)
n Mol. wt. m.p. (C) b.p. ( Urnbar) Refs.
o- 1 106.2 - 2 5 144/1013
2 210.3 66.5 177-1781127 5-7
m- 1 106.2 - 47.4 139/1013
2 210.3 296/1013 7,8
P- 1 106.2 13-14 138/1013
2 210.3 8 2 178124 7,9- 12,30
3 314.5 141-142 10,13
11.2. CYCLIC OLIGO(XYLYLENES)
I I
II Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
o- 2 208.3 112-112s 5,6,14
3 312.5 184.5 56
4 416.6 205 1 5
m- 2 208.3 132-133 290/1013 1 0
P- 2 208.3 285-287 8,11-13,19,30
3 312.5 170-171 10,,13,30
4 416.6 179-182 1 3
Carbon Chain Oligomers Containing Main Chain Cyclic Units Iv/ 91
TABLE 12. OLIGO(STILBENES) .[&,=,jo
n Mol. wt. m.p. (C) Refs.
1 180.2 124 1 7
2 282.4 2 6 5 16-18
3 384.5 350-352 1 7
4 486.5 360-374 16,17
5 588.7 395-400 16,17
6 690.9 415-420 16,17
7 793.0 4 2 5 16,17
TABLE 13. OLICO(BENZYLS) H- [(=+z]na
n Mol. wt. m.p. (C) Refs.
1 168.2 25.1
2 258.3 8 2 20,23
3 348.4 9 0 21,23
4 438.6 120 2 3
5 528.7 153-156 22,23
TABLE 14. OLIGO-(2,5-DIMETHYL-BENZYLS)
n Mol. wt. m.p. (C) Refs.
1 224.3 60-61 22,24
2 342.5 153-154 2 2
4 578.8 234-236 2 2
6 815.1 262-266 2 2
TABLE 15. OLIG0(2,3,5,6-TETRAMETHYL-BENZYLS)
II Mol. wt. m.p. (C) Refs.
1 280.5 155-156 22,25
2 426.7 263-264 22,26
3 572.9 305-307 2 2
4 719.1 335-337 2 2
REFERENCES
1. J. V. Braun, J. Reitz-Kopp, Chem. Ber., 74, 1105 (1941).
2. G. E. Goheen, J. Am. Chem. Sot., 63, 744 (1941).
3. E. Buchta, K. Geibel, Ann. Chem., 678, 53 (1964).
4. M. Busch, W. Weber, J. Prakt. Chem., 146, 1 (1936).
5. W. Baker, R. Banks, D. R. Lyon, F. G. Mann, J. Chem. Sot., 27
(1945).
6. A. C. Cope, S. W. Fenton, J. Am. Chem. Sot., 73, 1668
(1951).
TABLE 16. OLIGO(p-PHENYLENE OXIDES)
+oo-ln42
n Mol. wt. m.p. (C) Refs.
1 170.2 2 8
2 262.3 7 3 23,27
3 354.4 1 0 5 23,27
4 446.5 142 23,27
TABLE 17. OLIGO(p-PHENYLENE SULFIDES)
Kbln0
n Mol. wt. m.p. (C) Refs.
1 186.4 - 21.5
2 294.5 8 0 23,28
3 402.6 110 2 3
4 510.7 150 2 3
TABLE 18. OLIGO(p-PHENOXYPHENYLMETHANES)
+0c~2~0-]. ~-cJ
n Mol. wt. m.p. (C) Refs.
1 350.4 5 9 2 3
2 532.7 1 0 1 2 3
TABLE 19. OLlGO(DlPHENYLMETHANES)
I3 [ -w43],-H
n Mol. wt. m.p. (C) Refs.
1 168.2 25.1
2 334.5 1 1 5 4,29
3 500.7 180 4
4 666.9 2 4 0 4
7. G. H. Coleman, W. H. Holst, R. D. Maxwell, J. Am. Chem.
Sot., 58, 2310 (1936).
8. M. Swarcz, J. Chem. Phys., 16, 128 (1948).
9. T. Reichstein, R. Oppenauer, Helv. Chim. Acta, 16, 1373
(1933).
10. W. Baker, J. F. W. McOmie, J. M. Norman, J. Chem. Sot.,
1114 (1951).
IV/92 PHYSICAL DATA OF OLIGOMERS
11. C. J. Brown, A. C. Farthing, Nature (London), 164, 915
(1949); J. Chem. Sot., 3261, 3265, 3270, (1953).
12. D. J. Cram, H. Steinberg, J. Am. Chem. Sot., 73,569l (1951).
13. L. A. Errede, R. S. Gregorian, J. M. Hoyt, J. Am. Chem. Sot.,
82, 5218 (1960).
14. L. A. Errede, J. Am. Chem. Sot., 83, 949 (1961).
15. E. D. Bergmann, Z. P elchowicz, J. Am. Chem. Sot., 75,428l
(1953).
16. G. Drefahl, G. Ploetner, Chem. Ber., 94,907 (1961); 91, 1274
(1958).
17. G. Drefahl, R. Kuehmstedt, H. Oswald, H.-H. Hoerhold,
Makromol. Chem., 131, 89 (1970).
18. T. W. Campbell, R. N. McDonald, J. Org. Chem., 24, 1246
(1959).
19. H. E. Winberg, F. S. Fawcett, W. E. Mochel, C. W. Theobald,
J. Am. Chem. Sot., 82, 1428 (1960).
TABLE 20. PHENOL-FORMALDEHYDE AND RELATED
OLICOMERS
20.1. LINEAR PHENOL-FORMALDEHYDE OLIGOMERS
20.1.1. PHENOL-FORMALDEHYDE OLIGOMERS
& [CH&]:,
n Mol. wt. m.p. (C) Refs.
1 200.2 119-120 1-4
2 306.4 158-159 2-6
3 412.5 161-162
3,4
4 518.6 148-150 4,7
5 624.1 203-204 4
6 730.8 213-214 4
20.1.2. p-CRESOL-FORMALDEHYDE OLIGOMERS 20.1.3. p-rut BUTYLPHENOL-FORMALDEHYDE OLIGOMERS
20.1.2.1. 20.1.3.1.
n Mol. wt. m.p. (C) Refs.
2
3
4
5
6
7
8
9
1 1
228.3 126 8-10,56-58
348.4 214-215 8-11,56-58
468.6 1 7 3 8,9,56,57
588.1 130 12,56,57
708.9 215-217 1 2
829.1 225-230 1 2
949.2 167-170 1 2
1069.4 205-210 1 2
1189.5 175-180 1 2
1429.8 245 1 2
20. A. B. Galun, A. Kahtszymer, E. D. Bergmann, J. Org. Chem.,
27, 1426 (1961).
21. E. Connerade, Bull. Sot. Chim. Belges, 44, 411 (1935).
22. G. Montaudo, F. Bottino, S. Caccamese, P Finocchiaro, G.
Bruno, J. Polym. Sci. A-l, 8, 2453 (1970).
23. G. Montaudo, G. Bruno, P Maravigna, P. Finocchiaro, G.
Centineo, J. Polym. Sci., 11, 65 (1973).
24. R. C. Huston, D. T. Ewing, J. Am. Chem. Sot., 37, 2394
(1915).
25. C. M. Welch, H. A. Smith, J. Am. Chem. Sot., 73, 4391
(1951).
26. H. Kaemmerer, M. Harris, Makromol. Chem., 66,215 (1963).
27. H. Staudinger, F. Staiger, Ann. Chem., 517, 67 (1935).
28. E. Bourgeois, A. Fonassin, Bull. Chim. France, 9,941 (1911).
29. N. Wolf, Chem. Ber., 14, 2031 (1881).
30. J. R. Schaefgen, J. Polym. Sci., 15, 203 (1955).
20.1.2.2.
n Mol. wt. m.p. (C) Refs.
1 136.1 70-72 6 1
2 256.3 1 4 8 11,13-16
3 376.5 183-184 1 1
4 496.7 204-205 1 1
5 616.9 152-154 6 1
n Mol. wt. m.p. (C) Refs.
1 312.5 156 17,18,62
2 414.1 218-220 17,18,62
3 636.9 211 17,18,62
4 799.2 216-217 17,18,62
5 961.4 2 5 0 17,18,62
6 1123.6 249-250 17,18
7 1285.9 253-256 1 8
8 1448.1 224-226 1 7
1 0 1772.6 140 1 7
Phenol - Formal dehyde and Rel at ed Ol i gomers IV/93
20. 1. 3. 2.
P3)3C
20.1.8. OLIGOMERS WITH CARBONYL AND SULFONYL
BRIDGES
20. 1. 8. 1.
n Mol. wt . m.p. (C) Refs.
0 220. 4 70-71 6 1
1 340. 5 125-130 6 1
2 460. 7 82- 84 6 1
4 701.0 188-190 6 1
n Mol. wt. m.p. (C) Refs.
1 242. 3 106-107 23, 24, 56- 58
2 376. 4 122-123 24, 56, 57
20.1.4. 2,4,6-MESITOL-FORMALDEHYDE OLIGOMERS
C%+% ~;;+-j H
3 3 n
20. 1. 8. 2.
n Mol. wt. m.p. (C) Refs.
1 284. 4 188 1 9
2 432. 6 257 1 9
n Mol. wt. m.p. (C) Refs.
1 347. 2 1 7 9 25
2 517.4 238- 240 25
3 687. 6 246- 252 25
20.1.5. 4-CARBOXY-PHENOL-FORMALDEHYDE OLIGOMERS
OH r OH 1
20. 2. OLIGOMERIC PHENOL ALCOHOLS
20.2.1. OLIGOMERIC PHENOL ALCOHOLS
OH
H
I-0 1
0
CH2- O H
n
n Mol. wt. m.p. (C) Refs.
COOH L COOH] n
n Mol. wt. m.p. (C) Refs.
1 288. 3 305- 307 5 9
2 438. 4 3 1 0 5 9
20.1.6. 4-BROMO-PHENOL-FORMALDEHYDE OLIGOMERS
1 124.1 86- 87 3, 26
2 230. 3 121.5-123 3, 27, 28
20.2.2. PHENOL DIALCOHOLS HOCH2
n Mol. wt. m.p. (C) Refs.
1 358.1 183-184 1,60
2 543.1 237- 238 6 0
n Mol. wt. m.p. (C) Refs.
1 154.2 1 0 1 29- 32
2 260. 3 126-127 2 8
20.1.7. p-CRESOL-ACETALDEHYDE OLIGOMERS
20.2.3. p-CRESOL MONOALCOHOLS H
R n Mol. wt. m.p. (C) Refs.
n Mol. wt. m.p. (C) Refs.
H 1 241.3 1 4 1 20,21
H 2 373. 5 214-215 2 1
CH3 1 270. 4 135-135.5 2 2
CH3 2 404. 6 154-155 63
CH3 3 538. 7 204- 205 6 3
1 138.2 1 0 7 8, 33, 34
2 258. 3 1 4 8 8, 9, 35
4 498. 6 3 6
IV/94 PHYSICAL DATA OF OLIGOMERS
20.2.4. p-CRESOL DIALCOHOLS HOCH2
n Mol. wt.
1 168.2
2 288.3
3 408.5
m.p. (C) Refs.
133-134 13,37
151.5 9,35,38,39
203 9,39,40
20.2.5. p-tert BUTYLPHENOL DIALCOHOLS
HOCHz
n Mol. wt.
1 210.3
2 372.5
m.p. (C) Refs.
74-75 4 1
117-118 1 8
20.2.6. o-HYDROXYDIBENZYL ETHERS
n
2
Mol. wt.
318.4
m.p. (C)
8 5
Refs.
4 2
20.3. CYCLIC PHENOL-FORMALDEHYDE OLIGOMERS
20.3.1.
X R n Mol. wt. m.p. (C) Refs.
-CH*- -CH, 4 480.6 300 36,43
-WH3)3 4 648.9 344-346 18,44,
65.66
5 811.1 310 6 8
6 973.5 380- 381 65,66,68
8 1298.0 411- 412 65,66,68
-CsH5 4 728.9 407- 409 18,66,67
6 1093.4 408-410 66,67
8 1457.8 421-423 66967
-CsH11 4 753.1 330 1 8
-cHzcsH5 4 785.0 330 1 8
-C(CH3)2CH2CH3 4 705.0 280 1 8
-C(CH~)ZCH~C(CH~)~ 4 813.2 3 3 3 1 8
-CHzOCHz- -CH3 4 600.7 264-266 4 2
-WH3)3 3 576-8 2 4 5 4 5
20.3.2.
n
2
Mol. wt.
540.7
m.p. (C)
325-330
Ref.
4 6
20.3.3.
OH
R- CH,
R-CH,
OH
CH2
CH,-R
R n Mol. wt. Refs.
H 2 916.2 4 7
OH
CH2
1 1201.5 43,47
CH3
20.4. BRANCHED PHENOL-FORMALDEHYDE OLIGOMERS
20.4.1.
CH+ CH2+ CH,
CH2
CH3 -b
CH3
0
OH
CH3
Mol. wt. m.p. (C) Ref.
376.5 158 4 8
20.4.2.
R+ CH;+ CH2+ CH3
R2 R2
OH
R2 RI
RI RZ Mol. wt. m.p. (C) Refs.
H H 411.5 4 9
H CH3 453.6 184-187 30,50
CH3 CH3 495.6 185-186 5 1
20.4.3.
RI RI
RI
n Mol. wt . m.p. (C) Refs.
RI R2
n Mol. w.t m.p. (C) Refs.
H H 1 624.1 185-187 52.53
CH3 CH3 1 737.0 207-208 6,53,54
CH3 CH3 2 1217.5 190-191 5 4
REFERENCES
1. C. A. Buehler, D. E. Cooper, E. 0. Scrudder, J. Org. Chem., 81,
316 (1943).
2. S. R. Finn, J. W. James, C. J. S. Standen, J. Appl. Chem., 4,
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3. D. A. Fraser, R. W. Hall, l? A. Jenkins, A. L. J. Raum, J. Appl.
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(1957).
9. M. Koebner, Z. Angew. Chem., 46, 251 (1953).
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11. E. Ziegler, I. Hontschik, L. Milowiz, Montash. Chem., 78,334
(1948).
12. H. Kaemmerer, W. Rausch, H. Schweikert, Makromol. Chem.,
56, 123 (1962).
13. K. Auwers, Chem. Ber., 40, 2524 (1907).
14. K. Fries, K. Kann, Ann. Chem., 353, 335 (1907).
15. K. Hultzsch, Chem. Ber., 74, 989 (1941).
20. 5. HYDROQUINONE OLIGOMERS
References IV/95
20.5.1.
1 300.4 97-98 6 4
2 462.5 146-147 6 4
20.5.2.
R+cH=cH [+=CH] $
3 3
n
3
R n Mol. wt. m.p. (C) Refs.
H 0 300.4 97-98 6 4
1 462.5 192-193 6 4
CH3 0 328.4 162-163 6 4
1 490.6 2 4 2 - 2 4 3 6 4
2 652.8 283-284 6 4
3 815.0 306-307 6 4
4 971.2 326-328 6 4
16. A. Zinke, E. Ziegler, Chem. Ber., 74, 541 (1941).
17. H. Kaemmerer, K. Haberer, Monatsh. Chem., 95,1589 (1964).
18. A. Zinke, R. Kretz, E. Leggewie, K. Hoessinger, Monatsh.
Chem., 83, 1213 (1952).
19. S. R. Finn, J. W. G. Musty, J. Sot. Chem. Ind., 69 (Suppl. No.
l), s 3 (1950).
20. E. Adler, H. V. Euler, G. J. Gie, Arkiv Kemi, 16A, No. 12
(1943).
21. L. M. Debing, Trans. Electrochem. Sot., 90, 277 (1946).
22. H. V. Euler, E. Adler, J. 0. Cedwall, Arkiv Kemi, 15A, No. 19
(1942).
23. A. V. Bayer, V. Frewsen, Ann. Chem., 212, 344 (1882).
24. H. Kaemmerer, G. Buesing, H.-G. Haub, Makromol. Chem.,
66, 82 (1963).
25. H. Kaemmerer, M. Harris, Makromol. Chem., 62, 18 (1963);
J. Polym. Sci. A, 2, 4003 (1964).
26. L. Lederer, J. Prakt. Chem., 50, 223 (1894).
27. S. R. Finn, J. W. James, C. J. S. Standen, Chem. Ind., 188,
(1954); J. Appl. Chem., 4, 296 (1954).
28. A. T. Carpenter, R. F. Hunter, J. Appl. Chem., 3,486 (1953).
29. S. R. Finn, J. W. G. Musty, J. Appl. Chem., 2, 88 (1952).
30. J. H. Freeman, J. Am. Chem. Sot., 74, 6257 (1952).
31. H. Kaemmerer, M. Grossmann, Chem. Ber., 86, 1492 (1953).
32. J. Reese, Angew. Chem., 64, 399 (1952).
33. H. V. Euler, E. Adler, G. Eklund, 0. Toerngren, Arkiv Kemi,
15B, No. 9 (1942).
IV/ 96 PHYSICAL DATA OF OLICOMERS
34. 0. Manasse, Chem. Ber., 27, 2409 (1894).
35. P Maitland, D. C. Pepper, J. Sot. Chem. Ind., 61, 66 (1942).
36. B. T. Hayes, R. F. Hunter, J. Appl. Chem., 8, 743 (1958).
37. F. Ullmann, K. Brittner, Chem. Ber., 42, 2539 (1909).
38. F. Adler, Arkiv Kemi, 14B, No. 23 (1941).
39. S. R. Finn, G. J. Lewis, J. Sot. Chem. Ind., 69, 132 (1950).
40. S. Kyming, Arkiv Kemi, 15A, No. 2 (1941).
41. F. Hanus, E. Fuchs, J. Prakt. Chem., 153, 327 (1939).
42. H. Kaemmerer, M. Dahm, Kunstst. Plast., 6, 1 (1959).
43. B. T. Hayes, R. F. Hunter, Chem. Ind., 193, (1956).
44. A. Zinke, E. Ziegler, Chem. Ber., 77, 264 (1944).
45. K. Hultzsch, Kunststoffe, 52, 19 (1962).
46. H. V. Euler, E. Adler, B. Bergstroem, Arkiv Kemi, 14B, No. 30
(1941).
47. R. F. Hunter, C. Turner, Chem. Ind., 72, (1957).
48. E. Ziegler, Monatsh. Chem., 79, 142 (1948).
49. E. Ziegler, Oester, Chem. Ztg., 49, 92 (1948).
50. A. T. Carpenter, R. F. Hunter, J. Appl. Chem., 1, 217 (1951).
51. A. T. Carpenter, R. F. Hunter, J. Chem. Sot., 2731, (1954).
52. H. Kaemmerer, H. Lenz, Kunststoffe, 51, 26 (1961).
53. A. C. Davis, B. T. Hayes, R. F. Hunter, J. Appl. Chem., 7,521
(1957).
54. R. F. Hunter, C. Turner, J. Appl. Chem., 7, 528 (1957).
TABLE 21. OLIGO(PHENYLENES)
21.1. o-OLIGO(PHENYLENES)
21.1.1. LINEAR o-OLIGO(PHENYLENES) H H
n
n Mol. wt. m.p. (C) b.p. (C) Re f s .
3 230.3 5 9 3 3 2 12
4 306.4 119 4 2 0 1,3-6
6 458.6 2 1 7
375
8 610.8 3 2 0 5
21.1.2. CYCLIC o-OLIGO(PHENYLENES)
n Mol. wt. m.p. (C) Re f s .
2 152.2 1 1 1 4,5,7-9
3 228.3 196.5 10,ll
4 304.4 233 495
6 456.6 4 3 2 5
8 608.8 4 2 5 5
55. H. v. Euler, E. Adler, S. V. Kispeczy, A. M. Fagerlund, Arkiv
Kemi, 14A, No. 10 (1940).
56. H.-J. Eichhoff, H. Kaemmerer, D. Weller, Makromol. Chem.,
129, 109 (1969).
57. H.-J. Eichhoff, H. Kaemmerer, D. Weller, Makromol. Chem.,
132, 163 (1970).
58. H. Kaemmerer, G. Gros, H. Schweikert, Makromol. Chem.,
143, 135 (1971).
59. H. Kaemmerer, W. Lotz, Makromol. Chem., 145, 1 (1971).
60. H. Kaemmerer, G. Gros, Makromol. Chem., 149, 85 (1971).
61. M. B. Huglin, G. J. Knight, W. W. Wright, Makromol. Chem.,
152, 67, 83 (1972).
62. T. Carins, G. Eglinton, Nature (London), 196, 535 (1962).
63. H. Kaemmerer, A. Kiegel, unpublished results.
64. G. Manecke, D. Zeipner, Makromol. Chem., 129,183 (1969).
65. C. D. Gutsche, B. Dhawan, K. H. No, R. Muthukrishnan, J.
Am. Chem. Sot., 103, 3782 (1981).
66. C. D. Gutsche, Top. Curr. Chem., 123, (1984); Act. Chem.
Res., 16, 161 (1983).
67. C. D. Gutcshe, K. H. No, J. Org. Chem., 47,2708 (1982); C. D.
Gutsche, P. F. Pagoria, ibid., 50, 5795 (1985).
68. A. Ninagawa, H. Matsuda, Makromol. Chem., Rapid Com-
mun., 3, 65 (1982).
21.2. m-OLIGO(PHENYLENES)
21.2.1. LINEAR m-OLIGO(PHENYLENES) H
n Mol. wt. m.p. (C) b.p. (C) Re f s .
H
I
J n
3 230.3 8 9 365 12-14
4 306.4 86.5-87.5 4 1 9 3,6,15-17
5 382.5 117-117.5 12,15,16
6 458.6 1 4 8 3,15,17,18
8 610.8 129-131 15,17
9 689.9 195-200 1 8
21.2.2. CYCLIC m-OLIGO(PHENYLENES)
n Mol. wt. m.p. (C) Re f s .
6 456.6 509.5-5 11 1 9
8 608.8 449- 45 1 1 9
H
21.2.3. OLIG0(3-METHYL-m-PHENYLENES)
n Mol. wt. m.p. (C) b.p. (C) Refs.
2 182.3 9-9.5 2 8 0 20-23
3 272.4 6 5 1 2
Oligo(phenylenes) IV/97
21.3. p-OLIGO(PHENYLENES)
21.3.1. p-OLIGO(PHENYLENES) H
Solubility
n Mol. wt. m.p. (C) b.p. (C/mm) (g/L toluene) Refs.
1 7 8 . 1 5.5 8 0 . 1 m
2 154.2 7 1 1 5 6 430 2 4
3 230.3 2 1 5 376 7.4 3,12,14,25,26
4 306.4 322 428/10 0.12 3,12,16,21,25,26
5 382.5 3 9 5 < 0.005 12,16,21,25,27,28
6 458.6 465 3,29-31
21.3.2. OLIGO(3-METHYL-p-PHENYLENES) H
n Mol. wt. m.p. (C) b.p. (C) Refs.
1 92.1 - 9 5 110.6
2 182.3 213-274 22,23,32
3 272.4 4 3 3 3
21.3.3. OLIG0(2,5-DIMETHYL-p-PHENYLENES) H
Solubility
n Mol. wt. m.p. (C) b.p. (C) (g/L toluene) Refs.
1 106.2 13.3 138.4
2 210.3 53-54 7; 20,34
3 314.5 182-183 2 8 3 4
4 418.6 264-266 1 . 1 3 4
5 522.8 307-309 0.24 3 4
21.3.4. OLIG0(2,3,5,6-TETRAMETHYL-p-PHENYLENES)
H
Solubility
n Mol. wt. m.p. (C) b.p. (C) (g/L toluene) Refs.
1 134.2 79.2 196-198
2 266.4 136-137 3: 34,35
3 398.6 210-272 2 4 3 4
4 530.8 270-272 3.4 3 4
21.3.5. OLIG0(2,2-DIMETHYL-BIPHENYLENES)
H[-(=J&]f
Solubility
n Mol. wt. m.p. (C) (g/L toluene) Refs.
1 182.3 2 4 20,23,36
2 362.5 9 6 4 9 0 3 7
21.3.6. OLIG0(3,3-DIMETHYL-BIPHENYLENES)
H [&..-&j;
Solubility
n Mol. wt. m.p. (C) b.p. (C) (g/L toluene) Refs.
1 182.3 9-9.5 2 8 0 20-23.38
2 362.5 76.5 5% 21,37
3 542.8 142 8 7 3 9
4 723.0 273 <6.5 39,40
5 903.3 285 - 2 39.40
6 1083.5 298 <0.8 39,40
21.3.7. OLIG0(3,3-DIMETHYL-p-TERPHENYLENES)
.[w];
Solubility
n Mol. wt. m.p. (C) (g/L toluene) Refs.
1 258.4 140-141 4.9 27,31
2 514.7 2 5 8 0.4 3 7
IV/98 PHYSICAL DATA OF OLICOMERS
21.3.8. OLIG0(2,5-DIMETHOXY-p-PHENYLENES)
H
n Mol. wt. m.p. (C) b.p. (C) Refs.
1 138.2 5 6 212.6
2 214.3 1 0 5 20,41
3 410.5 189 4 1
4 546.6 2 4 6 4 1
21.3.9. OLIG0(3,3-DIMETHOXY-BIPHENYLENES)
Solubility
n Mol. wt. m.p. (C) b.p. (C) (gh toluene) Refs.
1 214.3 3 6 328 4 2
2 426.5 1 5 8 2 2 38,43
REFERENCES
1. W. Bachmann, H. T. Clarke, J. Am. Chem. Sot., 49, 2089
(1927).
2. C. F. H. Allen, F. P. Pingert, J. Am. Chem. Sot., 64, 1365
(1942).
3. J. A. Cade, A. Pilbeam, Tetrahedron, 20,519 (1964); J. Chem.
Sot., 114 (1964).
4. W. S. Rapson, R. G. Shuttleworth, J. N. van Niekerk, J. Chem.
SOL, 326 (1943).
5. G. Wittig, G. Lehmann, Chem. Ber., 90,875 (1957); G. Wittig,
G. Klar, Ann. Chem., 704, 91 (1967).
6. S. T. Bowden, J. Chem. Sot., 1111 (1931).
7. W. Baker, M. P. V. Boarland, J. F. W. McOmie, J. Chem. Sot.,
1476 (1954).
8. W. C. Lothrop, J. Am. Chem. Sot., 63, 1187 (1941).
9. G. Wittig, W. Herwig, Chem. Bet, 87, 1511 (1954).
10. C. Mannich, Chem. Ber., 40, 159 (1907).
11. P. G. Copeland, R. E. Dean, D. McNeil, J. Chem. Sot., 1689
(1960).
12. M. Busch, W. Weber, J. Prakt. Chem., 146, 1 (1936).
13. A. E. Gillam, D. H. Hey, J. Chem. Sot., 1170 (1939);
H. France, I. M. Heilbron, D. H. Hey, J. Chem. Sot., 1288
(1939); 1364 (1938).
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(1948).
15. R. L. Alexander, Jr., J. Org. Chem., 21, 1464 (1956).
16. G. F. Woods, F. T. Reed, J. Am. Chem. Sot., 71, 1348
(1949).
17. M. Bennett, N. B. Sunshine, G. F. Woods, J. Org. Chem., 28,
2514 (1963); W. Davey, D. H. Maass, J. Chem. Sot., 4386
(1963).
21.3.10. OLIG0(2,3-DIMETHOXY-p-QUATERPHENYLENES)
Solubility
n Mol. wt. m.p. (C) (g/L toluene) Refs.
1 366.5 183-184 1 3 4 3
2 730.9 276-277 0.2 4 3
21.4. OLICO(p-QUINONES) H
n Mol. wt. m.p. (C) Refs.
1 108.1 116.5
2 214.2 194 4 1
3 320.3 >230 4 1
4 426.3 230-270 4 1
18. L. Silverman, W. Houk, Anal. Chem., 27, 1956 (1955).
19. H. A. Staab, F. Binnig, Tetrahedron Lett., 3 19 (1964); Chem.
Ber., 100, 293 (1967); H. Braunling, F. Binnig, H. A. Staab,
ibid., 100, 880 (1967).
20. F. Ullmann, G. M. Meyer, 0. Loewenthal, E. Gilli, Ann.
Chem., 332, 38 (1904).
21. E. Mueller, T. Toepel, Chem. Ber., 72, 273 (1939).
22. G. F. Woods, A. L. Van Artsdale, F. T. Reed, J. Am. Chem.
Sot., 72, 3221 (1950).
23. E. A. Johnson, J. Chem. Sot., 4155 (1957).
24. E. Clar, Polycyclic Hydrocarbons, Academic, New York,
Springer, Berlin, 1964.
25. 0. Gerngross, M. Dunkel, Chem. Ber., 57, 739 (1924); 0.
Gerngross, C. Schachnow, R. Jonas, Chem. Ber., 57, 747
(1954).
26. H. 0. Wirth, K. H. Goenner, W. Kern, Makromol. Chem., 63,
53 (1963).
27. H. 0. Wirth, K. H. Goenner, R. Stueck, W. Kern, Makromol.
Chem., 63, 30 (1963).
28. T. W. Campbell, R. N. McDonald, J. Org. Chem., 24, 730
(1959).
29. P Kovacic, R. M. Lange, J. Org. Chem., 29, 2416 (1964).
30. T. Nozaki, M. Tamura, Y. Harada, K. Saito, Bull. Chem. Sot.
Japan, 33, 1329 (1960).
31. R. Pummerer, K. Bittner, Chem. Ber., 57, 84 (1924); R.
Pummerer, L. Seligsberger, Chem. Bet, 64, 2477 (1931).
32. F. Mayer, K. Freitag, Chem. Ber., 54, 347 (1921).
33. H. 0. Wirth, H. Hefner, W. Kern, unpublished results.
34. H. 0. Wirth, F. U. Herrmann, W. Kern, Makromol. Chem., 80,
120 (1964).
Heterocycl i c Ol i gomers IV/99
I
35. E. Marcus, W. M. Lauer, R. T. Arnold, J. Am. Chem. Sot., 80,
3742 (1958).
36. D. M. Hall, M. S. Lesslie, E. E. Turner, J. Chem. Sot., 711
(1950).
37. W. Kern, M. Seibel, H. 0. Wirth, Makromol. Chem., 29, 164
(1959).
38. W. Schlenk, M. Brauns, Chem. Ber., 48, 661 (1914).
39. W. Kern, W. Gruber, H. 0. Wirth, Makromol. Chem., 37,198
(1960).
40. W. Heitz, R. Ulhich, W. Kern, Makromol. Chem., 98, 29
(1966).
41. H. Erdtmann, M. Granath, G. Schultz, Acta Chem. Stand., 8,
1442 (1954).
42. N. Komblum, Org. Syn. Coll. Vol. III, 295 (1962).
43. W. Kern, H. W. Ebersbach, I. Ziegler, Makromol. Chem., 31,
154 (1959).
E. OLIGOMERS CONTAINING HETEROCYCLIC RINGS IN THE MAIN CHAIN
TABLE 22. HETEROCYCLIC OLIGOMERS
22. 1. OLIGO(FURAN)DERIVATIVES
22.1.1. OLIGO(FURFUiYL) ALCOHOLS H[ +cH2];H
n Mol. wt. m.p. (C) b.p. (Wmbar) ng Refs.
1 9 8 . 1 171/1000 1.4868 10. 11
2 178.2 - 2.5 141-143/12 1.5290 10-12.14
3 258.3 62-62. 5 192.5-295/8 lo-12,14
22.1.2. OLIGO(FURFURYL) FURANS H [ gCRIR,le 9
RI RZ n Mol. wt. m.p. (C) b.p. (Wmbar)
d? (g/cm31
nf Refs.
H H 1
2
3
4
H CH3 1
2
3
CH3 CH3 1
2
3
4
5
CH3 C2H5 1
2
3
C2Hs C2H5 1
2
3
1
2
148.2
228.2
308.3
388.4
162. 2
256.3
350.4
176.2
284.3
392.5
500.6
608.7
190. 2
312.4
434.6
204.3
340.4
476.6
216.3
364.5
78116
141-146/11
74-75
99-101
- 12
47.0147.5
Oil
83-85
-9to-8
13-17
86. 8-87. 6
91128
114-116/0.13
165-168/0.04
73-7617-8
120-123/1.3
163-16711.3
68-7013
143-14511.3
205-21011.3
76-7713
162- 16312
212-21512
94-9512
200-20512
1.102 1. 5048 10,12,14-15,39
1. 5324 10.12
10,12,14
10,14
1. 073 1. 4993 16,17
1 7
16,17
1. 043 1. 4966 17,18
17.18
1.030 1.5172 17.18
1 7
1 7
1. 033 1.4970 1 8
1. 045 1.5094 1 9
1.046 1.5173 1 9
1. 023 1.4978 2 0
1. 028 1.5089 2 0
1.034 1.5199 2 0
2 1
1. 018 1. 5221 2 1
22.1.3. 2,5-OLIGO(FURYLENES) H
n Mol. wt. m.p. (C) b.p. (Wmbar) die (g/cm3) Refs.
1 6 8 . 1 - 85.7 31.4/1013 0.9514120 1.4214120
2 134. 1 63-64115 1.5601122 39-41,42
3 200.2 62-63 3 2
IV / 100 PHYSICAL DATA OF OLICOMERS
22.1.4. FURANOPHANES
I \
f-7
0
R R n
R R n Mol. wt. m.p. (C) Refs.
H
CH3
4 376.4 140-142 16,17,22
r-2,c-7,c- 12,c- 1 I- 191.0-192.0 2 2
H
C2H5
4 432.5 83-88 2 2
r-2,c-7,c-12,c-ll- 152.0-153.0 2 2
CH3 CH3 4 432.5 243 18,23,24
CH3 CH3 5 540.7 Oil 1 7
6 648.8 182 17,18,24
CH3 C2Hs
4 488.5 174 18,19,22,24
C2H5 C2H5
4 544.7 249-250 18,20,24
H 4 592.8 268-269 21,24
22.2. OLIGO(THIOPHENE) DERIVATIVES
22.2.1. OLIGO(2.5-THIENYLENES) H [+I;,
22.1.5. TETRAHYDROFURANOPHANES
w
0
R R n
n Mol. wt. m.p. (C) Refs.
4 448.7 204- 209 17,18,20,21,23
r-(lS, 3S, 6R, 8S, llR, 13R, 16S, 18R)- 2 1 8 2 5
r-(lS, 3R, 6St 8R, llS, 13R, 16S, 18R)- 221 2 5
5 560.8 Oil . 1 7
6 673.0 75-80 1 7
n Mol. wt. m.p. (C) b.p. (Urnbar) nD Refs.
8 4 . 1 - 38.4
166. 3 33-34
248.4 96-97
330.5 215-216
412.5 257-258
494.8 304-305
576.9 327-328
659.0 364
22. 3. OLIGO(PYRROLE) DERIVATIVES
22.3.1. OLI GO( PYRROLE) DERI VATI VES
84.2/1013 1.5289
125116 1,27,28,34,41,42,44,49
1,3,26,28,30-33,42,44,47,49
1,3,27-29,41,42,44,46,49
1,3,28,29,42,48
3,27,28,42,44,46
3,29,48
42,46
I
No. Oligomers R n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
2 214.3 105-106 21,43
2 t$m CH3 2
I N
174.2 5 9
iI R IL
125-12614 3 5
36,37
2 1
22.3.2. OLIGO[2,5-(iV-METHYL)PYRROLENES] H 22. 4. OLIGO(PYRIDINE) DERIVATIVES
22.4.1. OLIGO(2,6-.PYRIDYLENES) H
n Mol. wt. m.p. (C) b.p. (Urnbar) Refs.
1 81.1 114-115/99.6
2 160.2 14-15 II-78jO.5 13,42
4 318.4 134 4 2
5 397.5 1 4 5 4 2
6 476.6 160 4 2
8 634.8 178-182 4 2
1 6 1267.6 240-256 4 2
1
H
n
n Mol. wt. m.p. (C) b.p. (Urnbar)
e
Refs.
1 79.1 - 4 2 115.5/1013 1.5095
2 156.2 70.1 273-275/1013 4,5
3 233.3 89-90 370/1013 2,4-6
4 310.4 219-220 5
5 387.5 2 6 5 5
6 464.5 3 5 0 5
22.4.2. OLIG0(3,5-PYRIDYLENES) H H
n
II Mol. wt. m.p. (C) b.p. (Urnbar) n4p Refs.
1 19.1 - 4 2 115.5 1.5095
2 156.2 6 8 291-292/981 439
3 233.3 249- 25 1 9
22.4.3. OLIGO(2,6-QUINOLYLENES) H
[-Ql.
n Mol. wt.
m.p. (C) b. p. (Urnbar)
rlz Refs.
1 129.2 - 15.6 238.1/1013 1.6268
2 256.3 144 798
3 383.5 267-269 8
4 510.6 348-350 8
22. 5. CYCLIC OLIGO(HETEROCYCLICS)
No. Mol. wt. m.p. (C) Refs.
1 188.2 189-190 3 8
2 220.3 194.5-196 3 8
REFERENCES
1. J. W. Sease, L. Zechmeister, J. Am. Chem. Sot., 69, 270
(1947).
2. Th. Kauffmann, J. Konig, A. Woltermann, Chem. Ber., 109,
3864 (1976).
3. W. Steinkopff, R. Leitsmann, K. H. Hoffmann, Ann. Chem.,
546, 180 (1941).
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5. F. H. Burstall, J. Chem. Sot., 1662 (1938).
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13. J. Gjos, S. Gronowitz, Acta Chem. Stand., 25, 2596
(1971).
14. K. Takano, Nippon Kagaku Zasski, 79, 955 (1958); Chem.
Abstr., 54,453Oe (1960); ibid., 80, 313 (1959); Chem. Abstr.,
55, 54538 (1961).
N+N N,N
Ref erences IV / 101
264.2 233 42,45
328.5 255-256 42,45
492.7 4 2 0 42,45
328.5 300-301 42,45
528.7 4 1 0 4 5
312.3 355-360 4 5
15. H. Gilman, G. F. Wright, J. Am. Chem. Sot., 55,3302 (1933).
16. W. H. Brown, H. Sanatzky, Can. J. Chem., 34, 1147 (1956).
17. Y. Kobuke, K. Hanji, K. Horiguchi, M. Asada, Y. Nakayama,
J. Furukawa, J. Am. Chem. Sot., 98, 7414 (1976).
18. R. G. A&man, W. H. Brown, G. F. Wright, J. Org. Chem., 20,
1147 (1955).
19. W. H. Brown, W. N. French, Can. J. Chem., 36, 537 (1958).
20. R. E. Beals, W. H. Brown, J. Org. Chem., 21, 447 (1956).
21. W. H. Brown, B. J. Hutchinson, M. H. MacKinnon, Can. J.
Chem., 49, 4017 (1971).
22. A. G. S. Hogberg, M. Weber, Acta Chem. Stand. B, 37, 55
(1983).
23. M. Chastrette, F. Chastrette, J. Sabadie, Org. Synth., 57, 74
( 1977) .
24. M. De Sousa Healy, A. J. Rest, J. Chem. Sot., Chem. Com-
mun., 149 (1981); J. Chem. Sot., Perkin Trans. I, 973 (1985).
25. M. Van Beylen, B. Roland, G. S. D. King, J. Aerts, J. Chem.
Res. (S), 388 (1985); (M), 4201 (1985).
26. J. Kagan, S. K. Arora, Heterocycles, 20, 1941 (1983).
27. J. Kagan, S. K. Arora, Heterocycles, 20, 1937 (1983).
28. J. Kagan, S. K. Arora, Tetrahedron Lett., 24, 4043 (1983).
IV / 102 PHYSICAL DATA OF OLICOMERS
29. J. Kagan, S. K. Arora, J. Org. Chem., 48, 4317 (1983).
30. K. E. Schulte, J. Reisch, L. Homer, Chem. Ber., 95, 1943
( 1962) .
31. H. J. Kooreman, H. Wynberg, Rec. Trav. Chim. Pays-Bas, 86,
37 (1967).
32. T. Asano, S. Ito, N. Saito, K. Hatakeda, Heterocycles, 6, 317
(1977).
33. J.-P. Beny, S. N. Dhawan, J. Kagan, S. Sundless, J. Org.
Chem., 47, 2201 (1982).
34. J.-P Morizur, Bull. Sot. Chim. France, 1331 (1964);
J.-P Morizur, C. R., Ser. C, 254, 1093 (1962).
35. W. H. Brown, W. N. French, Can. J. Chem., 36, 371 (1958).
36. A. V. Baeyer, Chem. Ber., 19, 2184 (1886).
37. V. V. Chelintzev, B. V. Tronov, S. G. Karmanov, J. Russ. Phys.
Chem., 48, 1210 (1916); Chem. Abstr. 11, 1418 (1917).
3 8 . H. E. Winberg, F. S. Fawcett, W. E. Mochel, C. W. Theobald,
J. Am. Chem. Sot., 82, 1428 (1960).
39. T. Reichstein, A. Grtlssner, H. Zschokke, Helv. Chim. Acta,
15, 1066 (1932).
40. R. Grigg, J. A. Knight, M. V. Sargent, J. Chem. Sot. C, 976
(1966).
41. R. E. Atkinson, R. F. Curtis, G. T. Phillips, J. Chem. Sot. C,
2011 (1967).
42. Th. Kauffmann, Angew. Chem., 91, 1 (1979). Angew. Chem.,
Int. Ed. Engl., 18, 1 (1979).
43. D. Dolphin, R. Grigg, M. V. Sargent, D. H. Williams, J. A.
Knight, Tetrahedron, 21, 3441 (1965).
44. D. D. Cunningham, L. Laguren-Davidson, H. B. Mark Jr.,
Ch. V. Pham, H. Zimmer, J. Chem. Sot., Chem. Commun.,
1021 (1987).
45. Th. Kauffmann, B. Greving, R. Kriegesmann, A. Mitschker,
A. Woltermann, Chem. Ber., 111, 1330 (1978).
46. J. Nakayama, T. Konishi, S. Murabayashi, M. Hoshino,
Heterocycles, 26, 1793 (1987).
47. J. Nakayama, Y. Nakamura, T. Tajiri, M. Hoshino, Hetero-
cycles, 24, 637 (1986).
48. J. Nakayama, Y. Nakamura, S. Murabayashi, M. Hoshino,
Heterocycles, 26, 939 (1987).
49. K. Tamao, S. Kodama, I. Nakajima, M. Kumada, A. Minato,
K. Suzuki, Tetrahedron, 38, 3347 (1982).
TABLE 23. OLIGO(SACCHARIDES)
23. 2. OLIGOMERIC HEXOSES
23. 1. OLIGOMERIC PENTOSES
23. 1. 1. OLI GO( P- XYLOPYRANOSES) a
r I 1
HO
n Mol. wt. m.p. (C)
M::
i n Hz0
I 150. 1 153 19. 2
2 282. 2 186- 187 - 25. 6
3 414. 4 21. 5- 216 - 48. 1
4 546. 5 224- 226 - 61. 9
5 678. 6 240- 242 - 72. 9
6 810. 7 237- 242 - 78. 5
7 942. 8 240- 242 - 74. 0
Ref s. 1- 3.
23. 1. 2. OLI GO( P- XYLOPYRANOSE ACETATES) =
CH3CO0
n Mol. wt. m.p. (C)
[aI2
c in CHC13
2 534. 5 155. 5- 156 - 74. 5 0. 9
3 750. 7 109- 110 - 84. 3 0. 6
4 966. 9 201- 202 - 93. 7 0. 8
5 1183. 1 249- 250 - 97. 5 1. 1
6 1399. 3 260- 261 - 102. 0 1. 5
23. 2. 1. MALTO- OLI GOO
HO-
qH20H
1
II Mol. wt. m.p. (C)
[al::
i n Hz0
1 180. 2 146 52. 6
2 342. 3 160- 165 136. 0
3 504. 4 160. 0
4 666. 6 177. 0
5 828. 7 180. 3
6 990. 9 184. 7
7 1153. 0 186. 4
a Ref s. 4- 6.
23. 2. 2. CYCLODEXTRI NS
n Mol. wt.
[aID (C = 1, Hz@
6 972. 8 149. 0
7 1135. 0 158. 8
8 1297. 1 170. 0
Ref s. 1- 3. a Ref s. 4- 6.
r
CH20H
1
HOFCH2 1
23.2.6. GENTIO-OLIGOSESa Hoc$-yot
1 bH In
23.2.3. CELLO-OLIGOSESa H
H O
Specific rotation
II Mol. wt. m.p. (C)
blD (C)
c in Hz0
1 180.2 150 52.5 2 0 4
2 342.3 2 2 5 d 34.6 2 0 8
3 504.4 2 3 8 d 21.6 2 6 4
4 666.6 253 d 16.5 2 3 3.4
5 828.7 2 6 7 d 11.0 3 0 4.1
6 990.9 2 7 8 d 10.0 3 0 1.2
7 1153.0 2 8 6 d 7.3 3 0 0.1
Refs. 7-14.
23.2.4. CELLO-OLIGOSE ACETATESa
CH3CO0 CH3CO0
r
cH2OCOCH3 1
la Mol. wt . m.p. (C)
[a] F-25
(c = 5, in CHCI 3)
1 390.4 1 1 3 101.6
2 678.6 229.5 41.0
3 966.9 223-224 22.6
4 1255.1 230-234 13.4
5 1543.4 240-241 4.2
6 1831.6 252-255 - 0.2
7 2119.8 263-266 - 4.4
a Refs. 7- 14.
23.2.5. ISOMALTO-OLIGOSES ~cjFp$
1
I
AH
1 n
n Mol. wt. m.p. (C) [a]D in Hz0
1 180.2
2 342.3
3 504.4
4 666.6
5 828.7
6 990.9
146
225 d
52.6
1 5 3
160
1 6 3
Oligobaccharides) IV / 103
It Mol. wt. m.p. (C) [aID in Hz0
1 180.2 150 52.5
2 342.3 190-195 9.6
3 504.4 - 10.5
4 666.6 - 19.5
Ref. 15.
r
qH20H
1
23.2.7. GALACTO-OLIGOSESa pqp~
1 bH Jn
n Mol. wt . m.p. (C) [a]D in Hz0
1 180.2 1 6 7 - 52.5
2 342.3 210-211 1 7 3
3 504.4 115-120 5 8
4 666.6 5 3
Ref. 15.
232.8. MANNO-OLIGOSESa kF;d.
H(
w---r I
L _In
Specific rotation
n Mol. wt. m.p. (C) [aID (Cl c, Hz0
1 180.2 132
2 342.3 193-194 - 7.7 2 5 0.9
3 504.4 137-137.5 - 23.3 1 . 3
4 666.6 232-234 - 3 1 1.6
a Refs. 16,17.
23. 3. OLIGOMERIC AMINO SUGARS
23.3.1. N-ACETYL CHITO-OLIGOSESa
r
qH20H
1
1
hHCOCH
in
Specific rotation
n Mol. wt. m.p. (C) b]D c in Hz0
1 221.2
2 424.4 260-262 d 17.2 0.5
3 627.6 290-311 d 2.2 0.9
4 830.8 290-300 d - 4. 1 1.0
5 1034.0 285-295 d - 9.1 1.0
6 1237.2 - 11.4 0.8
7 1440.4 - 12.6 0.3
Ref. 1.5. a Refs. 18.19.
IV/104 PHYSICAL DATA OF OLIGOMERS
REF ERENCES
1. R. L. Whistler, C.-C. Tu, J. Am. Chem. Sot., 74, 4334
(1952).
2. R. H. Marchessault, T. E. Timell, J. Polym. Sci. C, 2, 49
(1963).
3. C. T. Bishop, Can. J. hem., 33, 1073 (1955).
4. W. J. Whelan, J. M. 6ailey, P. J. P. Roberts, J. Chem. Sot.,
1293 (1953).
5. J. M. Bailey, W. J. Whelan, S. Peart, J. Chem. Sot., 3692
(1950).
6. K. Freudenberg, F. Cramer, Chem. Ber., 83, 296 (1950).
7. E. E. Dickey, M. L. Wolfrom, J. Am. Chem. Sot., 71, 825
(1949).
8. M. L. Wolfrom, J. C. Dacons, J. Am. Chem. Sot., 74, 5331
(1952).
9. L. Zechmeister, G. Toth, Chem. Ber., 64, 854 (1931).
10. K. Hess, K. Dziengel, Chem. Ber., 68, 1594 (1935).
11. C. S. Hudson, J. M. Johnson, J. Am. Chem. Sot., 37, 1276
(1915).
12. R. Willstaetter, L. Zechmeister, Chem. Ber., 46, 2401 (1913);
62, 722 (1929).
13. K. Freudenberg, G. Blomquist, Chem. Ber., 68, 2070 (1935).
14. H. Staudinger, E. V. Leopold, Chem. Ber., 67, 479 (1934).
15. W. Walter, in: H. M. Rauen (Ed.), Biochemisches Taschen-
buch, part 1, 2nd ed., Springer, Berlin, 1954, p. 98.
16. R. L. Whistler, C. G. Smith, J. Am. Chem. Sot., 74, 3795
(1952).
17. R. L. Whistler, J. Z. Stein, J. Am. Chem. Sot., 73, 4187
(1951).
18. S. A. Barker, A. B. Foster, M. Stacey, J. M. Webber, J. Chem.
Sot., 2218 (1958).
19. H. P Lenk, M. Wenzel, E. Schuette, Hoppe-Seylers Z.
Physiol. Chem., 326, 116 (1961).
SECTION V
PHYSICAL CONSTANTS OF
SOME IMPORTANT POLYMERS
A .
B .
C.
A .
Physical Constants of Rubbery Polymers
lsao Furuta, Shin-lchi Kimura, Masamichi lwama
Yokkaichi Research Laboratories, Japan Synthetic Rubber Co. Ltd., Yokkaichi Mie, Japan
Introduction V-l
Tables
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Table 6.
Table 7.
1,4-cis(96-98%)Poly(butadiene)
Poly(butadiene-co-acrylonitrile)
Poly(butadiene-co-styrene)
PolyfchloropreneKR Neoprene)
Poly(isobutene)-co-isoprene)Butyl
Rubber (IIR)
Polyisoprene, Natural Rubber
Ethylene-Propylene-Diene-
Terpolymer (EPDM)
References
INTRODUCTION
V- l
V- l
v-2
v-3
v-3
v-4
v-5
V-6
V-6
Where a range is given, there are available several
observations which differ. In most cases the differences
are thought to be real, arising from differences in the rubber
rather than from errors of observation. Where a single value
B. TABLES
TABLE 1. 1,4-cis(96-98%)POLV(BUTADIENE)
is given, it is either because no other observations are
available or because there seems to be no significant
disagreement among values within the errors of observa-
tion. Where values are not given, data have not been found.
Where dashes are shown, either the physical measurement
is impossible or the constant in question is not adequately
defined under the given conditions. The values shown refer
to specific vulcanizates cited in the corresponding refer-
ences. Other vulcanizates may yield a broader range of
values.
The values are expressed in the International System of
Units (SI), the modern metric system, described in National
Bureau of Standards Special Publication 330, 1981 edition,
and in American Society for Testing and Materials Metric
Practice Guide E380-85.
Values are given for constants at a temperature of 25C
(273.15 K) and a pressure of 1 normal atmosphere =
101.325 kPa.
Property Units Unvulcanized Refs.
Pure-gum
vul cani zat e Refs.
De n s i t y
Coefficient of expansion
Glass transition temperature
Specific heat
Thermal conductivity
Thermal diffusivity
Solubility parameter
Polymer-solvent interaction
parameter (25-30C)
kg/m3
K- ( x 106)
C
J/kg/K (x 103)
w/m/K (x 10-3)
m*/s (x lo-)
MPa I*
Sol vent
1.01 1
669 2
- 110 to -95 3
1.96 4 1.960- 1.970 1
200 5
17.0 6
n-Heptane 0.51 7
n-Hexane 0.53 7
Cyclohexane 0.45 8
Benzene 0.44 7
To l u e n e 0.36 7
VI2
PHYSICAL CONSTANTS OF RUBBERY POLYMERS
TABLE 1. contd
Property Units Unvulcanized Refs.
Pure-gum
vulcanizate Refs.
Equilibrium melting temperature K (C) 1.0 1 0
0 11
Temperature of most rapid crystallization K (C) - 52 to - 51 3
Heat of fusion of crystal J/kg (x 103) 47 11
169 1 0
Refractive index ND 1.526 1 2
Molar polarizability cm3 (x 10m25) 71.4 1 2
Dielectric constant (50 Hz) 2.3 3
Dielectric loss factor (50 Hz) 0.8 3
Compressibility Pa- (x 10-12) 500 2
Youngs modulus Pa (x 106) 1.3 9
Shear modulus Pa (x 106) 0.96 9
Storage modulus (1 Hz) log Pa 5.98 9
Loss modulus log Pa 4.19 9
Loss tangent 0.065 9
TABLE 2. POLY(BUTADIENE-co-ACRYLONITRILE)
Property Units Unvulcanized Refs.
Pure-gum
vulcanizate Refs.
Density
Glass transition temperature
Specific heat
Thermal conductivity
Thermal diffusivity
Solubility parameter
Polymer-solvent interaction
parameter (25-30C)
kg/m 3
C
J/kg/K (x 103)
W/m/K (x 10-3)
ms (x 10m9)
MPa /*
0.95 (20%) 3
1.02 (45%) 3
- 85 + A(20-40%) 3
(A =AN%)
1.970(40%) 3
250 (18-35%) 3
18.5-21.0 6
(18-39%)
AN%
Solvent 18 30 39
n-Heptane 0.96 1.88 3.6 9
n-Hexane 0.99 2.8 9
Dichloromethane 0.39 0.31 0.32 9
Cyclohexane 0.70 1.42 2.6 9
Benzene 0.39 0.31 0.32 9
To l u e n e 0.43 0.8 0.6 8
Refractive index ND 1.519 (20%) 3
1.521 (45%) 3
Dielectric constant ( lo6 Hz) 5.5 (27%) 3
4.8 (40%) 3
Dielectric loss factor (lo6 Hz) 35 (27%) 3
42 (40%) 3
n Bound acrylonitrile content ( = AN%)).
Poly(butadiene-co-styrene) and Poly(chloroprene)
VI3
TABLE 3. POLY(BUTADIENE-co-STYRENE) (23.5-25% BOUND STYRENE CONTENT)
Property Units Unvulcanized Refs.
Pure- gum
vulcanizate Refs.
Den&y
Coefficient of expansion
Glass transition temperature
Specific heat
Thermal conductivity
Thermal diffusivity
Solubility parameter
Polymer-solvent interaction
paramet er (2530C)
kg/m 3 933 43 980 1 7
(932.5-933.5) 43 940-1000 1 7
K- (x 106) 660 43 660 17,18,44
C -64 to - 5 9 43 - 5 2 2 1
J/kg/K (x 103) 1.89 45 1.83 24
W/m/K (x 10 -3) 190-250 46,47
m*/s (x 10mg) 90 48
MPa I* 17.0 6
Sol vent
n-Heptane 0.59 9
n-Hexane 0.66 9
Dichloromethane 0.47 9
Cyclohexane 0.48 9
Benzene 0.40 9
To l u e n e 0.31 1 3
Heat of combustion
Refractive index
Molar polarizability
Dielectric constant (1 kHz)
Dielectric loss factor
Electric conductivity
Compressibility
Bulk modulus (isothermal)
Youngs modulus
Shear modulus
Shear compliance
Storage modulus
Loss modulus
Loss tangent
Tensile strength
Ultimate elongation
J/kg (x 106) 56.5 43
N D 1.5345 43
(1.534-1.535) 43
cm3 (x 10-25)
2.5 33 2.66 33
0.0009 33 0.0009 33
Sm- (x lo-Is)
Pa- (x lo-**) 530 49 510 50
Pa (x 106) 1890 49 1960 49
Pa (x 106) 1.6 21,35
1. 0-2. 0 35
Pa (x 106) 0.53 2 1
0.3-0.7 35
Pa-t (x 10-6) 7 21,35
3-10 21,35
log Pa 5.82 40 5.88 64
(5.82-5.85) 40 5.64-6.20 64
log Pa 4.94 40 4.92 64
( 4. 56- 4. 94) 4-0 4.73-5.04 64
0.13 40 0.11 64
( 0. 05- 0. 13) 40
MPa 1.4-3.0 19,42
% 400-600 19,42
TABLE 4. POLY(CHLOROPRENE) (CR NEOPRENE)
Pure- gum
Property UIlitS Unvulcanized Refs. vulcanizate Refs.
I
De n s i t y kg/m3 1230 43,51,58 1320 1 7
Coefficient of expansion K-t (x 106) 600 46,58 610-720 17,58,59
Glass transition temperature C - 4 5 60 - 4 5 21,59,60,61
Specific heat J/kg/K (x 103) 2.2- 2.2 46 2.1-2.2 46
Thermal conductivity W/m/K (x 10-3) 192 58 192 58
Thermal diffusivity m2/s 10-9
Solubility parameter MPa I2 18.5 6
References page V- 6
VI4
PHYSICAL CONSTANTS OF RUBBERY POLYMERS
TABLE 4. contd
Property Units Unvulcanized Refs.
Pure-gum
vulcanizate Refs.
Polymer-solvent interaction
paramet er (25-30C)
Sol vent
Equilibrium melting temperature
Temperature of most rapid crystallization
Heat of fusion of crystal
Refractive index
Dielectric constant
Dielectric loss factor
Electric conductivity
Compressibility
Bulk modulus (isothermal)
Youngs modulus
Shear modulus
Shear compliance
Poissons ratio
Storage modulus
Loss modulus
Loss tangent
Tensile strength
Ultimate elongation
n-Heptane 0.85 9
n-Hexane 0.89 9
Dicyclomethane 0.53 9
Cyclohexane 0.69 9
Benzene 0.26 9
To l u e n e 0.70 1 3
K (Cl 328- 351 (55-78) 62,63
K (C) 268 (- 5) 65
J/kg (x 103) 95 63
ND 1.558 20
Sm- (x lo-t5)
Pa- (x lo-)
Pa (x 106)
Pa (x 106)
Pa (x 106)
Paa (x 10-6)
480 49,50
2080 50
log Pa
log Pa
MPa
%
261 (- 12) 65,66
6. 5-8. 1 3 3
0.03/0.86 3 3
3-1400 33
440 49,50
2270 50
1.6 21,35
0.52 2 1
2.0 19,21,35
0.49974 38
5.81 57,59
5.04 57,59
0.17 57,59
25-38 19,42
800- 1000 19,42
TABLE 5. POLY(ISOBUTENE-co-ISOPRENE) BUTYL RUBBER (IIR)
Property Units Unvulcanized Refs.
Pure-gum
vulcanizate Refs.
Coefficient of expansion
Glass transition temperature
Specific heat
Thermal conductivity
Thermal diffusivity
Solubility parameter
Polymer-solvent
interaction parameter
kg/m -3 917 5 1
K- (x 106) 750 53
C -71 53
J/kg/K (x 103) 1.95 23,24,29
W/m/K (x 10-3)
m2/s (x 10e9)
MPa / 16.0 6
933 52
930-970 1 7
560 52,54
- 63 2 1
1.85 24
130 47
70 5 5
Equilibrium melting temperature
Temperature of most rapid crystallization
Refractive index
Dielectric constant (1 kHz)
Dielectric loss factor
n-Heptane 0.48 1 4
n-Hexane 0.52 1 4
Dicyclomethane 0.58 1 4
Cyclohexane 0.44 1 4
Benzene 0.66 1 4
To l u e n e 0.56 1 4
K (C) 275 (1.5) 53
K (C) 239 (- 34) 53
ND 1.5081 43
2.38 33
0.003 33
2.42 3 3
0.0054 3 3
Solvent
T A B L E 5 . contd
Polyisoprene
VI5
Property Unit.3 Unvulcanized Refs.
Pure-gum
vulcanizate Refs.
Compressibility
Bulk modulus (isothermal)
Youngs modulus
Shear modulus
Shear compliance
Strage modulus
Loss modulus
Loss tangent
Tensile strength
Ultimate elongation
Pa- (x lo*)
Pa (x 106)
Pa (x 106)
Pa (x 106)
Pa- (x 10m6)
log Pa
log Pa
MPa
%
508 54
1970 54
1.0 21,35
0.33 21,35
0.2-0.5 19,21,35
3.1 2 1
6.50 56 5.64 57
5.98 56 5.48 57
0.3 56 0.7 57
18- 21 19,42
750-950 19,42
TABLE 6. POLYI SOPRENE, NATURAL RUBBER
Property Units Unvulcanized Refs.
Pure-gum
vulcanizate Refs.
Density kg/m 3
Coefficient of expansion
Glass transition temperature
Specific heat
Thermal conductivity
Thermal diffusivity
Solubility parameter
Polymer-Solvent interaction
paramet er (25-30C)
K- (x 106)
C
(-
J/kg/K (x 103)
W/m/K (x 10-3)
m*/s (x 10)
MPa I*
Sol vent
913 16
906-916 1 6
670 1 6
- 7 2 20
74 to - 69) 20
1.905 22,23
134 1 6
970 17,18
(920- 1000) 1 9
660 1 6
- 6 3 2 1
(- 72 to - 61) 2 1
1.828 24
1 5 3 25,26
70 27
1.7 6
n-Heptane 0.43 9
n-Hexane 0.47 9
Dichloromethane 0.40 9
Cyclohexane 0.53 9
Benzene 0.44 9
To l u e n e 0.39 9
Equilibrium melting temperature
Temperature of most rapid crystallization
Heat of fusion of crystal
Heat of combustion
Refractive index
Molar polarizability
Dielectric constant (1 kHz)
Dielectric loss factor (1 kHz)
Electric conductivity
Compressibility
Bulk modulus (isothermal)
Youngs modulus
Shear modulus
Shear compliance
Poissons ratio
Storage modulus
Loss modulus
K (Cl
K (Cl
J/kg (x 103)
J/kg (x 106)
NoK-
cm3 (x 10-25)
308.6 (35.5) 28
248 (- 25) 30
67.3 3 1
45.2 1 6
1.5191(25C) 32
313(40) 29
44.4 1 6
1.5264 1 6
2. 37- 2. 45 16,33
0.001-0.003 33
2.57 16,33
515 34
1940 34
2.68
0. 002- 0. 04
2-100
514
1950
1.3
(1. 0-2. 0)
0.43
0.3-0.7
2.3
(1.5-3.5)
0.49989
5.61
5. 49- 5. 78
3.80
3. 72- 4. 48
33
33
16,33
34
34
35,36
19,35
21,36
21,37
21,36
21,37
34,38,39
4 1
Sm-t (x 10-15)
Pa-t (x lo-*)
Pa (x 106)
Pa (x 106)
Pa (x 106)
Pa- (x 10e6)
log Pa
log Pa
5.61
5. 53- 5. 75
4.46
(4.43-4.65)
40
40 4 1
References page V- 6
VI6
PHYSI CAL CONSTANTS OF RUBBERY POLYMERS
TABLE 6. contd
Units Unvulcanized Refs.
Pur e- gum
vulcauizate Refs.
Loss tangent 0. 09 40 0. 016 41
0. 07- 0. 13 0.01-0.05
Tensile strength MPa 17-25 19,42
Ultimate elongation %
750- 850 19, 42
TABLE 7. ETHYLENE-PROPYLENE-DIENE-TERP~LYMER (EPDM)
Property Units Unvulcanized Refs.
Pure-gum
vulcanizate Refs.
Density
Glass transition temperature
Specific heat
Thermal conductivity
Thermal diffusivity
Solubility parameter
Polymer-Solvent interaction
parameter (25-30C)
kg/m3 0. 85 3
C - 60 t o - 69 1
J/kg/K (x 103)
2340 3
W/m/K (x 10-3)
m*/s (x 10mg)
MPa I2 16.0-16.5 6
Solvent
n-Heptane 0.44 15
n-Hexane 0. 49 16
Dichloromethane 0. 32 16
Cyclohexane 0. 35 15
Benzene 0. 58 15
Toluene 0. 49 15
Refractive index No 1.48 3
Youngs modulus Pa (x 106) 2. 0 13
Shear modulus Pa (x 106) 1.59 13
Storage modulus (1 Hz) MPa 1.59 13
Loss modulus (1 Hz) MPa 0. 12 13
Loss tangent (1 Hz)
0. 077 13
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VI7
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Physical Constants of Poly(ethylene) *
c
Lei Zhu, Fang-Chyou Chiu, Qiang Fu, Roderic P. Quirk, Stephen Z. D. Cheng
Maurice Morton Institute of Polymer Science, The University of Akron, Akron, OH 44325-3909, USA
A. Crystallographic Data and Crystallographic
Modifications
B. Molecular Parameters and Solution
Properti es
C. Crystallinity, Crystal Size and Crystallization
Ki net i cs
D. Equilibrium Thermodynamic Properties
v-9
v-9
V-l0
V-l 1
E. Other General Physical Properties V-l2
F. Effect of Chain Branching (Short) on Physical
Properti es V-l5
G. Properties of a Series of Selected
Polyfethylene) Sampl es V-l6
H. Properties of Typical Polytethylenes) V-l 7
I. References V-l7
A. CRYSTALLOGRAPHIC DATA AND CRYSTALLOGRAPHIC MODIFICATIONS
Lattice constants (nm)
Number of crystal
crystal Space
a, A or Y
chains per Molecular density
system
group
a b C
(deg.1
unit cell conformation (g/cm 3, Refs.
Orthorhombic stable form Pnam-D 2h 0.7417 0.4945 0.2547 2 Planar Zigzag (2/1) 1 .OO 3-7
Monoclinic metastable form C2/m-C 2h 0.809 f.a. = 0.253 b 0.479 p = 107.9 2 Planar Zigzag (2/1) 0.998 498
Hexagonal high-pressure form 0.842 - f.a.
- -
9-11
a Refs. 1,2.
b f.a. indicates fiber axis.
Not determined.
Temperature Dependence of Crystallographic Data for
Orthorhombic Poly(ethylene)
Temp. (K)
Lattice constants (nm) Specific
vol ume
a b c (cm3/g) Re f s .
4b 0.712 0.485 0.2548 0.945 1 2
1 0 0.716 0.486 0.2534 0.947 1 3
77 0.718 0.488 0.2534 0.953 1 3
77 0.715 0.490 0.2547 0.959 1 4
906 0.716 0.487 0.2546 0.953 1 2
1 9 5 0.727 0.491 0.2534 0.971 1 3
293 0.740 0.495 0.2543 0.999 5
(0.743) (0.494) (0.2543) (1.003) 5
297 0.742 0.496 0.2534 1.001 1 3
297 0.740 0.493 0.2534 0.993 3
297 0.736 0.492 0.2534 0.985 1 5
303 0.741 0.494 0.2547 1.002 1 4
Ref. 1. Data obtained by X-ray diffraction studies unless otherwise indicated.
b Data obtained by neutron diffraction.
The data of nonoriented samples are given without parentheses and those of
oriented samples are given with parentheses, both for high-density PE.
* Based on a table in the third edition, by R. P. Quirk and M. A. A.
Al samarrai e, The Mauri ce Mort on Inst i t ut e of Pol ymer Sci ence,
University of Akron, Akron, Ohio.
B. MOLECULAR PARAMETERS AND SOLUTION
PROPERTIES
Bond Angle and Bond Length
Wide angle Neut ron
X-ray a scattering
(Refs. 3,4,16) (Ref. 12)
BOND ANGLE (in degrees)
c - c - c 112.0 107.7
108.1
H-C-H 107.0 109.0
110.0
BOND LENGTH (nm)
c - c 0.153 0.158
0.157
C-H 0.107 0.106
0.107
Measurements taken at room temperature.
Temp. (K)
4
90
4
90
4
90
4
90
VI9
V/l0 PHYSICAL CONSTANTS OF POLY(ETHYLENE)
Dimensions of Linear Polyethylene Molecules
PED b
Temperature PEH Matrix
(C)
a, (x103)
23 (296.2) 78
150 (423.2) 100
150 (423.2) 80
57, (xlO3)
60
140
1 0
1 3 . 3
21.5
4.38
0.046
0.046
0.044
State Refs.
Crystalline 17
Molten 17
Molten 18
a Effect of temperature and state, neutron scattering measurements.
b Deuterated polyethylene.
Values in parentheses indicate temperature in kelvin.
+ (S2)~2 i s t he z average value of the radius of gyration of the molecule.
3 (Sz) i is the weight-average value of the radius of gyration of the molecule.
Molecular Dimensions of Linear Poly(ethylene)
(Unperturbed)a
33, (x105) ((r-i) ,/M,)1~2 [nm/(g/mole)1~2]
b-i) ,Pmax
1 . 2 5 0.192 7.80
2.69 0.215 9.86
4.65 0.190 7,73
c( In tetralin at 105C (378.2 K). (ri) w is the weight-average mean-square end-to-
end distance in nm; ;i;i, is the weight-average molecular weight; D is the diameter
of a spherical segment of the lattice model chain; and I,, is the length of the fully
extended chain (19); temperature dependence of (r,) (in long chain paraflinic
hydrocarbon solvents) is given by -din (ri)/dT = 1.2 x 1O-3 (20).
Effect of Molecular Weight on Paraclustering
Molecular weight
c
of tagged molecules $ =
Molecular weight (neutrons) (S2) $
w Mol ecul ar wei ght (g.p.c.) ;i;iy
3000 73f7 0.41
12000 7fl 0.18
60000 0.91 zto.1 0.049
140000 0.94 * 0.1 0.042
For deuterated poly(ethylene) in a protonated poly(ethylene) matrix with
molecular weight ca. 100000 by neutron scattering measurements (21). All sample
solution were blended in ortho-dichlorobenzene, quenched rapidly from the melt
and measured at 25C (298.2 K) (concentration of tagged molecules 5 5%).

+v )w
the weight-average value of the radius of gyration of the molecule; values
are in [nm/(g/mol) I/].
C . CRYSTALLINITY, CRYSTAL SIZE AND CRYSTALLIZATION KINETICS
Average molecular Melting point Degree of branching Crystal
wei ght Density p (g/cm3)
T (Cl
(CH3/100C) Crystallinity (a,) thickness 1 (nm)
Marlex 6015 1 5 . 0 x 104 0.980 1 3 1 (404.2) 0.05 0.94 23.9
Hostalen GC 5.0 0.969 129 (402.2) 0.10 0.83 1 9 . 8
Hostalen GF 1 2 . 0 0.968 128 (401.2) 0.64 0.85 1 8 . 4
Hoechst PA-190 0.9 0.954 124 (397.2) 0.84 0.76 1 4 . 1
Alkathene HD 24.5 0.952 1 2 1 (394.2) 0 . 9 1 0.76 12.0
Epolene C- 11 1 . 0 0.947 119 (392.2) 1 . 0 8 0.74 1 1 . 0
Lupolen KR 1051 5 . 1 0.943 120 (393.2) 1 . 3 0 0.70 1 1 . 4
BASF a Wachs 1 . 0 0.933 1 1 1 (384.2) 1 . 8 4 0.67 8 . 1
Lupolen KR 1032 5 . 3 0.931 1 1 5 (388.2) 2.50 0.60 9.2
Epolene C- 13 1 . 0 0.919 104 (377.2) 2.80 0.54 6 . 5
Lupolene 1810 H 5.4 0.928 106 (379.2) 3.00 0.59 6.9
Hoechst PA- 130 3.0 x 103 0.957 1 1 5 (388.2) 1 . 5 8 0.85 9.3
Epolene N- 10 2.5 0.925 1 0 5 (378.2) 2.25 0.61 6.8
Epolene N- 12 1.5 0.941 1 0 8 (381.2) 2.27 0.75 7.4
BASF a Wachs 5.6 0.936 106 (379.2) 2.32 0.68 6.9
Epolene N- 11 1.5 0.934 104 (377.2) 2.48 0.68 6.6
Hoechst PA-560 6.0 0.914 1 0 1 (374.2) 4.10 0.51 6 . 1
Epolene C- 10 7.0 0.919 99 (372.2) 4.19 0.60 5.8
Epolene C-l01 3.2 0.936 104 (377.2) 4.42 0.70 6.6
Hoechst PA-520 2.0 0.917 102 (375.2) 4.90 0.54 6.2
Epolene C-l2 3 . 7 0.906 8 3 (356.2) 6.94 0.50 5 . 1
a Depends upon chain branching; data given are representative values of typical commercial poly(ethylenes) (22).
b Crystallization from melt by rapid cooling at ambient temperature; crystallinity estimated from density.
c Values in parentheses indicate temperature in kelvin.
Equilibrium Thermodynamic Properties V/l1
Single Crystal Lame/la Thickness
Solvent Cryst. temp. (C) Cont. (%) Long period (nm) Refs.
HIGH DENSITY, POLY(ETHYLENE) (PHILLIPS MARLEX 50)
Tetrachloroethylene 50 (323.2)b 0.31 11.2 24
60 (333.2) 0.25 10.8 25
p-Xylene 72 (245.2) 0.46 11.0 26
78 (351.2) 0.58 14.0 24
Xylene 50 (323.2) - 9.25 23,26
60 (333.2) 10.2
70 (343.2) - 11.15
80 (353.2) 12.05
90 (363.2) 15.0
75 (348.2) 0.1 11.5 27
80 (353.2) 0.1 12.5
85 (358.2) 0.1 13.3
Melt 120 (393.2) 100 19.0 28
125 (398.2) 100 22.3
130 (403.2) 100 35.5
n-Butyl acetate 105 (378.2) 0.45 14.7 25
110 (383.2) 0.57 16.2 24
Diphenyl ether 120 (393.2) 0.47 20.2 24
125 (398.2) 0.37 17.3 25
LOW DENSITY POLY(ETHYLENE) (DUPONT ALATHON)
Butyl stearate 111 (384.2) 0.25
113.5 (386.7) 0.25
Squalene 155.5 (428.7) 0.25
Glycol dipalmitate 155.4 (428.6) 0.25
118 (391.2) 0.25
121 (394.2) 0.25
Tripalmitin 121 (394.2) 0.25
a Long pe r i ods f r om s ma l l a ngl e X- r a y s c a t t e r i ng, e f f e c t of c r ys t a l l i z a t i on t e mpe r a t ur e a nd s ol ve nt s ( 23) .
b Values in parenthesis indicate temperature in kelvin.
12.6,15.5 23
16.6
17.6
15.1
16.4
20.6
18.8
Crystallization Kinetic Parameters See table Rate of
Crystallization of Polymer in this Handbook, and Refs.
29-31.
D. EQUILIBRIUM THERMODYNAMIC PROPERTIES
Entropy of Fusion at Equilibrium Melting Temperature
(J/mol/K)
Value
AS,
9.81
9.60
9.91
At const ant vol ume ( AS, ) , 7.42
7.72
Glass Transition Temperature0 jb (C)
Refs.
32
33
34
33
35
Value Refs.
- 30 & 15 (243.2 f 15)c 37,38
-8Ozt 10 (193.2f 10) 39
- 128f5 (145.2f5) 40,41
a Re f . 36. Se e a l s o Tr a ns i t i on a nd Re l a xa t i on Te mpe r a t ur e s i n Se c t i on E.
b Considerable disagreement exists between different authors on the exact value of
the transition which can be identified as the glass transition temperature. See
Ref. 36 for a detailed discussion.
Values in parentheses indicate temperature in kelvin.
G/ass Transition Activation Energy 46-75 kJ/mol (42).
/feat Capacity, C, (J/molDQa
Temperature (K) Polymer
CP
Refs.
298.15 Crystalline 21.70
298.15 Amorphous 30.81
300 Branched 32.55
32.68
32.86
300 Linear 23.93
24.14
24.24
400 Molten 34.48
35.22
35.36
36.04
43
44
45
46
47
46
48
44,49
50
48
Ref. 2. For linear, amorphous, crystalline and molten poly(ethylene), (0-600 K),
see Table Heat Capacity of High Polymers in this Handbook, and also
Refs. 2.34.
Heat Capacity in Liquid (2) For molten po!y(ethylene)
(390-600 K)
C, = 4.325 x 10p2T + 17.919 [ f 1.2% (RMS deviation)]
References page V- 17
V/I2 PHYSICAL CONSTANTS OF POLY(ETHYLENE)
Heat Capacity in Amorphous G/ass (2) The heat capacity
of amorphous poly(ethylene) obtained from crystallinity
extrapolations was given in J/mol/K.
From 0.5 to 20 K:
C, = exp[-O.l35328(lnT) 3 + 0.393949(1n T)
+ 2.85597(1n T) - 7.845531
[& 2.2% (RMS deviation)]
From 10 to 260K:
I
C, = x A,T [ & 0.7% (RMS deviation)]
n=O
A0 = 1.0966333 Al = -0.11209575
A2 = 9.3092851 x 1O-3 A3 = -1.7095906 x 1O-4
A4 = 1.5885817 x 1O-6 A5 = -7.931924 x lo-
A6 = 2.0248831 x lo- A7 = -2.0616876 x lo-l4
Heat Capacity in Crystalline So/id (2) The heat capacity
of crystalline poly(ethylene) obtained from extrapolated
values was given in J/mol/K.
E. OTHER GENERAL PHYSICAL PROPERTIES
Coefficient of Thermal Expansion
From 0.4 to 20K:
C, = exp[-1.07155 x 10-2(lnT)3 +4.62622 x (lnT)*
+ 2.89948(1n T) - 9.128641
[+ 5.8% (RMS deviation)]
From 10 to 410K:
9
C, = xA,T [& 1.2% (RMS deviation)]
n=O
A0 = 1.1504009 A1 = -0.19842302
A2 = 1.2786634 x 1O-2 A3 = -2.4474207 x 10~~
A4 = 2.593176 x lO-(j A5 = 1.6647891 x lo-
A6 = 6.5926585 x lo- A7 = -1.5679761 x lo-l3
A8 = 2.0474114 x lo-l6 A9 = -1.1252521 x lo-
Heat Capacity Change at Glass Transition Tempera-
tures 10.5 J/mol/K at 237 K (2)
Heat of Fusion at Equilibrium Melting Temperature
4.1 f 0.2 kJ/mol (2,5 1)
Residual Entropy of the Glassy State at 0 K
So = 3.0 J/mol/K (2).
Temp (C)
Coefficient of expansion ( x 10)
Li near Cubical
Specific volume
ratio (V#25) b
- 35 (238.2)c 1 0 . 0 30
- 20 (253.2) 1 3 . 7 4 1
0 (273.2) 1 8 . 3 55
20 (293.2) 23.7 7 1
25 (298.2) 24.8 74
40 (313.2) 29.0 8 7
60 (333.2) 33.7 1 0 1
80 (353.2) 40.3 1 2 1
100 (373.2) 46.6 140
110 (383.2) 51.0 153
115 (388.2) 25.0 75
115-150 (388.2-423.2) 25.0 75
150 (423.2) 25.0 75
a Branched polyethylene (52,53); for data on amorphous linear poly(ethylene), see Ref. 40.
b VE is relative excess volume, V25 is the volume at 25C (273.2 K).
Values in parentheses indicate temperature in kelvin.
Density (Mg/m3) E (g/cm3)
0.969
0.975
0.986
0.997
1.000
1.012
1 . 0 3 1
1.055
1.094
1.130
1.140
-
1.168
Value Refs.
Amorphous (from extrapolation of data above the melting point) 0.855 54
Commercial high-pressure poly(ethylene) 0.915-0.935 55
Experimental high-pressure poly(ethylene) 0.940-0.970 55
Ziegler process (Refs. 56,57) poly(ethylene) 0.940-0.965 55
Phillips process (Ref. 58) poly(ethylene) 0.960-0.970 55
Crystal density (theoretical) See Crystallographic
Data and Crystallographic
Modifications in Section A
Unless otherwise stated, the values given are for 25C (293.2 K); see also Sections G and H.
Other General Physi cal Properti es V/l3
Dielectric Constant At 1OOkHz and 23C (296.2K): 2.3
(59)
Effect of Density on Dielectric Constant
Density (g/cm3) Dielectric constant (ASTM D 150)
Dielectric Strength
Temperature (C) Value ( x 106) (V/cm) b4
- 200 to 0 (73.2-273.2)d 7
50 ( 323. 2) 5. 3
100 ( 373. 2) 1. 8
0. 920 2. 28
0. 925 2. 29
0. 930 2. 30
0. 935 2. 31
0. 940 2. 32
a Ref. 63.
b Short-time test value (ASTM D149) is 16000-24000 V/cm, and depends upon
sample configuration and impurities (64).
c Intrinsic dielectric strength of LDPE is of the order of 8.0 x lo5 V/cm, if all chain
end, surface and impurity effects are eliminated (64).
d Values in parentheses indicate temperature in kelvin.
D Ref. 60. The relationship shown in this table is for pure poly(ethylene). Therefore,
considerable divergence from this relationship is caused by the presence of
impurities as well as addition of additives such as carbon black or other fillers.
Dielectric Loss tan S (1 x 10e4-1 x 10-3) (61,62).
The values of tan S depend on temperature and structure of
poly(ethylene) (61).
Frictional Properties
E/ectrica/ Properties See also Section H (65).
Flash Ignition Temperature ASTM Method E 136-58T:
340C (613.2 K) (66).
Coefficient of
friction (c)
Steel sliding on polymer Polymer sliding on steel Polymer sliding on polymer
Polished Abraded Polished Abraded Polished Abraded
Static (MS) 0. 60 0. 33 0. 60 0. 33 0. 60 0. 33
Kinetic (M K) 0. 60 0. 33 0. 60 0. 33 0. 60 0. 33
0. 50 0. 25
a Ref. 67.
Heat of Combustion
Densi ty
(Mg/m3) 3 (g/cm3)
0. 9391
0. 9220
0. 9053
a Ref. 68.
Methyl groups Heat of combustion AE
per 1OOOC at oms
@Jncs)
8. 3 - 46, 412
24. 7 - 46, 492
46. 2 - 46, 542
Heat of Fusion and Melting Temperature From
Differential Thermal Analysis Data
Melting point Heat of fusion
Poly(ethylene) type (C) Wbz)
Ma&x 50 (Phillips, linear) 135 (408.2) 245. 3
Super-Dylan (Ziesler, linear) 130 (403.2) 218.6
DYNH
(Union Carbide, branched) 112 (385.2) 1 4 0 . 6
Linear poly(ethylene)
from dilatometric measurements 280. 5
from calorimetric measurements 277. 1
Values in parentheses indicate temperature in kelvin.
Refs.
69
69
69
33
34, 70
ignition Limiting Oxygen /ndices (ILOI)a
650C ( 923. 2 K) 600C ( 873. 2 K) 550C ( 823. 2 K)
2. 8f O. l 3. 5f O. l 5. 7f O. l
0 Ref. 71. The method used (ASTM D2863-70) is defined as the minimum
volume fraction of oxygen required for ignition to occur.
Infrared Absorption Bands (72-79).
Far Infrared (80).
Intrinsic Viscosity See Section G.
Mechanical Properties See Section H.
Ultra-drawn polyethylene. See Refs. 81-90.
Elastic Compliance See Section G.
Elongation at Break (%) See Section H.
Hardness, Shore D See Section H.
Impact Strength, lzod See Section H.
low Temperature Brittleness See Section H.
Tensile Modulus See Section H. Also see Ref. 91 for
Youngs, shear and bulk moduli for more than 1,100
poly(ethylene) samples reported (within density range
from 0.90 to 0.98 g/cm3).
Tensile Strength See Section H.
Me/t index See Section G.
Me/t Viscosity See Section G.
References page V- 17
V/l4 PHYSICAL CONSTANTS OF POLY(ETHYLENE)
Melting Tempera furealb ( C)
Value Refs.
Poly(methylene) 136.5 * 0.5 (409.7 + 0.5)c
Linear poly(ethylene) 137.5 (410.7)
Linear poly(ethylene), high molecular weight fraction 138.5 (411.7)
From extrapolation of MP of n-Paraffins 141 f 2.4 (414.2 f 2.4)
T; (cc MW)b 141.4-145.5 f 1 (414.6-418.7 f 1)
a See also Section G and under Section F (Effect of chain branching on melting temperature).
b The estimated melting point of the infinite poly(ethylene) crystal is in dispute (see Refs. 30,95).
Values in parentheses indicate temperature in kelvin.
92
33
93
94
30
Molecular Properties of Typical Poly(ethylenes)
Groups per 100 carbon atoms
Densi ty
Polymer AT, (xlO-3) Wm3) CH3- -CH2CH3 -CH=CH2 -CH=CH- =C=CH2
Ziegler 50-60 0.960 3.6 0.5 0.09 < 0.02 0.06
Phillips 50-60 0.965 3 . 1 0.8 1 . 5 8 < 0.02 0.08
Solution polymerization 50-60 0.964 3.2 0.5 0.42 < 0.02 0.03
Phillips catalyst gas phase 350 0.954 2.8 < 0.2 0.65 < 0.02 0.04
Low-density PE 0.918-0.928 20-33 6 - 9 0.08-0.25 < 0.02-0.06 0.17-0.33
a Ref. 14.
Neutron Scattering Spectra See Refs. 96-98.
Nuclear Magnetic Resonance See Refs. 99- 110.
Solid State. See Ref. 111.
Permeability and Diffusion Constants See corresponding
table in this Handbook, and also Refs. 112,113.
Permeabilities at 30C (293.2 K) of Poly(ethylene)
Permeability
(cm3 STP) mm x lOlo
cm2s(cmHg)
1
Crystallinity (%) N2
02 (332
H20b
Av. 0.3290
60 1 . 9 0 x 10-9 5.5 x 10-9 35.2 x 1O-9 80 x 1O-9
90 0.66 2 . 1 7.4 -
78 0.33 1.1 4.3 -
8 1 0.27 1 . 0 6 3.5 1 3
a Ref. 114.
b 90% e.h. at 25C.
Raman Spectra See Refs. 115-123.
Refractive Index ng
Value Refs.
LDPE 1.51 124
MDPE 1 . 5 2 124
HDPE (melt index above 0.1) 1 . 5 4 124
Amorphous, n:&t 1 . 4 9 1 2 5
Crystal, o z pa 1.520 1 2 5
Y 1.582 122
a cy, p and y are refractive indices along the a, b and c crystallographic directions of
the crystal, respectively.
Dependence of Refractive Index on Chain Branching,
Crysfallinity and Density See Section F (Effect of Chain
Branching on Physical Properties).
Specific Refractivity
Temp. (C) v (cm3/g) n r
LOW DENSITY POLY(ETHYLENE) (ALATHON-10)
90 (363.2) b 1.159 1 . 4 8 0 1
100 (373.2) 1.178 1.4693
108 (381.2) 1.209 1.4575
113 (386.2) 1.239 1.4432
118 (391.2) 1.250 1.4392
124.4 (397.6) 1.256 1.4368
0.3293
0.3283
0.3297
0.3286
0.3289
0.3288
HIGH DENSITY POLY(ETHYLENE) (MARLEX 50)
130 (403.2) 1 . 2 6 1 1.4327
139.9 (413.1) 1.270 1.4297
150.6 (423.8) 1 . 2 8 1 1 . 4 2 6 1
0.3273
0.3297
0.3283
ar=v(n2- l)/(n + l), where 1/ and n are specific volume and refractive index
respectively. Ref. 52.
b Values in parentheses indicate temperature in kelvin.
Refractive Index Increment (dn/dc) See corresponding
table in this Handbook, and also Refs. 126-133.
Softening Temperature, Vicat See Section H.
Solvent- Nonsolvent Systems for Fractionation
Solvent
Xylene
p-Xylene
Tetralin
Nonsolvent Refs.
Triethylene glycol 134,135
Ethylene glycol monoethylene ether 1 3 6
2-Butoxyethanol 1 3 7
Poly(ethylene oxide) [mol. wt. 2001 138,139
Effect of Chai n Branchi ng (Short) on Physi cal Properti es V/l5
Transition and Relaxation Temperature@
Designation Temperature range (C)
Approximate activation
energy (kJ/mol) Refs.
60-80 (333.2-353.2)b > 420
- 20 to - 30 (253.2-243.2) 160-200 1 4 1
Y
- 80 to -90 (193.2-183.2) 46-15
- 120 to - 130 (153.2 -143.2) 3 2
a There is considerable disagreement in the literature on the phenomena associated with the various transition and relaxation
temperatures observed. Transition temperatures and temperatures associated with peaks in dynamic loss are collected together
under the above combined heading. The transition and relaxation temperatures associated with amorphous regions of branched
and linear poly(ethylenes) are designated as a, p, y, etc. in the descending temperature order (140).
b Values in parentheses indicate temperature in kelvin.
These frequently merge depending upon the crystallinity and frequency of the test method.
Frequency Dependence of Relaxation Temperatures in Dynamic Mechanical
Loss Measurements
HZ
a
P Y
T WI
HZ
T (W
H z
T (K)
HIGH PRESSURE, BRANCHED POLY(ETHYLENES)
0.3 3 4 0 0.3 268
1.2 327 4.1 268
3 9 333 150 253
150 355 5 4 0 265
2 0 0 3 6 0 5 2 0 2 8 0
6 0 0 385 6 0 0 0 3 2 0
4 x 104 2 3 6 0 4 x 104 275
1 x 105 2 3 2 0 1 x 105 283
- 1 x 105 285
-
-
5 x 105 285
2 x 106 3 6 0 2 x 106 295
-
-
2x 106 3 0 0
1.25 140
8.6 166
3 2 4 158
1.2 x 103 1 6 5
1.15 x 103 1 6 5
1.9 x 104 5 2 0 0
4 x 104 180
1 x 105 5 1 9 0
1 x 105 2 0 0
5 x 105 205
2 x 106 2 1 0
2 x 106 2 1 0
LOW PRESSURE, LINEAR POLY(ETHYLENES)
0.3 373 - 1.25 153
0.2 3 6 8 8 2 7 3 1 0 173
< 4 6 0 2 3 8 0 1 . 1 x 103 295 840 and 1.57 x lo3 1 7 3
3000 4 2 0 - - -
a Ref. 142.
Viscosity-Molecular Weight Relationship See corresponding table in this Handbook, and Ref. 52.
~
I
i
F. EFFECT OF CHAIN BRANCHING (SHORT) ON
PHYSICAL PROPERTIES
Effect on Density and Refractive Index
Methyl groups per
1000 C atoms
8 3
4 8
4 6
2 6
1 6
a Refs. 143, 52.
Densi ty Refractive index
(Mg/m3) = (g/cm3) rig
0.91 1.5060
0.917 1.5168
0.925 1.5152
0.929 1.5227
0.926 1.5260
Effect on Expansion Coefficient (Mean) and Specific
Volume of Crystalline Phasea
Methyl groups per l/V20
(AV/AT)(xlO-4,
1000 C atoms (- 150 to 100C) (O-1OWC) vzo
0.3 2.47 3.13 1.001
2 2.59 2.95 0.998
17.5 2.61 2.98 1.010
2 3 2.84 3.42 1.009
3 7 2.96 3.70 1.017
Ref. 52,144.
References page V- 17
V/l6 PHYSICAL CONSTANTS OF POLY(ETHYLENE)
Effect on Long Period Spacings and Crystallinity of
Completely Annealed Samples
Methyl
groups per Long period
1000 c spacing %
Poly(ethylene) atoms
(nm)
crystallinity Refs.
Branched (high pressure) 6 0 2 2 . 0 21 1 4 6
4 5 2 0 . 0 4 8
3 5 2 1 . 0 5 0
2 8 2 2 . 0 5 3
20 2 3 . 0 5 6
15 25.0 5 9
1 0 2 6 . 0 6 2
Linear 7 3 2 . 0 17 1 4 3 , 1 4 4
(Ziegler type catalysts) 5 3 6 . 0 19
Linear 2 42.0 8 8 5 8
(Phillips petroleum process)
a Ref. 52,145.
Effect on Melting Point Observed
Methyl groups per 1000 C atoms Melting point (C)
8 7 105 (378.2)b
28 113 (386.2)
28 108 (381.2)
8 123 (396.2)
0 132 (405.2)
a Both the amount and randomness of branching affect the melting point.
Experimental conditions used for the following data were not adequate for
equilibrium crystallinity and accuracy of melting points (52).
b Values in parentheses indicate temperature in kelvin.
C. PROPERTIES OF A SERIES OF SELECTED POLY(ETHYLENE) SAMPLES
Infrared functional groups
Sample No.
Optical melting
point (C)
Density a
Wcm3)
per 1OOC
methyl Vinyl
per 200C
Trans-unsaturation Vinylidene Carbonyl
PE 1 104.2 (377.4)f 0.9142 3.68 0.18 0.15 0.79 0.13
PE 2 112.4 (385.6) 0.9225 2.59 0.32 0.11 0.32 0.02
PE 3 112.2 (385.4) 0.9218 2.48 0.10 0.06 0.29 0.05
PE 4 113.7 (386.9) 0.9232 2.55 0 . 1 1 0.06 0.29 n.d.
PE 5 114.0 (387.2) 0.9219 2.46 0 . 1 1 0.05 0.30 0.01
PE 6 114.5 (387.7) 0.9228 2 . 3 1 0.06 0.05 0.26 n . d .
PE 7 113.5 (386.7) 0.9207 2.59 0 . 1 1 0.06 0.33 0.02
PE 8 112.0 (385.2) 0.9188 2.54 0.10 0.06 0.31 n.d.
PE 9 121.5 (394.7) 0.9334 1 . 4 0 0.04 0.02 0 . 1 1 0.87
PE 1 0 135.8 (409.0) 0.9549 0 . 1 1 . 8 2 0.04 0.15 < 0.005
PE 11 - 0.9554 0.165 0.86 - 0.17 -
Sample No.
Molecular weight
Weight Av. Number Av.
Intrinsic viscosity b
Wg)
Melt index
Melt viscosity d Elastic compliance e
(Pa s)
(MPa -)
PE 1 510000s 107OOh 19.5
PE 2 300000s 133OOh 15.1
PE 3 550000s 191OOh 9 6 . 1
PE 4 225000 i (16OOO)j 62
PE 5 500000 i (18OOO)j 15
PE 6 500000 i (22ooo)j 82
PE I 300000 i (45ooo)j 17
PE 8 800000 i (55ooo)j 97
PE 9 300000 i (27ooo)j 73
PE 1 0 144000k 115Ooh 116
PE 11 - - -
a Samples annealed for 1 hour at about 100C (373.2 K).
b a-Chloronaphtbalene, 125C (398.2 K).
ASTM D- 1238- 57T.
d Newtonian melt viscosity at 150C (423.2 K) and 4OOPa.
e Steady-state elastic compliance from creep recovery at 150C (423.2 K) and 400 Pa.
f Values in parentheses indicate temperature in kelvin.
8 Light scattering after optical clarification by high temperature uhracentrifugation.
h cryoscopy.
i Preliminary value, subject to revision.
j Best guess, subject to drastic revision.
Measured by osmometry.
1 . 8 0 64 63 x 1O-6
1 . 9 5 38 46
0.16 620 46
1 9 . 9 24 22
3.30 1 8 5 36
1 . 0 6 73 54
2.94 23 3 1
0.21 310 54
3.15 1 5 3 39 x 10-6
2.92 - -
- - -
Re f e r e n c e s V/l7
H. PROPERTIES OF TYPICAL POLY(ETHYLENES)
Property Low density ASTM type Ib Medium density ASTM type IIb High density ASTM type IIIb
Abrasion resistance, Taber
(mg11000 cycles) 10- 15
Brittleness, low temperature (C) <- 118 (155.2)
Coefficient of thermal expansion ( x 10m5)
[D 6961d (K-l) 1 0
Density [D 7921 (g/cm3) 0.910-0.925
Dielectric constant at 1 kI-Iz [D 1501 2.28
Elongation at break [D 6381 (%) 150- 600
Hardness, Shore D [D 17061 44-48
Impact strength, Izod [D 2561
(ft/lb/in notch) > 16
Power factor at 1 kHz [D 1501 < 0.0001
Heat capacity @I/kg/K) 1.916
Tensile modulus [D 6381 (MPa)=(N/mm*) 55.1-172
Tensile strength [D 6381 (MPa)=(N/mm*) 15. 2-78. 6
Vicat, softening temp. [D 15251 (C) 88-1006(x361~~5-373.2)
Volume resistivity [D 2571 (cm)
= Ref. 52, 147, 148.
6-10 2-5
<- 118 (155.2) < - 118 to - 73 (155.2-200.2)
- 13
0.926-0.940 0.941-0.965
- 2.32
100- 150 12- 700
45-60 55-70
>I6 0.8-14
- < 0.0001
1.916 1.916
172- 379 413-1034
12.4-19.3 17.9-33.1
99-124 (372.2-39.2) 112-132 (385.2-405.2)
- 6 x lo5
b ASTM designation D1248-72, Standard Specification for Polyethylene Plastics Molding and Extrusion Materials.
c Va l ue s i n pa r e nt he s e s i ndi c a t e t e mpe r a t ur e i n ke l vi n.
d The numbe r s i n s qua r e br a c ke t s r e f e r t o t he ASTM St a nda r ds , Ame r i c a n Soc i e t y f or Te s t i ng Ma t e r i a l s .
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V/l8 PHYSICAL CONSTANTS OF POLY(ETHYLENE)
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Bartlesville, Oklahoma.
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Physical Constants of Poly(propylene)*
Feng Bai, Fuming Li, Bret H. Calhoun, Roderic P. Quirk, Stephen Z. D. Cheng
The Maurice Morton Institute of Polymer Science, University of Akron, Akron, OH 4325-3909, USA
A. Crystallographic Data and Modifications H.
of lsotactic Polypropylenes v-21
B. Crystallographic Data and Modifications I.
of Syndiotactic Polypropylenes v-2 1
C. Dimensions of Poly(propylene) Molecules v-22 J.
D. Crystallinity and Crystallization Kinetics v-22
E. Equilibrium Thermodynamic Properties V-23 K.
F. Other General Properties V-24
G. Properties of Typical Mainly lsotactic
L.
Poly(propylenes) V-26
Properties of some Commercial
Polyfpropylene) Grades
Mechanical Properties of Poly(propylene)
Homopolymers
Mechanical Properties of Polyfpropylene)
Random Copolymers
Mechanical Properties of Poly(propylene)
Impact Copolymers
Ref erences
V-26
V-27
V-28
V-28
V-28
A . CRYSTALLOGRAPHIC DATA AND MODIFICATIONS OF ISOTACTIC POLYPROPYLENES
Lattice dimensions (nm) Number of Crystal
Stereoisomeric Crystal Space chains per Molecular density
form system
group
a b C
4 B, or Y
unit cell conformation (g/cm3) Refs.
I s ot act i c Monoclinic CL CZIC 0.665 2.096 0.650 P=99.33 4 Helix(3/1) 0.936 1
Monoclinic cc 1 c2ic 0.666 2.078 0.6495 p=99.62 4 0.946 2-4
Monoclinic CL* P21lC 0.666 2.078 0.6495 ,B=99.62 4 (TG)
3
0.946 2-4
Hexagonal 0 1.274 0.635 y= 120 9 Helix(3/1) 0.921 56
Hexagonal p 1 0.636 0.635 y= 120 9 W3 3 0.921 7
Hexagonal p 2 1.908 0.649 y= 120 9 0.922 23
Triclinc y 0.654 2.14 0.650 a=89 2 Helix(3/1) 0.954 9
p = 99.6 (W 3
y=99
Quenched Helix(3/1) l,lO-13
smectic
(-3 3
B. CRYSTALLOGRAPHIC DATA AND MODIFICATIONS OF SYNDIOTACTIC POLYPROPYLENES
Stereoisomeric
form
Crystal
system
Space
group
Lattice dimensions (nm)
a b C
Number of Crystal
chains per Molecular density
a, B, or Y
unit cell conformation (g/cm3) Refs.
Syndiotactic Orthorhombic c222, 1.450 0.580 0.740
observed in
fibers :f560
Orthorhombic Ibca 1.450 1.120 0.740
hi gh t emp. form
Orthorhombic 0.522 1.117 0.506
low temp. form
Triclinic Pl 0.572 0.764 1.16
2 Helix(W1) 0.90 14- 16
(T&z)2
ff =73.1
p = 88.8
Y = 112.0
Helix(W1)
(TzGd2
Planar
Zi gzag
Td&T2G2
0.90 17- 19
0.945 20-22
0.939 2 3
*Based on a table in the third edition, by R. P. Quirk and M. A. A.
Alsamarraie, The Maurice Morton Institute of Polymer Science,
University of Akron, Akron, Ohio.
Vf21
v/22 PHYSICAL CONSTANTS OF POLY(PROPYLENE)
C. DIMENSIONS OF POLY(PROPYLENE) MOLECULES*
Effect of Molecular Weight on Radius of Gyration
PPD matrix b
Method of PPH matrix
Crystallization M, ( x 103) if, ( x 103) MwIfi. (S2) j t od
Rapidly quenched 46 34 2.52 18.0
46 140 1.68 18.0
56 340 2.02 25.5
1 0 5 575 1.56 32.0
114 1540 1.48 50.3
Rapidly quenched from 46 34 2.52 18.0
melt and subsequently 46 140 1.68 19.0
annealed at 56 340 2.02 26.5
137C (410.2K) 105 575 1.56 34.7
114 1540 1.48 51.4
Isothermally crystallized 46 34 2.52 23.5
at 139C (412.2 K) 46 140 1.68 23.5
56 340 2.02 29.0
1 0 5 575 1.56 36.8
114 1540 1.48 58.0
a Measured by neutron scattering. Polymer >97% isotactic; Ref. 26.
b Deutrated poly(propylene).
+ (S*) :* and (S*);* are the z-average and weight-average values, respectively, of the radius of gyration of the molecule.
t In nm/(g/mol) I*.
(S) y t (nm) (9) ~/My2$
11.3 0.061
13.9 0.037
17.9 0.031
25.6 0.034
41.3 0.039
11.3 0.061
14.7 0.039
18.6 0.032
27.8 0.037
42.3 0.040
14.8 0.080
18.1 0.048
21.8 0.037
29.6 0.039
47.7 0.038
Neutron Sea ttering Measurements
(9) y2/l%fy2t
Method of crystallization Mel t Crystalline
Rapidly quenched 0.035 0.034
Isothermally crystallized at 139C (412.2 K) 0.035 0.038
Rapidly quenched from melt 0.035 0.036
and subsequently annealed at 137C (410.2 K)
+(S*) y is the weight-average value of the radius of gyration of the molecule; values are in mn/(g/mol) I/. For further
details and analysis, see Refs. 27-30.
Neutron Scattering See Refs. 24-30.
D. CRYSTALLINITY AND CRYSTALLIZATION KINETICS
Crystallinity and Melting Point of Samples from Multiple Solvent Fractionation
Soluhility of fractions in boiling solvents
Soluble in Insoluble in
Tm (Cl
Wide angle X-ray
crystallinity
(a)
- Trichloroethylene 176 (449.2)b 75-85
- n-Octane 174- 175 (447.2-448.2) 65-85
n-Octane 2-Ethylhexane 174-175 (447.2-448.2) 60-66
2-Ethylhexane n-Heptane 168- 170 (441.2-443.2) 52-64
n-Heptane n-Hexane 147- 159 (420.2-432.2) 41-54
n-Hexane n-Pentane 1 lo-135 (383.2-408.2) 25-37
n-Pentane Diethyl ether 106- 114 (379.2-387.2) 15- 27
a Refs. 31.32.
b Values in parenthesis indicate temperature in kelvin.
* See also corresponding table in this Handbook, and Refs. 24,25.
Crystallinities and Melting Temperatures of Mixtures of
Amorphous and lsotactic Poly@ropylene)b
Crystallinity
Isotactic Melting
fraction (%) Calculated Measured temperature (C)
100 67.2 67.7 174 (447.2)d
87.5 59.3 60.3 173 (446.2)
75.8 51.4 49.8 172-173 (445.3-446.2)
60 40.6 40.2 171-172 (444.2-445.2)
a Ether ext r act .
b 2-Ethylhexane extraction residues.
Refs. 33,34.
d Values in parenthesis indicate temperature in kelvin.
Crystallinity in /sotactic Poly(propylenes)
Crystalline
Sample Description and condition weight fraction
1. Heptane extract of crude polypropylene, 0.14
amorphous, highly atactic
2 . Isotactic, water quenched 0.31
3 . Same as 2, followed by annealing at 0.43
105C for 1 hr
4 . Same as 2, followed by annealing at 0.65
160C for 1/2 hr
a Ref. 35,36.
Effect of tsotacticity on Crystallinity
Sampl e Descri pt i on and condi t i on
Cryst al l i ne
wei ght
f ract i on
I. M, = 202000, I@,/,&, = 2.6, I s ot act i ci t y = 0.988 0.42-0.75
2. I@, = 159000, M,/I@, = 2.3, I s ot act i ci t y = 0.978 0.40-0.75
3. ti, = 189000, M,/M, = 3.0, I s ot act i ci t y = 0.953 0.38-0.60
4. M, = 209000, M,/M, = 1.8, I s ot act i ci t y = 0.882 0.30-0.45
5. MI, = 190000, fi,/fi, = 1.6, I s ot act i ci t y =0.787 0.20-0.25
Ref. 37.
Crystallization Kinetics See Table Rate of Crystal-
lization of Polymers and Refs. 38-49 for isotactic
poly(propylene), and Refs. 50-52 for syndiotactic
poly(propylene).
E. EQUILIBRIUM THERMODYNAMIC PROPERTIES
Equilibrium Melting Temperature, T,,
lsotactic poly(propylene) 187.5C (460.7 K) for the
crystal with an infinite size [reported data ranging from
183C-220C (456-493 K); for a detailed discussion, see
Ref. 341. It is also critically dependent upon the isotacticity
in crystalline samples.
Equilibrium Thermodynamic Properties VI23
Effect of lsotacticity on Equilibrium Melting
Temperature
Equi l i bri um
mel t i ng
temperature
Sampl e Descri pt i on and condi t i on (Cl
1 . bf,= 202000, iii,/fi, = 2.6, Isotacticity = 0.988 183.8 (457.0)b
2. fi, = 159000, I@,/,@, = 2.3, Isotacticity =0.978 182.8 (456.0)
3. M, = 189000, M,/fi, = 3.0, Isotacticity =0.953 180.2 (453.4)
4. M, = 209000, M,/M. = 1.8, Isotacticity=0.882 173.0 (446.2)
5. fi, = 190000, &f,/M, = 1.6, Isotacticity=0.787 163.0 (436.2)
a Ref. 37.
b Values in parenthesis indicate temperature in kelvin.
Syndiotactic poly(propylene) Equilibrium melting tem-
perature is critically dependent upon the tacticity of the
samples. For a sample with 95% of [r], 92% of [rr], and
86% of [rrr], and molecular weight higher than 40000, for
example, the equilibrium melting temperature is 160C
(433.2K) (53,54). For a 99% dyad sample, an actual
melting temperature of 163C (436.2K) can be observed
(55).
Equilibrium Enthalpy of Fusion, A Hf
Isotactic poly(propylene) 8.7 f 1.6 kJ/mol (56) [reported
data ranging from 2.65 kJ/mol to 10.94kJ/mol; for a
detailed discussion see Ref. 561.
Syndiotactic poly(propylene) Equilibrium enthalpy of
fusion is determined for samples with 95% of [r], 92% of
[rr], and 86% of [ml, and molecular weight higher than
40000, and is 8.0kJ/mol (53).
Equilibrium Entropy of Fusion, A$
lsotactic poly(propylene) 18.9 f 3.5 J/K/m01 (56).
Syndiotactic poly(propylene) No data is available.
Glass Transition Temperature, Tg
lsotactic poly(propylene) - 3.2C (270K) (56). The
agreement of T, values from various experimental methods
[e.g., dilatometry, dynamic mechanical measurements (at
low frequency), heat capacity and NMR (narrowing of line
width)] is not very good, but ranges from about - 30 to
f20C. The glass transition temperature depends on
thermal history (may also be tacticity) of the sample (57-
61). Activation energy, 117-152kJ/mol (57).
Syndiotactic poly(propylene) May be close to the glass
transition temperature of isotactic poly(propylene).
Heat Capacity, C, (J/Wmol) See Thermodynamic
Properties in this Handbook, and Ref. 62.
References page V - 28
v/24 PHYSICAL CONSTANTS OF POLY(PROPYLENE)
lsotactic poly(propylene) in the liquid The amorphous
liquid heat capacities above T, are given in J/K/m01
[ f2.5% @MS)] C, = 0.151291 T + 42.956
F. OTHER GENERAL PROPERTIES
Coefficients of Thermal Expansion (ASTM D 696) (K-l)
(Refs. 64-66)
lsotactic poly(propylene) in the solid The heat capa-
cities in the solid state are separately fitted to 100%
crystalline in various temperature ranges, all in J/K/mol:
lo-100 K [ f 0.4% @MS)]:
C, = exp[0.241028(ln 7j3 - 3.01364(1n 7)
+13.5529(1n I) - 18.76211
80-250 K [ IL 0.8% @MS)]:
C, = exp[O.l21683(ln Q3 - 1.90162(1n g2
+10.727(1n 7) - 17.68751
230-350 K [ k 1.7% @MS)]:
C, = 1.5912 x lo6 T2 + 0.3837 T - 64.551
The 0% crystalline amorphous state heat capacities in
various temperature ranges, all in J/K/mol.
lo-60K [ f 1.0% @MS)]:
C, = exp[0.327068(ln q3 - 3.688(1n Q2
+14.7469(1n 7) - 18.42811
50-180 K [ zt 0.7% @MS)]:
C, = exp[O.O0742669(ln n3 - O.l89318(1n Z)2
+2.10843(1n r) - 3.06991
From - 30C (243.2 K) to 0C (273.2 K) 6.5 x 1O-5
From 0C (273.2K) to 30C (303.2K) 10.5 x 1o-5
From 30C (303.2K) to 60C (333.2K) 14.5 x 1o-3
Density at 25C (298.2 K) (Mg/m3) = (g/cm3). See also
Section G.
lsotactic Crystalline 0.932-0.943
Amorphous (from extrapolation 0.850-0.854
of data above melting point)
Smectic form 0.916
Syndiotactic Crystalline 0.989-0.91
Amorphous (from extrapolation 0.856
of data above melting point)
Dielectric Constant See Section G.
160-260K [f 1.1% @MS)]:
C, = exp[O.O727139(ln n3 - 0.711627(1n n2
+2.31907(ln 2) + 0.779261
Electrical Properties: Conductivity
Syndiotactic poly(propylene) No data is available.
Electric field
(kV/cm)
Heat Capacity Data in the Crystalline and Amorphous
lsotactic Poiy(propyiene)
C, (JM/mol)
Temperature (K) Crystalline Amorphous Refs.
5 0 13.00 15.22 5 3
100 26.51 28.21 5 3
150 37.68 39.53 5 3
2 0 0 47.47 50.53 5 3
2 5 0 56.53 61.95 5 3
3 0 0 70.39 84.11 5 3
3 5 0 82.12 109.2 5 3
8.5 - 1 x 10-1s 6 7
10.5 7 5 3.2 x lo-l6 6 8
4 5 7.4 x 10-1 6 8
7 8
50.5
2.;
;
mw;; 6 9
6 9
2 4 81.2 2 x 10-16 7 0
39.7 1 x 10-16 7 0
7 8 2.2 x 10-18 6 9
50.5 1 x 10-1s 6 9
4 8 - 3.2 x lo-l8 7 1
7 8 2.3 x lo-* 6 9
144 81.2 1 x 10-14 7 0
39.7 1 x 10-14 7 0
7 8 2.8 x 10-1s 6 9
50.5 2 x 10-1s 6 9
d See also Section G.
Heat Capacity Changes at Glass Transition
Temperatures (J/K/mol)
lsotactic poly(propylene) 19.2 J/K/m01 at - 3.2C
(270 K) (63).
G Values for Radiation Cross/inking G(c.i.) and Chain
Scission G(Breaks)
Maximum and Minimum Values
Syndiotactic poly(propylene) May be close to that of
isotactic poly(propylene).
Residual Entropy of the Glassy State at 0 K Sa (J/K/mol)
lsotactic poly(propylene) 5.2 J/K/m01 (58).
Atactic 0.24 0.10 0.27 0.115
Isotactic film 0.21 0.10 0.14 0.069
Isotactic flake 0.27 0.10 0.18 0.068
Syndiotactic poly(propylene) No data is available. a Ref. 12.
Crystallinity
(%I
Conductivity at 72C
(mhos/cm) Refs.
G(hreaks) G(c.1.)
Maximum Minimum Maximum Minimum
.
At Room Temperature and in Vacuuma
Measured by
Atactic
Isotactic
L1 Ref. 12.
G(c.1.)
Solubility Elasticity
0.12-0.27 0.6-1.3
0. 07- 0. 25
0. 6
G(breaks)
Solubility or viscosity
0.10-0.24
0. 10- 0. 24
0. 9
5. 0
G-Values in Terms of Radiolytic Gas Yields
Atactic
Isotactic
a Ref. 72.
Ga s Irradiation T (C) G (gad
H2 25 2. 34
34 25 0. 095
HZ - 196 2. 55
(334 - 196 0. 058
HZ 25 2. 78
(334 25 0. 072
Ignition limiting Indices
650C ( 923. 2 K) 600C ( 873. 2 K) 550C ( 823. 3 K)
2. 8f 0. 1 3. 5 zto.1 5.7*0.1
a This method (ASTM D2803-70) is defined as the minimum volume of oxygen
required for ignition to occur; Ref. 73.
Infrared Absorption Bands (36,74-85)
Assignment in Infrared Spectrum Used for Crystallinity
Measurementsa,b
Crystalline phase Amorphous phase
Form wave numbers (cm-) wave numbers (cm-)
Isotactic 809 790
842 1158
894
997
Syndiotactic 866 1 1 3 1
977 1199
1230
a Used for tacticity measurements: ratio of absorption at 997cm- to that at
975 cm- (80,84,86).
b Ref. 36.
Sequence-Sensitive Vibration Band of Propylene Units
Position of
Type of
band (cm -) regularity Classification rib
998 Isotactic Helix band 10-12
973 Isotactic Regularity band 3- 4
841 Isotactic Helix band 1 2
977 Syndiotactic Helix band
962 Syndiotactic Regularity band
867 Syndiotactic Helix band
936
-
Band of isolated
propylene unit
a Refs. 74,87.
b Number of the units in sequence for the bands to appear,
Ot her General Propert i es VI 25
Far Infrared. See Ref. 88.
Mechanical Properties: Elongation at Break See Sections
GandH
Hardness, Shore D See Sections G and H.
Impact Strength, Izod See Sections G and H.
Low Temperature Brittleness See Sections G and H.
Melt Index (ASTM Method D 1238-577)
Molecular weight ( x 103) Melt index (23OC, 2.16 kg)
142 22. 8
180 7. 3
220 3. 5
292 1. 2
358 0. 39
Molecular Parameters of Typical Poly@ropylenes) (64)
Number of double bonds per 1000 C atoms <l
Type of unsaturation Vinylidene
fiu 220000- 700000
M 38000- 60000
fiii,lfin
5- 12
Nuclear Magnetic Resonance See Refs. 80,89-94.
Permeability and Diffusion Coefficients See correspond-
ing table in this Handbook and Refs. 95-97.
Permeability of Polypropylene Films to Various Gasesa
Permeability b (cm3/24 hr/lOO in.2/mil/atm)
Fi l m
02 (332 N2
Unoriented 250 800 40
Oriented 105- 150 300- 500 l o- 25
a Ref. 98.
b At 25C (298.2 K) adn 50% rh (ASTM D 1434-63).
Properties of Typical Poly(propylenes) See Sections G
and H.
Refractive Index nh5 =1.49 (66,99).
Refractive Index Increment (dn/dc) See corresponding
table in this Handbook, and Refs. 30,100.
Softening Temperature, Vicat See Sections G and H.
Sound Velocity (m/s (lOl- 103).
Unoriented: at 25C (298.2 K) 2.5 x 103
at 125C (398.2K) 125 x lo3
References page V - 28
V/26 PHYSICAL CONSTANTS OF POLY(PROPYLENE)
Specific Heat See Heat Capacity.
Specific Volume (cm3/gla
Form v, (Amorphous) vb (Crystalline)
Isotactic 1.176-1.172 10.73-1.060
Smect i c 1.092
Syndiotactic 1.165 1.114-1.10
a Ref. 64.
Tensile Modulus See Sections G and H.
Tensile Strength See Sections G and H.
Transition and Relaxation Temperatures Associated
with Peaks in Dynamic Loss
Transition
T CC)
Assignment and remarks
z (at 0.2 Hz) 0 :!7>8:) b
Difficult to resolve
Insensitive to changes in crystallinity;
long chain motion in amorphous portion
Y
- 80 (193.2) In atactic poly(propylene);
hindered movement of C-CHs units
6 < - 200 (< 73.2) Hindered rotation of CH s groups
a Designated as cy, p, y, etc. in order of descending temperatures; Ref. 104.
b Values in parentheses indicate temperatures in kelvin.
Ultra-Drawn Polypropylene See Refs. 105-108.
Viscosity-Molecular Weight Relationship See corre-
sponding table in this Handbook.
C. PROPERTIES OF TYPICAL MAINLY ISOTACTIC POLY(PROPYLENES)a,b
Property Value
Brittleness [D 7461 (C (K))
Deflection temperatures [D 6481 (C (K))
25 (298.2)
at 66 lb/in2 (4.64 kg/cm*) 96- 110 (369.2-383.2)
at 264 lb/in2 (18.6kg/cm2) 57-63 (330.2-336.2)
Density [D 7921 (Mg/m3) = (g/cm3) 0. 90- 0. 91
Dielectric constant at 1 kHz [D 1501 2.2-2.3
Dielectric strength [D 1491 (V/mil) 610 [430 at 120C (393.2K)]
(V/cm) x 10m3 240 [170 at 120C (393.2K)l
Dissipation factor (60 Hz- 100 MHz) [D 5101 3 x 10-4 - 1 x 10-3
Elongation at break [D 6381 (%) 500-900 [30 at - 40C (233.2 K)]
Environment stress cracking or Fsu time [D 16931 Does not stress crack
Flexnral modulus [D 7901 (MPa) = (N/mm*) 1172
Hardness, shore D [D 17061 70-80
Heat capacity (W/kg/K) 1.926 (see also Table I)
Izod impact strength [D 2561 (ft lb/in of notch) 0.4-6.0 [O.l-0.7 at - 20C (253.2 K)]
(cm kg/cm notch) 2.2-12 [0.55-3.9 at - 20C (253.2 K)]
Power factor at 1 kHz <0.002-0.001
Solvent resistance to hydrocarbons and chlorinated hydrocarbons Resistant below about 80C (353.2 K)
Stiffness in flexure [D 7473 (MPa) = (N/mm2) 1172
Tensile modulus [D 6381 (MPa) = (N/mm2) 1032-1720
Tensile strength [D 6381 (MPa) = (N/mm2) 29. 3-38. 6
Tensile yield elongation [D 6381 (%) 11-1.5 [11% at -40C (233.2K)]
Thermal conductivity [C 1771 (W/m/K) 11.7
Vicat softening temperature [D 15251 (C (K)) 138-155 (411.2-428.2)
Volume resistivity [D 2571 (0 cm) 106-10
a Properties at ambient room temperature, unless denoted otherwise. The numbers in square brackets in the first column refer to the ASTM (American Society for Testing
Materials) Standards.
b Refs. 64,66,99.
H. PROPERTIES OF SOME COMMERCIAL POLY(PROPYLENE) GRADES0
Grade
Property b Methodc Pipes and sheets Films Injection molding
Cast and tubular
film
Melt flow rate (g/lOmin) D 1238L 0. 25- 0. 35 1. 5-2. 0 5-7 7-10
Intrinsic viscosity at 230C (dl/g) ME 15071 2.6-3.0 2.0-2.4 1. 8-2. 4 1. 5-1. 9
Density (g/cm3) D 1505 0. 900- 0. 905 0.900-0.905 0.900-0.905
Crystallinity by X-ray (%) M E 149167 58-59 59-60 61-62 62.5-64.0
Mechani cal Propert i es of Poly(propylene) Homopol ymers VI27
Grade
Property b MethodC Pipes and sheets Films Injection molding
Cast and tubular
lilm
Crystalline mp by dsc* (C (K)) ME 150702
Isotactic index IS0 873
fitvIM, by gpce ME 15627
Spiral flow at 23OC, 60kg/cm (mm) ME 17544
Melt tension test
swelling per 24 s ME 17115
drawing ratio ME 17115
Linear mold shrinkage (%)
Tensile yield strength at 5 cm/mm D 638
(MPa)f
Tensile yield elongation (%) D 638
Flexural modulus (GPa)s D 790
Impact, Izod at 23C (J/m)* D 256
Hardness, Rockwell, C scale D 785B
Deflection temperature (C (K))
at 0.45 MPaf D 648
at 1.8 MPaf D 648
Vicat point at 9.807 MPaf (C (K)) D 1525
Yellow index on pellets (%) D 1925
Gloss on plate (%) D 523
Luminosity on plate D 1635
Coefficient of linear thermal expansion ( x 10m5)
from - 30C (243.2 K) to 0C (273.2 K)
from 0C (273.2 K) to 30C (303.2 K)
from 30C (303.2 K) to 60C (333.2 K)
Water absorption at 24 h immersion (W) D, 570
Environmental stress cracking i D 1693
Dielectric constant D 1531
at 1OkHz
at 1 MHz
at 1 GHz
Dissipation factor, h
at 1OkHz
at 1 MHz
at 1 GHz
Arc resistance, s D 495
161-163 (434-436) 161-163 (434-436)
> 96.0 > 96.0
8-10 7-9
390-450 525-550
162-164 (435-437) 163-165 (435-437)
>95.0
6-8
700-750
> 94.0
5-7
800-850
1. 57- 1. 60 1.60-1.63 1.63-1.64 1.63-1.64
500-700 1100-1300 1500-1700 2 2000
f 1.9 5 1.9 5 1.9 5 1.9
29-31 32-34 33-35 33-35
10-12 10-12 8-10 8-10
1. 1-1. 3 1. 3-1. 4 1. 5-1. 6 1. 6-1. 7
1.5-2.0 0.5-0.7 0.3-0.5 0.2-0.3
55-60 55-60 60-65 60-65
88-90 (361-363)
50-55 (323-328)
2 150 ( 2 423)
8-15
48-50
68-70
90-92 (363-365)
50-55 (323-328)
2 150 ( > 423)
4-8
48-50
270
92-94 (365-367)
55-60 (328-333)
2 150 ( 2 423)
3-6
49-51
270
> 94 (> 367)
55-60 (328-333)
2 150 ( 2 423)
3-6
49-51
270
6.5 6.5
10.5 10.5
14.0 14.0
0.03 0.03
Does not break Does not break
6.5 6.5
10.5 10.5
14.0 14.0
0.03 0.03
Does not break Does not break
2.2-2.6 2.2-2.6 2.2-2.6 2.2-2.6
2.2-2.6 2.2-2.6 2.2-2.6 2.2-2.6
2.2-2.6 2.2-2.6 2.2-2.6 2.2-2.6
< 0.0005 0.0005 0.0005 0.0005
< 0.0005 0.0005 0.0005 0.0005
<0.0005-0.0018 0.0005-0.0018 0.0005-0.0018 0.0005-0.0018
136- 185 136-185 136- 185 136-185
a Ref. 65.
d Differential scanning calorimetry.
g To convert GPa to psi, multiply by 145,000.
b Determined on Montedison Moplen poly(propylene).
Gel-permeation chromatography.
h To convert J/m to ft-lb/in., divide by 53.38.
D = ASTM; ME = Monte&on.
f To convert MFa to psi, multiply by 145.
i Igepal= 100%.
I. MECHANICAL PROPERTIES OF POLY(PROPYLENE) HOMOPOLYMERS
Heat deflection
Melt flow rates Flexural modulus Izod impact temp. 66 psi Hardness
[ ASTM: D12381 [D 7901 [D 2561 [D 6481 D 7851
Vpe
(g/l0 min) (MPa) (J/m) (C) (Rockwell R)
Compr. mold, pipe extrusion 0.5 1585 (230) b 160 (3.0)c 93 (366.2)* 95
Sheet, strapping extrusion 1.5 1480 (215) 70
(1.3)
8 7
(360.2)
-
High clarity, stiffness 2 1790 (260) 140 (2.6) 110 (383.2) 100
General injection molding purpose 4 1720 (250) 43 (0.8) 97 (370.2) 99
Rapid cycle injection molding 1 2 1655 (240) 27 (0.5) 99 (372.2) 97
Rapid cycle, high stiffness 1 2 1895 (295) 32 (0.6) 118 (391.2) 105
Thin wall injection molding 20 1720 (250) 32 (0.6) 100 (373.2) 104
Thin wall, high stiffness 20 2000 (290) 32 (0.6) 124 (397.2) 104
Multi-cavity molding 3 5 1310 (190) 32 (0.6) 90 (363.2) 98
Extrusion coating 40 1895 (275) 32 (0.6) 121 (394.2) 100
Coextrusion 70 1515 (220) 90 (363.2)
Fibers 100 1585 (230)
a Ref. 109.
b Values in parenthesis in this column indicate Flexural modulus in K psi,
Values in parenthesis in this column indicate Izod impact in ft-lb/in.
d Values in parenthesis in this column indicate temperature in kelvin.
References page V - 28
V/28 PHYSICAL CONSTANTS OF POLY(PROPYLENE)
J. MECHANICAL PROPERTIES OF POLY(PROPYLENE) RANDOM COPOLYMERS
Heat deflection
Melt flow rates Flexural modulus Izod impact temp. 66 psi Hardness
[ ASTM: D12381 [ D 7901 [ D 2561 [ D 6481 [ D 7851
bpe
(g/l0 min)
(MM (J/m) (C) (Rockwel l R)
Sheet extrusion 1 965 (140)b 80 (1.5)C 90 (363.2)d 80
Sheet extrusion 2.5 690 (100) 8 5 (1.6) 70 (343.2) 6 5
Sheet extrusion 3 1515 (220) 37 (7) 102 (375.2) 95
Film extrusion 3 260 (38)
Inj. molding, film, coextrusion 6 825 (120) 48 (0.9) 8 5 (358.2) 80
Film extrusion 6 495 (72)
Inj. molding, film, coextrusion 7 585 (85) 80 (1.5) 65 (338.2) 65
Inj. molding, film, coextrusion 1 0 860 (125) 37 (0.7) 8 5 (358.2) 80
Inj. molding, film, coextrusion 1 0 1135 (165) 54 (1.0) 9 1 (364.2) 88
Rapid injection molding 25 895 (130) 37 (0.7) 8 5 (358.2) 80
Rapid injection molding 25 1135 (165) 98 (371.2) 94
Rapid injection molding 35 1135 (165) 43 (0.8) 87 (360.2) 80
a Ref. 109.
b Values in parenthesis in this column indicate Flexural modulus in K psi.
c Values in parenthesis in this column indicate Izod impact in ft-lb/in.
d Values in parenthesis in this column indicate temperature in kelvin.
K. MECHANICAL PROPERTIES OF POLY(PROPYLENE) IMPACT COPOLYMERS
Melt flow rates Flexural modulus hod i mpact
[ASTM: D 12381 [ D 7901 [ D 2561
Qpe
(g/l0 min)
(MPa) (J/m)
Heat deflection
temp. 66 psi
[ D 6481
CC)
Hardness
[ D 7851
(Rockwel l R)
Compr. Mold, pipe extrusion
Sheet extrusion
Sheet extrusion
General purpose inj. molding
General purpose inj. molding
General purpose inj. molding
Blush resist., inj. molding
Blush resist., inj. molding
Blush resist., rapid inj. molding
Blush resist., rapid inj. molding
Blush resist., rapid inj. molding
Blush resist., rapid inj. molding
Blush resist., rapid inj. molding
0.5 1240 (180)b
1 860 (125)
2 965 (140)
4 1310 (190)
4 1035 (150)
6 930 (135)
11 1000 (145)
1 6 860 (125)
20 965 (140)
20 790 (115)
30 965 (140)
3 5 1310 (190)
50 1170 (170)
540 (1O)C
650 (12)
650 (12)
135 (2.5)
540 (10)
650 (12)
135 (2.5)
650 (12)
185 (3.4)
540 (10)
55 (1.0)
70 (1.3)
55 (1.0)
D Ref. 109.
b Values in parenthesis in this column indicate Flexural modulus in K psi
c Values in parenthesis in this column indicate Izod impact in ft-lb/in.
d Values in parenthesis in this column indicate temperature in kelvin.
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1.
2.
3.
4.
5.
6.
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90 (363.2)d 75
79 (352.2) 5 5
72 (345.2) 6 1
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75 (348.2) 65
90 (363.2) 70
77 (350.2) 72
80 (353.2) 40
77 (350.2) 67
8 5 (358.2) 65
80 (353.2) 80
90 (363.2) 8 5
1 1 7 (390.2) 90
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v/m
PHYSICAL CONSTANTS OF POLY(PROPYLENE)
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. Physical Constants of Fluoropolymers
Dewey L. Kerbow
DuPont Fluoroproducts, Wilmington, DE 19880, USA
Carleton A. Sperati
Chemical Engineering Department, Ohio University, Athens, OH, USA
A. Introduction
B. Physical Constants of Polyketrafluoroethylene)
Notes
Infrared Absorption Spectrum of
Polyketrafluoroethylene)
Ref erences
C. Physical Constants of Melt Processible
Fluorocarbon Polymers PFA and FEP
Notes
Ref erences
D. Physical Constants of Modified
Polyfethylene-co-tetrafluoroethylene)
Notes
Ref erences
E. Physical Constants of Polyfvinylidene fluoride)
Notes
Ref erences
F. Physical Constants of Amorphous
Fluoropolymers
Notes
Ref erences
G. Physical Constants of
Polykhlorotrifluoroethylene)
Notes
Ref erences
v-31
v-3 1
v-37
V-38
v-39
v-41
v-44
v-45
v-45
V-48
V-48
V-48
v-51
v-s2
v-52
v-54
v-s4
v-s5
v-s7
V-58
A. INTRODUCTION
Fluoropolymers are divided into two sub-classes: (a)
Fluorocarbon polymers, i.e., those that are made from
perfluoromonomers, and (b) All the others that are made
from monomers or comonomer systems that contain
hydrogen, chlorine, or both, along with enough fluorine
so that it contributes significantly to the properties and
performance of the polymer. At times, the term fluoro-
carbon or fluorocarbon polymers, are used improperly to
include all of the fluorine-containing polymers.
The commercially important fluorocarbon polymers are
poly(tetrafluoroethylene) (PTFE), poly(tetrafluoroethylene-
co-hexafluoropropylene) (FEP), poly[tetrafluoroethylene-
co-(perfluoroalkylvinyl ether)] (PFA), and amorphous
fluoropolymer (AF), typically copolymers of tetrafluoro-
ethylene and fluorinated dioxole. The second group of
fluoropolymers includes modified poly(tetratluoroethylene-
co-ethylene) (ETFE), poly(vinylidene fluoride) (PVDF)
(sometimes referred to as PVF2), and copolymers of
vinylidene fluoride, poly(chlorotrifluoroethylene) (PCTFE),
poly(chlorotrifluorethylene-co-ethylene) (EKTFE) and
poly(viny1 fluoride) PVF.
The wide range of fluorine content in the various
fluoropolymers (from 76 down to 39 weight percent
fluorine), details of crystallinity, conformation, molecular
weight, and other aspects of structure result in ranges of
properties so wide that a single table listing all the materials
and their properties is very cumbersome to use. Tables on
the various materials are separated, therefore, with a short
general comment on each material or class, at the beginning
of each table. Each table has its own notes and list of
references.
B. PHYSICAL CONSTANTS OF
POLY(TETRAFLUOROETHYLENE) -(CF2CF2)-
Polytetrafluoroethylene (PTFE) was the first fluorocarbon
polymer to be made and still retains the major part of the
total business. The extremely high melt viscosity of PTFE
having a molecular weight high enough for most applica-
tions precludes use of conventional methods of processing
that require molten polymer. As a result, innovative
procedures, quite different but not difficult, were devised
to prepare useful objects. Some properties of PTFE reflect
the unusual methods of processing.
VI32 PHYSICAL CONSTANTS OF FLUOROPOLYMERS
Property * Units
ASTM
or other
methods Value Remarks Refs.
Abrasi on Resi stance See Wear Factor
ASTM Standards
Material
Granular products
Coagulated dispersion products
Dispersion
Film and sheeting
Rods, tubes, and pipe lining
Molded basic shapes
IS0 Standards
Plastics - Fluoropolymer dispersions and
molding and extrusion materials
Part 1: Designation system and basis
for specifications
Plastics - Polytetrafluoroethylene (PTFE)
Semi-finished products
Part 1: Requirements and designations
Bond Angle, C-C Deg.
F-C-F
Bond Energi es
C-F
c - c
Id/m01
Bond Length, C-F A
Bulk Density of Molding Powder g/l
Chemi cal Resi stance
Coefficient of Friction
Coefficient of Thermal Expansion
Linear expansion K-l
Average values for temperature range indicated
25 to - 190C
25 to - 150C
25 to - 100C
25 to - 50C
25-0C
25-50C
25- 100C
25- 150 C
25- 200 C
25- 250 C
25- 300 C
Cohesi ve Energy Densi ty
Compressibility (calculated) MPa-
Compressi ve Strength Properti es
Stress at 1% deformation
Stress at 1% offset MPa
Yield strength MPa
At -251C MPa
At - 196 C MPa
At 23C MPa
At 55C MPa
At 100C MPa
MPa
MPa
See Note 2
D4894
D4895
D4441
D2686, D3293, D3308, D3369
D1675, D1710, D2902, D3295
D3294.D3297
IS0 12086- 1
IS0 13000- 1
D1457
D1894
See Conformation
108
482 70
290-335
1 6
1. 3- 1. 32
350-900
See Solvents
0.224 W.163
D696
99 x 10-6
D695
D695
D695
D695
D695
D695
D695
70
70
See Note 3
W is the load in grams,
calculated from Ref. 2
77
86
96
112
1 3 5
200
124
124
1 3 5
1 5 1
174
218
12.5 (est.); see also Solvent Absorption 79
28.8 x lo-
8
4.2
47094 - 231295(%C) + O.O4O(%C)
- O.O391(%C)3
7
190.4-0.862 (K) From 4 to 180 K
224
1 4 5
11.7
9
4.8
3 8
30
7 7
30
5 2
52
52
5 2
52
* See note 1.
Property Units
AS TM
or other
methods
Physical Constants of Poly(tetrafluoroethylene) v/33
Value Remarks Refs.
Conformation
Energy barrier to rotation
Gauche-rruns energy difference
truns--truns Energy difference
Contact Angle
Advancing
Receding
Continuous Use Temperature
kJ/mol
Id/m01
Deg.
Deg.
5.9f 1.7
4.6 f 2.9
C-C bond angle is at its 6
minimum energy at 162C
116 34
92
See Service Temperature
Creep
Compressive creep modulus
Mpa
Flexural creep modulus MPa
D695 186 After 100 h a t 0.6895 MPa 42,59
at 23C
2814 - 158.51%0 + 2.919(%@
-0.1638(&$ ~
Tensile creep modulus
MPa 6 1
Critical Shear Rate for Melt Fracture s-l 10-5
Cri ti cal Surface Tensi on mN/m 18.6
Crystal Structure Change See Figure 1 and Transitions
Crystalline Content wt.% c 762.25 - (1524.5/Density)
Crystallographic Data
Phase I See Figure 1
Separation of chain axis
Phase II: Triclinic structure
Repeat distance for
13 CF2 groups
Separation of chain axis
Phase III: High pressure form
Planar zig-zag structure
Monoclinic space group
Density
Phase IV: Hexagonal structure
Repeat distance for
15 CF2 groups
Separation of chain axis
A
A
A
g/cm3
A
A
A
Deg.
A
A
S=3.68 x lo-* T+5888
16.9
5.62 13
B2/m
2.74 at 12 bar
a=9.59
b =5.05
c = 2.62
y = 105.5
19.5
5.55
Deformation Under Load % Def. D621 12.93 - 0.3303 (%C)
- 0.002372 (%C)3
Density g/cm 3
Completely amorphous (never observed)
Crystalline (from X-ray and IR data)
Phase II (triclinic at < 19C)
Phase IV (hexagonal at 20-40C)
As polymerized
After melting and recrystallization
(void free polymer)
Melt (380C)
Depends on crystalline and
void contents
2.0 at 23C
2.344
2.302 at 23C
2.280-2.290 at 23C
1524.5/(762.25 - %C)
1.46
6.895 MPa for 100 h
%C from 45 to 90
See Note 1
After 100 h at 6.895 MPa
76
59
and 23C
At 380C 97
29
Calc from Ref. 77
Hexagonal structure similar
to Phase IV, but little or
no lateral congruence
T from 40 to 220C
13,25,61,100
27
1000 psi for 24 h
at 23C; %C from
50 to 90
16,61
76
See Note 1
See Note 5 77
See Note 1
100
67
77
77
49
Notes page V- 37; References page V- 39
v/34 PHYSICAL CONSTANTS OF FLUOROPOLYMERS
Property Units
ASTM
or other
methods Value Remarks Refs.
Depoiymerization Rate
Diffusion
El ectri cal Properti es
-Dielectric constant
At 60Hz
At 60Hz to 2GHz
Dielectric Strength
Dissipation factor
60Hz to 2GHz
Surface arc resistance
Surface resistivity, 100% RH
Volume resistivity, dry at 50% RH
Entangl ement MW
End Groups
Entropy of Fusion
Equation of State
Flammability
Also see limiting oxygen index
Flexural Modulus
At 23C
At -251C
At -196C
At - 101 C
At 23C
At 55C,
At 100C
Flexural Strength
Fuel Val ue
Gl ass Transi ti on Temperature
Glass-I transition
Glass-II transition
Hardness
Duromet er
Rockwell
Scleroscope
Heat Capacity
A t lO.OK
100.0 K
200.0 K
300.0 K
400.0 K
500.0 K
600.0 K
605.0 K (T,)
700.0 K
Heat Deflection Temperature
At 0.455 MPa (66 psi)
At 1.82 MPa (264 psi)
E
kV/mm
D150
D149
MVlm
V/mil
D150
S D495
ohmdsq D257
ohmcm D257
g/m01
MPa 29(C) - 1127
GPa 5.2
GPa 5
GPa 3.2
GPa 0.62
GPa 0.4
GPa 0.19
C
UL94 VE-0 See Note 9
D790 76
D790
DSC
Scale value
Scale value
D2240
D785
k.vkglK
DSC
UmolJK
C D648
See Thermal Degradation
See Permeability
20
(1 +0.238@/(1 -0.1190), D is density 24
2.1 30
The exact value depends on the thickness
of the test specimen as well as other test
variables
15.7-19.7
400-500
See Note 6
<3 x 10-4
700 See Note 7
3.6 x lo6
1019
77
30
77
77
77
3.7 x 103
See Note 8
See Melting
(P+a) (V-b) =B (T-c)
a = 405.2 bar; b = 0.500 cm3/g
c=114C; B=0.310cm3/g/K
49
9
48,87
No break in flexure
See Heat of Combustion
- 7 3
See Transitions, Alpha
See Transitions, Gamma
C from 40 to 90
52
52
52
52
52
52
D =42 +0.2(C)
J= 114.6 - 0.433(C)
s= 133 - 1.3(C)
0.9324-t 1.05 x 1O-3 T
Cr yst al l i ne Amor phous
1.228 (1.228)
19.37 19.37
34.47 (35.59)
45.09 51.42
53.81 59.24
61.62 66.05
67.58 69.37
67.88 69.54
73.300 72.69
See Note 10
132
60
4 5
76
69,103
44
7 7
Physical Constants of Poly(tetrafluoroethylene) VI35
Property Units
ASTM
or other
methods Value Remarks Refs.
Heat of Combustion
Heat of Crystallization
Heat of Formation
Heat of Fusion
Ignition Temperature
Impact Strength
I ntri nsi c Vi scosi ty
Infrared Spectra
MJ/kg
Id/m01
C
mug
Lamellar Thi ckness
w
L atti ce Energy
(per recurrent unit; calculated)
limiting Oxygen Index
Mechani cal l oss
Melt Viscosity
By capillary rheometer
By melt creep,
Energy of activation for melt flow
Melting
Melting peak temperature
Initial (irreversible)
Second and subsequent (reversible)
Equilibrium melting temperature
Forporous, expanded PTFE
Entropy of melting
Corrected to constant volume
Volume expansion during melting
C
C
C
C
J/K/m01
JlWmol
Increase of melting point with pressure Kcm*/kg
Heat of fusion
km?
kJ/mol
% Oxygen
Pas
Pas
kJ/mol
Molecular Weight See Note 15
Particle Size (Average calculated diameter) pm
Dispersion polymer
Coagulated dispersion polymer
Granular polymer
ASTM Type I
ASTM Type IV
D2863
D2236
D2116
D4591
D1457
D1457
D1457
Permeabi l i ty to Gases
Hel i um
Carbon dioxide
Nitrogen
Hydrogen
m3(STP) m/s/m/Pa (x 10i5)
Energy of activation for diffusion kJ/mol
Energy of activation for permeability Id/m01
Phase Di agram
Processi ng Temperature
PV limit
Radiation, Effects of degradation
in air
C
Pam/ s
Radicals/l0 6 C atoms 3.7 x 10-5D0.89
Recovery after deformation % D1147
5.1
See Melting - latent heat of fusion
813
See Melting - latent heat of fusion
494
See Toughness
300- 2000 Also see Solvents
See Table 1 See Note 1
O.O2(%C) - 0.9 Calc. from
35
10,22
49
71,74
17,51,56
91,105
26,57,80
8.5 412.5 8
>95
See Note 11
20
87
1.62 x lo-l4 M3.4
4 to 20 x 1OO at 360C
63-84
See Note 1 2
75,78
1,58
1,74
335-345 See Note 1 3 52
327 64
331.7 45,85
385 32,33
477 88
33.18
29%
0.095 89
82 See Note 1 4 44
log M, = 27.5345 - 12.14050 D is Density 18,40,77
log M, = 10.3068 - 5.1318 H is Heat of Crystallization
log(4.184H) in J/g 94
0.22
350-650
600-800
< 100
log PHe =3. 505 - O. O37( %C)
log Pco, = 2.605 - O.O37(%C)
log PN2 = 2.44203 - 0.037(%C)
7.35
27.6
19.7
See Fig. 1
350-400
50-250
Derived from Ref.;
D is dose in rads
% Recovery = 111 - O.S7(%C); 1/4 inch penetrator;
% C from 40 to 90 5 lb preload;
250 lb major load
47
104
76
76
76
60
60
60
27,77,102
46
37
96
Notes page V- 37; References page V- 39
V/36 PHYSICAL CONSTANTS OF FLUOROPOLYMERS
Property Units
AS TM
or other
methods Value Remarks Refs.
Refractive Index
Resistivity
Servi ce Temperature
Sol i d Vi scosi ty Pas
Sol uti on Vi scosi ty
Solvent Absorption
Perchloroethylene % wt. increase
Methylene chloride % wt. increase
Sol vents
Specific Gravity
Specific Heat
Speed of Sound
Longitudinal
Shear
mlsec
m/set
Standard Specific Gravity
(Relative molecular weight)
Surface Tensi on at 293 K mN/m
Tensi l e Strength Properti es
Modulus
At -251C
At - 196 C
At - 129C
At -73C
At 23C
At 100C
Yield Stress,
At -251C
At - 196 C
At -129C
At -73C
At -55C
At 0C
At 23C
At 158C
At 250C
Tensile strength
At 23C
GPa 4.1 52
GPa 3.4 52
GPa 2.5 52
GPa 1.8 52
MPa 340 52
MPa 69 52
MPa 1 3 1 52
MPa 110 52
MPa 79 52
MPa 53 52
MPa 26 52
MPa 1 2 52
MPa 1 0 52
MPa 5.5 52
MPa 3.4 52
MPa 270 - 0.39(%C) - 99.3 D
At 23C,
Elongation at break
At -251C
At - 196C
At - 129 C
At -73C
At 23C
Plateau modulus, 380C
MPa
% 2
% 6
% 90
% 160
% 200-400
MPa 1.7
Thermal Conductivity
25C
72C
W/ m/ K
W/m/K
Thermal Degradation
Enthalpy of depolymerization
Rate of depolymerization
Kinetic chain length (CL)
D542 1.376
See Electrical Properties
- 269 to 260C
104 - 106
See Note 16
At 3OoC, shear rate
O.l-loss
7
21,95,96
54,81
See Intrinsic Viscosity
% wt. gain = 24.85 - 2.456
HSP
2
0.7
See Note 17
HSP is Hildebrand
solubility parameter
1000 h in boiling liquid,
60% tryst.
1000 h in boiling liquid,
60% tryst.
66
See Note 18
1 MHz, 25C
See Density
See Heat Capacity
1410
730
49
49
D1457 Also see Molecular Weight
25.6
See Note 15 1 8
49
D638
17-34
D from 2.170 to 2.280 Mg/m3;
%C from 30 to 90
See Note 5 52
See Note 5
52
52
52
52
52
49
Cl77 K = 4. 86 x 1O-4 T+0.253 69
0.25 49
0.34 49
AH = 156000 - 27.9 (T-360) J/mol 69
See Ref. for details 7 3
log CL = 832O/T- 9.958 2 in kelvin 28,98
Notes VI37
Property Units
ASTM
or other
methods Value Remarks Refs.
Toughness
Izod impact strength, notched
- 51C
23C
77C
Tensile impact strength
Trans i ti ons
Alpha (Glass I)
Beta I (Crystalline transition,
crystal disordering relaxation)
Change with pressure
Latent heat
Volume expansion
Kinetics of the transition
Beta II
Beta I + Beta II
Entropy change, overall (19 + 30)
Due to volume change
(corrected to constant volume)
Gamma (Glass II)
Change of frequency (in Hz) of loss
peak with temp.
Alpha (Glass I)
Beta (crystalline relaxation)
Gamma (glass II)
Effect of temperature on
transition pressure
Transition between phases IV and I
Transition between phases II and IV
Triple Point
Unit Cell
vi scosi ty
Water Absorption
Wear Factor
Weatherability
J/ m
kPa/m 2
C
K/bar
kJ&
l&T
kJ/kg/K 0.0452
M/kg/K 0.028
Pa P=( -9l-57.8T+ l.99T2) x 10
Pa P = ( - 820 + 26.9 T+ 0.68 T2) x lo5
%
Pa-
D256 2 1
1 0 7 52
1 8 7 52
320 52
D1822 TIS = 3 379 - 45.1 (%C) See Note 1 15
See Note 1 9 2 3
126 At 1 Hz 5 3
1 9
0.0128
13.4
0.0058
30
See Note 20
- 80 at I Hz
57
53
23
log F=48.3759-368 kJ/(2.303RT)
log F = 24.97 - 142 kJ/(2.303Rg
log F=22.37-75 kJ/(2.303 RT)
50
See Figure 1, Crystallographic Data, and Transitions
See Crystallographic Data
See Melt Viscosity
See Solid Viscosity
See Solution Viscosity
0
3000 x 10-17
Excellent
See Note 21
See Note 22
77
46
NOTES
Many of the properties of PTFE are not constant but
change systematically with crytalline content, mole-
cular weight, void content, temperature, pressure, or
some other independent variable. Where available,
these inter-relationships are shown even though they
are usually empirical rather than fundamental.
Throughout the table, %C indicates percent crystal-
linity by weight.
3 .
American Society for Testing and Materials (ASTM)
standards on the fluoropolymers provide a con-
venient source for information on details of the
nature of a particular fluoropolymer, typical proper-
ties, methods of testing, and the like. For this reason,
pertinent Standard numbers are included in the
tables for each polymer. The fluoropolymer stan-
dards are the responsibility of the Fluoropolymers
4 .
Section of the Materials Subcommittee of the
Technical Committee on Plastics. The numerical
designation is D-20.15.12. More recently, the
International Organization for Standardization
(ISO) has issued materials standards which incorpo-
rate various aspects of the ASTM standards.
The exact value depends on the particular type or
grade of polymer that is being used.
Equations based on time-temperature superposition
are given in Ref. 42 for PTFE with a crystalline
content of approximately 58%. These relationships
permit calculation of tensile creep modulus at any
stress, time, or temperature in the temperature range
of 35-100C and stress levels below the elastic
limit. Ref. 41 provides similar data over a wider
range of conditions.
References page V - 39
V/38 PHYSICAL CONSTANTS OF FLUOROPOLYMERS
5. Reference 83 gives a value of 2.060 for the
amorphous density of PTFE. Internal inconsistencies
in this paper, however, need clarification before this
writer can accept the value given.
6. Precise measurements of dielectric loss (Ref. 71)
show peaks that correspond to the gamma transition.
The measured values of tan delta, however, were all
less than 300 x lop6 with some as low as 20 x 10p6.
7. No carbon track is formed.
8. Infrared methods show presence of carboxylic acid
monomer and dimer, perfluorovinyl, and acid
fluoride end groups in low molecular weight
products (Ref. 9). The methods currently available
are not sufficiently sensitive for quantitative work in
polymers of commercially useful molecular weights,
but the acid monomer and dimer ends have been
found in commercial materials using FTIR proce-
dures (Ref. 93).
9. This numerical rating for flame spread is not
intended to reflect hazards presented by this or any
other material under actual fire conditions.
10. The values given are selected from extensive tables
and plots of data in Ref. 44.
11. The mechanical loss factor is related to the transition
behavior. The value depends on temperature and
frequency of the dynamic mechanical stress, values
of the logarithmic decrement up to 0.55 have been
observed (see Ref. 53).
12. This relationship is applicable only to PTFE, with
molecular weights well below that required for the
applications of plastics (see Ref. 78).
13. The temperature observed for the first (irreversible)
melting point decreases with rate of heating. It also
differs with the type of polymer. Evidence in Refs.
39 and 72 suggests that details of DSC scan for a
first melting reflect aspects of molecular weight and
molecular weight distribution.
14. Inconsistencies in the results from various labora-
tories for the heat of fusion of PTFE and FEP have
not been resolved. Some aspects are discussed in
Refs. 86, 89, and 90.
15. Standard Specific Gravity (SSG), described in
ASTM D4894, D4895 and IS0 12086-1 (see Ref.
18 and 77), is a useful inverse measure of relative
molecular weight for homopolymers of TFE. Many
commercial polymers today, however, contain very
small amounts of modifiers that affect the rate and
extent of crystallization. With these materials,
therefore, SSG is meaningful as a measure of
relative molecular weight only within a given family
of PTFE resins. Estimating actual values of the
molecular weight of the highest molecular weight
commercial polymers has, to date, involved assump-
tions and extrapolation. These relationships, there-
fore, are, at best, a first approximation. In addition,
some references, such as Refs. 11 and 40, give
relationships for molecular weight as a function of
SSG with little or no documented basis for the
equation.
16. The recommended maximum service temperature is
260C (Ref. 21). There are, however, examples of
satisfactory use at higher temperatures. Gaskets in
totally enclosed systems, for instance, are used
repeatedly at 500C and 15 000 psi (103 MPa) (see
Ref. 19). PTFE also performs well at low tempera-
tures. In compressive strength tests at 4K, for
example, the polymer has been shown to have
ductile rather than brittle failure (Ref. 95).
17. Weight gain is noted with some chlorinated and
fluorinated liquids that contain no hydrogen (Ref.
82). The weight increase decreases with increasing
crystallinity (Ref. 78).
18. PTFE is inert to essentially all common chemicals
(see Refs. 64 and 65). It is, however, attacked by
molten alkali metals, elemental fluorine, and pure
oxygen at elevated temperatures, it can also react
under some conditions with alkaline earth oxides
and finely divided metals such as aluminum or
magnesium at elevated temperature. Sorption of
solvents is mentioned in Note 13. Solutions contain-
ing O.l-2% PTFE were obtained in perfluoroker-
osene CztFa(FCX-412) in the temperature range
290-310C (see Refs. 71 and 74).
19. Clear evidence for a crystalline transition at about
90C is presented in a series of papers by Araki,
Refs. 3-5. He also presents evidence for doublets in
the transitions Ref. 4, and points out that the alpha
and gamma transitions follow the so called 2/3
(Trouton) rule when compared with the first order
crystalline transitions at 19 and 327C Ref. 3. See
also evidence for a doublet in the freezing-point plot
shown in Ref. 65.
20. Data on the kinetics of the transitions not amenable
to presentation in tabular form are available in
Ref. 57.
2 1. Incorporation of finely divided fillers decreases wear
factor by as much as 500 to 1000 fold (Ref. 46).
22. No change in appearance or properties has been
observed after more than twenty years exposure in
Florida (see Ref. 21).
INFRARED ABSORPTION SPECTRUM OF
POLY(TETRAFLUOROETHYLENE)
(cm-) (pm)
Intensity a
3670 2.72 VW
3570 2.80 VW
3450 2.90 VW
3090 3.24 VW
2925 3.42 VW
2620 3.82 VW
2590 3.86 VW
References VI 39
(cm-)
(pm) Intensity (cm-)
(id Intensity a
2530 3. 95
2450 4. 08
2367 4. 22
2300 4. 35
1974 5. 07
1935 5. 17
1883 5. 31
1859 5. 38
1792 5. 58
1703 5. 87
1545 6. 47
1451 6. 90
1420 7. 04
1242 8. 05
8
6
4
1213 8. 24 VS
1152 8. 68 VS
932 10. 73 M
850 11. 76 Amorphous
778 12. 85 Amorphous
738 13. 55 Amorphous
718 13. 98 Amorphous
703 14. 22 Amorphous
638 15. 67 S
553 18. 08 s
553 18. 08 S
516 19. 38 vs
384 26. 04 Amorphous
a VS, very strong; S, strong; M, medium; W, weak, VW, wy weak.
Tri cl i ni c
crystal
Pseudohexagonal
crystal
I
40 60 80 100
Temperature (C)
Fi gure 1. Phase diagram for poly(tetrafluoroethylene).
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C . PHYSICAL CONSTANTS OF MELT PROCESSIBLE FLUOROCARBON POLYMERS PFA AND FEP
WA: f(CF2Wn(CF2@r
F
FEP: f(CF2CF2),(CF2CF )h
CF3
Unlike poly(tetrafluoroethylene), copolymers of tetrafluoro-
ethylene with perfluoro comonomers are made as relatively
low molecular weight (i.e., low melt viscosity) products
that can be processed by conventional melt procedures and
still have properties in the solid state that are similar or
superior to those of poly(tetrafluoroethylene). Both PFA,
poly[tetrafluoroethylene-co-perfluoro(alkoxy vinyl ether)],
and FEP, poly(tetrafluoroethylene-co-hexafluoropropylene),
are included in this table. Various perfluoro(aIkoxy vinyl
ethers) can be used for PFA. It has been reported that one
often used is perfluoro(propylviny1 ether) (14).
Data available for PFA and FEP are not as extensive as
for FTFE. In many respects, however, the properties of solid
FEP and, especially, PFA, are very similar to those of
PTFE. The values given in the table for PTFF, therefore,
can often provide useful guidance for the properties of non-
molten PFA or FEP for which no values are included in this
table.
Property units
A S T M
or other
methods Vahle
P F A
Remarks Refs. Value
F EP
Remarks Refs.
Abrasion Resistance
ASTM or IS0 Standards
Mat er i al
Mol di ng and ext r usi on powder s
Fi l m and s heet i ng
Rods , t ubes , and pi pe l i ni ng
Bond Energi es
C- C adj oi ni ng pendant gr oup
Bulk Density of mol di ng powder
Chemical Resistance
Coeffi ci ent of Fri cti on
!dhOl
, gfl
Coeffi ci ent of Thermal Expansi on
Li near expans i on
Aver age val ues f or t emper at ur e i ndi cat ed
~23
>23
20- 100
1 0 0 - 1 5 0
1 5 0 - 2 1 0
K-
Cohesive Energy Density
Comonomer Content
Compressive Strength Properties
MOdldUS
St r engt h
D3307, ISO12086-1
F781
Se e Not e 1
3 3 5 Se e No t e 2
1250 Se e No t e 3
Exc e l l e nt Se e No t e 4
D 1 8 9 4 0. 25
D 6 9 6
1 2 x 10-5
1 7 x 10-5
2 o x 10-5
wt.% I R
MPa
MPa D 695
See Taber Abrasi on
Se e Not e 1
D 2 1 1 6
D 3 3 6 8
D3296,F546
167 Se e Not e 2
1230-1250 See Not e 3 7
1 5 Exc e l l e nt See Not e 4 1 5
7 0. 27- 0. 67 5,7,15
5 . 7 x 1 0 -5
9 . 3 x 1 0 -5
1 1
1 1
1 1
3 6 2 4
1 0 - 1 5 Se e No t e 4 11,lO
9
9
23. 7- 25. 8 Se e Not e 3 7
Notes page V-44; References page V-45
VI42 PHYSICAL CONSTANTS OF FLUOROPOLYMERS
Property Units
ASTM
or other
methods Vahle
P F A
R e ma r k s Refs. Vahle
FEP
R e ma r k s Refs.
- 251C 251 9
- 196C 4 1 4 1 1
- 160C 2 0 7 9
2 3 C 1 5 9
5 5 C 1 1 9
100C 3 . 4 9
Continuous Use Temperature See Service Temperature
Creep
Tens i l e cr eep modul us
2 5 C
2 5 0 C
MPa
2 7 0 1 1
4 1 1 1
Critical Shear Rate for Melt Fracture
Critical Surface Tension
Deformation Under Load
Density
Depolymerization Rate
SC
% Def. D621
g/cm 3 = Mg/m 3
3-50 Se e Not e 3 6 2-20 See Not e 3 6
17. 8- 18. 6 See Not e 3 1 5
7 0 . 5 8
1 1 2. 12- 2. 17 9
0. 36- 0. 41 See Not e
2. 12- 2. 17
See Ther mal Degr adat i on
Electrical Properties
Di el ect r i c cons t ant
At 60 Hz to 2 GHz
At 1kHz to 1GHz
At 240 GHz
Di el ect r i c s t r engt h
D 1 5 0
2 . 1 9
1 1
1 1
1 1 13-100 See Not e 6 1 5
1 1 5 0 0 - 4 0 0 0
2. 06
2. 049
78. 8 ( on 0. 25 mm f i l m)
2 0 0 0
kV/mm
V/mil
D 1 4 9
D 1 5 0 Di s s i pat i on f act or
60 Hz to 1 MHz
At 1kHz
At IoOkHz
At 1 MHz
At 1OMHz
At I GHz
At 3 GHz
At 1OGHz
A t 240GHz
Sur f ace ar c r es i s t ance
Sur f ace r esi st i vi t y, 100% RH
Vol ume r es i s t i vi t y, dr y
At 50% RH
< 0. 0001
1 1 < 0. 0001
0. 00025
11
0. 0005
1 1 O.QOll
0. 0012
0. 0007
1 1
> 300
1 0 106
0. 000027
15
0.00008
1 5
0.00115
1 5
1 5
s D 4 9 5
ohmslsq D 2 5 7
0. 00124
> 300 Se e No t e 7
> IO
Se e Not e 7 9
9
ohm cm D 2 5 7 1 0 >108 9
Flammability
Al so see l i mi t i ng oxygen i ndex uL94 VE-0 Se e Not e 8 1 1 VE-0 Se e Not e 8 6
D 7 9 0 Flexural Modulus
At -268C
At - 196C
At - 101C
At 23C
At 55C
At 100C
At 200C
GPa
GPa
GPa
MPa
MPa
MPa
MPa
5. 31
4. 69
3. 24
1 1 655
3 4 5
110
1 1 4 1 . 4
15
655-690
55-69
50000-500000 See Note 9
No br eak
See Heat of Combust i on
Flex Life
Flexural Strength
Fuel Value
Fl exes MIT
D 7 9 0
11 5000-30000 Se e No t e 9 2
No br eak
Hardness
Durometer
Rockwel l
Scal e val ue D 2 2 4 0 D63-65 1 0 D55-66
Scal e val ue D 7 8 5 560 R 2 5
10,9
Heat Capacity See Speci f i c Heat
Physical Constants of Melt Processible Fluorocarbon Polymers PFA and FEP v/43
units
A ST M
ix other
methods Val ue
PFA
Remarks Refs. Vahe
FRP
Remarks Refs.
Heat Deflection Temperature
At 0. 455 MPa ( 66psi )
At 1. 82 MPa ( 264psi )
C
C
D 6 4 8
63-80
48-50
Heat of Combusti on
Heat of Fusi on
tmpact Strength
Lamellar Thickness
Li mi ti ng Oxygen Index
MUkg 5 . 4
nm
% Oxygen D 2 8 6 3 >95 1 1
Mel t Vi scosi ty
By capi l l ar y rheometer kPas
Mel t f l ow r at e dg/min
Ener gy of act i vat i on f or mel t f l ow kJ/mol
D2116
4-21
D 3 3 0 7 1-18
D 2 1 1 6
4 3 . 1
Mel ti ng
Mel t i ng poi nt
C
%
Kibar
kJ/kg
302-306
Vol ume expansi on dur i ng mel t i ng
I ncr eas e of mel t i ng poi nt wi t h pr es s ur e
Lat ent heat of f us i on D S C 21-26
Mol ecul ar Wei ght Al so see Mel t Vi scosi t y
20000&45OCOO
Parti cl e Si ze ( aver age di amet er )
Di sper si on Pol ymer 0. 1
Permeability to Gases
Car bon di oxi de
Oxygen
Ni t r ogen
ng cm/m2-s
Phase Diagram
Processing Temperature
PV Li mi t
3 7 0 - 3 9 5
Radi ati on, Ef f ect s of
degr adat i on i n ai r
C
Pam-s
psi tI/min 5OcG
Mai nt ai ns Tens i l e pr oper t i es
bet t er t han does PTFE
Refractive index
Resi sti vi ty
Service Temperature
II::
C
D 5 4 2 1. 35
Se e El e c t r i c a l Pr ope r t i e s
- 200 t o 260
So/vents N o n e
Speci fi c Gravi ty See Densi t y
Specific Heat
2 0 C
2 5 C
100C
150C
2 6 0 C
kJkg/K D S C
Taber Abrasi on
Tensi l e Strength Properti es
Modul us
At 23C
Yi el d st r ess
At 23C
At 250C
g/MHz
MPa
CS- 17 wheel ;
1OOg l oad
D 6 3 8
MPa
13-15 Se e Not e 3
3.5-4 Se e Not e 3
Se e Not e 3 I
Se e Not e 3 I
1 1
See Mel t i ng
See Toughness
See Not e 3 6
See Not e 3 1 1
See Not e 1 0 6
See Not e 3 1 1
I
11
Se e No t e 4
70-77
51-57
33-53
9 5
1. 62 x 10-3M-3.4
8-50
0.8-18
4 6
2 5 3 - 2 8 2
8
0. 725 t o 1.74C
per MPa
2 4 . 3
25OOCG6OOOOO See Not e 3 1 7
0.1
2 7 3
6 3 7
9 1
Se e Not e 3 3
See Not e 3
See Not e 3
See Not e 1 0
See Not e 1 1
See Not e 3
See Not e 1 2
See Not e 1 3
9,7
9 . 7
1 8
6
6,1,12
6
9
9
9
6
1 1
1 0
1 1
11,7
1 0
2 2
320-380 6
10 t o 100 t i mes be t t e r
thanFTFE See Not e 1 4 1 5
1. 344 1 1
- 250 t o 206 9,7
N o n e See Not e 4 1 5
1. 09 9
1. 17 9
1 . 3 9
1 . 5 9
4 See Not e 3 9
1 1 1 2 See Not e 3 9
1 1
Notes page V - 44; References page V- 45
Vf44 PHYSICAL CONSTANTS OF FLUOROPOLYMERS
Property Units
AS T M
or other
methods VdW
P F A
R e ma r k s Refs. Value
FEP
R e ma r k s Refs.
Tens i l e s t r engt h
At - 196C
At 23C
At 250C
El ongat i on at br eak
At - 196C
At 23C
At 250C
Thermal Conducti vi ty
- 253C
- 129 t o 182C
23C
Thermal Degradati on
Ent hal py of depol ymer i zat i on
Rat e of depol ymer i zat i on
Toughness
Izod i mpact s t r engt h, not ched
- 196C
- 54C
23C
Transitions
Al pha (Gl ass I)
Beta
Gamma (Glass II)
Act i vat i on ener gy f or change
of f r equency ( i n Hz) of l oss
peak wi t h t emp
Al pha (Gl ass I)
Bet a ( cr ys t al l i ne r el axat i on)
Gamma (Glass II)
Effect of temperature on the
f r equency of peak l oss
Gamma (Glass II)
Uni t Cell Phase II is similar to PWE 23
Vi s c os i t y See Mel t Vi scosi t y
Water Absorpti on % incr. i n wt . D570 0. 004 7 <O.l 9
Wear Factor ingmin/ft/lb/lx 700-1800 1 0
Weatherabi l i ty Exc e l l e nt 1 0 Exc e l l e nt 9
%
MPa
129 1 1
28-31 See Not e 3 1 1 14. 5- 21 See Not e 3 9
12- 14 See Not e 1 5 1 1
8 1 1
260- 300 1 1 240- 300 See Not e 3 9
480- 500 1 1
WltnK Cenco Fi t ch
Cl77
%h
J/m
C
D256
Si mi l ar t o PlFE
64
No br eak
1. 4 9
2. 4 9
0. 209 7
log(%/h) = 10. 08
- 131 kU(2.303RZ'j
See Not e 16 9
1 1
1 1
2. 9
No br eak
1 5
9
70- 126, 0- 15 mol% HFF
See Not e 3 1 6
-7oto - 1 0 See Note 3 1 6
- 90 1 6
80 8
1 8 8
log F=22.43-76M/(2.303 RZJ
talc from data 8
in Ref.
NOTES
1. Comments on ASTM and IS0 standards for
fluoropolymers are in Note 2 for the table on PTFE.
2. The values are estimated based on high-spot work on
degradation of the polymers.
3. The exact value depends on the type or grade of
polymer that is being used.
4. PFA and FEP are insoluble in all common solvents
and are highly resistant to essentially all common
chemicals (see Ref. 1, 2, and 15). They are
however, attacked by molten alkali metals, elemen-
tal fluorine, and pure oxygen at elevated tempera-
tures. Also, they can react, under some conditions,
with alkaline earth oxides and finely divided
metals such as aluminum or magnesium at
elevated temperature. Solutions containing 0.1 to
2% FEP were obtained in perfluorokerosene
Physical Constants of Modified Poly(ethylene-co-tetrafluoroethylene) VI45
5.
6 .
7 .
8 .
9 .
1 0 .
1 1 .
C2iFa (FCX-412) in the temperature range 290-
310C.
Calculated from data in Ref. 6. The melt flow rate
was determined using standard conditions at 372C.
Determined by 3.0 x IR Ratio. The IR ratio is the
Ref. 3 gives melting temperature, T,, as a function
absorbance at 980 cm- (10.2 pm)/absorbance at
2350 cm- (4.23 urn) (see Ref. 1, 2).
of wt.% comonomer, X, and lamellar thickness, L.
Thickness is from 0.025 to 2.5 mm. The value
decreases with increasing thickness.
No carbon track is formed (see Ref. 7).
This numerical rating for flame spread is not
intended to reflect hazards presented by this or any
other material under actual fire conditions.
The MIT flex test is run with a thickness of
0.254 mm.
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
D.
Y. Akatsuka, M. Noshiro, Y. Jitsugiri, Reports Res. Lab. Ashai
Glass Co., Ltd., 26 [2] 111 (1976); also, Paper PO-~ at the 8th
International Symposium on Fluorine Chemistry, Kyoto,
Japan, Aug. 26, 1976.
M. I. Bro, B. W. Sandt, US Patent 2, 946, 763.
J. P. Colson, R. K. Eby, J. Applied Phys., 37, 3511,
(1966).
DuPont Polymer Products Department, Technical Information
on PFA, 7119185.
DuPont Polymer Products Department, Teflon@ PFA Product
Guide, Bulletin E-33272-2.
DuPont Polymer Products Department, Extrusion Guide for
Melt Processible Copolymers and its Supplement, Bulletins
E-41337-1 and E-41338-1.
DuPont Polymer Products Department, Technical Services
Laboratory, Personal Communication.
R. K. Eby, F. C. Wilson, J. Applied Phys., 33,2951-55 (1962).
S. V Gangal, (with 68 references), in: Kirk-Othmer (Ed.),
Encyclopedia Chem. Tech., vol. 11,3rd ed., Wiley, New York,
1980, p. 24.
R. L. Johnson (with 19 references), Tetrafluoroethylene
Copolymers with Perfluoroalkoxy Pendant Groups, in Ency-
clopedia of Polymer Science and Technology, Supp. No. 1
(1976).
R. L. Johnson (with 20 references) in: Kirk-Othmer (Ed.),
Encyclopedia Chem. Tech., vol. 11,3rd ed., Wiley, New York,
1980, p. 42.
12. W. J. Koros, J. Wang, R. M. Felder, J. Appl. Polym. Sci., 26,
2805 (1981).
13. H. A. Larsen, G. R. Dehoff, N. W. Todd, Modern Plastics,
36 (8), 89 August, 1959.
14. V. J. Leslie, and L. S. J. Shipp, Structure Property Relation-
ships of Fluoropolymers, IX Int. Symp. of Fluorine Chem.,
Avignon, Sept. 3-7, 1979.
15. D. I. McCane, (with 72 references), Encyclopedia of Poly-
mer Science and Technology, vol. 13, Wiley, New York,
1990, p. 654.
16. N. G. McCrum, B. E. Read, G. Williams, Anelastic and
Dielectric Effects in Polymeric Solids, Wiley, New York,
1967.
17.
18.
19.
20.
21.
R. E. Putnam, (with 12 references), in: R. B. Seymour, G. S.
Kirshenbaum (Eds.), High Performance Polymers: Their
Origin and Development, Elvesier, 1986, p. 279.
C. A. Sperati, Results cited previously in Polymer Hand-
book, 2nd (Ed.), page V-36.
H. W. Starkweather, Jr., Macromolecules, 10, 1161 (1977).
Starkweather, H. W., Jr., Zoller, P and Jones, G. A., J. Polym.
Sci., Poly. Phys. Ed., 22, 1431 (1984).
H. W. Starkweatber, Jr., J. Polym. Sci., Polym. Phys., Ed., 20,
2159 (1982).
22. J. J. Weeks, I. C.. Sanchez, R. K. Eby, C. I. Poser, Polymer, 21,
325 (1980).
23. J. J. Weeks, R. K. Eby, E. S. Clark, Polymer, 22, 1496 (1981).
The equation is
l/Tm = 1.622 x 1O-3 + 2.52 x 10-3X(1 +X)
+ (1.92 x lo-/L)
12. The rate of increase of the melting point decreases
with increasing pressure.
15. Mechanical properties of PFA at elevated tempera-
ture but below its melting point generally are
13. Inconsistencies in the results from various labora-
superior to those of PTFF! at the same temperature.
tories on heat of fusion of PTFE and FEP have not
16. Calculated from data in Ref. 9.
yet been resolved. This value is for a sample of FEP
with a density of 2.148 Mg/m3.
14. Moderate crosslinking can occur to offset degrada-
tion (see Ref. 15).
PHYSICAL CONSTANTS OF MODIFIED POLY(ETHYLENE-co-TETRAFLUOROETHYLENE) -[CH2-CH2-CFZ-CF2]-
Commercially useful copolymers of ethylene and tetra- suitable for long term use (Ref. 7). One key requirement,
fluoroethylene became feasible when it was discovered for example, is the ability to withstand exposure at
that the use of a small amount of a modifier, often a high temperature without rapid embrittlement. The
termonomer, resulted in polymers with properties amount of modifier is very low and the exact amount
Notes page V- 48; References page V- 48
V/46 PHYSICAL CONSTANTS OF FLUOROPOLYMERS
and nature of a modifier has been kept proprietary by each
manufacturer, and may be different for different grades
within a product line.
The commercial modified poly (ETFE) materials are
essentially alternating copolymers (Ref. 10). In molecular
formula, they are isomeric with poly(vinylidene fluori-
de)(PVDF), and can be considered equivalent to a PVDF
that has a head to head, tail to tail structure. Many
important physical properties of modified ETFE copoly-
mers, however, are very different from and superior to those
of available PVDF materials. (These properties do not
include the remarkable piezoelectric and pyroelectric
performance of PVDF.)
Property Units
AS TM
or other
methods Value Remarks Refs.
ASTM or IS0 Standards
Molding and extrusion powders D3159,
ISO12086-1
See Note 1
Excellent
0.4
1,2,4
5
Chemi cal Resi stance
Coefficient of Friction D1894
Coefficient of Thermal Expansion
Linear Expansion (average values
for temperature indicated)
20-30C
50-90C
140-180C
D696
K-
9 x 10-5
9.3 x lo-s
14 x lo-s
Compressi ve Strength Properti es
M o d u l u s
Strength
Stress at 1% deformation
Yield strength
MPa
MPa
MPa
MPa
D695
860
50
10.3
19.3
Continuous Use Temperature See Service Temperature
Creep
Flexural creep modulus GPa
SC
D674 5. 5 aft er 1OOh
Critical Shear Rate
For melt fracture
200- 10000
Deformation Under load % D621 4.11
Density
Crystalline (from X-ray and IR data)
After melting and recrystallization
Melt at processing temp.
1.9 5
1.7 6
I
1.3 3
Dielectric Constant See Electrical Properties
Dielectric Strength See Electrical Properties
Dissipation Factor See Electrical Properties
El ectri cal Properti es
Dielectric constant
At 60Hz to 1 MHz
A t 1kHz
& D150
Dielectric strength
kv/mm
kvlmm
vlmil
D149
D150
2.5
2.6
See Note 2
5
5
5
5
1
1
1
See Note 3
See Note 4
3
5
5
59 at 0.25 mm thickness
16 to 80
400 to > 2000
3
4
4
See Note 5
See Note 5
Dissipation factor
A t 1kHz
Surface arc resistance
Surface resistivity, 100% RH
Volume resistivity, dry
At 50% RH
0.0008
75-110
> 104
5
S
ohmslsq
ohm cm
D495
D257
D257
See Note 3
4
> 106 5
Physical Constants of Modified Poly(ethylene-co-tetrafluoroethylene) V/N
Property Units
AS TM
or other
methods Value Remarks Refs.
Flame Rating
Also see Limiting Oxygen Index v-o See Note 6 3
Flex life flexes
MPa
UL94
MI T
D790
5500- 12000 See Note 7 4
Flexural Modulus
At 23C 827- 1380 133
Hardness
Duromet er
Rockwell
Scale value
Scale value
C
C
MJ/kg
D2240
D785
D 648
D70 3
R20 5
Heat Deflection Temperature
At 0.455 MPa (66 psi)
At 1.82 MPa (264 psi)
104
74
5
5
Heat of Combustion
Heat of Fusion
impact Strength
Limiting Oxygen Index
low Temperature Fmbrittlement
5
Melt Viscosity
By capillary rheometer
Melt flow rate
Melting
Melting point
Heat of fusion
% Oxygen
C
Pas
dglmin
C
kJ&
D2863
D746
D3159
D3159
DSC
13.7
See Melting
Se e To u g h n e s s
30
<-100
5
4
(0.7-10) x lo3 See Note 3 3
3.7-16 See Note 3 3
225-270 6
46.1 2
Molecular Weight (5-12) x lo5 See Note 8 1 0
Permeabi l i ty to Gases
Hel i um
Carbon dioxide
Oxygen
Nitrogen
Gas transmission rate
Water vapor
m3(STP) m/s/m*/Pa (x 10)
405
1 1 3
45
1 4
ng cm/m*/s
E96 752 5
Processi ng Temperature
PV limit
Radi ati on, Effects of
Refractive Index
Resi sti vi ty
Servi ce Temperature
Specific Gravity
Specific Heat
C
Pa m/s
ng
C
kJikg/K
325- 345
< 70000
D542 1.403
See Note 9
See Electrical Properties
< - 100 to 150
See Density
1. 9-2. 0
658
5
Tensi l e Strength Properti es
M o d u l u s
At 23C
Yield stress
At 23C
Tensile strength
At 23C
Elongation at break
At 23C
D638
MPa
MPa
MPa
%
830 5
21.5
38-48
100- 350
Thermal Conductivity W/m/K Cl77 0.238
See Note 10
See Note 10
56
W
6
Toughness
Izod impact strength (notched)
- 54C
23C
N
J / m
D256
106- 190
No break
See Note 10 6
6
Not es page V- 48; References page V- 48
VI48 PHYSICAL CONSTANTS OF FLUOROPOLYMERS
Property Units
AS TM
or other
methods Value Remarks Refs.
Trans i ti ons
Alpha
Gamma
Unit Cell
a
b
C
7
vi scosi t y
Water Absorption
Wear Factor
Weatherability Excellent 1
C
C
A 9. 6 S e e Note 11 5
A 9. 25
A 5. 0
Degrees 9 6
% increase in wt.
Pa-
in 3 min/ft/lb/hr
145 at 100Hz
- 120at 1Hz
1 0
1 0
See Melt Viscosity
D.570 <0. 02 3
6000 x lo- See Note 12 5
NOTES
1. See additional comments in Note 2 for the table on
PTFE.
2. Extensive tables with data on the resistance to a
wide variety of chemicals are given in the refer-
ences.
3. The exact value depends on the particular type or
grade of polymer that is being used.
4. Tested at 13.8 MPa and 50C.
5. The value decreases with increasing thickness.
6. This numerical rating for flame spread is not
intended to reflect hazards presented by this or any
other material under actual fire conditions.
REFERENCES
1. DuPont Polymer Products Department, Tefzel@ Design
Handbook, Bulletin E-31301-1.
2. DuPont Polymer Products Department, Tefzel@ Chemical
Use Temperature Guide, Bulletin E- 18663- 1.
3. DuPont Polymer Products Department, Extrusion Guide for
Melt Processible Copolymers and its Supplement, Bulletins
E-41337-1 and E-41338-1.
4. DuPont Polymer Products Department, Tefzel@ Product Bul-
letin, E-07229.
5. R. L. Johnson with 24 references, in Encyclopedia of
Polymer Science and Technology, Supp. no. 1 (1976)
p. 269.
7. The film tested is 0.25 mm thick.
8. In dibutyl adipate at 250C.
9. Poly(ETFE) can be crosslinked by ionizing radia-
tion.
10. The exact value depends on the particular type or
grade of resin used as well as the method used to
prepare the test specimen.
11. The unit cell is believed to be either orthorhombic or
orthoclinic.
12. Wear factor is decreased to 16 x 10 lo by use of glass
fiber filled polymer.
6. R. L. Johnson with 24 references, in: Kirk-Othmer (Ed.),
Ency. Chem. Tech. vol. no. 11, 3rd ed., Wiley, New York,
1980, p. 35.
7. R. E. Putnam Development of Thermoplastic Fluoropoly-
mers, in: (Eds.) R. B. Seymour, G. S. Kirshenbaum, High
Performance Polymers: Their Origin and Development,
Elsevier 1986, p. 279.
8. J. C. Reed, J. R. Per ki ns, Pr esent ed at 21st I nt er nat i onal Wi r e
and Cabl e Symposi um, At l ant i c Ci t y, NJ Dec. 6 1972.
9. H. W. St arkweat her, J. Pol ym. Sci . , Pol ym. Phys. Ed. , 11, 587
(1973).
10. C. Wu, W. Buck, B. Chu, Macromolecules, 20, 98 (1987).
E. PHYSICAL CONSTANTS OF POLY(VINYLIDENE FLUORIDE) -(CHpCF2)-
Poly(vinylidene fluoride), PVDF, has been used since addition, it is now known that PVDF has very unusual
the early 1960s because of its chemical resistance and valuable piezoelectric and pyroelectric properties (see
combined with very good mechanical properties. In Ref. 12).
Physical Constants of Poly(vinylidene fluoride) v/49
Property Units
AS TM
or other
methods Value Remarks Refs.
Abrasi on Resi stance
S a n d
Tabor
ASTM Standards
Material
Molding and extrusion powders
Rods, tubes, and pipe lining
Chemi cal Resi stance
Coefficient of Friction
Coefficient of Thermal Expansion
Linear expansion
25 to 50
Compressi ve Strength Properti es
M o d u l u s
Strength
Conformation
u-form (also termed Type II)
p-form (also termed Type I)
y-form (also termed Type III)
&form
Continuous Use Temperature
Crystal Forms
Density
Dielectric Constant
Dielectric Strength
Di ssi pati on Factor
El ectri cal Properti es
Dielectric constant
At 60Hz
A t 1kHz
At 1MHz
A t 1GHz
Dielectric strength
Dissipation factor
60 Hz
A t 1kHz
At 1 MHz
At 1 GHz
Surface arc resistance
Volume resistivity, dry
At 50% RH
Flammability
Also see Limiting Oxygen Index
Flexural Modulus
At 23C
Flexural Strength
Fuel Value
Hardness
Duromet er
Rockwell
pm-
mg/lOOO cycles
D968
CS-17 wheel
4.0 9
6-12; 7.0-9.0 85
D3222
F491
See Note 1
Generally excellent
0.48; 0.14-0.17
See Note 2
D1894
D696
K-l
6.9
(7.9-14.1) x 10-5 9
MPa 1000-1400
MPa 55-100
1 2
1 2
1 2 See Note 3
Trans-gauche-trans-gauche
All tram, i.e. planar zig-zag
C See Service Temperature
See Conformation
1.75-1.78
See Electrical Properties
See Electrical Properties
See Electrical Properties
g/cm3 = Mg/m3 1 2
6 D150
8.4- 13.5 1 2
7. 46-13. 2 1 2
6.0-7.6 1 2
2.9 5
260-950 S e e Note 4 9 kV/mm D149
D150
0.049, 0.012-0.019 9.12
0. 013- 0. 019 1 2
0.15-0.22 1 2
0.110 9
50-60 9 D495
D257 2 x 104 9
UL94 vo See Note 5 1
S
ohm cm
D790
1200-1800
59-75
See Heat of Combustion
9
9 D790 See Note 6
Scale value
Scale value
D2240
D785
70-80 9
Notes page V- 51; References page V- 52
V/SO PHYSICAL CONSTANTS OF FLUOROPOLYMERS
Property uni ts
AS TM
or other
methods Value Remarks Refs.
Heat Capacity
100K
lS(JK
230K
250K
J/kg/K 13
443.5
618.5
891.8
785.6
C
C
C
C
D648
112-140, 150
112-140, 150
80-90, 100
80-90, 100
9,12
9,12
MJ/kg
But/lb
14.9
6 400
See Melting
Se e To u g h n e s s
I
7
See Note 7
% oxygen D2863 44
9,7
See Note 8
D1238 5-180 at 265C 1 2
C
PC/N
D3418 154- 184 5
d(31) = 21-28
d(32) = 2.3
d(33) = - 32
1 2
Pol ymorphi c Phases Four documented, others
See also Conformation s us pe c t e d
1 2
C
uC/K/m *
rig
C
D542
200-300
27-40
Exceptionally resistant
to degradation
1.42
See Electrical Properties
150
See Note 9
1 2
512
512
2
2
0.9-1.6 in DMF at 125C
3.03 x 10m5 MW.70,
talc. from Ref.
1.93 x 1O-4 MW.68,
in dimethyl acetamide
See Note 10
1 2
I
5
See Notes 8 and 11
See Note 8 2,15
Specific Gravity D792
Soluble in selected solvents;
swells in acetone
1.75-1.80
kJ/kg/K DSC 1.26-1.42
0.85
28.4
50.3
80.6
93.1
See Note 12
5
11
Heat Deflection Temperature
At 0.455 MPa
At 66psi
A t 1.82MPa
At 264 psi
Heat of Combustion
Heat of Fusion
Impact Strength
Infrared Spectra
Limiting Oxygen index
Mel t Vi scosi ty
Melt flow rate
Melting
Melting point
Piezoelectric Coefficient
Processi ng Temperature
Pyroelectric Coefficient
Radi ati on, Effects of
Refractive Index
Resi sti vi ty
Servi ce Temperature
Sol uti on Vi scosi ty
Intrinsic viscosity
Solvent Absorption
Sol vents
Specific Heat
10K
1OOK
200 K
300 K
340 K
Speed of Sound
Longitudinal
Shear
m/S
13
13
1930
715
8
Property Units
ASTM
or other
methods
Physical Constants of Poly(vinylidene fluoride)
Value Remarks
v/s1
Refs.
Tensi l e Strength Properti es
M o d u l u s
At 23C
Yield stress
At 23C
At 100C
Tensile strength
At 23C
At 100C
Elongation at break
At 23C
At 100C
Thermal Conductivity
Toughness
Izod impact strength (notched)
23C
Izod impact strength (unnotched)
Trans i ti ons
u
P
Y CT,)
Vi scosi ty
Water Absorption
Weatherability
D638
MPa
MPa
MPa
MPa
MPa
%
W/m/K
W/m/K
J/m 160- 530 8
N/ m 1700-3 100 5
C
C
C
% increase in wt.
Cl77
D256
1340-2000 See Note 6 5
36-59 See Note 6 5
19- 23 See Note 6 5
36-56 See Note 6
19- 23 See Note 6
25-500 See Note 6 5
400-600 See Note 6 9
loo-O.126
0.1-0.13
Dilatometry
130 at 1OOkHz
0 at 1OOkHz
- 4 0
- 30 at 100 kHz
D570
See Melt Viscosity and
Solution Viscosity
0.03-0.06
Superb
5
9
5
1 4
1 4
5
1 4
1 2
1 2
NOTES
1 .
2.
3.
4.
5.
Comments on ASTM and IS0 standards 6. The exact value depends on the particular type or
for fluoropolymers are in Note 2 for the table on grade of resin used as well as the details used to
PTFE. make the test specimen.
PVDF is resistant to most inorganic and organic
chemicals at room temperature. It is, however,
especially sensitive to attack by amines (Ref. 3).
References (6), (14), and (15) have many pages of
tables with information on the specific effect of
different chemicals.
Many of the useful properties of PVDF stem from
its existence in various conformations. The topic
is not amenable for detailed presentation in
tabular form, but it is discussed in depth in
Ref. (12).
The value decreases with increasing thickness of the
specimen being tested.
This numerical rating for flame spread is not
intended to reflect hazards presented by this or any
other material under actual fire conditions.
7. Each conformation has its characteristic infrared
spectra. See Ref. (9) for a general spectra and
Ref. (12) for a discussion and references to the
extensive literature.
8. Good solvents are dimethyl acetamide, dimethyl
formamide, hexamethyl phosphoramide, and
dimethyl sulfoxide. Some highly polar solvents such
as ketones and ethers, are absorbed.
9. PVDF can be crosslinked by ionizing radiation
resulting in an increase in high temperature modulus
and very little degradation.
10. Calculated from data in Ref. (12) at page 200.
11. Reference (14) has 23 pages of Tables with informa-
1 2 .
tion on the effect of many different chemicals.
Reference (11) has extensive tables for PVDF at
temperatures from 10 to 340 K.
References page V - 52
v/52.
PHYSICAL CONSTANTS OF FLUOROPOLYMERS
REFERENCES
1.
2.
3.
4.
5.
6.
7.
F.
Machine Design, April 19 (1981) p. 128.
W. S. Barnhart, and N. T. Hall, Poly(vinylidene fluoride) with
18 references, in: Kirk-Othmer (Ed.) Encyclopedia of
Chemical Technology, Vol. 9, 2nd ed., Wiley, New York,
1966, p. 840.
M. I. Bro, J. Appl. Polym. Sci., 1, 319 (1959).
J. E. Dohany, A. A. Dukert, S. S. Preston III, Vinylidene
Fluoride Polymers (with 109 references), in: Encyclopedia
of Polymer Science and Technology, 14, (1965) p. 600.
J. E. Dohany, and L. E. Robb, Poly(vinylidene fluoride) (with
147 references), in: Kirk-Othmer (Ed.) Encyclopedia of
Chemical Technology, vol. no. 11, 3rd ed., Wiley, New
York, 1980, p. 64.
ForaflonE Polyvinylidene Fluoride, Product Bulletin from
PCUK (with 68 references classified as to properties covered),
Produits Chimiques Ugine Kuhlmann, now Atochem, Inc.
R. L. Johnson, in: Encyclopedia of Polymer Science and
Technology, Supp. No. 1 (1976) p. 269.
PHYSICAL CONSTANTS OF AMORPHOUS FLUOROPOLYMERS
8.
9.
10.
11.
12.
13.
14.
15.
KF Polymer@ Polyvinylidene Fluoride, Product Bulletin from
Kureha Chemical Co., Ltd.
Kynara Poly(vinylidene fluoride), Product Bulletin from
Pennwalt Corporation.
Kynar@ Piezo Film, Technical Manual, lo-M-1 l-83-M, Penn-
walt Corporation.
W. K. Lee, C. L. Choy, J. Polym. Sci., Polym. Phys. Ed., 13,
619 (1975).
A. J. Lovinger, Poly(vinylidene fluoride) (with 368 refer-
ences), Chapter 5, in: Bassett, D. C. (Ed.), Developments
in Crystalline Polymers-l; Applied Science Publishers,
London, 1982.
J. E. Mark (Ed)., Physical Properties of Polymers Hand-
book, AIP Press, Woodbury, NY, 1996.
SolefB Solvay PVDF, Product Bulletin from Solvay & Cie.
Tables of Chemical Resistance of Sole@ PVDF, Bulletin
from Solvay & Cie.
Two major families of amorphous fluoropolymers have
been developed. Both rely on in-chain rings to reduce
crystallinity in the homopolymer and in copolymers with a-
olefins such as tetrafluoroethylene and chlorotrifluoroethyl-
ene. One incorporates 2,2-bis-trifluoromethyl-4,5difluoro-
1,3-dioxole (PDD) in copolymers with tetrafluoroethylene
or chlorotrifluoroethylene (TEFLON@ AF) and the other is
based on monomers such as Soxaperfluoro-1,6-heptadiene,
which when polymerized, produce the structure below
(CYTOPB). Amorphous fluoropolymers are soluble in a
variety of fluorinated solvents and can be cast into thin films
as well as conventionally melt processed. Optical properties
are a significant market utility. Cost is a major considera-
tion, however, compared to crystalline fluoropolymers.
TEFLON@ AF CYTOP@
-y-y-CF-CF2-
9 ,CF2
CF2
Property Units
A S T M
or other
methods
TEFLON 8 AF CYTOPS
Vallle Remarks Ref s. Value Ref s.
1600 grade 2400 grade
Mel t vi scosi t y
2 5 0 C
3 5 0 C
Chemical Properties
Wat er abs or pt i vi t y
Chemi cal r es i s t ance
Sol ubi l i t y
Cont act angl e, wat er
Critical surface energy
Cr i t i cal s ur f ace t ens i on
% D570 <O.Ol <O.Ol
Deg
104 105
dynes/ cm 15. 6- 15. 7 15. 6- 15. 7
Yc
mNN 1 2 . 1 1 1 . 9
Yom
InNiM 1 3 . 9 1 3 . 8
Densi t y g/cm 3 D 7 9 2 1. 78 1. 67
El ectri cal Properti es
Di el ect r i c s t r engt h
Di el ect r i c cons t ant
1 MHZ
1 GHz
13.6GHz
Pas D 3 8 3 5 1 0
kv/(O.l mm)
kvlmm
D 1 4 9 2 . 1 1 . 9
D 1 5 0
1 . 9 3 1. 89
1. 934 1. 904
1. 93 1. 897
1. 927 1. 89
2650
5 4 0
4 co.01 5
See Not e 1 4
See Not e 2 1 1
3. 10 110 4
1 0
3
1 2. 03 2
1 0
1 9 2
49 2.1-2.2 2
1
1
.
Physical Constants of Amorphous Fluoropolymers v/s3
Property Units
ASTM
or other
methods
TEFLON &AF CYTOPE
Value R e ma r k s Refs. Value Refs.
1600 grade 2400 grade
Di s s i pat i on f act or
1 MHz
1 GHz
13.6GHz
Sur f ace ar c r es i s t i vi t y
Vol ume r es i s t i vi t y
Fl ammabi l i t y, l i mi t i ng oxygen i ndex
Fractional free volume
Hardness
Rockwel l
Durometer
2 3 C
150C
2 2 0 C
Opti cal Properti es
Refractive index
dn/dt
Below T,
Above T,
We a t he r a bi l i t y
Opt i cal t r ans mi s s i on
St r es s opt i cal coef f i ci ent
Infrared spectra
Abbe number
Pe r me a bi l i t y c oe f f i c i e nt s
Oxygen
Ni t r ogen
Car bon di oxi de
Wat er vapor
Hel i um
Hydrogen
Met hane
Et bane
Et hyl ene
Tensi l e Properti es
Tens i l e s t r engt h, at br eak
2 3 C
150C
220C
El ongat i on, at br eak
2 3 C
150C
2 2 0 C
Tensile Modulus
Compr essi ve st r engt h
Compr essi ve modul us
Tens i l e s t r engt h at yi el d
Flexural modul us
2 3 C
2 0 0 C
2 2 0 C
Thermal Properties
Tr ans i t i on t emper at ur es
T, Y
P
6
The r ma l s t a bi l i t y
s
ohm cm
%02
(8-20) x 1O-5 (8-30) x 10m5
D150 0. 00012 0. 00012
0. 00018 0. 00024
0. 0002 0. 00035
D 4 9 5
D251
9 5 9 5
0. 327
4 7 x 10-4
180 2
>lO 2
4
8
D 7 8 5
D 1 7 0 6
1 0 3
77
7 0
9 1 . 5 1 0
1 0
7 5
6 5
ng D 5 4 2 1.31
c-l (x lo-c)
-71
- 329
Exc e l l e nt
% D 1 0 0 3 >95
B 4 . 5
1. 29 4 1. 34
- 78
- 378
Exc e l l e nt
>95
Exc e l l e nt
Se e Not e 3
4,6
See Note 4 4
Se e Not e 5 7
See Note 6 4
See Note 7
438
9 2 113
34000
130000
99 000
49 000
280 000
4 1 0 0 0 0
270 000
2 2 0 0 0 0
340 000
180000
350 000
9 0
34 000
4
4 CB
117000
MPa D 6 3 8 1 0
1 0
3 5 2
21
8
2 6
4
8
8
1540
90 D 6 3 8
1 7
8 9
MPa
MPa
MPa
psi
MPa
1550 A
3900 3600
1800
1000
1600
7 0 0
1 6
1 0
C
C
160
8 8
- 203
See Note 8 1 0 8 2
At lO*Hz 9
9
4 > 400 2 3 6 0
Notes page V- 54; References page V- 54
.
V/S4 PHYSICAL CONSTANTS OF FLUOROPOLYMERS
TEFLON 8 AF CYTOP E
Property
upper use temperature
Thermal expansion
Li near
Vol ume
Wei ght l os s i n ai r
after 1 hour at temp. 260C
3 6 0 C
3 8 0 C
4 0 0 C
4 2 0 C
Ther mal conduct i vi t y
Def l ect i on t emper at ur e
66 psi
264 psi
Speci f i c vol ume
Below T,
Above T,
Radiation effects
Charge storage effects
ASTM Value R e ma r k s Refs. Vallle Refs.
or other
Units methods 1600 grade 2 4 0 0 grade
C 2 8 5
C ( x 10-6) 14 8 1 4
c-l (x lo-e) 2 6 0 301 1 0
% NOIW
% 0. 29
% 0. 53
% 1. 94
% 8. 83
W/m/K 2 9 5 K 0. 116 1
D 6 4 8 1 0
156 2 0 0
154 174
1
cm3/g 0.548 f(1.22 x 10-4)T 0.570+(1.37 x 10-4)T
cm/g 0. 476 + (5.64 x 10 -4)T 0 . 4 2 8 +( 7. 75 x 1 0 -4)T
See Not e 9 5
See Note 10
NOTES
1 .
2.
3.
4.
5.
6.
See Refs. (2,3) for data on chemical resistance and
physical property performance in various solvents.
See Ref. (15) for types of solvents and degree of
solubility of amorphous fluoropolymers.
See Ref. (8) for optical transparency data.
Brewster = lo-l3 cm2/dyn.
See Ref. (10) for infrared spectral interpretation.
Abbe Number = (refractive index at sodium D line
minus l)/(refractive index at hydrogen F line minus
refractive index at hydrogen C line).
REFERENCES
1. W. H. Buck, P. R. Resnick, Teflon Af Technical Information
Bulletin H-52454- 1, DuPont; Wilmington, DE, 1993.
2. CYTOP Technical Bulletin, Asahi Glass: Yokohama, Japan,
1988.
3. M. H. Hung, P. R. Resnick, B.E. Smart, W. H. Buck, in: (ed);
J. C. Salamone, Polymeric Material Encyclopedia, CRC
Press, NY, 1996.
4. I. Pinnau, L. G. Toy, J. Membr. Sci., 109, No. 1, 125 (1996).
5. M. S. Jahan, D. R. Ermer, D. W. Cooke, Rad. Phys. Chem., 41
(l-2), 77 (1993).
6. H. W. Starkweather, Jr. P Avakian, R. R. Matheson, Jr.
J. J. Fontanella, M. C. Wintersgill, Macromolecules, 24
(13) 3853 (1991).
7. C. J. Drummond, G. Georgaklis, D. Y. C. Chan, Langmuir, 12
(ll), 2617 (1996).
8. J. H. Lowry, J. S. Mendlowitz, N. S. Subramanion, Opt. Eng.,
1992, 31 (9), p. 1962.
7.
8.
9.
1 0 .
9. s.
centiBarrier = lo- x (cm3(STP) cm/s/cm Hg/cm2.
T, of 2,2-bis(trifluoromethyl)-4,5-difluoro- 1,3-diox-
ole homopolymer is 330C. Glass transition
temperature is a strong function of comonomer
content.
See Ref. (5) for a discussion of radiation effects on
optical and physical properties.
See Ref. (12) for charge storage data of amorphous
fluoropolymers.
P. Andersson, 0. Andersson, G. Backstrom, Int. J. Thermo-
physics, 18 (l), 209 (1997).
10. T. C. Nason, T.-M. Lu, Thin Solid Films, 239 (l), 27 (1994).
11. P. Gunther, H. Ding, R. Gerhard-Multhaupt, Proceedings of
the 1993 IEEE Conference on Electrical Insulation and
Dielectric Phenomena, 197-202 ( 1993).
12. H. Ding, Proceedings of the 8th International Symposium on
Electrets (ISE 8), 89-94 (1994).
13. A. N. Hammoud, E. D. Baumann, E. Overton, I. T. Myers,
J. L. Suthar, W. Khachen, J. R. Laghari, IEEE Conference on
Electrical Insulation and Dielectric Phenomena, 549-554
(1992).
14. Teflon AF Amorphous Fluoropolymer Product Information
product brochure 2041038, DuPont Company, 10/92.
15. Teflon AF Amorphous Fluoropolymer Product Information
product brochure 231577B, DuPont Company, 10192.
16. CAS Subscription Database PLASPEC, accession nos.
400-11002 and 400-11003, (accessed Apr. 1977).
.
Physical Constants of Poly(chlorotrifluoroethylene) v/s5
C. PHYSICAL CONSTANTS OF POLY(CHLOROTRIFLUOROETHYLENE)
Poly(chlorotrifluoroethylene) (PCTFE) was the first of the that materials with molecular weight suitable for plastics
fluoropolymers to be made (Ref. 3). It was not until the applications became available.
work of W. T. Miller and his colleagues during the research
for the Manhattan (atom bomb) project (Ref. S), however, -[CFCl-CF2]-
Property Units
ASTM
or other
methods Value Remarks Refs.
ASTM and IS0 Standards
Material
Molding and extrusion powders D1430,12086- See Note 1
Film and sheeting
Chemi cal Resi stance
D3.595
Coefficient of Thermal Expansion
Linear expansion K-t
(average values for temperature indicated)
- 80 to 20C
20-50C
D696
See Note 2
4.5 x lo-s
7 x lo-s
4
Compressi ve Strength
Properties
M o d u l u s
Strength
Stress at 1% deformation
D695
6
6
MPa 1350
MPa 380
MPa 13.8 See Note 3
Continuous Use Temperature
Creep
Deformation Under Load
Density
C See Service Temperature
Very low Creep
6.86
1 0
8 % Def. D621
g/cm3 D792
2.10 Amorphous 1 0
2.12 Crystalline 1 0
2.15 1 6
El ectri cal Properti es
Dielectric constant
At 60 Hz, - 40C
At 60Hz, 25 C
At 60Hz, 170C
A t 1OOkHz
A t 100MHz
Dielectric strength
Dissipation factor
100Hz
A t 1kHz
Surface arc resistance
Surface resistivity, 100% RH
[megohms],
Volume resistivity, dry
At 50% RH
D150
2.2
2.6
3.2
2.9
2.5
15- 200 kV/mm D149
D150
S D495
ohm&q D257
ohmcm D257
See Note 4
0.02-0.06
0.025-0.027
360
105
See Note 8
See Note 8
1.2 x 108 6
Flammability
Also see Limiting Oxygen Index
UL94 VEO See Note 5 6
Flexural Modulus
At 23C
At 23C
At 100C
D790
MPa 1250
p s i 180000
MPa 14420
6
Not es page V- 57; References page V- 58
.
V/S6 PHYSICAL CONSTANTS OF FLUOROPOLYMERS
Property Units
ASTM
or other
methods Value Remarks Refs.
Flexural Strength MPa
p s i
D790 73.8
10700
Hardness
Duromet er
Rockwell
Scale value D2240 D75-80 6
Scale value D785 S85 1
Heat Capacity
80 K
200
300
320
J/kg/K DSC 900
278.7
625.7
859.5
906.7
Heat Deflection Temperature
At 0.455 MPa (66 psi)
At 1.82 MPa (264 psi)
D648
C 130 6
70 6
Heat of Fusion
impact Strength
I ntri nsi c Vi scosi ty
limiting Oxygen Index
mug
% Oxygen D2863
See Melting
Se e To u g h n e s s
0.9-1.7
100
Melt Viscosity
By capillary rheometer Pas 1-10 at 230C See Note 6 4
Melting
Melting point
Latent heat of fusion
C
km
Cal/g
D T A
DSC
210-215
1.2
3.6-8.4
Molecular Weight
See also Zero Strength Time 50000- 100000
150000-190000
Permeabi l i ty to Gases
Hel i um
Carbon dioxide
Oxygen
Nitrogen
Hydrogen
m3(STP) m/s/m*/Pa x lOI5
21.7
1.4
0.4
0.05
9.8
Processi ng Temperature C
7:
C
280-305
Radi ati on, Effects of
Refractive Index
Resi sti vi ty
Servi ce Temperature
D542
Little effect
1.435
-2OOto200
Sol uti on Vi scosi ty See Intrinsic Viscosity
Solvent Absorption Generally low
Sol vents None at room temperature
Specific Gravity See Density
Specific Heat
0C
211C
240C
kJ/kg/K 0.84
kJ/kg/K 1. 7-4. 6
kJ/kg/K 4.2
See Note 11
See Note 7
See Note 8
See Note 9
1
4
6
6
6
4
5
7
6
6
1 0
See Note 10
See Electrical Properties
6
6
6.10
See Note 2 6,7,10
See Note 11 4
See Note 7
4
4
4
Physical Constants of Poly(chlorotrifluoroethylene1 v/s7
Property
Tensi l e Strength Properti es
M o d u l u s
At 25C
Tensile strength
At 23C
At 125C
Elongation at break
At 23C
At 125C
Thermal Conductivity
At 3.5C
At 60.8C
Thermal Degradation
UIlitS
MPa
MPa
MPa
%
%
W/m/K
AS TM
or other
methods
D 638
Cl77
Value Remarks Refs.
14000 6
40
4
150
400
3.09 x 10-4 4
3.23 x 1O-4 4
Degrades at temperatures above See Note 12 4
260C
Toughness
Izod impact strength, notched
24C
Transitions
;
Y
Transmi ttance Properti es
Luminous transmittance
Haze
Vi scosi ty
Water Absorption
Weatherability
Zero Strength Time (ZST)
J / m D256 267 6
C
150 at 1 Hz See Note 13 1
90 at 1 Hz See Note 13 1
- 37 at 1 Hz See Note 13 1
% D1003 >90 See Note 14 6
% D1003 <4
See Melt Viscosity and
Solution Viscosity
% Increase in wt. D570 0.00 2
Excellent
S D 1430 200-750 See Note 6 and 6,lO
Note 8
NOTES
1 .
2.
3.
4.
5.
6.
Comments on ASTM and IS0 standards for
fluoropolymers are in Note 2 for the table on PTFE.
PCTFE is resistant to most inorganic and organic
chemicals at room temperature and to most
inorganic chemicals such as strong oxidizing agents
over a wide range of temperature. It is especially
useful in liquid oxygen service. References (4), (6),
and (10) have many pages of tables with information
on the specific effect of different chemicals.
The value is the stress at 0.3% deformation after
24h.
The value decreases with increasing thickness of the
test specimen.
This numerical rating for flame spread is not
intended to reflect hazards presented by this or any
other material under actual fire conditions.
The exact value depends on the particular type or
grade of resin used.
7.
8.
9.
1 0 .
1 1 .
1 2 .
1 3 .
1 4 .
The value increases with increasing crystallinity.
ZST is a measure of relative molecular weight of
PCTFE.
PCTFE is noteworthy for its very low permeability.
PCTFE generally maintains properties when
exposed up to about 18 Mrad of ionizing radiation.
Further improvement in resistance can be obtained
by incorporating small concentrations of vinylidene
fluoride during polymerization.
Soluble at 100C in 2,5-dichlorobenzotrifluoride.
Another solvent is 1,2,3,4-tetrafluorohexachloro-
butane.
The degradation involves random scission rather
than unzippering.
Specimens were 80% crystalline.
For amorphous polymers.
References page V - 58
VI58 PHYSICAL CONSTANTS OF FLUOROPOLYMERS
REF ERENCES
1. A. J. Bur in: (Ed) L. A. Wall, Fluoropolymers, Wiley,
Interscience, New York, 1972.
2. S. Chandrasekaran, Chlorotrifluoroethylene Homopolymer
(with 91 plus 2 general references), in: Encyclopedia of
Polymer Science and Engineering, Vol. 3, Wiley, New York,
1987, p. 463.
3. I. G. Farbenindustrie, Brit. Pat. 465, 520, May 3 (1987).
4. F. J. Honn (with 32 references), in: Kirk-Othmer (Ed.)
Encyclopedia of Chemical Technology, 1st ed., Wiley,
New York, p. 69 1.
5. H. S. Haufman, M. S. Muthana, J. Polym. Sci., 6,252 (1951).
6. Kel-F@, Engineering Manual, 3M Company.
7. Kel-F@, Technical Information Manual, 3M Company.
8. J. E. Mark (Ed)., Physical Properties of Polymers Hand-
book, AIP Press, Woodbury, NY, 1996.
9. W . T. Miller, US Patent 2, 564, 024, Aug. 14, 195 1.
10. P. C. U. K. Bulletin on Voltalee [PCTFE] Molding
Powders.
11. A. C. West (with 57 references), in: Kirk-Othmer (Ed.)
Encyclopedia of Chemical Technology, vol. no. 11,
3rd ed., Wiley, New York, 1980, p. 49.
Physical Constants of Poly(acrylonitrile)*
Siegfried Korte
Bayer AC, Leverkusen, FR Germany
A. Tables of Physical Constants v-59 Table 6. Polymerization: Kinetic and
Table 1. Crystallinity/CrystaIlization Behavior v-59
Thermodynamic Data V-62
Table 2. Electric and Electronic Properties V-60
Table 7. Solubility/Solution Properties V-62
Table 3. Fiber Properties V-61
Table 8. Special Solid State Properties V-63
Table 4. Further Properties of Acrylic Fibers V-61
Table 9. Thermal and Thermodynamic Data V-64
Table 5. Optical Properties V-61
B. References V-64
A. TABLES OF PHYSICAL CONSTANTS
TABLE 1. CRYSTALLINITY/CRYSTAlllZATlON BEHAVIOR
Property Value Remarks Refs.
Crystallographic data
Unit cell dimensions
See table
See also corresponding
chapter of this Handbook
With molecular modelling calculations of PAN
References are made to unit cell parameter,
crystal system, density, melting point, heat of fusion
1
Axis
Tacticity
a (A) b 6, c ck
System Refs.
Syndio 5.99 5.99 - Hexagonal 2
Syndio 21.18 11.60 5.1 Grthorhombic 3
Syndio 10.6 11.60 5.04 Grthorhombic 4
Syndio 10.2 6.10 5.10 Orthorhombic 5
Syndio 10.55 5.8 5.08 Ortborhombic 6
Syndio 21.0 11.9 5.04 Orthorhombic I
Syndio 10.7 12.1 5.1 Orthorhombic 8
Is0 4.74 4.74 2.55 Tetragonal 9
Crystallinity (%)
Crystal size Lim (A)
See table
See table
Samples: gel spun PAN-fibers. The role of
macromolecular entanglements is discussed
1 0
Molecular weight
MdglmoU
Draw rati o
(fiber)
Crystallinity
(%I
Crystal $ze
LIOO (-4)
6 x lo4
12 x 106
See Ref.
2.0-7.0
2.0-6.0
18. 5-32. 0 43.5-66.0
27. 5-39. 5 45.5-78.0
Degree of PAN-crystallinity as a function
of crystallite thickness and polymer tacticity
*Based on a similar table in the third edition, by W. Fester, Hoechst AG,
FR Germany.
11
v/s9
VI60 PHYSICAL CONSTANTS OF POLY(ACRYLONITRILE)
Property Value Remarks Refs.
Crystallization temperature T, b (C) 95-100 Determined in propylene carbonate 12,13
153.6 1 4
Density (g/cm 3,
Crystallization from PAN/H20 - melt under pressure
1. 15- 1. 1s Sample: flakes and films 12,16,17
1.17-1.19 Sample: fiber 1 8
Orientation factor See Ref. Sample: stretched films
X-ray diffraction studies
Chain-orientation factors were measured by IR-dichroism. 15
The reported unit cell dimensions, especially the c-dimension along the chain axis, can only be regarded as estimated because of the diffuse meridian and polar reflections in
the X-ray diffraction studies.
bThe dissolution and crystallization temperatures given here are obtained from a free radical poly(acrylonitrile). They are sensitive to chain irregularities in the polymer,
Sampl es of poly(acrylonitrile) obt a i ne d f r om di f f e r e nt s our c e s s how ma r ke d di f f e r e nc e s i n t he di s s ol ut i on a nd c r ys t a l l i z a t i on t e mpe r a t ur e s , a l t hough t he y ha ve s i mi l a r IR-
spectra, X-ray diffraction patterns and densities.
TABLE 2. ELECTRIC AND ELECTRONIC PROPERTIES
Property Value Remarks Refs.
Dielectric Constant
&
&RT
&He
E (T> 373K)
Dissipation factor
EN
tan6=F
tanb (T > 373 K)
Piezoelectric constants
4.2-6.5 (60-lo6 Hz)
5.68 * 0.84 (293 K)
3.29~tO.17 (3.8K)
See Ref.
0.033-0.
See Ref.
See Ref.
Sample: film
Sample: film
Temperature dependence: Arrhenius type behavior
Sample: discs from powder
19,20
2 1
Variation of E with temperature at various frequencies 22,23
113 (60-106Hz) Sample: film
(E, E loss and storage dielectric constants)
Comparison of the mechanical and dielectric values
of tan 6 as function of temperature (10 Hz)
Sample: discs from powder
19,20
24
Variation of tan 6 with temperature at various frequencies 22
1.5 x 10-12
30.8 x 1O-3
0.963
Driver constant d3, (C/N)
Generator constant g3, (V m/N)
McGinnies parameter x
Conductivity (S/cm)
Radiation induced conductivity
Dipole moments in solution
Magnetic susceptibility (e m n/g)
Photoelectric properties
Photocurrent (A/cm 2,
Electronic properties
Ionization potential (eV)
Electron affinity (eV)
Surface work function (eV)
4.8 x lo-l4 (293 K)
8.4 x lo-l2 (373 K)
See Ref.
See corresponding chapter
of this Handbook
See Ref.
See Ref.
8.2
3.9
5.8
17,25
Sample: film (sandwich)
Data from the current-voltage characteristics at various
temperatures
26,31
Sample: film (40 pm) sandwich 2 7
Sampl e: PAN-foam 2 8
Sample: thin film (plasma-polymerized) 2 9
Sample: thin film (plasma-polymerized) 30
Fiber Properties and Optical Properties VI61
I
TABLE 3. FI BER PROPERTI ES
Property
Conventional
acrylic fibers
(285% AN)
(Refs. 18, 32-36)
PAN-fiber
Dral on T
(100% AN)
(Ref. 35)
High strength
acrylic fibersb
(Refs. 38,39)
Acrylic fibers
from isotactic
PANC
(Ref. 40)
Fiber fineness (dtex)
Density (g/cm 3,
Tenaci t y [21C/65% RH] (cN/dtex)
Tenacity [wet/dry ratio] (%)
Elongation E [21C/65% RH] (%)
Elongation [wet/dry ratio] (%)
Initial modulus [(Elongation E --t 0)] (cN/dtex)
Modulus in hot water [9oC] (cN/dtex)
Relative knot tenacity
(%I
Relative loop tenacity (%) 30-80
0.6- 19.0
1.14-1.19
1. 8-4. 5
75-95
30-60
loo- 120
30-100
1. 0-5. 5
(Ref. 37)
70-90
3.3-17.0 1. 0-4. 0
1.17-1.19
3.5-6.0 10-20 8.0-20.0
80-100
25-40 7-10
Xl00
95-160 140- 270
15. 0-21. 0
=70
~60
4.5-6.5
(cN/dtex)
The properties of acrylic fibers manufactured by conventional processes of wet or dry spinning are dependent on spinning conditions and the monomer content in the polymer
itself. Some trade names of acrylic fibers: Acrilan, Cashmilon, Courtelk, Dolan, Dralon, Euracryl, Leacryl.
bPolyacrylonitrile fibers with high tensile strength are prepared under special conditions: Use of polyacrylonitriles with high molecular weight (iii, > 5.0 x 10s g/mol), wet or
dryjet/wet spinning and forming a fiber with a gel structure, afterwards stretching to high degrees (draw ratios 15-30).
Fibers are made from polyacrylonitriles with highly isotactic content (mm ., 0.40). They are prepared by anionic polymerization with a special catalyst.
TABLE 4. FURTHER PROPERTI ES OF ACRYLI C FI BERS
Property Value0 Remarks Refs.
I Elastic recovery [(l-c&) x 1001 (%) Effects of acids and alkalis 36,42
I
& = 2.0% 90-95 Good to excellent resistance to mineral acids,
E = 5.0% 50-90 fair to good resistance to weak alkali, and
moderate resistance to strong cold solutions of alkali
Torsion modulus (cN/dtex) 10- 17
Fiber shrinkage [in water, 95C] (%) Effects of bleaches and solvents
Drawn fiber 14-22 Good resistance to strong bleaches and common solvents;
Thermoset fiber u 1.0 Unaffected by dry cleaning solvents;
Water absorption [(21C/65% RH)] (%) 1. 0-1. 5 Can be bleached with sodium chlorite
Water retention (%) 4.0-12.0b Resistance to mildew, aging, sunlight, abrasion
Glass transition temperature (C) Not attacked by mildew;
Dry
85-95 Good resistance to aging, sunlight and abrasion
We t 50-60
I Melting/decomposition temperature (C) 250-320
Heat resistance in air (C) 140
Fire limiting oxygen index (LOI) (C) 1 8
4 1
a Refs. 18, 21-36. b Ref. 41.
I
TABLE 5. OPTI CAL PROPERTI ES
I Property Value Remarks Refs.
Birefringence
/
A, , = 1211 --nl - 0.005 Sample: PAN-fiber 32
- 0.0017 (skin) Sample: PAN-fiber (kidney-shaped) 44
- 0.0047 (core)
Refractive index
ni 1.158 45
(
n II
1.50-1.53 Sample: PAN-fiber 19,32,44
ni 1.51-1.53
See also corresponding chapter of this Handbook
Refractive index increments See Ref. Measured and calculated for different solvents 46
See also corresponding chapter of this Handbook (A = 546 nm)
I
Polarizability
PII
0.0735
PI 0.074
Optical anisotropy in solution See corresponding chapter of this Handbook 44
II I and n 1) are refractive indices measured with incident light having the vibration vector perpendicular and parallel to the fiber axis, resp&vely.
References page V / 64
Vf62 PHYSICAL CONSTANTS OF POLY(ACRYLONITRILE)
TABLE 6. POLYMERIZATION: KINETIC AND THERMODYNAMIC DATA
Property Value Remarks Ref.
Heat of polymerization (KJ/mol)
Rate constants of free radical polymerization
(propagation, termination and
transfer constants)
Heats and entropies of polymerization
Activation energies of polymerization
Activation enthalpies and entropies
of stereo-control in free radical polymerization
Stereoregularitf
- 72.4 f 2.2
See corresponding chapter of this Handbook
See corresponding chapter of this Handbook
See corresponding chapter of this Handbook
See corresponding chapter of this Handbook
See table
43
Mad tacticity (O/o)+
Polymerization
[II DMF Wg) &@Mso) (g/mol)
Is0 Hetero Syndio Refs.
Radical 1.97-6.87 25-29 47-51 22-27 47
Anionic 2.17-2.26 30-31 43-46 23-27 47,48
Anionic 5.3 x 104 26.7 48.8 24,524 40
Anionic 0.2 x 104-5.1 x 106 47-72 21-36 10-20 49,50,5 1
Urea clathrate
UV-irradiation 0.22-1.56 56-71 22-32 7-12 52
y-irradiation (post) 0. 79- 3. 05 69-87 lo-23 3-8 48
y-irradiation (in source) 1.81-4.96 48-65 25-36 9-16 5 3
t Tacticity of PAN was determined by H-NMR, *H-NMR and 13C-NMR, computing the spectra, and by decoupling techniques.
Spectral data a
Nuclear magnetic resonance spectrum
H-NMR, 2H-NMR
r3C-NMR
Solid-state NMR
Infrared spectrum
See Refs.
See Refs.
See Refs.
See Refs.
Configuration of PAN 54-58
Stereoregularity of PAN 48,53,59-61
Chain conformation and 62-64
phase structure of PAN
65-72
LI St e r e or e gul a r i t y a nd s pe c t r a l da t a we r e pr ope r l y pr ovi de d wi t h s e pa r a t e ge ne r i c t e r ms . .
TABLE 7. SOLUBlLITY/SOLUTION PROPERTIES
Property Value Remarks Refs.
So l v e n t s
Solubility
Hildebrand parameter
62 [J/cm31 I2
Dissolution of highly isotactic PAN
Dimethylformamide, dimethyl sulfoxide,
dimethylacetamide, ethylene carbonate,
propylene carbonate, malononitrile,
succinonitrile, adiponitrile,
y-butyrolactone, cont. sulfuric and nitric
acid, cont. salt solutions: LiBr, NaCNS,
ZnC12;
31.5 (exp.); N 26.0 (estim.)
See also corresponding
chapter of this Handbook
See Ref.
Intrinsic viscosity (7)
Solvent dependence See Ref.
See also corresponding
chapter of this Handbook
Solvents and Nonsolvents
73,74
Estimated values from empirical formulae
of HildebramhScott and Askadskii
7 5
Solution temperature as function of
isotacticity and molecular weight
76
77,78
Data and factors which convert [n]-
values from one solvent into another
79
Special Solid State Properties VI63
Property
Temperature dependence See table
Value Remarks Ref.
Sol vent T(C) Huggins coefficients
-Cd In WdT)
N,N-Dimethyl- 25 34 0. 14- 0. 19
formamide 3 5 3 3
NJ-Dimethylacetamide 0.27
Dimethyl sulfoxide 0.08
60% HNOs 0.05
y-Butyrolactone 0.14
0.13-0.17
Hydroxyacetonitrile 0.07
acetonitrile
Viscosity-molecular weight relationship
Dilute solution properties
Unperturbed dimensions of
linear chain molecules
See corresponding chapter in this Handbook
See corresponding chapter in this Handbook
Mar k- Houwi nk- Sakur ada equat i on
80
Partial specific volume See corresponding chapter in this Handbook
Huggins and Schulz-Blaschke coefficients
Sedimentation and diffusion coefficients
See corresponding chapter in this Handbook
See corresponding chapter in this Handbook
Parameters of isotactic PAN See Ref. Effects of stereoregularity on
Mark-Houwink-Sakurada equation
for different solvents, further on the
radius of gyration (S*), the
second virial coefficient A2 and
the conformation parameter
Parameters of ultrahigh molecular See Ref.
weight PAN
Dependence of molecular weight on
radius of gyration (S*), second 81
virial coefficient A 2 and intrinsic
viscosity [n]
Viscosity and related parameters See Ref. q-values, activation parameters of
viscous flow, voluminosity 82
and shape factor at different
temperatures (Solvent: DMF)
Flexibility parameter (X) 7. 20- 7. 68 Solvent: DMF
(Theta conditions) X is defined by Kratky-Porod for 8 3
Dissolution temperature0 (C)
random-coiled polymers
125- 130 In propylene carbonate 12,13
a The dissolution aad crystallization temperatures given here are obtained from a free radical poly(acrylonitrile). They are sensitive to chain irregularities in the polymer.
Sampl es of poly(acrylonitrile) obt a i ne d f r om di f f e r e nt s our c e s s how ma r ke d di f f e r e nc e s i n t he di s s ol ut i on a nd c r ys t a l l i z a t i on t e mpe r a t ur e s , a l t hough t he y ha ve s i mi l a r IR-
spectra, X-ray diffraction patterns and densities,
TABLE 8. SPECIAL SOLID STATE PROPERTIES
Property Value Remarks Refs.
Gas permeability (P) [,, t , ,z baA
02 (film, 25C) 2.15 x lo-l5
(film, 25C/65% RH) 150-195 x 10-15
Relationship between published and
CGS permeability units
84,85,86
CO2 (film, 25C) 11.8 x lo-l5 1
g x cm 298.82 cm3(STP) x cm
sxcm*xbar=- M sxcm*xcmHg
Hz0 (film, 25C)
Polymer surface energy S (m N/m)
Critical surface tension yc (dyn/cm)
Vickers mi crohardness Hv (kg/mm2)
18.4 x lo-lo
58.8
49.9154.1
See corresponding chapter of this Handbook
11-24
Where M is the molecular weight of the
penetrant gas
Calculated from cohesion parameters and
refractometric data
HV is a function of load L (L = 20-60 g)
Sample: film
8 7
8 8
89
References page V I64
V/64 PHYSICAL CONSTANTS OF POLY(ACRYLONITRILE)
TABLE 9. THERMAL AND THERMODYNAMIC DATA
Property Value Remarks Refs.
Heat capacity Cp See table Cp-data based on measurements in the solid state
Enthalpy function HT - Ho See also corresponding Enthalpy and entropy functions
Entropy function ST - So chapter of this Handbook are calculated
T (W
Cp (J/mom) HT -Ho (J/mol) ST -So (J/molK)
50 13.77 244.7 7.546
100 30.23 1388 22.73
150 40.44 3167 37.02
200 49.77 5410 49.87
250 58.48 8101 61.84
300 68.84 11277 73.40
350 80.83 15012 84.89
370 86.18 16681 89.53
Heat capaci t y Cp (T > Ts) See Ref.
Specific heat of combustion Ah, (KJlg) 30.6 (expt.)
31.5 (talc.)
250-310
248
238-299
530.9
See Ref.
Thermal decomposition temperaturea (C)
Initial decomposition temperature (C)
Exotherm decomposition range (C)
Heat of oligomerization AH (J/g)
Thermal decomposition
activation energies and products
Glass transition temperature
T, (Cl
Melting point T, (C)
Trn (HzO) (0
Thermal conductivity K
(mW/cm/K)
Coefficient of expansion (K-l)
Volume (l/V) x (dV/dT) p
Linear (l/V) x (dV/dZ+)p
See also corresponding
chapter of this Handbook
85-104
110
651105
See Ref.
See Ref.
See also corresponding
chapter of this Handbook
N 320
184.7
See also corresponding
chapter of this Handbook
0.022 (5 K)
0.440 (20 K)
1.600 (100K)
2.8 x 10m4-3.8 x 10m4 (above T,)
1.4 x 10m4-1.6 x 10m4 (below Ts)
1.6 x 10e4-2.0 x 10e4 (above T,)
1.0 x 10m4 (below Ts)
Calculated heat capacity data for states
above the Glass transition temperature
Ah, is related to other parameters,
such as oxygen index and char residue
Data from DSC and thermogravimetry analysis
Ranges of decomposition and activation energies
for the thermal degradation in air and nitrogen
Various data cited in the
3/e of Polymer Handbook
Sample: film
Method: fluorescence probe technique
Existence of two transition temperatures
in thermomechanical analysis
Effects of solvents and
thermal treatment on T,
Chain-length dependence of T,
Normally PAN decomposes before melting
Melting temperature in the wet state
under self generated pressure
Sample: discs from powder 1 0 1
90
9 1
92
3 3
9 3
94
9 5
96
97
97
98
99,100
1 4
45,102,103
104,105
The thermal decomposition temperature determined by thermogravimetric analysis ranges from 250C for a PAN-sample prepared with an ionic catalyst, to 310C for a
commercial fiber. Pyrolysis of poly(acrylonitrile) carried out in the absence of oxygen at SOC-800C yields HCN and low molecular weight nitriles such as monomer, dimer
and methacrylonitrile leaving a residue with a condensed ring structure.
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(03.02.1988).
67. D. 0. Hummel, F. Scholl, Atlas der Kunststoff-Analyse,
Carl Hanser Verlag, Mihrchen, Verlag Chemie GmbH, 1968.
68. N. Grassie, J. N. Hay, J. Polym. Sci., 56, 189 (1962).
69. C. A. Levine, G. H. Harris, J. Polym. Sci., 62, 100 (1962).
.
VI66 PHYSICAL CONSTANTS OF POLY(ACRYLONITRILE)
70. A. Bernas, R. Bensasson, I. Rossi, P. Barchewitz, J. Chem.
Phys., 59, 1442 (1962).
71. D. Mathien, M. Defranceschi, G. Lecayon, J. Delhalle,
Chem. Phys., 171, 133 (1993); 188, 183 (1994).
72. M. Minagawa, F. Yoshii et al., Macromolecules, 21, 2387
(1988).
73. Houben - Weyl, Methoden der Organischen Chemie Mak-
romolekulare Stoffe, Vol. E 20/2, Georg Thieme Verlag,
Stuttgart, 1987, p. 1192.
74. C. E. Schildknecht, Vinyl and Related Polymers, Wiley,
New York, 1952, p. 270.
75. A. V. Rajulu, P. M. Sab, A. A. Askadskii, Ind. J. Chem., 33B,
1105 (1994).
76. M. Minagawa, K. Miyano, T. Morita, F. Yoshii, Macromo-
lecules, 22, 2054 (1989).
77. M. L. Miller, J. Polym. Sci., 56, 203 (1962).
78. H. Kobayashi, J. Polym. Sci. B, 1, 299 (1963).
79. H. Kobayashi, Y. Fuji&i, Chem. High Polm., (Japan) 19,81
(1962).
80. K. Kamide., H. Yamazaki, Y. Miyazaki, Polym. J., 18, 819
( 1986) .
81. M. Bercea, S. Ioan, B. C. Simionescu, C. I. Simionescu,
Polym. Bull, 27, 571 (1992).
82. R. Joseph et al., Polym. Int., 26, 89 (1991).
83. C. Gonzales, F. Zamora, G. M. Guzman, J. Macromol. Sci. -
Phys. B, 26, 257 (1987).
84. M. Salame, J. Polymer Sci., Symp., 45, 1 (1973).
85. H. Takahashi, T. Sugimori, K. Aoki, H. Itoh, Mitsubishi
Rayon Co. LTD, European Patent 0363960 (18.04.1990).
i
86. S. A. Stem, J. Polym. Sci. A-2, 6, 1933 (1968).
87. S. M. Yagnyatinskaja et al., USSR. J. Phys. Chem., 44, 1445
1
(1970).
88. L. M. Pritykin, J. Colloid Interf. Sci., 112, 539 (1986).
1
89. P. Parashar et al., Polymer Testing, 11, 185 (1992).
90. U. Gaur, S. Lau, B. B. Wunderlich, B. Wunderlich, J. Phys.
8 Chem. Ref. Data, 11 (4), 1065 (1982).
1
91. H. S. Bu, W. Aycock, B. Wunderlich, Polymer, 28, 1165
I
(1987).
92. S. C. Ng, K. K. Chee, Polymer, 34, 3870 (1993).
93. P. Bajaj, M. Padmanaban, Eur. Polym. J., 20, 513 (1984).
94. M. W. Sabaa et al., Polym. Degrad. Stab., 23, 257
(1989).
/
95. J. Brandrup, E. H. Immergut, Polymer Handbook,
3rd. ed., Wiley, New York, 1989. I
96. J. Appl. Polym. Sci., 54, 827 (1994).
/
97. M. R. Padhye, A. V. Karandikar, Appl. Polym. Sci., 33,1675 I
(1987).
98. K. ODriskoll, R. A. Sanayei, Macromolecules, 24, 4479 I
(1991).
99. W. R. Krigbaum, N. Tokita, J. Polym. Sci., 43, 467
(1960).
100. G. Hinrichsen, Angew. Makrom. Chem., 20, 121 (1974).
101. N. S. Batty, D. Greig et al., Polymer, 24, 258 (1983).
102. H. J. Kolb, E. F. Izard, J. Appl. Phys., 20, 564 (1949).
I
103. G. I? Lanzl, quoted in Ref. 1.
104. W. H. Howard, J. Appl. Polm. Sci., 5, 303 (1.961).
105. C. E. Black, quoted in Ref. 1.
I
/
,
Physical Constants of Poly(vinyl chloride)*
E. A. Collins
Consultant, Avon Lake, OH, USA
C. A. Daniels
The Geon Company, Avon Lake, OH, USA
D. E. Witenhafer
Consultant, Dublin, OH, USA
Birefringence See Stress Optical Coefficient.
Branching
Branching Content (Branches per 1000 Monomer
Units (Cz)) as a Function of Polymerization
Temperature
-CH- -CCI- -CCI- H/ Cl
dHICl LH,CH~CI dH2c~c~c~2c~2c~ -c-bc-
Ref s .
45 3.9 < 0.1 0.5 < 0.1 la
2 4.2 4.6 0.2 0.2 0.6 0.8 0.2 11
0.3 1
80 4.9 0.3 1.3 0.3
100 5.0 1.4 2.1
0.8
:I
All data from 13C-NMR.
Extrapolated to 0 subsaturation, reduced with BusSn as per Ref. 3.
bReduced with Bu 3 Sn as per Ref. 4.
Brittle to Ductile Transition Pressure (kbar) Value of
0.2kbar, measured under tensile deformation of 10% per
minute at 25C.
(5)
Coefficient of Thermal Expansion (K-l)
< Tg before annealing, 6.6-7.3 x 10e5
(6)
after annealing, 6.9 x lop5
>Tg 17.0-17.5 x 1O-5
With plasticizer.
Coefficient of Friction
PVC on Steel
(7)
(8)
Pl asti ci zer (S) Static Dynami c
25.9 0.350 0.719
3 1 0.495 0.787
35.5 0.645 0.857
39.4 0.797 0.925
aDi-2-ethylhexyl phthalate (DOP), di-iso-decyl phthalate (DIDP), n-octyl-n-decyl
phthalate (DNODP). A value of 0.45-60 for unplasticized PVC with steel has been
reported (9). For further data see Ref. (10).
*The authors wish to acknowledge contributions from L. A. Utracki,
A. R. Berens, G. Pezzin, J. Lyngaae-Jorgensen, J. Runt, E. Baer, and
T. Hjertberg.
Compressibi/ity (MPa-) (x 106)
(11)
Uniaxially Stretched PVC
Elongation ( %) v II
YI
8 5 4.88 8.0
125 4.25 8.45
160 3.57 8.75
See al so Ref s. 12,13, and 36.
Creep
Crystallinity (%)
From Density Measurements
(14S5)
(16)
T
palym ((3
Crystallinity (%)
9 0 11.3n
55-60 11.3
5 0 13.2
2 0 15.0
- 15 57.3
- 7 5 84.2
Assumes amorphous density equals 1.385 g/cm3 and crystal-
line density equals 1.44g/cm (19). Since the crystalline
density for highly crystalline (e.g., single crystal) PVC is
considerably greater than 1.44g/cm3; as shown in the table on
crystallographic data, the above % crystallinity values for the
low temperature polymerized PVCs are greatly overestimated.
As pointed out by Kostyuchenko and co-workers (20). if a
crystalline density of 1.497g/cm3 or greater is used, the
calculated percent crystallinity values agree better with X-ray
diffraction measurements.
VI68 PHYSICAL CONSTANTS OF POLYWNYL CHLORIDE)
Crystallinity cant d
From X-Ray Diffraction Measurements
Tpolym CC)
90 fraG 1
frac. 3
53 frac. 1
A
B
2 5
- 60
Crystallinitya (%) (17)
10.4
5.4
10.4
6.5
8.2
12.2
23.1
34.7
T pob
50
- 2 0
- 4 0
- 60
polym. in propionaldehyde
polym. in n-butyraldehyde
Crystallinityb (%) (18,40)
13c
1 7
20.5,20
23,25
33
a Values obtained using the X-ray diffraction method of Hermans and Weidinger (21) and a double hump amorphous curve.
b X-ray diffraction method with Lorentz-polarization and atomic scattering factor corrections.
c Using a single hump amorphous X-ray curve and the method of Hermans and Weidinger (21), Lebedev and co-workers (22) (see also Ref. 17) report several commercial PJC
crystallinites in the range 20-27%. In general, their method gives higher values than that of DAmato and Strella (17).
From IR Measurements
Crystallinity from IR measurements deemed (by the
authors) to be less accurate than NMR are in references
42,44-46 and 56.
From Calorimetric Measurements (Unfractionated
Polymers)
(23)
M
T
polym (0
Crystallinity (%)
23,200 15 18.4
38,700 65 15.5
53,500 52 15.3
66,700 52 14.4
136,000 25 11.9
155,000 25 11.8
Crystallographic Data See under Unit Cell.
Density (g/cm3)
Function of Polymerization Temperatures
(16)
Tpolym (Cl M,
Density (20C)
90 23,750 1.391
55-60 75,000 1.391
50 91,250 1.392
20 172,250 1.393
- 15 106,300 1.416
-75 105,300 1.431
Dielectric Properties
Dielectric Constant (8)
(26)
Dependence on Thermal History
History
Original state
Quenched from 200C in ice water
Quenched from 130 to - 70C
Quenched from
(24)
Density (20C)
1.3743
1.3656
1.3716
130 to - 70C and kept at RT for 6.5 h
Annealed at 65C for 136 h
Annealed at 90C for 136h
and slowly cooled
Annealed at 90C for 136h
and quenched to - 20C
1.3743
1.3745
1.3834
1.3817
Effect of Temperature on Density
(253)
T(C)
Densi ty
20 1.392
5 1 1.383
82 1.368
90.6 1.362
91 1.357
25 40 60 80 90 100 110 120 140
60Hz 3.50 3.51 3.70 4.25 6.30 10.30 11.89 12.05 11.76
1 kHz 3.39 3.40 3.61 4.09 5.05 7.77 10.21 11.30 11.27
1okHz 3.29 3.34 3.45 3.89 4.45 5.77 8.50 9.96 10.94
Dielectric Loss Factor (8)
I T(C)
25 40 60 80 90 100 110 120 140
60Hz 0.110 0.116 0.125 0.172 0.410 1.20 0.675 0.481 1.65
1kHZ 0.081 0.081 0.080 0.120 0.500 1.415 1.645 0.630 0.319
1OkHz 0.058 0.058 0.050 0.110 0.920 1.37 1.35 1.22 0.490
T polym = 50C; [q] = 1.17; M, = 66,700; M, = 162,000. See also Ref. 27
,
Physical Constants of Poly(vinyl chloride) VI69
Dynamic Viscosity
Elongation at Break (%)
(122,134)
(28)
,
Tpdpl
(C)
Test temp.
(Cl IrlY 0.0026 0.020
Strain rate (s-l)
0.20 2.0 2 0 2 0 0
7 0 2 5 6 8
6 5 2 5 7 5
5 6 2 5 91.3
5 0 2 5 116.9
7 0 6 0 6 8
6 5 6 0 75.0
5 6 6 0 91.3
5 0 6 0 116.9
7 0 8 0 6 8
7 0 100 6 8
171.5 18.5
194.5 20.0
196.7 21.0
210.7 23.0
71.6
160
2 0 7
243
13.5
14.2
18.0
16.5
20.0
23.8
26.0
27.0
168
16.5 17.0 13.3
21.0 19.5 16.0
21.0 19.5 16.0
17.0 18.5 17.0
20.0 16.5 24.0
22.5 ,22.5 27.5
25.0 22.0 30.0
26.5 22.5 35.0
8 2 6 0 4 1
2 4 0 1 6 8 1 5 7
Intrinsic viscosity (ml/g) in cyclohexanone, 30C.
Fntha/py Entropy as a function of pressure and tempera-
ture.
(29)
Fatigue (135,136)
First Normal Stress Difference (118,119,145)
Flory-Huggins Parameter See Polymer-Solvent Interac-
tion Parameter.
Flow Activation Energy AE, (kJ/mol) (30,31,32,33,34)
Dependence on Temperature and Molecular Weight
AE, Wmol)
Tpdylll
(Cl LVNa 1os- 100s~ lOOOs-
5 0.131 - 150.7 134.9
5 0.693 92.1 119.7 60.2
5 0.909 165.5 103.1 54.2
5 1.750 43.4 30.5 30.4
4 0 0.640 178.4 102.8 54.0
4 0 0.682 157.4 105.2 45.0
4 0 1.225 108.6 57.7 34.6
7 0 0.495 147.7 97.0 52.4
7 0 0.680 126.9 84.3 43.6
Li mi t i ng vi s cos i t y number i n cycl ohexanone, 30 C.
Dependence on Shear Rate
Shear rate (s-l) >22oc
0.3 95.6
3 -
3 0 -
190-220C < 190C
363.7 152.4
244.8 145.7
159.6 121.7
Glass Transition Temperature See also corresponding
chapter in this Handbook.
Effect of Pressure: dT,ldP (Watm) 0.013 (35-38)
Effect on Molecular Weight and Polymerization
Temperature
(39)
Intrinsic viscosity [q] a
T
polym CC) 50
7 5 100 125 150
7 0 78.5 8 2 8 3 83.56 84.5 b
5 0 8 0 8 4 8 5 8 6 86.5
4 0 8 1 8 5 8 7 88.5 8 9
3 0 8 4 8 7 8 9 8 9 9 0
2 0 8 5 8 8 9 0 90.5 9 1
5 8 6 9 1 9 3 94.5 95.5
- 1 5 9 2 8 7 1 0 0 101.5 1026
In cyclohexanone, 30C (ml/g).
bExtrapolated from experimental data
Effect of Polymerization Temperature on T, and T,
(numbers give Refs.).
60 f lo
- 100 -75 -50 -25 b l 25 a0
Polymuitolfon lmpwalur~ T IV.1
l 75 +mo l 125
The lines through the data points represent the best least
squares fit of the collective authors data.
References page V - 74
.
V/TO PHYSICAL CONSTANTS OF POLY(VINY1 CHLORIDE)
Glass Transition Temperature cant d
Dependence on Polymerization Temperature (47)
T, ((3
T,I,, (0 fill WP) Initial Final b
9 0 8 0 7 8
5 0 8 0 8 5 8 3
0 108 9 7 8 8
- 2 0 1 0 3 100 9 0
- 30 125 100 9 1
- 4 0 1 0 1 9 0
- 5 0 1 0 5 9 1
- 6 0 9 0 1 0 7 9 5
a[q] measured at 25C in cyclohexanone.
bAfter thermal cycling to 230C. See also Ref. 48.
Heat Capacity See corresponding table in this Handbook
and Refs. 49-52.
Effect of Thermal Cycle on Cp
(47)
ACP (~10) (J/g/C)
Tpolym (C) M Wg)
Initial Final b
9 0 28.9 29.3
5 0 8 0 27.2 27.6
0 108 24.3 25.1
- 2 0 103 1 5 . 1 22.2
- 3 0 125 10.9 20.9
- 4 0 10.5 20.1
- 5 0 18.0
- 6 0 9 0 6.3 16.3
[v] measured at 25C in cyclohexanone. bAfter heating to 140C.
Heat of Combustion (kJ/kg) - 19000. (53)
Heat of Fusion (kJ/mol)
11.3
12.65
2.76
3.28 (most probable value
according to Ref. 56)
3.56
3.91
(41)
(54)
a (55)
(16)
(57)
(58)
Heat of Dilution 30C PVC-tetrahydrofuran (23)
PVC-cyclohexanone
Heat of Polymerization (kJ/mol)-96 to - 109 (59-61)
Huggins Coefficient
(62)
Intrinsic Viscosity - Molecular Weight Relationship
See corresponding chapter in this Handbook and Refs.
63-89.
Mark-Houwink Parameters for PVC as a Function of Temperature (115)
Sol vent Temp. range (C) a K Wk)
Cyclohexanone 20-60 0.803 1.847 x lo--4.85 x lo- T
Cyclopentanone 20-60 0.861 9.086 x 10-5-1.55 x 1O-5 T
THF 20-50 0.851 1.087 x lo-*-l.67 x 10m5 T
k-values can be calculated for any temperature T (C) within the temperature range given.
Me/f Viscosity See Appendix 1 and Refs. 3 1-34,118,
119,144.
Permeability See chapter Permeability Coefficients,
Diffusion Constants, and Solubility Coefficients of Poly-
mers in this Handbook, and Refs. 24,92,93-99.
Diffusion Constants in PVC
Gas log loD (cm2/s)
(A) GASES, AT 25C (92)
He - 5.5
H2 - 6.3
Ne - 6.6
N2 - 8.4
Ar - 8.9
02 - 7.9
(32 - 8.6
CH4 - 8.9
E D Wmol)
20.7
34.5
31.5
62.0
51.5
54.4
64.5
70.3
Gas log IoD (cm2/s) ED Wmol)
Hz0 - 7. 6 41.8
Kr - 9.4 62.8
(B) ORGANIC VAPORS, AT 3oC, LOW ACTIVITY (90)
n-C4H10 . - 13.6
n-C5H 12 - 13.9 81.6
n-c 6H 14 - 14.9
C6H6 - 13.7
CH30H - 10.4
C2H50H - 12.4
n-C3H70H - 13.2
n-C4H90H - 13.9
CH3CI - 11.3 59.9
cc14 - 17.1 108.4
C2H3C1 - 11.7 71.2
W 312CO - 12.8
SF6 - 16.1 100.0
Physical Constants of Poly(vinyl chloride) VI71
Poisson Ratio 0.38.
(100)
Polymer-Solvent Interaction Parameter See corre-
sponding chapter in this Handbook and Refs. 68,101-114.
Reciprocal dispersive power Vd 59.3
Critical angle (A = 589.3 nm) 56.23
Temperature coefficient of
refractive index 0.0001142/C.
Refractive Index PVC (p = 1.384 g/cm3)
(14)
Specific Heat Capacity See chapter Heat Capacity in
Wave length (nm) Refractive index
this Handbook, and Refs. 49,50.
486.1 1 S4806
Second Virial Coefficient See corresponding chapter in
589.3 1.54151
this Handbook and Refs. 43,77,84,116,117.
656.3 1.53843
Shear Modulus (120-122,134)
Dynamic Test Results for Rigid PVC Formulation at Frequencies = 0.06-600 (rad/s) and at Temperatures
140-220C
w (radk)
220C 210C 200C 190C
G (Pa) G (Pa) G (Pa) G (Pa) G (Pa) G (Pa) G (Pa) G (Pa)
5.9749 E -2
9.4700 E -2
1.5008 E-l
2.3787 E -1
3.7700 E - 1
5.9749 E - 1
9.4700 E - 1
1. 5008 EO
2. 3787 EO
3. 7700 EO
5. 9749 EO
9. 4700 EO
1. 5008 El
2. 3787 El
3. 7700 El
5. 9749 El
9. 4700 El
1. 5008 E2
2. 3787 E2
3. 7700 E2
5. 9749 E2
3. 669 E3
4. 775 E3
6. 028 E3
7. 644 E3
1. 012 E4
1. 272 E4
1. 606 E4
1. 976 E4
2. 506 E4
3.109E4
3. 859 E4
4. 652 E4
5. 650 E4
6. 862 E4
8. 120 E4
9. 904 E4
1.177 E5
1.461 E5
1.699 E5
2. 136 E5
2.673 E5
3. 442 E3
4. 472 E3
5. 736 E3
7. 047 E3
8. 847 E3
1. 096 E4
1. 302 E4
1. 684 E4
2. 060 E4
2. 477 E4
3. 031 E4
3. 645 E4
4. 001 E4
4. 549 E4
5. 219 E4
5. 885 E4
6. 552 E4
7.293 E5
8.475 E4
9. 848 E4
1. 189 E5
1. 256 E4
1. 493 E4
1. 813 E4
2.201 F/t
2. 732 E4
3. 177 E4
3. 859 E4
4. 488 E4
5. 404 E4
6. 340 E4
7. 374 E4
8. 515 E4
9. 692 E4
1.103 E5
1. 261 E5
1.473 E5
1. 684 E5
1.934 E5
2. 249 E5
2.560 E5
3.109 E5
9. 933 E3
1. 096 E4
1. 285 E4
1. 468 E4
1. 706 E4
1. 999 E4
2. 283 E4
2. 758 E4
3. 205 E4
3. 645 E4
4. 309 E4
4. 838 E4
5. 166 E4
5. 638 E4
6. 142 E4
6. 810 E4
7.139 E4
7.947 E4
9. 039 E4
1.028 E5
1.236 E5
3. 205 E4
3. 586 E4
4. 153 E4
4. 727 E4
5. 594 E4
6. 340 E4
7. 154 E4
7. 935 E4
9. 033 E4
9. 976 E4
1.102 E5
1.218 E5
1.369 E5
1. 512 E5
1.663 E5
1.893 E5
2.136 E5
2. 400 E5
2.673 E5
3. 109 E5
3.696 E5
1.684 E4
1. 827 E4
1. 998 E4
2. 245 E4
2. 530 E4
2. 771 E4
3. 031 E4
3. 448 E4
3. 805 E4
4. 147 E4
4. 859 E4
5. 204 E4
5. 391 E4
5. 885 E4
6. 413 E4
7. 108 E4
7. 618 E4
8. 587 E4
9. 435 E4
1.073 E5
1.444 E5
6. 882 E4
7. 470 E4
7. 971 E4
8. 955 E4
1.011 E5
1. 111 E4
1. 238 E5
1.304 E5
1. 440 E5
1.510 E5
1.625 E5
1. 751 E5
1.876 E5
2.050 E5
2.173 E5
2.431 E5
2.616 E5
2.852 E5
3. 136 E5
3.539 E5
4.081 E5
2.711 E4
2. 782 E4
2.941 I34
3. 137 E4
3. 389 E4
3. 598 E4
3. 772 E4
4. 199 E4
4. 517 E4
4. 817 E4
5. 432 E4
5. 526 E4
5. 885 E4
6. 013 E4
6. 552 E4
7. 293 E4
7. 957 E4
8. 369 E4
9. 848 E4
1.120 E5
1.594 E5
178C 170C 160C 140C
w (rad/s) G (Pa) G (Pa) G (Pa) G (Pa) G (Pa) G (Pa) G (Pa) G (Pa)
5.9749 E -2 1.055 E5 3.137 E 4 1.484 E5 3.724 E 4 1.802 E5 3.971 E4 2.613 E5 4.236 E4
9.4700 E -2 1.150 E5 3.360 E 4 1.625 E5 3.756 E4 1.850 E5 4.006 E4 2.658 E5 4.272 E4
1.5008 E - l 1.201 E5 3.507 E 4 1.697 E5 3.821 E 4 1.949 E5 4.058 E4 2.693 E5 4.291 E4
2.3787 E -1 1.352 E5 3.645 E 4 1.834 E5 3.904 E4 2.124 E5 4.128 E4 2.751 E5 4.349 E 4
3.7700 E - 1 1.471 E5 3.821 E 4 1 . 9 6 5 E5 4.075 E 4 2.256 E5 4.291 E4 2.873 E5 4.537 E 4
5.9749 E -1 1.570 E5 4.058 E 4 2.078 E5 4.327 E4 2.386 E5 4.517 E4 3.000 E5 4.716 E4
9.4700 E - 1 1.675 E5 4.199 E 4 2.198 E5 4.365 E 4 2.449 E5 4.615 E4 3.039 E5 4.903 E4
1.5008 EO 1.842 E5 4.615 E 4 2.295 E5 4.817 E4 2.524 E5 5.051 E 4 3.118 E5 5.283 E 4
2.3787 EO 1.948 E5 4.817 E 4 2.417 E5 5.029 E 4 2.751 E5 5.386 E4 3.242 E5 5.621 E4
3.7700 E O 2.025 E5 5.226 E 4 2.524 E5 5.456 E 4 2.873 E5 5.744 E4 3.356 E5 5.940 E4
5.9749 E O 2.198 E5 5.769 E 4 2.635 E5 6.021 E 4 2.987 E5 6.205 ETA 3.459 E5 6.357 E 4
9.4700 E O 2.328 E5 5.844 E 4 2.711 E5 6.506 E4 3.073 E5 6.703 E 4 3.468 E5 6.829 E 4
1.5008 E 1 2.452 E5 6.217 E4 2.816 E5 6.523 E 4 3.177 E5 6.865 E 4 3.601 E5 6.939 E4
2.3787 El 2.662 E5 6.552 E 4 3.030 E5 6.987 I.34 3.361 E5 7.169 E4 3.809 E5 7.293 E4
3.7700 El 2.791 E5 7.139 E4 3.177 E5 7.452 E 4 3.434 E5 7.712 E 4 3.943 E5 7.959 E 4
5.9749 El 3.069 E5 7.613 E 4 3.434 E5 7.947 E 4 3.776 E5 8.293 E 4 4.170 E5 8.587 E4
9.4700 El 3.177 E5 8.296 E4 3.617 E5 8.585 E 4 4.029 E5 9.049 E4 4.488 E5 9.354 E 4
1.5008 E 2 3.464 E5 8.848 E4 3.977 E5 9.039 E4 4.298 E5 9.517 E4 4.893 E5 9.899 E 4
2.3787 E 2 3.744 E5 1.015 E5 4.261 E5 1.028 E5 4.606 E5 1.079 E5 5.321 E5 1.111 E5
3.7700 E2 4.117 E5 1.144 E5 4.586 E5 1.199 E5 - - -
5.9749 E 2 - - - - -
Storage, G, and Loss, G, are in Pascal. Data from L. A. Utracki, SPE Techn. Papers 31, 1024 (1985); J. Vinyl. Technol. 7 (4), 150 (1985). M, of PVC tested is 90.700 (GPC
in THF), LVN 30C in 93 ml/g cyclohexanone.
,
References page V - 74
V/72 PHYSICAL CONSTANTS OF POLY(VINYL CHLORIDE)
j
Specific Refractive Index Increment See corresponding
chapter in this Handbook.
Specific Volume
As a function of temperature and pressure.
(29)
Spectral Data
a. Infrared absorption bands.
b. Nuclear magnetic resonance
(high resolution spectra).
c . Carbon- 13 magnetic resonance
(chemical shift assignment)
(123)
(124-126)
(127-129)
Stress Optical Coefficient (sot)
-2ooto +50 - 6.5 (132,133)
The value of the SOC becomes positive at T,, but there is
some arbitrariness associated with it because above T, the
plots of birefringence change with stress and have an S
shape.
Tacticity (Fraction of syndiotactic dyads) Thermal conductivity of system PVC/di-Zethylhexyl
Dependence on Polymerization Temperature phtbalte (see Ref. 139).
Tpolyn (Cl
Tacticity * Refs.
5 5 0.55 130
5 0 o.55c 129
2 5 0.57 130
0 0.60 130
- 3 0 0.64 130
- 5 0 0.66 130
- 7 6 0.68 130
Data based on 13C NMR measurements.
bHigh tacticity data may be low due to insolubility during measurement as
discussed in Ref. 131.
Bernoullian order.
Tensile Modulus (MPa) = (N/mm*)
T (Cl Value Refs.
- 196C 7584 137a
- 120C 5171 137
- 75C 3861 137
20C 2 9 6 4 137
30C 3000 146
40C 2930 1 4
50C 2427 1 4
60C 1 5 5 1 1 4
70C 2 7 6 1 4
Stress-Strain measurements at strain rate of 0.00250 s -I.
*Measured in creep (100 s, 0.2% strain).
Thermal Conductivity (W/m/K) (138,140)
T (C)
Thermal conductivity
- 170 0.129.
- 150 0.134
- 125 0.139
- 1 0 0 0.144
- 7 5 0.148
- 5 0 0.152
- 2 5 0.155
0 0.158
2 0 0.160
3 0 0.161
4 0 0.162
5 0 0.163
6 0 0.164
7 0 0.164
8 0 0.165
9 0 0.165
100 0.165
Molecular weight, sample polymerization temperature
and syndiotactivity do not influence the thermal conductiv-
ity of polymers appreciably, except in the case where
tacticity leads to crystallization.
Thermal Diffusivity (140) :
T WI Density (g/cm3)
Thermal diffusivity
( x 10m4) (cm*/s)
2 0 0
2 2 0
2 4 0
2 6 0
273
2 8 0
293
3 0 0
3 2 0
3 4 0
3 5 2
3 6 0
3 8 0
4 0 0
4 2 0
4 4 0
4 6 0
4 8 0
1.417
1.415
1.413
1.409
1.407
1.405
1.402
1.400
1.393
1.385
1.379
1.374
1.334
1.306
-
-
-
-
14.40
13.95
13.46
12.96
12.60
12.42
11.92
11.83
11.13
10.14
9.22
8.41
7.65
7.30
7.13
7.04
6.99
7.06
APPENDIX 1: APPARENT MELT VISCOSITY OF UNMODIFIED PVC V/T3
Unit Cell
PVC sample type
Crystal
system
Space
group
Unit cell parameters (A)
Monomers Calc. densi ty
a b c per unit cell (g/cm3) Refs.
Commercial, polymerized at
50-60C
Solution blended high molecular
weight, low crystallinity
commercial polymer and low
molecular weight, high
crystallinity polymer
Single crystals, polymerized at
- 75C
Single crystals, low molecular
weight, polymer made in
n-butyraldehyde
Orthorhombic
Orthorhombic
Orthorhombic
Orthorhombic
Pacm
Pacm
Pacm
10.6 5.40 5.10 2 1.44 1 9
10.4 5.30 5.10 2 1.48 1 4 1
10.32O 5.32a -
-
(1.49)b 142
10.24 5.24 5.08 2 1.53 1 4 3
Calculated from published d-spacings of major diffraction peaks.
bCalculated density assuming c = 5.10 (A) and 2 monomers per unit cell.
Unperturbed Dimensions See corresponding chapter in
this Handbook.
Viscosity-Molecular Weight Relationship See Intrinsic
Viscosity.
Zero Shear Viscosity
(34)
APPENDIX 1: APPARENT MELT VISCOSITY OF UNMODIFIED PVC PREPARED AT VARIOUS POLYMERIZATION TEMPERATURESb (PAS)
(xl09
Shear rate (s-l)
L.V.N. Melt temp.
Wk) (C) 2.95 7.37 14.7 29.5 73.7 147 2 9 5 7 3 7 1470 2950
110 30.5 190
110 30.5 205
10d 40.1 140
7 0 40.1 150
7 0 40.1 160
7 0 40.1 170
7 0 40.1 180
7 0 40.1 190
7 0 40.1 2 0 0
7 0 40.1 2 1 0
7oe 49.5 140
7 0 49.5 150
7 0 49.5 160
7 0 49.5 170
7 0 49.5 180
7 0 49.5 190
7 0 49.5 2 0 0
7 0 49.5 2 1 0
7 0 54.8 2 1 0
7 0 54.8 2 2 0
7 0 6 8 160
7 0 6 8 170
7 0 6 8 180
7 0 6 8 190
7 0 6 8 2 0 0
7 0 6 8 2 1 0
7 0 6 8 2 2 0
6 5 75.4 180
6 5 75.4 190
6 5 75.4 2 0 0
6 5 75.4 2 1 0
6 5 75.4 2 2 0
6 5 8 6 180
6 5 8 6 190
- -
-
1128.3
639.83
281.4
100.9
32.12
11.95
9.03
-
2336.4
1433.6
839.9
398.4
146.6
55.34
22.1
12.7
16.23
- -
573.1 340.7
332.2 200.6
153.9 97.1
62.08 42.2
21.2 15.5
7.22 5.94
3.82 2.02
5.31 2.71
1209.8 721.6
711.03 424.5
431.9 258.9
231.5 142.9
91.9 58.7
34.3 25.5
13.7 11.3
7.53 5.54
8.66 8.12
- -
2464.2 1172.2
1196.9 599.14
562.8 320.5
244.2 144.9
94.2 62.1
48.1 29.5
19.4 15.5
976.7 522.7
545.1 254.1
271.1 128.5
95.6 56.7
52.6 33.2
9 3 0 448.5
686.2 381
-
-
705.5
359.27
205.9
100.8
46.6
23.5
13.2
318.4
158.9
85.3
43.1
25.9
273.3
243.6
1.18 0.72 0.82 0.77 0.61 0.52 0.40
0.63 0.39 0.48 0.30 0.22 0.21 0.20
2 0 2 97.85 54.6 30.0 13.3 6.41 3.08
120.8 60.5 35.6 20.44 9.45 4.91 2.47
62.4 34.4 21.8 13.41 6.56 3.14 20.4
28.1 16.9 11.35 7.65 4.37 2.72 1.62
11.42 1.85 5.78 4.38 2.80 1.94 1.21
5.15 4.03 3.24 2.65 1.87 1.35 0.95
1.86 2.02 1.92 1.4 1. 21 0.95 0.68
1.38 0.89 1.02 0.935 0.175 0.65 0.504
423.5 191.6 102.1 51.11 20.2 9.29 4.24
223.0 119.92 64.7 34.5 15.2 7.43 3.50
155.3 76.6 43.8 24.2 10.72 5.41 2.71
89.6 47.8 29.1 17.2 8.14 4.43 2.32
43.2 26.1 17.3 11.2 5.92 3.49 1.98
19.4 13.4 9.75 6.58 3.99 2.56 1.52
9.5 1.36 5.81 4.48 2.95 2.02 1.33
4.54 3.99 3.43 2.82 2.06 1 . 5 1.04
7.31 6.71 5.14 4.71 2.94 20.3 1. 31
5.26 4.29 3.82 3.24 2.39 1.72 1.18
389.9 173.66 89.55 45.76 17.69 8.47 4.01
218.53 113.21 64.04 34.39 14.44 7.16 3.49
125.6 64.7 37.7 21.8 10.3 5.52 2.92
69.8 40.1 25.5 15.5 7.75 4.40 2.44
35.0 23.7 16.6 11.0 5.94 3.55 2.01
19.6 14.6 1 1 . 1 8.02 4.68 2.92 1.73
11.7 9.34 7.51 5.71 3.62 2.51 1.57
195.6 103.5 58.7 31.26 13.3 6.87 3.46
1 0 1 53.6 31.9 19.0 9.25 5.01 2.63
59.8 36.3 23.1 14.2 7.2 4.15 2.32
33.1 22.1 15.7 10.5 5.53 3.36 2.02
21.4 14.9 10.96 7.75 4.49 2.73 1.64
1 9 8 8 4 45.1 23.22 9.77 4.92 2.46
1 4 8 8 2 48.1 25.5 1 1 . 1 5.7 2.93
References page V - 74
VI74 PHYSICAL CONSTANTS OF POLY(VINYL CHLORIDE)
I
Shear rate (s-l)
L.V.N.C Melt temp.
bW (C) 2.95 7.37 14.7 29.5 73.7 147 2 9 5 7 3 7 1470 2950
6 5 8 6 2 0 0
6 5 8 6 2 1 0
6 5 8 6 2 2 0
6 5 91.3 180
5 6 91.3 190
5 6 91.3 2 0 0
5 6 91.3 2 1 0
5 6 91.3 2 2 0
5 6 91.3 2 3 0
5 6 91.3 2 4 0
5 0 116.9 180
5 0 116.9 1 8 5
5 0 116.9 190
5 0 116.9 2 0 0
5 0 116.9 205
5 0 116.9 2 1 0
5 0 116.9 2 2 0
5 0 116.9 2 3 0
4 2 141.2 190
4 2 147.2 2 0 0
4 2 147.2 2 1 0
4 2 147.2 2 2 0
4 2 147.2 2 3 0
4 2 147.2 2 4 0
4 0 122.5 190
4 0 122.5 2 0 0
4 0 122.5 205
4 0 122.5 2 1 0
4 0 122.5 215
2 8 2 0 8 190
2 8 208 2 0 0
2 8 208 2 1 0
2 8 2 0 8 2 2 0
2 5 240.5 2 0 0
2 5 240.5 2 1 0
2 5 240.5 215
2 5 240.5 2 2 0
2 5 240.5 225
2 5 240.5 2 3 0
2 5 240.5 2 4 0
229.5 138.7 100.6
163.9 94.96 71.05
-
1898.2
1139.9
857.7
286.9
154.9
92.1
82.3
1884
1452.2
1062
783.2
584.1
424.8
265.5
-
1878.6
1626.9
1352.7
968.4
-
-
2041.3
1162
445.4
-
902.1
584.7
3 5 0
155.0
90.8
60.5
11.9
933.9
730.1
633.6
410.7
318.4
226.0
147.5
132.9
897.0
703.2
567.6
415.3
2 9 9
243.6
867.8
-
244.5
-
573.1
373.8
207.1
112.0
55.9
48.7
54.7
562.5
464.3
3 9 8
251.4
209.6
156.0
106.12
79.7
537.1
420.8
319.7
231.5
164.5
199.3
511.0
323
170.5
-
338.8
2050.0
1658.7
1104.9
665.6
1513.3
1503
1340.7
1355.7
958.4
-
-
- -
185.6 133.4
916.5 543.5
740.6 452.3
493.4 282.4
332.5 214.7
647.4 387.4
603 343
562.5 311.5
572.6 332.2
421.3 250.9
409.8 222.0
426.4 223.2
67.75
53.3
26.25
292.0
250.4
130
79.2
49.5
37.7
44.6
3 0 4
284.1
251.7
177.9
131.4
105.1
75.4
58.1
276.1
252.1
206.3
142.5
106.2
151.1
285.6
-
111.5
98.4
94.0
284.9
239.6
167.7
138.4
223.0
2 0 0
180
190.9
159.3
136.1
132.3
38.75 34.02 13.67
33.1 21.4 13.5
17.13 11.8 7.88
124.2 65.3 35.1
113.5 60.1 31.5
7 4 43.3 23.4
45.1 28.5 18.7
31.3 18.5 1 3 . 1
24.6 17.0 11.1
31.0 24.1 20.1
126.3 67.12 36.11
126.8 66.1 34.25
116.2 59.96 30.8
87.02 45.1 24.03
78.9 43.5 22.83
59.43 39.3 21.64
44.4 28.02 18.8
36.0 23.2 14.7
113.5 58.4 31.8
108.5 55.9 28.2
93.3 48.9 25.3
73.5 39.9 21.2
60.2 35.2 19.0
89.7 53.2 33.5
117.9 58.5 29.2
80.8 41.5 21.0
64.4 36.6 19.4
53.5 28.7 14.76
5 3 35.7 20.2
117.8 63.1 33.55
102.8 52.2 27.4
85.5 46.9 25.03
69.3 39.5 22.1
94.98 49.08 26.55
90.2 46.6 23.5
80.44 41.76 21.4
83.3 43.9 22.5
15.35 40.33 21.03
67.7 37.5 19.7
64.2 36.5 20.2
6.71 3.77 2.01
7.23 4.37 2.47
4.22 2.56 1.56
14.86 7.43 3.66
13.5 6.87 3.53
10.2 5.45 2.85
9.08 4.81 2.54
7.21 4.27 2.31
6.0 3.98 2.48
10.0 6.367 3.611
14.86 7.32 3.39
14.22 7.0 3.4
13.16 6.58 3.24
10.61 5.57 2.92
9.87 5.25 2.79
9.29 4.93 2.60
8.49 4.62 2.51
8.34 4.67 2.57
13.3 6.36 3.04
12.3 6.15 3.07
10.7 5.52 2.17
9.19 4.93 2.85
8.44 4.55 2.48
-
12.7
9.09
8.35
6.28
8.73
14.92
11.94
10.44
9.96
11.67
10.4
9.49
9.63
9.23
8.86
8.53
- -
6.45 3.14
- -
4.37 2.25
3.28 1.72
4.56 2.39
7.25 3.35
6.07 2.87
5.33 2.66
5.33 2.73
5.84 2.81
5.4 2.7
5.2 2.6
5.07 2.57
4.92 2.60
4.62 2.46
4.52 2.53
Ref. original data, E. A. Collins, unpublished.
bMelt viscosity data obtained using a capillary having a 90 entrance angle, length 1 .O in and diameter 0.05 in. No correction applied to the data. All samples contained 2.5
parts dibutyltin dioctylthioglycolate stabilizer-per 106 parts resin.
Li mi t i ng vi s cos i t y number , det er mi ned i n cycl ohexanone 30 C.
dModified with 5 parts trichloroethylene/lOO parts vinyl chloride monomer.
eModified with 3 parts trichloroethylene/lOO parts vinyl chloride monomer.
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235 (1973).
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Physical Constants of Poly(vinyl acetate)
M. K. Lindemann
Consultant, Greenville, SC, USA
Property Value Remarks Refs.
Absorption of Wafer (%) Approx. 3-6 At 20C for 24 to 144 h
4 At 23C
6 At 70C
Adhesi ve Strength
Lap shear (Mpa)
Peel strength (N/cm)
3.9 Al umi num
1.9 Al umi num
Chai n Di mensi ons and Entangl ement Spaci ngs See Refs.
Cohesi ve Energy (J/mol) 26000-36000
Cohesi ve Energy Densi ty (J/cm3) 3.69 x lo*
Compressi bi l i ty (cm 3/g/atm) 1.8 x 1O-5
Isot hermal (bar-) ( x 10e5)
At 80C 6.2
A t 100C 6.6
At 120C 7.1
Decomposition Temperature (C)
Degradati on, Thermal
150
T'/* =269"C; ,I&,=7 lkJ/mol;
monomer yield: none
Density (Mg/m 3, = (g/cm 3,
At 20C
At 25C
At 50C
At 120C
At 200C
At the melting point
At T= 35-100C
At T=-30 to +2oC
As a function of pressure
1.191
1.19
1.17
1.11
1.05
1.28
1.2124-8.62 x 1O-4 T+0.223 x 1O-6 T*
1.196-3.37 x 1O-4 T
See Refs.
Dielectric Constant
Of oligo PVAC
As a function of MW
3.5
8.3
See Ref.
See Ref.
Di el ectri c Di ssi pati on Factor ( t an 6) 1.5 x 102 At 50C and 2 x lo3 kHz
26 x lo* At 120C and 2 x lo3 kHz
Di el ectri c l oss Versus Frequency
Dielectric Strength (V/cm) ( x 10m3)
See Ref.
394
307
In the glassy state
Temperature at which the polymer
loses 50% of its weight,
if heated in vacuum for 30 min
At 50C and 2 x lo3 kHz
At 150C and 2 x lo3 kHz
At various temperatures 95
At 30C
At 60C
1 6
26
65,66
130
144- 146
52
58
1
1 1 3
1 5
52
16,24,26
58
113
113
113,114,115
34
59
96
34
v/77
V/78 . PHYSICAL CONSTANTS OF POLY(VINYL ACETATE)
Property Value Remarks Refs.
Di el ectri c Rel axati on Parameters See Refs.
Di pol e Moment (ESU (per monomer uni t ))
(debye units)
2.3 x lo-l8
1.77 x 10-18
4.8 D
Dynami c Mechani cal Loss Peak (C)
Elongation At Break (%)
Gas Di ffusi vi ty
70
10-20
See Ref.
Gas Permeabi l i ty See Refs.
Nr for PVAC below T,(cm/s/bar) 6 x lo-i0
Na for PVAC above T, 5 x lo-*a
02.73dry film 2.7 x 1O-9
Gas So/ubi/ity (cm 3(STP)/cm

3 bar) N2 0. 02
02 0. 04
H2 0. 023
121- 129
22,23
59
33
27
52
53,94
52
At 20C
At 150C
For oligo PVAC, n = 5
At 1OOHz
At 2oC, %RH
For Nz. 02. CO2, H2
Diffusion and sorption of CO2
(below and above Tg)
100
At 298 K 52
See Refs. Gel Permeation Chromatography
Gel Properti es
Swelling pressure, elastic modulus
and shear modulus parameters of PVAC
networks in toluene and acetone
Glass Transition Temperature (C)
Universal calibration 90,91,92
See Ref. 166
28-31
25.8
31.4
23.6
34-39
<30
11
0.022
See Refs.
2 5
63 Isotactic PVAC M, N lo5
Atactic PVAC M, N 1.66 x lo5
Atactic PVAC M, N 3922
DV
We t
PVAC containing 4.20% water
65
66 I
1 8
6264
\
Pressure dependence (K/bar)
As a function of MW
Activation energy for the glass transition
(J/mol)
Hardness (Shore units)
Heat Capacity @J /kg)
AH, = 1.8 x lo5 60
L 80-85 At 20C 27
At 30C 2 1
A t Ts=304K 67
1.465
cp(liquid) = 1.77
C
p(glass) = 1.27
0.116 68
At T=320K
At T=370K
A t T=80K
Cv(liquid) = 1.51
c
v(glass) = 1.20
Cp(liquid) = 1.8409 &J/kg); 158.48 (J/mol/K)
Cp(l+d) = 1.898 @J/kg); 163.37 (J/mol/K)
Cp(gtass) = 0.323 &J/kg); 27.81 (J/mol/K);
53.7 (AC,, J/mol/K)
ACp = Cp(liquid) - Cp(g~ass)
At T,=304K
14.147
A t T=300K C,(,i,,,) = 1.183 &J/kg); 101.86(J/moVK)
Heat Conducti vi ty (J/ s/ m/ K) 0.159 52
Heat Distortion Point (C) 50 1 6
,Heat of Polymerization (kJ/mol) 87.5 31.32
hdex of Refraction (n &
At 20C
At 20C
At 20C
2 8
104,105
At 20C medium acetate type
At 20C low acetate type
1.5013
1.5100
1.5174
1.4903
1.523-1.57
At 6563 A
At 4861 A
Physical Constants of Poly(vinyl acetate) v/79
Property Value Remarks Refs.
At 2OC, molding compound
At 20.7C
At 30.8C
At 52.1C
At 52.1C
At 80C
At 142C
Spec. refraction index increment in
various solvents
1.4685
1.4669
1.4657
1.4600
1.4600
1.4480
1.4317
See Ref.
@nldJ
52
infrared Spectrum Important bands (cm-): 606, 950,
1025, 1250, 1740, 2850, 2865, 2923,
2932, 2950
See Ref.
39,102,131,132
1 3 3
69 Temperature dependence of IR bands at
loo-20C
At very low temperature
/nferfacia/ Tension (mN/m)
See Ref.
yc=37
14.5
8.4
9.9
4.2
10.5
11.0
9.8
At 20C with polyethylene
At 2oC, with poly(dimethylsiloxane)
At 20C with polyisobutene
At 20C with polystyrene
W i t h polyethylene
Linear PVAC with polyethylene
Branched PVAC with polyethylene
70
120
9
11
9
11
1 0 1
1 0 1
101
internal Pressure (J/m)
At 0 C
At 20 C
At 28 C
At 40 C
At 60 C
2.554 x 10
2.847 x 10
3.978 x 10
4.313 x 10s
4.187 x 10
6,29,30
40-51,77
136- 139
73
74
Intrinsic Viscosity - Molecular Weight
Rel ati onshi p
See corresponding table in this Handbook
From moderately cont. solutions
In 6-methyl-3-heptanone, at 66C
In 3-heptanone, at 26.8C
At 8 temperature, methanol, 6C
and also Refs.
See Ref.
[q] = 0.078 x M/
[v] = 0.082 x M I*
[q] =O.lOl x Ml/* 134,135
Mechani cal Properti es
Modulus of elasticity (MPa) = (N/mm )
Rubbery shear modulus (N/mm*)
Notched impact strength (cm kg/cm*)
1274-2255
13
>lOO
ASTM-D256 27
52
27
Molar Volume At 25C (cm3/mol) 74.25 99
Nucl ear Magneti c Resonance Spectra See Refs. 36,81,82
Shift with Eu and Pr reagents, improved See Ref. 78
resolution
Solvent and temperature effects
Conformational information
See Ref.
See Ref. Syndiotactic PVAC
79
80
Wavelength of 6328 A
Optical Configuration Parameters (Ao) (A3)
A c e t o n e - 20
Benzene 4.0-5.9
106
1 0 7
108
106
1 0 7
109
107
1 0 9
107
1 0 7
1 0 7
1 0 7
107
Bromobenzene 9.4
Bromoform - 20
Carbon tetrachloride - 16
Carbon tetrachloride - 2 6
Chlorobenzene 1 4
Chloroform - 34.9
Chloroform - 24
Cyclohexane - 23
Dichloroethane - 3 6
Dichloroethane - 39
Tetrabromoethane -25
References page V - 83
V/SO PHYSI CAL CONSTANTS OF POLY(VINYL ACETATE)
Property Value Remarks Refs.
Tetrabromoethane
To l u e n e
To l u e n e
To l u e n e
o-Xylene
Chl oroform
Chl oroform
1,3,5-Triethylbenzene
L-Radiation Effect
Yields of crosslinking
Yields of scission
Raman Spectra
Softening Temperature (C)
Sohbility
SohbXty Parameter (G(MPa) 1/2)
At 25C
At 50C
At 125C
6d
4
6h
s
Sol uti on Properti es
Unperturbed radius of gyration (A mollg)
Viscosity
nSpec in various solvents
Huggins constant, KH
Sol vent I nteracti on Parameters
- 3 3
1 0
13.5
1 9
2.0
8 1
- 2.68
- 1.90
0.3
0.15
0.07
0.06
See Ref.
35-50
See Ref.
See Refs.
18.6-19.9
21.07
19-4
17.9
19.0
10.2
8.2
23.1
See Ref.
Q=O.107
Log no=logK+a log c=p log M,
where logK= - 28.518, o =5.599,
and p=3.411
See Ref.
A c e t o n e 0.37
Chlorobenzene 0.41
Chl oroform 0.34
Methanol 0.47
To l u e n e 0.50
Benzene 0.37
Dioxane 0.34
Temp. 50C; v* = 1.0
Temp. 50C ; v2 = 0.6
Oxygen atmosphere
Nitrogen atmosphere
Oxygen atmosphere
Nitrogen atmosphere
Solvent-polymer activity in ethyl
acetate, acetone, benzene
In many solvents
Dispersion forces contribution
Polar forces contribution
Hydrogen bonding contribution
Total S=S;+S;+b;
Linear PVAC
Diethyl phthalate solution
At c = 5-4Og/lOO cc
1 0 6
1 0 7
1 1 2
1 0 9
1 0 7
1 0 7
110,111
110,111
1 6 5
2,3,4,5 *
56, 140
55
57
52,141
3 5
8 3
84
89
52
Solvent Temp. (C) Volume fraction, 42 Interaction parameter, 1 Refs.
Acetaldehyde
A c e t o n e
Acetonitrile
Ally1 chloride
Benzene
n-Butane
2-Butanol
2-Butanone
125- 140 1 0.35-0.32 150
25-29 0 0.40 151-153
30-40 0.8 0.34 154
30-50 1 0.31-0.39 154
loo-140 1 0. 32- 0. 21 148,150
125- 140 1 0.54-0.49 150
40 1 0.27 154
5 0.2 0.46 1 5 5
20 0 0.42 162
30 0.4-0.8 0.45-0.29 156
35-62 0 0.51-0.42 1 5 7
30-50 1 0.30-0.26 154
80- 140 1 0. 44- 0. 25 148,150,158
125- 145 1 0.37-0.32 149,159,160
100 1 1.97 1 4 8
135 1 0.31 159
10-45 0 0.43 1 5 1
100- 140 1 0.34-0.20 148,150
Physical Constants of Poly(vinyl acetate) VI81
Solvent Temp. (C) Volume fraction, 92 Interaction parameter, 1 Refs.
Butyl acetate
Butylbenzene
Butylcyclobexane
Carbon tetrachloride
Chlorobenzene
I-Chlorobutane
Chl oroform
Chloromethane
1-Chloropentane
1 Chloropropane
Cycloheptane
Cyclohexane
Cyclohexene
Cyclohexanol
Cyclooctane
Cyclopentane
cis-Decahydronaphthalene
n-Decane
1-Decanol
1,l -Dichloroethane
1,2-Dichloroethane
Dichloromethane
Dimethylphthalate
1,4-Dioxane
n-Dodecane
Ethanol
Ethyl acetate
Ethylbenzene
n-Heptane
1-Heptanol
n-Hexadecane
n-Hexane
1 -Hexanol
Isopropylamine
Methanol
Methyl acetate
2-Methyl-2-propanol
Nitroethane
n-Nonane
n-Octane
1-Octanol
1 -0ctene
n-Pentane
1 -Pentanol
2-Pentanone
Propane
1-Propanol
2Propanol
Propyl acetate
Propylamine
n-Tetradecane
Tetrahydrofuran
1,2,3,4-Tetrahydronaphthalene
3,3,4,4-Tetramethylhexane
To l u e n e
1 , 1 , 1 -Trichloroethane
Trichloroethylene
1,2,3-Trichloropropane
2,2,4-Trimethylpentane
n-Undecane
Vinyl acetate
Wa t e r
100
125- 145
125- 145
90-135
loo-135
100- 135
80-135
100
100
40
100
loo-140
100
135
100
100
125- 145
100- 145
1 3 5
100
loo-140
100
25
25
loo-140
125- 145
50
100
20
100
loo-135
loo-120
1 3 5
1 3 5
loo-120
1 3 5
40
125- 140
100
1 3 5
125- 140
loo- 145
90-120
1 3 5
1 3 5
100
loo-135
1 3 5
100
30-50
loo-135
125- 140
100
40
135
100- 140
125- 145
125- 145
80-140
100
100
15-50
loo-120
loo-145
30
40
1
1
1
1
1
0
0
0
0
1
1
1
1
1
1
0
1
1
0.4-0.8
0.51 1 4 8
0.95-0.88 160
1.90-1.75 160
0. 85- 0. 63 148,149,158
0. 28- 0. 33 148,149
0.73-0.66 148,149
20.17-20.09 148,149,158
0.25 148
0.82 1 4 8
0.75 154
1.63 148
1. 65- 1. 16 148,149,150,158,160
1.18 148
0.44 149,159
1.67 1 4 8
1.53 1 4 8
1.65-1.50 160
2. 5- 2. 01 148,149,159,160
0.81 159
0.19 148
20. 04- 0. 00 148,150
20.14 148
0.400 1 5 1
0.407 1 5 1
0. 17- 0. 03 148,150
2. 48- 2. 27 159,160
0.47 1 5 7
0.80 1 4 8
0.415 162
0.36 148
0. 66- 0. 58 148,159
2. 14- 1. 63 148,150,158
0.55 159
2.99 159
2.06-1.71 148,158
0.49 159
0.66 154
0. 77- 0. 73 150
0.30 148
0.30 159
0.14-0.19 150
2.38-1.88 148,149,159,160
2.3-1.94 148,158
0.65 159
1.55 149
2.06 148
0. 59- 0. 41 148,159
0.38 149
3.2 148
1. 3-1. 0 154
0. 64- 0. 38 148,159
0.44-0.35 150,159
0.42 148
0.61 154
2.70 159
0.30-0.14 148,150
0. 83- 0. 77 160
1. 72- 1. 56 160
0.56-0.40 148,150,158,159
0.49 148
0.40 148
0.38 1 5 1
2.17-1.86 1 5 8
2.7-2.14 148,159,160
0.41-0.22 156
2.5 1 6 1
References page V - 83
V/S2 PHYSICAL CONSTANTS OF POLY(VINY1 ACETATE)
Property Value Remarks Refs.
Specific Heat
Conformational (dE,,,,i/dT)
See also Heat Capacity
1.3
1.8
Syndiotactic
Isotactic
8 5
Softening Point
As a function of MW
Speci fi c Vol ume (l/kg)
See Refs. 116,117,118
9,13
19,61
77
(Umol)
0.823 f 6.4 x 1O-4 x T T= loo-200C
0.84 At T,
1.073 Monomer
0.841 Polymer
0.08774 One mole repeating unit 1 0 3
Stress Rel axati on Curves See Ref. 22-61.8C 20,97
Surface Resi stance (R/cm) 5 x 10-1 15
Surface Tensi on (mN/m)
At 20C
At 140C
At 180C
At 150C
9,10,11,12,86
36.5
28.6
25.9
27.9
- d,/dT= 0.066 (mN/m)
,yds = 27.4 f 0.1
y&=15.4+0.7
Ysolid = 42.85 3~ 0.8
.
58,87,101
58,119
8 5 Dispersive
Polar
Tot a l
Tensi l e Strength (MPa) = (N/ mm) 29. 4-49. 0
See Table in Ref.
At 20C 1 6
96
Thermal Conducti vi ty (W/ m/ K)
Pressure and temperature dependence
0.159 1 6
See Ref. 8 8
0.159 116
Thermal Expansion Coefficient (K-l)
At 0 C
At 20 C
At 40 C
At 60 C
At 80 C
At 100 C
Cubic
Linear above T,
Bel ow T,
2.8 x 1O-4
2.8 x 1O-4
7.13 x 10-4
7.17 x 10-4
7.20 x 1O-4
7.23 x 1O-4
6.7 x 1O-4
22 x 10-5
7 x 10-5
1 1 3
1525
17,27
Theta Temperatures
Polymer
-
M, (x 10-4) Dispersity
Sol vent 0 Temp. KB (x 104)
WWIM) (Cl [dl/g (g mol wt) -/I Refs.
Poly(viny1 acetate)
Linear
87-346
2. 7-126. 8 2.0
1.02-1.05
Methyl isopropyl
ketone/n-heptane
(73.2126.8)
n-heptanelmethyl
isopropyl ketone
(27.3172.7)
Ethyl n-butyl ketone
Ethyl isoamyl ketone
Methanol
Ethyl n-butyl ketone
Carbon tetrachloride
Ethanol
3-Heptanone
Cetyl alcohol
Ethanol
3-Heptanone
2 5 1 5 1
30 9.2 152
4.1-83
0.35-150
3.0-32
29
66
6
29
46.4
1 9
29
123
12-15
26
9.29 1 5 3
8.20
10.1 154
9.55 1 5 5
1 6 3
Branched
0.8-130 5.37 156
1 6 3
Ref erences VI 83
Property Value Remarks Refs.
Ukraviolet Radiation h(nm)
Absorption, cut-off
Quantum yields (mol/Einstein)
(in air) at X = 254
Acetic acid formation
Carbon dioxide formation
Carbon monoxide formation
Methane formation
Chain scission
Crosslinking
Ultraviolet Spectra
Youngs Modulus (MPa) = (N/mm)
Vi scoel asti c Response
X-Ray Diffraction
240 142
143
0.01
0. 0065
0. 0069
0. 0038
0. 05 (in air), 0.066 (in nitrogen)
0.0025 (in air), 0.047 (in nitrogen)
See Ref. 30, 38
600 At 25C and 50%RH 8
See Refs. 167-171
See Ref. Wide angle 98
L1 Pol ymer vol ume fract i on.
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Physical Constants of
Poly(methyl methacrylate)*
W. Wunderlich
ROHM GmbH, Darmstadt, FR Germany
Property Value Remarks Refs.
Birefringence (a 1- (~2) (cm3)
Segmental anisotropy
Ceihg Temperature (K)
Coefficient of Thermal Expansion (K-l)
Linear
Volume
Compressibility (MPa-I) (x 106)
Density (mg/m3) = (g/cm 3,
Di ffusi on 02 i n PMMA (cm/s) ( x 10)
Hz0 in PMMA (g cm/cm/h)
Dielectric Constant
Dissipation Factor (tan 6)
Elongation at Break (%)
2x10-25
2ox 10-25
478
7x10-5 o-50C 2
2.60~ 1O-4
2.55~10-~
CT,
3
4
2.72~ 1O-4
CT,
2.25x10-4
<T&T
5
5.80~ 1O-4
<T&T
6
5.60~ 10m4
T,
3
T,
4
5.80~ 1O-4
5.75x10-4
Tg
5
T,
6
245 T =20C 7
290 60 C 7
355 100C 7
390 109.3 C 7
500 119.8C 7
530 129.7C 7
561 150C 8
644 200 C 8
1.195 0 C 9
1.190 20 C 1 0
1.188 25 C 11
1.150
T,
1 2
0.5 0.21 bar, 25C 1 3
1.0 0.4 bar, 25C 13
1.4 1 bar, 25C 13
3.8 1 bar, 20C 1 4
5.2 Permeability 15
3.6 50 Hz, 25 C 1 6
3.0 1 KHz, 25C 1 6
2.6 1 MHz, 25C 1 6
2.57 30 GHz, 25C 17,18
2.59 138 GHz, 25C 1 8
0.062 50 Hz, 25 C 1 6
0.055 1 KHz, 25C 1 6
0.014 1 MHz, 25 C 1 6
0.007 30 GHz, 25C 17,18
0.010 138 GHz, 25C 18
4 10 5 M, < 2 x lo5 48
5.5 2 x lo6 5 M, 48
*Data are valid for normal radical polymerized PMMA if no tacticities
are given.
Benzene
Benzene, isotactic
1
47
V/t38 PHYSICAL CONSTANTS OF POLY(METHY1 METHACRYLATE)
Property Value Remarks Refs.
Entanglement Molecular Weight
Entropy of fo/ymerization (kJ/mol/K) *
Extinction Modulus (mm-) (x 104)
Flexural Strength (MPa) E (N/mm 2,
G/ass Transition Temperature T, (K)
Dependence on Tacticity
7000
-117
- 40.3
5.5
5
1.9
1
1 4 5
378
377
25C to solid polymer
-63C
647 nm
633 nm
514 nm
400 nm
DIN 53452
Dilatometric
49
1 9
19,20
2 1
2
2 1
2
48
6,12
5
c
Tacticity (triad analysis)
T, (C)
Is0 Hetero
Syn
41.5 0.95 0.05 0.00
54.3 0.73 0.16 0.11
61.6 0.62 0.20 0.18
104.0 0.06 0.37 0.56
114.2 0.10 0.31 0.59
119.0 0.04 0.37 0.59
120.0 0.10 0.20 0.70
125.6 0.09 0.36 0.64
134.0 0.01 0.18 0.81
22
22
5
2 2
49 i
5
22
49
Hardness (MPa) E (N/mm *)
Heat Capacity &J/kg/K)
Heat Conducti vi ty (W/ m/ K)
Heat of Combustion @J /kg)
Heat of Polymerization (kJlmo1)
/mpact Strength, Sharpy (M/m 2,
Modul us of El asti ci ty (MPa) E (N/mm*)
Modul us of Shear (MPa) = (N/mm*)
Mechani cal l oss Factor ( t an 6)
Optica/ Absorption (dBkm)
Partial Specific Volume (cm3/g)
Rate Constants of Polymerization
Contraction constant E
Monomer density d (g/cm 3,
Chain propagation k, (l/mol/s)
Chain termination kt (l/mol/s)
ki/k,val ue
Termination mode
Relative contribution of
combination x,
Thermal initiation rate
Ri,th (mOl/k)
Transfer to monomer CM
Transfer to polymer Cp
1 9 5
0.585
0.878
1.255
1.42
1.72
2.05
2.38
2.35
2.50
0.19
- 26.2
- 57.8
20
3300
DIN 53456
- 173 C
- 100 C
0 C
25 C
100C
120C
180C
240 C
300 C
To solid polymer
IS0 1790 fu
25 C
Dynami c
25C, 10 Hz
25C, 10 Hz
514.5 nm
20C i n monomer
20C i n monomer
70C i n monomer
48
2 3
23
2 3
2 3
2 3
2 3 i
2 3
24
24 I
50
I
2 5
1 9
5 1
2
1700
0.08
84
0.812
0.819
0.833
2
26
I
52
1 0
27
1
1 0
--E = 0.2256 + 4.81 x 10-4t + 4.1 x lo-*t*
d =0.9659 - 1.2129 x 10-3t
+1.6813 x lo-%* - 1.0164 x 10-8t3
In k, = 17.68 - 3762/T
In kt = 24.91 - 2536/T
In kifk,= 10.45 - 4988/T
0 <T 5 100C 28
0 =T = 130C
313 < T 5 353K
313 5 T 5 353 K
3 1
29
29
29
In T, = -4.1 + 1160/T
In Ri,th = 1.7 - 131OO/T
34
I
3 1
In CM = -2.60 - 2855/T 313 5 T 5 353 K 3 1
1.5 - 2.5 x 1O-4 313 5 T < 353K 30
*mol: monomer unit.
Ref erences v/ a9
Property Value Remarks Refs.
Pressure dependence of
polymerization rate
activation volume AV,,i (cm3/mol)
Refracti ve Index
nD
ne
- &/dT (K-l)
Abbes number (rn)
Resistivity (ohm cm)
Sol vents
Thermal Conducti vi ty (W/ m/ K)
Theta Sol vents and Temperatures
Acetonitrile
Heptanone-4
Isoamyl acetate
n-Butyl chloride
Heptanone-3
n-Propanol
Unit Cell
Unperturbed Dimensions
KB = $/A4 (cm*mol/g)
Vel oci ty of Sound (m/s)
Vicat Temperature (K)
Viscosity-Molecular Weight
Relationship* [q] =KMa (cm3/g)
- 23. 6
- 19. 0
1. 492
1. 494
1. 502
1. 2 x 10-4
3.1 x 10-4
51.8
>105
0. 160
0. 193
0. 250
0 = 3O. O"C
I 9 = 40. 4"C
B = 57. 4"C
0 = 35. O"C
0 = 26. 5"C
8 = 3O. O"C
0 = 4O. O"C
e = 15. 9"C
e = 84. 4"C
5. 2 x lo-*
2700
2850
385
393
20C 32
30 C 33
=589 nm
=546 nm
=436 nm
<Ts
Ts
See chapter on Solvents-
Nonsolvents in this Handbook
- 20C
o- 50C
100C
Syndiotactic
Isotactic
Syndiotactic
Isotactic
Syndiotactic
Isotactic
See corresponding chapter in
this Handbook
See also corresponding chapter
in this Handbook
2 MHz, 25C
5 MHz, - 40C
M, = 1. 2 x lo5
M, >5 x lo6
See also chapter Viscosity-
Molecular Weight Relationship
in this Handbook
Solvent T (0 K (~10~) a
2
2, l O
22, l O
53
53
50
2
35
36, 37
38
39
40
40
40, 41
41
42
42
42
42
43. 44
45
46
50
50
A c e t o n e 20 1 0 0. 68 43
Benzene 30 5. 2 0. 76 54
THF 25 10. 4 0. 70 54
n-Butyl chloride 35 = I 9 50 0. 50 43
Chl oroform 25 4. 8 0. 80 54
Water Absorption (%) 2. 0 Saturation T = 23C 55
REFERENCES 7.
1 . V. N. Tset kov, N. N. Boi t zkova, Vysokomol . Soedi n, 3, 1176
( 1960) .
2. G. Schreyer, Konst rui eren mi t Kunst st offen, Carl Hanser,
Milnchen, 1972.
3. P. Heydemann, D. H. Guicking, Kolloid-Z., 193, 16 (1963).
4. J. Hennig, Diplomarbeit TH, Darmstadt, 1961.
5. J. C. Wittmann, A. J. Kovacs, J. Polym. Sci. C. 16, 4443
( 1969) .
6 . S. Loshaek, J. Polym. Sci., 15, 391 (1955).
8.
9.
10.
11. W. G. Gall, N. G. McCrum, J. Polym. Sci., 50, 489 (1961).
12. S. S. Rogers, L. Maudelkern, J. Phys. Chem., 61, 945 (1957).
13. R. E. Barker, Jr., J. Polym. Sci., 58, 553 (1962).
14. J. R. MacCallum, A. L. R&kin, Eur. Polym. J., 14,655 (1978).
K. H. Hel l wege, W. Knappe, P Lehmann, Kol l oi d- Z. , 183, 110
( 1962) .
B. P. Shtarkman, J. M. Monich, S. A. Arzhakov, N. Yu
Averbakh, Vysokomol. Soedin A, 18, 1047 (1976).
H. J. Kolb, I.F. Izard, J. Appl. Phys., 20, 564 (1949).
D. Panke, W. Wunder l i ch, RGhm GmbH, Dar mst adt , unpub-
lished results.
* Molecular weights were determined by means of light scattering and sedimentation.
v/90 PHYSICAL CONSTANTS OF POLY(METHYL METHACRYLATE)
15. F. Bueche, J. Polym. Sci., 14, 414 (1954).
16. G. Schreyer, Kunststoffe, 55, 771 (1965).
17. E. Amrhein, Kolloid-Z., 216-7, 38 (1967).
18. W. Zeil, R. Sistig, W. Frank, V. Hoffman, Ber. Bunsenges.
Phys. Chem., 74, 883 (1970).
19. H. Sawade, J. Macromol. Sci. C, 3, 313 (1969).
20. R. W. Warfield, M. C. Petree, J. Polym. Sci. A, 1, 1701 (1963).
21. B. Crist, M. E. Marhic, G. Ravio, M. Epstein, J. Appl. Phys.,
51, 1160 (1980).
22. E. V. Thompson, J. Polym. Sci. A-2, 4, 199 (1966).
23. R. Hoffmann, W. Knappe, Kolloid-Z., 247, 763 (1971).
24. V. Bares, B. Wunderlich, J. Polym. Sci. A-2, 11, 861 (1973).
25. K. Krekeler, P. M. Klinke, Kunststoffe, 55, 758 (1965).
26. J. Heiboer, Kolloid-Z., 148, 36 (1956).
27. G. V. Schulz, M. Hoffmann, Makromol. Chem., 22, 220
28. D. Panke, M. Stickler, W. Wunderlich, Makromol. Chem., 184,
175 (1983).
29.
30.
31.
32.
M. Stickler, Internal Report Rohm GmbH, Darmstadt, 1978.
T. Comer, Adv. Polym. Sci., 62, 97 (1984).
M. Stickler, G. Meyerhoff, Makromol. Chem., 179, 2729
(1978).
T. Sasuga, M. Takehisa, J. Makromol. Sci.-Chem. A, 12,
1307 (1978).
33.
34.
35.
36.
M. Yokawa, Y. Ogo T. Imoto, Makromol. Chem., 175, 179
(1974).
G. V. Schulz, G. Henrici-Olive, S. Olive, Z. Phys. Chem.
(Frankfurt), 27, 1 (1960).
R. E. Barker, R. Y. S. Chen, R. S. Frost, J. Polym. Sci.,
Polym. Phys. Ed., 15, 1199 (1977).
E. Calvet, J. P. Bros, H. Pinelle, Compt. Rend, 260, 1164
(1965).
37. K. Eiermann, Kolloid-Z., 198, 5 (1964).
(1957).
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
A. B. Baschirow, J. W. Selenew, S. K. Achundow, Plaste
Kautschuk, 23, 351 (1976).
E. Cohn-Gibsberg, T. G. Fox, H. Maron, Polymer, 3, 97
(1962).
R. G. Kirste, G. V. Schulz, Z. Phys. Chem. (Frankfurt), 27,301
(1961).
G. V. Schulz, W. Wunderlich, R. G. Kirste, Makromol. Chem.,
75, 22 (1964).
J. Sakurada, A. Nakajima, 0. Yoshizaki, K. Nahamae, Kolloid-
Z., 186, 41 (1962).
G. V. Schulz, R. G. Kirste, Z. Phys. Chem. (Frankfurt), 36, 171
(1961).
W. Wunderlich, Makromol. Chem., 182, 2465 (1981).
F. Pluemer, Kolloid-Z., 176, 108 (1961).
A. M. North, R. A. Pethrick, D. W. Phillips, Polymer, 18, 324
(1977).
H. Sawada, Thermodynamics of Polymerization, Marcel
Dekker, New York, 1976.
M. Buck, in: Kunststoff-Handbuch, vol. 9, Carl Hauser,
Miinchen, 1975.
K. Fuchs, Chr. Friedrich, J. Weese, Macro-molecules, 29,
5893 (1996).
G. Schreyer, J. Lehmann, in: Kunststoff-Hand-buch, vol. 1,
Carl Hauser, Miinchen, 1990.
Th. Amdt, Internal Report Rohm GmbH, Darmstadt, 1996.
P. Avakian, W. Y. Hsu, P. Meakin, H. L. Snyder, J. Polym. Sci.,
Polym. Phys. Ed., 21, 647 (1983).
J. M. Cariou, J. Dugas, L. Martin, P. Michel, Appl. Optics,
25, 334 (1986).
H. L. Wagner, J. Phys. Chem. Ref. Data, 16, 165 (1987).
J. Lehmann, Materialien in ihrer Umwelt, DWS, Karlsruhe
(1996).
Physical Constants of Poly(styrene)
David Schrader
Designed Thermoplastics Research, The Dow Chemical Company, Midland, Ml, USA
Property Value Remarks Refs.
Bi refri ngence Di spersi on
An(x)
An (546 nm)
Coefficient of Thermal Expansion (K-t)
Linear
Volume
Coefficient of Friction
Cohesi ve Energy Densi ty
Common Sol vents
Compressi bi l i ty (MPa-)
Compressi ve Modul us (MPa) = (N/mm*)
Creep/Stress Rel axati on
30
6-8 x 1O-5
1.7-2.1 x 1O-4
5.1-6.0 x 1O-4
0.515
0.744
>2
0.25
2.65
See solubility parameter
Toluene, perchloroethylene,
carbon tetrachloride,
carbon disulfide, tetralin,
dioxane, MEK, pyridine,
cyclohexanone, ethyl acetate
220 x 10-6
3000
A = 0.8905
B=0.275 x 10-gcm2
C = 0.153 x lo-* cm4
< T, (unoriented) 3 .
CT,
7a
T,
7a
20-80C 7b,7c
100C 7b
120C 7b
100C 7c
llO-120C 7c
Unoriented
See Ref.
I I I
I
/
100 1.000
Ti me (min)
Figure 1. Typical creep behavior for rubber-modified styrene polymers.
Crystal l ographi c Data
Densi ty (mg/m 3,
Amorphous
Crystalline
d,/dT (g/cm3/K)
d,ldT (g/cm3/K)
See under Unit Cell
1.04- 1.065
1.111
1.12
- 2.65 x 1O-4
- 6.05 x 1O-4
CT,
Tg
2 1
34
3
18a
35
394
2
L5
6
6
v/91
V/ 92 PHYSICAL CONSTANTS OF POLY(STYRENE)
Property Value Remarks Refs.
Dielectric Constant (8)
Amor phous
Crystalline
Dissipation Factor
Amorphous
Crystalline
Dynami c Mechani cal Loss Peaks
1Hz
7kHz
Entanglement Molecular Weight
Glass Transition Temperature, Ts (C)
Heat Capacity, Cp @J/kg/K)
dCr/dT (k.l/(kg K*))
Heat Capacity vs. Temperature
2.49-2.55 at 1 kHz (curve flat to 1 GHz) 3
2.61 at 1 kHz (curve flat to 1 GHz) 16a
15 x 10-4 at 1 kHz (curve flat to 1 GHz) 3
3 x 10-4 at 1 kHz (curve flat to 1 GHz) 16a
Tg=300K
T,=138K
T;=48K
19100
80
90
(lcw
1.185 (1.139)
1.256 (1.394)
1.838 (1.821)
4.04 x 10-s
See Fig. 2
T, (K) = 373 - (1.0 x 105/M,)
0 C
50C
100C
50C
16b
16b
16c
43
6
8
9
3,12
3,12
3.12
3
36-37
Poly(styrene) i
3 - 1;

-
I
I
I I
9 I
Y
; L/
Temperature (K)
Figure 2. Heat capacity vs. temperature curves for amorphous, atactic, and isotactic polyktyrenes).
Heat of Combustion (kUmo1)
Heat of Fusion (kI/mol) (1
Crystalline
Heat of Polymerization (k.l/mol)n
Heat of Solution (kJ/mol)
Infrared Spectrum
Intrinsic Viscosity vs. MW
Limiting Oxygen Index (%)
Melting Point TM (C)
Melt Viscosity - Molecular Weight
Rel ati onshi p
To solid polymer
To solid polymer
In monomer
See Ref.
See Ref.
- 4.33 x 103
8.37 f 0.08
9.00
- 67.4
- 69.9
- 3.60
Various solvents
18.1
240
(250)
log nr = 3.4 log M-k
Atactic
Isotactic
T (C) M range k
217 2 38,000 13.04
281 100000-600000 14.42
13a,14
1 0
2
15
13a
13a
1 3 b
3 8
44
1 0
11
3 1
32a
3 9
mol: Monomer unit.
Physical Constants of Poly(styrene) v / 9 3
Property Value Remarks Refs.
M W Distribution Curves
(For representative poly(styrenes))
5.0
4.0 -
.J Anionic
3.0
Le
r;
2.0
1.0
0.0 L
103 104 105 106 10
Mol . wt.
Figure 3. Molecular weight distribution curves for representative poly(styrenes).
Nucl ear Magneti c Resonance Line width (gauss)
Optical Dispersion, q F - q c
Poissons Ratio
Refractive Index, no
dnn/dT (K-l)
Resistivity (Ohm cm)
Sohbility Parameter (J/m 3, I* x 10 -3
Soni c vel oci ty (m/s)
Speci fi c Gravi ty
Stress-Opti cal Coeffi ci ent ( br ewst er s)
Stress-Strai n Curves
Surface tension, 293 K, mN/m
(S dynkm) (Ps/air)
syndiotactic
Tensi l e Modul us, E (MPa) = (N/mm *)
dE/dT (N/mm ?K) = (MPa/K)
Thermal Conductivity (W/m/K)
-
-
T (C) Value
0 6.7
50 6.5
100 5.0 ,
150 1.0
peaks (ppm) at 3.0, 3.5 (aromatic), \
8.4 (CH2)
1.92 x lo-
0.325
0.33
1. 59- 1. 60
1.42 x 1O-4
1o*o-102s
16 . 6-20 . 2 (8 . l-9 . 9 (cal/cm3)1/2)
2100
1. 04- 1. 06
10.1
9.5
8.3,8.7
See Figs. 4-6 (next page)
40.7
3200
3400
4200
4.48
0.105
0.116
0.128
Thermogravi metri c Anal ysi s
In vacua (lOC min-I)
wt. loss (%) T (Cl
0 275
5 330
1 0 343
20 360
32b
Referred to tetramethylsilane as + 10.0 32c
X=486.1nm
X = 656.3 nm
3
3
3
20
3
3
17a
40
X =589.3 nm
3
4 1
Monofilament 22
Extruded sheet 22
Compression molded 22
42

45
.I _
47
Unoriented 6 1 9
18a
Oriented monofilament 18b,18c
1 9
0 C 3
50C 3
100C 3
17b
wt. loss (%) T(C)
40 390
60 408
80 422
100 450
References page V-95
v/94 PHYSICAL CONSTANTS OF POLY(STYRENE)
I
I
I
I
I
I
I
8
i
Monodi sper se poly(styrene)
I I
.
A
I I I I
1 2 3 4
Log t (set)
Figure 4. Stress relaxation curves for monodisperse polyktyrene).
I
I
I
I
I
I
Pol ydi sper se poly(styrene)
\
122C
127C
I I I I I
2 3 4
Log t (set)
X
1C
\
\
5
Figure 5. Stress relaxation curves for polydisperse polyktyrene).
I I I I I I I II I
8000
5o-I
S A N - 7 0 0 0
030
0 2 4 6 8 10 12 14 16 18 20 22
El ongat i on (%)
Figure 6. Stress-strain curves for styrene-based polymers.
Property Value Remarks Refs.
Unit Cell (A)
a0
bo
co
21.9
22.08
21.9
22.08
6.63
6.626
Rhombohedral system; 18 monomer
units in cell
1
2
I
2
1
2
Physical Constants of Poly(styrene) v/95
Property Value Remarks Refs.
Ukraviolet Spectrum (in vacua) Absorption bands at 260, 194 and 80nm
Viscosity - Molecular Weight Relationship See also corresponding chapter in this Handbook 33
Water Absorption at Equilibrium
(23"C,50% RH) 0.05% 46
Solvent T (C) Sol vent Method K ( x 103) a Refs.
ATACTIC
Benzene
Benzene
Toluene
Toluene
Toluene
Benzene
Toluene
Toluene
30
25
25
25
30
30
30
25
Benzene
Toluene
Butanone
Butanone
Butanone-isopropyl
Alcohol
Toluene
Toluene
Cyclohexanone
Osmotic 9.7 0.74 23
Osmotic 11.3 0.73 24
Osmotic 13.4 0.71
Light scattering 1 7 0.69 25
Light scattering 9.23 0.72 26
Osmotic 10.6 0.735 27
Osmotic 11.0 0.725
Sedimentation velocity 9.77 0.73 28
ISOTACTIC
Benzene 30 Toluene Osmotic
Toluene 30 Toluene Osmotic
Benzene RT Toluene Osmotic
Benzene 25 Toluene Osmotic
Toluene 25 Butanone Light scattering
Constants determined by the method and solvent given in these columns; [q] = KMa, in ml/g.
REFERENCES
10.6 0.735 27
11.0 0.725
9.5 0.77 29
9.79 0.744 30
1 7 0.69 25
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(1949).
7b. H. J. Karam, W. C. Sager, K. S. Hyun, The Dow Chemical
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7c. M. Lund, The Dow Chemical Company, unpublished
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57, 483 (1962).
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effect of residual monomer, low-molecular-weight poly-
mer, ethylbenzene, and plasticizers being to depress T,,
the value given by these authors represents the limiting
glasstransition temperature at high molecular weights.)
10. R. Dedeurwaerder, J. F. M. Oth, J. Chim. Phys., 56, 940
(1959).
11. T. W. Campbell, A. C. Haven, Jr., J. Appl. Polym. Sci., 1,
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(1947).
16a. F. L. Saunders, R. C. Mildner, The Dow Chemical Com-
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16b. K. -H. Illers, Z. Electrochem., 65, 679 (1961).
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Sci. A-3, 3, 2693 (1965).
17a. P. Woodland, The Dow Chemical Company, unpublished
data.
17b. J. G. Cobler, The Dow Chemical Company, unpublished
data.
18a. Strength and Stiffness, in: Plastics Design Data, Dow
Technical Chemical Publication, 1965 revision.
18b. L. Kin, The Dow Chemical Company, unpublished data.
18~. R. D. Andrews, J. F. Rudd, J. Appl. Phys., 28, 1091
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19. J. F. Rudd, Gurnee, J. Appl. Phys., 28, 1096 (1957).
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Reinhold, New York, 1962.
21. E. F. Gumee, J. Polym. Sci. A-2, 5, 817 (1967).
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V/96
23.
24.
25.
26.
27.
28.
29.
30.
31.
32a.
32b.
32~.
33.
34.
PHYSICAL CONSTANTS OF POLY(STYRENE)
R. H. Ewart, H. C. Tingey, Abstracts 11 lth Am. Chem.
Sot. Meet., April 1947; quoted in Fox and Flory, J. Am.
Chem. Sot., 73, 1915 (1951).
C. E. H. Bawn, R. F. J. Freeman, A. R. Kamaliddin, Trans.
Faraday Sot., 46, 1107 (1950).
P Outer, C. I. Carr, B. H. Zimm, J. Chem. Phys., 18,830
(1950).
S. N. Chinai, P. C. Scherer, C. W. Bondurant, D. W. Levi,
J. Polym. Sci., 22, 527 (1956).
F. Danusso, G. Moraglio, J. Polym. Sci., 24, 161
(1957).
H. W. McCormick, J. Polym. Sci., 36, 341 (1959).
F. Ang, J. Polym. Sci., 25, 126 (1957).
W. R. Krigbaum, D. K. Carpenter, S. Newman, J. Phys.
Chem., 62, 1586 (1958).
T. G. Fox, P. J. Flory, J. Polym. Sci., 14, 315 (1954).
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129 (1964).
R. Kosfeld, Kolloid-Z., 172, 182 (1960).
F. A. Bovey, G. V. D. Tiers, G. Filipovich, J. Polym. Sci.,
38, 73 (1959).
R. H. Partridge, J. Chem. Phys., 47, 4223 (1967).
Roff, Scott, Pacitti (Eds.), Handbook of Common Poly-
mers, CRC Press, Florida, 1971, p. 46.
35.
36-37.
38.
39.
.40.
41.
42.
43.
44.
45.
46.
47.
Kirk-Othmer, Encyclopedia of Chemical Technology,
vol. 21, 3rd ed., 1978, p. 806.
Polymer Handbook, 2nd ed., Wiley, New York, 1974,
p. III/217; see also this edition.
Polymer Handbook, 2nd ed., Wiley, New York, 1974,
p. IV/17; see also this edition.
Kirk-Othmer, Encyclopedia of Chemical Technology,
vol. 21, 3rd ed., 1978, p. 808.
Polymer Handbook, 2nd ed., 1974, p. IV/352; see also this
edition.
Roff, Scott, Pacitti (Eds.), Handbook of Common Poly-
mers, CRC Press, Florida, 1971, p. 47.
Kirk-Othmer, Encyclopedia of Chemical Technology,
vol. 21, 3rd ed., 1978, p. 805.
J. T. Seitz, Measurement of Entanglement length in
Broad Molecular Weight Systems, 50th jubilee, Rheol.
Sot., Boston, 1979.
H. Ohe, K. Matsura, Text. Res. J., 45, (1 l), 778 (1975).
S. Wu, Polymer Interface and Adhesion, Marcel Dek-
ker, knew York, 1982, p. 88.
B. Mauer, Dow Chemical Co., Midland, 1988, unpub-
lished water absorption data.
A. Sciutto, F. Ga-bassi, L. Meda, R. PO, L. Pozzi, Appl.
surface Sci., 125 (3-4), 287 (1998).
Physical Constants of Poly(oxymethylene)
K.-F. Muck
Ticona, Kelsterbach, FR Germany
Property Value Refs.
Homopolymer (density 1.418-1.419g/cm3)
Equilibrium concentration, 60C
Aniline (wt.%)
m-Cresol (wt.%)
Dimethylformamide (wt.%)
Water (DIN 53 472, after 96 h), (mg)
(wt.%)
Gain in volume, 60C (vol.%)
Aniline
m-Cresol
Dimethylformamide
Average sorption coefficient, 25C
Water
Activation Energy of fo/ymerization (kllmol)
Of radiation induced trioxane
In source polymerization
Post polymerization > 50C
< 50C
44-55C
45-55C
Of cationic polymerization of trioxane
In ethylene dichloride
In the solid state
Anisotropy of Solid State Extruded POM
Arc Resi stance (s) (ASTM D495)
Homopol ymer
Copol ymer
DIN 53484, VDE 0303, part 5
Copol ymer
Ceiling Temperature (C)
Polymerization of formaldehyde (gas) + poly(oxymethylene) (solid)
At 1 bar
At different pressures calculated from Ref. 66
P (bar)
9.60
16.48
5.73
20 -30
N 0.14-0.21
13.7
23.0
8.6
See Ref.
-21; 121
167
287
126
165; 174
79.5
36
See Ref.
129 (bums)
240 (bums)
L4
119
127
116
120
137
126
133
tc (0
72
72
72
72
72
8 1
8 1
127
73
73
66
2 5
9
22
90
94
95
67
0.36 100
0.62 110
1.06 120
1.75 130
2.81 140
4.44 150
6.85 160
10.36 170
Polymerization of trioxane (gas) -+ poly(oxymethylene) (solid) 36 94
v/97
V/98 PHYSICAL CONSTANTS OF POLYtOXYMETHYLENE)
Property
Chemi cal Resi stance
Coefficient of linear Thermal Expansion (K-l)
20-100C (VDE 0304)
Amorphous > T, (ASTM D 696)
Copol ymer
Homopolymer DIN 52328, ASTM 696
Copolymer
Cohesi ve Energy, 25C (kI/mol)
Cohesi ve Energy Densi ty (J/m3) W2 ( x 10 m3)
25C
Liquid, 25C, theroretical value
Comonomer Distribution by pYrolysis/GC
Comparative Figure of Tracking
CrystaKnity (%)
Homopol ymer
2oC, from density-data
25C, from X-ray-data
135C from X-ray-data
14oC, from X-ray-data
145C, from X-ray-data
150C from X-ray-data
155C from X-ray-data
157C from X-ray-data
16OC, from X-ray-data
177C from X-ray-data
Delrin 150, 20C from density data
Delrin 550, 2oC, from density data
Copol ymer
20C
Hostaform C2520, M, 80000
20C from density data
Hostaform C9020, M, 58000
20C from density data
Homo- and copolymers, from density data
Trioxane/dioxolane copolymers with different
comonomer content
Dependence on irradiation
.
Value
See Refs.
1.0-1.4 x 10-4
1.2 x 10-4
0.85 x 10m4
0.81 x 1O-4
1.1 x 10-4
9.88
22.8
20.9
600
64 -69
71
75
73.0
73.1
75.4
16.9
67
80.0
95.5
64.0
68.7
56 -59
56.6
58.7
See Ref.
See Ref.
See Ref.
Refs.
13,19
3
6
13
13
4
1
4
107
1 3 8
5
6
6
70
70
I O
I O
6
I O
70
5
5
5
5
5
56
7 1
98
Crystallographic Data
Poly(oxymethylene)
Crystal system
Space group
Mol. helix
Unit cell axes (A)
No. of units
P C (Mgmm3)
Packing density
Phase transition
Transition energy
Orth + Trig (kI/mol) (-OCH2)
Orth, two forms
Cryst. packing density
Pa (Mg/m3)
Amorphous packing density
Heat of fusion (k.I/mol)
Glass transition temperature (K)
Trig
P3 or P32
2* 915
4.411
4.471
11.39
9
1.491
0.65
See Ref.
+ 0.6
0.18
1.25
0.65
9.19
1 9 1
Orth
P222
2* 2/l
4.767
1.660
3.563
4
1.533
0.81
-
-
6 1
99
1 1 5
1 0 0
101
60,61
6 1
t
Physical Constants of Poly(oxymethylene)
V/W
Property Value Refs.
For trioxane-1,3-dioxolane copolymers
Crystal structure of radiation induced polytrioxane and
tetroxane
Deformation Under Load (%)
(ASTM D621, 13.8 Mpa at 50C 24hr)
Homopol ymer
Copol ymer
Entanglement in Solid State
Density ( 10m3 kg/m3) E (g/cm 3,
Homopol ymer
Dehin 500
After annealing
Dehin 150, 20C
Delrin 550, 20C
Copolymer, 20C
Hostaform C2520, M, 80000
Hostaform C9020, M, 58000
Copolymers, 20C; after annealing; mol fraction
of di oxol ane comonomer
0.075
0.15
0.18
0.25
0.30
0.34
Poly(oxymethylene)
Trigonal, amorphous
Crystalline
Orthorhombic, crystalline
Degradation (initial) Under N2
Homopolymer (C)
Copolymer (C)
Depolymerization, Energy of Activation (kJ/mol)
Poly(oxymethylene)diol thermal depolymerization 90- 150C
loo-120C
130-150C
135- 190 C
170-285C
172- 188 C
Cationic depolymerization - 30 to + 33C
130-150C
Anionic depolymerization 130-150C
135- 170 C
Poly(oxymethylene)diacetate and dimethyl ether
Thermal degradation,
240-340C
280-350C
199- 331 C
Autoxidative degradation, 160C
Thermooxidative degradation, 145-160C
Depolymerization Rate (min-)
Poly(oxymethylene)diol
Vdepol = &hem FOM) + kbas UOM) (Amine)
See Ref.
See Ref.
0.5
1.0
See Refs.
1.420 f 0.005
1.434 f 0.004
1.427
1.435
1.412
1.416
1.412
1.388
1.380
1.363
1.358
1.346 (average values)
1.25
1.491
1.533
318
324
42
113
82.9 f 12.6
83.8
109
71*10
80.0 f 9.6
87.5 f 12.6
27.2 zt 6.3
62.0 f 7.5
234
134
117
117,121
6 1
See Ref.
7 1
1 0 5
73
73
128,129
7
7
5
5
5
5
7 1
6 1
6 1
6 1
1 2 1
53
9
8
11
1 0
88
1 2
8
8
1 3
11
1 0
53
52
53
5 1
T(C) &,em(xl@)
kbPS (~10~)
1 3 5 1.6f0.2 4.1 f0.2
150 3.5fO.l 7.7 f 0.5
160 5.0 f 0.5 11.6fl.O
170 7.4* 1.0 17.0 f 2.0
References page V- 110
V/l00 PHYSICAL CONSTANTS OF POLY(OXYMETHYLENE)
Property
Di el ectri c Absorpti on (Homopol ymer)
a-Absorption
B-Absorption
y-Absorption
Dielectric Constant ( 10 3 Hz)
DIN 53 483, ASTM D 150-59 T
Value
Near 1OHz at about 140C
1 kHz- 1 MHz at 60- 100C
,lGHz
3.6-4.0
.
Refs.
4 9
3,73
Dielectric Loss, tan 6 ( lo3 Hz) (15-50) x 10e4; See also Ref. 3
DIN 53 493. ASTM D 150-59 T 7,14,15,16,138
Di el ectri c Strength (kV/mm)
DIN 53 481 (50 Hz, 0.5 kV/s, f i l m 0.2 mm) 50 -70 3
Homopol ymer 33 1 3 8
Copol ymer 3 5 138
Diffusion (films)
Water
Activation energy, apparent (kJ/mol)
Copol ymer 0- 80C
Copolymer, branched, 50C
Diffusion coefficient, average, 25C (cm/s)
Copol ymer
Copolymer, branched
Copolymer, linear and branched
Carbon dioxide
Activation energy (k.l/mol)
Copol ymer
Copolymer, branched
Diffusion coefficient (cm */s)
Copol ymer
Copolymer, branched
Formaldehyde
Diffusion coefficient (dc) (cm *Is)
41.5 18
44.4 2
2.7 x lo-*
7.0 x 10-s
See Ref.
48.9
38.5
1.4 x 10-s
4.4 x 10-a
Dissipation Factor
At lo3 Hz (ASTM D150)
Homopol ymer
Copol ymer
El asti c Modul us (N/ mm)
DIN 53457 (1 mm/min)
Elongation at Break (%)
DIN 53455 (50mrn/min)
Low molecular mass
High molecular mass
ASTM D638 (5 mm/min)
Homopol ymer
Copol ymer
Elongation at Yield (%)
Homopol ymer
Copolymer
T ((3
dc (cm%)
60 2.14 x 1O-9
40 1.34 x 10-s
2 1 1.0 x 10-s
3 x 10-s
4 x 10-s
2600 - 3400 6 3
20 -40
35 -70
15-75
50-75
1 2 1 3 8
7 1 3 8
6 3
6 3
3
53
53
13
13
. 38
138
Physical Constants of Poly(oxymethylene) v/101
Property Value Refs.
fnthdpy &J/kg)
Homopolymer 0 K
50K
1OOK
200 K
300 K
Copol ymer OK
50K
1OOK
200 K
300 K
Entropy &J/kg/K)
Homopolymer 0 K
50K
1OOK
200K
300 K
Copolymer 0 K
50K
1OOK
200 K
300 K
0 1 9
6. 909 19
29. 69 1 9
102.6 1 9
222. 5 1 9
0 1 9
6. 948 1 9
29. 40 1 9
100.9 1 9
211.4 1 9
0 1 9
0. 2097 1 9
0.5167 19
1.007 1 9
1.487 1 9
0 1 9
0.2123 1 9
0.5153 1 9
0. 9974 19
1.439 1 9
Entropy of Fusion (kJ/mol/K)
Of homopolymer at constant pressure
Of homopolymer at constant volume
Poly(oxymethylene), equilibrium value
8.21 x 10m3 2 0
4. 98 x 1O-3 2 0
10.70 x 10-s 5 7
Entropy of Polymerization (J/moVK)
Formaldehyde (gas, 1 bar, 298 K) + poly(oxymethylene) (solid)
From heat capacity data
From equilibrium pressure data
Formaldehyde (liquid, 298 K) + poly(oxymethylene) (solid)
Trioxane + poly(oxymethylene) at 298 K
Gas t solid
Gas + liquid
Liquid --+ liquid
Liquid + solid
Solid + solid
At 323 K in dichloroethane
Tetraoxane (solid) + poly(oxymethylene) (solid) at 298 K
- 175kO.8 1 9
- 169.5 zt 2.9 6 6
- 128.4 zt 0.9 2 5
- 175 9
- 129 1 9
- 183 2 1
- 13 6f 17 9 0
86. 7 96. 94
- 156 2 2
- 155 96, 94
- 106 96, 94
0 96, 94
- 49. 0 96, 94
- 6. 7 96, 94
$18It16 6 6
See Ref. 6 5
-41 9 2
3.41 i 0.06 6 6
Entropy of Trimerizafion (J/Wmol trioxane)
Formaldehyde (gas) + trioxane (tryst.) at 298 K
Formaldehyde (gas) + trioxane (gas) at 298 K
Fati gue Behavi or
Of acetal homopolymer
Flammability
Radiant heat
flux (kW/m*)
- 526f 13 9 1
-375f12 9 1
See Ref. 5 4
126
Ignition time (s)
TI, (Cl
2 1 248 277
2 5 184 278
2 8 138 282
3 4 7 9 288
References page V- 110
v/102 PHYSICAL CONSTANTS OF POLY(OXYMETHYLENE)
Property Value Refs.
Flammability UL 94 1 3 8
(l.Smm sheet)
Yellow card 2060
Class HB
Flexural Modul us (N/mm *)
ASTM D790 at 23C
Homopol ymer 2830 7 3
Copol ymer 2590 7 3
Flexural Strength at Yield (N/mm )
ASTM D790
Homopol ymer 97 7 3
Copol ymer 90 7 3
Flexural Stress at Conventional Deflection
MPa = (N/mm*)
DIN 53452 105-120 3
Flow Temperature ( C)
ASTM 569
Homopol ymer 184 73
Copol ymer 174 73
Formal dehyde
Melting point (C) - 118 73,76
Boiling point (C) - 19 73,76
Heat of vaporization at bp (kJ/mol) 700 73,76
Heat of combustion at 23C (gas) (k.l/mol) - 562 73,76
- 570.77 f 0.42 8 3
Density of liquid (g/cm3) at - 20C 0.815 73,76
at - 80C 0.917 73,76
Explosive limits, % by vol. in air 7-72 73
Standard enthalpy
Format i on of formal dehyde (kJ/mol) - 104.9 f 1.4 66
- 116 82
- 108.57 8 3
-97.1 93
Free Energy of Polymerization (kJ/mol)
Formaldehyde (gas, 298 K) + poly(oxymethylene) (solid) - 2.9 19,94
- 3.9 68
- 17 93
Trioxane (298 K) + poly(oxymethylene) - 1.8 82,65
Gas + solid - 17.6 96,94
Gas -+ liquid - 6.07 96,94
Liquid --+ liquid - 0.4 96,94
Liquid -+ solid - 3.8 96,94
Solid + solid - 6.3 96,94
- 9.9 66
See Ref. 6 5
In dichloroethane at 323 K - 5.4 92,94
Tetraoxane (solid, 298 K) + poly(oxymethylene) (solid) - 4.4 66
Friction Coeftkient
Against rotating steel shaft, dry (roughness height N 2 urn, loading pressure
p = 0.05 N/mm *, sliding speed 100 mrn/min)
Dynami c 0.15-0.25 63
Static 0.20-0.30 63
GPC of Macrocyclic POM See Ref. 114
Cl ass Transi ti on Temperature (K) See Second-Order Transition Point
Hardness Ball rndentation (MPa) = (N/mm*)
DIN 53456 EJISO 2039 after 30 s 130- 160 3
1
a
3
85
I4
14
94
9 4
94
66
6 5
,94
66
63
63
114
3
Physical Constants of Poly(oxymethylene) v/103
Property Value Refs.
Heat Capacity (J/mol/K)
Homopolymer 0 K
50K
100 K
200 K
300 K
Copol ymer OK
50K
100K
200 K
300 K
Molten poly(oxymethylene)
190.0 K (T,)
200. 0 K
273.15 K
298.15 K
300.0 K
400. 0 K
457. 0 K (T, )
500.0 K
600.0 K
Crystalline poly(oxymethylene)
OK
SOK
1OOK
200 K
273.15 K
298.15 K
300 K
390 K
For the temperature range T= 25- 140C
At mole fractions of oxyethylene units X2 co.16
For detailed information, see Ref. and corresponding table
in this Handbook
For the temperature range T= 205 K to melting point
Heat Deflection Temperature Under Load (C)
Martens method (DIN 53 458)
Heat Distortion
A (IS0 R 75)
B (DIN 53 461)
(ASTM D648)
Homopol ymer
Copol ymer
Heat of Combustion (kJ/mol)
Poly(oxymethylene)
Heat of Degradation (kJ/mol)
Needle-like poly(oxymethylene) crystals
Heat of Formation (kJ/mol)
Homopolymer, 25C (standard enthalpy)
Heat of Fusion (kJ/kg)
Poly(oxymethylene), theoretical value for 100% crystallinity
Homopolymer (acetyl end groups)
Copolymer (trioxaneR% ethylene oxide)
Poly(oxymethylene), at equilibrium
Poly(oxymethylene), needle like crystals
Poly(oxymethylene), extended chain crystals
Poly(oxymethylene), fibrillar products
0 19,37
9.94
16.69
28.82
42.79
0
9.97
16.40
26.56
41.11
53.58 58
53.95
56.67
57.60
57.67
61.39
63.51
65.11
68.83
0
10.10
16.68
27.15
34.94
38.26
38.52
54.00
Cp(X,, ?-) = 36.75 + 0.1425 (T- 25) + 80X2
See Refs.
6 1
8 5
55,56,68
61,71
102,103,104
65-70 63
120-130 63
160-170 63
124 73
110 73
- 508.78 rt 10 68
-511.6k1.7
25
55.05
62
- 171.4 68
181-192 1 5
236 70
390 119
315 -336
15
166 57
315 62
310 87
252 62
References page V- 110
353 K
Value from combustion data
Value from calorimetric data
Trioxane + poly(oxymethylene) at 298 K
Gas -+ solid
Property
From solid state polymerization
Heat of Polymerization (k.l/mol)
Formaldehyde (gas, 1 bar, 298 K) + poly(oxymethylene) (solid)
Values obtained from equilibrium data
Gas -+ liquid
Liquid + liquid
Liquid + solid
Solid + solid
Tetraoxane + poly(oxymethylene)
Solid --f solid
In dichloroethane
At 329-333 K
At 323 K
Heat of Solution (kJlmo1)
Water in branched copolymer, 50C
Heat of Sublimation
Heat of Trimerization (kJ/(mol trioxane))
Formaldehyde (gas) -+ trioxane (gas), at 298 K
Formaldehyde (gas) --+ trioxane (solid), at 298 K
Huggins Coefficient
Impact Strength (charpy) (k.I/m*)
+ 23C
- 30C
impact Strength (charpy) (notched) (W/m*)
Homopol ymer + 23C
Homopolymer - 30C
Copol ymer + 23C
Copolymer - 30C
infrared Spectra
IR Spectra
Macrocyclic POM
Interchain Distance (A)
Poly(oxymethylene)
Poly( 1,3-dioxolane)
Latti ce Energy (kI/mol)
Heat of sublimation of poly(oxymethylene) at 0 K (theoretical value)
Mechani cal Properti es
Impact modified poly(oxymethylene)
Homopol ymer
Copol ymer
v/104 PHYSI CAL CONSTANTS OF POLY(OXYMETHYLENE)
Value Refs.
264 8 4
234 1 6
- 66.4f 1.0 59,66
- 5 1 . 3 f 0 . 3 2 5
- 54.4 2 5
- 59.8 2 6
69.9 5 9
- 7 1 . 1 2 1
- 72.0 2 2
- 55.7 zk 6.3 90
- 68.2 21
- 55.4 6 8
- 66.2 8 0
- 63.6 94
- 48.1 6 5
- 4 1 . 5 59,94
- 0.4 59,94
- 22.6 59,94
- 8.4 59,94
- 4.6 f 3.9 66
See Ref. 6 5
- 3. 32 f 0. 16 86
- 26.25 f 0.25 80
- 17.6 92
19.3
See Lattice Energy
- 139.2f2.1
- 194.0 f 2.5
- 188
- 187
See Viscosity - Molecular
Weight Relationship
2
9 1
9 1
69
80
180 1 3 8
160 1 3 8
9 1 3 8
7 1 3 8
6.5 1 3 8
6.5 1 3 8
See Refs. 28,51,101,
110,136
937 cm- 91
See Ref. 1 1 0
4.47 7 1
4.54 7 1
15.9* 1.7 4
See Ref. 50
See Ref. 7 7
Physical Constants of Poly(oxymethylene) v/105
Property Value Refs.
Melt index (MI) - Molecular Weight (A4,) Relationship (dg/min)
M, = 6200- 129000; 190C
Melting Data
At equilibrium
Melting Point (C)
Homopol ymer
Delrin 150
Extended chain fibers
Folded chain spherulites
As a function of crystallization temperature
From solution polymerization of trioxane, ionically initiated
Fibrous product
Powdery product
From vacuum sublimation of trioxane
Poly(oxymethylene) dimethylethers
Monomer
Dimer
Trimer
Tetramer
Pentamer
Copol ymer
Hostaform C2520, M, = 80000
Hostaform C9020, M, =58000
Various kinds and contents of comonomers
Copolymers with Of 214 /6/l mol% dioxolane
Trioxane- 1,3-dioxolane copolymers (average values)
Mol e fract i on of 1,3-Dioxolane
0.075
0.15
0.18
0.25
0.30
0.34
Poly(oxymethylene), homopolymer
Equilibrium melting temperature
MI=1.30~10~xM m3.55
w 29
See Ref. 57
1 8 1 5
182.5 f 0.5 30
174 30
See Ref. 3 1
186- 187 30
178-180 30
195-200 30
- 105.0
- 69.7
- 42.5
- 9.8
18.3
167
170
See Ref.
See Ref.
5
5
32
32
7 1
166
156
154
147.5
141.5
134
184f2 57
186.4 70
189.2 70
Modulus, Tensile (1 mm/min) (MPa) = (N/mm*)
DIN 53 457 2600-3400 3
See Ref. 78 Morphology
Mould Shri nkage (cm/cm)
ASTM D 95
Homopol ymer
Copol ymer
0.021 73
0.020 73
See Refs. 79
NMR-Spectra See Refs.
2D Dipolar 13C See Refs.
Crystalline 13C See Refs.
Oligomers R-(OCH2), -R
Boiling points R = -0CH3 (C)
n=2
n=3
n=4
n=5
105.0
155.9
201.9
242.3
Density R = -OOC-CH3, 25C (g/cm3)
n=l
n=2
n=3
Poly(oxymethylene), liquid, 25C, theoretical value
1.1283 35
1.1610 3 5
1.1823 3 5
1.328 A
33,34,114
106,112,116,
122
111,113,117,120
References page V- 110
V/106 PHYSICAL CONSTANTS OF POLY(OXYMETHYLENE)
Property
Value Refs.
Heat of vaporization
Infrared data R = -0OCCH 3
See Ref.
Wave number (cm-) Absorption (cm - x mol -)
n=l 1760 395
n=2 1755 330
n=3 1755 330
Melting points
Oligo (oxymethylene) dimethyl ether n = 2-5
Vapor pressure
Oligo (oxymethylene) dimethyl ether n = 2-5
See Ref.
See Ref.
Permeability See Refs. and corresponding chapter in this Handbook
Permeability, Apparent Activation Energy (kJlmo1)
Water
Homopolymer, melt index 2.3; 50C
Copolymer, linear, melt index 2.5; 50C
Copolymer, branched, melt index 3.9; 50C
Copolymer, 25C
Copolymer, branched, 25C
Carbon dioxide
Copolymer, 25C
Copolymer, branched
23.0 2
29.7 2
25.1 2
13.0 17
6.3 17
Photoradical Ageing
Radi ol ysi s (Gamma)
Raman Spectra
Powder/single crystal (cm -)
31.4 17
25.1 17
See Ref. 134
See Ref. 1 3 3
See Refs 110,136
909 9 7
Refractive Index (nD)
Extended chain crystals (fibers), different samples
n
nl
Poly(oxymethylene) at 25C DIN 53491
1.545-1.553 30
1.489 30
1.48
63
Rockwel l Hardness
Homopol ymer
Copol ymer
M94, R120
M80
Rupture Behavior (Creep) for Medical Application
See Ref.
Schulz-Blaschke Coefficient See Viscosity - Molecular
Weight Relationship
Second-Order Transition Point
Gl ass Transi ti on Temperature (K)
Homopol ymer
E-Relaxation, activation energy (kJlmo1)
For POM single crystal
T<40C
40C<T<90C
T> 90C
7 3
7 3
1 3 7
See Ref. 5 5
1 9 1 6 1
198 6
188
23
190 2 3
199 24
155
1 0 5
159
4
3 5
4
4
73,79
36
36
36
Physical Constants of Poly(oxymethylene) v/107
Property
Shear Strength (N/mm 2, ASTM D732
Homopol ymer
Copolymer
Shear Modulus (GPa)
5K
77K
293 K
Shrinkxge of Fibers
Sol vents
Value
66
53
5.0
4.7
1.5
See Ref.
Refs.
73
73
118
109
Sol vent
Dissolving Gel temp.
temp. (C)
(0
Refs.
Phenol 109 58 1
oChloropheno1 -
70 1
Aniline 130 102 1
Cyclopentanone
-
112 1
Ethylene carbonate 145 1 1 7 1
Cyclohexanone
-
119 1
Benzyl alcohol 132 119 1
Acetic anhydride 120 1
Formamide 150 135 1
Speci fi c Vol umes (cm3/g)
Homopol ymer
Delrin 150, at 20C
Delrin 550, at 20C
Crystalline phase
Varying temperatures, r (C)
Amorphous phase
Varying temperatures, t (C)
Copol ymer
Hostaform C2520
Hostaform C9020
Amorphous, phase (varying amount (x))
of copolymer, wt.% dioxolane, 20C
Amorphous phase (varying temperatures, I (C))
0.7008
0.6968
V,=O.669+7.85 x lo- r+5.93 x lo- t-*
V,=6.64 x 10-l +2.16x 1O-4 i
V,=O.792+3.07 x 1O-4 t
v, = 0.7553 + 5.78 x 1O-4 (t- 20)
0.7082
0.7064
V20=0.7553+0.08674 X
a
V,=O.7578+5.78 x 1O-4 (t- 20)
V,=O.7437+5.78 x 1O-4 t
5
5
38
7 1
38
5
5
5
5
5
57
St ress- St rai n Curves
Surf ace Resisfivity (ohm)
Homopol ymer (ASTM D257)
Surface Tension, max (dyukm)
Taber Abrasi on
ASTM D1044, 1OOOg load, CS-17 wheel, mg per 1000 cycles
Homopol ymer
Copol ymer
Tensi l e Modul us (MPa)
DIN 53457
Homopol ymer
Copol ymer
Ultra high tensile moduli tubes from a tensile drawing process
under dielectrical heating
Dependence on molecular weight
Tensile Creep Modulus (MPa)
Homopolymer, 1 h
Homopolymer, 1000 h
See Ref.
2 x 103
46.5
20
1 4
2600-3400
3200
2900
63000
See Ref.
2800
1500
39
73
130
73
73
63
1 3 8
138
49
1 2 3
1 3 8
138
References page V- 110
1
V/l08 PHYSICAL CONSTANTS OF POLY(OXYMETHYLENE)
Property Value Refs.
,
Copolymer 1 h (MPa)
Copolymer 1000 h (MPa)
Tensi/e Strength at Break (N/mm 2,
ASTM D638
Homopol ymer
Copol ymer
Fibers
Dependence on molecular weight
Thermal Conducti vi ty at 20C (W/ m/ K)
VDE 0304
Thermal Expansi on
Dependent on irradiation
2500
1300
69
59
See Ref.
See Ref.
0.292
See Ref.
1 3 9 !
1 3 9
I
I
13 :
7 3 ;
1 0 8 / j
131 i
3,63
98
Thermal Expansi on
Dependent on structure
See Refs. 131,132
Thermo-Acousti c Properti es
At 298 K
CL (10-3K-)
S::
B*
A*
124,125
0.243
1.114
1.020
1.034
Thermodynamic Data
Poly(oxymethylene), recommended values
Tracki ng Resi stance
DIN 53480
VDE 303
See Refs. 58.61
KA3b 63 I
KC >500 63
Tri oxane
Boiling point (C)
Boiling point of azeotrope, 30% water, 70% trioxane (C)
Density, 65C (g/cm3)
Dielectric constant, 20C 1.6 MHz
Di pol e moment
Enthalpy &J/kg)
OK
50K
IOOK
200K
273.1613
298.16K
Entropy (kJ/kg/K)
OK
50K
1OOK
200 K
273.16 K
298.16 K
298.16K (gas, 1 bar)
Explosive mixtures with air (vol.%)
Flash point (C)
Heat of combustion, 23C (kJlmo1)
Heat of sublimation (kJ/mol)
Heat of solution in dichloroethane at 50C: trioxane (tryst.) -t
trioxane (soln.) (kJlmo1)
Heat of vaporization at b.p. (kJ/mol)
114.5 64 I
91.3 64 I
1.17 40
3.2-3.4 4 0
2.18 x lOI8 64
0
7.97
32.29
104.9
178.2
208.0
0
0.244
0.573
1.064
1.373
1.477
3.165 f 0.038
3.207 f 0.001
3.5-28.7
45
1492
56.6
55.39
15.0fO.l 80
41.5 73
40.6 65
62-64 3 8
22
22 /
L
2 2
65
64
64
73.89
73
65
Melting point (C)
* Acoustic parameters.
Physical Constants of Poly(oxymethylene) v/109
Property
Molecular weight
Solubility in different solvents
Solvents
Specific heat &l/kg/K)
OK
50K
1OOK
200 K
273.16K
298.16K
Vapor pressure at 25C (kPa)
Standard enthalpy, formation of trioxane (kJ/mol)
Thermodynamic data, others
Value
90.08
See Ref.
Water, alcohols and ethers
0
0.312
0.5161
0.8783
1.138
1.237
1.7
-509f5
-521&4
See Ref.
Refs.
40
7 5
22
73
66
8 1
65
Unit Cell Spacings
Vicat Softening Point (C)
DIN 53 460/ASTM D1525-65 T
ASTM D1525
Homopol ymer
Copol ymer
Viscosity - Molecular Weight Relationships
[q] = K x MO (ml/g)
See Crystallographic Data
160-170
157
1 5 1
162
See also corresponding chapter in this Handbook
3
138
138
73
Sol vent t v-3 K (~10~)
Molecular
No. of samples wei ght
range
a FRa WPb ( x 10-S) Method Refs.
p-Chlorophenol, 2% cx-pinene 130 54.3
60 41.3d
lH, IH, SH-octafluoropentanol-1 110 13.3
Phenol-tetrachloroethane
(25-75 wt.), 2% cr-pinene 90 12.16
Phenol 90 11.3
Dimethylformamide 150 44.0
130 22.4
Hexafluoroacetone 25 46.0
sesquihydrate + triethylamine
0.66 ? ? ? OS cited in Ref. 41
0.124 - 4 62-129 LS 29
0.81 - 4 62-129 LS 29
0.64 8 - 1. 1- 92 EC 42
0.76 ? - ? OS cited in Ref. 43
0.66 - 4 89- 285 LS 74
0.71 7 - 1. 5- 15 EG 45
0.74 7 - 1. 5- 15 EG 45
Fr act i onat ed.
bPolymer unfractionated.
OS - Osmotic measurement; LS - Light scattering; EG - Viscosity measurement.
%I hh
Huggins coefficient kH, qspiC = 17 + kHq2c
Hexafluoroacetone hydrate 25C
Hexafluoroacetone-water mixtures
Hexafluoroacetone-sesquihydrate + triethylamine, 25C
Hexafluoroacetone-water (1 : 1.7 mol) -t triethylamine, 25C
p-Chlorophenol/2% a-pinene (60C)
Schulz-Blaschke coefficient KSB. qsplC = KsB[~] x qhsp + [v]
Hexafluoroacetone hydrate, 25C
Hexafluoroacetone-water mixtures, 25C
Phenol-tetrachloroethane, 1 : 3 (per weight), 90C
Vol ume Resi sti vi ty (ohm cm)
Film 0.2 mm, DIN 53 482/ASTM D257-61
Water Absorption
DIN 53472 (mg)
After 96 h immersion
0.41
See. Ref.
0.3 1
0.30 f 0.02
0.40
0.29
See Ref.
0.23
0.21
>105
20-30
44
44
45
46
47
44
44
43
48
3
63
References page V- 110
V/l10 PHYSICAL CONSTANTS OF POLY(OXYMETHYLENE)
Property Value Refs.
ASTM D570 (%)
After 24 h immersion
Homopol ymer
Copol ymer
Equilibrium, (50% r.h.)
Homopol ymer
Copol ymer
Yield Stress (MPa)
Homopol ymer
Copol ymer
0.25 7 3
0.22 7 3
0.2 13
0. 16 73
7 1 1 3 8
66 138
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Physical Constants of
Poly(oxyethylene-oxyterephthaloyl)
(Poly(ethylene terephthalate))
Mark Rule
1 Coca Cola Plaza NW, TEC 147, Atlanta, GA, USA
Properties of films are given for Mylar@ Type A (DuPont)
biaxially oriented and crystalline films. Properties of
filaments are given for various products.
Property Value Refs.
Birefringence of Filaments (sodium light) *
Draw Ratio
2.0 0.040
3.0 0.092
4.0 0.167
5.0 0.193
Bursting Strength (g/cm *)
1 mil film, 23C 46 x lo2
Brillouin Light Scattering See Ref. 4
Coefficient of Friction (film)
Kinetic, film to film 0.45
film to steel 0.14
Coefficient of Thermal Conductivity (film) (W/m/s/K)
(See also Thermal Conductivity)
100C 37.5 x 10-s
Coefficient of Thermal Expansion (film) (K-l)
20C50C 1.7 x 10-s
Melt 6.55 x 1O-4
Coefficient of Volume Expansion (K-l)
Crystalline, below T, 1.7 x 10-4
Crystalline, above T, 3.94 x 10-4
Compressibiky (melt) (MPa) ( x 106) 6.99
Conductivity for Direct Current See Fig. 1 overleaf
Crystallographic Data See Unit cell
Density (Mg/m3) E (g/cm3)
0% Crystalline 1.333
100% Crystalline 1.455
Amorphous, non-oriented 1.335
*Value sensitive to semicrystalline morphology.
1
23
23
6
293
23
5
7
5
8 1
82
9
Property Value Refs.
Partly tryst., non-oriented
Partly tryst., oriented
Highly tryst., non-oriented
Calculated, crystal
1.385 9
1.390 9
1.420 1 0
1.515 11
(1.501) 1 2
Dielectric Strength (film) (V/cm)
23
23C, 60Hz 2.95 x lo6
150C 60 Hz 2.75 x lo6
Dielectric Constant (film) 23
23C 60Hz 3.30
23C, 1 kHz 3.25
23C, 1 MHz 3.0
23C, 1 GHz 2.8
15OC, 60 Hz 3.7
Di ssi pati on Factor (film)
23C, 60Hz
23C, 1 kHz
23C, 1 MHz
23C, 1 GHz
150C 60 Hz
0.0025
0.0050
0.016
0.003
0.00040
2.3
F/a& Constants (filaments) (Pa-)
Oriented
S 11 transverse
S 33 longitudinal
S 44 torsional
s12
s13
Unoriented
S r t or S 33extensional
S 44 torsional
1 3
16 x lo-lo
0.71 x 10-10
14 x 10-10
- 5.8 x 10-t
-0.31 x lo-0
4.4 x 10-10
11 x 10-10
Enthalpy of Fusion (kl/mol) 2.69
Entropy of Fusion (J/mol/K) 48.6
1 0
1 0
Folding Endurance (film) (cycles)
23C 300 000
2,3
v/ 113
I
v/ 114 PHYSICAL CONSTANTS OF POLY(OXYETHYLENE-OXYTEREPHTHALOYL) (POLY(ETHYLENE TEREPHTHALATE))
Amor phous
--- - Ctystallme
wOr i ent ed &Cr yst al l i ne
10-12
10-l
2 lo-
Y
E
2 10-N
b
10-l
10-18
250 260 270
Mel t i ng poi nt (T)
c
Mel t i ng poi nt (C)
I I I I 1
t 2. 2 2. 4 2. 6 2. 8 3. 0
T $ X lo3 (k-l)
Figure 2. Effect of diethylene glycol (DEG) content on melting
point. Melting point PC) = 271-273 (2,29).
Figure 1. Direct current conductivity at various temperatures
and degrees of orientation and crystallinity (8).
Property Value Refs. Property Value Refs.
Glass Transition Temperature* (C)
Amorphous 67
Crystalline 8 1
Crystalline and oriented 1 2 5
Heat capacity See Specific heat
Heat of Combustion @J /kg) - 2.16 x lo4
Heat of Sorption (film) (kJ/kg/mol)
Carbon dioxide - 3.1 x 104
Met hane - 2.3 x lo4
Solubility of Carbon Dioxide
25- 115C. O-20 atm
Hygroscopic Coefficient of Expansion (film) (cm/cm%/RH)
20-92% RH, 1.1 x 10-s
Impact Strength (film) (Urn)
23C 2.4 x lo*
infrared Spectra See Refs. 18-25
7,14
1 4
1 5
1 6
1 7
83
23
23
lnsu/ation Resi stance (film) (Mohm mfds)
100C 5000
130C 400
150C 100
*Value sensitive to semicrystalline morphology.
26,27,28
Melting Point (C)
Equilibrium
Commercial PET
(metastable crystallites)
Effect of diethylene glycol content
280 (310)
250 -26.5
See Fig. 2
1 l(12)
23
29
Mel t Vi scosi ty vs. Intri nsi c Vi scosi ty
Melt viscosity
(Pas) at 280Ca
Intrinsic viscosity (ml/g),
30C in s-tetrachloroethanel
phenol (40/60)
0.45 IO
4.5 20
25.0 30
95.0 40
115.0 50
145.0 60
800.0 70
1180.0 80
20000.0 90
a Taken from Fig. 14 of Ref. 2.
Moisture Absorption (%)
Immersion in water at 25C for 1 w 0.8 27,28
Nucl ear Magneti c Resonance Spectrum See Refs. 13,30,3 1
Physical Constants of Poly(oxyethylene-oxyterephthaloyl) (Poly(ethylene terephthalate)) V/l15
Oligomers - acyclic
Mol ecul ar Melting
Structure wei ght poi nt (C)
H(GA) , OHa 210.2 1 7 8
H(GA) 20H 402.4 200-205
H(GA) 30H 594.6 219-223
179- 183
186
H(GA) ,-G-H 254.2 109-110
HtGA),-G-H 446.4 173-174
H(GA) 3 -G-H 638.6 200-205
H(GA)4-G-H 830.8 213-216
H(GA) s -G-H 1023.0 218-220
HO-A-(GA) ,OH 358.3 >360
HO-A-(GA)20H 550.5 280-281
HO-A-(GA)30H 742.7 268-270
HO-A-(GA)40H 934.9 252-255
HO-A-(GA)sOH 1127.1 233-236
G= -OCHzCH2e; A = -OCaCO-
Refs.
32
32
32
33
34
32
32
32
32
32
32
32
32
32
32
Property
Oligomers - cyclic
Value Refs.
CYCLIC DIMER
Melting point (C)
Unit cell (nm)
175,224
229
a = 0.858
b=1.275
c=O.801
P=90.7
33
35
35
CYCLIC TRIMER (B-TYPE CRYSTAL)
Melting point (C) 319 3 3
317 -320 36
321 37
Crystalline transition (C) 199 37
(A-type + B-type) 1 9 5 38
CYCLIC TETRAMER
Melting point (C) 326 33
CYCLIC PENTAMER
Melting point (C) 256 33
O/igomers - lso/ation See Ref. 39
Optical Haze* (ASTM D1003-61) See Ref. 40
Permeability (film) See corresponding chapter in this Handbook.
Water (cm2/s) (2.1 l-9.97) x 10e9 84
Photoacousti c Spectroscopy See Ref. 41
Poissons Ratio (Oriented filament)
Extensional 0.44
Transverse 0.37
Raman Spectra
Frequency (cm-t ) 1730
1618
1096
857
632
278
*Value sensitive to semicrystalline morphology.
1 3
21,42-46
Property Value
Refractive index (film), (Na Light)
Amorphous, 25C 1.5760
Crystalline and biaxially oriented, 1.64
23C
80,9O,lOoC
Refractive Index Increment (specific) (cm3/g)
(in hexafluoroisopropanol solution)
0.257 * 0.004
Resi sti vi ty
Surface (ohm/cm 2,
23C, 30% RH 2 X 105
23C, 80% RH 2 x 10
Volume (ohm cm)
23C 108
150C 10 l4
Rheological Spectrum See Refs. 48,49
Refs.
2
8 5
47
23
Service Temperature (C) 22
- 60 to + 1.50
Shri nkage (film) (%) 2-3 3
15oC, 30 min.
Solubility Constants (film) (cm3/STP cm3/Pa) ( x 107)
3 mil, 25C Nitrogen 4.3
Oxygen 7.5
Met hane 19.7
Argon 0.8
So/vents See chapter Solvents-Nonsolvents in this Handbook
1 7
Solvent-Nonsolvent for Fractionation
Sol vent Nonsolvent
o-Chlorophenol Hexane
Phenoptetrachloroethane (1 : 1) Gasoline
Phenol/chlorobenzene (1: 1) Gasoline
Phenol/dichlorobenzene (2 : 3) Benzene
Phenol Cyclohexane
Phenol Ethanol
50
5 1
52
53
54
55
Sonic Ve/ocity (filaments) (m/s) 56
1OkHz unoriented 1400
Highly oriented 5900
Specific Heat &J/kg/K) C, = 4.184 (A + (B x T)) 57
Effective
Condition temperature
of polymer A B ( x 104)
T CC)
Molten polymer 0.3243 5.65 270 to 290
Flake 0.2502 9.40 -20 to 60
Yarn (undrawn) 0.2469 10.07 - 5 to 60
Yarn (drawn) 0.2482 9.89 - 10 to 55
Yam (drawn + annealed) 0.2431 9.23 - 10 to 80
0.2502 9.31 100 to 200
References page V / 117
V/116 PHYSICAL CONSTANTS OF POLY(OXYETHYLENE-OXYTEREPHTHALOYL) (POLY(ETHYLENE TEREPHTHALATE))
Property Value Refs.
1.2-40 K See Ref.
Below 1 K See Ref.
Stick Point Temperature (C) 230-240
Stress-Strai n Curves for Fi l aments See Refs.
Surface Tension (mN/m) = (dynkm)
Solid/liquids, 25C 39.5
42.1
Molten, 290C 21 It 3
Tear Strength (film (g/m)
Initial, 23C 23.6 x lo6
Propagating, 23C 0.59 x 106
Tensile Strength (film) (Mpa) = (N/mm*)
23C, 172
Thermal Conducti vi ty (film) (W/m/K)
33C 0.147
1.2-40K See Ref.
Below 1 K See Ref.
Thermal Diffusivify (film) (cm* s)
33C 9.29 x 1O-4
Torsional Modulus (MPa) z (N/mm2)
Oriented filament 720
58
59
4
60,61
62
63
64
23
23
65
58
59
65
13
Intrinsic Viscosity - Molecular Weight Relationships (Unfractionated)
Property Value Refs.
Transition Temperatures (C)
From second moment (NMR) measurements on fibers
Unoriented 12O~t5 13,31
Oriented 140 * 10
Unit Cell (nm) 66,11,12
Previously accepted Corrected Corrected
(Ref. 66) (Ref. 11) (Ref. 12)
X-RAY DIFFRACTION (291 K)
it
0.456 0.448 0.450
0.594 0.585 0.590
c 1.075 1.015 1.076
;
98.5 99.5 1 0 0 . 3
118 118.4 118. 6
Y
112 111.2 1 1 0 . 8
ELECTRON DliFRACTlON (Ref. 67)
a 0.452 61
b 0.598
c 1.077
;
101
1 1 8
Y
1 1 1
Viscocity-Molecular Weight Relationship See Sections I, II
Youngs Modulus (MPa) = (N/mm *)
Oriented Filament - extensional 1.41 x 104 13
- transverse 0.063 x lo4
Zero Strength Temperature (film) (C) 248 6 8
Solvent
T (Cl
K ( x 104)
Molecular weight
a range ( x 10m3) Method Refs.
Trifluoroacetic acid 30 4.33 0.68 26-118
Tetrachloroethanelphenol (5 : 3) 30 2.29 0.73 26-118
o-Chlorophenol 25 6.56 0.73 12- 25
o-Chlorophenol 25 3.0 0.71 13-28
Tetrachloroethane/phenol (1 : 1) 25 2.1 0.82 5-25
Tetrachloroethane/phenol (1 : 1) 20 1.27 0.86 5-21
Tetrachloroethane/phenol (1 : 1) 20 7.55 0.685 3-30
Phenol/2,4,6-trichlorophenol (10 : 7) 29.8 2.10 0.80 l-8
oChloropheno1 25 6.31 0.658 6-70
PhenohTetrachloroethane (3 : 2) 25 7.44 0.648
Hexafluoroisopropanol 25 5.20 0.695
Pentafluorophenol 25 3.85 0.723
Hexafluoroisopropanol/pentafluorophenol (1 : 1) 25 4.50 0.705
Methylene chloride/hexafluoroisopropanol (7 : 3) - 4.03 0.691
6-70
6-70
6-70
6-70
o-Chlorophenollchloroform (1 : 3) 2 5 1.49 0.56 9-100
Light scattering
Light scattering
Osmometry
End group
End group
End group
End group
End group
Size exclusion
chromatography
Light scattering
Light scattering
Light scattering
Light scattering
Light scattering
Size exclusion
chromatography
Chromatography
69
69
70
7 1
7 2
7 3
54
74
76
7 7
(y)=K x Ma.
Intrinsic Viscosity - Molecular Weight Relationships (Fractionated)
Re f e r e n c e s v/ 117
Solvent
T (Cl K ( x 104)
Mol ecul ar wei ght
a range ( x 10m3) Method Refs.
o-Chlorophenol 25
Dichloroacetic acid 25
Trifiuoroacetic acid 25
Phenolketrachloroethane (2 : 3) 25
o-Chlorophenol 25
Tetrachloroethane/phenol (1 : 1) 20
PhenoUdichloroethane (2 : 3) 20
o-Chlorophenolkhloroform (1 : 9) 25
1.9 0.81 15-38 End group 78
67 0.47 15-38 End group 78
1 4 0.64 15- 38 End group 78
1 4 0.64 15-38 End group 78
4.25 0.69 20-200 Sedimentation diffusion 79
0.9 0.87 5-21 End group 73
0.92 0.85 S-30 End group 53
0.584 0.91 4-30 Size exclusion chromatography 80
(Tj) =K x Ma.
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Physical Constants of
Poly(oxytetramethylene-oxyterephthaloyl)
and Copolymers with Tetramethylene
Oxide Thermoplastic Elastomers*
K. B. Wagener
Department of Chemistry and Center for Macromolecular Science & Engineering, University of Florida,
Gainesville, FL, USA
The literature gives different chemical abbreviations for this
segmented polyester/polyether copolymer, such as PBT/
PTMO, PBT/PTHF (where PTHF abbreviates polytetrahy-
drofuran), and PBT/POTM (where POTM abbreviates
polyoxy-tetramethylene). Occasionally, components of the
abbreviation are reversed (as in PTHF/PBT). All these
abbreviations represent the same copolymer, which is
available with different weight percentages of polyether
being present.
Weight percentage polyether in copolymer a
Property O%b 10% 25% 35% 50% 60%
Hardness, shore D
Density (mg/m3)
Coefficient of expansion (vol/K)
@- 20C
20C
80C
THERMAL PROPERTIES
80 74
1.30 1.21
210 x 10-6 240 x 10m6
210 x 10-6 330 x 10-e
510 x 10-6
63 5 5 45 3 8
1.23 1.20 1.16 1.12
360 x 10m6 300 x 10-s
420 x 1O-6 450 x 10-e
540 x 10-6 600 x 10m6
480 x 1O-6 660 x 10-s
Glass transition temp. (C)
Heat capacity, C, (kJ kg/K) @ 100C
Melting temperature (C)
Heat of fusion (M/kg)
ELECTRICAL PROPERTIES
55 I48 = 44 124 =
1.35 1.61
223 221
54 60
2/-28< - 23 I- 46 - 50 - 60
1.72 1.78 1.95 2.01
210 202 1 8 3 192
4 1 38 29 25
Dielectric constant (1 kHz)
Dissipation factor (1 kHz)
Volume resistivity (ohm m)
MECHANICAL PROPERTIES
3.0 3.35
0.002 0.037
5.10 x 104 8.8 x 103
4.1 4.3
0.017 0.012
1.2 x 1011 2.5 x lOto
4.5 4.5
0.006 0.005
Ultimate elongation (%) (ASTM D 412)
Tensile strength (MPa) (DIN 53504)
Initial slope of stress-strain curve, Youngs
200 360 540 570 700 650
52 45 38 32 2 1 1 7
modulus (MPa)
Storage modulus G (log MPa)
Loss modulus G (log MPa)
Loss tangent G/G
Resilience (rebound) (%)
2600 830
2.74 2.70
0.78 1.58
0.011 0.076
300 170 90 53
2.17 1.94 1.60 1.25
0.96 0.48 0.08 - 0.27
0.062 0.035 0.03 0.03
40 53 60 6 5
a tin = 1000 for the polyether except for the 60 wt.% copolymer, in which fi, = 2000.
b 0% refers to the properties for pure poly(oxytetramethylene-oxyterephthaloyl) (poly(butylene terephthalate)).
Two different measurement values are given, top tan a/top G, 1 Hz.
d Top of highest peak.
* All data are unpublished results from the Akzo Fibers and Polymers
Research Laboratories, Arnhem, The Netherlands.
v/ 119
Physical Constants of Various Polyamides:
Poly[imino(I -oxohexamethylene)],
(Polyamide 6)
Poly(iminoadipoyl-iminohexamethylene),
(Polyamide 66)
Poly(iminohexamethylene-iminosebacoyl),
(Polyamide 610)
Poly[imino(I -oxododecamethylene)],
(Polyamide 12)
Rakesh H. Mehta
E.I. DuPont de Nemours & Co., DuPont Nylon, Chattanooga, Tennessee, USA
Property Polyamide 6 Pol yami de 66 Polyamide 610 Polyamide 12 Ref.
Abrasi on See Wear Resistance 1 3
Absorption (%)
Water, moldings 20-90C saturation
Ethanol, moldings 20C saturation
Butanol, moldings 20C saturation
Glycol, moldings 2oC, saturation
Methanol, moldings 2oC, saturation
Propanol, moldings 20C saturation
Adhesive Bond Strength, tensile (MPa) = (N/mm)
PA-aluminium
PA-steel
PA-copper
Birefringence, (A .)
n II
nl
9.5 f 0.5 8.5 It 0.5 3.3 * 0.3 1.6ztO.2
9-17 9-12 8-13 9
5-9 4-8
8-12 -
6-13 2-10
2-4 -
12-16 9-14
1 6 8S
9-13 9-12
1 0 -
1.580 1.582
1.530 1.519
68
70
76
39
39
39
5 1
5 1
55
* This table includes data compiled by R. Pfltiger for the third edition of Polymer Handbook.
v/ 121
v / 1 2 2 PHYSICAL CONSTANTS OF VARIOUS POLYAMIDES
Brittleness Temperature, ASTM D746 (C) 57-59
PA-6 PA-66 PA- 610 PA- 12
DAM SO%RH DAM SO%RH DAM 50%RH DAM 5O%RH
- - - 8 0 - 65 [M, = 18000] - 90 - 62
- -
- - 100 - 8 5 [M = 340001 -
- - -
Bulk Modulus B (N/mm *) 4400 3300 2300 4000
(Crystalline rods, dry)
Chemi cal Resi stance of Nyl ons at 23 C
Acetic acid (10%) 3O 3
Acetaldehyde (40%) 2 2
Acetone (100%) 1 1
Butanol (100%) 1 I
Carbon tetrachloride (100%) 1 1
Diesel oil (100%) 1 1
Ethanol (96%) 1 1
Formic acid (3%) :d 3
(10%) 4
Gasoline unleaded (100%) 1 1
Heptane (100%) 1 1
Hydrogen peroxide (2%) 4 4
Dichloromethane (100%) 2 2
Perchloroethylene (100%) 1 1
Phenol (75%) 3 3
Potassium hydroxide (10%) 1 1
Sulfuric acid (10%) 4 4
Toluene (100%) 1 1
Transformer oil (100%) 1 1
Considerable absorption and/or attack; limited product life.
Limited resistance, absorption causing dimensional changes and slight reduction in properties.
Resistant, little or no absorption.
Material is soluble or decomposes in short time.
57,59
2b
1
1
1
2
1
1
1
-
1
1
2
3
2
3
1
2
1
1
Coefficient of Friction (dry)
(a) Average depth of roughness R z in (pm) *
0 . 1 0.35
0.5 0.33
1 . 0 0.32
2.0 0.32
4.0 0.36
6.0 0.43
(b) Average surface pressure in (MPa) = (N/mm)
R, Optimal R, 1.5-3pm
0.02 0.40
0.05 0.36
0 . 1 0.35
0.15 0.38
0.2
0.3
0.4
0.5
0.6
0.7
0.8
1 . 0 0.43
1 . 2
5.0 0.48
1 5 . 0 0.48
R, ~0.3 urn Stick-slip-motion
Average surface pressure 0.1 MPa; surface temperature <4OC.
0.5
0.43
0.38
0.35
0.38
0.46
R, 1.5-3pm
0.40
0.36
0.35
0.38
0.44
0.50
0.51
Stick-slip-motion
0.4
0.32
0.29
0.26
0.24
0.23
0.22
0.21
0.19
0.18
0.55
0.45
0.38
0.35
0.37
0.40
R, 0.5-l pm
0.40
0.36
0.35
0.38
0.44
0.50
0.51
Stick-slip-motion
13
13
13
Coefficient of Thermal Expansion (K-l) ( x 104)
Coefficient of linear Thermal Expansion, ASTM D696 (lo- mrn/mmC)
Physical Constants of Various Polyamides V/ l 2 3
57.59
PA-6 PA-66 PA- 610 PA- 12
DAM 5O%RH DAM 5O%RH DAM 5O%RH DAM 5O%RH
-
8.1
-
9 14.9
- -
(a) Linear crystalline 20C
100C
Monoclinic cx a
CLC
cLb
Triclinic CL a
CCC
7-10
10-14
6.2
23.4
- 4.5
(b) Volume, 20C tryst. (K-t) ( x 104)
Cohesive Energy See Solubility Parameter
2.7
Compressi bi l i ty (MPa)
(a) Dependence on temperature and pressure (talc. from PV7)
20 (C) 50 (MPa)
100
150
300
120 50
100
150
300
200 >lOO
(b) Dependence on water content
< 1.5%
>-2%
melt 335 x 10-6
Compressi ve Strength (MPa) = (N/mm *)
Compressi ve St ress, 1% Deformat i on, ASTM D695 (MPa)
20
Temperature 20C strain: 1%
(molded; 2.5% H20) strain: 2%
strain: 4%
strain: 6%
Compressi ve Modul us, ASTM D695 (MPa)
2410
Compressi ve Yi el d St ress, 1% Offset, ASTM D695 (MPa)
8 3
Crysfa//ographic Data See also Unit Cell Dimension
Effect of Crystallinity on Solvent Absorption (% Weight Gain)
7-10 8-10 11
10-14 20-23
52
2.1
22.0
52
2.8 3.8 2.9 5 5
62 x 1O-6 (50)
58
54
50
1 2 5
1 1 5
95
75
- >300 (17)
137 x 1Om6 (48)
226 x 1O-6 (48)
280 x 1O-6
5 1
34 2 1
1 4
28
56
70
2830 2070
9 1 7 3
200 x 10-6
320 x 1O-6
200 x 10-6
650 x 1O-6
57-59
1 3
58
58
59
PA-6 PA-66 PA- 610 PA-12
Agent b C b C b C b C
Wat er 11
Methanol 1 9
Ethanol 1 7
Benzene 1
Toluene 1
Acetone 4
Benzoyl alcohol 5 5
Dichloromethane 20
Chloroform 34
b: low crystalline material.
c: high crystalline material.
9 1 0 7.5 4 3 - -
3 1 4 9 1 6
9
- -
3 1 2 3 13 8 - -
0 1 0 1
1
- -
0 1 1 3 1 - -
3 2 1 5 1 - -
11 38 3 40 11 - -
8 1 6 1 0 24 1 3 -
1 9 27 5 40 2 1 -
References page V- 132
v/ 124 PHYSICAL CONSTANTS OF VARIOUS POLYAMIDES
Property Polyamide 6 Polyamide 66 Polyamide 610 Polyamide 12 Ref.
Crystallization
Crystalline Density, X-ray (g/cm3)
Max. linear growth rate of crystals
Vmax @*m/S)
Activation energy E,(kJ/mol)
1.23 1.24 1.16
-
6 5
3.3 2 0 5 1
56.5 64.5 53.6 5 1
Density (Mg/m3) = (g/cin3)
Crystalline c1, monoclinic
y, hexagonal
y, monoclinic
y, pseudohexagonal
cx, triclinic
cz, triclinic
1.24 (53)
1.13
1.17
1.155 (42)
Mel t 270
0
C!l?iiinic 0.960
Moldings, amorphous 1.09
crystalline 1.12-1.14
Correlation with crystallinity
(moldings)
1040
a=950- -
density
Deformation Under Load, ASTM D621 (%)
1 4 MPa
28 MPa
1.6 1.4
1.8 1.5
1.220 (47)
1.24
1.248
0.989
1.09
1. 13-1. 145
830- 900
density
1.034 (9)
1.156 (8)
0.913 0.840
1.05 1.01 3 6
1.09 1.04 (15) 3 6
3 6
58.59
- -
Dielectric Constant e, Dielectric Loss, tan 6 ( x 1 04)
Frequency (s-l) 102 103 104 105 106 10 108 109
PA (C) .sr tan8 8, tans E, tan& E, tans E, tan8 Ed tan& e, tans Ed tan S
6 - 30 3.1 140 3.1 100 3.0 100 3.0
0 3.2 120 3.2 120 3.2 140 3.2
3 0 3.5 6 5 3.5 100 3.4 140 3.4
6 0 5.2 8 4 0 4.6 6 0 0 4.2 5 2 0 3.8
9 0 15.9 2 9 0 0 11.5 1650 8.8 1500 7.1
23/50% RH* 10.9 1450 7.3 1400 5.6 1450 4.5
6 6 - 3 0 3.1 120 3.1 1 0 5 3.1 1 0 5 3.0
0 3.3 110 3.3 120 3.2 1 3 5 3.2
3 0 3.6 85 3.5 1 2 5 3.4 180 3.4
6 0 5.0 8 1 0 4.6 5 9 0 4.3 4 6 0 4.0
9 0 1 0 2 0 0 0 8.9 1450 7.6 1300 6.2
23/50%RH* 7 . 5 1 1 0 0 5.9 1020 4.8 1000 4.1
610 - 30 3.0 120 3.0 110 3.0 100 3.0 110 3.0 150
0 3.0 130 3.0 130 3.0 130 3.0 140 3.0 170
+30 3.2 100 3.2 150 3.1 170 3.0 200 3.0 2 1 0
+60 4.6 9 0 0 4.2 6 5 0 3.9 5 7 0 3.5 540 3.4 5 4 0
f90 1 3 2 5 0 0 10.5 1700 8.5 1700 6.5 1900 5.2 1900
20/65%RH* 6 . 5 2 0 0 0 5.4 1500 4.5 1300 4.0 1000 3.5 8 0 0
1 2 - 3 0 3 0 170 3.0 160 2.9 100 2.9 5 0
0 3.1 2 0 0 3.1 2 0 0 3.0 190 3.0 130
3 0 4.0 7 0 0 3.5 5 0 0 3.3 4 5 0 3.1 3 5 0
6 0 11.5 2300 8.5 2 0 0 0 6 2 3 0 0 4.5 1300
9 0 >20 >5000 1 5 2 0 0 0 1 3 1600 1 0 2 6 0 0
160 3.0 200
170 3.1 2 2 0
190 3.3 2 4 0
540 3.6 5 5 0
1900 5.7 2100
1300 3.8 9 2 0
130 3.0 1 6 5
160 3.1 2 0 0
215 3.2 2 5 0
390 3.7 3 7 0
1450 5.0 1600
900 3.7 700
3.0 180
3.1 2 3 0
3.2 3 0 0
3.4 5 5 0
4.4 1900
3.5 5 5 0
3.0 160
3.0 200
3.1 255
3.5 3 6 0
4.0 1300
3.4 4 5 0
3.0 130
3.0 190
3.0 210
3.3 5 0 0
4.0 1500
3.2 5 5 0
3.0 120 3.0 5 5
3.1 160 3.0 100
3.2 3 0 0 3.1 2 0 0
3.3 480 3.2 2 6 0
3.7 1250 3.4 5 5 0
3.3 3 2 0 3.2 190
3.0 100 3.0
3.0 160 3.0
3.1 220 3.0
3.3 320 3.1
3.4 810 3.2
3.3 2 8 0 3.2
3.0 8 0 3.0
3.0 160 3.0
3.0 170 3.0
3.1 3 6 0 3.0
3.5 8 0 0 3.1
3.1 3 5 0 3.0
4 9
8 1
1 3 5
2 4 0
4 4 0
170
5 5
100
130
2 5 0
3 5 0
2 0 0
a Ref. 5.
b Saturated
Dielectric Strength (V/cm) ( x 10 -4)
(VDE 0303, part 2; IEC-243, electrode K2O/P50)
DV
Dry 100C
Moist ISO- 1110
100 120 100
4 0 4 0
-
6 0 8 0 6 0
9 0
2 5
Physical Constants of Various Polyamides v/ 125
Property Pol yami de 6 Polyamide 66 Polyamide 610 Polyamide 12 Ref.
Diffusion See also table Permeability Constants in this Handbook
Coefficient D H20, 20C
(cmh) x lo8 60C
100C
Activation energy Hz0
E&J/mol)
0.4 0.2 0.1 0.3 (16)
5.5 3.5 1.5 7 (16)
55 35 30 85 (16)
46 58 65 71 (16)
Elongation (IS0 R527) ultimate (%)
Molded (s = 3 mm), dry
Molded (s = 3 mm), moist
ISO-1110
Molded at yield
Dry film, NK 23/50, s = 25 pm
Longitudinal
Transverse
Biaxially oriented
Longitudinal
Transverse
>50 40 >50 >50
>50 >50 >50 >50
1 0 6 8
300
330
70
50
fnthdpy (H/kg)
Temperature T (C) (Ref. to 20C)
60
100
200
250
300
Pressure (MPa) = (N/mm2)
(T= 25C)
100
:T= 150C)
0
100
200
60 85 80 80
135 170 160 165
380 420 400 500
585 590 580 650
750 850 700 800
70 17
140 1 7
250 1 7
340 17
420 1 7
Entropy of Fusion (J/mol/K)
Crystalline 44-47.5 83-86 110-114 5 1
Equation of State* (melt)
(p + r)(2)-- w) = RTIM, r (bar)
w (cm3/g)
M!A
2040 (27), 2890 (18) 4590 (18) 540 (5 1) 3640 (18) 5 1
0.817 (27), 0.778 (18) 0.735 (18) 0.77 (51) 0.837 (18)
1 0 5 (U), 59 (18) 35.4 (18) 35.3 (18)
F/exura/ Strength, ASTM D790 (MPa) 57,59
Temp. (C)
PA-6 PA-66 PA-610 PA-12
DAM 5O%RH DAM SO%RH DAM 50%RH DAM 5O%RH
-40 145 - - - - - -
- 30
- - - - - -
86 -
2 3 - - 117 42 - - 55-57 37-44
24 113 40 - - - - 1 7 -
8 0 23- 20 - - - - - - -
*Spencer and Gilmore; R = 82.06 (cm3bar/mol/K); u = specific volume (cm3/g) (51).
References page V-132
V/126 PHYSI CAL CONSTANTS OF VARI OUS POLYAMI DES
Glass Transition Temperature, Ts (C) 57-59,61-63,67-69
DAM 5O%RH loo%RH
A B C D C D c D
PA-6 56 65,67 59,65,75 41.60 20 3 - 2 2 - 3 2
PA-66 82 6567 66,78,80 46,48 35 1 6 - 15 - 37
PA-610 56 46.50 65,67,70 42,5 1 40 - 1 0
PA-12 29 25,32 54,62,- 42,- - 42 -
A: Estimated from melting temperature: T, = 2/3 x T,,,; 9,lO.
B: Calculated from group contribution, 9.10.
C: Dynamic measurements with torsion pendulum; 9,10,11,12.
D: Static Measurement: DSC inflexion point of mechanical property versus temperature or method not identified; 9- 18.
Griheisen Parameter yg 0.58 0.49 0.45
Hardness
Rockwel l Hardness, ASTM D785
PA-6 PA- 66 PA- 610
DAM SO%RH DAM 5O%RH DAM 5O%RH
R116-119 R97-101 R118-121 R108 RllO-111 -
Dry, 23C Ml00 M 105 R 75
Moist ISO- 110, 23C M 70 M95 M 60
Ball Indentation Hardness H358/30 (MPa) = (N/mm2) (DIN 53 456). (ISO-2039)
Dry, 23C 150 160 120
Dry, nucleated, 23C 160 170
Moist ISO- 110, 23C 70 100-110 80
Heat Capacity See also corresponding table in this Handbook
20C crystalline (J/mol/K) 204 374 502
Heat of Combustion &J /kg) - 31.400 - 31.400
Heat of Crystallization (W/kg) - 46.5 -54
Heat Distortion Temperature
ASTM D648 (C)
PA-6 PA- 66 PA- 610
Load
MPa DAM 5O%RH DAM 5O%RH DAM 5O%IW
0.5 - 235 - 175 160
1.8 55-75 - 90 6 6 6 0
0.64 51,55
57-59
PA- 12
DAM 5O%RH
R106-110
R 110
98
354 5 5
51
25
57,59
PA- 12
D A M 5O%RH
120 -
5 0 250
(ISO-R 75) (C)
Molded, dry, 0.45(N/mm2) = (MPa) method B
Molded, dry, 1.8(N/mm2) method A
Heat of Formation See Enthalpy
>160 >200 >160 150
55-90 100-110 65-85 5 5
Heat of Fusion (kJ /kg)
Crystalline from AH,
Crystalline from AH,,, for a-structure
Amorphous, annealed 8 h at 50C
190 (25) 196 (25) 215 95 (15)
230-278
240-260 (24)
4 5 45 (15)
Heat of Sorption (J/mol)
H20 c 150C -45.6 x lo3 (43)
Melt - 76.8 x lo3 (14) - 58.5 x 103 (37)
** To = ( d?V, / C, (55) where (Y is the coefficient of expansion (K-l), B is the bulk modulus (N/mm2), V, is the molar volume (cm3/mol), C, is the
specific heat capacity (mJ/K/mol).
Physical Constants of Various Polyamides v/127
Property Polyamide 6
lgnifion Temperatures (ASTM D1929-1977) ( C)
Flash-ignition temperature 400
Self-ignition temperature 440
/mpact Strength, Izod, notched, ASTM D256 (J/m)
PA-6 PA-66
Temp.
(Cl DAM 5O%RH DAM 5O%RH
-40 48 - 43 -
23 53 267 53 107
Polyamide 66 Pol yami de 610 Polyamide 12 Ref.
390 415
57-59.62-64
PA-610 PA-12
DAM 5O%RH DAM 5O%RH
43 - 55
53 85 60 64
Tensile Impact Strength, ASTM Dt822 (KJ/m2) 57-59
PA-6 PA-66 PA-610 PA-12
DAM 50%RH DAM 5O%RH DAM 5O%RH DAM 5O%RH
Short 147-250 - 158 231 168- 200 - - -
[hi,, = 180001
Long - Not broken 504 1470 - - -
[M, = 180001
535 Not broken
[M, = 340001
Notched, Charpy, DIN 53453 (MPa)
DAM (20C)
Conditioned 4 months, 20C and 65% RH
Izod (ISO-180, method 1A) (J/m)
Dry, 23C
Dry, - 40C
Moist, ISO- 1110, 23C
3-6
Not broken
50-100
30-50
120
Infrared Spectrum See Ref. 21 and DIN 53746 (draft)
Magnetic Susceptibility (cm/g) ( x 106)
Mechanical loss, tan 6 (IS0 537)
(y=O.l-10Hz) dry 20
dry 40
dry 60
dry 80
dry 100
(< lo4 Hz) dry 23
(lo3 Hz) 0. 72% HZ0
(lo3 Hz) 120
0.016
0.048
0.175
0.127
0.064
Melting Point (IS0 3 146, method C) (moldings) (C)
Equilibrium melting point
a-Crystalline
Pressure dependence
Me/ f Vi scosi ty
Flow activation energy* Ee (kJ/mol)
Coefficient K of zero-shear-rate-
melt viscosity ** (Pa s)
220
231 (32)
260
See Ref. (27)
60
9.5 x lo-l4 (250C)
57-59
2-3 4-10 -
12-30 13- 15 -
40-60 50 50-200
30-50 3 5 -
110 75
0.7610.63 5 1
0.016 0.016 0.01
0.026 0.10 0.048
0.083 0.17 0.16
0.127 0.10 0.08
0.064 0.055 0.048
io.02 (68)
0.12 (68)
0.2 (68)
262
270
See Ref. (45)
220 1 7 8 57,59
187 (15)
60 60 60 3 1
7.2 x lo-l4 (280C) 3 1
*v=vo(To) exp[- %(+- A)]
**7j o(Mw) = K f&' 34
( >
References page V- 132
V/128 PHYSICAL CONSTANTS OF VARIOUS POLYAMIDES
Property Polyamide 6 Polyamide 66 Polyamide 610 Polyamide 12 Ref.
Modul us (MPa) m (N/mm)
Bulk modulus - See Compressibility and Bulk Modulus B
Loss modulus G See Mechanical Loss
Elasticity modulus (Young) (ISO-R527)
23, dry 3000
23, moist ISO- 110 1500
loo, dr y 500
3300 2400 1400
1700 1500 1200
600 400 200
Plexural modul us, ASTM D790 (MPa) 57-59
PA-6 PA-66 PA-610 PA-12
Temp.
(C) DAM 50% RH 100% RH DAM 50% RH 100% RH DAM 50% RH 100% RH DAM 50% RH 100% RH
- 4 0 3010 3650 3650 3240 3450 - 2240 2520 - 1790 - -
2 3 2720 970 410 2830 1210 480 1970 1100 690 1410 1030 -
77 520 340 240 690 570 - 480 - - - -
Shear modulus G (IS0 537)
Dry, 23C
Dry, nucleated
Dry, 100C
Dry, 200C
Apparent creep modulus (ISO-899)
Ec/1000/20 (23C, 50% RI-I)
Nucleated
1100 1300 800 500
1500 1700
200 300 120 100
80 150
230 400 400 300
440 450
Mol d Shri nkage, (ASTM-D955) (%)
(mold temp. 60C; 80 x 10 x 4mm)
1.4 1.6 1.2 1.1
Moi sture Absorpti on See Absor pt i on
Molecular Weight, (repeat unit) 113.2 226.3 282.4 197.3
Oxygen Index (ASTM-D2863) (%)
DV
25-27 28-29 24 26
Permeability See table Permeability Coefficients in this Handbook
Poi sson Rati o
(a) Moldings, 20C
(b) Extruded rod; room temp.
compressive axial strain 0.1
0.2
0.4
0.6
0.33 0.3-0.4 0.3-0.4 0.3-0.4
/
2 9
I
29 I
29 !
0.1-0.25
0.3-0.36
0.40-0.44
0.43-0.45
0.38
2 9
51
64 j (c) Power factor at lo3 Hz, dry 0.02-0.06
(d) vs. temperature: 100C 0.46
Mel t 0.50
(e) Limiting pressure velocity of nylon against steel &Pa x 0.5 m/s)
70
0.02
0.47
0.50
-
0.50
0.04
0.44 (51)
0.50
60 :
I
8 5 70
Refractive Index, q.
Single crystals
u, talc.
p, talc.
y. obs.
Moldings
1.475 (8) 1.475
1.565 (8) 1.525
1.58 (8) 1.565
1.53 1.53 1.53
Resistance to Tracking (IEC-Publ. 112)
Met hod CT1
CTI-M
CT1 600 CT1 600 CT1 600 CT1 600
Cl-I-M 600 CTI-M 600 CTI-M 600
Shear St rengt h, ASTM D732 (MPa)
Physical Constants of Various Polyamides V/ 129
57-59
DAM
PA-6 PA-66 PA- 610 PA- 12
SO%RH DAM 5O%RH DAM 5O%RH DAM 5O%RH
59 - 66 57 58 - 34 -
Shrinkage See Mold Shrinkage
So/ubi/ify Parameter (J/cm 3, I2
Amorphous, 25C 27.8 27.8
So/vents See table Solvents-Nonsolvents in this Handbook
Sonic Velocity, 20C (m/s) 1400-2300 (fibers)(26) 2770 (mouldings) (40)
26 5 1
Specific Heat (J/g-K) 1.7 1.7 1.7 1.26 57,59
Effect of temperature (C)
0
40
80
120
160
200
220
240
260
280
1.38 1.30 1.38
1.67 1.55 1.76
1.97 1.97 2.13
2.30 2.30 2.22
2.68 2.68 2.47
-
2.72 2.89
-
2.76 8.16
-
3.35 3.10
-
11.51 2.64
-
3.14 2.68
58,59
-
-
-
-
-
-
-
-
Specific Volume, at varying pressures (MPa) and temperatures (cm3/g)
At 25C
At m 0.875
50 0.865
100 0.860
200 0.850
At 100C
At m 0.895
50 0.885
1 0 0 0.875
200 0.860
At 200C
At m 0.945
50 0.925
100 0.910
200 0.890
At 300C
At m 1.055
50 1.020
100 0.995
200 0.960
6 1
0.880 1.005 0.985
0.875 0.985 0.975
0.865 0.970 0.960
0.855 0.950 0.945
0.905 1.045 1.020
0.890 1.020 1 .oOO
0.880 1.000 0.985
0.865 0.970 0.960
0.950 1.125 1.130
0.935 1.085 1.095
0.920 1.060 1.070
0.895 1.020 1.030
1.050
1.020
0.995
0.955
1.210
1.150
1.110
1.060
1.210
1.150
1.110
1.070
Surface Tension, critical @N/m)
23C 40-47; 43
Melt, 265C 36
Taber Abrasion, D1044 (mg loss/1OOO cycles); CS-17 wheel, 1OOOg load
5
-
40; 44
36 37
3 1 38,5 1
2 5 22
7 [M, = 18000]
4 [M = 340001
5-6
57.59
-
Temperature Index/Thermal Endurance Profile: Typical Values (C)
Not stabilized
5000h 8 5
20000 h 70
Heat stabilized
5000 130
20000 120
57,59
85
-
70
-
130
120
-
100
References page V- 132
v/130 PHYSICAL CONSTANTS OF VARIOUS POLYAMIDES
Tensi l e Strength 57-59
Temp.
(C)
PA-6 PA-66 PA-610 PA-12
DAM SO%RH DAM SO%RH DAM 50%RH DAM SO%RH
ASTM D638 (MPa)
- 4 0 120 -
23 81 69
II 6 8 59
Tensile Strength at Yield, ASTM D638 (MPa)
- 4 0 120 119
23 81 50
7 7 30 28
108 1 0 3 83
83 77 59
62 4 1 3 7
83
- -
49 55 52
3 7
- -
108 103 8 3
83 79 -
8 3 59 59 49 52 4 1
62 4 1 29 - 24
-
Tensile Elongation at Yield, ASTM D638 (%)
-40
- -
2 3 9
-
77 -
4 6 1 0 1 3
- -
5 20 1 0 30 1 0 20
30 30 30
- - -
Tensile Elongation at Break ASTM D638 (%)
- 4 0 8 4
23 150 300
II 310 325
20 20 20
60 >200 100
340 350 300
30
- -
220 250 250
- - -
(ISO-R 527) (MPa) F (N/mm)
Dry, 23C
Dry, 100C
Moist, 23C (% water)
Moist, 23C (saturated in H20)
Monofi l ament s 23C 50% RH
draw ratio 4.3 : 1
5.0: 1
80, 90 (nucleated) 90 70 50
30 40 20 11
50 (2%) 60 (2%) 50 (1%) 30 (0.9%)
22 3 5
475-550 575-600
675 -775 650-850
Thermal Conducti vi ty (W/ m/ K)
Moldings
Crystalline (moist) 30C
Amorphous (moist) 30C
Melt 250C
25C dependence on pressure
X (25 kbar)
X0
Relative thermal index for 3 mm thickness
Not stabi l i zed
Electrical
Mechanical
with impact
without impact
Heat stabilized
Electrical
Mechanical
with impact
without impact
0.23 0.23
0.43 0.43
0.36 0.36
0.21 (33) 0.15
1.89 1.83
1 2 5 1 2 5 6 5
75 7 5 65
8 5 8 5 65
130 130
1 0 5
110
1 0 5
110
Thermal Diffusivity (cm*/s) 1.8 x 1O-3
100C 1.4 x 10-s
Melt 250C 0.65 x 10m3
Unit Cell Dimensions
0.23
0.35
1.90
0.25
2.03
1 9
19
12
2
57-59
110
75
95
1.4 x 10-s 12
PA Crystal system
Unit cell parameters (A) Angles
Space Units in Densi ty
group a b C a
P Y
cel l (Mg/m 3, E (g/cm3) Refs.
6 cc-Monoclinic c; 9.56 8.01 17.24 67.5 8 1.23 2 0
cL-Monoclinic G 4.81 7.61 17.1 79.5 4 1.21
n-Monoclinic 9.65 8.11 17.2 66.3
P-Monoclinic 4.8 3. 6-4. 1 4 1
Physical Constants of Various Polyamides v/131
PA
66
610
1 2
Unit cell parameters (A) Angles
Space Units in Densi ty
Crystal system group a b C a
B Y
cell (Mg/m 3, E (g/cm 3, Refs.
y-Monoclinic 9.14 4.84 16.68 1 2 1 4 1.188 24
a-Triclinic g 4.9 5.4 17.2 48.5 77 63.5 1 1.24 8,lO
P-Triclinic 4.9 8.0 17.2 90 77 67.5 1.248 8
Pseudohexagonal 60 (> l&C) 7,44
a-Triclinic 4.95 5.4 22.4 49 76.5 63.5 1 1.157 8
b-Triclinic 4.9 8.0 22.4 90 77 67.5 2 8
Monoclinic p21/c 4.79 31.9 9.58 120 4 1.034 9
(Pseudohexagonal) (fiber axis)
Melt Viscosity Coefficient K of Zero Shear Rate Melt-Viscosity (Pas) Q,(M,) = K(M,/g mol)3.4 70,71
9.5 x 1O-4 (250C) 7.2 x 1O-4 (280C) - -
Vi scosi ty - Molecular- Weight Relationships
71-75
Nyl on Sol vent K ( x 103) (mol/g) a M ( x 104) Refs.
PA-6 HCOOH (88% vol.) 22.6 0.820 0.6- 12.0 1
H2S04 (40% vol.) 59.2 0.690 0.3-1.3 1
Trifluoroethanol 53.6 0.750 1. 3-10. 0 1
PA-6,6 m-cresol 240.0 0.610 1. 4-5. 0 0
HCOOH (90% vol . ) 35.3 0.786 0.6-6.5 0
H2S04 (96% vol.) 115.0 0.670 1. 4-5. 0 0
o-Chlorophenol 168.0 0.620 1. 4-5. 0 0
PA-6,lO m-cresol 13.5 0.960 0.8-2.4 3
PA-12 m-cresol 46.3 0.750 1. 3-13. 0 2
H2S04 (96% vol.) 69.4 0.640 1. 0-13. 0 2
Polyamide viscosity: 9 = K x Ma; see Melt Viscosity, and corresponding table in this Handbook,
Volume, Specific (cm3/g)
2OC, Amor phous
27oC, Mel t
20C
Change on melting
Melt, 27oC, 1 bar
Volume, Molar (cm 3/mol)
2oC, Crystalline (rods)
2oC, Amor phous
2oC, Amorphous, cal cd. from
group contribution
Volume Resistivity (Ohm cm)
Relative humidity 0% (dry)
Saturated at 50% RH, 20C
20C (saturated) 100% RH
Temperature 6oC, dry
Dry, 100C
Dry, 150C
At 50% RH, 100C
Wear Resi stance (&km)
R, (pm) average roughness height a
0.1
0.5
1.0
2.0
4.0
6.0
0.917 0.917
1.032 1.018
0.8 13 cr-monoclinic 0.82 (47) a-triclinic
0.02-0.03 0.02-0.03
1.040 1.010
100 198
103 207.5
104.2 208.3
1 x 105
2 x 10
4 x 108
8 x 10
3 x 109
0.30 0.28
0.32 0.30
0.35 0.35
0.57 0.48
0.80 0.52
1.00 0.55
P (N/mm) average surface pressure (R, optimum, see also Coefficient of Friction)
0.02 0.11 0.10
0.05 0.29 0.24
0.10 0.57 0.48
0.25 1.40 1.20
1 x 105
3 x 10
1 x 109
6 x 10
3 x 109
1079
4 x 10
0.95
1.095
0.865 (8)
0.02-0.03
260 1 9 5 55
271 199.5 36
1 x 105
2 x 102
3 x 100
5 x 10
5 x 108
0.99 36
0.966 (9) y-monoclinic
0.03
1.19
105
104
103
107
109
0.20
0.25
0.60
1.00
2.50
3.90
1 3
0.12 13
0.30
0.60
1.50
References page V- 132
V/l 32 PHYSICAL CONSTANTS OF VARIOUS POLYAMIDES
Property Pol yami de 6 Pol yami de 66 Pol yami de 610 Polyamide 12 Ref.
1 .oo 5.70 4.80 6.00
5.00 28.00 24.00 30.00
15.00 86.00 72.00 90.00
a Average surface pressure: 0.1 N/mm ; surface temperature: < 40C
REFERENCES
1. As long as no other specific reference is cited, the values for
varying polyamides were selected on the basis of the infor-
mation from the technical manuals of the corresponding
suppliers:
PA66: sMaranyl Al00 (ICI), @Zytel 101 (DuPont). !%Jltra-
mid A3K (BASF). Designation: ISO-1874-PA66, MR(H),
14-030.
PA6: %apron 8200 (Allied Chemical), &Durethan B31F
(Bayer), @Ultramid B3K (BASF). Designation: ISO-1874-
PA6. MRH, 14-030.
PA610: @Ultramid S3K (BASF). Designation: ISO-1874-
PA610, MRH, 14-020.
PA12: aGrilamid L20 (Ems-Chemie). %estamid L1901
(Hiils). Designation: ISO-1874-PA12. G, 18-010.
Preparation of test specimens and determination of proper-
ties according to ISO-1874-2 (1987) and ISO-DP294.
Further property values were taken from the VDWDE-
Werkstoffblatt, No. 2479, Blatt 1 (1978). VDI-Verlag,
D-4000 Dusseldorf (F. R. Germany) Polyamid-Formstoffe,
unverstarkt, a paper which was produced in cooperation
with the above named suppliers. This leaflet contains also
further approved values for other homopolyamides such as
PA1 1, PA612 and PA6-3-T.
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9. G. Cojazzi, A. Fichera, C. Garbuglio, V. Malta, R. Zannetti,
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11. M. Dole, B. Wunderlich, Makromol. Chem., 34, 29 (1959).
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14. 0. Fukumoto, J. Polym. Sci., 22, S. 263 (1956).
15. S. Gogolewski, K. Gzerniawska, M. Gasiorek, Colloid &
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16. G. Goldbach, Angew. Makromol. Chem., 32, 37 (1973).
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18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
F. Hafner, Th. Mietzner (BASE Abt. Informatik; ,1986), talc.
from PVT-functions for %ltramid B4, A3K and EGrilamid
L 20.
K.-H. Hellwege, R. Hoffmann, W. Knappe, Kolloid-Z. Poly-
mer, 226 (2), S109 (1968).
D. R. Holmes, C. W. Bunna, C. J. Smith, J. Polym. Sci., 17,
159 (1955).
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H. Kunze, Dissertation TH Aachen 1958.
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J. Pellon, W. G. Carpenter, J. Polym. Sci. A, 1, 863 (1963).
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A. Reichle, A. Prietzschk, Angew. Chem., 74, 562 (1962).
L. G. Roldan, H. S. Kaufman, J. Polym. Sci. B, 1, 603
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E.-O. Schmalz, Faserforschg., Textiltechnik, 20 (1 l), 533
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G. F. Schmidt, H. A. Stuart, Z. Naturforschg., 13a, 222
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46. H. W. Starkweather, G. E. Moore, J. E. Hansen, Th. M.
Roder, R. E. Brooks, J. Polym. Sci., 21, 189 (1956).
47. H. W. Starkweather, R. E. Moynihan, J. Polym. Sci., 22,363
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48. H. W. Starkweather, J. Appl. Polym. Sci., 2 (5), 129 (1959).
49. H. W. Starkweather, J. F. Whitney, D. R. Johnson, J. Polym.
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50. H. Tautz, L. Strobel, Koll. Z., Z. f. Polym., 202 (1) S.33
(1965).
51. Van Krevelen, D. W., P J. Hoftyzer: Properties of Poly-
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52. J. H. Wakelin, A. Sutherland, L. R. Beck, J. Polym. Sci., 42
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53. L. G. Wallner, Makromol. Chem., 79, 279 (1948).
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55. R. W. Warfield, E. G. Kayser, B. Hartmann, Makromol.
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56. A. Zosel, Colloid Polym. Sci., 263, 541 (1985).
57. Trade Literature
(a) Design Handbook for DuPont Engineering Plastics,
DuPont, 1997, Module II, 232409E
(b) Ultramide PA, Product Line, Properties, Processing,
BASF Plastics, B568e, (9110) 9.91.
(c) Ultramida T PA, Product Line, Properties, Proces-
sing, BASF Plastics, B605e, 8.90.
(d) Ultramid~ PA, Range Chart, BASF Plastics, F568/le,
5.90.
(e) Product Sheet Nylon Resin 6,10, Monsanto Co.
(f) Rilsan@, Design Guide to a Versatile Engineering
Plastic, Atochem Polymers, Inc., 4/84.
(g) Engineering Thermoplastics, Versamids Huls Amer-
ica, Inc.
(h) A Guide to Properties and Uses of Nylon 12, Huls
America, Inc., Datasheets.
(i) Product Selection Chart, Grilamid@, Nylon 12, EMS
Industries, GG5-805.
(i) Caprot? Nylon Homopolymers for Molding and Extru-
sion, Allied Signal, ERG-02-6/9 1.
(k) Vydyne@ Nylon, Monsanto Company, 1994, MPP-5-
210.
(1) Technical Information, Rilsana, Elf Atochem, North
America, Inc.,Technical Polymers, 1998.
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T. M. Roder, L. T. Sherwood, in: M. I. Kohan (Ed.), Nylon
Plastics, Wiley, New York, 1973, p. 327.
59. J. C. L. Williams, S. J. Watson, P. Boydell, in: M. I. Kohan,
(Ed.), Nylon Plastics Handbook, Hanser/Gardner Publi-
cations, Cincinnati, OH, USA, 1995, p. 291.
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(Ed.), Nylon Plastics Handbook, Hanser/Gardner Publi-
cations, Inc., Cincinnati, OH, USA, 1995, p. 151.
61. A. Dharia and S. J. Grossman, Antec 1987, 590.
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467 (1987).
63. S. W. Shalaby, P. Moy, in Engineering Materials Hand-
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p. 447.
64. J. A. Brydson, Plastics Materials, Butterworth-Heine-
mann Ltd., Oxford, Great Britain, 1989.
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1988.
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Physical Constants of Cellulose*
J. Ganster, H.-P. Fink
Fraunhofer Institute for Applied Polymer Research, Teltow-Seehof, FR Germany
A. Introduction V-l 35
B. Solid State Properties V-l 36
Table 1. Unit Cell Dimensions V-l 36
Table 2. Density V-l 36
Table 3. Average Ordered Fraction of Cotton
and Linters Measured by Various
Techniques V-l 36
Table 4. Average Ordered Fraction Measured
by Various Techniques V-l 37
Table 5. Degree of Crystallinity V-l 37
Table 6. Crystal I ite Sizes V-l 38
Table 7. X-ray Orientation of Cellulose
Fi bers V-l 40
Table 8. Heat Capacity V-l 40
Table 9. Thermal Expansion Coefficient V-l 41
Table 10. Other Thermal Properties V-l 41
Table 11. Refractive Index and Birefringence V-l 44
Table 12. Resistivity V-l 44
Table 13. Dielectric Constant and Loss
Factor at 1 kHz V-l 45
Table 14. Other Electrical Properties V-l 46
Table 15. Crystal Elastic Modulus Et in Chain
Direction V-l 46
Table 16. Fiber Strength, Elongation and
Modulus V-l 47
C. Solution Properties V-l 47
Table 17. Typical Non-Aqueous Cellulose
Sol vent s V-l 47
Table 18. Other Solvents V-l 48
Table 19. Viscosity - Molecular Weight
Rel at i onshi ps V-l 48
Table 20. Second Virial Coefficients V-l 50
Table 21. Sedimentation and Diffusion
Coefficients V-l 50
Table 22. Partial Specific Volumes, vz V-l 51
Table 23. Geometrical Chain Characteristics v-151
Table 24. Polymer-Solvent Interaction
Paramet ers V-l 52
D. References V-l 52
A. INTRODUCTION
For the present edition of Polymer Handbook the former
chapter, Properties of Cellulosic Materials has been
considerably shortened and restructured. Besides leaving
out the infrared spectrum and some properties not
considered genuinely physical, the main alteration is the
omitting of the vast field of cellulose derivatives altogether.
This is to be justified in view of the space given to the other
polymers dealt with in the section, Physical Constants of
Some Important Polymers. Each of the cellulose deriva-
tives (or at least each class), we think, would have required
an entry of its own. Accordingly, we restricted ourselves to
materials, the main component of which is native or
regenerated cellulose. Therefore, we explicitly refer to the
previous edition (1) for its wealth of data on cellulose
derivatives, liquid crystals therefrom, nonglucose hydro-
carbons and noncellulosic substances in cellulosic materi-
als, and first order rate constants and energies of activation
of homogeneous hydrolysis. Moreover, much useful
and recent information can be found in the Proceedings
of the Cellucon Conferences (2), the pertinent ACS
volumes (3) and a number of monographs (4-9), whereas
cellulose research before 1955 is well documented in
Refs. (10,ll).
* Based on the table in the third edition, by A. GrGbe, Fraunhofer-Institut fiir GrenziSchen-und Bioverfahrenstechnik, Stuttgart, Germany.
v/135
V/136 PHYSICAL CONSTANTS OF CELLULOSE
B. SOLID STATE PROPERTIES
TABLE 1. UNIT CELL DIMENSIONS
Modification Space group a 6) b 6) c (4 K () p (1 Y (I
Remarks Refs.
1,
Pl 6. 74 5. 93 10. 36 117 113 81 Natural occurrence 12,13b,c
(algae, bacteria)
:I?
p21 7. 85 8. 14 10. 34 90 90 96. 6 Natural occurrence (higher plants) 14c,15b,16b
p21 8. 01 9. 04 10. 36 90 117.1 Obtained by alkali treatment 17,18
III 10.25 7. 78 10. 34 Z8 90 122. 4 Obtained by liquid ammonia 1 9
IV
treatment
8.01 8.12 10.34 90 90 90 Obtained by heat treatment 20
of cellulose III
Due to the very limited number of available X-ray reflections, atomic coordinates are difficult to determine. The question of chain orientation (parallel VS. anti-parallel
packing) cannot be considered ultimately settled, although a parallel arrangeknt is widely accepted for Cellulose I, whereas Cellulose II is thought to crystallize in an anti-
parallel packing mode. In each of the five cells given in the table, the c axis is parallel to the chain axes. The I, cell contains a single chain with two glucose units, while all the
other cells consist of two chains with two glucose units each.
b References deal with the same modification.
Atomic coordinates given.
TABLE 2. DENSITY
Type of cellulose Density (g/cm j) Refs.
Cellulose I 1.582-1.630a 21, 22, 23, 24, 25, 26, 27
Cel l ul ose I, 1.58 1 2
Cellulose I B 1. 62- 1. 64 14,16
Cellulose II 1.583-1.62 22, 24, 28, 26
Cellulose IV 1.61a 22
Cotton 1.545-1.585 29,30,31,32,33,34
Ramie ca. 1.55 26, 35
Fl ax 1. 541 36
Hemp 1.541 36
Jute 1.532 36
wood pulps 1.535-1.547 26,31,37,25,38,39,33
Cuprammonium fibers 1.519-1.531 31,32,34
Polynosics 1.489-1.528 40,41
Viscose fibers (and films) (rayon and staple) 1.508-1.548 31, 32, 38, 42, 43, 44
High tenacity viscose fibers 1.498-1.524 42, 45
a Calculated from X-ray or electron diffraction data.
TABLE 3. AVERAGE ORDERED FRACTION OF COTTON AND LINTERS MEASURED BY VARIOUS TECHNIQUESaab
Average crystallinity Number of publications Approximate average crystallinity value
value for cotton and involved in the average
Technique linters (S) crystallinity value wood pulp Regenerated cellulose
PHYSI CAL
X-ray diffraction 73 25 60 35
Density 64 1 8 50 35
ABSORPTI ON AND SWELLI NG CHEMI CAL
Deuteration 58 5 45 25
Moisture regain 58 50 25
Hallwood-Horrobin 67 3 55 35
Nonfreezing water ca. 85 1 50
Acid hydrolysis 90 26 85 70
Alcoholysis ca. 90 4
Periodate oxidation 92 4 92 80
Nitrogen tetroxide oxidation ca. 70 1 50
Formylation 79 7 35
Iodine sorption 87 9 85 60
NONSWELLI NG CHEMI CAL
Chromic acid oxidation 99. 7 1
Thallation 99. 6 2
a Ref. 46.
b Most of these values are general averages of several published values: the number of publications involved in each average is given in the third column. The term
crystallinity value does not imply that any particular method measures crystallinity or order in any strictly defined sense, or that the various methods measure precisely the
same type or level of order/disorder; with the chemical methods for instance, the value given is merely the fraction of the material that is not readily accessible to, and thus not
able to, react with the particular reagent.
Degree of Crystallinity v/ 137
TABLE 4. AVERAGE ORDERED FRACTION MEASURED BY VARIOUS TECHNIQUES
Technique Cotton
Mercerized Wood Regenerized
cotton
PdP
cellulose
X-ray diffraction 0.73 0.51 0.60 0.35
Density 0.64 0.36 0.50 0.35
Deuteration or moisture regain 0.58 0.41 0.45 0.25
Acid hydrolysis 0.90 0.80 0.85 0.70
Periodate oxidation 0.92 0.90 0.92 0.80
Iodine sorption 0.87 0.68 0.85 0.60
Formylation 0.79 0.65 0.75 0.35
Ref. 46.
TABLE 5. DEGREE OF CRYSTALLINITYa
Type of cellulose DCb(%) Refs.
xf(%o)
k (lo-) (nm) Refs. Crd(%) Refs.
Natural Fi bers
Ramie 60-71 48,49,50,51
54-74 54
49 55
44-47 52
57 4 53
45 52
37-46 2.5-3 5 3
59
59
60
49
63
60
56-59 2.4-3.9 6 1
47 52
49
63
60
57-60 3.4-4.2 6 1
42 52
64-65 3.1-3.2 67
56-63 6 5
43-49 2.1-2.6 65
48
48 73-79 3.3-3.9 68
Ramie, mercerized
Flax
Linen
Hemp
Manila hemp
Sisal
Jute, Corchorus olitorius
Jute, Cord-torus capsularis
Flax, bleached
Cotton, different origins
67 56
66k3 57
6Ok3 57
42&4 57
38f2 58
65f3 58
70
79
5 1
57
68
62
64
62
66
56
58-66
47-67
Average 67,
range 64-69
69-71
7 1
Average 70,
range 66-74
Cotton, mercerized
Cotton, linters
Cotton, linters, mercerized
70
73
Average 48,
range 41-55
Algal Cel l ul ose
From Valonia veniricosa Average 68,
range 65-70
Bacteri al Cel l ul ose
From Acetobacter xylinum
Cellulose from Woody Plants
Cellulose from different plant stems
Cellulose from different woods
Cellulose from Pinus rudiata
(5, 10, and 15 annual ring)
Bagasse
Pulps
Different wood pulps
49-58 56
62-64 56
73-55 69
58 56
62-70 48,49,60,51 56-68 70
62-65 56
49-77 7 1
67 52-66 72 Different dissolving pulps 64 63
Different wood pulps, mercerized 49 55
43-56
References page V- 152
V/ 138 PHYSICAL CONSTANTS OF CELLULOSE
TABLE 5. contd
Type of cellulose DCb(%) Refs. xf(%) k (lo-) (nm*) Refs. Crd(%) Refs.
Man-made Ceihdosic Fibers
Viscose rayon, normal grade
Viscose staple fibers, normal grade
Viscose fibers, mercerized
High tenacity viscose rayon
High wet modulus (HWM) viscose
fibers
Polynosic-fiber
Cuprammonium rayon
Cuprammonium rayon, mercerized
Saponified acetate fibers
For&an
Regenerated carbamate fibers
Lyocell-type fiber
Cellulosic Fi l ms
Cellophane
Cuprophane
Blown films from NMMO solution
Others
Amorphous powder, obtained by
dry-grinding viscose rayon
38- 40
Average 27,
range 13-36
30- 39
48, 49 27 1. 58 67 35 74
50, 75, 76
60
48, 49, 76, 78
40- 41 63
Average 27, 60
range 30-52
40- 52 50, 55, 75
23- 56 48,49,50,75,76,80
27- 44 48, 49, 75, 76, 78
33- 36
34
77
79
35. 6
40- 44 47, 48, 50
41 63
49 55
Average 38 49
39- 54 49, 76, 78, 82
43 83
30- 40 48, 49, 78
8 85, l O
42 1. 75
45 2. 1 84
46 2. 9 84
38- 41 2. 6- 2. 8 84
38 81
42 79
52 48 8 1
48 79
50 79
67 57 19
Amorphous powder, obtained by dry 35- 40 1 0
grinding viscose rayon, recrystallized
Different cellulose samples 36- 44 73
Regenerated cellulose precipitated 45- 53 82
from viscose as flake
Precipitated P-cellulose 50- 62 83
a According to Hermans (49~1) relative and absolute X-ray methods can be distinguished. DC and x, values are absolute ones as well as some of the Cr values. The Ruland-
Vonk-method provides additionally a lattice disorder factor k representing the amount of lattice distortions. The so-called crystallinity index or ratio values derived from
relative methods as peak height ratios are omitted here. For these, the reader is referred to the third edition (1).
* According to Hermans and Weidinger (47,48).
According to the method of Ruland (86) and Vonk (87).
d According to other methods.
TABLE 6. CRYSTALLITE SIZES
Type of cellulose Lateral dimensions (A) Width and thickness (A) Range of length (b) Refs.
50- 60
50
155- 230
100
40
5813
60
64
50- 100
100
146
150
62x49
64x50
88
500 89
128 90
56
91
92
93
94
95
96
91
98
99
100
TABLE 6. contd
ljpe of cellulose Lateral dimensions (A) Width and thickness (A)
Crystallite Sizes v/ 139
Range of length (A) Refs.
Cotton linters
Ramie
5 1
47-60
65
16-26
50-100
59
68
70
<400
61 x 167
Hemp
Flax
Linen
Jute
Bamboo
Manila hemp
Sisal
Algal cellulose (Woniu)
Bacterial cellulose (Acetobacter xylinum)
Chaetomorpha melagonium
Tunicin
Different wood samples
Cellulose from different plant stems
Bagasse
Different wood pulps
Different dissolving pulps
48-55
46-55
47-66
62
46-50
44
44
49f3
51.5
55
52f3
55
49 x 4
<70
38f2
38f3
148 x 53
89-124
89- 101
112
84 x 70
58-83
53-65
55
169 x 114
84 x 34
37-40
35-36
35
58-70
32-60
1400-2200
41-47
50-70
75-95
39-42
54
76
70-85
Normal viscose fibers
HWM viscose fibers
(80- 100) x (30-40)
(77-90) x (29-49)
High tenacity rayon 120
Normal viscose rayon 140
Polynosic fibers
93 x 32
110x25
110 x (69-72)
130 x 25
42-51
20-31
93
80-100
400-2550
600- 2500
189
1 9 5
174
140
130
65-70
75- 105
110- 156
114
154
120- 140
189
160
1 0 1
102
52
1 0 3
46
104
105
56
106
107
94,99
97
108
109
52
46
72
110
1 1 1
112
105
9 1
97
58
97
56
58
97
58
88
58
58
113
110
105
9 1
99
110
105
91
99
99
56
56
56
56
72
67
105
77
90
104
67
77
90
1 1 5
79
104
1 1 5
1 1 5
116
77
90
1 1 5
* Mean cross-sectional area (A*),
References page V- 152
v/140 PHYSICAL CONSTANTS OF CELLULOSE
TABLE 6. contd
Type of cellulose Lateral dimensions (A) Wi dth and thi ckness (A) Range of length (A) Refs.
Tufcel-fibers
Isotropic Hermans viscose fibers
Fortisan
Regenerated carbamate fibers
Lyocell-type fibers
Cellophane
Cuprophane
Blown films from NMMO-solution
35-41 112 110,117
50-200
1 1 8
loo-160 160 90
43-57 110
49-51
1 1 1
160 1 1 5
(67-88) x (26-47) 79
70 x (25-46)
79
42 1 4 3 67
36-53
84
33-53
84
30-41
84
TABLE 7. X-RAY ORIENTATION OF CELLULOSE FIBERS
Material @ (I Refs.
f x
Refs.
Cotton
Cotton, mercerized
Ramie
Ramie, mercerized without tension
Ramie, mercerized and reoriented
Hemp
Fl ax
Jute
Sisal
Coir
Viscose rayon, normal grade
Viscose staple fibers, normal grade
Lilienfeld rayon
High-tenacity viscose cord rayon
Viscose tire cord
High-wet modulus (HWM) viscose fibers
Modal fibers cond.
Modal fibers wet
Polynosic fibers (Tufcel)
Isotropic viscose model fibers, without stretching
Isotropic viscose model fibers, after intense stretching
Cuprammonium rayon
Fortisan
Lyocell-type fibers cond.
0. 31- 0. 91 76,120,10,121
0.30-0.67 76,78
0.70-0.94 76,10,121
0. 39- 0. 998 50,76,122,121
0.94-0.97 1 2 3
0. 45- 0. 993 76,122,120,121,78
0.57 124
0.30 124
0.94 123
0.06-0.15 1 2 5
up to 0.90 1 2 5
0.86 1 0
0.7-0.99 76,122,120,78,121
0.62-0.63 124
0.67-0.94 126
> 0.9 67
0.94 1 2 3
0.33-0.35 124
Tencel
Lyocell-type fibers wet
a For native fibers the spiral angle @between cellulose microfibrils (crystallites) and fiber axis is filed. The degree of uniaxial orientation of crystallites is given for regenerated
fibers and some of the native by the Hermans orientation factor,f,, according to Ref. (10). As existing data for regenerated fibers largely depend on spinning conditions, ranges
off, are given.
14.25-16.20 6 1
13.25-17.39 127
9.7-13.7 6 1
7.5 128
6.2 1 2 8
10 128
8.0 128
20.0 128
45 128
0.62-0.70 6 1
0.64-0.72 6 1
0.97 1 0
0.90 1 0
0.98 1 0
0.96-0.97 119
TABLE 8. HEAT CAPACITY
Type of cellulose
To (K) C,(To) (JlglK) a (x 103) (J&K) Tm (K) Remarks Refs.
Amorphous 350 1.414 8.08 435 129
Wood 350 1.364 5.06 435 129
Jute 350 1.339 4.64 435 129
Cotton 350 1.318 4.21 435 129
100% crystalline 350 1.230 1.42 435 Extrapolated 129
Wood 1 0 0.0205 4.20 300 Independent o f crystallinity 130
TABLE 8. contd
Thermal Expansion Coefficient and Other Thermal Properties v / 1 4 1
Type of cellulose
To UQ C,(To) (JWW a (x 103) (J/&K) Tm (K)
Remarks Refs.
Amorphous 300 1.266 6.0 400 Ball milled 130
Wood ( 40% tryst.) 300 1.240 5.5 400 Ball milled 130
Wood ( 65% tryst.) 300 1.226 4.9 400 Ball milled 130
100% crystalline 300 1.238 4.2 400 Extrapolated 130
Ramie 213 1.775 0 373 Average 1 3 1
Fl ax 273 1.344-1.348 0 373 Average 132
Hemp 273 1.327-1.352 0 373 Average 132
Jute 273 1.357 0 373 Average 1 3 2
Viscose rayon 273 1.357 0 373 Average 132
273 1.415-1.595 0 373 Average 131
Cuprammonium fibers 273 1.357 0 313 Average 132
Paper 213 1. 17- 1. 32 0 373 Average 1 3 3
a The constant pressure specific heat capacity C,(?J as a function of temperature T is expressed in linear approximation as C,(T) = C,(T,) + a (T- Ta ). To < T,, a being
the slope and T, marking the interval of validity.
TABLE 9. THERMAL EXPANSION COEFFICIENT
Type of cellulose T(C) aa (x 10) (K-l) aJ ( x 105) (cm3/g/K) Remarks Refs.
Hydrogel
Cellulose I
Cellulose II
Amorphous sulphate cellulose
Cotton (Cellulose I)
High strength cord a
High strength polynosic
High strength cord b
Rayon
Wood pulp
Cotton linters
Different papers
Cotton, rayon
Various celluloses
Linters
15-70
RTc-150
150-200
RT-150
150-200
RT-150
150-200
RT-150
150-200
RT- 100
100-150
RT- 100
100- 150
RT- 100
100- 150
-45, -5
55, 80
- 150 to 225
105- 150
105-150
105-150
-4 to 25
-4 to 25
-4 to 25
- 30 to 25
6.3-25
1 3
23
5.1
1.6
11
1 6
- 0.64
1.6
-31
68
5.1
1 6
7.9
1 9
7/P
17/P
7.1-36.7
0.7
0.4
1.8
0.2-0.75
0.79- 1.62
8
X-ray (101) reflexion
(101)
(10-l)
(10-l)
(002)
NW
(040)
(040)
(101)
(101)
(10-l)
(10-l)
(OW
(OW
p = Cellulose density in g/cm 3
p = Cellulose density in g/cm 3
X-ray (002) reflexion
3.59
5.76
5.52
Machine direction
Cross machine direction
51-60
40
134
1 3 5
1 3 5
1 3 5
1 3 5
1 3 5
1 3 5
1 3 5
1 3 5
1 3 5
1 3 5
1 3 5
1 3 5
1 3 5
1 3 5
136
136
137
138
138
1 3 8
139
139
139
140
140
141
142
1 4 3
Linear expansion coefficient.
b Cubic expansion coefficient d@/dT; specific volume.
Room temperature.
TABLE 10. OTHER THERMAL PROPERTIES
Property Type of cellulose Value Remarks Refs.
Decomposition point (C)
Start of thermal degradation (C)
Cellulose 200-270 144
Cotton 150 145
Viscose rayon 180 145
Linters 225 146
Bleached sulfite pulp 225 146
Kraft pulp 240 146
Filter paper 220 Under nitrogen 147
References page V- 152
V/142 PHYSICAL CONSTANTS OF CELLULOSE
TABLE 10. contd
Property Type of cellulose Value Remarks Refs.
Fast endothermal degradation (C)
Flammability of fibers
Ignition temperature (C)
Self ignition temperature (C)
External ignition temperature (C)
Maximum flame temperature (C)
Fast endothermal degradation (C)
Heat of combustion (kJ/kg)
Rate of heat combustion (J/s/cm)
Limiting oxygen index
Heat of crystallization @J/kg)
Heat of recrystallization &J/kg)
Heat of transition (kJ/kg)
Heat of formation &J/kg)
Linters = 300 1 4 6
Bleached sulfite pulp = 330 1 4 6
Cotton
Viscose rayon
Cotton
Cotton
Cotton
Cotton fabric
Linters
Bleached sulfite pulp
Cotton
Cellulose powder
390, 400
420
400
350
880
850- 1050
812-945
x 300
= 330
290
300-500
19-25% O2
Heating rates 169-225 K/s
Under nitrogen
148,149
1 4 8
1 5 0
1 5 0
1 5 0
151
1 5 2
1 4 6
1 4 6
1 5 0
153,154
Cotton fabric 15090
Cotton fleece 15540
Cotton 18855
Cotton fabric 15452
Under nitrogen
Under flowing nitrogen, char
yields 89.4-8.7 wt.%
Measured in air
Bomb-calorimetric technique
Measured in air, independent
of fabric weight
155
1 5 5
1 5 0
1 5 6
Regenerated cellulose 14732
Fabric 54.2 (J/cm*)
Cellulose diacetate 17179
Cellulose triacetate 17598
Cotton fabric 331
0.184
0.197
0.183
0.185
1.34
1.22
1. 15- 1. 18
1.32
1.327-1.251
1.273-1.35
1.235
105.9 f 5.0
In air, bomb calorimetric
technique
Fabric
Fabric
Twill weave fabric, 241 gm-
Bleached and mercerized
1 5 6
1 5 7
1 5 6
1 5 6
1 5 8
Cotton
Viscose rayon
Cotton
Cellulose
Cotton
1 4 9
1 4 9
1 5 9
1 5 2
1 6 0
161
1 3 3
1 3 3
1 6 2
1 3 2
161
1 6 3
Merceri zed cot t on
Cellulose, extrapolated to
100% crystallinity
Cellulose I
Cellulose II
Amor phous cel l ul ose+
Cellulose II
Cellulose I + cellulose II
Cellulose
Heat of solution (kJ/kg) of dry material Cotton in cuane
Cotton in EtxPhNOH
Rayon in cuane
Rayon in EtjPhNOH
Ball milled cellulose in
Et 3PhNOH
38.1 1 6 5
5949.7 166
108.0 1 6 3
142.5 1 6 7
95.5 1 6 3
138.3-153 1 6 8
243 167
Cellulose II in Et 3PhNOH 182.7
Cotton 1235, 1194-1327
Differential heat of sorption of
liquid water @J/kg) Cotton 1090
1332
Egyptian cotton
121.8
134.8
41.9
972- 1040
964- 1006
1047
1214
Cotton, dried by solvent exchange 1047
Cotton, mercerized 1173
Linters 1143
Linters mercerized 1327
o-34 C
O-100 C
By wetting
At zero regain
At zero regain, from
sorption isotherm at
zero regain, 27C
At zero regain
At zero regain, 25C
At zero regain, 26C
At zero regain, 26C
At zero regain
At zero regain
At zero regain
1 6 4
164
8 5
1 6 7
169,170,171
1 7 2
1 7 3
174,26
174,26
1 7 5
176
176
1 7 1
177
1 7 7
TABLE 10. contd
Property Type of cellulose
Thermal Expansion Coefficient and Other Thermal Properties v / 1 4 3
Value Remarks Refs.
Flax
Wood pulps
For&an
Cuprammonium fibers
Normal viscose fibers
Viscose fiber
Viscose fiber, dried by
Solvent exchange
Cotton
Cotton, mercerized
Viscose rayon
Heat evolved by 1.0 g of fibers going Cotton
from 40% RH to 70% RH in Joule
Viscose rayon
Integral heat of wetting of dry material Cotton
&J/kg) wetting in water at zero regain
Cotton, average value
Cotton, bleached
Cotton. mercerized
Cotton, mercerized,
average value
Cotton, ball milled
Linters
Ramie
Flax
Wood pulps
Regenerated cellulose
Fortisan
Cuprammonium rayon
Viscose fibers
Wetting in methanol
Wetting in bases, acids and salt
solution, AHsalt ~ AHu>o
#J&l
Polynosic fibers
Cotton
Cotton
Cotton, mercerized
Ramie
Wood pulp
Wood pulp, different
degrees of refining
Dissolving pulp
Different viscose fibers
Cotton
Thermal conductivity (W/m/K) Cotton
Rayon
Sulfite pulp, wet
Sulfite pulp, dry
Laminated kraft paper
1248,1206
1173-1256, 1098
1235, 1169
1214, 1115
1173-1215
1050, 984,
917-1022, 1277
1549
1172
At zero regain
At zero regain
At zero regain
At zero regain
At zero regain
At zero regain, 26C
At zero regain, 26C
293
201-281
230
318
268-297
84
At 60% RH
At 65% RH
At 60% RH
At 60% RH
At 65% RH
1 6 8
33.9-56.2 At 20-25C
40.6
46.5
40.0, 39.0
62.0-78.8, 62.6
62.6
At 20C
At 20-25C
At 20-25C
75.2 At 20-25C
90.5 At 20-25C
44.8-57.8 At 20-25C
34.4-48.6 At 20-25C
39.4-54.4 At 20-25C
49.4-71.2 At 20-25C
83.8- 106.4 At 20-25C
76.2 At 20-25C
93.8 At 20-25C
68.2-105.5 At 20-25C
68.2-82.5 At 20-25C
83.1-87.8 At 20C
7.3 At 20-25 C
1 0 . 2 5% NaOH
62.2 17.5% NaOH
62.0 18% NaOH
83.8 18% NaOH
56.4 18% NaOH
67 20% NaOH
1 1 . 2 5% NaOH
78.3 17.5% NaOH
67.0-81.0
-68
25-47
31.8-36.4
62.8-67.8
4.6
3 . 5
3.1
5.4
3 . 8
0.071
0.054-0.07
0.8
0.067
0.13
20% NaOH, 25C
18% NaOH, 20C
5% NaOH
5% NaOH
17.5% NaOH
0.1 M H2S04
3 M NaCl
3 M KC1
3 M MgCI>
3 M CaC12
Density 0.5 g/ml
169,174
177,178
171,174
171,174
171,174
171,174
171,174
1 7 6
1 7 6
169
1 4 5
171
169
169
1 4 5
1 4 5
169,171,26,175
177,179,180,181
182
46
182,183
171,177
181,184,182
46
1 8 5
163,177,185,186
26,181,180
169,180
177,179,181,180
177
1 7 1
169
163,169,171,177,
181,180,187,188
183
189
46
190
190
1 9 1
192
190
1 9 3
190
1 9 0
194
1 9 5
1 8 3
196
196
182
1 9 7
1 9 7
1 9 7
1 9 7
1 9 8
1 4 9
1 9 9
199
200
References page V- 1.52
v/ 144 PHYSICAL CONSTANTS OF CELLULOSE
TABLE 10. co&d
Property Type of cellulose Value Remarks Refs.
Different papers 0.029-0.17 2 0 1
Alkali cellulose 0.0581 Density 0.2 g/ml 202
0.0465 203
0.0674 204
Transition points (C)
Glass transition Cellulose 230 205
220-245 206
Secondary transitions Cellulose 19-23 1 4 2
25 207
Paper -20,+15, x35, -60 208,140,205
Cellulose x 200 205
Endothermal process Cotton 134 H= 134 J/g 209
Bleached linters 1 3 1 H= 131 J/g 209
Sulfite pulp 137 H= 145 J/g 209
Sulfate pulp 147 H= 124 J/g 209
Microcrystalline powder 109, 131 H= 120-143 J/g 209
114 H= 118 J/g 209
See al so Tabl e 17, Typi cal Non- Aqueous Cel l ul ose Sol vent s.
TABLE 11. REFRACTIVE INDEX AND BIREFRINGENCE
ljpe of cellulose
nn
Refs. a
tive cellulose fiber (Cellulose I)
Fl ax
Hemp
Cotton
Jute
Ideally oriented regenerated cellulose fiber
(Cellulose II)
Fortisan
High tenacity rayon
Polynosics
Polynosics cord
Normal viscose fibers
Viscose cord
Cuprammonium fibers
Cellophane
1.618 1.544
1.595-1.601 1.525-1.534
1.571- 1.595 1.517-1.532
1.585-1.591 1.526-1.530
1.573-1.595 1.527-1.534
1.577 1.536
1.578 1.523
1.542-1.553 1.509-1.513
1.556-1.570 1.518-1.531
1.529-1.552 1.512-1.520
1.548-1.571 1.519-1.534
0.074 26
0.061-0.071 26,210,211,212,213,214,215
0. 054- 0. 067 212,214,216
0. 055- 0. 065 216,217
0. 040- 0. 062 210,212,214,218,45,219,215
0.041 214
0.055b 220,(221)
0.043 c 26
0.045 222
0. 029- 0. 043 45,(212,223,224)
0. 036- 0. 043 45,40,(221)
0.0410-0.0415 225
0. 013- 0. 040 226,(212,45,223,224,40,227),215
0. 0350- 0. 0370 225
0. 018- 0. 037 26,212,218,222,(212,214)
0.011, 0.0145, 0.0044 228
References in parenthesis give additional data
b Bone dry.
Condi t i oned.
TABLE 12. RESISTIVITY
Material pa (a cm) Rf (CUgcm*) Remarks Refs;
Pure cellulose
Cotton
Raw cotton
108
2 x 107
2.4 x lo9
8 x lo5
5 x 10s
229,230
52% RH , 30C moi st ure 231
dependence investigated
7 x 106 65% RH, 20C 231
35% RH, 0.18 GPa static pressure 232
75% RH, 25C 233,234d
233.234d
Dielectric Constant and loss Factor v/ 145
TABLE 12. contd
Material pW cm) Rf(R gcmm2) Remarks Refs.
Cotton, washed 12 x 106 - 37 x 106
Cotton, purified 9. 3 x 10s
Ramie 6 x lo4 - 1.8 x lo6
Ramie, purified 5. 7 x 106
Hemp 1 x 107
Jute, purified 2. 5 x 10
Flax, purified 6. 6 x 10s
Viscose rayon 1 x 106 - 3 x 106
Cuprammonium rayon
Fortisan
Mercerized cotton
Regenerated cellulose
Cellophane cuprophane
Insulating paper
Insulating kraft paper
6. 75 x 10
107
100 - 3 x 102
=2x 104
5 x 107
102
104
10
4 x 107
1.2 x 107
10s - 109
2. 6 x lo8
3. 5 x 107
6. 6 x 106
Me = lo%, 20C moisture dependence investigated
M = lo%, 2OC, moisture dependence investigated
M = lo%, 2oC, moisture dependence investigated
M = lo%, 2OC, moisture dependence investigated
M = lo%, 20C moisture dependence investigated
M = lo%, 2oC, moisture dependence investigated
M = lo%, 20C moisture dependence investigated
x 80% RH, 3OC, moisture dependence investigated
M= lo%, 2oC, moisture dependence investigated
35% RH, 0.18 GPa static pressure
M = lo%, 20C moisture dependence investigated
M = lo%, 20C. moisture dependence investigated
M = lo%, 2OC, moisture dependence investigated
65% RH, 20C
Air dry
M<1 %
M= 12%
2O"C, air dry
lOOC, air dry
20C
100C
234
234
234
234
234
234
234
234
234
232
234
234
234
229
235
236
237
237
238
238
239
239
a Specific resistance (resistance of unit cross section per unit length).
b Mass specific resistance (product of p and density).
c Rel at i ve humi di t y.
d These references give additional data.
e Moisture content (wt.%).
Y
TABLE 13. DIELECTRIC CONSTANT AND LOSS FACTOR AT 1 kHz
Material e.b tan ac Range of lgd (v)~ Remarks Refs.
Pure cellulose (from spruce)
Cotton
Jute
Hemp
Ramie
Alpha wood pulp
Bleached sulphite pulp
Paper
Viscose rayon
Regenerated cellulose film 6. 7- 7. 5
Cellophane 7. 6
7. 2
3. 2
6. 1
2. 76
2. 85- 3. 05
4. 6
105
16
50
11. 2
45
7. 9
6. 15
2. 9
3. 03
1. 2- 4
3. 0
6. 7
0. 02
<0. 02
0. 03
1. 4 2- 5
1. 55 2- 5
1. 2 2- 5
1. 28 2- 5
1. 15 2- 5
0. 85 2- 5
<0.02 1. 7- 5. 3 Bone dry, 21C
0.18 2- 7 Dry, WC, temperatures
0.01 1.8-6 22C (- 40 to 90C investigated)
2- 8
3- 4
3- 4
2- 7
3- 4
3- 4
Bone dry, 20C
Bone dry, 21C
25C
Unbeaten, density 1.0 g/cm3
Beaten, density 1 .O g/cm 3
Dry, 0C temperatures
up to 60C investigated
Along fiber
Transverse to fiber
Along fiber
Transverse to fiber
Along fiber
Transverse to fiber
3OC, vacuum dried at 30C
Unbeaten, density 1.0 g/cm3
Beaten, density 1.0 g/cm3
up to 60C investigated
20- 70C
240
241
242
243
243
244
245
245
245
245
245
245
192
243
243
299
241
244
246
247
o More data for the frequency range indicated in the table and for other temperatures, humidities etc. are found in the references given.
b Real part of dielectric constant.
c Quotient of imaginary and real part of dielectric constant (loss factor).
d Decadic logarithm.
Measuring frequency.
References page V- 152
V/146 PHYSICAL CONSTANTS OF CELLULOSE
TABLE 14. OTHER ELECTRICAL PROPERTIES
Property Material Value Remarks Refs.
Dielectric strength (break
down voltage) (kV/mm)
Native cellulose fiber
Insulating paper
Isoelectric point (pH)
Zeta-potential (mV)
Condenser paper
Cellophane
Wood pulp
Cotton
Cellulose
Cotton
Cotton linters
Viscose fiber
,:
Acetate grade dissolving pulp
Cross-Bevan cellulose
Chlorite holocellulose
Chemical pulps, bleached
Chemical pulps, unbleached
Mechanical and semi-mechanical
pulps
Beech kraft pulp
Unbleached wood sulfite pulp
Unbleached spruces sulfite pulp
Unbleached sulfate pulp
Bleached birch sulfate pulp
Viscose rayon
Spruce sulfite bleached
Spruce sulfite unbleached
Beech sulfite bleached
Birch sulfite unbleached
50
DV
248
7.1-9.2 20C 50 Hz, thickness 0.11-0.12 mm, 249
4.7-12.1
30-50
2.15
2.5
21.0
30
21.1
28.5 126
21.1
9.31126
- 23.7
0.71-0.83 g/ml, RH = 65%
Oven dry, DC
Thickness 1 mm, 50 Hz
0. 02 M HCl-KCl-buffer
Fines from filter paper, Whatman No. 1
Fines
In water
In water, fines
In lo-* N KC1
Poly ( 1,l -dimethylpiperidinium-
3,5-diallymethylene chloride), M, = 50000,
monolayer, in 1O-4 N KC1
In water, fibers washed with distilled water
In 10m4 N NaCl
I n 10e5 N KC1
Fines
Fines from Eucalyptus reagnans
Fines
Fines
Fines
250
2 3 5
2 5 1
252
253,254a
2 5 5
253,254
253,254
253,254
256b,257b
258
22127
17.3
17.7
22.9
32.0
17- 33
23. 5-33. 1
17.2-46.1
256,257
259b
259
253,254
253,254a
253,254
253,254a
253,254
20.6 Oven dried at 130C 260
9 Distilled water, 20C 2 6 1
23 Distilled water 262
1 8 Distilled water 262
2 1 Distilled water 262
26 NaBH4-reduced sample, distilled water 263
14.2 In water 264
16.2 In 10e4 N KC1 264
14.9 In water 264
16.0 In 10m4 N KC1 264
18.6 In water 264
21.7 In 10m4 N KC1 264
15.1 In water 264
19.0 In 10m4 N KC1 264
a These references give additional data.
b More concentrations and/or media investigated.
TABLE 15. CRYSTAL ELASTIC MODULUS El IN CHAIN
DIRECTION
Modification
E, Wa) Refs.
I 138 265
120- 135 266
II 8 8 265
106- 112 266
III 1 8 7 265
111 I I
i)
58 265
IV1 75 265
Typical Non-Aqueous Cellulose Solvents V/147
TABLE 16. FIBER STRENGTH, ELONGATION, AND MODULUS
Qpe of cellulose
Breaking strength (cN/tex) Breaking elongation (%)
DV
Wet
Dry
Wet
Modul us (cN/tex)O
Dry
Wet Refs.
cotton
Flax
Jute
Hemp
Ramie
Sisal
Banana
Coir
Palmyrah
Talipot
Viscose rayon (normal)
Viscose rayon (high tenacity)
Viscose staple (high wet
modulus, normal)
Viscose staple (high wet
modulus, polynosics)
Lyocell type
ZnClz t ype
LiCl-DMAc type
NaOH type
26-43
40-80
- 3 0
41
59
36-43
53-58
9-15
16-20
17-30
14-22
3.5-54
16-26
26-53 18-42 7-15 8-20 265- 795 lb
6 1 58 8 9
15- 25 7-10 15-25 18-27
20-29 8-13 6 10-12
16-17 4-6 15- 21 16- 23
26-47
41-85
30-31
2-5
23-43
7-17
8-10
2.5-3
1. 7-1. 9
2.2
3.7
3. 6-5. 1
2.4-3.6
17-47
7-15
2.7-5.2
25-30
9-20
14-30
11
2.5-3
1. 7-1. 9
20-40
14-26
22-30
370-720 lb
1760 lb
1720 lb
2170 270
1460 270
1170-1520 271
2000- 2440 271
260-520 271
404-560 272
1045-1494 272
290-680 lb
609- 883 lb
424-600 lb
1950
450- 1100
971-1290
490 273
, 274
275
25-63 216
To convert to MPa multiply value by ten times the density value when expressed in g/cm3.
b Data taken from references 76,267-269.
C. SOLUTION PROPERTIES
TABLE 17. TYPICAL NON-AQUEOUS CELLULOSE SOLVENTS~b
Number of components Substance group Examples
Unicomponent N-Alkylpyridinium halogenides
Oxides of tertiary amines
Bicomponent Dimethyl sulfoxide (DMSO) containing solvents
Liquid ammonia/sodium or ammonium salts
Dipolar aprotic solvents/LiCl
Pyridine or quinoline containing systems
Tricomponent
Liquid SOslsecondary or tertiary amines
NH3 or amine/salt/polar solvent
NH3 or amine/SO2 or SW12 polar solvent
Ethylpyridinium chloride
N-Methylpiperidine-N-oxide
N-Methylmorpholine-N-oxide
N,N-Dimethylcyclohexylamine-N-oxide
DMSO/methyl amine
DMSOKaCl2
NH3/NaI (NH41)
NHsMaSCN (NH4SCN)
NH3/NaNOs
NHdNCd-b)&
N,N-Dimethyl acetamide (DMA)/LiCl
N-Methylpyrrolidone/LiCl
N-MethylcaprolactamGCl
N-Hexamethyl phosphoric acid triamide/LiCl
Dimethyl urea/LiCl
Pyridine/resorcinol
Quinoline/Ca(SCN) 2
SO 3/ triethyl amine
NHs/NaCl/morpholine
NHs/NaCl/DMSO
Et hyl ene diamine/NaI/N,N-dimethyl formamide
Diethylamine/SO2/DMSO
A very extensive list including sketches of phase diagrams, is given in Ref. (1).
b In most cases a preactivation of the cellulose is required.
Ref. 277.
References page V- 152
V/148 PHYSICAL CONSTANTS OF CELLULOSE
TABLE 18. OTHER SOLVENTSa
Substance group Examples Refs.
Strong bases in aqueous solution
Strong bases in aqueous solution
Tetraalkyl bases (molecular weight >150)
Metal complex solutions
Mineral acids b HCl, HBr
H2S04
HN03
H3P04
Inorganic salts in aqueous solution
Trifluoroacetic acid
LiCl
ZnCl 2
Ca(SCN) 2
Inorganic salts in concentrated solutions or melts,
single and/or multicomponent systems
Ca(SCN) 2
LiCl, LiJ, LiSCN, CaBr2, Ca(SCN)2
Ca(SCN) z/CH20
LiSCN 2.5H20
KSCN + NaSCN + Ca(SCN) 2 3H20
KSCN + NaSCN + DMSO
Ca(SCN)2.3HzO+CH20
Li SCN, NaSCN, LiJ, NaJ, KJ
LiOH
NaOH
NaOH + ZnO
NaOH + Be0
Tetraethylammoniumhydroxide and some higher homologs
Tri met hyl benzyl ammoni umhydroxi de (T&on B)
Dimethyldibenzylammoniumhydroxide (Triton F)
Tetraalkylphosphonium hydroxides
Tetraalkylarsonium hydroxides
Trialkylsulfonium hydroxides
Trialkylselonium hydroxides
[Cu(NHs)4](OH)2 (Cuoxam, Guam)
Modi fi ed cuoxam
[Cu(en)2](OH)2 ( Cupr i eet hyl enedi ami ne, Cuene, CED)
Cu : biuret : alkali
[Co(en)s(OH)z (Cooxene)
[Ni(NHs)s](OH)2 (Nioxam)
[Ni(en) s](OH) 2 (Nioxene)
[Zn(en) 31 (OH) 2 (Zincoxene)
[Cd(en) s](OH) 2 (Cadoxene)
Complex solution of the Na-salt of Fe-tartaric acid in diluted
NaOH solution (FeTNa)
219
280,281
282,283,284
280,285,281
286,287,288,289,290
291,292,293
28 1,294,295
296,297,298,299,300
298,301
302
3 0 3
304,305
304,305
304,305
304
306,46
3 0 7
307,8 1
307,308,309
307,308
310,311,312
313,311
313,311
314
1 4 4
315
292
316,317
170
318,319
320
321,322
323,324
323,325
323,325
323,326,327
323,328
a Excerpt from the table in Ref. (1); cf. also (278) as a modem reference.
b Dissolution usually accompanied by strong degradation of the cellulose chains.
TABLE 19. VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPSa
Viscosity range, q Nature of Method of
Solventk
Km (x 10) Wg) a ( x 10m2) (mug) G (s-l)
T (Cl
sample calibration Refs.
Cuoxam 0.308 1.0
11.3 0.657
10.1 0.661
56.4 0.523
0.85 0.81
1.70 0.77
0.268 1.0
0.70 0.9
0.545 0.9
0.33 1.15
0.099 1 0
3.3 0.76 >4.25
0.18 1.0 <4.25
0.237 1.0 1. 2- 5. 05
1.30 0.81 0.3-6
0.9-9
0.2-4
0.2-4
4.7- 16.8
4.7- 16.8
4.7-16.8
1. 75-19. 7
4.8-28
l-28
4.7-16.8
20
25
25
20
20
20
500
25
FC
F
Ue
U
U
U
U
U
U
E U
F, U
F, U
U
F
OS b (acct.)
Comp d
Comp.
SDf
SD
SD
SD (camp.)
SD (CN)s
SD (CN)
SD
SD, LS h
CN)
SD (CN)
SD (CN)
S
LS (CN)
329
330
330
3 3 1
332
1 0
333
334
335
336
337
338
338
339
240
TABLE 19. contd
Viscosity - Molecular Weight Relationships v / 1 4 9
Solvent k
Km (x 10) Wg)
Viscosity range, q Nature of Method of
a ( x 10m2) (ml/g) G (s -)
T (Cl
sample calibration Refs.
Gene
Cadoxene
FeTNa
1.06 0.905
0.498 1.0
0.395 1.0
0.334 1.0
0.412 1.0
0.364 1.0
1.01 0.9
0.85 0.9
0.358 1.0
0.153 1.0
5.10 0.76
0.277 1.0
0.762 0.936
2.9 0.8
0.268 1.0
Mean: 0.575 0.96
5.47 0.75
0.315 1.01
0.235 1.0
0.124 1.0
4.13 0.76
0.225 1.0
0.427 0.94
0.593 0.94
9.33 0.72
3.56 (3.38) 0.77
3.85 0.76
0.563 1.0
0.599 1.0
1.13 0.9
1-21.4
l-2.4
2.4-21.4
< 10
< 10
2.3-27.2
1 .O-28
1. 0- 28
6-18
Gd60
G-+60
G--,60
500
G+60
G+60
25
25
25
E U
E U
E U
F
> 600
< 600
1. 9-21. 3
1. 7-3. 9
0.5-7.5
1. 9-6. 5
<18
2-11
2-11
20
20
U
E U
E U
U
U
E U
E U
U
500
20
25
20
25
20
20
>5.3
<5.3
< 10
> 10
<18
0.4-1.2
500
500
2.5-22
20
20
20
25
25
20
20
20
F, U
U
U
U
E U
E U
E U
U
F
F
U
F
U
U
E U
3.57 0.805 2.5-22 20
F, U
0.519
0.571
0.502
0.407
0.355
0.303
0.201
0.39-0.46
2.8
5.31
5.31
LiCYDMAc 1.278
Zincoxene 0.585
Tetraethylammonium 0.26
hydroxide (2.3 M)
0.58
LiOH solution = 0.34
Ca(SCN)z solution x0.5
H3P04 N 1.3
1.71
HzS04 (50%) solution 1.64
10% NaOH solution 0.43
1.0
1.0
1.0
1.01
1.0
1.0
1.0
1.0
0.84
0.78 b
0.775
1.19
0.936
1.0
3-16
3-16
3-16
6.6-20
< 13
<16
<8
G-+60
G-+60
G - 6 0
G-+60
20
20
20
20
20
20
20
2.4-21.2
4.9-31.5
1.68-15.15
1.48-11.64
>400 25
30
20
20
1.0
1.0
1.0
1.0
0.94
0.92
1.0
2.4-12.2
> 2.25
> 1.78
(49, 72)
20
20
20
20
25
20
20
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
Comp. 341,342
Comp. 341,342
Comp. 341,342
OS (CN) 335
Comp. 343
SD (CN) 344
SD (CN) 334
SD (CN) 335
SD 345
SD (CN) 337
SD (CN) 338
SD (CN) 338
SD, LS 346
Kj (OS) 347
Comp. 348
Comp. 349,350,351
SD 352
SD 3 5 1
SD 353
SD, LS 337
SD (CN) 338
SD (CN) 338
SD (CN) 338
SD (CN) 338
SD (CN) 338
LS 352
SD, LS 354
Comp. 355
Comp. 355
Comp. Calculated from
356
Comp. Calculated from
SD
SD
SD
SD
SD
SD
SD
Comp.
LS
LS
LS
OS
OS (via CN)
356
357
357
357
345,357
353
353
353
358
346
359
360
3 6 1
362
363
OS, camp. 364
OS 363
OS 363
OS 363
K 365
K 366
OS 363
The constants K, and a given in the table are defined by the equation [r~] = K&4, [q] and M being intrinsic viscosity and molecular weight, respectively. G is the shear rate.
* Osmot i c measur ement s.
Fractionated.
Vi scosi met r i c compar i son.
Unfractionated.
f Measurement by sedimentation-diffusion.
8 Cellulose nitrate used for calibration.
f Meas ur ement by l i ght s cat t er i ng.
Meas ur ement by s edi ment at i on.
j From kinetic data.
See also Table 17, Typical Non-Aqueous Cellulose Solvents.
References page V - 152
v/150 PHYSICAL CONSTANTS OF CELLULOSE
TABLE 20. SECOND VIRIAL COEFFICIENT
The second virial coefficient listed in the table below is defined by the equation
~/c=RT[1/M+A2c+Asc2+~~~]
where x is the osmotic pressure, C the concentrations R the gas constant, T the temperature, M the molar mass, and A3 the third virial coefficient.
Range of A2 ( x 103)
Solvent c
TN)
DPa range
Cuoxam 20 195- 12500
Cadoxene 25 175- 5820
FeTNa 25 230-3950
LiCUDMAc 30 110-4320
a Degree of polymerization.
b Number of single values given.
See also Table 17, Typical Non-Aqueous Cellulose Solvents.
(cm3mol/g2) Remarks Refs.
0.8-3.0 No trend, Vb = 12 3 6 7
1. 1-1. 8 No trend, V= 9 352
3.0-4.4 No trend, V= 10 360
3.5-5.3 Monotonous decrease (one outlier), V = 9 3 6 1
TABLE 21. SEDIMENTATION AND DIFFUSION COEFFICIENTS
The sedimentation and diffusion coefficients for non-vanishing concentrations s and D, respectively, are calculated from s- = so (1 +k,c) and
D =De( 1 + koc), respectively, with sa, Da, d, and ko listed in the table, where c is the cellulose concentration.
Solvent a
T (Cl
Mb (x 10e3) (g/mol) SO (x 1013) (s)
k, (cm3k9
Ds (x 10) (cm2/s) kd (cm3k) Refs.
cuoxam
Cuene
Cadoxene
20 1 9
20 2 1
20 27
20 35
20 44
20 45
20.7 53
20 75
20 1 1 5
20 137
20 150
20 160
20 1 8 5
20 230
20 320
20 340
20 354
20 400
20 490
20 500
20 535
20 569
20 570
20 680
20 1200
20 1275
20 1500
20 1750
20 1900
20 2000
20 5900
2 5 9.5
2 5 1 7 5
1 2 10.1
1 2 18.8
1 2 24.5
1 2 33.6
25 43
25 1 1 5
25 1 5 5
25 210
25 275
25 435
25 745
1.6
1.9
50
20
4.6
2.6 50
3.8 110
4.1
6.3
7.2
170
390
6.5 390
7.2 520
6.3 380
6.3
6.5
9.2
320
690
10.3
10.4
14.0
10.8
17.5
8.3
5.5
0.74
1.04
1.13
1.25
1.80
2.87
2.75
3.17
3.80
4.53
5.49
600
900
1000
860
1700
1 5 3 1.77
367 1.06
370 0.75
465 0.64
7100 0.58
1000 0.44
1410 0.31
2.85
2.75
1.97
1.87
1.54
1.57
5.4
1.04
0.97
0.72
0.84
0.63
0.59
0.54
0.66
0.72
0.50
0.54
0.43
0.45
0.37
0.37
0.37
0.32
0.26
0.29
0.23
0.2
0.25
0.18
0.1
0.95
1.2
9.7
10.6
50
109
45
1 1 3
0
149
144
30
201
149
75
1 6 5
1 4 5
1 4 3
105
130
1 1 5
264
218
190
295
250
854
320
350
320
250
1200
367
367
1 7 3
367
1 7 3
367
368
1 7 3
367
367
1 7 3
367
367
1 7 3
1 7 3
1 7 3
367
1 7 3
1 7 3
1 7 3
367
367
173
1 7 3
173
367
1 7 3
173
1 7 3
1 7 3
1 7 3
369
369
354
354
354
354
352
352
352
352
352
352
352
Geometrical Chain Characteristics V / 151
TABLE 21. contd
Solvent
T C-3
Ma (x 10e3) (g/mol) SO (x 1013) (s)
k @m3/g) Do (x 10) (cm%)
kd(cm3k)
Refs.
FeTNa
LiCVDMAc
20 1 1 1 1.75 0.89
20 201 2.17 0.60
20 364 2.98 0.46
20 539 3.35 0.35
30 125 0.318
30 152 0.293
30 162 0.287
30 178 0.248
30 182 0.250
30 320 0.175
30 354 0.145
30 463 0.124
30 700 0.092
0
345
345
345
345
361
361
361
0
3 6 1
361
361
361
361
361
See also Table 17, Typical Non-Aqueous Cellulose Solvents.
b Cellulose molecular weight.
TABLE 22. PARTIAL SPECIFIC VOLUMES, v2
Solvent a
~2 (cm3k) T V-2 Refs.
Cuoxam 0.664 20
0.642 19.8
Cuene 0.65 25
Cadoxene 0.50 25
FeTNa 0.654 20
See also Table 17, Typical Non-Aqueous Cellulose Solvents.
173
368
352
352
370
TABLE 23. GEOMETRICAL CHAIN CHARACTERISTICS
Listed properties:
Characteristic ratio
Unperturbed chain dimension
Cm = (R*),,/(nl*2
A = {(R),,/M}
Conformation parameter
0 = (R*)o/(R*)o.~
Persistence length
Linear expansion coefficient
where
q = lim{ (Rl t )}/I with nl -+ co
as = {(s*)/(~*)o)*
(R) a - Averaged squared chain end-to-end vector in unperturbed state
n - Degree of polymerization
1 - Monomer unit length (5.18 A)
M - Mol ar mass
(R*) ,,r - Same as (R*) e, but for freely rotating chain
(Rl t ) - Averaged projection of chain end-to-end vector onto first bond-vector
(s*) - Averaged squared radius of gyration
(s*) a - Same as (s*) for the unperturbed state.
Property Solvent a
T V-3
Value Remarks Refs.
Cuoxam
Cadoxene
FeTNa
LiWDMAc
Cadoxene
LiCI/DMAc
Cadoxene
FeTNa
LiCl/DMAc
Cadoxene
FeTNa
LiCl/DMAc
LiCllDMAc
Cuoxam
LiCI/DMAc
25
25
30
20
30
2 5
25
30
25
25
30
25
20
30
15.8
45.2
91.9
48-60
1. 18- 1. 92
2.74-4.12
2.78
4.70
6.71
42
1 2 3
252
1 lo-160
Xl
1.03- 1.07
Monotonous
M-dependence
Gaussian coil limit
Gaussian coil limit
Gaussian coil limit
Various methods
361
361
361
367
371
361
361
361
361
361
361
361
372
367
361
l
a See also Table 17, Typical Non-Aqueous Cellulose Solvents
References page V- 1.52
v/ 152 PHYSICAL CONSTANTS OF CELLULOSE
TABLE 24. POLYMER-SOLVENT INTERACTION PARAMETERS
This parameter x (Flory-Huggins parameter) figures in the equation for the reduced partial molar Gibbs energy of mixing of the solvent AG r /RT (R - gas
constant, T - temperature) in the following way:
AGi/RT=ln(l -c~z)+~oz+x(o:
(~2 being the volume fraction of the polymer (cf. the corresponding chapter in this Handbook).
Solvent
Concentration
(wt.% cellulose)
x
Remarks Refs.
Water
NMM0.1H20a
NMMO
NMMO with 13-15 wt.% water
Saturated with water
5-15
3-15
0.124
0.435-0.44
0. 528
- 3
0. 5
0.35-0.40
<- 20
25 C, cotton fiber
25C, viscose rayon
25C, cellophane
Melting point depression
DP N 450, concept not applicable
313
313
313
314
375
316
a NMMO-N-methylmorpholine-N-oxide.
D. REFERENCES
1. J. Brandrup, E. H. Immergut (Eds.), Polymer Handbook,
3rd edition, V/l 17, Wiley, New York, 1989.
2. J. F. Kenedy, G. 0. Phillips, P A. Williams (Eds.), Cellu-
lose - structural and functional aspects, Ellis Horwood Ser.
in Polym. Sci. Technol., Ellis Horwood, Chichester 1989,
Cellulosics-Chemical, Biochemical and Material
Aspects, and Cellulosics-pulp, fiber and envrionmental
aspects, Ellis Horwood Ser. in Polym. Sci. Tehnol., Ellis
Horwob, Chichester 1993; Cellulose and Cellulose Deri-
vatives: Physico-Chemical Aspects and Industrial Applica-
tions, Woodhead, Cambridge, 1995.
3. R. H. Atalla (Ed.), The Structures of Cellulose, ACS
Symp. Ser. 340, Washington DC 1987; Th. Heinze,
W. G. Glasser (Eds.), Cellulose Derivatives: Modification,
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Physi cal and Mechanical Properties of
some I mportant Polymers
Phillip T. DeLassus, Nicole F. Whiteman
The Dow Chemical Company Freeport, TX 77541, USA
A. Introduction V-l 59
B. Narrative Descriptions V-l 59
1. Multipurpose Polymers V-l 59
2. Polyolefins and Barrier Polymers V-l 60
3. Styrenics and Engineering Thermoplastics V-l 60
4. Elastomers V-l 61
C. Properties of Commercial Polymers V-l 62
Table 1. Multipurpose Thermoplastics V-l 62
Table 2. Polyolefins and Barrier Polymers V-l 64
Table 3. Styrenics and Engineering
Thermoplastics V-l 66
Table 4. Elastomers V-l 68
A. INTRODUCTION
This section of Polymer Handbook focuses on critical
polymers in the commercial world. The polymers were
chosen because they already have a large economic impact
or are likely to have an economic impact during the lifetime
of this Handbook. Hundreds of polymers are the subjects of
study and application in the world. Many of these have
commercial status. However, including all of them would
compromise the utility of this chapter. Properties for all the
polymers of this section plus many others are included with
more details in various chapters of this Handbook.
Because of their cost and properties, polymers in this
section often get first consideration for applications, or are
the benchmarks against which alternative materials are
compared. The data in the tables of this section can be used
for rapid comparison against performance requirements.
Brief narrative descriptions of the polymers are given in
the next section. More complete descriptions can be found
in other places; the Handbook of Plastic Materials and
Technology (I. I. Rubin (Ed.), Wiley Interscience, 1990) is
an excellent resource.
A common set of properties are given in Section C. In
many cases, the data are not available or are not relevant. In
some cases, we have chosen to highlight a specific example
of a family of polymers. However, in some cases, selecting
a single member of a family did not represent the range of
applications and properties available, so we included the
ranges or subclassifications. Often the sources of data on
polymer properties disagree. We have assumed that the
disagreements were honest results of subtle differences in
the polymer or the test. In some cases we report averages, in
some cases we report the best value, and in other cases
we report ranges. The reader is advised to refer to the
specific product literature and to consult the technical
service representatives of the suppliers. Standard or typical
abbreviations for each polymer are also included.
B. NARRATIVE DESCRIPTIONS
1. Multipurpose Polymers
Po/y(ethy/ene terephthalate) (PET) This polymer is
usually made by a two-step condensation polymerization
of the dimethyl ester of terephthalic acid and ethylene
glycol. Articles made with this polymer can be either semi-
crystalline or amorphous. Applications include fibers for
carpeting and clothing, bottles (especially for soft drinks),
and films for food packaging and magnetic tapes.
Poly(ethylene terephthalate, 1,4cyclohexane dimetha-
no/) (PEW This polymer substitutes enough 1,4-cyclo-
hexane dimethanol for ethylene glycol in the backbone (to
prohibit crystallization). Applications include food packa-
ging and injection molded parts.
Poly(vinyl chloride) (PVC) Applications for this polymer
fall into two broad categories depending upon formulation.
The name for this polymer is often freely abbreviated as
vinyl.
Flexible poly(vinyl chloride) This type typically contains
30-40 wt.% additives, especially plasticizers, to lower the
glass-transition temperature. Applications include hoses,
films, flooring, and automotive interiors.
Rigid poly(vinyl chloride) This glassy polymer is used for
molding and profile extrusions with less additives. Typical
applications include pipe, house siding, window frames,
and bottles.
Ethylene-methacrylic acid copolymers, partially neu-
tralized with sodium or zinc (lonomer) The most impor-
tant applications are for food packaging as films or sheets.
They adhere to nylon in coextrusion, and they heat seal well.
v/159
V/160 PHYSICAL AND MECHANICAL PROPERTIES OF SOME IMPORTANT POLYMERS
Ethylene-acrylic acid copolymers (EAA) These adhesive
copolymers typically have between 3 and 20 wt.% acrylic
acid. They are often used in extrusion coating to provide a
heat seal layer for packaging, especially when good flavor/
aroma retention is needed.
Ethylene-vinyl acetate copolymers (EVA) The range of
compositions can be from 2-50 wt.% vinyl acetate. Tough,
clear films are made with copolymers having low levels of
vinyl acetate (2-7 wt.%). Hot melt adhesives are an
application for higher levels of vinyl acetate (18-40 wt.%).
Polytetrafluoroethylene (PTFE) This homopolymer of
tetrafluoroethene has a wide range of valuable properties.
Applications often rely on the very low surface energy
(useful for non-stick coatings), the chemical resistance to
many liquids (useful for gaskets and liners), and the wide
range of service temperatures.
Ethylene-styrene inferpolymers (ES/) These copolymers
exhibit a very wide range of properties depending on
composition. At low levels of styrene, the copolymers are
crystalline, flexible, thermoplastics. At intermediate levels
of styrene, the copolymers are amorphous and highly
elastomeric. At high levels of styrene, the copolymers have
a mixture of glassy and rubbery properties with a glass-
transition temperature ranging to above room temperature.
Applications vary as widely as the properties, including
new areas for thermoplastics.
Poly(lacfic acid) (PLA) This compostible polymer is
synthesized from renewable resources. The properties vary
according to the composition (D- and L- conformations).
Applications include food packaging as film or molded
cups.
2. Polyolefins and Barrier Polymers
Po/yethy/ene family The total usage of all members of this
family is the greatest of all thermoplastics. Most members
of the family are easy to fabricate and have low cost. The
properties vary widely across the family. Food packaging is
a frequent application.
High density polyethylene (HDPE): This set of highly
crystalline polymers is used in molding and film applica-
tions, with milk jugs being a prime example. These
polymers are less flexible than other polyethylenes.
Low density polyethylene (LDPE): This set of branched
polymers is less crystalline than HDPE. Members are
flexible and clear, with moderate toughness.
Linear low density polyethylene (LLDPE): These are
copolymers of ethylene with modest amounts of butene,
hexene, or octene linear a-olefins. Grades are available for
films and for molding. Films typically show good tough-
ness. Some grades are suitable for fibers.
Very low density polyethylene or ultra-low density
polyethylene (VLDPE or ULDPE): These are also copoly-
mers of ethylene and linear a-olefins; however, they have
densities less than 0.915 g/cm3. They have improved
toughness and sealability compared to LLDPE.
Polyolejn plastomer (POP): New catalyst technologies
allow synthesis of these materials which include these with
lower densities. Copolymers over a wide range of
composition yield a wide range of properties for films,
fibers, and molding applications.
Polypropylene (PP) Most applications use the isotactic
form. Oriented (OPP) and unoriented films are used often
for food packaging, sometimes in combination with
vinylidene chloride copolymers. Polypropylene fibers are
used for webbing in outdoor furniture, carpets, and both
woven and non-woven fabrics. Polypropylene is also an
important engineering thermoplastic.
Vinylidene chloride copolymers (PVDC) This set of
polymers includes resins for extrusion and molding, resins
for solution coating, and latexes for coating. A variety of
comonomers are used to achieve different properties. The
barrier properties are important for food packaging.
Typically, these polymers are used with other polymers
such as polyethylene or polypropylene in multi-layer
structures.
Ethylene-vinyl alcohol copolymers (EVOH) These
polymers are actually hydrolyzed copolymers of ethylene
and vinyl acetate. They are excellent barriers to mass
transport, especially when dry. They find applications in
both flexible and rigid packaging for food, typically as part
of a multi-layer structure.
3. Styrenics and Engineering Thermoplastics
Polystyrene family These inexpensive polymers span
the range of engineering thermoplastics. They are easy
to fabricate by either extrusion or molding. Typically,
small amounts of additives are used, including extrusion
aids, mold releases, FR agents, UV stabilizers, and
plasticizers.
General purpose polystyrene (GPPS): This homopoly-
mer is transparent and glossy. It quickly sets after molding
to give stiff parts. Polystyrene can be made into foam
articles such as insulating board or cups, using extrusion
techniques or by expanding beads. Other applications
include food packaging and molded parts in appliances.
High impact polystyrene (HIPS): This rubber-modified
composite typically contains 1 - 10 wt.% rubber, generally
polybutadiene, to give added toughness. It is also used in
many applications including food packaging and molded
parts.
Styrene-Acrylonitrile copolymers (SAN): A typical
copolymer has 70 wt.% styrene and 30 wt.% acrylonitrile.
These clear polymers have excellent dimensional stability
and long-term toughness. Furthermore they are resistant to
a wide range of solvents.
Rubber-modi$ed styrene-acrylonitrile copolymers
CABS): This material has a continuous SAN phase with
about 15 wt.% rubber modification, generally polybuta-
diene. In most applications, impact resistance is the reason
for the selection of ABS. Applications include housings and
covers for appliances and tools, plus a variety of automotive
moldings.
Syndiotuctic polystyrene (SPS): This semi-crystalline
polymer can be used at higher temperatures. Applica-
Narrative Descriptions V/161
tions include molded parts that must maintain close
tolerances.
Polycarbonate (PC) This polymer is usually made in
large scale by the condensation of phosgene and bisphenol
A. It has great impact strength and excellent optical
properties; hence, it is used for lenses, compact discs,
glazing, instrument panels, and high-volume food services
wares. It can be modified with reinforcing fibers, FR
agents, and stabilizers. Development of new applications is
intense.
Nylon fami/y These are polyamides resulting from the
condensation reaction of an amine function and an acid
function. As a family, they are tough and hard. They are
resistant to many liquids and have low coefficients of
thermal expansion. They can be reinforced with glass
fibers, carbon, and minerals. Applications include
molded parts for electrical power transmission, molded
parts for a wide range of automotive functions, pulleys,
bearings and items which need good abrasion resistance
and toughness.
Nylon 6: This homopolymer of caprolactam is in the
middle of the range of nylons for toughness, hardness, and
heat distortion.
Nylon 6,6: This copolymer of hexamethylene diamine
and adipic acid has the greatest hardness and highest
resistance to heat deformation and lowest toughness of the
nylon family.
Po/y(methy/ mefhacrylafe) (PMMA) This important
member of the acrylate family is often freely abbreviated
acrylate. It has moderate toughness and excellent optical
properties. It is hard. Hence, applications include glazing,
fibers for transporting light, instrument panels, and pack-
aging.
Polyoxymethylene (Acetal) Acetal resins are derived
primarily from formaldehyde although copolymers are
common. Endcapping is done to reduce the rate of degrada-
tion. These polymers are strong, tough, and stiff, and they
have a low coefficient of friction against many materials.
They are creep resistant and are extremely resistant to
fatigue. Applications are often based upon dimensional
stability and solvent resistance.
4. Elastomers
Poly(organosiloxanes) (silicone polymers) Most silicone
polymers are either homopolymers or copolymers of
dimethylsiloxane. They have high flexibility over a wide
range of temperatures. They repel water strongly.
Membranes are an important application for elastomeric
grades. Other applications include stopcock grease, car
polishes, and anti-stick formulations.
Chlorinated polyethylene (CPF) After a starting poly-
ethylene has been chlorinated, the resulting material is
typically 25-50 wt.% chlorine. The properties range from
thermoplastic to elastomeric. Applications for CPE include
automotive hoses, tubing, and wire jacketing plus extensive
membranes for roofing. It can be an impact modifier for
PVC.
Polyolefin elastomers (POE) These copolymers of ethy-
lene and an a-olefin are made with single-site catalysts.
They have very low densities. Materials can be designed for
a wide range of applications.
Polyurethane elastomers (some TUP, thermoplastic
polyurethane) These terpolymers can be used uncured
for most applications; however, selected grades can be
cross-linked to enhance properties. As a family these
elastomers are tough and wear resistant. They have
excellent chemical resistance and flexibility. They can have
excellent clearity. Applications include cable jackets, Auto-
motive fascia, connectors, fittings, and many, many more.
Ethylene-Propylene-Diene Terpolymers (EPDM) These
terpolymers typically contain a few percent of a diene such
as hexadiene. This material is easy to fabricate and then is
usually heat-treated at 125C to 175C to induce cr6ss-
linking. The physical properties are much different after
crosslinking. Commonly, they are heavily formulated for
applications which include wire jacketing systems, auto-
motive hoses, and roof sheeting.
V/162 PHYSICAL AND MECHANICAL PROPERTIES OF SOME IMPORTANT POLYMERS
C. PROPERTIES OF COMMERCIAL POLYMERS
TABLE 1. MULTIPURPOSE THERMOPLASTICS
Property Uni t Test method PET PETG Rigid PVC Flexible PVC b
MECHANICAL
Density
Tensile strength
Tensile modulus
Flexural modulus
Elongation to break
Notched Izod at
room temp.
Hardness
THERMAL
Deflection
T @ 264 psi
Deflection T @ 66 psi
Vicat softening point
UL temp. Index
UL flammability
code rating
Linear coefficient
of thermal expansion
ENVIRONMENTAL
Water absorption 24 h
Clarity
Outdoor weathering
FDA approval
CHEMICAL RESISTANCE TO:
Weak acid
Strong acid
Weak alkali
Strong alkali
Low molecular weight
solvents
Alcohols
ELECTRICAL
Dielectric strength
Dielectric constant
Power factor
OTHERS
Melting point
Glass transition temp.
Special
g/cm 3
MPa
MPa
MPa
%
J / m
C
C
C
C
mm/mm/C
%
% Transmission
%
D570
D1003
D1435
<O.l 0.5
88 90
Not suggested Not suggested
Yes Yes
<0.5
Transparent
Opaque
Special formula
available
Varies
Possible
D543
D543
D543
D543
D543
D543
Good
Fai r
Fai r
Fai r
Good
Fair
Poor
Fair
Poor
Fai r
Fair
Not attacked
Not to slightly
attacked
Not attacked
Not to slightly
attacked
Not attacked
Not attacked
Not attacked
Not attacked
Resists
Ketones, chlorinated
hydrocarbons attack
Minimally attacked
kV/mm D149 26
D150 3.3
D150 0.03
l/8-15.7
l/16/-22.1
3.2
10-50
32-40
0. 007- 0. 020
9.9- 15.8
3.3-4.5
0. 04- 0. 14
C D3418 245-265 None 1 7 5 Varies
C D3418 80 8 1 8 1 Varies
D792
D638
D638
D638
D638
D256
D78.5
D648
D648
D1525
UL746B
UL94
D696
1.4
Hoop-172
axial-69
Hoop-4275
axial-2206
79
1.27
50
1724
2000
180
90
R105
63
71
180
HB
9.1 x 10-s
1.39
5 5
2800
40-80
Shore D 65-85
66-77
63-82
v-o
9-18 x 1Om6
1. 18- 1. 70
5.5-26.2
4.8-12.4
150- 450
Varies
Varies
Varies
Varies
13-45 x 10-6
Varies
Clear, translucent,
a Bottle grade. b Range includes plasticizers and fillers.
9.5% acrylic acid, extrusion coating resin. f High styrene content.
E
Multipurpose Thermoplastics v /I63
Pol ymer name
Ethyl ene-methacryl i c
aci d copol ymer EVAd EAAe PTFE ESIf PLAg
0.94 0.93-0.957 0.938 2.2 0.950- 1.050 1.25
33 6.2-28 17.6 2 1 12- 41 53
410 3-12 3450
220 6.9-110 410
400 650-950 600 40 200-500 4.1
608
Shore D 60
No break
A: 73-98
D: 24-47
No break
D55-D70
Shore A 60-100 1 6
55.6
1 2 1 4 4
73
137
36-82 76
VE-0
18-30 x lo- 9.9
co.05
Opaque
co.5
Yes
0.1
Transparent to
translucent
6
Yes Yes Yes
Not attacked
Slow attacked
Not attacked
Not attacked
Not attacked
Attacked by
sulfuric acid
Not attacked
Not attacked
Not attacked Good
Not attacked Good Not resistant
Not attacked Good
Not attacked Good
Slight swell Soluble Not attacked Varies Varies
Slight swell Not attacked Not attacked Good
0.04 25.4
2.4 2
0.003 <0.0002
2.2-2.6
93
Neck in is 6.6cm at
25pm; minimum
coating weight is
10 g/m*
327
-100
Surface energy
at 20C N
20 erg/cm *
0. 001- 0. 008
- 2 0 t o +35
Has Dead Fold
178
63
Combustible;
amorphous
grades are
transparent
Ionomer; partially neutralized with sodium.
8 Sheet extrusion grade, low D isomer, semi-cyrstalline.
d Properties range for family.
V/164 PHYSICAL AND MECHANICAL PROPERTIES OF SOME IMPORTANT POLYMERS
TABLE 2. POLYOLEFINS AND BARRIER POLYMERS
Property Uni t Test method HDPE a LDPE b LDPE c LLDPE
MECHANICAL
Density
Tensile strength
Tensile modulus
Flexural modulus
Elongation to break
Notched izod at room temp.
Hardness
g/cm 3
MPa
MPa
MPa
%
J / m
D792
D638
D638
D638
D638
D256
D785
THERMAL
Deflection T @ 264 psi C
Deflection T @ 66 psi C
Vicat softening point C
UL temp. index C
UL flammability code rating
Linear coefficient of mm!mm/C
thermal expansion
D648
D648
D1525
UL7468
UL94
D696
ENVIRONMENTAL
Water absorption 24 h
Clarity
Outdoor weathering
FDA approval
% D570
%Transmission D1003
% D1435
CHEMICAL RESISTANCE TO:
Weak acid
Strong acid
Weak alkali
Strong alkali
Low molecular weight
solvents
Alcohols
D543 Not attacked Not attacked Not attacked Not attacked
D543 Minimally attacked Minimally attacked Minimally attacked Minimally attacked
D543 Not attacked Not attacked Not attacked Not attacked
D543 Not attacked Not attacked Not attacked Not attacked
D543 Minimally attacked Minimally attacked Minimally attacked Not soluble
D543 Not attacked Not attacked Not attacked Not soluble
ELECTRICAL
Dielectric strength
Dielectric constant
Power factor
KV/mm D149 16-24
D150 2.2-3.0
D150 0.00005-0.003
OTHERS
Melting point
Glass transition temp.
Special
C
C
D3418 130- 137
D3418 Not measurable
0. 941- 0. 967
19-30
800- 1400
700- 1700
10- 1000
27-160
65-95
120- 130
100-200 x 10-6
<O.Ol
Yes
0.921 0.923
10.3 9.6
165.5 248
620 270
42.7 at - 50C 48 at - 50C
4 1
9 1 93
N 250 x 1O-6 -250 x 1O-6
<O.Ol
Translucent
Yes
<O.Ol
Yes
2.2 2.2
0.0003 0.0003
- 35 inferred - 35 inferred
Minimum heat seal;
temperature: 132C
0.92
MD 56.5
CD 37.0
MD 183
CD 169
MD 600
CD 750
66
106
160-200 x lO-j
Yes
2.3
< 0.0005
1 2 5
- 35 inferred
a Properties of range.
For injection molding.
38 mol% ethylene
b General purpose, for film & molding.
f Blown film grade, film properties reported.
Polyolefins and Barrier Polymers V 1165
Pol ymer name
LLDPEe VLDPE (or ULDPE)f POP8 P P PVDC h EVOH
0.917
15.9
221
283
850
40 at - 50C
96 80
160-200 x 1O-6 N 250 x 1O-6
co.01
Y e s Y e s 21 CFR 177.1520 (c) 1.1
Not attacked Not attacked
Minimally attacked Minimally attacked
Not attacked Not attacked
Not attacked Not attacked
Not soluble Minimally attacked
Not soluble Not attacked
Not attacked
Minimally attacked
Not attacked
Not attacked
Minimally
attacked
Not attacked
Excellent
Varies with
acid
Excellent
Good
Nonpolar swells;
polar excellent
Excellent
2.3 -2. 2
< 0.0005 N 0.0003
- 35 inferred
0.912
MD 57.9
CD 49.6
MD 122
CD 135
MD 575
CD 700
0.896
MD 49
CD 43
MD 600
CD 710
0.903
35.5
1380
1690
Depends on specimen
molding, history
37
100
<O.Ol <O.Ol
- 4 5
Oxygen permeability
at 23C:
3200 nmol/m.s. GPa
- 38 inferred
Seal initiation
temperature: 102C;
Oxygen
permeability at 23C:
1900nmol/m.s.GPa;
Toughness (D882)
-MD 97 J/cm 3
-CD 127 J/cm3
55
1 0 1
154
115
HB
90 x 10-6
< 0.03
24-28
2.25
0.0003
164
- 2 0
1.7 1 . 1 7
34.5 60
516.8
2 5 240
37.4
60
49
1 3 5
v-o
34 x 10-5
0.1
8 5
moderat e
discoloration
Yes
> 1.0
Yes
Not attacked
Not attacked
Minimally to
badly attacked
Minimally to
badly attacked
Not attacked
Not attacked
160 1 7 5
- 4 62 (Dynamic)
Oxygen Oxygen
permeability permeability
at 23C: at 23C 65%
0.2 nmoll RH = 0.08
m.s. GPa; nmo1lm.s. GPa;
WVTR (37.8C, WVTR at 40C
90% RH): 90%RH = 1.4
0.06 g mil/ g.mil/lOOin.*
100 in. * day
day
For extrusion coating. d For blown film, mechanical properties for blown film with blow up ratio 2:3.
8 Homogeneous catalyst, blown film grade, film properties reported. h Extrusion grade.
v/166 PHYSICAL AND MECHANICAL PROPERTIES OF SOME IMPORTANT POLYMERS
TABLE 3. STYRENICS AND ENGINEERING THERMOPLASTICS
Property unit Test method GPPS HIPsb SANC ABSd
MECHANICAL
Density
Tensile strength
D792 1.04 1.04 1.08
D638 46 24 82
Tensile modulus D638 1650 3860
Flexural modul us
g/cm3
MPa
MPa
MPa
%
J / m
D638 1910 4070
Elongation to break D638 1.5 52 3
Notched izod at room temp. D256 93 112 27
Hardness D785 M60-M84 M29 M80
THERMAL
Deflection T @ 264 psi
Deflection T 0 66 psi
Vicat softening point
UL temp index
UL flammability code rating
Linear coefficient of
C
C
C
C
D648 86
D648 95
D1525 107
UL746B 50
UL94 NA to V-O
74 103
87 108
1 0 1 1 1 1
50 60
NA to V-O HB
thermal expansion mm/mm/C D696 9.0 x 10-s 9.0 x 10s 6.7 x 1O-5
ENVIRONMENTAL
Water absorption 24 h % D570
D1003
D1435
0. 05- 0. 07 0.05-0.07 0.05-0.40 0.20-0.45
87-89 Opaque
Yellows Fai r
1.04
40
2140
2580
25
72
R104
103
- 107
1 1 1
- 6 0
HB
6.7 x 1O-6
No Possible
Not attacked Not attacked
Minimally Minimally
attacked attacked
Not attacked Not attacked
Minimally Minimally
attacked attacked
Minimally Minimally
attacked attacked
Clarity %Transmission
Outdoor weathering %
FDA approval
CHEMICAL RESISTANCE TO:
Weak acid
Strong acid
Weak alkali
Strong alkali
Low molecular
weight solvents
D543
D543
D543
D543
D543
Alcohols D543
ELECTRICAL
Dielectric strength
Dielectric constant
kV/mm D149
D150
Power factor D150
OTHERS
Melting point
Glass transition temp.
Special
C
C
D3418
D3418
Yes Yes
Attacked by Attacked by
Hydrocarbons, Hydrocarbons,
Aromat i c Amines,
Ketones, Aldehydes
Aromat i c Amines,
Ketones, Aldehydes
Minimally
attacked
19.7 11.8-19.7 N 14
2.54 2.50-2.52 ~2.8
2 x 10-4 6 x 1O-4 N 0.009
Minimally
attacked
16- 31
-3. 1
0. 007- 0. 015
-110
Other grades include
high impact,
high gloss, and
heat-resistant
74-110 93- 105 1 1 5
a General purpose.
c 30% Glass-filled ignition resistant.
i General purpose grade.
* Rubber modified, extrusion grade.
f General purpose grade.
j General purpose grade.
Styrenics and Engineering thermoplastics V 1167
Pol ymer name
SPS
1.44
95.1
9600
9600
1.8
70
PCf
1.2
72
2480
2410
150
961
R118/M74
221 132
263 138
263 158
v-o v- 2
30.5 x 10-6 6.84 x lo-
0.01 0.15
87- 91
Good
Good
Good
Good
Varies
Good Good resistance Resistant
23.6
3.1
0.001
270
Possible
Attacked
Attacked
Attaked
Varies
1 7
2.93
0.005
(230)
150
Index of refraction:
1.586
Nyl on 68 Nyl on 6.6h PMMA ACETAL
1.13 1.14
80 90
50 65
3000 3400
1500 1700
2414 2896
966 2206
50- 100 20
200 80
5 3 37
96 64
M-86 M-90
55-75 104
> 160 >200
v- 2
81 x lO-6
3 It 0.4
Not resistant
Not resistant
Good resistance
Good resistance
Good resistance
100 120
60 80
3.5 3.2
7.0 5.0
0.023 0.025
0.3 0.2
220
-
1.17-1.20 1.41
55-76 6 1
2400-3100 2829
2800- 3400 2588
2-5 40-75
16- 32 53-80
M80-100 M78-M80
71-102
74- 113
95-110
v-2
81 x 1Om6
HB
5-9 x 10-s
110
1 5 7
105
94HB
8.5 x 1O-5
2.8 zt 0.3 0.2-0.4
9 1
Very slight yellowing
at 3 years
Yes; for less than
8% alcohol
0.22
Opaque
Yes
Not resistant
Not resistant
Resistant
Resistant
Resistant
Not attacked
Minimally attacked
to soluble
Not attacked
Not attacked
soluble to
Not attacked
Consult supplier
Badly attacked
Not attacked
Not attacked
Not attacked
Not attacked to
badly attacked
Not attacked
- 2 0
2.8
20
3.7
0.02-0.03 0.006
255 1 6 5
1 0 5
Injection molding grade. d Solution, low gloss.
g For injection molding, heat stabilized. A General purpose.
V/168 PHYSICAL AND MECHANICAL PROPERTIES OF SOME IMPORTANT POLYMERS
TABLE 4. ELASTOMERS
Property Unit Test method Silicone
MECHANICAL
Density
Tensile strength
Tensile modulus
Flexural modulus
Elongation to break
Notched izod at room temp.
Hardness
THERMAL
Deflection T @ 264 psi
Deflection T @ 66 psi
Vicat softening point
UL temp. index
UL flammability code rating
Linear coefficient thermal expansion
ENVIRONMENTAL
Water absorption 24 h
Clarity
Outdoor weathering
FDA approval
CHEMICAL RESISTANCE TO:
Weak acid
Strong acid
Weak alkali
Strong alkali
Low molecular weight solvents
Alcohols
ELECTRICAL
Dielectric strength
Dielectric constant
Power factor
OTHERS
Melting point
Glass transition temp.
Special
g/cm
MPa
MPa
MPa
%
J / m
C
C
C
C
mm/mm/C
%
% Transmission
%
kV/mm
C
C
D792
D638
D638
D638
D638
D256
D785
D648
D648
D1525
UL746B
UL94
D696
D570
D1003
D1435
D543
D543
D543
D543
D543
D543
D149 16-22
D150 3.0-3.5
D150 0. 001- 0. 01
D3418
D3418
0.97, greater when filled
1. 0-5. 5
200-850
Shore A 20-60
10-19 x 10-s
0.1
Fair
Fair
Varies
a Flexible casting resins, e.g RTV.
b Range for elastomeric grades, 25-36 wt.% chlorine.
c Homogeneous catalyst, molding grade.
d Polyester Polycaprolactone Resin.
e Fully formulated.
Elastomers V /169
Polymer name
CPEb POEC TPtld EPDMe
1. 10- 1. 16
21-Sep
At 200% elongation 1.2-11.7
300-800
No break
Shore A > 60
Flexible
Flexible
Flexible
Not attacked
Not attacked to badly attacked
Not attacked to badly attacked
Not attacked to badly attacked
Not attacked to badly attacked
Not attacked to minimally attacked
14. 8-19. 7 900
4.3-5.1 3.0-3.5
0.1 0. 004- 0. 008
- 20
0.87
1 8
22
> 1000
Shore A 72
1.20
42
8
8 3
425
Shore A 93A
0.86, Polymer
6-16
1.2-5.6 at 50% elongation
-
100
-
Shore A 57-93
Varies
4 1
<O.Ol
Varies
Not attacked Stable Excellent
Minimally attacked Medi um Excellent, Varies
Not attacked Stable Excellent
Not attacked Medi um Excellent, Varies
Minimally attacked No effect to attacked Fair, Varies
Not attacked No effect Good
60 Varies
- 55 - 15
Medi um Varies
0.3
Possible
Opaque
Excellent
Some
Most Grades Amorpnous
Taber Abrasion resistance 10 mg
SECTION VI
SOLID STATE PROPERTIES
Crystallographic Data and Melting Points
for Various Polymers
Robert L. Miller
Michigan Molecular Institute, 1910 West St. Andrew Rd., Midland, MI 48640, USA
A. Introduction
1. Nomenclature
2. Examples of Polymer Names
2.1. Polymer Names Based on Source
2.2. Polymer Names Based on Structure
References for introduction
B. Crystallographic Data for Various Polymers
Table 1. Polyfolefins)
Table 2. Poly(vinyls) and Polyfvinylidenes)
Table 3. Poly(aromatics) and Polyfimides)
Table 4. Polyfdienes) and Polyfdiynes)
Tabl e 5. Polyfpeptides)
Table 6. Polyfamides)
Tabl e 7. Polyfesters)
Table 8. Polyfurethanes) and Polyfureas)
Table 9. Polyfethers)
Table 10. Polyfoxides)
Table 11. Polyfsulfides) and Polyfsulfones)
Table 12. Polyfsaccharides)
Table 13. Other Polymers
C. Melting Points of Polymers
D. Appendix: Formula Index to the Tables
E. References
VI-I
VI-I
VI-2
VI-2
VI-3
VI-5
VI-5
VI-6
VI-I 3
VI-I 5
VI-22
VI-26
VI-33
VI-40
VI-49
VI-51
VI-52
VI-57
VI-59
VI-64
VI-71
VI-I 13
VI-1 59
A. INTRODUCTION
These tables contain data for approximately 2700 polymers.
In general, the format and organization of the tables follows
that used in the 2nd edition of the Polymer Handbook
(Section B: Crystallographic Data; Section C: Melting
Points; Section D: Formula Index and Section E: Refer-
ences). The Formula Index is included as an aid to the
searcher: it permits one to determine the polymer name
used in these tables from the structural line formula for the
polymer of interest.
To avoid the duplication of data for polymers appearing
in both the Crystallographic Data and Melting Point tables,
the entry in the Melting Point table has been flagged with
an asterisk (*).
1. Nomenclature
Contrary to the rest of the Polymer Handbook, the ACS-
IUPAC nomenclature proposals (1,2) for naming regular
single-strand organic polymers have not been adopted for
these tables. Basically, the nomenclature used in this
portion of the Polymer Handbook is that of the 1st and
2nd editions and of the 1967 recommendations of the
IUPAC Nomenclature Committee (3). The majority of
polymers were named as the bivalent radical(s) comprising
the constitutional repeating unit (CRU), with priority in
naming given to (a) incorporation of important structural
features (amide, ester, oxide, etc.) and (b) emphasis on
symmetry of the CRU (when present). As in the past, many
common polymers (poly(styrene), poly(viny1 chloride),
etc.) were named according to source names.
In the majority of cases, the polymer was named
according to its structure, particularly when the CRU
was composed of two or more subunits following each
other in a regular fashion. An example is poly(ethylene
terephthalate). With more complicated structures, the
CRU was divided into its possible subunits, each of which
was treated as a bivalent radical and so named. One of
the subunits was treated as the parent compound, for
example, the terephthalic acid of the above example.
For poly(amides) and poly(esters), the acid was chosen as
the parent compound; for poly(urethanes) it was the
isocyanate.
Whenever the CRU (or a portion thereof) exhibited a
center of symmetry, naming began with the central subunit
using Chemical Abstracts/IUPAC names for the constituent
bivalent radicals (see under examples). Conjunctive names
were used as needed in constructing names. For symme-
trical units, this process of naming could be continued
indefinitely.
Unsymmetrical bivalent units were named with replace-
ment nomenclature, or from end to end, depending upon the
complexity of the bivalent radical and the ease of naming
by the alternative choices. Replacement nomenclature was
used, for example, to name poly(hexamethylene 6-oxa-
heptadecanediamide). The polymer from the symmetrical
oxyacid would be named poly(hexamethylene oxydicapryl-
amide).
VI/l
VI/2 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
More complicated structures without symmetry were
named end to end. This method was particularly appropriate
for the poly(oxides) of the form fR-O-R/-Oh (and for
the analogous sulfides, sulfones, ureas, and anhydrides)
and for the poly(o-amino acids) and for the poly
(o-hydroxy acids). The constitutional hydrocarbon
subunits were ordered alphabetically in naming the polymer
as, for example, in poly(methyleneoxy pentamethylene
oxide).
example, the source-named polymer, poly[(tetramethylsil-
phenylene) siloxane], appears in these tables as poly(p-
phenylene tetramethyldisiloxanylene).
For silicon-containing polymers, bivalent radical names
replaced the source-based silanekiloxane names. For
For the regular polymers of multipeptides, a cyclic
permutation of the individual peptide residues in the
constitutional base unit was performed to permit alpha-
betical ordering without loss of directional or sequential
sense. Thus, poly(alanylglycyl-proline) is the name given to
polymers prepared form (ala-gly-pro), (gly-pro-ala), and
(pro-ala-gly), but not from (ala-pro-gly) or from either of its
cyclic permutations.
2. Examples of Polymer Names
2.1. Polymer Names Based on Source
Olefin, Vinyl, and Acyclic Polymers
[-CH2-CH2-I,,
[-CH - CH?-1,
I
CH2 - CH3
[-CH - CH2-1,
I
CN
[-CH - CH2-],,
I
Cl
[-CH - CH2-1,
I
COOCH 3
Poly(amides)
[-NH-CH2-COO-],
Poly(ethylene)
Poly( 1-butene)
Poly(acrylonitrile)
Poly(viny1 chloride)
Poly(methy1 acrylate)
[-NH-(CHZ)~-COO-].
[-NH-(CH2)4-COO-]n
[-NH-(CH2)5-COO-],
[-NH-(CH2)6-COO-],
[-NH-(CH2)7-COO-]n
[-NH-(CH2)s-COO-],
[-NH-(CH&,-COO-]
[-NH-(CH2),o-C00-],
[-NH-(CH2),I-C00-],
Poly(oxides)
[-CH2-O-1,
[-CHO-] n
I
CH3
Poly(esters) are treated similarly.
Poly(glycine)
Poly(3-aminopropionic acid)
(poly(P-alanine))
Poly(Caminobuyric acid)
Poly(S-aminovaleric acid)
Poly(b-aminocaproic acid)
Poly(7-aminoenanthic acid)
Poly(%aminocaprylic acid)
Poly(9-aminopelargonic acid)
Poly(lO-aminocapric acid)
Poly( 1 1-aminoundecanoic acid)
Poly( 12-aminolauric acid)
Poly(oxymethylene)
Poly(acetaldehyde)
[-CH2-CH2-O-1,
[-CH - CH2 - O-l,,
I
CH3
[-CH2-CH2-CH2-O-1,
2.2. Polymer Names Based on Structure
(a) Linking Radicals
-CHa-CH2-
-CH2-CH2-CHa-
-CH2-CH2-0-CH2-CH2-
0
i
- CH2- CH2- s- CH2- CH2-
0
CH3
-CH2 - CH2 - CH2 - P - CH2 - CH2 - CH2-
- CH2- CH2 CH2- CH2-
CH3
(b) Parent Compounds
-OOC-COO-(-NHOC-CONH-)
-OOC-CH2-COO-
Poly(ethylene oxide)
Poly(propylene oxide)
Poly(trimethylene oxide)
Ethylene
Trimethylene
Oxydiethylene
Ethylenedioxy-diethylene
Sulfonyldiethylene
methylphosphinidene-ditrimethylene
p-Phenylenediethylene
4,4-Biphenylenediethylene
4,4-Methylenediphenylene
4,4-Ethylidenediphenylene
4,4-Isopropylidenediphenylene
4,4-Butylidenediphenylene
4,4-(2,2-Butylidene)diphenylene
4,4-Oxydiphenylene
4,4-Sulfonyldiphenylene
Oxalate (oxamide)
Malonate (malonamide)
Succinate (succinamide)
Glutarate (glutaramide)
i nt r oduct i on VI /3
References page VI- 159
VI /4 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
-OOC-(CH2)4-COO- Adipate (adipamide)
-OOC-(CH2)s-COO- Pimelate (pimelamide)
-OOC-(CH2)s-COO- Suberate (suberamide)
-00C-(CH2)7-C00- Azelaate (azelaamide)
-OOC-(CHz)s-COO- Sebacate (sebacamide)
-OOC-(CH2)s-COO- Nonanedioate (nonanediamide)
-OOC-CH2-CH2-0-CH2-CH2-COO- Oxydipropionate
-OOC-CH,
-0
CH2- COO- p-Phenylene diacetate
- OOC- (CH2)2
-0
(CH2)2- COO-
p-Phenylenedipropionate
-ooc~coo-
4,4-Dibenzoate
-OOC+CH2eC00- 4,4-Methylenedibenzoate
4,4-Oxydibenzoate
?
-ooc~~~coo-
-WC-CH2&O+H2-COO-
4,4-Sulfonyldibenzoate
4,4-Oxydiphenylenediacetate
-OOCoO-CH2-CH2-0 () C O O -
- - u
-OOC-CH2-NaN-CH2-COO-
4,4-(Ethylenedioxy)dibenzoate
p-(Phenylenedioxy)diacetate
@-Carboxyphenoxy)acetate
1,4-Piperazinediacetate
(c) Polymer Names
Poly(esters) 2
[- CH2- CH2- OOCOCOO-].
[- CH2- CH2- OOCWCOO-].
[- CH2- CH2- OOC- CH2
-0
CH2- COO-], ,
[- CH2-CH2- OOC-
Poly(ethylene terephthalate)
Poly(ethylene 4,4-dibenzoate)
Poly(ethylene p-phenylenediacetate)
Poly(ethylene 4,4-isopropylidenedibenzoate)
Poly(ethylene 4,4-sulfonyldibenzoate)
Poly(urethanes)
Y ::
[-CHz-CH2-CH2-0-C-NH-CH2-CH2-NH-C-O-],,
Poly(trimethylene ethylene-urethane)
2 Poly(amides) are treated similarly.
Poly(oxides), Poly(sulfides), Poly(amines)
HCHZ)~-O-(CH~)~-I~
HCH2)2-WCH2),-ln
[-(CH2),-NH-(CH2),-1,
REFERENCES FOR INTRODUCTION
1. ACS Structure-based Nomenclature for Linear Polymers,
Macromolecules, 1, 193 (1968).
2. IUPAC Appendices on Tentative Nomenclature, Symbols,
Units, and Standards - Number 29, Nomenclature of Regular
Single-strand Organic Polymers, November 1972 - Macromo-
lecules, 6, 149 (1973).
3. 1967 IUPAC Report on Nomenclature, J. Polym. Sci. B, 6,257
( 1968) .
6. CRYSTALLOGRAPHIC DATA FOR VARIOUS
POLYMERS
The following table presents crystallographic data for about
750 polymers (and for their many polymorphs) grouped,
according to the generic structure of the constitutional base
unit, into poly(olefins), poly(vinyls) and poly(vinylidenes),
poly(aromatics) and poly(imides), poly(dienes) and poly-
(diynes), poly(peptides), poly(amides), poly(esters), poly-
(urethanes) and poly(ureas), poly(ethers), poly(oxides),
poly(sulfides) and poly(sulfones), poly(saccharides), and
other polymers. Where a polymer might be included in
more than one group the following group definitions were
used:
1 .
2.
3.
4.
5.
6.
PoZy(oZeJns): those olefin polymers not containing
aromatic rings; all substituted derivatives of these,
excluding the vinyl and vinylidene polymers. For
example, poly(ethylene), poly(tetrafluoroethylene),
and poly(cyclopentene), but not poly(styrene) or poly-
(vinyl chloride).
Poly(vinyls) and Poly(vinylidenes): those vinyl and
vinylidene polymers containing atoms other than
carbon and hydrogen, excepting the poly(ethers). Thus,
poly(viny1 chloride) but not poly(methylviny1 ether).
Poly(aromatics) and Poly(imides): those hydrocarbon
polymers containing aromatic rings, including hetero-
cyclic ones. Thus, poly(styrene), poly@-xylylene), and
poly@-phenylene pyromellitimide).
PoZy(peptides): those polymers whose basic structure,
ignoring substituents, is poly(Zaminoacetic acid), that
is, poly(glycine). This group contains mainly the
synthetic poly(a-amino acids).
Poly(amides): all amide polymers except the poly(a-
amino acids), which are separately grouped under
poly(peptides).
The remaining categories contain polymers according
to functional groups as, for example, the poly(esters).
Poly(ethers) and poly(oxides) are differentiated accord-
Crystallographic Data for Various Polymers VI/S
Poly(ethylene trimethylene oxide)
Poly(ethylene trimethylene sulfide)
Poly(ethylene trimethylene amine)
ing to whether the ether linkage is in the side-group
or in the chain backbone, respectively. For example,
poly( 1-butoxy-2-chloroethylene) is a poly(ether) and
poly(oxymethylene) is a poly(oxide).
7. Those polymers not otherwise categorized, such as
the poly(phosphazenes) and the poly(siloxanes), are
grouped in the other category.
Within each group, polymers are listed alphabetically
according to the basic structure, ignoring substituents
(excepting the polypeptides, all of which have the same
base structure). Substituted polymers are listed alphabeti-
cally according to the substituent under the entry for the
unsubstituted polymer. Thus, poly(tetrafluoroetbylene) and
poly(bmethyl- 1 -pentene) appear, respectively, under poly-
(ethylene) and poly( 1-pentene).
Included as part of the polymer name column is the
molecular weight of the chemical repeat unit of the chain,
that is, of the constitutional base unit. This is given in
parentheses just below the polymer name. The values
reported are in grams per mole.
Unless otherwise indicated, the reference cited in the last
column applies to all of the data in that line of the tables.
Where an entry in a line has been taken from a source
different from that listed in the reference column, a solidus
(/) separates the value of the entry from the reference
citation. For example, one value of the melting point of
poly(l-butene) is given as 126112 which is to be read as
126C according to Ref. 12.
The crystal system, where known, is given in column 2
of the table, using the abbreviations given later. The next
column contains the space group symbol (the Schoenflies
notation is used because of the limitations of common
printers at mainframe installations) with the subscript
portion of the symbol preceding the superscript portion.
Thus, according to Ref. 14, the poly(ethylene) unit cell is
orthorhombic (Ortho) with space group 0:: (D2h-16). For a
fuller discussion of space group symbols, see International
Tables for X-Ray Crystallography, Vol. I, Kynoch Press,
Birmingham, England, 1952.
The dimensions of the unit cell (a, b, c) are given next, in
Angstroms (1 A = 0.1 nm). c is the fiber axis. Unless
otherwise indicated, the unit cell angles are all 90. Where
only one angle differs from 90, its value is given. When all
three angles differ from 90, their values are listed in the
order o, p, y. The next column contains the number of
constitutional base units in the unit cell described.
Columns 9 and 10 contain the densities of the com-
pletely crystalline and of the completely amorphous
polymer, respectively. The values given, normally appro-
References page VI- 159
VI / 6 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
priate to room temperature, are in grams per cubic
centimeter (1 g/cm3 = lo3 kg/m3). For uniformity crystal-
lographic densities (column 9) have been recalculated on
the basis of the 1969 IUPAC atomic weight values.
Melting points in degrees Celsius and heats of fusion in
kilojoules per mole are listed in the next two columns. The
heats of fusion correspond to the amount of substance
represented by the molecular weight associated with each
polymer name.
Column 13 of the tables indicate briefly the conforma-
tion of the polymer chain in the crystal (in a helical
notation) either as reported in the reference cited or as
inferred from the value of the fiber axis. The designation
IZ *p/q specifies the number (n) of skeletal atoms in the
asymmetric unit of the chain and the number of such
asymmetric units (p) per q turns of the helix in the
crystallographic repeat. Thus, poly(ethylene), as listed, has
two carbon atoms in the backbone with one such unit per
turn in the repeat - it is designated as a 2 * l/l helix.
Alternatively, poly(ethylene) considered a poly(methylene)
would be designated as a 1 * 2/l helix - an entirely
equivalent description of the conformation. Note that IZ may
differ from the number of chain atoms in the constitutional
base unit. On the one hand, isotactic poly(propene) has two
skeletal atoms in the asymmetric unit and three units per
turn (2*3/l). On the other hand, syndiotactic poly-
(propene) with the same constitutional base unit as isotactic
poly(propene) has four skeletal atoms in the asymmetric
unit and two units per turn (4 * 2/ 1). In this case, 12 signifies
the number of skeletal atoms in the stereobase unit. A fuller
discussion of this helical notation is given in Hughes and
Lauer, J. Chem. Phys., 30, 1165 (1959) and in Nagai and
Kobayashi, J. Chem. Phys., 36, 1268 (1961).
This list of polymers and data is not considered to be
exhaustive. The compiler expands it as new information is
unearthed and he is quite receptive to notification of
omissions and/or corrections and to submission of unpub-
lished data. All of the data in this table cannot be
considered to have the same validity - the number of
polymers for which detailed, accurate, and reliable crystal
structure analyses have been conducted is still quite limited.
The reader may find it desirable to refer to the original
literature cited so as to gain a fuller appreciation of the
reasons for apparent discrepancies within the tables.
The following abbrevaitions have been used in the tables.
Tti Triclinic
Mono Monoclinic
Ortho Ort horhombi c
Tet Tetragonal
Rho Rhombohedral (trigonal)
Hex Hexagonal
P Pseudo
Phex Pseudohexagonal
TABLE 1. POLY(OLEFINS) (-HCH-CHR-)
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (gkm3) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b e Angl es Z Cryst al . Amorph. a
(w
kJ/mol (n *p/q) Refs.
Poly(acetylene)
tmns-
I.
( 2 6 . 0 4 )
Phex
MIXlO
OTthO
Or t ho
Or t ho
Mono
Por t
Or t ho
Or t ho
Or t ho
Or t ho
II.
cis-transoid
Ortho
Mono
Ortho
Or t ho
Or t ho
Or t ho
Or t ho
ci s - ci s oi d
Or ht o
H&Y
D2h-16
C2h-5
C2h-5
D2h-16
D2h-16
D2h-16
D2h-16
4 . 2 4 . 2 2.43
4.26 1.33 2.46 a = 91.4
1.32 4 . 2 4 2 . 4 6
1.31 4.065 2.45
5.62 4.92 2 . 5 9 2
4 . 2 4 1.32 2.46 p = 91.5
7.41 4.08 2.48
3.99 7.29 2.51
7.20 4.15 2.44
7.31 4 . 0 6 2.45
7.26 4 . 2 4 2.47
1.46 4.08 2.46
7.38 4.09 2.451
7.330 4 . 0 9 0 2.451
3.13 3.73 2.44 y = 9 8
7.61 4.39 4.47 b
7.14 4 . 3 2 4.47
7.68 4 . 4 6 4.38
1.45 4.30 4.406
7.62 4.46 4.38
7.61 4.39 4.36
7.66 4.42 4 . 3 8 4
7.62 4.44 4 . 3 8 4
5.12 5.12 4.84
1
2
2
2
2
2
2
2
2
2
2
2
2
2
1
4
4
4
4
4
4
4
4
3
1.16
1.126
1.33
1.178
1.207
1.133
1.153
1.184
1.186
1.189
1.137
1.15s
1.166
1.174
1.286
1.158
1.157
1.153
1.227
1.162
1.187
1.165
1.166
1.180 2*3/l 9 7 7
2* l/l
2* l/l
2*1/l
2* l/l
2% l/l
2* l/l
2* l/l
2* l/l
2*1/l
2t l/l
2t l/l
2* l/l
2* l/l
2* l/l
2*1/l
2*2/l
2*2/l
2*2/l
2*2/l
2*2/l
2*2/l
2*2/l
2*2/l
6 9
9 8 2
981
919
9 8 0
1213
1228
1229
1281
1282
1283
1323
1324
1369
9 8 0
945
9 7 6
9 7 8
1229
1282
1323
1324
1369
TABLE 1. contd
Poly(olefins)
m/7
Polymer
tryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph.a
WY
kJ/mol (n *p/q) Refs.
-, difluoro-
trans-
( 6 2 . 0 2 )
cis-
-, compl ex wi t h:
alkali metals
C S
I.
K
I .
II.
Na
I.
R b
I .
II.
SbF6
a nd
Poly(allene)
I. (40.06)
II.
III.
-, tetrafluoro-
( 1 1 2 . 0 3 )
Or t ho 7.58 4 . 2 9 2.48
ortho 8.03 4.47 4 . 6 4
Tet 9.09 9.09
Tet 8.46 8.46
ortho 5.94 16.37
Tet 8.5 8.5
Tet 8.75 8.75
Or t ho 6.16 16.68
Mono 8.66 7.36 2 . 4 y = 101
Hex 9.8 9.8 5 . 4
Ortho
Mono
D2h-6
c2-2
or C2h-2
8.20 7.81
6.37 5.12
3.88
3.8gb y = 96.6
3.88
Tet C4-2 6.88 6.88 15.4
2.554
2.473
1.071
1.058
2.042
2*1/l
2*2/I
1385
1385
1230
1230
1231
1230
1230
1231
1261
1261
38
1221536 2*2/l
2*2/l
2*2/l
126 2*8/l
or D4-3
Poly(allylbenzene), see Poly(propene) 3-phenyl-
Poly( 1-butene)
i s ot act i c
I.
( 5 6 . 1 1 )
II.
III.
syndiotactic
I .
II.
-, 3-methyl-
(70.14)
RhO
Hex
RhO
D3d-6 17.7 17.7 6.50 18
17.3 17.3 6.7 18
17.70 17.70 6.5 1 18
Tet
Tet
Tet
Tet
Tet
s4- 1
S4-1
D2d-7
15.42 15.42 21.05 4 4
14.89 14.89 20.87 4 4
14.85 18.85 20.6 4 4
14.91 14.91 20.76 4 4
14.5 14.5 21.1 4 4
Or t ho
ortho D2-4
12.49 8.96
12.38 8.88
12.38 8.92
Or t ho D2-5 16.9 6.05
Or t ho D2-5 16.81 6.06
Mono c2-2 9.94 13.9
C2h-5
C4v-12
0.95 1 126112
0.96 0.87 132/250
0.950 133
0.950 0.868 1361277
0.95 139
0.95/12 0 . 8 6 0 1351320
13.9/82 2 *3/l
6.071277 2 * 3 / 1
7.57 2*3/I
8.011285
7.01
6.921320
1381380
1421984
1421313
4 . 0 6 1 3 2 0 2 * 1 l/3
6.281277 2* 1113
6.911285 2* 1113
8.16 2*11/3
*40//11
35
4 5
1284
2 5 2
9 8 3
391
0.819
0.886
0.902
0.888
130/380
1241277
1261313
120
1221320
0.868
106/277
1 lo/984
8 6 6
2 0 7
3 5 0
1284
9 1 4
1195
2 0 7
8 7 6
531
461
( 7 . 6 )
7.56
7.45
7 . 6
(0.876)
0.897
0.906
6.491277 2*4/I
2*4/l
2*4/l
7.78
7.73
20.4
20.0
8 0.937 4 5 4*2/l
8 0.946 4*2/l
2 2 0.964? 4*5/3
1435
1449
1435
1449
Mono
Mono
Mono
Por t
Tet
Mono
9.55 8.54 6.84 y = 116.5 4 0.933 300/48 17.3182 2*4/l 9
9.55 17.08 6.84 y = 116.5 8 0.933 306/632 2*4/l 5 4 9
19.1 17.8 6.85 y= 116 16 0 . 8 9 0 310/90 2*4/l 231
19.25 17.20 6.85 y = 116.5 16 0.918 300/282 2+4/l 3 5 5
34.3 34.3 6.85 6 4 0.925 2*4/l 431
19.25 17.20 6.63 y = 116.5 16 0.948 2*4/l 2 8 0
References page VI-159
VI/8 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 1. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. WY kJ/mol (n *p/q) Refs.
-, 3-methyl- [1,3-via hydride shift]
( 7 0 . 1 4 )
-, 4.phenyl-
( 1 3 2 . 2 1 ) Por t a- 2
5. 4 7. 8 55
681319
332
10. 4 18. 0 6. 61
6. 55
6 1.064 0. 962 158
SO/ 90
1.041 1591282
168/187
4. 6 2*3/ l 483
2*3/ l 67
4. 36 1195
-, 4-trimethylsilyl-
( 1 2 8 . 2 9 ) Or t ho
Poly(2-butene-air-ethylene)
( 8 4 . 1 6 ) Mono C2h-5
Poly(chlorotrifluoroethylene-&ethylene)
(144. 52) Hex
10.97 20. 02 6. 46
10. 92 1. 73 9. 10
9. 86 9. 86 5. 02
5
6 0.901 206 2*3/ l 772
a=130 4
3
0. 950 0. 87 135 4*2/ l 324
1.703 262 18. 8 4%l/l 635
264 13.30 637
Poly( 1,3-cyclobutylene)
-, l-cyano-
(79.10)
Poly( 1,2-cycloheptylene-&ethylene)
(124. 23)
Poly( 1,2-cyclopentylene-&ethylene)
(96.17) Or t ho
Or t ho D2h-17
or D2h-I4
Poly( 1,3-cyclopentylene-akmethylene)
25. 3
9. 0
370
74
3*8/ 847
9t l/l 259
8. 76 7. 83 9. 02 4 1.032
8. 76 8. 05 9. 00 4 1.006 185
4*2/ l 247
4*2/ l 412
ortho 7. 69 6. 21 4. 80 2 1.190 146 4*1/ l 267
Or t ho 13. 30 15. 52 4. 80 8 1.101 128 4* l/l 340
Tti Ci -1 4. 40 5. 39 12. 30
1. 42 5. 00 12. 40
13. 2
66,104,118 1 0. 985 lO* l/l 471
C2h-5 p=94. 2 2 1.001 801562 32. 91562 10*1/l 530
341250
401537
2* 150
Or t ho
Mono
7. 5 88 6. 7
5. 3 108 7. 7
8 0. 93 90
911872
83
751949
2*4/ l 949
p=94 8 0. 93 2+4/ l
2*
949
Tti Ci- 1 66,104,118 1 0. 986 l 2* l/l 417
Mono C2h-5
4. 40 5. 39 14. 78
7. 43 5. 00 14. 85 p = 93. 5 2 1.003 801439
841562
41.21562 12* l/l 530
13. 2 45148
491872
491250
2* 150
Or t ho
ortho
ortho
Or t ho
Ortho
Ortho
D2h-I6 137185
1421315
141/ 206
1451351
141/ 286
D2h-16
7. 40 4. 93 2. 534 2 1.008
7. 428 4. 934 2. 532 2 1.004
7. 36 4. 94 2. 534 2 1.011
7. 418 4. 946 2. 546 2 0. 997
7. 406 4. 939 2. 547 2 1.000
7. 407 4. 949 2. 551 2 0.9961
8. 03/ 85 2* l/l
8.12/262 2* l / l
7. 70186 2* l/l
8. 67/ 700 2* l/l
7.791156 2* l/l
2*1/l
7. 621343
8. 371260
7. 84 5. 56 120 63, 71, 82 96
4. 05 4. 85 2. 54 r=105 1
0. 999
0. 99 1
1.003
1.004
0. 966
0. 855 1461362
0. 887
0. 811
0. 852 141 8. 2
2* l/l
2c l/l
14
892
15
535
311
1421
138
363
406
939
72
58
( 82. 15)
Poly(decenamer)
trans-
III.
(138.25)
IV.
Poly( 1 -decene)
I. (140. 27)
Poly( 1 -docosene)
I. (308. 59)
II.
III.
Poly(dodecenamer)
trans-
III.
( 1 6 6 . 3 1 )
IV.
Poly( 1 -dodecene)
I. (168.32)
Poly(ethylene)
I. (28.05)
single crystal
II.
TABLE 1. contd
Poly(olefins) VI /9
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm3) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
(I b c Angl es Z Cryst al . Amorph.a c-3 kJ/mol (II *p/q) Ref s.
I I I .
( hi press. )
-, chlorotrifluoro-
(116.47)
-1 ethylsilyl-
i sotacti c
(86.21)
-, tetrafluoro-
II. (50.01)
I and IV.
(> 20C)
I I I .
( hi press. )
-, trifluoro-
(82.02)
Pmono
M o n o
Tli
ortho
Tet
C2h-3
7.11
8.09
4.285
8.46
4 . 2 6
Hex 6.34
He x 6. 5
Hex 6.438
He x 6.385
He x 6. 4
He x C3I-2 2 1 . 6 0
Phex
Tli
Tli
M o n o c2-2
Phex
Tri
He x
He x
He x
He x
5.54
4 . 8 8 2
5.59
5.59
9.649
5.61
9.52
5.61
5.66
5.65
5.67
M o n o C2h-3 9.50
ortho D2h-16 8.73
ortho D2h-16 8.53
He x 5.59
He x 5.63
He x 5.61
Poly(ethylene), complexes with
-, perhydrotri phenyl ene
He x
-, urea
(at 83 K)
Poly(ethylidene)
(28.05)
He x
Ortho
OtthO
Poly(heptenamer)
trans-
I .
(96.17)
Poly( 1-heptene)
I. (98.19)
Ortho
-, Smethyl-
(112.22)
6) M o n o
C3, CR) Tet
Poly( 1-hexadecene)
II. (224.43) Ortho
C6-6
or C6h-2
14.34
8.22
8.30
12.38
D2h-16
or C2v-9
7.40
c2-2 18.40
s4- 1 20.00
7. 5
5.46 2.534
4 . 7 9 2.53
4 . 8 2 0 2.54
4.88 2.45
4 . 2 6 8.52
6.34 35
6.5 35
6.438 41.5
6.385 42
6 . 4 42. 5
4 3
2 1 . 6 0 6 . 5 0
5.54 16. 8
4.875 5.105
5.59 16.88
9.76 16.88
5.648 1.3
5.61
5.59 17.06
5.61 16. 8
5.66 19.50
5.65 19.54
5.67
5.05 2.62
5.69 2.62
5.72 2.62
5.59 2.50
5.63 6.75
5.61
14.34 4.78
8.22 11.02
13.81 11.00
6.28 2. 5
5.00 17.10
6.45
6.40
10.62 6.36
20.00 38.76
6 3 . 2 6 . 6
y = 96.5 2 0.953 2* l/l 5 5 7
y = 107.9 2 0.998 2*1/l 2 5 3
90,110,108 1 1.002 2*1/l 2 5 4
2 0.920 2* l/l 7 9 2
4 1.20 2*4/l 9 4 6
1 4
1 4
Approx. 17
1 7
1 7
1 6
2.222
2.11
2.18
2.217
2.18
2.08149 220149 5.02/88 2 * 14/l
210146 2*14/l
2221341
2*17/
2*17/l
2*16/l
2.19149 1.925
2.192 2.032 2 1 5
2 0 8
2 1
7 7 7
2 9 6
6 2 9
2 0 5
1 3 9
1 1 6
1 8 0.981 2+3/l 4 8 9
y= 119.5 13
90,87,87 4
y = 119.3 13
,O = 90 2 6
Y
2
y = 119.3
88,90,92 2 6
1 3
1 5
1 5
2.406
2.744
2.347
2.344
2.344
2.011195
2.381
2.358
2.302
2.306 2.060
y = 105.5 4
4
4
2.304
2.742
2.552
2.598
327146 3.4/1195 1*13/l 1 1
1*4/ 2 6 6
1*13/6 2 0 9
1* 131 6 0 2
Irreg 9 8 7
l* 1316 1 2 8 6
1*13/l 1321
3 3 0 2.87/91 1 * 13/l 1 1
330/101 4.10/989 1 * 15/7 2 0 9
3 4 6 4.64 1 * 151 9 8 8
332189 1 * 1517 1 2 8 6
33411357 6 6
1*2/l 6 8 1
1*2/l 8 5 7
1*2/l 9 8 6
1 2.013 2221726 5.41726 2* l/l
3 2.205 2131985 5.441985 2 *3/l
3 8 9
8 5 4
1 1 9 2
2 1.071 181 4* l/l 1 1 2 4
9 9 2
9 9 3
4 0.958 lOQ/617
1951619
200/618
1*2/l 1 7 8
4 1.010 511439 7*2/l 9 7
171250 2*3/l 1 5 0
2*3/l 3 5 9
0 = 90 6 0 . 9 0 0
7 6 0.913
521129 2*3/l 6 7
2*3/l 6 8 5
2 * 1916 6 8 5
8 0.95 681250 2*4/l 1 5 0
9 4 7
Poly(hexafluoroisobutylene-all-vinylidene f l uori de)
(228.08) OlthO c2v-21 10.64 18.37 7.83 8 1.980 3 2 7 4*2/l
References page VI- 159
VI/10 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 1. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (&m3) Melting Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. 0
(Qn
kJ/mol (n *p/q) Ref s.
Poly( 1 -hexene)
(84.16)
-, 4methyl-
(98.19)
-, Smethyl-
(98.19)
Poly(isobutene)
(56.11)
M o n o 22. 2
ortho 11. 7
T e t 19.64
Tet Cl - l 19.85
He x 10. 2
M o n o c2-2 17.62
ortho D2-4 6.94
Ortho D2-4 6.88
Poly(norbomene), see Poly( I-vinylene-3-methylene)
Poly( 1-octadecene)
II. (252.49) Ortho
I I I . He x
Poly(octamethylene)
7. 5 70.4 6.6
4 . 2 4 4 . 2 4
-, l-methyl-
(126.24)
Poly(octenamer)
trans-
I I I .
(110.20) Tli Ci - 1
I V . M o n o C2h-5
cis- M o n o C2h-6
Poly( 1-octene)
(at 90 K)
(112.22)
M o n o 5.6 38 7 . 6 /3=97 8 0.93
Poly(pentenamer)
trans-
I .
(68.12)
Poly( 1-pentene)
i sotacti c
la.
(70.13)
Ortho C2v-9
or D2h-16
M o n o
M o n o
Ib.
M o n o
IIa.
M o n o
Port
IIb.
I I I .
syndiotactic
Port
Ortho D2-4
-, 5-amino-
-7 -, N,N-diisobutyl-
(197.37)
-1 -, N,N-diisopropyl-
(169.31)
-, 4,4-dimethyl-
(98.19) Tet
Tet
s4- 1
8.89 13. 7 y = 94.5 1 4
26. 9 13. 7 2 8
19.64 14.00 2 8 0.845
19.85 13.50 2 8 0.858
10. 2 6 . 5 0
10.17 6.33
11.96 18.63
11.91 18.60
9.78
4 . 3 4 5.41 9.78
7.43 5 . 0 0 9.90
4.58 9 . 5 0 17.11
7.28 4 . 9 7 11.90 4 1.051
11.35 20.85 6.49 p=99.6 1 2
21.15 11.20 6 . 4 9 @=99.6 12
22. 4 21. 2 6.49* y=91 2 4
6. 5
24. 3 19. 3 6.50*
6 . 6 0
35.65 20. 2 7.136
19.30 16.90 7.08
19.60 16.75 7.08
2 1 . 2 0 11.48 14.39
y = 96 2 4
y=91 40
y= 1 1 6 1 6
y= 115.3 16
2 8
6.85
4 2 2.94
1 1 2 2*
7.32 1 3 0 2*
20. 3 20. 3 13. 8 2 8 0.803
20.35 20.35 7.01 1 6 0 . 8 9 9
2311282
350/90
380/441
2r7/2
2*4/l
0 . 7 2 6
3
@=90 6
1 6
1 6
0.835
0.862
0 . 9 6 4
0.978
8
64,105,119 1 1.008
/3=95.2 2
/3=98 4
0 . 9 9 9
0.993
0.923
0 . 9 2 2
0.907
0.96
0 . 9 2 2
0.907
0 . 8 9 8
0.887
0.931
-55148 2*7/2 1 5 0
2*7/2 1 5 0
2OQ/9 2*1/2
1901632 2*7/l
1 3 0 2*3/l
1 lo/282 2*3/l
0.915 44166 12.0/82 2 *S/5
0.912/53 2*8/3
0 . 8 4 2
61
5 6 9
9
6 8 5
3 4
8 0 1
1 3 9
SO/6 2*4/l
loo/90
2*
1 5 0
4 9 3
- 5 10. 9 8* 6 3 9
671439 20.1/284
731284 8* l/l
0.867 7 6 25. 3
771562 23.81562 8 * l/l
621439
8*2/l
3 8 21. 0
1 2 6
4 7 6
1 3 7 7
5 3 0
9 0 5
1 3 7 6
5 2*4/l
lo- 38/48
lo/872
1 2 0 9
2 3 12.0/682 5 *2/l
341682
1 4 7
130/276 6.28/501 2 *3/l
130/380 2*3/l
111/501 2+3/l
0.85
2*3/l
2*3/l
75/48 4.00/501
3 5 5
3 5 5
9 3 1
4 0 8
3 5 5
9 3 1
1 5 2
8 1 8
3 5 5
781282
SO/9
791501
2*4/l
2*4/l
2*4/l
2*7/2
3 5 5
8 3 4
1 4 5 2
191
191
4 3 1
4 4 2
TABLE 1. contd
Poly(olefins) VI/11
Polymer
-, S-hydroxy-
(86.13)
-, 3-methyl-
( 84. 16)
-, 4methyl-
i s ot a c t i c
I.
( 84. 16)
II.
III.
IV.
(hi press)
V.
s yndi ot act i c
-, S-trimethylsilyl-
( 142. 32)
Poly(propene)
i s ot a c t i c
I.
( 42. 08)
II.
III.
quenched
s yndi ot act i c
I.
II.
III.
-
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. (C)C kJ/mol n (n *p/q) Refs.
Tet C4-6 13. 35 13. 35 6. 80 8 0. 922
Tet
Tet
Tet
Tet
Tet
Tet
Tet
Tet
Tet
s4- 1
s4- 1
D2d-7
18. 66 18. 66 13. 80 2 8
18. 70 18. 70 13. 54 2 8
18. 53 18. 53 13. 76 2 8
18. 54 18. 54 13. 84 2 8
18. 50 18. 50 13. 76 2 8
18. 60 18. 60 13. 85 2 8
18. 63 18. 63 13. 85 2 8
18. 70 18. 70 13. 68 2 8
18. 66 18. 66 13. 65 2 8
Tet
Tet C4-6
19. 16 19. 16
19. 36 19. 36
19. 38 19. 38
19. 46 19. 46
0. 814
0.826
0. 828
0. 822
0.83 1
0. 817
0. 814
0. 818
0. 823
0. 828
0. 855
0.846
0. 853
0. 8408
Hex 16. 88 16. 88
Hex 22. 17 22. 17
0. 808
0.883?
Tet s4-1 18. 03 18. 03
7. 12 1 6
7. 05 1 6
6. 98 1 6
7. 022 1 6
6 . 5
6. 31 1 8
6. 69 1 8
46. 91 4 8
6. 55
0.880
Mono
Mono
Tri
Mono
Mono
C2h-6
Ci- I
C2h-5
6. 65 20. 96 6. 50 ,B= 99.3 1 2 0. 938
6. 66 20. 78 6. 495 ,!3 = 99.62 1 2 0. 946
13. 36 11. 00 6.502 93,81,108 1 2 0. 935
6. 65 20. 73 6. 50 p= 99.7 12 0. 947
6. 63 20. 78 6. 504 /!3 = 99.5 1 2 0.949
6. 64 20.88 6. 51 p=98.7 1 2 0.940
6. 69 20. 98 6.504 p = 99.5 1 2 0.93 1 Mono
Hex
Rho
Rho
O r t h o
Hex
I&O
O r t h o
Rho
Tri
Tli
O r t h o
Tet
O r t h o
O r t h o
O r t h o
Phex
O r t h o
C2h-5
C2h-3
C2h-5
D3-4
C3-2
D2h-24
D2-2
D2-5
D2h-21
C2v-9
6. 65 20. 80 6. 50 0x99.33 1 2 0. 945
12. 74 12. 74 6. 35 1 2
19. 08 19. 08 6. 49 2 7
6. 38 6. 38 6. 33 3
19. 08 11. 01 6. 490 1 8
22. 03 22. 03 6. 490 3 6
19. 08 19. 08 (6.49) 2 7
11. 03 19. 08 6. 49 1 8
1 1 1 1 6 . 5 9
6. 47 10. 71 y = 99.07 6
6. 54 21. 40 6. 50 89,100,99 1 2
8. 54 9. 93 42. 41 4 8
5. 97 5. 97 6
0.939
0.922
0.939
0.922
0. 922
0. 922
0.92 I
0. 92
0.946
0. 935
0.88067
1 4 . 5 5 . 8
14. 50 5. 60
14. 50 11. 20
5. 22 11. 17
1 . 4 8
7. 40 8
7. 40 1 6
5. 05
5.06 4
1 1 . 8
0. 898
0. 930
0. 930
0. 898
0.947
6 . 5 2* 191
3621632
2731129
200/441
2+4/l 6 2 2
>0.835
235148
2281282
2381632
250194
0. 838
125
7 5
2 1 0
133/71 2*3/l 6 7
0.85/45
0.854
0.907/l 12
176110
1891392
1861394
2081676
1651282
1781349
183/380
180/250
2201974
2201975
186/1003
1471789
200/975
1701974
192/1212
183/1404
0.858/393 161/415
1381545
0. 858 160/1459
19.7182 2 * 712
11.91370 2 t 712
9.9/1195 2*7/2
5.211288 2 * 712
5.5/1331 Irreg.
2*7/2
2*7/2
2*7/2
2*7/2
2*4/l
2*4/l
2*4/l
2*4/l
2*
2*3/l
2*3/l?
4 * 1217
9.92182 2 *3/l
7.961478 2 *3/l
8. 81394 2 * 3/l
5.80/676 2 * 3/l
10.51474 2 * 311
10.0/358 2 f 3/l
6.161182 2*3/l
7.911251 2*3/l
10.9/83 2 *3/l
6.911195
9. 311212
4.221189 2 c 3/l
8.211212 2*3/l
4.0/1404 2*3/l
2*3/l
2*3/l
2*3/l
2*3/l
3*3/l
2*3/l
2*3/l
cf ref
2*3/l
1.881545 4*2/l 1 6 9
2.1/1195 4*2/l 4 3 0
8.3/1458 4*2/l 1 3 3 0
8.0/1459 4 0 9
4* l / l 3 0 6
4*/l 1 4 3 0
4* 8 4 5
55
9 3 6
8 9 4
4 5 2
3 3 3
6 7
6 8 9
1177
1198
9 4
8
8
1197
1453
8 4 5
1454
9 9 0
1455
1 2 7
3 0 8
1 7 0
5 1 9
6 2 6
131
1 3 6
3 3 0
9 9 1
1 6 6
4 8 5
1 9 6
3 0 8
3 0 8
1456
1457
1 6 4 2
3 0 8
5 9 2
1408
9 4 3
References page VI- 159
VI/12 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 1. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm3) Melting Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. cwR kJ/mol (n *p/q) Refs.
(hi press.)
IV.
(252.48)
-, 3-cyclohexyl-
I. (124.23)
Tli
Tet
II. Rho
-, 3-cyclopentyl-
(110.20) Tet
Tet
-, hexafluoro-
(150.02)
-, 3-phenyl- [allylbenzene]
(118.18)
Cl-l 5.72 7.64 11.60 73.89.112 1 0.942 12* l / l 1460
c4-5
or S4-2
21.06 21.06 20.09 4 0 0.926 230190
2151282
2141328
2 * 10/3 431
c4-3
or C3i-2
19.12 19.12 6.33 9 0.926 2*3/l 431
c4-5
or S4-2
20.34 20.34 47.49
47.40
9 6 0.894 210/328
225190
2 * 2417 431
9 6 0.899 2 * 2417 625
-, 3-silyl-
(72.18)
-, trimethylsilyl-
(114.26)
Poly(propene-At-ethylene)
s yndi ot act i c
(70.14) Mono
Poly( 1 -tetradecene)
II. (196.38) Or t ho
Poly(tetrafluoroetbylene-air-ethylene)
(128.07) Mono
Ortho
Poly(vinylcyclobutane)
(82.15) Tet
Poly(vinylcycloheptane)
(124.23) Tet
Poly(vinylcyclohexane)
I. (110.20) Tet
Tet
II. Tet
Poly(vinylcyclopentane)
I. (96.17) Tet
II. Tet
III. Tet
Poly(vinylcyclopropane)
I. (68.12)
RbO
II. Tet
C4h-6 23.4 23.4 6.5 16 0.927
C4h-6 21.99 21.99 6.43 16 0.942
21.76 21.76 6.50 16 0.95 1
c4-5
or S4-2
20.48 20.48 44.58 9 6 0.940 2 * 2417 431
C4h-6 20.14 6.50 16
c4-5
or S4-2
D4h-1
or D4h-7
20.14
20.14
20. I4
37.3
19.5 4 8 0.969 2 * 1213 431
37.3 19.8 0.927
C3-2
or c3-3
S4-2
13.6 13.6
6.5
6.48 9
40
0.98 1
15.21 15.21 20.85 0.938 2* IO/3 526
Poly( 1-vinylene-3-cyclopentylene) [norbomene]
trans-
(94.16)
Mono
cis- Mono
20.30
11.19
1.5
9.6 9.25
8.57 11.20
9.46 5.81
5.0 y = 96 4 1.93
5.04 4 1.758 1.684 2 6 7
4* l / l
4* l / l
7 2 2
1287
1321
34.12 34.12 6.6 6 4 I.14 2281437 2*4/l 431
> 300/437 2*4/l 431
305/90
300/282
3721441
3831328
2*4/l 431
2*4/l 67
5.13 4.78
4.64 4.22
20.30
6.40
6.45 128/71 2*3/l 6 7
6.50 360171 2*3/l 67
11.62
56.0
9.00 y = 67.03
6.6
11.8
11.56 y = 73.5
9.84 y = 68.1
8 0.94
2
2
160 2*4/l 268
230/90
208/187
1851282
2*3/l 67
5 5
571250
571872
2701441
2921328
2 3 0
2 0 2
I.150
1.749
1450
2*4/l 150
2*4/7 431
2 * 10/3 431
2*3/l
175
526
5*2/ 620
5*2/l 1451
5*2/l 1451
a The numbers after the solidus (/) are reference citations.
b The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
Poly(vinyls) and Poly(vinylidenes) VI/13
TABLE 2. POLY(VINYLS) AND POLY(VINYLIDENES) (-HCH-CHR- and -HCH-RCR-)
Polymer
tryst
syst.
Space
&TOP
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
point f us i on conf orm.
a b c Angl es Z crystal. Amorph. a (w kJ/mol * (n *p/q) Refs.
Poly(acrylamide)
-, N,N-dibutyl-
(183.30) Hex 26.3 26.3
-, N-isopropyl-
(113.16)
Poly(acrylic acid)
-1 ally1 ester
(112.13)
-, biphenyloxyhexamethylene ester
(324.42) Phex
-, set-butyl ester
(128.17) ortbo
-, rerr-butyl ester
(128.17)
Or t ho
-, p-carboxyphenyl ester
23.5 23.5
17.92 10.34
6.3 12 0.97
(1.W
2 * 3/l
1.118 1.070 2 0 0 2*
6.5 9 0 2*3/l
6.48 6 1.043 2*3/l
6.49 6 1.062 130 2*3/l
6.45
6.48 6 1.047
193116 2*3/l
2 0 0 2*3/l
6.68 b /3= 124
6.42
4 1.445 2*
12 1.239 81 2*3/l
6.5
6.32
162/120
162
1781541
5.91541 2*3/l
1.08
5.18 1.18 115 4* l/l
(5.1) 16 1.125
5.04 8 1.137
5.10 4 1.111
5.00 8 1.273
5.08 4 1.134
(5.1)
y= 120 2 1.07
5.04 16 1.119
(5.1) 8 1.07
317177
3411499
4.86/77-
5. 23177 4* l/l
4* l/l
4* l / l
4* l/l
4* l/l
4* l/l
4*1/l
4* l/l
7.096 2 4 1.201 2*4/
2.55 1 1.538
8.2 16 1.32
2*1/l
2*4/l
93
102
2 7 8
1122
401
6 7
401
865
401
6 7
149
113
7 6
4 8 6
5 7 5
133
162
2 1 0
3 2 2
1001
1332
1631
8 0 4
1631
133
1461
17.92 10.50
21.50 7.42
17.92 17.92
(192.17)
-, isobutyl ester
(128.17)
-9 isopropyl ester
i s ot act i c
(114.14)
s yndi ot act i c
Poly(acrylonitrile)
s yndi ot act i c
(53.06)
II?
i s ot act i c
(gel)
Mono
Ch t h o
Hex 5.99 5.99
21.18 11.60
10.6 11.6
C2v-16 10.20 6.10
18.1 6.12
10.55 5.80
6.1 6.11
21.0 11.9
C2v-9 10.7 12.1
9.03 5.24
21.48 11.55
21.18 11.71
Phex
ortho
Or t ho
Or t ho
Tet
Tet
4.74 4.74
11.4 11.4
Poly(isopropenylmethy1 ketone)
(84.12) Tet 15.08 15.08 8.54 16 1.151 2 4 0 2*4/l
2401255
200/379
3 4 7
Poly(methacrylic acid)
-3
methyl ester
i s ot act i c
(100.12) Por t
OI l hO
Oh0
Tti
ortbo
syndiotactic
it-st stereocomplex (1 : 2)
Mono
21.08 12.17 10.55 2 0 1.228
21.08 12.17 10.50 2 0 1.234
20.98 12.06 10.40 2 0 1.264
20.57 12.49 10.56 93.88.91 2 0 1.228
D2h-24 41.96 24.34 10.50 8 0 1.240
1.22131
1.19131
16013 1 5.021871 2 * 512 3 0
2201855 2*5/l 5 2 0
vi ref 8 6 8
*10/l 1002
* 10/l 1462
200131 4*5/2 3 0
21.5 16.5 18.4 y= 112 *9/l 1397
73.6 260/1006 * 3014 1005
-, -, chloroacetone complex
syndiotactic
Mono 43.5 43.5 35.4 y= 107 4 * 3714 1004
References page VI- 159
VI /14 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 2. contd
Polymer
Cryst
syst.
Space
FouP
Unit cell parameters Densi ty (g/ cm 3, Melting Heat of Chai n
poi nt f us i on conf orm.
n b c Angl es Z Cryst al . Amorph. a
(Cl
kJ/mol a (n *p/q) Ref s.
-1 octadecyl ester
s yndi ot act i c
( 338. 58) Hex
Poly(methacrylontirile)
I. (67.09) Phex
11. Mono
Poly(thiolacrylic acid)
-. see-butyl ester
( 144. 23) Rho
-9 isobutyl ester
( 144. 23) Mono
-1 isopropyl ester
(130.20) Rho
-3 propyl ester
( 130. 20) Mono
Poly(viny1 acetate)
-, trifluoro-
( 140. 06) O r t h o
Poly(viny1 alcohol)
(44.05) Mono
Mono
Mono
Mono
Mono
quenched O r t h o
single crystal Hex
12 complex Mono
Poly(viny1 bromide)
(106.95) O r t h o
Poly(viny1 chloride)
(62.50) O r t h o
O r t h o
O r t h o
Mono
single crystal O r t h o
Poly(viny1 fluoride)
(46.04) Hex
O r t b o
Mono
Poly(viny1 formate)
i s ot a c t i c
( 72. 06) RbO
s yndi ot act i c
Poly(vinylidene bromide)
( 185. 85) Mono
Poly(vinylidene chloride)
( 96. 94) Mono
Mono
Mono
Mono
Poly(vinylidene fluoride)
(1 (II) Mono
(64.04) O r t h o
Mono
O r t h o
Mono
Mono
4. 73 4. 73 3 0 . 2 1 0. 961 3 6 5 0 0
9. 03 9. 03 6. 87
7. 87 8. 97 6. 87
1 3 . 5 7. 71 7. 62
4 0. 918
4 0. 918
8 1. 134
250/436 2*
3 = 97.7 2*4/l
4 2 7
7 2 9
4 2 7
C3-2 6. 35 2*3/l 4 0 1
cs-2 6. 42 2* 4 0 1
C3-2 6. 42 2* 4 0 1
G-2 6 . 4 2*3/l 4 0 1
9. 54 12. 44 4 . 8 4 1. 633 175/821 2* 6 3 8
C2h-2 7. 81 5. 51 2.52 y = 91.7 2
7. 81 5. 43 y = 91.5 2
7. 805 5. 485 2.533 Y = 92.2 2
C2h-2 y = 92
y = 93
c2v-20
7. 81 5.50 2.52 b
7. 84 5. 52 2.526
7. 42 5. 25 2.52b
5. 45 5. 45 2. 51
1. 87 5. 53 2. 525 b
1. 350
1.34/410
1. 350
1. 345
1. 352
1. 343
1. 490
1. 133
1.291/l
1.27/410
1. 26153
1. 269
2321310
243/480
2651323
228 1433
267/450
6.871433 2* l/l
6.991480 2 * l/l
7.1/1195 2* l / l
y = 93.3
2*1/l
2+ l / l
2* l / l
2*1/l
2* l / l
2 9
3 1 6
132
1 8 4
2 6 1
1441
261
1 5 1
1424
D2h- 11 11.0 5 . 6 5 . 1 4 2. 26 1 1 7 4+ l/l 7 7 2
D2h-11
D2h-11
1 0 . 6 5 . 4 5 . 1
10. 40 5. 30 5. 10
10. 11 5. 27 5. 12
10. 65 5. 20 5.15h
10. 24 5. 24 5. 08
4 1. 42
4 1. 477
4 1. 522
4 1. 456
4 1. 523
1.41/413
y = 90
2731372
3101423
2121143
D2h-11
111372 4* l / l 7
4.9/835 4 * l/l 2 3 5
2.81145 4% l / l 6 4
3.31423 4t 111 140
4*1/l 7 1 8
c2v- 14
4. 93 4. 93 2. 53
8. 57 4. 95 2. 52
4. 938 4. 938 2. 518 y= 120
1 1. 436
2 1. 430
1 1. 4377
200179
2301434
7.54179 2* I /I 6 2
2*1/l 2 3 6
2* l / l 1463
C3v-6-
D3d-6
1 5 . 9 1 5 . 9 6. 55 1 8 1 SO2 2*3/l 2 3 2
5 . 0 4*1/l 2 3 2
25. 88 13. 87 4.77 b y = 109.8 1 6 3. 065 3 3
C2h-2
c2-2
6. 71 12. 51 4.68 b y= 123 4 1. 954
13. 69 6. 296 4.67 b y = 124.8 4 1. 948
22. 54 12. 53 4.68h y = 95.8 1 6 1. 958
6. 73 12. 54 4.68 b y = 123.6 4 I.957
1.66143 200/721 4*1/l
190/46 4*1/l
1 9 5 5. 68
2*2/l
1. 7754
9 1 5
3 2
3 3
2 4 5
2 3 1
4 6 2
p = 107
C2v-4
c2-2
C2v-9
C2b-5
c2-2,l
y = 92.7
5. 02 2 5 . 4 4. 62
4.96 9. 64 4. 62
17. 72 11. 68 4.57 b
9. 66 4. 96 4.64
4. 96 9. 64 4. 62
9. 64 5. 02 4. 64 b
p = 90
y=91.1
1 0 1. 888
4 1. 925
1 6 1. 801
4 1. 913
4 1. 925
4 1. 895
1.681716
1.67/710
1851434 6.71823 171
1701995 6.21886 4 * l / l 9 9 4
220/443 5.961726 4* t/t 4 1 7
1711373 2*2/l 4 1 8
1 7 8 4r l/l 6 0 4
178/726 4* l / l 168
Poly(aromatics) and PolyGmides) VI/15
TABLE 2. contd
Polymer
tryst
syst.
Space
group
Unit cell parameters Density (g/cm 3, Melting Heat of Chain
point fusion conform.
a b c Angles Z crystal. Amorph.
WY
kJ /mol (II *p/q) Refs.
Port
ortho
c2-2 5.02 9.63 4.62
9.60 5.00 4.655
9.80 5.05
8.45 4.88 2.55
8.58 4.91 2.56
8.47 4.90 2.56
8.60 4.97 2.57
4.96 9.58 9.23
8.66 4.93 2.58
4.97 9.66 9.18
4.96 9.67 9.20
4.96 9.64
4.96 9.64 4.62
4 1.904
4 1.904
4
2 2.022
2 1.972
2 2.002
2 1.936
p=92.9 8 1.942
g=97 2 1.945
8 1.930
p=93 8 1.930
W/846
21311464
2*2/t 563
5 9 7
7 5 0
4 1 7
6 0 4
4 1 8
5 9 7
9 9 6
6 0 4
9 9 7
9 9 8
9 9 9
1000
P (1) Ortho
Ortho
ortho
OlthO
Y (III)
Mono
Mono
ortho
Mono
6 (IV)
(polar alpha) Ortho
Poly(vinylmethy1 ketone)
(70.09) Tet
Tet
C2v-14
CZv-14
C2v-14
G-4
C2-3
C2v-16
2121443 2* l / l
191 2*1/l
2071942 2* l / l
2181846
197
1841995
23111464
8*1/l
2* l/l
8* l/l
8*1/l
4* l/l
4*1/l C2v-9 4 1.925
s4- 1 14.52 14.52 14.40 2 8 1.073
14.56 14.56 14.10 28 1.090
2*7/2 164
2*7/2 3 7 9 170
The numbers after the solidus (/) are reference citations.
b The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
TABLE 3. POLY(AROMATICS) AND POLY(IMIDES)
Polymer
Cryst
syst.
Space
ww
Unit cell parameters Density (g/cm 3, Melting Heat of Chain
point fusion conform.
a b c Angles Z Crystal. Amorph. n
WY
kJ /mol a (n *pfq) Refs.
Poly(4,4-benzobisthiazole-diphenylene pyromellitimide)
(556.57) ortho D2-3 5.70 8.11 24.8
Poly(2,6benzothiazole)
(133.17) Port 6.044 3.417 12.19
Poly(2,5(6)-benzoxazole)
(117.11) Port 6.061 3.384 11.58
Poly(4,4-biphenylene 3,3,4,4-biphenylenetetracarboximide)
(442.43)
-, 2,2-bis(trifluoromethyl)-
(578.43) Mono 15.40 9.90 20.25
Mono 15.40 9.918 20.21
-, 2,2-dimethyl-
(470.48) Tli 20.49 15.30 40.0
-, 3,3-dimethyl-
(470.48) Ortho 16.7 13.0 20.5
Poly(4,4-biphenylene 4,4-carbonyl(3,3-dicarboxy)-dibenzamide)
(506.47) 21.2
Poly(4,4-biphenylene 3,3,4,4-carbonyldiphenylenetetracarboximide)
(470.44) 21.6
Poly(4,4-biphenylenedioxy-3,3-biphenylene pyromellitimide)
(550.53) Ortho 7.89 6.29 25.11
OlthO 7.85 6.37 25.31
Poly[2,2-(4,4-biphenylene) 6.6~diquinoline]
-, di-p-phenyl-
(558.63) ortho 16.2 5.31
Poly(4,4-biphenylene 4,4-oxy(3.3~dicarboxy)-dibenzamide)
(494.46)
Poly(4,4-biphenylene 3,3,4,4-oxydiphenylenetetracarboximide)
(458.43)
Poly(4,4-biphenylene 1,Cpyromellitamide)
(402.36)
Poly(4,4-biphenylene pyromellitimide)
(366.33)
8.58 5.48
Or t ho D2h-9 8.57 5.51
21.4
21.0
21.3
16.1
16.6
16.6
16.78
2 1.612 22* l/l 1433
2 1.756 5*2/l 1235
2 1.638 5*2/l 1235
1.480 1335
y = 56 4 1.501
y = 56.2 4 1.4977
62,52,80 16 1.443 1.341
18* l / l 1494
18 * l/l 1495
18*2/l 1584
8 1.404 18* l/l 1289
21* l/l 1178
19* l / l 1178
2 1.467
2 1.444
23* l / l 1475
34* l / l 1498 3 8 8
2 1.008 20r l/l 1500
21 *l/l 1178
900/1018 19* l/l 1178
16* l / l 1178
9 0 8
827/1018 15* l/l 9 2 8
15* l / l 1476
References page VI- 159
2 1.559
2 1.535
VI/16 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 3. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm3) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. (fJa
kJ/mol a (n *p/q) Refs.
Poly(2,2-bithiophene)
-, 3,3didecyl-
(444.78) Or t ho 17.6 4.5 15.6 2
-, 3,3-dihexyl-
(332.56) Or t ho 11.8 4.5 15.6b 2
-, 3.3.dioctyl-
(388.67) Mono C2h-4 14.6 4.42 14.73 p=90 2
Or t ho 14.5 4.5 15.6 2
Or t ho 14.6 4.42 15.70 2
Poly(4,4-carbonyldiphenylene pyromellitimide)
(394.34) 3l.Ob
Or t ho 7.9 6.65 32.8 4
Poly(decamethylene 3,3,4,4-oxydiphenylenetetracarboximide)
(446.50)
23.5
Poly(decamethylene pyromellitimide)
(354.40) Mono 19.8 4.61 19.2 y = 96 4
Poly(dodecamethylene 1,4,5,8-naphthalenetetracarboximide)
(432.52) Tri 6.23 4.68 19.1 90,111,100 1
Poly(dodecamethylene pyromellitimide)
M Mono 5.58 4.89 18.9 y = 108.4 1
(382.46) 18.96
P Mono 18.95 4.54 21.5 y = 101.3 4
21.43
ii 2 2 . 0 5 2 0 . 9 5
Poly(3,4-ethylenedioxydiethylenedioxydiphenylene 3,3,4,4-oxydiphenylenetetracarboximide)
(606.59)
Poly(3,4-ethylenedioxydiphenylene 3,3,4,4-oxydiphenylenetetracarboximide)
(518.48)
Poly(2,7-fluorenylene 1,4-pyromellitamide)
(414.37) 15.9
Poly(2,7-fluoenylene pyromellitimide)
(378.34) 16.3
Poly(hexamethylene 3,3,4,4-oxydiphenylenetetracarboximide)
(390.40) 19.5
Tri 8.34 9.18 19.6 90,134,117 2
Poly(hexamethylene pyromellitimide)
(298.30) 24.88
Poly[4,4-(isophthaloyldiamino).diphenylene 3,3,4,4-oxydiphenylenetetracarboximide]
(620.58) Or t ho 9.84 4.95 28.5 2
Poly[4,4-(isophthaloyldiamino)-diphenylene p-phenyleneditrimellitatediimide]
(768.69) Or t ho 6.03 7.58 73.6 4
Poly[4,4-(isophthaloyldiamino).diphenylene pyromellitimide]
(528.48) 24.2
1.20
1.33
1.36
1.27
1.27
1.520
1.350 3 1 8
32311267
1.409 308
1.289
1.401 2 9 7
30511267
(1.462) 238
1.485 3 2 0
1.518
Poly[isophthaloyl-4.4-diphenylenedioxy-4,4-diphenylene 3,3,4,4-carbonyldiphenylenetetracarboximide]
(786.75) Or t ho 8.07 6.135 37.50 2 1.07
Poly(4,4-methylenediphenylene pyromellitimide)
(380.36) 29.1
Or t ho 8.20 6.55 32.4 4 1.452
14.1
Poly(metbylene-p-phenylene)
(90.12) Or t ho 8.16 6.32 9.90 4 1.172
-3 a-methyl-
(104.15) Ortho 10.42
Poly(methylene-3,5-toluene)
-, 2,6-diamino-
(134.18) Ortho 12.82
Poly(2,6-naphthalene 2,4-cyclobutylenedicarboxylic acid)
-, bis(2,4-dichlorophenyl) ester
(558.24) Tri Ci-1 6.00
5.97 9.62 4 1.156
13.83 9.69 8 1.037
8.93 13.48 70,94,101 I 1.396
2 6 8 88.0
3 4 0 72.5
4 3 0
1.382
3 5 0
170
1421744
219/1007
6*2/l 1485
6*2/l 1485
6*2/l 1484
6*2/ l 1485
6*2/l 1486
908
16*2/l 1013
21* l/l 896
17* l/l 1395
201 l/l 1015
19* l/l 1395
1371
19* l / l 1015
1371
1371
1371
1493
15* l/l 1178
14* l/l 1178
896
17* l/l 1015
1395
26* l / l 1190
33 *2/l 1191
22* l/l 1191
1335
34* l / l 1498
9 0 8
16*2/l 1013
1014
5*2/l 745
5*2/l 848
4*2/ l 1351
9*1/l 9 5 0
TABLE 3. contd
Poly(aromatics) and Poly(imides)
VI /17
Polymer
Clyst
syst.
Space
group
Unit cell parameters Density (g/cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es E Cryst al . Amorph.= (w
kJ/mol Lz
(n *p/q) Refs.
Poly(4,4-neopentylenedioxydiphenylene 3,3 ,4,4-carbonyldiphenylenetetracarboximide)
(572.57) Mono 9.60 5.82 24.6 y = 81.1
Poly(nonamethylene 3,3,4,4-oxydiphenylenetetracarboximide)
(432.48) 21.3
Poly(nonamethylene pyromellitimide)
(340.38) 32.0
Poly(octamethylene 3,3,4,4-oxydiphenylenetetracarboximide)
(418.45) Tri 8.37 4.95 21.5 90.38.104
Tli 8.37 4.95 21.5 90,38,104
Poly(octamethylene pyromellitimide)
(326.35) Mono 20.8 4.76 16.9 y = 95.5
Poly(3,4-oxydiethylenedioxdiphenylene 3,3,4,4-oxydiphenylenetetracacboximide)
(562.34)
Poly(3,4-oxydiphenylene 3,3,4,4-biphenylenetetracarboximide)
(458.43) Mono 14.8 8.20 20.6 y = 56
Poly[4,4-((4,4-oxydiphenylene)-dioxy)-diphenylene p-phenyleneditrimellitatediimide]
(806.74) 5.68 8.09 78.6
Poly[4,4-((4,4-oxydiphenylene)-dioxy)-diphenylene pyromellitimide]
(566.53) 8.44 5.66 53.4
53.4
Poly(4,4-oxydiphenylene 3,3,4,4-oxydiphenylenetetracarboximide)
(474.43) Mono 5.17 10.85 38.2
Poly[4,4-oxydiphenylene 3,3-( p-phenylene)-ditrimellitatediamide]
(658.58)
Poly(4,4-oxydiphenylene p-phenyleneditrimellitatediimide)
A. (622.54) Mono 5.56
5.56
B. 13.12
Poly(4,4-oxydiphenylene 1.4.pyromellitamide)
(418.36)
Poly(3,4-oxydiphenylene pyromellitimide)
(382.33) Ortho
oltbo D2-9
Poly(4,4-oxydiphenylene pyromellitimide)
I. (382.33) Ortho
ortbo
Or t ho
oltbo
8.48
5.15
6.35
6.31
c2-2 4.66
8.36
c2-2 6.45
II.
Poly(m-phenylene)
(76.10)
Poly@-phenylene)
(76.10)
-3 compl ex wi t h:
K
(1/2K/unit)
SbCl5
(l/2 Sblunit)
SbFS
(l/3 Sb/unit)
Or t ho 5.93
Or t ho
Or t ho
Or t ho
Or t ho
Or t ho
D2h-9 6.04
15.6
Hex 12.0
P@
7.81
7.80
8.06
7.82
1.79
26.3
7.94 58.0
1. 94 59.0
28.7
7.84 57.0
15.2
5.62 33.65
8.48 33.2
4.05 32.6
3.97 32
5.96 32.9 b
5.63 33.03
4.01 32.58
15.9
4.70 33.00
5.53 4.20
5.56 4.20
5.55 4.30
5.60 4.20
5.51 (4.20)
15.6 4.35
6.2 4.2
12.0 4.2
y = 103.7 4 1.514 427/1018
y = 86 4 1.619
p = 86 4 1.591
1.366
8 1.410
1.410
1.583 15*2/l 1477
1.569 15*2/l 1478
597/1018
y=lOO
y = 90
4=100
4
4
2
2
2
4
2
2
2
2
2
2
2
4
2
3
1.514
1.58
1.411
1.633
1.507
1.380
7901964 6. 901964 3*
1.393
1.388
1.334
1.374
1.402
<550/735 15.01964 4s l/l 475
1400/964 4* l/l 1290
4*1/l 1334
4*1/l 1448
4* l / l 1466
4*2/l 5 0 8
2 1.400
3 0 3
>350
1 1.372 1.30
1 1.396 2 0 2
4 1.301 3 6 2
38311267
3 0 4 80.2 1493
4 1.469
4 1.484
4 1.475 547/1018
24* l/l 1499
20* l/l 1015
1395
1267
19* l / l
8 9 6
19* l/l 1015
15*1/l 1395
18* l / l 1289
37*2/l 963
26*2/l 963
908
20*2/l 6 8 4
26 *2/l 1178
27*2/l 658
27*2/l 963
1178
1335
27*2/l 963
17* l/l 1178
1335
16*2/l 6 4 2
16*2/l 6 8 4
877
16*2/l 1471
16*2/l 1478
1178
16*2/l 1477
4*1/l 1231
4* l/l
4*1/l
1393
1393
References page VI-159
VI/18 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 3. contd
Polymer
Clyst
syst.
Space
group
Unit cell parameters Density (g/cm) Melting Heat of Chai n
poi nt f us i on conf orm.
a b C Angl es Z C@bll. Amorph. WY kJ/mol a (n *p/q) Refs.
Poly@-phenylene benzobisoxazole) [PBO]
(234.21) Mono
Mono
Mono cs-2
Por t
-, complex with poly(phosphoric acid)
I. Mono
II. Mono
Poly(p-phenylene benzobisthiazole) [PBT]
(266.34) Mono
Mono
Mono
-, complex with poly(phosphoric acid)
OlthO
Mono
Poly(p-phenylenecyclobutylene)
5.64
11.20
11.20
11.8
12.6
7.0
5.83
11.96
11.79
15.9
8.15
-, 2,4-dipyridyl-
(284.36) Or t ho D2h-15 19.16
Ortho D2h-15 18.9
Poly@-phenylene 2,4-cyclobutylenedicarboxylic acid)
-, dietbyl ester
(274.32) Mono C2h-5 8.62
-, dimethyl ester
(246.26) Tri Ci- 1 6.04
-, diphenyl ester
(370.40) Mono C2h-5 7.50
-, dipropyl ester
-9 -, 2,4-dicyano-
(352.39) Mono C2h-2 6.19
3.58 12.07
3.540 12.050
3.54 12.05
3.54 12.1
y = 100.4
y = 101.3
y = 101.3
1
2
2
2
1
2
2
4
4
2
1
2
2
1.622 11* l/l 1263
1.660 11*1/l 1488
1.660 11 *l/l 1489
1.55 11 *l/l 1490
11.6 12.2 y = 98
5.8 12.0 y=99
1492
1492
3.54 12.35 y = 96
3.555 12.35 -( = 100.9
3.539 12.514 y=94.0
1.745
1.716
1.698
1016
1017
1488
20.6 36.9
24.49 37.2
2 5 0
y = 94.5 2.15
11 *l/l
11*1/l
11*1/l
11*3/l 1316
1491
10.69 7.45
10.5 7.53
1.238
1.26
7*1/l
7* l/l
2 0 2
723
9.98 8.166 p= 102 1.327 893
7.42 7.82 101,106,72 1.284 893
7.506 p = 102 1.292
3471723 7*1/l
4151723 7*1/l
4201723 7* l/l 893
20.1 7.58 /3 = 96 1.248
Poly[4,4-((4.4-(p-phenylenedioxy)-diphenylene)-dioxy)-diphenylene p-phenyleneditrimellitatediimide]
3351723 7*1/l 893
(898.84) 5.66 8.14 43.5 2
P0ly[4,4-((4,4-@-phenylenedioxy)-diphenylene)-dioxy)-~phenylene pyromellitimide]
(658.62) 8.44 5.66 31.3 2
31.3
Poly[4,4-(p-phenylenedioxy)-diphenylene 4,4-oxy(3,3-dica&oxy)-dibenzamide]
(602.56) 24.6
Poly[4,4-(p-phenylenedioxy)-diphenylene 3,3,4,4-oxydiphenylenetetracarboximide]
1.489 42* l/l 9 6 3
1.463 31 *l/l 9 6 3
9 0 8
27* l/l 1178
(566.52) T r i 10. 52 b.45 26.1
26.0
90,95,98 4 1.472 25* l/l
1.341
6 8 4
1178
1335
Poly[4,4-(p-phenylenedioxy)-diphenylene p-phenyleneditrimellitatediimide]
34.5 2 1.515 6 5 8
19.8 1178
19.6 1178
43.4
43.4
21.7
4 1.515
32* l/l
21* l/l
22* l/l
20*2/l 9 6 3
9 0 8
1178
21.8
22.09
21.0
,9= 98.7 2 1.562 21* l/1
2 1.553 21* l / l
6 8 4
1477
1178
14.0 8 1.69 7*2/l 1496
16.6
16.9
17* l/l
15r l/l
12* l/l
1178
1178
12.2 1178
17.3
(714.64) ortho 5.64 8.05
Poly[4,4-(m-phenylenedioxy)-diphenylene l,4-pyromellitamide]
(510.46)
P0ly[4,4-@-phenylenedioxy)-diphenylene 1,4-pyromellitamide]
(510.46)
P0ly[4,4-(m-phenylenedioxy)-diphenylene pyromellitimide]
(474.43) 8.76 5.47
Poly[4,4-@-phenylenedioxy)-diphenylene pyromellitimide]
(474.43) Mono 5.64 8.30
OlThO 8.23 5.58
Poly@-phenylene-1,3,4-oxadizaole)
lx Or t ho D2-4 12.35 6.55
(144.13)
Poly[p-phenylene 4,4-oxy(3,3-dicarboxy)-dibenzamide]
(418.36)
Poly@-phenylene 3.3. 4,4-oxydiphenylenettracarboximide)
(382.33)
Poly(p-phenylene 1,4-pyromellitamide)
(326.26)
TABLE 3. contd
Polyfaromatics) and Poly(imides) VI/19
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm j) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z crystal. Amorph. a
(w
kJ/mol u (n *p/q) Refs.
Poly(m-phenylene pyromellitimide)
(290.23) O r t h o
Poly@-phenylene pyromellitimide)
( 290. 23)
Poly(p-phenylenevinylene)
(102.14) Mono
-3 complex with:
AsFs Ortho
ClO, O r t h o
FeCl3 O r t h o
HzSO4 O r t h o
SbFs O r t h o
Poly(2,5-pyrazinecyclobutylene)
-, 2,4-diphenyl-
(284.36)
Poly(styrene)
i s ot a c t i c
( 104. 15)
gel
s yndi ot act i c
u
P
Y
-3 complex with:
CH#Zlz
C7Hs
I2
-, p-ferr-butyl-
-> -3 isotactic
( 160. 26)
-, o-fluoro-
-> -3 isotactic
( 122. 14)
-, p-fluoro-
-> -> i s ot a c t i c
( 122. 14)
-3 a- met hyl -
- 1 -, isotactic
( 118. 18)
-, -, (p-methyl-
-, -, -, isotactic
( 132. 21)
O r t h o
O r t h o
Ortho
Ortho
D2h-15
C2v-5
1 0 . 8 1 8 . 4 7.4 4 1. 28 3 2 1 7 * 2 / l 5 5 8
18. 36 10. 88 7. 52 4 1. 257 3431723 7*2/l 5 6 4
18. 36 10. 88 7. 52 4 1. 257 7 * 2 / l 9 5 0
18. 40 10. 89 73. 45 4 1. 265 7 * 2 / l 1 2 3 8
Rho D3d-6 22. 08 22. 08 6. 626 1 8 1. 113
RbO D3d-6 2 1 . 9 2 1 . 9 6. 65 1 8 1. 127
RbO D3d-6 22. 08 22. 08 6. 594 1 8 1. 118
1. 114
O r t h o 2 1 . 0 1 6 . 4
3 0 . 6
3 0 . 6 4 8
Mono
Hex
Hex
C2h-5
D3h-4
19. 84 12. 90
26. 26 26. 26
2 6 . 3 2 6 . 3
5. 06
5. 045
5 . 1
5. 06
5. 08
5. 06
7 . 5
7 . 7
y = 9 5 8 1. 072
1 8 1. 033
1 8 1. 02
O r t h o D2h-16 8. 81 28. 82 8 1. 077
O r t h o D2h-10 2 1 . 4 1 7 . 1 7 . 5
7 . 7
7. 71
7. 71
7. 79
16 1. 01
Mono
C2h-5 17. 48 13. 27
C2h-5 17. 58 13. 26
C2h-5 17. 29 12. 85
y= 1 2 2 8 1. 114
y = 121. 2 8 1. 100
y = 120. 3 8 2. 054
4*2/l 1 3 7 0
4*2/l 1 4 1 9
4*2/l 1 4 3 6
4 * 2 / l 1 4 7 4
4*2/l 1473
0. 950 3 0 0
308/1372
1 9 8
Rho C3v-6 22. 15 22. 15 6. 63 1 8 1. 296
8. 30
8. 25
270175 2*3/l
265175 2*4/l
2*4/l
123
P o r t D2-4 1 7 . 6 1 2 . 1 8 0.924
6 7
7 9 1
Rho 6.6 2*3/l 3 5 7
7. 72 7. 18 2 1 . 5 4 1. 618 10*2/l 1013
8. 58 5. 48
1 2 . 3
1 2 . 3 2 1. 667 11*1/l
9 0 8
9 2 8
7. 90 6. 05 6. 58
8 . 1 6 . 1 6.6
1. 286 6* l/l 1 2 3 6
1. 24 6* l/l 1465
10. 10 6. 60 6. 58
9. 40 6. 60 6. 58
10. 80 6. 70 6 . 6
10. 45 6. 60 6. 58
10. 32 6. 60 6. 58
on= 1 2 3 2
cy = 1 2 3 2
2
2
2
2
2
6* l/l 1 3 9 9
6*1/l 1 3 9 9
6*1/l 1465
6* l / l 1 3 9 9
6* l / l 1 3 9 9
1.04- 240/10 9.00/x9 2 * 3/l 6
1.065/17 250/90 8.37/114 2 * 3 / l 1 2 8
24211415 8. 511415 2*3/l 1 3 8 8
1. 024 1 3 9
1. 052 2351282 10/l 121 4 1 1
4*6/l 1 0 0 8
4*6/l 1 0 0 9
26611372 8. 611407 4* l/l 1 4 1 8
2 6 9 1 1 4 0 7 4* l / l 1 3 8 8
4* l / l 1 4 7 0
2 7 0 4* l / l 1291
28611417 4* l / l 1 3 7 0
4* l/l 1 4 1 8
4*2/l 1401
4*2/l 1 4 1 9
224/888 lO.O/SSS
References page VI- 159
V I / 20 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 3. contd
Polymer
tryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z C@2ll. Amorph. (CY kJ/mol (n *p/q) Refs.
-, m-met hyl -
- , -9 isotactic
(118.18) Tet s4-1 19.81 19.81 21.74
57.1
Tet c4-5 19.9 19.9 78.9
or S4-2 57.0
-, o- met hyl -
- , -9 isotactic
(118.18) Tet C4v-12 19.01 19.01 8.10
44 1.012 2 1 5
215174
1.005
2* II/3 80
2*29/8 163
2*40/ 431
1 1 103
16 1.073 360174 2*4/l 125
-, -3 -3 isotactic
(136.17) 8.05
-, p-methyl-
-> -7 isotactic
(118.18) 12.9
-3 -> syndiotactic
I. - 7.8
360175 2*4/l 61
1.04167 205/1402
180/1472
17311372
ZOO/1472
2* 103
1471
II. -7. 8
III. ortho D2h-16 13.36 23.21 5.12
IV. -5. 1
(mesomorphic)
V. -5. 1
-3 trimethylsilyl-
-3 -3 isotactic
(176.34) 60.4
Poly[4,4-(terephthaloyldiamino)-diphenylene pyromellitimide]
(528.48) Mono C2h-5 8.64 5.18 25.38
Poly[4,4-(terephthaloyldiamino)-diphenylene p-phenyleneditrimellitatediimide]
(768.69) 37.63
Poly@-terphenylene pyromellitimide)
(442.43) 20.9
8.58 5.48 20.9
Poly(2,2:5,2-terthiophene)
-, 3.3-dioctyl-
(470.79) Or t ho 14.7 4.33 23.55
Poly(4,4-thiodiphenylene p-phenyleneditrimellitatediimide)
(638.61) ortllo 6.61 8.02 53.6
Poly(4.4~thiodiphenylene pyromellitimide)
8 0.977 4*1/l
1471
1471
1471
1471
2 8 4 103
a = 9 0 2 1.545 23*2/l 1191
34*2/l 1191
2 1.495 19t l/l
9 0 8
9 2 8
2 1.04 9*2/l 1486
4 1.493 27*2/l 808
Or t ho
29.4
8.57 6.31 61.5 8 1.576 16*4/l
9 0 8
1013
ortho
Mono
Or t ho
7.80 5.55 8.03
7.83 5.55 8.20 p = 9 6
1.79 5.53 7.7
7.80 5.55 8.03
1.569 3*2/l 1276
1.539 3*2/l 1276
1.64 3*2/l 1336
1.569 3*2/l 1448
22.32 16.76 7.71 Y = 95.5 8 1.021 3*2/l 1630
Mono
Mono
ortho
Mono
Mono
22.08 16.72 7.76 y = 95.6
c2-2 22.36 17.40 7.77 y = 90.5
23.9 3.8 15.6
51.9 7.74 7.8b y = 8 6
c2-2 22.54 17.17 7.749 y = 90.3
21.54 17.17 7.750 y = 90.3
1.036 3*2/l 1630
0.977 3*2/l 1447
1.042 3*4/l 1482
0.94 3*2/l 1487
0.985 3*2/l 1447
1.03 10 3*2/l 1630
Or t ho 25.83 7.75 7.77
OtthO 51.9 1.14 8.0
Or t ho 21.71 3.97 7.8
Mono 19.8 9.37 8.07 y = 71
1.069 3*2/l 1479
1.04 3*2/l 1481
1.24 3*2/l 1483
l/l40 3*2/l 1623
OXthO 24.74 4.21 7.8 2 1.25 3*2/l 1483
-3 -3
p-fluoro-
(398.39)
Poly(2,5-thiophene)
(82.12)
-, 3-decyl-
r*
(222.39)
(at 120C)
P
(at 173K)
(at 12OOC)
-, 3-dodecyl-
I. (250.44)
II.
-, 3-hexadecyl-
(306.55)
TABLE 3. contd
Poly(aromatics) and Poly(imides) VI/21
Polymer
Cryst
syst.
Space
lFOP
Unit cell parameters Density (g/cm3) Melting Heat of Chai n
point f us i on conf orm.
II b c Angl es Z crystd. AmOrph. WY kJ/mol a (n *p/q) Refs.
-, 3-hexyl-
(166.28) Ortho
ortbo
-, -, iodine doped
OITIIO
-, 3-methyl- (with 50% CF3S03-)
(96.15) Hex
-, 3-octyl-
I. (194.34) ortbo
ortbo
ortbo
Mono
II. Mono
-, 3-phenyl-
-3 -, 4-octyl-
(270.43) Or t ho
-, 3-tetradecyl-
(278.50) Ortho
Poly(tridecamethylene pyromellitimide)
(396.49)
Poly(undecamethylene pyromellitimide)
16.63
33.6
7.75 7.77 4 1.069 3*2/l 1479
7.66 7.7 8 1.11 3*2/l 1481
23.15 7.77 2 4 1.932 3*2/l 1480
19 12.2 2 2 1.63 6*11/l 1259
7.63 7.7
3.61 7.8
3.81 7.85
7.67 7.8
9.43 8.07
8
2
2
y = 87 8
y = 72 4
2
1.06 3*2/l 1481
1.32 3*2/ l 1483
1.063 3*2/l 1486
1.03 3*2/ l 1487
1.166 3*2/l 1623
7.44 0.840 3*2/l 1637
3.82 7.8 2 1.26 3*2/l 1483
39.2 263 1395
32.0 2 9 2 1395
12.30
12.00
12.5
12.3
12.00
7.44
6.47
7.44
0.988
1.193
0.958
> 3201228
6.39 1.208
2+3/l 126
2*3/l 8 2 5
2*3/l 1010
2*3/l 6 0 7
2*3/l 8 1 3
21.20 8.10 16 1.125 360175 2*4/l 122
2 1 2
15.49
6.7
6.56 9 1.153 2*3/l
185
861
6.10 9.16 p = 102.5 4 1.086
33.6 6.58 31 1.138
10.64 6.55 p= 134.7 2 1.179
10.64 6.55 p= 135 2 1.19
4251142 30.2182
1.05 4201219
375182
435/l 187
4001395
4401546
6*2/l 2 2 3
6+1/l 4 2 6
6*1/l 5 9 5
6*1/l 1181
5.25
20.52
20.52
6.53
6.55
6.58
6.55
p=95 2 1.250
16 1.158
16 1.153 4 2 0
4 1 2
6*1/l
6*1/l
6*1/l
2 2 3
1011
426
2 2 4
12.8 6.55
12.8 6.55
90,90,135 2
p= 135 2
p=135 2
1.312
1.32
2901395 6*1/l 1012
6* l/l 1181
13.4 6.55 1.20 1701395 6* l/l 1181
37.25
19
41.3
17.40
20.3
42.0
15.3
28.4
24.73
(368.43)
Poly(Nviny1 carbazole)
(193.25) Hex
Hex
ortbo
Phex
RbO
Poly( l-vinyl naphthalene)
(154.21) Tet
Poly(2-vinylpyridine)
(105.14)
RbO
Poly@-xylylene)
ci Mono
(104.15) Ch t h o
Mono
Mono
12.30
12.00
21.6
12.3
12.00
C4v-12 21.20
C3-2 15.49
11.68
21.3
5.92
5.9
Mono 8.10
Rho c3-1 20.52
Hex 20.52
Tri
Mono
5.92
5.9
Mono
Mono
P
-, chloro-
(138.60)
-1 ethyl-
(132.21)
-, isopropyl-
(146.23) 5.9 14.1 6.55 p= 135 2 1.26 6*1/l 1181
a The number after the solidus (1) are reference citations.
* The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
References page VI- 159
VI/22 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 4. POLY(DIENES) AND POLY(DIYNES)
Polymer
Cryst
syst.
Space
grouP
Unit cell parameters Density (g/cm3) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Al&-S Z Cryst al . Amorph.
WY
kJ/mol a (n *p/q) Refs.
1,4-Poly(2,3-azabutadiene)
-3 l,Cdiethyl-
trans-
(112.18)
1,2-Poly( 1,3-butadiene)
s yndi ot act i c
(54.09) O r t h o
i s ot a c t i c
RhO
1,4-Poly( 1,3-butadiene)
t r ans-
I. Phex
(54.09) Mono
II. (>65C) Phex
Hex
cis-
Mono
Mono
Or
-, 2-rerr-butyl-
cis-
( 110. 20) Tri
-, chlorinated
ci s - t hr eo- di s yndi ot act i c
( 125. 00) Mono
trans-erythro-diisotactic
Mono
-, 2-chloro- [chloroprene]
t r ans-
( 88. 54) O r t h o
ortho
cis-
-, l-cyan0
t r ans-
( 79. 10)
-, 2,3-dichloro-
t r ans-
I.
( 122. 98) Mono
II. O r t h o
-, -,
thiourea complex
Mono
Mono
-, 2,3-dimethyl-
trans-
( 82. 15)
O r t h o
cis-
-1 -3
thiourea complex
Mono
-, 2-methyl- [isoprene]
t r ans-
k8.12)
Mono
P (LM) O r t h o
O r t h o
D2h- 11
D3d-6
10. 98 6. 60 5. 14
1 7 . 3 1 7 . 3 6 . 5
C2h-5
4.54 4.54 4.9
8. 63 9. 11 4. 83
4. 88 4. 88 4. 68
4. 95 4. 95 4. 66
C2h-5
cs-4
C2h-6
8. 53 8. 16 12. 66 p=83.33 8 0. 821 6.31335 9.21353
4. 60 9. 50 8. 60 p= 109 4 1. 011 1 8*1/l
13. 95 20. 78 1 5 . 3
C2h-4
C2h-5
7. 37 5. 30 10. 10
7. 05 8. 05 5.10
D2-4 8. 84 10. 24 4. 79
9 . 0 8. 23 4.79
4 . 8
C2h-5
C2v-9
C2Hh5
C2h-5
4.86
5. 34 9. 95 4. 80
8. 81 12. 34 4.80
9. 87 15. 83 12. 53
9. 91 15. 85 1 2 . 5
C2v-9
4. 35
9. 13 13. 00 4.70
7.0
C2h-5 10. 40 15. 47 1 2 . 5
C2h-5
D2-4
8. 70
8. 76
7. 98 6. 29 8. 77
7. 78 11. 78 4. 72
7. 85 1 1 . 9 4.8b
4. 12 4* l / l 1504
4 0.964
1 8 0. 96
p= 114 :
1. 03
1. 036
1 0.930
1 0. 908
2 2
p= 134 2
p= 100 2
4
4
/3=93.5 2
4
p = 114.1
p = 114.1
4
p = 114.4
p= 102 4
4
4
0. 908 1 0 6 4* 11/3 3 6 7
1. 463 4*2/l 7 6 8
1. 456 4* l/l 7 6 8
1. 356
1. 658
1. 604 4* l / l
1. 565 4* l/l
1. 44 5 6 5
1. 44 8 0 3
0. 978
1. 22 8 0 3
1. 051
1. 046
1. 009
1 5 4 4* l/l
1 2 0 2*3/l
100/352 10.0/352 4% l / l
96145 1 13.8/451 4* l / l
0. 891 551624 6. 311624
1411352 4.611352 41 l/l
148144 5.991342 4+ l/l
1451451 4.611451
1 4 2 1 6 2 4 3. 621624
0. 902 12/l 121
1151229 8.37/81 4* l / l
80/81 4* l/l
70/l 157
4*1/l 2 7 5
2 6 0
272 1221 4* l/l
198
80/l 121 13/1121 4*2/l
lo/1128
0. 905
65146 8.0/1128 4r l/l
64181 10.6/287 4* l / l
3 7
4 9 6
1195
1 5 4
5 5 0
6 0
1 2 4
1195
2 2 1
5 6 5
6 9 9
1 0 4
6 9 9
2 2 0
2 8 8
5 0 2
7 1 5
1127
4 0
2 8 8
TABLE 4. contcl
Poly(dienes) and Poly(diynes) VI/ 23
Polymer
tryst
syst.
Space
fFOP
Unit cell parameters Densi ty (g/ cm 3, Melting Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es L crystd. Amorph. n WY kJ/mol (n *p/q) Refs.
Or t ho 7.83 11.87
6 VW
Mono
E
cis-
Mono
ortho
Mono
ortho
-, -1 3-chloro-
t r ans-
(102.56)
-7 -3 hydrochlorinated
(104.58) Por t
Or t ho
-, 2-methylacetoxy-
t r ans-
(126.15) Ortho
C2h-5
D2h-15
C2h-5
-, perhydrotriphenylene complex
trans-
2 phtplmonomer Hex C6h-2
cis-
-, 2-propyl-
trans-
(96.17)
-3 urea complex
Hex D6-2
1,4-Poly(l,3-butadiyne)
-, 1,4-(4,4-diphenyleneglutarate)-
(330.34) Mono C2h-6
Mono C2h-6
Poly(chloroprene), see Poly(butadiene), 2-chloro-
1,12-Poly( 1,l I-dodecadiyne)
macromonomer Mono C2h-5
(160.26)
cross-polymer Mono C2h-5
5,8-Poly(5,7-dodecadiynediol)
-, 1,12-bis(N-butoxycarbonyl)methylurethane-
(508.61)
ortllo D2-3
-, 1,12-bis(ethylurethane)-
(336.43) Mono C2h-5
Mono
( hi t emp) Mono C2h-5
Mono
-, 1,12-bis(phenylurethane)-
(432.52) Mono C2h-5
Mono C2h-5
-, 1,12-bis(p-toluylsulfonyl)-
(502.64) Tti Ci -1
(1lOK) Tri Ci -1
10,13-Poly(10,12-heptacosadiynoic acid)
(as Li salt)
(400.65)
5.9 7.9
7.84 5.99
7.80 6.29
12.46 8.89
25.2 8.97
26.3 8.9
12.4 8.9
5.83 10.38
11.9 10.4
16.2 9.3
14.26 14.26
10.95 6.65
8.22 8.22
23.12 7.87
20.8 8.0
13.25 7.63
9.17 9.92
5.33 54.36 4.88
53.86 10.98 4.880
18.30 10.78
18.13 10.81
19.93 9.58
18.9 10.89
6.229 39.03
6.205 39.16
20.13 6.11
20.01 6.02
6 5 1268
4.75
9.2 y = 94
8.10 p = 92 8 1.009
8.20b 16 0.976
8.15b y = 109.5 16 1.01
8.15b 8 1.101
4 . 9 4*1/l 165
8.95 p=90 4 1.282 115 4*2/l 2 2 9
9.lb 8 1.23 110 4*2/l 7 0
4.75
4.78
9.2
11.01
9. 69 p = 111.29
9.7 0=106
14.156 y = 118.5
12.2 y = 123.5
4.89 y = 95
4.8gb y = 94
4.83 b y = 91
4.83 b y = 91
4.909 fl= 106.85
4.906 p = 106.42
4.91 95,94,89
4.91 95,94,89
4 1.025
4
4
1.06
4
1
4
4
4
4
4
2
4
2
2
2
2
2
2
1
1
1.17 135 4* l/l 165
1.079 183/1124 7 9 8
0.95
1.336 4*2/l 9 4 8
1.41 4*2/l 9 1 3
0.847
1.146
1.195
1.170
1.163
1.169
1.212
1.124
1.258
1.259
1.391
1.420
821287 4* l / l
0.906 78/630
781568
80/l 170
74/81 12.7/81 4*2/l
80/287
871568
89/l 170
0.906/53 28/81 4.40/81 8* l/l
0.910/47 36150 4.6/1195 8* l / l
141287 8* l/l
36/1169
4 2 8*1/l
421368
12* l/l
5 0 2
1195
5 0 2
4 9 2
4 9 2
4 0
2 8 8
124
1019
1019
3 6 8
8 2 7
1318
1320
1318
1320
9 5
1353
381
381
References page VI- 159
VI/ 24 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 4. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm ) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. WY kJ/mol (n *p/q) Refs.
1,4-Poly(l,3-heptadiene)
trans-
i s ot a c t i c
( 96. 17) MOIIO
-, 6.methyl-
trans-
i s ot a c t i c
(110.20)
1,4-Poly( 1,3-hexadiene)
trans-
i s ot a c t i c
(82.15) ortho
-, 5-methyl-
trans-
i s ot a c t i c
(96.17)
2,5-Poly(2,4-hexadiene)
rrans-erythro-diisotactic
( 82. 15)
-, 2,5-dimethyl-
trans-
( 110. 20)
c2-2 8. 62 7. 95 4. 85 p = 99 2 0. 973 851371 4* l / l 3 7 5
4. 85 1 1 9 4* l / l 3 7 1
D2-4 14. 02 8. 02 4. 85 4 1. 000 821371 4* l/l 2 7 4
4. 85 8 8 4* l/l 3 7 1
2 . 3 8 4 2* l / l 5 2 5
4 . 8 2 6 5
2651376
4* l / l 1 8 3
2,5-Poly(2,4-hexadienedioic acid)
trans-erythro-diisotactic
-, diisopropyl ester
(226.27) O r t h o
2,5-Poly(2,4-hexadienoic acid)
14. 16 10. 28 9. 70 4 1. 064 2301420 8* l / l 4 2 0
Ci - 1 9.67 + 10. 70 17. 79
Ci - 1 7.214 7. 245 18. 59
93,90,90 8 1. 838
104,97,96 4 1. 823
3 4 7
3 3 4
4+2/l 1 1 2 3
8*1/l 1188
1123
11. 36 9. 70 4.80
4. 80
1. 056 4* l/l
4* l/l
4* l / l
4* l/l
4* l/l
4* l/l
4* l / l
3 8 4
3 8 4
4.80 3 8 4
4.80 3 8 4
4. 80 3 8 4
4. 80
4 . 8
3 8 4
1 2 0 8
4*2/l 1 2 0 8
C2h-5 13. 03 17. 55 4.92b
C2h-5 12. 82 17. 33 4.886 t
y = 108.7
y = 108.3
C2h-5 12. 87 17. 40 4.907 b y = 108.3
2 1. 273
2 1. 316
2 1. 300
9 5 1
6 1 1
8 3 0
14. 21 20. 67 4.75 b Y = 106.8
C2h-5 4.176 15. 78 4. 703 p = 110. 34
C2h-5 4. 115 16. 05 4. 819 p = 106. 08
4.109 16. 09 4. 793 a = 106. 4
1. 258
1. 196
1. 203
C2h-5 15. 14 17. 96 4. 88 y = 98.42 4 1. 277
4* l / l
4* l/l
4* l / l
4* l/l
4* l / l
4* l / l
4* l / l
4* l / l 1 2 4 0
rrans-erythro-diisotactic
-, 6-amino-
0.5 CdCl&it Tli
(254.25) Tti
-1 -1 hydrochloride
( 163. 60)
-, butyl ester
( 168. 24) O r t h o
-3 ethyl ester
( 140. 18)
-3 isoamyl ester
( 182. 26)
-3
isobutyl ester
( 168. 24)
-3 isopropyl ester
( 154. 21)
-3 methyl ester
( 126. 16)
trans-three-diisotactic
-methyl ester
( 126. 16)
2,5-Poly(2,4-hexadiyne)
-, 1,6-di(N-carhazoyl)-
( 408. 50) Mono
Mono
Mono
-3 -, hexabromo-
Mono
2,5-Poly(2,4-hexadiynediol)
(50 nxad) Mono
( annld) Mono
(110.11) Mono
-9 1,6-bis(ethylurethane)-
( 252. 27) Mono
TABLE 4. contd
Poly(dienes) and Poly(diynes) VI/25
Polymer
Cryst
syst.
Space
vow
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. a
WY kJ/mol (n *p/q) Ref s.
-, 1,6-bis(phenylsulfonyl)-
-1 -, di-p-fluoro-
(426.41) Mono C2h-5
Mono C2h-5
Mono C2h-5
-, -, di-p-methoxy-
(450.48) Tli Ci -1
-, 1,6-bis(phenylurethane)-
I. (348.36) Tli Ci -1
(5 dioxane/unit)
II.
III.
-, 1,6-bis-(p-toluylsulfonyl)-
I. (418.48) Mono C2h-5
Mono C2h-5
Mono C2h-5
II. (120K) Mono C2h-5
-. I-@-toluylsulfonyl)-6+-fluorophenylsulfonyl)-
I. (422.44) Mono
II. (143 K) Mono
Poly(isoprene), see Poly(butadiene), L-methyl-
10, 13-Poly( 10,12-nonacosadiynoic acid)
(as Li salt) O r t h o
(428.70)
1,9-Poly( 1,8-nonadiyne)
macromonomer Mono c2-2
(118.18)
cross-polymer Mono C2h-5
l,CPoly( 1,3-octadiene)
trans-
i s ot act i c
(110.20)
2,5-Poly(2,4,6-octatriynediol)
(134.14) Mono C2h-5
-, 1,8-bis(phenylurethane)-
(372.38) Mono C2h-5
10,13-Poly( 10,12-pentacosadiynoic acid)
(as Li salt)
(372.59)
1,2-Poly( 1,3-pentadiene)
trans-
s yndi ot act i c
(68.12)
-, 4-methyl-
i s ot act i c
II. Tet
(82.15)
s yndi ot act i c
I.
II.
1,4-Poly( 1,3-pentadiene)
trans-
i s ot act i c
(68.12& oltho
ortho
cis-
i s ot act i c
Or t ho
syndiotactic
Mono
D2d-10 17.80
D2-4
19.73
19.80
D2-4 9.47
C2h-5 6.34
13.93 14.06 4.906 y = 113.3 2 1.606 4+ l / l 1378
13.89 14.10 4.91 b y = 113.2 2 1.602 4+ l/l 1379
13.96 14.10 4.914 y = 113. 56 2 1.597 4* l / l 1380
12.72 8.543 4.902 b 110,103,79 1 1.542 4* l / l 1021
16.78 12.53
14.49 14.94 4.9106 y = 118.14
14.53 14.96 4.912* y = 118.21
14.91 14.48 4.93 y = 118.0
14.93 25.56 4.910* y = 92
14.22 14.52 4.909 * y = 116.1 2 1.541 4* l/l 1337
14.10 14.43 4.906 * y = 116.3 2 1.566 4*1/l 1337
7 0 4 1.04 4* l/l 1268
7.88
9.30
8.11 4.89
5.67 21.OOb
17.5 4.85
y = 90.8 4
p= 101. 71 4
0.837 9*2/l 1023
1.016 9*2/l 1023
4.85 87 371
4.11
24.65
19.59 4.80 p= 109 2
30.74 4.89 p=92.2 8
1.219 7 8 0
1.336
4*1/l
4* l/l
4*1/l 7 8 0
6 0 1268
5.1 10 4% l/l 2 3 0
17.80 36.50
11.73
5.05
7 2 0.849 1671707 2 * 18/5 4 8 8
12* l/l
4* l / l
1502
1502
4.85 4.8
4.86 4.85
5.97 8.15
8.15
0.98 95 4* l / l 189
0.969 104/l 126 4*1/l 2 0 0
0.982 8 4 4
263
9.12 8.50
8.50
4
4
4
a = 105.9 4 0.957
4*2/l
44 4*2/l
8*1/l
53 8*1/l
1431
2 3 4
4.89 * 84,83,69
4.9
4.9
4.9
2 1.340 4* l / l
4* l/l
4* l/l
7 1 6
7 4 9
7 4 9
7 4 9
1.482 102/1020 35/1020 4t l / l 8 9 8
1.477 4*1/l 1277
1.479 4* l / l 1381
1.484 4* l / l 8 9 9
References page VI- 159
VI /26 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 4. contd
Polymer
tryst
syst.
Space
group
Unit cell parameters Density (gkm3) Melting Heat of Chain
point fusion conform.
a b c Angles Z crystal. Amorph. WY kJ /mol a (n *p/q) Refs.
-, 2-methyl-
trans-
i sot act i c
CRT)
(82.15)
(153K)
cis-
i s ot act i c
a (- 130)
B CRT)
Mono C2h-5
Mono C2h-5
ottho D2h-15
OtiO D2-4
-, 3-methyl-
cis-
i s ot act i c
(82.15) I.
m.
s yndi ot act i c
II.
1,4-Poly(l,3pentadiynol)
-, 1-N-carbazoly-
(245.28) Mono C2h-5
2,5-Poly(5-phenyl-2,4-pentadienoic acid)
rrans-etytbro-diisotactic
-, butyl ester
(230.31)
-methyl ester
(188.23)
1,24-Poly(l,l1,13,23-tetracostetrayne)
cross-polymer Mono C2h-4
(322.54)
12.89 9.186
12.78 9.084
10.74
9.30
13.04
7.73
4.820b p=93.5
4.824b p = 93.6
7.87
7.90
0.958 195/1365 4* l/l
0.977 4* l / l
0.990 175 4*2/l
0.96 1 165 4*2/l
16511365
8.02
6.97
8.6
*2/l
*3/l
8* l/l
16.49 19.51 4.873 b y = 124.27 4 1.257 4* l/l 1354
4.80 4* l/l
4*1/l
1.136
384
4.80 384
26.8 * 8.254 4. 91 * y = 119.6 2
a The number after the solidus (/) are reference citations.
b The unit cell parameter assignment has been changed from that published so as to make c the fiber axis
TABLE 5. POLY(PEPTIDES) gNH-CHR-CO)-
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm ) Melting Heat of Chain
point fusion conform.
a b c Angles Z Crystal. Amorph. a WY kJ /mol 0 (n *p/q) Refs.
Poly(L-alanine)
u helix hex 8.55
(71.08)
P
OlthO 4.79
Ortho 4.734
-, phenyl-
a helix Hex 11.55
(147.18)
o helix Tet 11.28
Tet 12.86
Poly(P-alanine), see Poly(3-aminopropionic acid)
Poly(L-afanyt-D-alany]-L-afanykJ-vabne)
(312.37) OtThO 9.5
Poly(L-alanyl-L-alanylglycine)
(200.22) Ch t h o 9.44
-phenyl- [2nd alanyl]
(275.31)
Poly(L-alanyl-L-alanylglycyl-L-prolyl-L-p~lylglycine)
(450.49) Ortho 10.5
Poly(L-alanyl-u-alanyl-L-valyl-u-valine)
(340.42) O&O 9.5
8.55 70.3 4 7 1.246 3*47/13 507
10.7 6.88 4 1.339 3*2/l 507
10.54 6.89 4 1.373 3*2/l 509
11.55 3 * 18/5 1025
11.28 5.91 4 1.300 3*4/l 1024
12.86 5.59 4 1.057 3*4/l 1025
31.0 11.0
9.96 20.94 b
8 1.281 12* l / l 1046
8 1.351 9*2/l 7 5 3
15 9* 7 7 4
29.5 18* 755
34.1 11.0 8 1.269 12* l / l 1046
Poly(peptides) V I
I27
TABLE 5. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (gkm3) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es z Cryst al . Amorph. a
WY
kJ/mol a (n *p/q) Refs.
Poly(L-alanyl-4-aminobutyric acid)
(156.18) Ortho
Poly(L-alanyl-6-aminocaproic acid)
(184.24) Or t ho
Poly(L-alanyl-3-aminopropionic acid)
(142.16) Or t ho
Poly(L-alanyl-1 1-aminoundecanoic acid)
(254.37) Or t ho D2-5
Poly(L-alanyl-5-aminovaleric acid)
(170.21) Ortho
Poly(L-alanyl-L-glutamylglycine)
y- et hyl - -3
(285.30) Mono
Poly(L-alanylglycine)
I. (128.13) Ortho
Or t ho
II. Or t ho
9.4 9.9 9.2 4 1.21
9.4 9.8 11.56 4 1.16
9.4 9.8 16.1b 8 1.21
4.19 10.35 29.8 4 1.144
9.4 10.7 20.7 * 8 1.09
.
9.54 8.54 21.36 ~=I06 4 1.133
9.42 8.87 6.95 b 4 1.466
9.44 8.96 6.94 4 1.450
4.72 14.4 9.6 4 1.30
Poly(L-a1anylg1ycyl-L-alanylglycyl-L-alanylglycyl-L-alanylglycyl-~-alanylglycyl-~-al~ylglycyl-~-glut~ylglycine)
(990.98) Or t ho 9.64 9.62 48.65 4 1.459
Poly(L-alanylglycyl-~-alanylg1yclyl-L-al~ylglycyl-~-alanylg1ycyl-~-al~ylglycyl-~-glutamylglycine)
(850.84) Or t ho 9.57 9.70 41.70 4
Poly(~-alanylglycy1-~-a1anylglycyl-L-alaylglycyl-~-alany1glycyl-L-glutamylglycine)
(710.70) ortho 9.48 10.28 34.15
Poly(L-alanylglycyl-L-alanylglycyl-~-alanylglycyl-L-g1ut~y1glycine)
I. (570.56) Or t ho 9.48
II. Ortho 9.48
Poly(L-a1anylglycyl-L-alanylglycy1-L-serylglycine)
(400.39) Or t ho 9.39
Poly(~-alany1glycyl-L-alanyl-~-pro1yglycyl-L-proline)
(450.49) ortho 10.5
Poly(L-alanylglycylglycine)
II. (185.18) Mono 8.86
(monohydrate) Mono c2-2 11.0
Poly(L-alanylglycylglycylglycine)
Il. (242.24) Hex 4.89
Poly(L-alanylglycyl-L-proline)
dry
Hex 11.9
wet Hex 11.4
(225.25)
Poly(~-alanylglycyl-L-prolyl-~-prolyglycy1-L-proline)
(476.53) Or t ho 10.6
Poly(L-alanyl-L-prolyglycine)
with Hz0 Mono c2-2 8.6
(225.25)
Poly(~-alanyl-~-prolylglycyl-~-prolyl-~-prolylglycine)
(476.53) Hex 11.9
Poly(L-alanyl-D-valine)
(170.21) Por t 9.1
Or t ho 9.5
Poly(2-aminoisobutyric acid)
(85.11) Hex 8.1
-, dichloroacetic acid complex
(106.60) Hex C3v-6 21.8
(1 DCA/6 residues)
Poly(L-arginine)
-, hydrochloride
a h e l i x Hex 14.7
(2.5 H*O/residue)
(192.65)
P
Mono 9.26
(>5 HgO/residue)
17.34 18.8
10.60 27.80
9.05 20.55 b
29.5
4 1.226
4 1.356
42* l/l
36* l/l
30* l/l
24* l/l
24% l/l
1633
1648
4 1.522 18* 1 5 4
18* 155
22.0 9.42
4.8 9.45
4.89 36.60
11.9 28.8
11.4 9.3
28.7
p=90 9 1.507 9*1/l 596
p=90 2 1.35 9* l / l 7 4 0
3 1.592 12*3/l 7 4 0
10 1.06 9 * 10/3 6 1 4
3 1.07 9*3/l 614
18* 155
1.2 9.4
11.9 29.5
14.7 6.2
29.4 11.1
8.7 5.96
21.8 5.95
p=90 2 1.4 9*1/l 6 1 6
5 1.093 18* 155
4 1.28 6* l/l 1176
16 1.459? 6*2/l 1046
3 1.08 9 6 7
18 1.301
3*3/l
3*3/l 1053
14.7 27.0 18 1.406 3* 18/ 641
22.05 6.76 7=108.9 4 1.438 3*2/l 641
4
1.460
1.394
8* l / l
lO* l / l
1*2/l 9 6 9
15*2/l 1619
9*2/l 9 6 9
9*2/l 7 5 6
6* l/l 591
6*1/l 7 5 4
6*2/l 741
9 6 9
9 6 9
1648
1648
1648
References page VI-159
VI/28 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 5. contd
Polymer
tryst
syst.
Space
group
Unit cell parameters Densi ty (g/cm 3, Melting Heat of Chai n
poi nt f us i on conf orm.
a b E Angl es 2 CQd2d. Amorph. WY kJ/mol a (II *p/q) Refs.
Poly(L-aspartic acid)
-, l%enzyl-
o helix
(205.21)
racemic
-9 -3 p-chloro-
c( helix
(239.66)
w helix
-9 -, p-methyl-
c( helix
(219.24)
w helix
-, a-n-butyl-
I. (171.20)
II.
-, u-ethyl-
- , -, 2-methoxy-
(173.17)
-, b- et hyl -
- . -9 2-phenyl-
c( helix
(219.24)
P
x helix
>2OOC
?
-7 u-isobutyl-
I. (171.20)
II.
-, p-n-propyl
P
(157.17)
-9 -3 3-phenyl-
(232.26)
(at 140C)
Poly(L-cysteine)
13.85 13.85 5.30
13.80 13.80 5.42
13.88 13.88 5.3
21.4 4.28 5.68
14.9 14.9 27.0
14.8 14.8 2 7
23.3 23.3 5.20
16.4 13.4 5.2 y=99
14.9 14.9 2 7
16.6 13.4 5.28 y=108
13.5 13.5 19.9
13.45 13.45 20.6 y=120
14.15 14.15 4.90
Tet
Tet
Tet
OtThO
4 1.341 3*4/l 582
4 1.320 3*4/ l 703
4 1.34 3*4/l 837
2 1.310 3*2/ l 1026
Hex
Hex
Tet
Mono
D6-3
D4-4
18 1.380 3*18/5 6 0 6
4 1.40 3* 1815 1505
8 1.128 3*4/l 6 0 6
18 1.41 3*4/l 1505
Hex 4 1. 26 3 * 1815 1505
Mono 4 1.304 3*4/l 1505
Hex
Phex
Tet
c2-2
C4-2
13 1.177 4* 13/4 1507
13 1.145 4* 1314 1508
4 1.338 4*4/l 1508
Phex cz-2 12.40 12.40 20.74 r=120 13 1.354 4L 1314 1508
Tet 13.2 13.2 27.0 18 1.393 3 * 18/5 1027
ortho 17.7 4.76 6.83
OIlhO 20.3 11.7 19.89
Hex 17.1 17.1 19.89
Hex 23.4 23.4
2 1.265
17 1.310
17 1.229
3*2/ l 1027
3 * 1714 1028
3 * 1714 1028
1027
OtthO 13.5 23.4 19.9 2 6 1.176
Hex 13.5 13.5 19.9 13 1.177
Tet 14.0 14.0 4.95 4 1.172
Tet 13.98 13.98 4.94 4 1.178
Mono c2-2 9.57 25.08 6.79b -, 8 1.288
286/1310 4* 1314 1312
4 * 1314 1506
4*4/l 1312
4*4/l 1506
3*2/ l 5 7 9
Hex 15.6 15.6 10.5 7 1.220 3*7/2 1628
OFthO 28.0 16.1 10.5 14 1.141 3*7/2 1628
4.76 32.4 6.95 b
4.89 32.8 6.89 b
14.28 14.28 5.55
4 1.470 3*2/l 5 7 8
4 1.426 3*2/l 5 7 8
4 1.322 3*4/ l 1029
27.5 27.5 27.0 5 6 1.232 3 * 1815 7 2 0
C4-2
-, s-benzyloxycarbonyl-
P
I. Oh0
(237.27)
II. Ortho
-,
s-benzylthio-
w helix Tet
(225.32)
Poly(2,4-diaminobutyric acid)
-, N-benzyloxycarbonyl-
(234.26) RhO
POly(D-ghtaIIIiC acid)
-, y-benzyl-
-, -> chloro-
meta
(253.68)
ortho
para
Phex
Phex
Ortho
Hex
15.30 15.30 26.99 r=60.23 1 8 1.382 3* 1815 9 3 2
15.07 15.07 27.15 y=60.03 18 1.420 3L 18/5 9 3 2
15.24 26.40 10.68 14 1.372 3*7/2 9 3 2
15.24 15.24 10.67 7 1.374 3*7/2 1033
Poly(peptides) V I I29
TABLE 5. contd
Polymer
Clyst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c AIlgkS 2 crystal. Amorph. y
WY kJ/mol (n *p/q) Ref s.
-, y-n-hexyl-
CL helix He x
(213.27)
-, y-methyl-
a hel i x He x
(143.14)
P ortho
Poly@-glutamic acid)
P
I . M o n o
(129.12) M o n o
I I . M o n o
Ortho
-, y-n-amyl-
(199.25) He x
He x
-, y-benzyl-
(x helix
A. M o n o
(219.24) He x
B. Tti
M o n o
M o n o
(dry) Ortho
M o n o
C. He x
( racemi c) He x
M o n o
He x
D. He x
E . He x
single crystal M o n o
racemic mixture
15.89 15.89 27 1 8 1.08 3* 18/5 8 5 9
12. 0 12. 0 3 * IS/5 1 1 6 2
9.49 19.09 7.07
9.44 23.31 6.81
8 1.484 3*2/l 9 5 4
8 1.266 8 1 2 y=90
9.66 9.10 6.98 b
9.79 9.35 6.82b
9.75 8.06 6.84b
4.95 15. 6 6 . 9 0
y=105
y=105
y=104
1.447 3*2/l 5 8 5
1.422 3*2/l 9 6 6
1.644 3*2/l 9 6 6
1.610 3*2/l 8 3 6
15. 1 15. 1 (27) 1 8 1.12 3*18/5 1 0 4 0
1 5 1 5 21 1 8 1.13 3 * 1815 1279
15. 3 14. 6
3 0 3 0
15.25 15.25 27. 0
25. 2 15. 0 26. 8
15.88 13.00 27. 1
14.76 2 5 . 4 0 64.11
29.06 13.20 27.27
14.95 14.95 27. 1
14.95 14.95 106
15.05 14.78 27
14. 8 14. 8 10.50
39.05 39.05 10.58
6 4 . 3 6 6 4 . 3 6 10. 5
5.52 5.11 22.25
y= 121. 7
84,84,122
y= 122. 5
y= 113. 7
/3=96
y=56
y = 119. 4
3 * 1815 1 0 3 0
3 * 1815 9 5 2
3 * 1815 5 8 7
3 * 18/5 7 0 2
3 * 1815 9 5 2
*43/12 157
3 * 1815 1 0 3 0
3 * 1815 5 8 4
*71/20 5 8 4
3 *: 18/5 1 0 3 0
3a7/2 1 0 3 0
3*7/ 9 5 3
3*7/2 1 0 3 0
9 2 6
7 2
1 8
3 0
1 8
8 6
3 6
1 8
7 1
1 8
1.257
1.278
1.279
1.303
1.260
1.305
1.260
1.252
1.279
1.277
1.285
1.171
4 9
/3=97.8
I . Ol TbO 24. 4 15. 4
I I . M o n o 25. 6 15. 6
-3 -, chloro-
meta
( racemi c)
(253.68)
o r t h o
( racemi c)
pCllTl
( racemi c)
-, y-n-butyl-
(185.22)
(at 100C)
-, y-calcium
P (wet)
-, y-n-dodecyl-
(29744)
-, y-ethyl-
a hel i x
I .
(157.17)
He x 15.50 15.50 27.10 1 8 1.345 3 * 18/5 1 0 3 2
He x 15.49 15.49 26.84 1 8 1.360 3 * 1815 1035
ortho 2 6 . 5 0 30.60 27.02 7 2 1.384 3 * 1815 1 0 3 2
He x 15.24 15.24 27.23 1 8 1.384 3 * 1815 1 0 3 4
ortho 15.24 2 6 . 4 0 10.67 1 4 1.374 3*7/2 1 0 3 2
Ortho 15.12 26.09 10.72 1 4 1.394 3*7/2 9 3 2
Phex
Ortho
14. 1 14. 1
(27)
25. 4 14.66 27
M o n o c2-2 9.40 12.82 6.83 b y = 100. 3 5 8 5
He x 27. 6 27. 6
Phex
Phex
T.
I I I .
H.
Tet
Phex
ortho
12. 5 12. 5 27. 0
12.16 12.16 108.9
16. 4
11.72 11.72 108.9
12. 9 12. 9 108. 9
22.95 13.25 108.9
-> -3 2-chloro-
(191.61)
-3 -3 2-phenyl-
(233.27)
Phex 11. 7 11. 7 16.56 Y= 118. 7 1 1 1.760 3* 11/3 1 0 3 6
He x 15.60 15.60 (27)
ortho 15.38 26.65 54. 4
1031
1 0 3 1 Y = 107. 7
r=114 1 8 1.13 3 * 18/5 1 0 4 0
3 6 1.101 3 * 18/5 1 0 4 0
y= 1 1 0 1 8 1.18
y = 109. 5 7 3 1.255
y=123
7 3
7 3
1.274
1.25
1.151
3*18/5 8 2 6
.I3120 9 5 5
3*11/3 1 0 3 6
3 * 73120 9 5 5
3 * 73120 9 5 5
3 * 73120 9 5 5
1.225
1.251
3 * 1815 1038
3* 1815 1 0 3 9
References page VI- 159
7 2
VI/30 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 5. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm j) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b e Angl es Z Cryst al . Amorph.
WY
kJ/mol u (n *p/q) Refs.
-, y-n-hexyl-
( 213. 28)
-, y-methyl-
c( helix
( 143. 14)
Hex
Hex
Hex
Hex 11. 95
Hex
OtthO
Hex
Hex
precursor to cz (3 chloroform08 men)
Hex
Hex
(at 170C) Rho
P
O r t h o
-, -3 dimethyl phthalate complex
25% Hex
extracted Phex
-3 y-n-octyl-
(241.33) Hex
-, y-n-propyl-
(171.20) Phex
(at 150C) ortbo
Rho
-3 -9 3-phenyl-
( 247. 29)
-, y-sodium
tl helix
(hydrated)
P (wet)
Poly(L-glutamine)
Hex
Hex
P o r t
-1 AS-(4.hydroxybutyl)-
(200.24) O r t h o
-> N5-(2-hydroxyethyl)-
(172.18) Pt et
-, NS-(3-hydroxypropyl)-
( 186. 21) O r t h o
Poly(o-glutamyl+glutamic acid)
1 5 . 8 1 5 . 8 2 7 1 8 1. 09 3 + 1815 1040
1 5 . 5 1 5 . 5 2 7 1 8 1. 14 3 * 1815 1279
11. 96 11. 96
11. 95 2 7 . 0
11. 79 11. 79
2 7 . 5
11. 95 20. 70
11. 82 11. 82
11. 58 11. 58
2 6 . 9
97. 26
4 3 . 2
103. 0
26. 33
1 8 1. 256 3 * 18/5 5 8 8
1 8 1. 281 3 * 18/5 5 7 6
1 8 1. 321 3 * 18/5 8 5 8
6 5 (1.284) t 65118 5 8 3
5 8 1. 290 3 * 2918 5 8 9
6 9 1. 316 *69/19 1204
1 8 1. 399 3 * 1815 1650
12. 75
12. 75
21. 27
4. 725
4. 70
12. 75
12. 75
21. 27
1 8
1 8
1. 282
1. 287
1. 210
2 1
2 7 . 0
2 6 . 9
176. 0
6. 83
6. 83 4 1. 410
3 * 1815 1293
3 * 18/5 1338
117132 1204
3*2/l 7 0 2
3*2/l 1037
2 7 . 6 2 7 . 6
2 3 . 9 2 4 . 9 2 7 y= 121.4
7 2
7 2 1. 248
3*18/5 1041
3*18/5 1041
1 7 . 1 1 7 . 1 2 7 1 8 1. 06 3 * IS/S 1279
1 4 . 4 1 4 . 4
( 27)
2 4 . 6 1 4 . 2 6 0 . 0
2 4 . 3 2 4 . 3 6 0 . 0
y=130 1 8 1. 19 3*18/5 1 0 4 0
8 0 1. 085 *40/11 1 0 4 0
1 2 0 1. 112 *40/11 1533
16. 30 16. 30
(27)
1 8 1. 190 3 * 18/5 1038
1 5 . 9 1 5 . 9 7 9 4
1 4 . 4 7.0* 4.7 7 9 4
1 4 . 8 1 2 . 4 6 0 . 4 4 0 1. 200 3*40/11 9 3 5
1 2 . 1 1 2 . 1 2 7 1 8 1. 30 3 -c 18/S 9 6 8
1 4 . 6 1 2 . 3 43.2 2 9 1. 156 3 * 2918 9 2 4
1 5 . 2 1 5 . 2
1 4 . 9 1 4 . 9
26.0 2 6 . 0
2 2 . 9 2 2 . 9
9. 52 2 2 . 5
2 7 1 5 . 8
26. 92 15. 54
2 7 . 1 1 5 . 5
1 7 . 0 1 7 . 0
1 7 . 0 1 7 . 0
1 8 . 2 1 8 . 2
2 2 . 6 2 2 . 6
2 5 . 3 2 4 . 4
2 6 . 4 2 5 . 6
2 8 1 9 1. 235 3 * 19/s
2 6 . 6 1 8 1. 281 6*9/5
3 2 . 4 6 6 1. 267 6* 1116
9. 46 1 6 1. 356 6~ l/l
5. 40
5. 40
2 5 . 6
2 5 . 6
5 6 . 3
5 3 . 1
2 0 . 2
5 0 . 0
y=117
y=llS
y=66
8
8
2 2
2 2
5 6
7 2
3 6
1. 289 6*2/l
1. 284 6*2/l
1. 250 6* 1115
1. 250 6* 1115
1. 262 6 * 1415
1. 116 6 * 1815
1. 180 6*9/2
1. 318 6 * 2715
8 8 5
1042
1272
1042
1215
8 8 5
1042
1272
8 8 5
1272
1214
1 2 1 4
1214
1 2 1 4
Hex 1 5 . 9 1 5 . 9 2 6 . 5
Hex 2 7 . 5 2 7 . 5 3 2 . 4
Hex 2 4 . 2 2 4 . 2 4. 75
Hex 1 7 . 6 1 7 . 6 2 5 . 7
1 8 1. 204 6*9/5 1042
6 6 1. 205 6* 1116 1272
8 1. 286 6+ l/l 1042
2 2 1. 236 6* 1115 1272
4. 77 4. 77
9. 54 3. 67
7.0
7. 0446 y=113
2 1. 30 3651795 3*2/l 5 8 1
4 1. 669 3*2/l 1239
-, y-benzyl-
c( helix
(219.24)
P
o helix
x helix
n-n 5.6
n--x 7.2
x--x 9.0
n-n 10.8
-, y-ethyl-
- , -1 2-phenyl-
(x helix
( 233. 27)
P
x helix
Poly(glycine)
I. (57.05)
Hex
Hex
Hex
Hex
O r t h o
O r t h o
Hex
Hex
Hex
Hex
Mono
Mono
Mono C2h-5
TABLE 5. contd
Poly(peptides) VI/31
Polymer
tryst
syst.
Unit cell parameters Density Wm3) Melting Heat of Chain
point fusion conform.
a b c Angl e Z CQ@d. Amorph. a
WY
kJ /mol (II *p/q) Refs.
4.8 9.3 3 1.53 3*3/l 2 7 3
4.79 35.1
3.96
4. 79 112. 8
15.20 16.95 b 16 1.389
4.79 22.2 3 1.447
II. Hex C3-2 4.8
Poly(glycyl-6aminocaproic acid)
I. (170.21) Hex 4.79
II. Mono 4.76
Poly(glycyl-1Zaminododecanoic acid)
II. (254.37) Hex 4.79
Poly(glycyl-3-aminopropionic acid)
I. (128.13) Or t ho 9.51
II. Hex 4.79
Poly(glycyl-3aminopropionic acid-3aminopropionic acid)
(199.21) Hex 4.79
Poly(glycyl-1 I-aminoundecanoic acid)
I. (240.35) OtthO 9.60
II. Hex 4.79
Poly(glycylglycyl-L-proline)
with Hz0 Mono cz-2 12.2
w/formic acid Mono c2-2 13.5
(211.22)
Poly(glycylprolylhydroxyproline)
(267.28) Hex
4.79 35.2 3 1.419 11*3/4 1313
37.5 b 15*2/l 1391
4.79 15* 1391
4.9 9.3
4.9 9.3
Poly(glycyl-L-prolyl-L-proline)
dry
Hex
(251.29)
-, a-phenyl-(glycyl)
(327.38) OlthO
Poly(L-histidine)
-, l-benzyl-
(227.27) Phex
-, hydrochloride
( 1 H rO/residue) Mono
(190.61)
Poly(L-isoleucine)
B
Ch t h o
(113.16) Ortho
Poly(L-leucine)
a helix Hex
(113.16)
P
Ortho
Poly(L-lysine)
c( helix Hex
(128.18)
P
O&l0
-, E-benzyloxycarbonyl-
u helix Hex
(262.31)
-, hydrobromide
(1.4 HzO/residue) Ortho
(234.31)
-, hydrochloride
CL helix Hex
> 84% RH
(164.64)
B dry
Ortho
65% RH Oh0
Poly(L-lysyl-L-lysyl-L-valine)
LX helix Hex
(355.48)
P
ortho
(with 2HCl)
-, di-benzyloxycarbonyl-
P
ottbo
(623.75)
13.7 13.7 28.2
12.5 12.5 28.7
D2-4 14.3 13.5 9.4
17.4 17.4 27.0
14.95 14.95 45.0
4.80 22.36 6.88
4.8 23 6.6
13.22 13.22
4.80 23.56 6.88
19.55 19.55
9.44 17.16 6.8b
16.69 16.69 26.90
D2-3 9.52 16.44 6.80
16.80 16.80
4.62 15.20 6.66
4.71 16.67 6.66
15.87 15.87
9.35 15.04 20.88
9.38 28.24 20.22
3
p=113
6
1.216 27611524 10 *3/l 1311
1311
1.131 230/1524 6*16/l
7*2/l
7*3/l
1512
1294
1294
p=90 2
p=94 2
1.4 9*1/l 6 1 5
9*1/l 6 1 5
10
10
0.97 9*10/ 6 1 2
1.07 9*10/ 6 1 3
4 1.198 9* l / l 9 6 5
y=130 18
y=116.5 4 5
1.085
1.582
3* 18/5 7 1 9
3 * 1514 1295
4 1.018
4 1.032
4
6 1.16
18 1.208
3*2/l 8 0 6
3*2/l 1025
3* 8 0 6
3*2/l 806
3* 5 8 6
3*2/l 5 8 6
3* 18/5 517
4 1.46 3*2/l 9 2 3
6 6 6
4 2.338 6 6 6
4 6 6 6
9* 1047
9*2/l 1047 4 0.969
8 1.547 9*2/l 1048
References page VI- 159
VI/32 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 5. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
la b c Angl es Z C@d. Amorph. (cja kJ/mol (n *p/q) Refs.
Poly(I.-methionine)
IX helix Hex
(131.19)
Poly(D-methionyl-L-methionine)
P
Mono
(131.19)
Poly(L-omithine)
-, N-benzoyl-
c( helix HEX
(218.26)
11.49 11.49 70.5 4 7 1.270 3 *47/13 867
18.05 4.71 14.66b /3= 110.4 8 1.492 6*2/l 850
15.0 15.0 26.5 18 1.263 3 * 18/5 1373
-, -,p-bromo-
m helix
8297.15 *
Or t ho D2-4 24.6 18.4 5.68 8 1.535 3*4/l 1373
-1 -1 p-chloro-
o helix
(252.70)
Or t ho D2-4 24.1 18.5 5.68 8 1.326 3*4/l 1373
-1 -, p-fluoro-
w helix
(236.25)
Or t ho D2-4 23.8 18.7 5.68 8 1.241 3*4/l 1373
-, N-benzyloxycarbonyl-
I. (248.28) Mono
Phex
Hex
II. Or t ho
Tet
III. Or t ho
-, hydrobromide
c( helix Hex
(>86% RH)
P (wet) Or t ho
(to 85% RH)
Poly(L-proline)
I. (97.12) Hex
II. Rho
RbO
Rho
23.3 22.7 16.2 y=119.2 2 2 1.213 3*11/3 7 2 0
23.0 22.6 (16) y=119.5 2 2 1.238 3*11/3 1043
22.8 22.8 16.4 2 2 1.228 3*11/3 1296
29.40 14.70 27.0 3 6 1.272 3 * 1815 1043
20.8 20.8 60.00 8 0 1.270 3*40/l 1296
22.09 19.95 60.00 8 0 1.247 3*40/l 1296
15.0 784
4.60 30.2 6.64 8 3*2/l 784
-, acid complexes
-, acetic Tet
-, formic Tet
-, propionic Tet
highly solvated Ortho
-, hydroxy-
A. (113.12) Hex
B. >66% RH Phex
-> -, O-acetyl-
II. (155.15) Hex
Poly(L-serine)
-, O-acetyl-
P
Or t ho
(129.12)
Poly(L-tyrosine)
-, O-benzyloxycarbonyl-
(297.31) Mono
Poly(L-valine)
t( helix Hex
(99.13)
P
Or t ho
Or t ho
c2-2 9.05
c3-3 6.62
c3-3 6.62
c3-3 6.68
9.13
8.92
9.13
9.00
9.05 19.0 10 1.197 3 * 10/3 5 9 0
6.62 9.36 3 1.362 3*3/l 5 1 0
6.62 9.31 3 1.369 3*3/l 5 1 2
6.68 9.36 3 1.338 3*3/l 511
9.13 19.0
8.92 19.0
9.13 19.0
25.1 19.0
10
10
10
3 * 1013 701
3 * 10/3 701
3 * 10/3 701
701
c3-3 12.3 12.3 9.15 9
15.75 15.75 22.88 y = 120.47
1.410
11.4 11.4 9.3 6 1.48
3* 5 8 0
3 * 813 1044
3*3/l 737
9.7 1 6.48 9.6b 3 1.065 3*3/l 7 0 6
18.0 1.20 3*11/3 849
11.43 0.970
4.79
D2-4 4.80
18.0 16.5 y=l22 1 1
11.43 ( 2 7 ) 18
19.00 6.88 4
19.14 6.59 4
1.052
1.088
3 * 18/5 1025
3*2/l 806
3*2/l 1045
a The number after the solidus (/) are reference citations.
b The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
Poly(amides) VI /33
TABLE 6. POLY(AMIDES) (-NH-X-NH-CO-Y-CO- or -NH-X-CO-) see al so POLY(PEPTIDES)
Unit cell parameters Densi ty (g/ cm ) Melting Heat of Chai n
Cryst Space poi nt f us i on conf orm.
Polymer syst.
group
a b c Angl es Z Cryst al . Amorph. a WY kJ/mol a (n *p/q) Refs.
Poly(2-aminoacetic aci d) , see Pol ygl yci ne
Poly@-aminobenzoic acid)
(119.12) ortho D2-4
Ortho D2-4
Ortho D2-4
Poly(3-amino-2.butenoic acid)
i rrad. i n vacuum
(83.09) M o n o
irrad. in air
M o n o
Poly(3-aminobutyric acid)
(85.11) Ortho
Poly(Caminobutyric acid)
a M o n o
(85.11) M o n o c2-2
M o n o
P
M o n o
6 Hex
-, 4-benzyloxycarbonyl-(L)
I. (219.24) M o n o
11. Hex
-, 4-methyloxycarbonyl-(L)
(143.14) He x
Poly( IO-aminocapric acid)
cl Tli
(169.27)
Y
Phex C2h-5
Hex
Poly(6-aminocaproic acid) [caprolactam]
7.71 5.14 12. 9 4 1.548 5501735 6*2/l 8 1 1
7.71 5 . 1 4 12. 8 4 1.560 6*2/l 9 0 2
7.75 5 . 3 0 12.87 4 1.497 6*2/l 1 4 3 4
19.11 8.54 10.665 p = 97. 6 4* 1 5 3 0
21.90 10.13 12.461 R = 96. 8 4t 1 5 3 0
10. 9 9 . 6 4 . 6 4 1.17 3 3 0 4* l/l 5 0 3
9 . 4 4 8.22 12.lb
9.29 7.97 12.24b
9.79 8.31 12.25
12.24
4.65 4.65
y=116 8 1.340
y=114.5 8 1.375
r=117 8 1.273
2601337 5*2/l
2601244 5*2/l
5*2/l
5*2/l
2 7 2
4 5 7
1 5 0 9
4 5 8
4 5 8
9.62 19.30 12.30
13.14 13.14 10. 0
/3=71.1 8 1.35 5*2/l 1 3 5 9
5 1.22 5*5/2 1 3 5 9
10.90 10.90 10. 0 5 1.16 5t5/2 1 3 5 9
9.80 5.12 27.54 54,90,110 4 1.110 11*2/l 1 2 3 7
4.78 9.56 26. 9
4 . 9 4 . 9 26. 5
y= 1 2 0 4 1.056 1881337 11*2/l 9 7 1
2 1.02 1771146 11*2/l 6 1
9.56 8.01 17.24b y=67.5 8 1.232
4.81 7.61 17.10b y = 79. 5 4 1.221
9.65 8.11 17.2b y = 66. 3 8 1.220
9.45 8.02 17.08 y=68 8 1.252
9.66 8.32 17. 0 y=65 8 1.214
4.77 4 . 0 6 17.25 y=66.5 2 1.224
9.71 8.19 17.40 y=115 8 1.199
1.09/839 2 1 5
2231153
2231244
2261293
214/304
2721839
260/1051
0.917 2281346
1.114 2501532
1.10
y=120
q/=121
4 . 8 4 . 8 8. 6
4.85 4.85 8. 4
9.35 4.81 16.606
9.33 4.78 16.886
4.79 4 . 7 9 16. 7
4.82 7.82 16.70
9 . 1 4 4 . 8 4 16.68
4.83 7.83 16.68
4 . 9 0 16.28 8.22
4 . 8 6 4.65 16.87
20.8/155 7*2/l 3
18.1/216 7*2/l 2 6
23.0/405 7 *2/l 1 3 5
21.61343 7*2/l 2 1 2
26/1121 7*2/l 3 3 4
19.41839 7 *2/l 8 9 1
27/1050 7*2/l 1 0 4 9
27. 3 1 0 5 0
24.11697 4 4 9
18.51534 2 1 3
7*1/l 2 2 2
7*1/l 1 0 5 2
1X6/839 7 *2/l 3 3 6
27/1050 7 *2/l 2 4 6
7*2/l 2 7 2
7*2/l 2 7 9
7*2/l 6 9 7
7*2/l 6 9 7
7*1/l 2 6
7*2/l 8 9 1
1.09/839 2721839
y= 121
y=60
1.250
1.23
1.10
1.10
1.162
1.165
1.132
1.194
1.188
1.191
1.146
1.138
9.13 17. 9 16.2b y = 59. 7 1 5 1 0
M o n o c2-2 9.15 4 . 8 4 16.96 b y=90
Poly(6-aminocaproic acid-&l 1-aminoundecanoic acid)
(296.46) 22. 5
Poly(6-aminocaproyl-5-aminovaleryl-3-aminopropionic acid)
(297.40) Tli 4 . 9 10. 7 21. 6 51.77.62
Poly(8-aminocaprylic acid)
Lx M o n o c2-2 9. 8 8. 3 22.4b y= 115
(141.21)
1
1
4
4
2
4
4
4
4
2
4
2
8
1.125 225119 7*2/l
226136
440
1 8 4 19* l/l 7 1 4
1.28 18* l/l 1 4 3 7
1.14
1.18
185/146 30/l 195 9 *2/l
2 0 2
2001244
218/838
2 7 2
1 5 3
CI
(113.16)
M o n o
M o n o
M o n o
M o n o
M o n o
M o n o
M o n o
c2-2
c2-2
c2-2
c2-2
He x
He x
M o n o
M o n o
He x
Ortho
M o n o
Ortho
RhO
M o n o
C2h-5
C2h-5
M o n o C2h-5
Or c2-2
P
Y
>15OC
-, complex with I2
-3 D-(-)-3-methyl-
(127.19)
References page VI- 159
VI/34 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 6. contd
Polymer
Cryst
syst.
Spa-
FOP
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
0 b c Angl es Z cry&II. Amorph. a
WY
kJ/mol (n * p / q ) Refs.
P
Mono
Y Hex
Hex
Phex C2h-5
Poly(2-aminocyclopentylenecarboxy acid)
(111.14)
Poly(7-aminoenanthic acid)
(127.19) Tli Cl-l
Tli Ci- 1
4.79
4.9
4.77
8.25
9.8
4.9
-, (R)-3-methyl-
(141.21)
-, @)-l-methyl-
(141.21)
-, (R)-%methyl-
(141.21)
-, (R)-6-methyl-
(141.21)
Poly(aminoformic acid)
-, Nbutyl-
(99.13) Phex 13.3
Poly(2aminoisobutyric acid), see Poly(peptide) Section
Poly(l2-aminolauric acid)
Y
Hex
(197.32) Hex
Phex C2h-5
Mono
Mono
Mono
formed during planar extrusion
Tri
Poly(9-aminopelargonic acid)
(155.24) Tli CL1
Tri Cl-l
Poly(2aminopropionic acid), see Poly(alanine)
Poly(3-aminopropionic acid) [P alanine]
c( Mono c2-2
(71.08) Mono
P
Or t ho
-, 2-butyl-2-methyl-
(141.21)
-, 2,2-dimethyl-
I. (99.13)
II.
OlThO
4.80
4.70
4.79
4.87
4.90
9.28
9.28
4.9
9.7
9.33
9.60
9.56
11.57
-, 2-ethyl-2-methyl-
(113.16)
-, 3-methyl-, see Poly(3-aminobutyric acid)
-, 2-methyl-2-propyl-
(127.19)
Poly(3-aminopropyl-5-aminovaleryl-6-aminocaproic acid)
(297.40) Tri 4.9
Poly( 18-aminostearic acid)
Y
Mono 4.76
(281.48)
Poly(2-aminotetrahydropyran-6-carboxcylic acid)
(127.14) Mono c2-1 11.79
4.79 21.7
4.9 21.7
9.54 21.9
4.54 7.8
2 1.088
2 1.04
4 1.087
1.04/495
-f=120
18/1121 9*2/l
9*2/l
9*2/l
121
212
61
971
2 1.26 4*2/l 1059
10.0 9.8 56.90.69 4 1.18
5.4 9.85 49,77,63 1 1.21
2331215 8~ l / l
2251146 8*1/l
2 1 7
2231291
918
61
153
1.20
9.24 179 4 7 9
9.43 176 4 7 9
9.11 182 4 7 9
9.57 188
13.3 15.4
4.80 32.1
4.10 31
9.58 31.9b
9.38 32.2b
4.67 32.1
4.85 31.35
5.29 31.35
5.4 12.5
9.7 12.6
16 1.12 1751528 2*8/3 5 2 2
0.972 208/l 172
1791177
y= 120
y= 121.5
y= 121.7
y = 124.4
59,90,60
2 1.023
2 1.10
4 1.034
4 1.045
2 1.048
4 1.126
0.99
4 1.223
49,77&l 1 1.15
64,90,67 4 1.07
2 1 0
1941146
1981292
2091177
13*2/l
13*2/l
13*2/l
13*2/l
13*2/l
13*2/l
13*2/l
lO* l/l
lO* l/l
895
6 6 0
6 8 0
7 5 9
1054
421
9 1 8
8.73 4.78 *
8.96 4.78 b
7.56 4.78
8.3
y= 120 4 1.400
y = 122.5 4 1.361
3 4 0
3301337
35711403
491
1265
4 1.366 1265
7 2
4* l/l
4* l/l
4* l/l
4*2/l
4*
8.4
10.95 8.39
8.5
8 1.239
189173
2 7 3 13
2 6 8
270/402
7 6
4*2/l
4*2/l
8.4
10.7 21.6
9.52 46.9
14.40 19.43
5 1.77.62 1.28
y= 120 1.016
4*2/l
18* l/l
19*2/l
r=98 1.292 Doubl e
7 4
3 0 5 5 * 10/3
TABLE 6. contd
Poly(amides) VI/35
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm ) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b e Angl es Z Cryst al . Amorph. a
(W kJ/mol a (n *p/q) Refs.
Poly( 11 -aminoundecanoic acid)
tl TKi Cl-l 9.5
(183.30) Tli 4.78
Tti Ci -1 4.9
Tri 9.6
Tli 4.78
4.78
II. Mono 9.75
Y
Mono 9.48
Poly(S-aminovaleric acid)
ct Tli Cl-l 9.5
(99.13)
Poly(4,4-benzanilidylene terephthalamide)
(357.37)
Poly( 1,3-cyclohexylenedimethylene adipamide)
cis-
(252.36) Tri 4.8
Poly( 1,3-cyclohexylenedimethylene dodecanediamide)
cis-
(336.52) Tli 4.8
Poly( 1 &zyclohexylenedimethylene suberamide)
cis-
(280.41) Tli 4.8
Poly(decamethylene adipamide) [10.6]
(282.43)
Poly(decamethylene azelamide) [ 10.91
(324.51)
Y
Phex
Poly(4,4-decamethylenedipiperazine sebacamide)
(476.75)
Poly(decamethylene 4-octenediamide)
trans-
(308.47)
Poly(decamethylene phosphinylidenedipropionamide)
-1 methyl-(diacid)
(344.44)
Poly(decamethylene sebacamide) [ 10.101
(338.54) Tri 4.9
Poly(decamethylene succinamide) [10.4]
(254.37) Tli 4.9
Poly(dodecamethylene oxamide) [ 12.21
(254.37)
Poly(dodecamethylene phosphinylidenedipropionamide)
-, methyl-(diacid)
(372.49)
Poly(dodecamethylene malonamide) [12.3]
(268.40) Mono 8.48
Poly(dodecamethylene sebacamide) [12.10]
c( TKi 5.0
(366.59)
P
Tri 5.0
Poly(dodecamethylene succinamide) [12.4]
(282.43) Tli 4.9
10.0
4.13
5.4
4.2
4.13
15.0 60,90,67
13.1 90,75,66
14.9 49,77,63
15.0 72,90&l
14.9 82.75.66
14.1 a= 63. 5
8.02 15.0b y=115
4.5 29.4b y= 118.5
7.68 14.78
5.6 7.5 48,90,67
18.63
12.6 29.6 26,85,75
19.0 44.6 16,90,83
14.5 34.8 22,85,76
20.0
2
24.1
2 0
5.4 27.8 49,76,63
25.6
5.5 19.8 49,77,63
19.5
21.55
4.71
5.25
8.16
5.5
41.30 p= 101
29.2 51,75,63
29.2 90,75,68
22.3 49,77,63
4
1
1
2
1
4
4
2
2
2
2
1
1 1.18
1.10
1.343
1.15
1.19
1.174
1.145
1.10
1.30
1.19
1.12
1.15
1.14
1.101
1.15
1.15
1.17
183/292 27/1161 12* l / l 9 1 8
1.01 2 2 0 411343 12* l/l 365
1821146 12*1/l 61
194/101 12*1/l 5 9
186 12* l/l 263
1881444 12* l/l 1057
226/l 161
12* l / l 5 2 9
12* l / l 5 2 9
1056
2581402 6*1/l 9 1 8
18* l/l 1425
253/1201 13*2/l 1058
19*2/l 1058
15*2/l 1058
2 3 0 18* l / l 110
2361244
2401544
2141137 68.21405 21*
36.71159
65
130/159 69.1/159 28 *
1291402
243 20* l/l 6 5 7
173 19* l / l 831
2031244 51.1/118 22* l/l 1412
197 34.71159 *l / l 110
198/454 72.0/405
2161137 32.71160
242 16~ l / l 1626
2 3 0 161; l/l 743
180 831
17*2/l 1523
1731339 24* l/l 1513
24* l/l 1513
237 18* l / l 1626
References page VI- 159
VI/36 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 6. contd
Polymer
Cryst
SYSt.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Melting Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Crystal. Amorph. WY
kJ/mol a (n *p/q) Refs.
Poly[4,4 -(ethylenedioxydiphenylene)-ditrimethylene adipamide]
25* l/l 5 1 6
1.337 3 1 2 8*1/l
2091291
2261339
2501244
1629
6 5
2011244 6. 5
1.105 2141244 16* l/l
20512
1961339
22811625
16* l/l
6 3
6 5
1871339
208/244
6 5
2301244 6 5
1.24
1.240
1.204
1.241
1.214
1.208
1.225
1.220
1.152
1.165
1.25
1.10
1.119
1.09152 26512 46.5/82 14 * l / l
1.121495 270/289 40/155 14* l / l
301/1166 36.8/216 14* l / l
280/1121 68/1121 14* l / l
58/1166 14* l / l
46.91405 1 4 * l/l
1.095 53. 2
1.069
269. 5 4 3 . 4
1.095 4 1 . 9
1.09/495
2 5
4 0 2
4 0 7
8 9 1
1 1 8 0
1 4 0 9
1179
5 4
1 1 8 0
1179
2 5
1 0 6 0
1 4 0 9
1.08
14* l/l
14* l/l
14* l/l
14* l/l
17*2/l
1.258
1.105
2261244
1851339
2411402
4 0 2
13*2/l
13*2/l
11*2/l
1 5 1 4
1 5 1 4
1.218 24111524 1523
2 5 9 16* l/l
lO* l/l
13 * l/l
6 5 7
1.280 320/402 9 5 6
1.409 1 7 0 1 3 8 4
1.16 22815 1 30.6/160 18* l / l 2 5
1.189 2151291 56.51137 18* l / l 8 9 1
1.152 1.041 2331244 58.61405 5 4
1.189 2251454 5 2
1.17 2 1 6 153
1.20 18 * l/l 2 5
(438.57)
Poly(ethylene-L-tartaramide)
-, di-o-methyl-
(202.21) Tli
Poly(heptamethylene adipamide) [7.6]
Y
Phex c2-2
(240.35)
26. 3
4.95 6.87 9 . 1 0 59,90,106
Poly(heptamethylene azelamide) [7.9]
Y
Phex
(282.43)
Poly(heptamethylene pimelamide) [7.7]
(254.37) Phex cs-1 4 . 8 2 18.95 b y=120
Y
Phex
Poly(heptamethylene sebacamide) [7.10]
Y
Phex c2-2
(296.46)
Poly(heptamethylene suberamide) [7.8]
Y
Phex c2-2
(268.40)
Poly(hexamethylene adipamide) [6.6]
WI
I . Tli Ci - 1
(226.32) M o n o
Tli
Tli
Tli
Tli
18.95
4 . 9 5 . 4 17. 2 48,77,63
15. 7 10. 5 17. 3 p=73
5 . 0 0 4 . 1 7 17. 3 81,76,63
4.87 5.26 17.15 50.76.64
4 . 9 7 5.47 17.29 48377962
4 . 9 6 5 . 5 2 17.41 48,76,62
I I . Tli
P
Tri Ci - 1
high temp. Tri
(170C) Tli
Poly(hexamethylene azelamide) [6.9]
(268.40) M o n o
Poly(hexamethylene glutaramide) [6.5]
(212.29) M o n o C2h-6
(at 190C) M o n o
Poly(hexamethylene malonamide) [6.3]
(184.24) M o n o
Poly(hexamethylene 4-octenediamide)
trans-
(252.36)
Poly[hexamethylene oxamide) [6.2]
(170.21) Tli Ci - 1
Poly(hexamethylene m-phenylenedisulfonamide)
(318.41) M o n o C2h-3
Poly(hexamethylene sebacamide) [6.10]
a Tri Ci - 1
(282.43) Tli
4.95 5.45 17.12 52,80,63
4 . 9 8. 0 17. 2 90,77,67
5 5. 9 16.23 57,80,60
4.91 5.87 16.50 56,81,60
7. 8 5. 3 40.156 r=87
4 . 6 0 8.62 30.95 b p=114
5.23 8.50 30.55 p= 1 1 0
8.60 4 . 6 2 25.70 a= 100.4
19. 1
5.15 7 . 5 4 12.39 32,74,62
7 . 7 0 7 . 7 6 14. 1 p=117
4 . 9 5 5 . 4 2 2 . 4 49,76,63
4 . 8 6 5.05 22.35 55.76.62
P
Tri Ci - 1 4 . 9 8. 0 22. 4 90,77,67
1
2
1
1
1
2
2
1
9
1
1
1
1
1
2
1
1
4
4
4
4
1
2
1
1
2
TABLE 6. contd
Poly(amides) VI/37
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm j) Mel ti ng &at of Chai n
point f us i on conf orm.
a b E Angl es Z Cryst al . Amorph. WY kJ/mol a (n *p/q) Refs.
Poly(hexamethylene suberamide) [6X]
( 2 5 4 . 3 7 ) Tli
Mono 9.60
quenched Phex
Poly(hexamethylene succinamide) [6.4]
( 1 9 8 . 2 6 ) Tli
9.7
4 . 9
Poly(hexamethylene-L-tartaramide)
-, diGmethyl-
( 2 5 2 . 3 2 ) Tti
Poly(hexamethylene terephthalamide) [6.T]
( 2 4 6 . 3 1 )
5.00
Poly(methylene adipamide) [ 1.61
( 1 5 6 . 1 8 ) Mono CZh-6 8.04
Poly(4,4-methylenedicyclohexylene azelamide)
trans-, trans-
( 3 6 2 . 5 6 ) Ortho 9 . 4
Poly(4,4-methylenedicyclohexylene dodecanediamide)
t r am- , t r ans-
I . ortho c2v-5 9.30
( 4 0 4 . 6 4 ) ortho 9 . 4
II. Mono 9 . 5 0
Poly(4,4-methylenedicyclohexylene pimelamide)
tram-, trans-
I. Onho 9 . 4
( 3 3 4 . 5 0 )
II. Mono 9.51
Poly(4,4-methylenedicyclohexylene sebacamide)
tram-, trans-
( 3 7 6 . 5 8 ) Ortho 9 . 4
Poly(4,4-methylenedicyclohexylene suberamide)
tram-, trans-
( 3 4 8 . 5 3 ) ortbo 9 . 4
Poly(4,4-methylenedicyclohexylene tetradecanediamide)
tram-, trans-
( 4 3 2 . 6 0 ) Or t ho 9 . 4
Poly(4,4-methylenedicyclohexylene tridecanediamide)
tram-, trans-
(418.66) ortho 9 . 4
Poly(4,4-methylenedicyclohexylene undecandediamide)
tram-, trans-
( 3 9 0 . 6 1 ) Or t ho 9 . 4
Poly(4,4-methylenediphenylene dodecanediamide)
I. (392.54) ortho 11.10
II. Ortho
III. Ortho
Poly(methylene dodecanediamide) [ 1.121
(240.35) Mono C2h-6
Poly(methylene glutaramide) [ 1.51
(142.16) RhO D3-5
Poly(methylene malonamide) [ 1.31
(114.10) Hex
Poly(methylene pimelamide) [ 1.71
(170.21) RhO D3-5
Poly(methylene sebacamide) [l.IO]
(212.29) Mono C2h-6
10.52
9.64
8.12
4 . 7 9
4 . 7 9
4.79
8.10
8.26 19.7
9.7
5.3 14.8
6.84 13.20
15.6
4 . 7 9 20.2b
6.1 39.5
6.06 4 5 . 0
6.1 45.5
5.22 52.6
6.1 35.8
5.32 40.5
6.1 4 1 . 4
6.1 3 7 . 6
6.1 4 9 . 4
6.1 4 7 . 4
6.1 43.5
4 . 9 6 44.7
4 . 9 6 4 4 . 7
4 . 9 6 44.7
4.79 35.2b
4 . 7 9 26.1
4 . 1 9 18.0
4.79 34.5
4 . 7 9 30.0b
y=115
y= 120
51,77,62
62,90,112
-(=90
y=96.6
y = 99.6
y=90
y=90
1
4
1
1
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
3
3
3
3
4
1.193
2321244 6 5
2351291 16* l/l 1515
241/1202
1515
1.25 2 1 5 12* l / l 1626
212/402
1.191 2 3 0 12* l/l 1629
371 14* l / l 828
3711829
D350/291
I . 333 285/ 1524 9*2/l 1522
306/402
1.06 20*2/l 1315
1.060 23*2/l 1315
1.03 23*2/l 1315
1.037 23*2/I 1315
1.08
1.093
18*2/l 1315
18*2/l 1315
1.05 21*2/ l 1315
1.07 19*2/l 1315
1.02 25*2/l 1315
1.02 24*2/I 1315
1.04
1.059
1.118
1.220
1.166
I . 366
1.589
1.237
1.211
22*2/l 1315
2 9 0 23*2/l 1440
25611443
23*2/ l 1440
23*2/l 1440
25911524 15*2/l 1522
8*3/l 1522
6*3/2 1313
10*3/l 1522
26014024 13*2/l 1522
26611524
26811537
References page VI-159
VI/38 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 6. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm3) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. a cva kJ/mol n (n *p/q) Refs.
Poly(methylene suberamide) [ 1.81
(184.24) MIXlO C2h-6
Poly(nonamethylene azelamide) [9.9]
(310.48)
Y
Phex
Poly(nonamethylene malonamide) [9.3]
(226.32) ortho
Poly(octamethylene azelamide) [8.9]
Y
Phex
( 2 9 6 . 4 6 )
Poly(octamethylene malonamide) [X.3]
(212.29) Mono
Poly(octamethylene suberamide) [8.8]
(282.43) Tli
Poly(octamethylene succinamide) [8.4]
(226.32) TIi
Poly(octamethylene-L-tartaramide)
-, diGmethyl-
(286.37) Tli
Poly(octamethylene terephthalamide) [8.T]
(274.36)
Poly(pentamethylene azelamide) [5.9]
( 2 5 4 . 3 7 )
Poly(pentamethylene glutaramide) [5.5]
( 1 9 8 . 2 6 ) Mono C2-3
Poly(pentamethylene malonamide) [5.3]
(170.21) Or t ho
Poly(pentamethylene pimelamide) [5.7]
Y
Mono CA-2
(226.32)
Poly(pentamethylene terephthalamide) [5.T]
(232.28)
-, 2-methyl-(diamine)
(246.31) Or t ho
Poly(3$phenanthridinonediyl terephthalamide)
(355.35) Mono
Poly(m-phenylene adipamide)
(218.26)
Poly(p-phenylene dodecanediamide)
( 3 0 2 . 4 2 )
Poly(m-phenylene isophthalamide)
( 2 3 8 . 2 5 ) Or t ho
Tri Cl-l
Tli Cl-l
Or t ho
-, hexamethylphosphorictriamide complex
( 5 9 6 . 6 6 ) Mono
(2 HMPT/monomer)
Poly@-phenylene phthalamide)
(238.25) Ortho D2h-14
Poly@-phenylene pimelamide)
(232.28)
Poly(m-phenylene sebacamide)
(274.36)
Poly@-phenylene sebacamide)
( 2 7 4 . 3 6 )
8.08 4.79 2 5 . 2 r=90 4 1.255 2 7 6 1 1 5 2 4
24.0
11*2/l
20* l/l
1522
177
18912
1651339
1 65
8.32 4.71 32.70 4 1.173 14*2/l 1523
2 2061244 65
8.50 4.71 30.70 p= 101.7 4 1.172 2 3 3 1 1 5 2 4 13 *2/l 1523
1 2161291
2251244
65
4.9
5.00
5 . 4 17.3 51,77,62 1 1.20 2 5 4 14* l/l 1626
6.82 15.7 57,90,111 1 1.175 2 0 8 14* l/l
16* l/l
l6* l/l
12* l/l
1629
17.9 335 828
19.5 1791291
8.30 4.79 13.8 y=90 2 1.200 1981291
24711625
1624
8.47 4 . 6 2 22.40 4 1.290 1951402
24811524
10*2/l 1523
4.83 9.35 16.62 y=58.9 2 1.169 2 2 8
1831291
14* l/l
14.1 3 5 4
3531829
13* l/l 828
4.61 36.7 26.5 16 1.460 1529
8.1 6.5 17.2 r=60 1.50 1063
11.8 3 4 4
2961402
13*2/l
16* l/l
11*1/l 828
21.2 828
6.7 4.71 11.0
5.27 5.25 11.3
5.36 5.36 11.3
5.1 5 23.2
112,111,88
113,113,88
1.14
1.470
1.443
1.34
3751135
3901748
1.33
735
856
878
1062
9.43 16.94 11.3 fi= 123.4 1.315
22.8 5.5 8.1 1.56
19* l/l
lO* l/l
IO* l/l
lO* l/l
10*2/l
lO* l/l
14* l/l
17* l/l
18* l/l
396
14.7
14.9
18.5
3 7 2 828
2 5 8 828
3 3 4 828
TABLE 6. contd
Poly(amides) VI/39
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z crystal. Amorph.
WY
kJ/mol (n *p/q) Ref s.
Poly(m-phenylene suberamide)
( 2 4 6 . 3 1 )
Poly@-phenylene suberamide)
( 2 4 6 . 3 1 )
Poly(m-phenylene terephthalamide)
( 2 3 8 . 2 5 )
-, 4-methyl-(d&nine)
( 2 5 2 . 2 7 ) Mono
Poly(p-phenylene terephthalamide)
I. (238.25) Por t cs-1
Mono
Mono C2h-5
Ortho
Mono
Por t cs-2
Or t ho
8.57
7.87
7.728
7.80
7.78
7.79
7.88
7.60
II. 8.0
single crystals & sphemlites
-, 2,2-difluoro-
(274.23) Por t 8.6
Poly(p-phenylene 2,5-thiophenediamide)
( 2 7 2 . 4 6 ) Mono 4.29
PoIy(piperazine adipamide)
( 1 9 6 . 2 5 )
Poly( 1,Cpiperazine 1,3-cyclobutylenedicarboximide)
-, 2,4-diphenyl-(diacid)
trans-
( 3 4 6 . 4 3 ) ortho 8.74
Poly( 1 ,Cpiperazine 4-octenediamide)
trans-
( 2 2 2 . 2 9 ) Mono C2h-5 4 . 5 4
Poly(piperazine sebacamide)
( 2 5 2 . 3 6 )
Poly(2,5-pyrimidine terephthalamide)
(240.22) ortho 7.3
Poly(4,4-sulfonyldiphenylene terephthalamide)
( 3 7 8 . 4 0 )
13.0 3 0 2
16.3 3 7 4
500/748
7.54 22.11
5.18 12.9
5.184 12.81
5.19 12.9
5.28 12.9
5.18 12.89
5.22 12.9
5.04 12.78
4 . 8 12.7
5.1 12.9
4 . 8 12.7
11.5
p=116.3 1.308
y=90
y = 90.04
y=90
y = 92.2
1.504
1.542
1.515
1.493
1.522
1.491
1.616
500/748
600/735
cu=88
1.50
(Y=88
5 . 0 13.0
5.09 25.2
9.2
1.63
y=98 1.489
355
5.93 9.22
10.00 13.50
1.204
a= 110.2 1.283 2521657
180/81 26.0/81
5.1 12.8
15.45
4
2
2
2
2
2
2
2
2
2
2
1
2
2 1.67
Poly(terephthaloyldihydrazo-di(p-aminobenzoyl) terephthalamide)
(562.54) Por t
Poly(tetramethylene adipamide) [4.6]
( 1 9 8 . 2 6 ) Tri Cl-l
Mono
Tli
8.5 4 . 9 29.69
4.95 5.47 14.66
9 . 6 8.26 14.7
4.9 5.5 14.8
Poly(tetramethylene azelamide) [4.9]
Y Phex
(240.35)
Poly(tetramethylene malonamide) [4.3]
156.18* Mono
Poly(tetramethylene 4-octenediamide)
trans-
(224.30)
Poly(tetramethylene succinamide) [4.4]
(170.21) Tli
8.65
4 . 9
4.62 20.40
17.0
5.5 12.3 49,77,62 1 1.29
Poly(tetramethylene-L-tartaramide)
-, di-o-methyl-
(230.26) Tli 5.00 7.06 10.80 59,90,110 1 1.270 2 6 6 lO* l/l 1629
48.78.64
y= 115
46,78&l
/3= 102.5
4
1.303 27711524
2
1.51
1.245
1.246
1.29
2951291
308/51
3 5 0 41.6
319/1518
2231339
2531402
2 9 4
d
287 I402
15* l/l 828
16* l/l 828
11*2/l 1398
12* l/l 761
12* l/l 1061
12* l/l 9 0 2
12* l/l 1525
12* l/l 1527
12* l/l 1620
12* l/l 1638
1526
12* l/l 9 5 8
1526
1297
12* l/l 1528
11*2/l 1532
lO* l/l 3 8 6
9* l/l 9 3 4
12* l/l 873
16t
12* l/l 1531
1203
28* l/l 7 6 0
12* l/l 1516
12* l/l 1517
12* l/l 1655
65
9*2/l 1523
14* l/l 6 5 7
lO* l/l 1626
References page VI-l 59
VI/40 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 6. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Melting Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z crystal. Amorph.
WY kJ/mol LI (n *p/q) Refs.
Poly(tridecamethylene tridecanediamide) [ 13.131
Y Mono 9.22 4.94 34.41 p= 121.1 2 1.044 1.01 > 183 91.2 28*1/l 1519
( 4 2 2 . 7 0 ) Mono 4.88 4.13 34.0 y= 121 1 1.043 17211521 28* l / l 1520
Poly(m-xylylene adipamide)
( 2 4 6 . 3 1 ) Mono 5 . 1 0 4 . 7 0 15.2 y/=69.6 1 1.198 2461326 13*1/l 8 4
Tli Ci -1 12.01 4.83 29.8 15,26,65 2 1.250 2441544 13*2/l 4 5 9
Poly@-xylylene sebacamide)
( 3 0 2 . 4 2 ) Tli 5.74 4.81 20.6 16,55,65 I 1.168 300/290 18*1/l 2 0 4
2811385
2911454
2681291
a The number after the solidus (/) are reference citations.
b The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
F
TABLE 7. POLY(ESTERS) (-O-X-O-CO-Y-CO- or -O-X-CO-)
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm j) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b e Angl es Z Cryst al . Amorph. (1
WY
kJ/mol a (n *p/q) Refs.
Poly(4,4-bicyclohexylene sebacate)
-, tram-, trans-
(364.53) Mono 11.16
smect i c Mono 11.98
Poly(4,4-bicyclohexylene undecanedioate)
-, trans-, trans-
(378.55) Mono 12.4
smect i c Mono 12.3
Poly(4,4-biphenylene 4,4-biphenylenedicarboxylate)
5.21 19.48 p=49.0 2 1.400 20* l/l 1636
5.48 19.76 p=52.5 2 1.176 20* l/l 1636
5.21 23.0
5.55 20.6
1.229
1.144
7.83 5.50 2 0 . 6 6
p=43.5 2
p=51.4 2
2 1.464
7.20 5.23
21* l/l
21 *l/l
20* l/l
16*
1636
1636
1622
1622
12.51 7.561 6 7 . 6 6 16 1.4292 16*4/l 1562
9.25 8.28
(6.9)
y = 96.5 1.08 3 6 0 6* l/l 3 6 4
9.16 8.22 12.9 4 1.164 253 6*2/l 3 6 4
13.5 2251162 12* l/l 763
6.938 9.761 15.97 R=41.4 2 1.181 1241547 14* l/l 1262
551547
6.486 9.482 13.51 p=45.9 2 1.259 14lf541 12* l/l
Poly( 1,4-cyclohexylenedimethylene terephthalate)
t rans-
(274.32) Tli 6.31
Tri Ci- 1 6.46
cis-
Tli 6.02
621547
6.63 14.2 89,47,114 1
6.65 14.2 89,47,115 1
6.01 13.7 89,53,112 1
1.266
1.260
3181547
1.319 2561547
14r l/l
14* l/l
14* l/l
1193
199
1077
199
(392.11) Or t ho
Poly(4,4-biphenylene terephthalate)
(316.31) Or t ho
Poly(3,4-carbonyldiphenylene terephthalate)
( 3 4 4 . 3 2 ) ortho C2v-17
Poly(l,3-cyclobutylene carbonate)
-, 2,2,4$tetramethyl-
t rans-
(170.21) Tri
cis-
Or t ho
Poly(l,4-cyclohexylene adipate)
t rans-
(226.27)
Poly(l,4-cyclohexylenedimethylene adipate)
t rans-
I . Mono C2h-5
(254.33)
cis-
Poly( 1,4-cyclohexylenedimethylene succinate)
t rans-
(226.27) Mono C2h-5
cis-
TABLE 7. contd
Polyfesters) VI /41
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Melting Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es z Cryst al . Amorph. (w kJ/mol (II *p/q) Ref s.
Poly(l,4-cyclohexylene sebacate)
trans-
( 2 8 2 . 3 8 )
Poly(decamethylene adipate) [ 10.61
( 2 8 4 . 4 0 ) Mono
Poly(decamethylene azelate) [10.9]
( 3 2 6 . 4 8 ) Mono
Poly(decamethylene glutarate) [ 10.51
(270.37) Mono
Poly(decamethylene 3-hexenedioate)
( 2 8 2 . 3 8 )
Poly(decamethylene octadecanedioate) [ 10.181
(452.72) Mono
Poly(decamethylene 4-octenedioate)
( 3 1 0 . 4 4 )
Poly(decamethylene oxalate) [ 10.21
( 2 2 8 . 2 9 ) Mono
Mono
Poly(decamethylene sebacate) [IO. lo]
(340.50) Mono
Poly(decamethylene suberate) [ 10.81
( 3 1 2 . 4 5 ) Mono
Poly(decamethylene succinate) [ IO.41
(256.34) Mono
Poly(decamethylene terephthalate) [ lO.T]
( 3 0 4 . 3 9 ) Tli
5 . 0
5.11
7 . 4 22.1
7.43
5.0
5.0
4.94
7.4 51.7
7 . 4 4 1 . 6
7.65
5.47
4.74
7.38 37.5 p=115 2
4.05 y = 109
5.28
6.75
5 . 0
7.00 17.0
7.05 17.0
7 . 4 27.1
5 . 0 7 . 4 24.6
5.07 7 . 5 0
5.0
4.62
7.4 19.6
6 . 3 0 20.10
Poly(decamethylene 4,4-terephthaloyldioxydibenzoate)
(544.60) ortho 53.7
Poly(dodecamethylene adipate) [ 12.61
5.04
18.5
39.9 57.7
7.42
Poly(dodecamethylene NJ-dodecamethylenediterephthalamate)
(662.91) Tti 5.01 6.93
Poly(dodecamethylene 3.hexenedioate)
(310.44)
Poly(dodecamethylene 4-octenedioate)
(338.49)
Poly(dodecamethylene suberate) [ 12.81
(340.50)
Poly(ethylene adipate) [2.6]
(172.18) Mono
Mono C2h-5
Mono
Mono
4 . 9 4 7 . 6 4
4 . 7 4 4.07
5.03 7.52
25.7 30.7
5.47 7.23
7.26 5 . 4 0
5.47 7.24
11. 71
11.72
10.85
11.55
Poly(ethylene A-N-azelaoyldi(p-aminobenzoate))
(452.52)
Poly(ethylene azelate) [2.9]
(214.26) ortho 7.45 4.97
Mono 25.7 30.7
ortho 5 . 0 7 . 4
46.77 130,55,130 1 1.213
26.3
31.5
31.2
31.2
2 1. 16
4 I . 13
4 1. 17
1.096
2 1.207
/3=129 2 1.206
2 1.13
2 1.14
2 1.17
107,96,113 1 1.022
1.287
y=lO9
p=103.8 4 0
p=113.5 2
a = 67.7 2
p= 113.5 2
1.275
1.345
1.453
1.363
1.302
,9= 103. 8 8:
4
1.220
I.190
1.23
1.233
1511762 16*1/ l 7 6 3
80/8l 42.7/81 18* l/l 106
7 4 4 4 1079
771300 45.61405
691137 41.9/81 21*2/l 106
50.71405
581764 17 *2/l 106
6 6 3 6 18* 1079
93 30* l/l 521
5 3 4 4 201; 1079
791305 14* l/l 106
14* l / l 1171
80/137 50.2/81 22* l/l 106
771767 56.51405
731291 30.2/301
51.5/160
751764 20* l/l 106
7 7 5 7 1079
681290 16r l/l 106
731764
138/81 46.1/81 18* l / l 6 8
129199 44.0/405
131/453
30 * 2/l 1352
7 8 5 2 20* 1079
197/782 140/782 40* l/l 8 7 4
I . 124 1195
7 7 46 20* 1079
57 55 22* 1079
8 0 6 8 22* 1079
52127 15.9/265 IO* l/l 105
541291 21.0/571 IO* l/l 2 0 3
471265 lO* l/l 211
50146 lO* l/l 5 2 3
1.204 551543 21.7 1074
1.219 651571 1195
1386
1.119
461543 13*2/l 108
13*2/l 105
13*2/l 109
4 7 43.7 1074
References page VI- 159
VI/42 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 7. contd
Polymer
Cryst
syst.
Space
k!roup
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z crystal. Amorph.
(w
kJ/mol a (n *p/q) Refs.
Poly(ethylene 4.4~dibenzoate)
(268.27) Tri Ci- 1 5.73
Poly(ethylene N,N-dodecamethylenediterephtbalamate)
(522.64)
3.77 14.73
Poly(ethylene 4,4-(ethylenedioxy)-dibenzoate)
c( M o n o
(328.32)
7.83 10.33 18.68
P oral0 7.28
Poly(ethylene 2,5-furandicarboxylate)
(182.13) Tti 5.75
Poly(ethylene N,N-hexadecanedioyldi@-aminobenzoate))
5.65 18.64
5.35 20. 1
(550.70)
Poly(ethylene isophthalate) [2.1]
I. (192.17) Tti Ci - 1
I I .
Tti
Poly(etbylene 2,6-naphthalate)
(242.23) Tti
Ci - 1
Ci - 1
Poly(ethylene oxalate) [2.2]
(116.07) Ortho
Poly(ethylene p-oxybenzoate)
a Ortho
(164.16) ortbo
D2h-14
D2-4
D2-4
P
M o n o C2h-5
Poly(ethylene pimelate) [2.7]
(186.21)
Poly(ethylene 1,4-piperazinedicarboxylate)
(200.19)
Poly(ethylene sebacate) [2.10]
I. (228.29) M o n o
M o n o C2h-5
M o n o
M o n o
M o n o
II. Tri
Poly(ethylene suberate) [2.8]
(200.23) M o n o
M o n o
M o n o
Ci - 1
C2h-5
Poly(etbylene succinate) [2.4]
a M o n o
(144.13) M o n o
OltbO D2h-10
P
Poly(ethylene terephthalate) [2.T]
(192.17) Tli Ci - 1
Tli
Tri
Tli
Tri
Tli
34. 6
5.20 7.08 14. 8
14. 8
21. 0
5.41 6.35 21. 2
6.5 1 5.75 13. 2
3.825 5.72 13. 2
6.44 6.22 11.93
10.52 4.75 15.68
10.49 4.75 15.60
11. 2 14. 7 18.99 1 6 1.395
8.19 11.07 19.05 p=114.8 8 1.391
10. 4 2 4 5 lO* l/l 3 8 6
5.5 15 16. 9
5.58 7.31 16.76
5.52 7.30 16.65
5.52 7 . 4 16. 9
25. 7 30. 7 16.67
5.39 7 . 6 0 16.76
5.51 7.25 14.28
5. 0 7 . 4 14. 1
5.50 7.25 14.10
p=65 4
p= 115.5 2
p= 115.0 2
p=65
p=103.8 4;:
105,112,72 2
1.20
1.229
1.247
1.21
1.187
1.264
1.086
1.140
1.335
1.337
721265 13.8/265 14* l / l 100
79146 35/405 14* l / l 521
731539 32.0/571 14* l / l 5 2 3
761137 29.1/137 14* l / l 109
78/302 25.6/158 14~ l / l 105
831571 1195
14* l/l 1072
p=114.5 2
2
p=114.5 2
1.281
1.27
1.300
1.249
751571 26.51571 12* l/l 2 0 3
55127 12* l / l 108
12* l/l 5 2 3
6 3 26. 2 1074
1.147 1195
5 . 0 7 . 4 8.32
9.05 11.09 8.32
7.60 10.75 8.33
9.50
2 1.55
p= 102.8 4 1.176
4 1.407
4.56 5.94 10.75 98,118,112 1 1.457
5.54 4 . 1 4 10.86 107,112,92 1 1.472
4.52 5.98 10.77 101,118,111 1 1.477
4.48 5.85 10.75 100,118,111 1 1.515
4.48 5.80 10.71 100,118,111 1 1.530
4 . 5 0 5.90 10.76 100,119,111 1 1.503
90,90,79 1 1.426 3461291 14* l/l
33311552
1551
2 4 4 102. 6 30*
1.210
7 8 2
1195
p=83.1 4 1.454 1078
2 1.422
2 8 8 26. 2 1 8 * l/l
240/290
2401291
1 8 * l / l
134,90,112 2 1.575 9*2/l 7 4 2
1386
109.136.96 2 2 . 0 3 4
1.358 1.346
9*2/l
1 4 3
2 4 0
116,136,84 2 1.478 9*2/l
3 9 8
1 1 1
3 9 8
5 7 2
81,114,100 1
y=96 1
4
1.406 260/291 12* l/l 9 2 0
1.400 33711342 2511342 12* l/l 1555
1.613 1721678 6*2/l 6 7 5
4 1.392
4 1.403
2031327 9*2/l
2241345 9*2/l
2201354
21511174
9*2/l
9*2/l
4 9 4
901
3 5 6
4 9 4
9 1 9
4 . 2 7 8 1.162 291764 29.8 ll* 1074
108/290 8*1/l 108
103/302 8*1/l 105
8* l/l 6 7 5
8*1/l 1539
2 6 5 24.1/87 lO* l / l 2 7
284/264 22.6/157 10 * l / l 195
2671265 9.21265 lO* l/l 4 0 0
270/374 25/405 10 * l / l 8 5 3
265/290 16.7/155 lO* l / l 1061
3 1 0 32/1071 lo* l / l 1075
I
I
1
1
1
1
1
I
I
I
I
I
I
F
F
F
Poly(esters) VI/43
TABLE 7. contd
Polymer
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
Cryst Space poi nt f us i on conf orm.
syst.
group
a b c Angl es crystal. Amorph. a
WY kJ/mol (n *p/q) Ref s.
TIi 4. 44 5. 91
Tri 4. 52 5. 92
Tli 4. 53 5. 87
4. 01 5. 83
Tri 4 . 6 2 5. 92
Poly(glycolic acid), see Poly(2-hydroxyacetic acid)
Poly(heptamethylene sebacate) [7.10]
( 298. 42)
Poly(heptamethylene terephthalate) [7.T]
( 262. 31)
Poly[heptamethylene (4,4-terephthaloyldioxy)-4,4-dibenzoate]
( 502. 52)
Poly(hexadecamethylene adi pat e) [ 16. 61
( 368. 56)
Poly(hexadecamethylene 3-hexenedioate)
( 366. 54)
Poly(hexadecamethylene 4-octenedioate)
trans-
( 394. 60)
5. 05
4. 93
4. 87
Poly(bexadecamethylene suberate) [16.8]
( 396. 61) M o n o
Poly(hexamethylene adipate) [6.6]
( 228. 29) O r t h o
6. 47
5. 00
10. 08
Poly(hexamethylene 4,4-dibenzoate)
a M o n o c2-2
( 324. 38)
10. 98 11. 47 19. 62 p=89.7
P
M o n o 13. 39
Y
M o n o c2-2 9. 70
Poly(hexamethylenedi(6-hydroxycaproamide) adipate)
( 454. 61)
12. 84 39. 19 p = 84. 7
9. 20 19. 39 p=83.0
37. 50
1. 46
7. 59
4. 03
7. 38
7. 40
3 7
1. 32 16. 83
Poly(hexamethylene N-N-dodecamethylenediterephthalamate)
( 578. 75) Tli 5. 02 6. 87
Poly(hexamethylene N,N-hexamethylenediterephthalamate)
( 494. 59) Tri Ci - 1 5. 07 6. 87
10. 67
10. 70
10. 73
10. 75
10. 68
100,117,112 1
100,118,111
100,119,111
y = 120
100,128,105
1 5 . 0
4 9 . 2
y= 109
p= 1 1 5
39. 21 128,54,131
31. 78 127,53,132
1
1
1
Poly(hexamethylene 3-hexenedioate)
( 226. 27)
Poly(hexamethylene 4-octenedioate)
( 254. 33)
Poly(hexamethylene oxalate) [6.2]
( 172. 18) M o n o
Poly(hexamethylene sebacate) [6.10]
( 284. 40) M o n o
Poly(hexamethylene suberate) [6.8]
( 256. 34)
1. 515 280/960 26.9/960 10 * l/l 1158
1. 480 2451412 27. 81472 10 * l/1 1 1 5 9
1. 501 2181124 23. 31887 10 * l/l 1543
1. 466 lO* l/l 1555
1. 58 lO* l/l 1 6 4 4
251301 19 *
981453 13* l/l
27*2/l
1 1 7 4
1561
8 6 6 3 24*
8 7 5 6 24*
1 0 7 9
1 0 7 9
1 0 7 9
0.823? 8 7 9
1 0 7 9
1. 221 1. 096
7 0 5 4 26*
851879 54.51819
1 0 9 6 6 . 4 26* l/l
8 7 6 6 26*
561290 3 8 . 1 14* l/l
5811079 3211079
57 1539
581764
611807
1 1 1 9
1. 308 1. 22 2141291 18 * l/l
200/1552
230/1566
18*2/l
18* l/l
1 5 5 6
1. 284
1. 254
1 5 5 6
1 5 5 6
1105
1. 252
1 4 2 26*
2141782 1161782 34* l/l
1. 167
8 7 4
1 1 9 5
1. 314 2531182 92. 91782 28 * l/l 8 7 4
2651781 1 1 9 5
6. 75 6. 85 11. 95 p=129 2 1. 332
5. 52 7 . 4 0 22. 15 /3=115 2 1. 152
Poly(hexamethylene terephthalate) [6.T]
( 248. 28) Tli
Tri Ci - 1
4. 57 6. 10 15. 40 105.98.114 1 1. 146
9. 98 9. 52 15. 40 120,98,95 4 1. 133
a M o n o 9 . 1 1 7 . 2 1 5 . 5 a = 127. 3 6 1. 28
M o n o 9 . 1 0 0 17. 56 15. 74 a = 127. 8 6 1. 245
1. 236
1. 225
6 1 2 1 14*
2 0 2 2 16%
661305 lO* l/l
721764
7 8 38/809 18% l/l
671290 221301
6 7 3 4 16*
581291
651764
160/81 34.8/81 14* l/l
161/405 33.5/405 14* l/l
154199 35. 31159
14* l/l
14* l/l
1 0 7 9
1 0 7 9
1171
5 2 1
1079
6 8
8 1 4
1 0 7 0
1184
References page VI- 159
VI/44 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 7. contd
Polymer
Cryst
syst.
Space
lwP
Unit cell parameters Densi ty (g/ cm 3, Melting Heat of Chain
poi nt f us i on conf orm.
a b c Angl es Z crystal. Amorph. WY
kJ/mol (n *p/q) Ref s.
P
I. Tli
Tri
Tri CLI
Tri Ci - 1
(at 135C) Tri CL1
Il . Tri
Y
Tli
(from soln.)
Poly(Zhydroxyacetic acid) [glycolic acid]
4 . 8
4.91
5.217
4.68
4.84
5.217
5. 3
5. 7 15. 7 104,161,108 1
5.68 15.44 103,118,109 1
5.284 15.74 129.98.96 1
11.57 15.51 105,114,109 2
5 . 7 4 15.53 104,116,106 1
10.57 15.74 129,98,96 2
13. 9 15. 5 124.130.88 2
(58.04) OtthO D2-4 6.36 5.13
ortho D2h-16 5.22 6.19
1.25 14* l/l 1070
1.285 14* l/l 1160
1.277 1 7 4 14*1/l 1184
1.279 14* l/l 1544
1.227 14* l/l 1544
1.277 14* l/l 1184
1.30 14* l/l 1070
7 . 0 4 4
7.02 4
1 2
1.678 223/305 11/1121 3*2/l 3 1 2
1.700 2 3 3 121464 3 *2/l 4 9 0
1.69 3*2/l 6 0 5
1.707 1.50 2 3 0 4 6 5
17. 8 17. 8
7.52 5 . 7 0
7.62 5 . 7 0
7.47 5.67
7. 5 5. 7
11. 1 3. 7
9. 2 5. 3
9.24 5.28
9.11 5.26
18. 4
12.49
12.56
12.55
12. 6
12. 6
12. 6
12. 4
12.50
3 6 1.422
4 1.490
4 1.462
4 1.501
4 1.48
4 1.54
4 1.32
4 1.308
>320/881 vi ref
>350/882 6*2/l
6*2/l
6*2/l
6*2/l
6*2/l
6*2/l
6*2/l
6*2/l
8 8 0
1065
1182
1340
154s
1065
1545
1065
1340
1545
2 6 . 8 0 9 . 6 12. 6 8 1.07 6*2/l 1646
19.80 9 . 6 12. 6 8 1.13 6*2/l 1646
17.80 9 . 6 12. 6 8 1.17 6*2/l 1646
16.95 16.95 12.36 1 6 1.213 2 9 4 6*2/l 1646
16.95 16.95 12.86 1 6 1.166 6*2/l 1646
14.20 9 . 6 0 12.48 8 1.266 6*2/l 1646
7. 8 5.55
7.44 5.79
7.32 5.35
7. 5 5. 7
9.18 5.30
15. 6 3 . 6
9 . 0 5 . 2
8.86 5 . 1 2
10. 8
10.90
10.44
10. 9
10.90
2
2
2
2
2
2
2
2
4
4
4
4
4
4
4
4
4
4
1.39
1.388
1.594
1.40
1.229
5 8 5
lO* l/l
lO* l/l
lO* l/l
lO* l/l
lO* l/l
10. 8
10.90
1.29
1.318
lO* l/l
lO* l/l
1546
1550
1554
1622
1550
1546
1546
1550
12.71 3.85 10.50 90.90.90 1.778 lO* l/l 1639
5 . 5 0 9.06 7.78 y=92
5.43 8.94 7.75
1.441 1 1 5 4*2/l 2 1 7
1.484 1151190 4*2/l 8 6 2
5.76 13.20 5.96
5.76 13.20 5 . 9 6
5.71 13.06 5.89
5.73 13.14 5.93
5.73 13.15 5.96
1.262
1.262
1.302
1.281
1.273
1161422 13/1216 4*2/l
1681570 4*2/l
170/900 4*2/l
4*2/l
2 0 3 1 1 5 3 5 4*2/l
1.177 1 9 7
4 . 7 0
4 1 9
771
6 9 8
1382
1534
1216
771
7.45 4 . 9 6 27. 1 1.129
7 . 4 9 6 4 . 9 7 4 17.30
7.47 4 . 9 8 17.05
1.175
1.195
801309 11*2/l
1.091712 551560 15.41623 7 *2/l
641623 7*2/l
108
5 5 9
561
D3-7
D2-4
D2-4
Poly@-hydroxybenzoic acid)
I. (120.11) He x
OKtbO
OltbO
oral0
OIlhO
Il.
OtlbO
Ill. OltbO
(high temp. ) o r t b o
-, 3-n-decyl-
(260.38) OFthO
-, 3+hexyl-
(204.27) OlthO
-, 3+pentyl-
(190.24) Ortho
-, 3-n-propyl-
l a . Tet
(162.19)
lb. Tet
Il . OlThO
Poly(4,4-hydroxybibenzoic acid)
I. (196.20) o r t b o
Ortho
oltho
ortho
(at 280C) Ortho
Il .
Il l . OHhO
Ortho
-, 3-bromo-
(275.10) Tli Ci - 1
Poly(3-hydroxy-3-butenoic acid)
(82.07) M o n o
o r t b o D2-3
Poly(3-hydroxybutyric acid)
I. (86.09) Ortho D2-4
OlthO D2-4
O&O
Ortho D2-4
ortho
Il .
Poly(lO-hydroxycapric acid)
(170.25) Ortho
Poly(6-hydroxycaproic acid)
(114.14) Ortho
Ortho
D2-4
D2-4
TABLE 7. contd
Poly(esters) VI /45
Polymer
Cryst
syst.
Space
FOP
Unit cell parameters Densi ty @cm ) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b C Angl es Z ClJ&d. Amorph. a
(w
kJ/mol (n *p/q) Ref s.
OtthO D2-4 7.48 4 . 9 8 17.26 4 1.179
Poly(S-hydroxy-2-( 1,3-dioxane)-caprylic acid)
trans-
( 2 2 8 . 2 9 ) Ortho 7.487
cis-
Mono 7.842
Poly(4-hydroxymetbylene-2-( 1,3-dioxolane)-caprylic acid)
5.117 13.56 2 1.459
5 . 4 7 6 12.34 y = 96.45
13.52
2 1.440
cis-hans-
( 2 2 8 . 2 9 ) ortbo
Poly(2,6-hydroxynaphthoic acid)
I. Mono
( 1 7 0 . 1 7 ) Or t ho c2v-5
(at 370C) Ortho c2v-21
Il.
-, Sbromo-
( 2 4 9 . 0 6 ) Mono C2h-5
Poly(2-hydroxypropionic acid) [lactic acid]
2 Por t
( 7 2 . 0 6 ) Ortho
ortho
P
D,L-stereocomplex
Tli Cl-l
Poly(3-hydroxypropionic acid) [propiolactone]
a
( 7 2 . 0 6 )
P
-, 3-chloromethyl-
i s ot act i c
( 1 2 0 . 5 4 )
-, 3-dichloromethyl-
i s ot act i c
( 1 5 4 . 9 8 )
s yndi ot act i c
( 3 1 9 . 9 6 )
- 2,2-diethyl-
a ortbo
(128.17)
B
-, 2,2-dimethyl-[pivalolactone]
w.
(100.12) Mono C2h-5
Mono C2h-5
Mono C2h-5
P
Y
ortho D2-4
ortho D2-4
-, 3-ethyl-[3-hydroxyvaleric acid]
i s ot act i c
(100.12) ortho D2-4
(racemic) ortho
-, 2-ethyl-2-methyl-
i s ot act i c
P
(114.14) Por t
-, D,L-2-ethyl-2-methyl-
ortho
c2-1
1.367 5.186 2 1.468
7.8 12.3
1.66 5.98
9.28 5 . 6 4
11.6 3.85
17.4 p=97 8 1.36
17.12 4 1.441
17.04 4 1.267
13.02 4 . 0 6
10.7 6.45
10.34 5.97
17.15 p= 101
27.8
4 1.859 8*2/l 1639
2 0 1.247
10.37 5.98 28.0 2 0
1.290
1.378
8.8
9.16 9.16 8.70 109,109,110
7.02
6 1.274
7.76 4 . 5 0
7.73 4.48
4 . 8 2
4 . 7 6
4.71 y=90
6 . 1 9
2
2
1.440
1.449
7.89 4* l/l 1090
5.77 146 9 0 0
11.55 8* l/l 1090
8.3 10.2 4 . 5 2 1.12
4.63
9.02 11.64
9.05 11.58
9.03 11.62
4 1.234
4 1.234
4 1.237
8.23 11.27
8.23 11.28
6.02 y = 121.5
6.03 y= 121.5
6.01 b y= 121.5
4 . 1 6
6.04
6.02
4 1.187
4 1.190
9.52 10.08 5.56 4 1.246
9.32 10.02 5.56 4 1.281
9 . 1 0 7.44
11.8 34.2
4.75
4.75 p=90
7.1
2
16
1.179
1.06
6911368 7*2/l 1420
16.4 1368
1.093 1501797 13* l/l
1.093 1201797 13* l/l
7 9 6
7 9 6
1.093 531797 13* l / l
8*2/l
8*2/l
8*2/l
7 9 6
1547
1548
1548
1547
3 * IO/3 6 6 3
215 1064
1.248 6.69 1175
3 * 10/3 1557
184 14.6 1367
3*3/l 1557
3*3/l 1557
122/317 9.1/1121 4*2/l
1.360 841623 8.61623
4* l/l
4* l/l
120 4* l/l
146
27511195
3 1 4
1195
3 1 4
6 8 9
8 4 0
9 0 0
258/1088 21/1088 4* l/l
4* l/l
1087
1087
1.10/551 2401551 14.91551 4 * 2/l 321
268/1085 4*2/l 6 8 3
269/1411 4*2/l 23
2 3 4 4*1/l 8 1 6
4*2/l 1092
4*2/l 1390
110/9Kl 4*2/l
108 4*2/l
130/1538
1183
8 1 0
120 4* l/l
W/l211 4* l/l
4*2/l
1089
1536
1536
References page VI- 159
VI/46 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 7. cont d
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b e Angl es Z Cryst al . Amorph. a WY
kJ/mol a (II *p/q) Refs.
-
-, 3-isopropyl-
i s ot act i c
(114.14) Or t ho 10.63 18.13 6.49
-, 2-methyl-
opt. active
racemic
(86.09)
-3 3-methyl-, see Poly(3-hydroxybutyric acid)
-, 2-methyl-2.propyl-
i s ot act i c
(128.17) Ortho D2-3 10.6 11.1 6.7
or D2-4
-3 D,L-2-methyl-2-propyl-
I. (128.17) 5.9
Or t ho 17.9 13.5 12.0
II. Ortho 7.48 10.1 4 . 7 4
-, 3.trichloromethyl-
isotactic Mono 11.79 10.99 11.24
( 1 8 9 . 4 2 ) 11.27
Poly(3-hydroxyvaleric acid), see Poly(3-hydroxypropionic acid), 3.ethyl-
Poly(4,4-isopropylidenediphenylene adipate)
-, 3,3, 5,5 -tetrachloro-
(476.18)
Poly(4,4-isopropylidenediphenylene carbonate)
(254.28) Ortho D2-2 11.9 10.1 21.5
Mono 12.3 10.1 20.8
Or t ho 12.1 10.1 22.0
Poly(lactic acid), see Poly(2-hydroxypropionic acid)
Poly(4,4-methylenediphenylene carbonate)
(226.23) Or t ho C2v-9 5.0 10.5 22.0
Poly[nonamethylene N,Nl-adipolydi(p-aminobenzoate)]
(508.62)
Poly[nonamethylene N,N-azelaoyldi(p-aminobenzoate)]
(550.70)
Poly(nonamethylene azelate) [9.9]
(312.45)
31.0
33.3
Poly[nonamethylene NJ?-glutaryldi(p-aminobenzoate)]
(494.59)
Poly[nonamethylene N,N-hexadecanedioyldi@-aminobenzoate)]
( 6 4 8 . 8 8 )
Poly[nonamethylene iV,N-sebacoyldi(p-aminobenzoate)]
( 5 6 4 . 7 2 )
Poly(nonamethylene terephthalate) [9.T]
( 2 9 0 . 3 6 )
29.8
4 1 . 0
34.3
17.6
Poly[nonamethylene NJ-tetradecanedioyldi@-aminobenzoate)]
(620.83)
Poly[nonamethylene NJ-tridecanedioyldi(p-aminobenzoate)]
(606.80)
Poly(octamethylene adipate) [8.6]
(256.34) 5.10 7.42
Poly(octamethylene 3-hexenedioate)
(254.33)
38.6
37.5
y = 108.0 8 1.817 275/l 199 4*2/l
7x84
8 1.212
4 1.08
16 1.174
2 1.19
4 1.301 1.240
1.307
1.314 1.20
1.256
1.30 1.20
8 9
79/900
95 5.2 1341
100 4.8 1341
4*2/l 698
4*2/l 1536
152 14.6 1651
110 4*2/l 7 8 5
971959 8*2/l 1086
4* l/l 7 8 5
283 33.9 17 * 7 1 3
267157 27.91566 12 *2/l
2 3 0 36.81299 12 *2/l
2631370 12*2/l
3171930
2301438
2601736
29511121
30211233
3 3 5 1 1 0 6 6
2 4 0 12*2/l
3001438
2781736
651405 43.1/159 20*
49.01405
85199
901453
17* l/l
67 41 16* 1079
6 6 3 6 16* 1079
1091
1090
5
4 3 5
1549
283
4 3 5
1386
1386
1386
1386
1386
1386
1386
TA
-
P O
-
PO:
PO
P O
P O
P O
P C
P C
P C
PC
PC
PC
PC
PC
PC
PC
P C
PC
-.
PC
PC
PC
TABLE 7. contd
Poly(esters) VI/47
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm3) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z crystal. Amorph.a
(w kJ/mol (n *p/q) Refs.
Poly(octamethylene 4-octenedioate)
( 2 8 2 . 3 8 )
Poly(octamethylene suberate) [8.8]
( 2 8 4 . 4 0 )
Poly(octamethylene terephthalate) [8.T]
( 2 7 6 . 3 3 )
Poly(oxydiethylene sebacate)
( 2 7 2 . 3 4 ) Tet
4.81 4 . 0 7
5.05 7.44
17.6 17.6
y=109 3 9 3 4
7 0 4 2
132199
441325
471767
461765
100 4 4 . 4
13911654
38.0 3 2 1.229
18* 1079
18* 1079
16+ l/l 1174
17*2/l 105
13* 1653
1386
2 1.198 43/l 120
1 1.354
2 1.318
2 1.341
1161291
134199
140/815
142/807
2 1.358
14* l/l 1119
13* l/l 8 1 4
13*2/l 1069
13*2/l 1160
13*2/l 1069
1386
14.37 L3.55 10.24 125,44,111 4 1.283 20.8
7.83 5 . 6 4 26.37 p=97.9 2 1.383
11.4 7 . 7 18.0 4 1.29 1.172 2 8 0
12* l/l 8 6 9
24* l/l 1621
8 3 2
4 1.365
2 1.500
4 2 5
5.61 3.96 2 3 . 9 0 2 1.502
2 1.502
4 1.478
2 1.272
600/1375
2
2
1.30
1.02
12.77 10.08 12.58 y=90 4 1.297
28.0 4 . 8 9 12.48 y= 114.8 4 1.354
34011375
7.88 5.27 12.62 2 1.740
12.77 10.18 12.58 4 1.342
13.04 9 . 5 1 4 12.24 y = 80.87 4 1.463
13.31 9 . 7 3 2 12.15 y=81.01 4 1.411
11*2/l 1553
11*2/l 1553
11*2/l 1553
12* l/l 1406
12*2/l 1621
12* l/l 1406
12* l/l 1641
12* l/l
12* l/l 1374
12* l/l 1558
12* l / l 1429
12* l/l 1389
12* l/l 1426
12* l/l 1426
4 1.368 12* l/l 1558
2
2 1.611
410/1564 7*2/l 1563
400/ 1565 7*2/l 1645
18.1
Poly(oxydiethylene terephthalate)
( 2 3 6 . 2 2 )
Poly[pentamethylene NJ-hexadecanedioyldi@-aminobenzoate)]
( 5 9 2 . 7 8 )
Poly(pentamethylene pimelate) [5.7]
( 2 2 8 . 2 9 ) Mono 6.14 7.37
Poly(pentamethylene terephthalate) [5.T]
0. Tri Ci -1 6.21 4 . 5 6
( 2 3 4 . 2 5 ) Tli 4 . 6 9 5.79
Tli 4 . 6 8 5.77
35.6
17.16 p=54.6
12.50 89,114,116
2 4 . 6 6 112.94.105
24.42 114,87,106
2 8 . 1 6 126.74.120
3 2 . 0
P
Tli 4 . 9 6 5.82
Poly[pentamethylene N,N-tridecanedioyldi@-aminobenzoate)]
( 5 5 0 . 7 0 )
Poly@-phenylene adipate)
( 2 2 0 . 2 2 ) Tri
Poly(p-phenylene 4,4-dibenzoxyterephthalate)
(480.43) Mono
Poly@-phenylene m-carboranedicarboxylate)
( 3 0 6 . 3 2 ) Ortho
Poly@-phenylene isophthalate)
I. (240.22) Mono
II. oltbo
Poly(m-phenylene terephthalate)
( 2 4 0 . 2 2 ) Ortho
Poly@-phenylene terephthalate)
(240.22) Mono
Mono
( at 475 C) ortbo
-, 2,5-di-n-hexadecyl-(diacid)
( 7 2 1 . 0 8 ) Mono
Ortho
-, phenyl- (diol)
(316.31) Mono c2-2
Mono
-, chloro- (diol)
(274.66) ortho
6.97 6.92 24.32
5.58 3.92 24.32
(L=95
7.98 5.33 12.64
7.85 5.48 25.38
9.25 5 . 4 0 12.56
p=98.98
p=98.6
26.2 7.3 12.6
2 5 . 6 7 . 2 1 2 . 7 3 4
a=130
Poly[(phenyl-p-phenylene terephthalate)-co-(l-phenylethyl-p-phenylene terephthalate)]
(330.34) Ottho c2-2
as spun Mono
annealed Mono
Poly(p-phenylene thioterephthalate)
-, phenyl- (dithio acid)
(348.43) Mono 29.9 4.81 12.57 y= 110.7
Poly(pivalolactone, see Poly(3-hydroxypropionic acid), 2,2-dimethyl-
Poly(propiolactone), see Poly(3-hydroxypropionic acid)
Poly(terephthalic anhydride)
(148.12) OlthO 6 . 0 4 3 . 9 7
Mono 6.02 3.76 13.49 Cl=90
References page VI- 159
VI/48 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 7. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b e Angl es Z Cryst al . Amorph. WY kJ/mol (n *p/q) Refs.
Poly(tetradecamethylene adipate) [ 14.61
( 3 4 0 . 5 0 )
Poly(tetradecamethylene 3-hexenedioate)
(338.49)
Poly(tetradecamethylene 4-octenedioate)
( 3 6 6 . 5 4 )
Poly(tetradecamethylene suberate) [ 14.81
( 3 6 8 . 5 6 )
Poly(tetramethylene adipate) 14.61
ct Mono
( 2 0 0 . 2 3 )
5.00 7.40
4.94 7.64
4.91 4.05
5.03 7.46
6.73 7.94
8 0
8 0
y= 109 63
82
14.20 p=45.5 1.229 481325
541539
601766
451696
5 9 22* 1079
4 9 22s 1079
55 24* 1079
6 6 24* 1079
12* l / l 1073
P
o r t ho 5.062 7.325
Poly[tetramethylene N,N-azelaoyldi (p-aminobenzoate)]
(480.56)
Poly[tetramethylene N,N-hexadecanedioyldi(p-aminobenzoate)]
(578.75)
Poly(tetramethylene isophthalate) [4.1]
(220.22)
14.67 1.222
26.6
12* l/l 1073
1386
35.2 1386
1.309
26.0
1.268 152.5 42.3 11*2/l 1 1 1
150 807
6011325
621425
671766
17/301 16*
2.08/425
5.21 9.14
5.23 9.08
10.94
10.79
10.90
11.90
/3= 124
/3= 123.9
2
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
4
4
1.324 341696
1.344 1141766
lO* l/l 689
lO* l/l 1540
1541
lO* l / l 1541
4 . 8 3 0 5.953 11.67 100,64,69
5.96 4.87 11.71 116,100,110
4.87 5.99 11.67 100,116,111
5.96 4.83 11.62 115,100,111
4.83 6.05 11.45 100,117,111
4.83 5.94 11.59 100,115,111
4.89 5.95 11.67 98,116,110
4.82 5.93 11.74 100,116,111
1.395
1.394
1.392
1.406
1.440
1.403
1.36
1.404
1.08/111
1.355
1.283
1.37
1.332
1.330
1.320
1.28/824 2341807
232199
31/405 12* l / l 786
32/111 12* l / l 814
12* l / l 933
4.703 6.738
4.95 5.67
4.7 5.8
4.73 5.83
4.73 5.75
4.73 5.88
.-dibenzoate]
8.42 5.79
13.12 55,58,56
12.95 102,122,100
13.0 102,121,105
12.90 102,119,105
13.11 104,121,101
13.06 103,120,104
2211453
24511362 12* l/l 851
12* l/l 860
2 2 4 12*1/l 864
12* l/l 883
12* l/l 1158
1.256 30.8 1071
14* l/l 786
14*1/l 864
14* l/l 883
14* l/l 933
14* l/l 1160
14* l/l 1339
24.83 p= 101.8 1.290 24* l/l 1559
1.35 2 2 0 12*2/l 435
2401540
1.50
1.55
F
F
P
R
PC
PC
-3
-
nr
br
TA
(-
-
PO1
-
PO1
Poly(tetramethylene sebacate) [4.10]
(256.34)
Poly(tetramethylene succinate) [4.4]
(172.18) Mono C2h-5
Mono
P
Poly(tetramethylene terephthalate) [4.T]
ci Tli
( 2 2 0 . 2 2 ) Tri Ci -1
Tri
Tli Ci -1
Tli
Tli Ci -1
Tri
Tli
5 . 6 8.7 22.2
21.5 38 11*2/l 107
45/300
461609
22.6 1386
P
Tli
Tli Ci -1
Tli
Tli
Tri
Tli
Poly[tetramethylene (4,4-terephthaloyldioxy)-4,4
(460.44) Mono c2-2
Poly(4,4-thiodiphenylene carbonate)
(244.27) Ortho C2v-9
Poly(trimethylene adipate) [3.6]
( 1 8 6 . 2 1 ) Mono 5.0 7.4
Poly[trimethylene N,N-adipolyldi@-aminobenzoate)]
( 4 2 4 . 4 5 )
Poly[trimethylene N,N-azelaoyldi(p-aminobenzoate)]
( 4 6 6 . 5 3 )
Poly(trimethylene azelate) [3.9]
( 2 2 8 . 2 9 ) Mono 5 . 0 7 . 4
26.4
27.7 4 1.48 5 0
601609
14*2/l 107
Poly(urethanes) and Poly(ureas) VI/49
TABLE 7. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm3) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cl-JfStal. Amorph. a
cva
kJ/mol a (n *p/q) Refs.
Poly(trimethylene dodecanediote) [3.12]
( 2 7 0 . 3 7 ) Mono
Poly(trimethylene glutarate) [3.5]
( 1 7 2 . 1 8 ) Mono
5 . 0 7 . 4 35.8
5.0 7.4 15.4
4
2
1.36 61 17 *2/l
1.00 3 9 lO* l/l
531609
Poly[trimethylene N,N-glutaryldi(p-aminobenzoate)]
( 4 1 0 . 4 3 ) 21.3
Poly[trimethylene N,N-hexadecandioyldi@-aminobenzoate)]
( 5 6 4 . 7 2 ) 35.0
Poly[ttimethylene N,N-malonyldi@-aminobenzoate)]
( 3 8 2 . 3 7 ) 18.5
Poly(trimethylene octadecanedioate) [3.18]
( 3 5 4 . 5 3 ) Mono 5.0 1.4 51.6 4 1.23
Poly(trimethylene pimelate) [3.7]
( 2 0 0 . 2 3 ) Mono 5.0 1.4 23.6 4 1.52
Poly(trimethylene sebacate) [3.10]
( 2 4 2 . 3 2 ) Mono 5.0 1.4 31.3
Pt et 31.2 31.2 33.5
Ottho D2-4 5.032 1.532 31.33
y=90
4 1.39
9 6 1.184
4 1.3554
Poly[trimethylene N,N-sebacoyldi(p-aminobenzoate)]
( 4 8 0 . 5 6 )
Poly(trimethylene suberate) [3.8]
( 2 1 4 . 2 6 ) Mono 5 . 0
27.8
7 . 4 26.1 4 1.47
Poly(ttimethylene succinate) [3.4]
(158.15) Mono 5 . 0 7 . 4 15.2 4 1.87
Poly(trimethylene terephthalate) [3.T]
( 2 0 6 . 2 0 ) Tti Ci -1 4.58 6.22 18.12
Tli Ci- 1 4.637 6 . 2 6 6 18.64
Tti 4 . 5 9 6.21 18.31
Tti 4 . 6 4 6.27 18.64
Poly[trimethylene N,N-tridecanedioyldi(p-aminobenzoate)]
( 5 2 2 . 6 4 ) 31.7
Poly(trimethylene undecanedioate) [3.1 l]
( 2 5 6 . 3 4 ) Ortho 5.0 1.4 32.4
Poly(4,4-vinylenedipbenylene dodecanedioate)
97,89,111
98,93,111
98,90,112
98,93,111
1.432
1.319
1.428
1.317
4 1.42
-, methyl-
1S (420.55) Mono 11.1 7.9 27.8
1M Mono 13.4 4 . 9 4 27.8
2 (at 151 C) Mono 14.5 5.17 27.5
3 (at 172 C) Mono 14.6 5 . 2 0 27.5
Mono C2h-5 13.83 5.28 21.3
p=84
p=40
p=40
p=40
p= 138.6
1.15 24* l/l 1076
1.81 24* l/l 1076
1.054 24* l/l 1076
1.041 24~ l/l 1076
1.059 24* l/l 1560
107
107
1386
1386
23 *2/l 107 7 6
761307
3 7
511609
12*2/l 107
5 3
561305
581609
491696
15+2/l 107
15*2/l 105
15*2/l 1542
1386
13*2/l 107 41
521609
4 7
52/300
521609
9*2/l 107
11*2/l
11*2/l
11*2/l
11*2/l
9 1 7 233199
227 1453
2211291 1068
1080
1386
5 9 16*2/l 107
a The number after the solidus (/) are reference citations.
b The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
TABLE 8. POLYWRETHANES) AND POLY(UREAS) (-O-X-O-CO-NH-Y-NH-CO- or -O-X-NH-CO) and
(-N~~-X-NH-C~-NI~-Y-NI~-C~- or -NH-X-NH-CO-)
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
n b e Angl es Z Cryst al . Amorph. (w kJ/mol (n *p/q) Refs.
Poly(decamethylene hexamethylenediurethane)
(342.48) 154 56.5 22* 1653
148.634
1611473
References page VI- 159
VI/SO CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 8. contd
Polymer
Cryst
syst.
Unit cell parameters Density (g/cm3) Melting Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es z Crystal. Amorph.a WY kJ/mol (n *p/q) Refs.
Poly(decamethylene 4,4-methylenediphenylenediurethane)
( 4 2 4 . 5 4 )
Poly(ethylene decamethylenediurethane)
a
( 2 8 6 . 3 7 )
P
Poly(ethylene 4,4-ethylenediphenylenediurethane)
( 3 2 6 . 3 5 ) Tti
Poly(ethylene hexamethylenediurethane)
a Tti Ci -1 4.93
( 2 3 0 . 2 6 )
Y
Tti Ci -1 4 . 5 9
Poly(ethylene 4,4-methylenediphenylenediwethane)
(3 12.32) Hex
Poly(ethylene nonamethylenediurethane)
( 2 7 2 . 3 4 )
Poly(heptamethylene hexamethylenediurethane)
(300.40)
Poly(heptamethylene 4,4-methylenediphenylenediurethane)
(382.46)
Poly(heptamethyleneurea)
(156.23)
Poly(hexamethylene hexamethylenediurethane)
(286.36) Tli Ci- 1 5.05
Pol y( hexamet hyl ene 4,4-methylenediphenylenediurethane)
I. (368.43) TIi 4.99
Tri 5.1
11.
Poly(hexamethylene trimethylenediurethane)
(244.29) Tli Ci -1 5.04
Poly(hexamethyleneurea)
(142.20)
Poly(4,4-methylenedicyclohexylenethiourea)
trans-, tram-
(252.42) OtthO 9.67
Poly(4,4-methylenedicyclohexyleneurea)
tram-, trans-
( 2 3 6 . 3 6 ) ortho 9 . 2 0
Poly(4,4-methylenediphenyleneurea)
( 2 2 4 . 2 6 ) Mono a-2 4 . 7 2
Poly(nonamethylene hexametbylenediuretbane)
( 3 2 8 . 4 5 )
Poly(nonamethylene 4,4-methylenediphenylenediurethane)
( 4 1 0 . 5 1 )
Poly(octamethylene hexamethylenediurethane)
( 3 1 4 . 4 3 )
Poly(octamethylene 4,4-methylenediphenylenediurethane)
( 3 9 6 . 4 9 )
4 . 5 8 16.8 6 2 7
5.14 13.9 6 2 7
15.7
15.0
3 1 2 18* l/l
113,103,109 1 1.266 170 42/1653 14* l/l
1841402
1661473
y=l19 1 1.333 170 l4* l/l
2 3 9
23711653 4811653 17 * l/l
168 17*2/l
146 4 8 . 5 19*
1511473
4 1 4
1125
3 6 . 2 414
1653
20.7 1125
1653
4 . 5 4 21.9
1981473 22* l/l
191 50.6
10.6/404 lO*
112,108,108 1 1.226 165 52/1653 18* l/l
1711473
1641634
1501291
6 2 7
5.1
4 1 . 5
4 1 . 6
19.2
114,114,84 2 1791634 5211653 21*2/l
116.116.85 2 1.41 2001473 20*2/l
111,111,111 2 1.275 15*2/l
300/402 13.9/404 9*
>300/291
2681634
1125
1627
1637
5 . 0 4 34.65 1081
6 . 1 7 24.6 4 1.142 12*2/l 1315
6 . 2 2 23.8
11.33 11.64
4 1.153
y= 116.5 2 1.337
12*2/l
12* l/l
21*
1315
1084
21.8
18.9
19.7
22.8
192 6 9 . 0 25 *
1661634
1941473
174 18* l/l
18* l/l
147 5 2 3
190 58.6
1941473
157 55.2
1521634
1621473
1653
24* 1653
20* 1653
1721634 5911653 2 3 * l/l
2011473
1653
4 1 4
4 1 4
4 1 4
1125
1
I
I
F
F
F
F
P
P
P
P
P
-
n
b
T
-
R
-
P C
P C
-.
PC
P C
Poly(ethers) VI/51
TABLE 8. cont d
Unit cell parameters Density (g/cm 3, Mel ti ng Heat of Chai n
Cryst Space poi nt f us i on conf orm.
Polymer syst.
group
a b c Angl es Z Cryst al . Amorph. (w kJ/mol a (n *p/q) Refs.
Poly(oxydiethylenedioxydiethylenedioxydiethylene hexamethylenediurethane)
(534.69)
Poly(pentamethylene hexamethylenediurethane)
( 2 7 2 . 3 4 ) Mono C2h-3 4 . 7 0 8.36
Poly(pentamethylene 4,4-methylenediphenylenediurethane)
(354.41)
Poly(pentamethyleneurethane)
( 1 2 9 . 1 6 )
Poly(tetramethylene hexamethylenediurethane)
( 2 5 8 . 3 2 ) Tli
Tli
Tri Ci -1
4.95 8.65 19.17 90,104,60 2
9.05 8.38 19.1 90,115,63 4
4.98 4.71 19.4 116,105,109 1
Poly(tetramethylene 4,4-methylenedicyclohexylenediurethane)
trans-, trans-
I. (352.48) Tli 5.1 10.2
II.
28.1 29* l/l 875
39.0 y=115 4 1.302 158 4211653 17 *2/l
1571473
2351402
1511633
6 2 7
18.6
37.5
41.3
Poly(tetramethylene 4,4-methylenediphenylenediphenylenediurethane)
I. (340.38) Tri Ci- 1 5.31 5.26 38.61
II. Tri Ci -1 5.06 5.06 36.97
17.0
III. Tti 5.05 4.67 37.9
Tli 4 . 9 2 5.66 38.35
19.2
Poly(tetramethylene trimethylenediurethane)
(216.24) Tli Ci- 1 5.06 5.04 30.10
Poly(trimethylene hexamethylenediurethane)
( 2 4 4 . 2 9 ) M0u0 C2h-3 4 . 7 0 8.36 33.9
Poly(trimethylene 4,4-methylenediphenylenediurethane)
I. (326.35)
II.
17.6 22711653 4711653 18 + l/l 1627
16.2 2411473 18* l/l 1125
115,85,94 4
114,115,96 2
115,108,95 2
116,116,84 2
124,104,86 2
112,113,110 2
y=115 4
1921473 5111653 20* l/l
189/944 33.7/944 8*
150/291
1551444
1125
1.248 180/291 48/1653 16* l/l
1.510 173/101 16* l/l
1.258 184
1821473
1841402
6 6 2
3 3 4
6 2 7
1.33 19*2/l 1643
19*2/l 1643
1.438 19*2/l
1.340 19*2/l
1.523 194/634 19*2/l
1.324 2481473 19*2/l
23211653 5311653
1.337 13 *2/l
1.344 168 4211653 15*2/l
1671633
1631473
1567
1567
1082
1083
1273
1081
6 2 7
a The number after the solidus (/) are reference citations.
b The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
TABLE 9. POLY(ETHERS) (-HCH-CHOR-)
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/cm ) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. (1 c-3 kJ/mol (n *p/q) Refs.
Poly(benzylviny1 ether)
(134.18)
Poly(butylviny1 ether)
(100.16) Rb o
-, 2-methyl-
(114.19)
C3i-2 23.7 23.7
Poly(sec-butylvinyl ether), see Poly(propylviny1 ether), l-methyl-
Poly(rerf-butylvinyl ether)
(100.16) Tet C4h-6 18.84 18.84
6.30 162/l 14 2*3/l 253
6.50 18 0.947 0.92 641114 2*3/l 3 6 0
6.50 140 2*3/l 3 8 2
128/608
7.65 16 0 . 9 8 0 160 2*4/l 2 6 9
260/l 14
2381281
References page VI- 159
VI/52 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 9. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Melting Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. n (w kJ/mol (n *p/q) Refs.
Poly(ethylene)
-, I-butoxy-2-chloro-
trans-
( 1 3 4 . 6 1 )
cis-
6.5 2*3/l 2 4 2
8.6 2*4/l 2 4 2
20.8 2* 10/3 2 4 2
13.77
13.8 2 2 6
2*7/2 61
2*7/2 141
16.8 9 . 7 0 6 . 5 0 6 0.942
0.94
117
117
165/l 14
170/28 1
115146
2*3/l 161
269
2*3/l 152
17.2 17.2 35.5 6 8 0 . 9 2 6
0.93
191/281
9 8
190/l 14
2 * 1715 161
269
16.20 16.20 6.50
16.25 16.25 6 . 5 0
15.2 15.2 16.4
9.02 9.02 16.0
9.02 9.02 16.6
18.2 10.51 6.50
18
18
1.175
1.168
w/114 2*3/l 176
2*3/l 4 2 9
3 2 1.011 2*8/3 383
10 1.062 4*5/2 514
10 1.024 4*5/2 5 5 4
6 0.915
0.91
216/281
155
216/l 14
2*3/l 161
269
18.25 35.5
35.3
6 8 0 . 9 5 6 1771608 2 * 1715 4 2 4
170 2 * 1715 382
-, I-chloro-2-isobutoxy-
trans-
( 1 3 4 . 6 1 )
-, I-isobutoxy-2-methyl-
trans-
( 1 1 4 . 1 9 )
1
1
I
1
1
I
I
I
F
F
-
Poly(isobutylviny1 ether)
( 1 0 0 . 1 6 ) Or t ho
Poly(isopropylviny1 ether)
( 8 6 . 1 3 ) Tet
Poly(methylviny1 ether)
( 5 8 . 0 8 ) RbO D3d-6
RhO D3d-6
Poly(wmethylviny1 methyl ether)
s yndi ot act i c Tet
( 7 2 . 1 1 ) Phex
Hex
Poly(neopentylviny1 ether)
(114.19) Or t ho
Poly(propylviny1 ether)
-, l-methyl-
(100.16) Tet
a The number after the solidus (/) are reference citations.
b The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
TABLE 10. POLY(OXIDES) (-X-O-Y-O- or -R-O-)
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Allgks Z Cryst al . Am0rph.O WY
kJ/mol n (n *p/q) Refs.
Poly(acetaldehyde)
( 4 4 . 0 5 ) Tet C4h-6 14.63 14.63 4 . 7 9 16 1.142 1651329 2*4/l 92
-, 2-chloro-
( 7 8 . 5 0 ) Tet C4h-6 4 . 8 0 2*4/l 387
- 2,2-dichloro-
( 1 1 2 . 9 4 ) Tet C4h-6 5.22 264/l 387
-, 2,2,2-trichloro-
( 1 4 7 . 3 9 ) Tet C4h-6 6.45 >220/338 2*4/l 387
PoIy(2-butene oxide)
trans-
(72.11) Or ht o D2-4 13.72 4 . 6 0 6.90 4 4 1 . 1 0 0 1141399 3*2/l 397
OldlO D2-4 13.79 4.65 6.96 4 1.073 MI/527 3*2/l 800
cis-
OldlO 11.20 10.44 7.01 8 1.169 162/399 3*2/l 397
TABLE 10. contd
Poly(oxides) VI /53
Polymer
clyst
syst.
Space
group
Unit cell parameters Density (g/d) Melting Heat of Chai n
poi nt f us i on conform.
a b c Allgk Z crystal. Am0rph.O
WY
kJ/mol (n *p/q) Ref s.
Poly(butyraldehyde)
( 7 2 . 1 1 ) Tet C4h-6
Poly(l,3-cyclobutyleneoxymethylene oxide)
-, 2,2,4,4-tetramethyl-
20.01 20.01 4.78 16 1.001 2251329 2*4/l 9 2
;56.23)
P
cis-
a
P
Poly(decamethylene oxide)
( 1 5 6 . 2 7 ) ortbo 7.40 4 . 9 4
ortho D2h-16 7.40 4.93
Poly( 1,3-dioxolane), see Poly(ethyleneoxymethylene oxide)
Poly(l,3-dioxolane), see Poly(methyleneoxytetramethylene oxide)
Poly(dodecamethylene oxide)
( 1 8 4 . 3 2 ) OtthO 7 . 4 0 4 . 9 4
Poly(epichlorohydrin), see Poly(ethylene oxide), chloromethyl-
Poly(4,4-ethylenediphenyleneoxyheptamethylene oxide)
-, 3-methyl-
( 3 2 4 . 4 6 ) Mono 11.4
Poly(4,4-ethylenediphenyleneoxynonamethylene oxide)
-, 3-methyl-
( 3 5 2 . 5 2 ) Mono 20.1
Poly(4,4-ethylenediphenyleneoxypentamethylene oxide)
-, 3-methyl-
( 2 9 6 . 4 1 ) Tri 12.7
10.4
28.3
9.61
Poly(4,4-ethylenediphenyleneoxyundecamethylene oxide)
-, 3-methyl-
( 3 8 0 . 5 7 ) Mono
Poly(ethylene oxide)
I. (44.05) Mono
Mono C2h-5
Mono cs-2
Mono
Mono
Mono
Mono
20.8 27.4 25.5
9. 5 12.0 19.56
8.05 13.04 19.48
8.03 13.09 19.52
7.95 13.11 19.39
8.02 13.4 19.25
8.16 12.99 19.30
7.5 1 13.35 19.90
II.
-7
ren-butyl-
i s ot act i c
(100.16)
Tli Ci- 1
Tet D2d-8
syndiotactic
-, chloromethyl- [epichlorohydrin]
(92.52)
Orthb D2-4
or c2v-9
Or t ho c2v-9
Or t ho
or t ho D2-4
-, isopropyl-
(86.13) OIthO D2-4 12.85 7.52 5.55
11.5
5.75
11.5
5.75
27.49
27.29
32.53 4 1.030 13*2/l 4 8 2
18.9
22.3
47.3
4.71 4.44 7.12 63.93.111 2
15.42 15.42 24.65 3 6 1.022
7.05
12.14 4 . 9 0 7.07
12.16 4 . 9 0 7.03
12.24 4 . 9 2 6.96
12.15 4 . 8 6 7.07
4
4
1.033
1.042
y=84.1 6
y = 88.6
1.450
vi. ref.
44,96,100 1 2 1.495
y=84.1
y= 101 3 6
p= 125.4 28
p=125.1 2 8
p=124.6 2 8
p= 126.9 28
p=126.1 2 8
p = 118.6 28
vi. ref. 23 * l/l 1574
1.207
1.229
1.220
1.231
1.238
1.239
1.169
1.227
1.235
1.197
1.461
1.467
1.466
1.472
1.067
2 6 0
2601369
6*
2 8 5
2851369
6*
7 9 11*2/l
791181 11*2/l
72/180
19* l/l
21*1/l
17*3/l
1.131366 66181 8.29181 3 *7/2
701538 9.51665 3 * 712
621180 8.04/498 3 * 712
721318 11.71466 3 * 712
691728 9.411728 3 * 712
751964 7 . 8 6 1 9 6 4 3 *7/2
761567 8.711195 3 * 712
1.123 751665
1.124 7011189 7.33
1351691
NO/692
1501693
1521527
631691
117
121
135/318
116 10.6
5 3
3*2/l
109
3 0 3
194
188
2 2 7
4 6 0
1164
190
3 9 0
7 9 0
3*9/4 7 1 7
3*2/l
3*2/l
3*2/l
3*2/l
119
194
5 5 5
601
8 0 0
1280
3*2/l 8 0 2
361
361
361
361
4 8 2
6 8 9
1574
1574
1574
References page VI-159
VI/ 54 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 10. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm j) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b e Angl es Z Cryst al . Amorph. c-3 kJ/mol (n *p/q) Refs.
Poly(ethylene oxide), complexes with:
-, p-bromochlorobenzene (3 per 10 residues)
O r t h o c2v-12
-,
p-bromofluorobenzene (3 per 10 residues)
OtThO c2v-12
-, p-chloroiodobenzene (3 per IO residues)
O r t h o c2v-12
-1 p-chlorotoluene (3 per 10 residues)
O r t h o
-1 p-dibromobenzene (3 per 10 residues)
O r t b o
O r t h o c2v12
-1 p-dichlorobenzene (3 per 10 residues)
O r t h o czv-12
-> mercuric compounds
-1 -1 H@rz
I . O r t h o
(1 Hg/4 residues)
-7 -3 H g C 1 2
I . OtiO
(1 Hg/4 residues) Ottho
II. OldlO
(1 Hgkesidue)
-, -1 &I 2
-, p-nitrophenol
Tti Ci - 1
-1 perhydrotriphenylene
-, resorcinol
lx M o n o
(1 R/2 residues) O r t h o
P
-, sodium iodide
(1 NaV3 EO) M o n o
-3 sodium perchlorate
(1 Na/3 EO) M o n o
-> thiocyanates
-, -1 pot assi um
1 s al t : 4 EO Tti
( dbl e. hel i x)
-3 -9
s o d i u m
1 salt:1 EO M o n o
1 s al t : 3 EO M o n o
1 s al t : 4 EO Tt i
(dble. helix)
-, trifluoromethane sulfonate
(1 salt/3 EO) M o n o
-, urea
(9 urea/4 R) R h o
R h o
CZh-5 16. 05 14. 25 9. 84
C2v-9 10. 50 10. 18 9. 776
C2h-5
C2h-5
CZh-5
C2h-5
C2h-5
D3-4
16. 58 9. 58 28. 10
16. 38 9. 46 28. 56
16. 78 9. 73 28. 24
8. 63 9. 27 28. 41
8. 37 4 . 8 4 27. 98
16. 74 9. 68 27. 98
16. 48 9. 51 27. 86
13. 73 8. 66 11. 80 1 6 2 . 5 4 0 7 3 2
1 3 . 5 1 7 . 1 1 1 . 6
13. 55 8. 58 11. 75
7. 75 12. 09 5. 88
13. 52
11. 72 5. 55 15. 57
6. 87
18. 15 8. 41 7. 98
18. 32 8. 578 8.346
11. 37 8. 18 8. 10 80,66,89 8 1. 343 3*4/l 1100
7. 55 12. 10 5. 83 p=97.5 4 1. 574 6* l/l 1432
16. 83 10. 64 7. 19 y= 125. 5 1 2 1. 351 9 * 2 / l 1432
10. 25 8. 43 7. 23 91,61,104 8 1. 616 3*4/l 1100
16. 77 10. 07 8.613
10. 43 10. 43 9. 12
10. 52 10. 52 9. 259
91,87,104 6 1. 389 9*2/l 1570
p=112
y = 122. 3 1 2 1. 819 9*2/l 1343
y= 123. 1 6 1. 540 9*2/l 1571
y= 121. 0 6 1. 5355 9*2/l 1572
Poly(ethyleneoxymethylene oxide) [ 1,3-dioxolane]
I . ( 74. 08) Tli Cl-l 12. 32 4. 66 2 4 . 7 y= loo.9
3 6 . 6
II. O r t h o D2H-15
III. Hex
Poly(formaldehyde), see Poly(oxymethylene)
Poly(heptaldehyde)
( 114. 19) Te t C4H-6
9. 07 7. 79 9. 85
8. 07 8. 07 2 9 . 5
2 5 . 9 2 5 . 9 4. 52
4 0 1. 510 9111232 3 * 10/3 1278
4 0 1. 449 3 * 10/3 1278
4 0 1. 665 8211232 3 * 10/3 1278
2 0 1. 199 3 * 10/3 1232
1 0 1. 682 9 6 . 5 3 * 10/3 1207
4 0 1. 682 9811232 3 * 10/3 1278
4 0 1. 341 83/1232 3 * 10/3 1278
3 2 2. 22
1 6 2. 177
4 3. 804
6*2/l
6+ l/l
731
7 3 2
7 3 3
7 3 2
3 * 2 / l 1173
1 6 1. 262
8 1. 260
3*4/l
9 3 3*4/l
71/1568
1099
1568
4 1. 3408
1431734
3*4/l
7 3 0
1569
1 5 1. 325 55/506 17.11973 5*5/l
8
1 8
1 6
1. 414
1. 331
1. 000
9 3 1 5 . 5
55 1937 5*2/l
601937 5*6/l
690
5 0 5
1163
6 8 8
6 9 0
0 . 8 8 0 147 2*4/l
150/329
TABLE 10. contd
Poly(oxides) VI/55
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b e Angl es Z Cryst al . Amorph. n
(w
kJ/mol (n *p/q) Ref s.
Poly(hexamethylene oxide)
( 1 0 0 . 1 6 ) Mono
Mono
C2h-6 5.65 9.01 17.28 p= 134.5 4 1.060
C2h-6 5.64 8.98 17.32 p= 134.5 4 1.063
Poly(hexamethyleneoxymethylene oxide)
( 1 3 0 . 1 9 ) Or t ho C2v-9
Poly(isobutylene oxide)
( 7 2 . 1 1 ) Ortho D2-4
Ortho D2-4
8.4 4.85
10.76 5.76
10.80 5.88
Poly(isobutyraldehyde)
( 7 2 . 1 1 ) Tet
Poly(4,4-isopropylidenediphenyleneoxytrimefhylene oxide)
-, 2-hydroxy- (alkyl)
( 2 8 4 . 3 6 ) OITbO D2h-24 16.31
Poly(isopropylidene oxide)
( 5 8 . 0 8 ) Tet s4- 1 14.65
Poly(isovaleraldehyde)
( 8 6 . 1 3 ) Tet 20.6
Poly(4.4~methylenediphenylene oxide)
( 1 8 2 . 2 2 ) Or t ho 8.10
Poly(methyleneoxypentamethylene oxide) [ 1,3-dioxocane]
( 1 1 6 . 1 6 ) tri Ci -1 8.36
Poly(methyleneoxytetramethylene oxide) [ 1,3-dioxepane]
( 1 0 2 . 1 3 ) ortbo C2v-9 8.50 4.79 13.50 4 1.234 14* l/l
3 0 14.5
Poly(nonaldehyde)
( 1 4 2 . 2 4 ) Tet
Poly(nonamethylene oxide)
( 1 4 2 . 2 4 ) ortbo
Poly(octamethylene oxide)
I. (128.22) Mono C2h-6
30.56 30.56 4.52 16
7 . 3 6 4 . 9 4 12.45 2 1.044 7 3
5.67 9 . 0 4 22.45 p=134.5 4 1.038 6 7
741727
741799
83/l 167
2*4/l
lO* l/l
9*2/l
II. ortbo
Poly(oxacyclobutane) [trimethylene oxide]
I. (hydrate)
(58.08)
Mono C2h-3 12.3 1.27 4 . 8 0 p=91 4 1.178
II. RllO
III. Or t ho
IV.
-, 3Jbisazidomethyl-
(152.16)
-, 3,3-bischloromethyl-
u Or t ho
(155.02) Or t ho
ortbo
Or t ho
P
Mono
Mono
Or t ho
C3v-6 14.13 14.13
D2-5 9.23 4 . 8 2
D2h
D2h-16
C2v-9
17.85 8.16 4.8 4 1.47
8.16 17.85 4.82 4 1.466
17.85 8.16 4.67 4 1.514
17.85 8.15 4.78 4 1.481
cs-1
or Cs- 2
cs-3
c2v-12
6.85 11.42 4.15 p= 109.8 2
11.42 7.06 4.82 y=114.5 2 1.456
13.01 11.71 4.61 4 1.447
1.36 4.93 22.43 4 1.046
8.41
7.21
4.79
18 1.194
4 1.203
1.47
1.472
19.34 7.90 8 1.515
14.65 10.22 2 8 1.231
20.6 5.2 16 1.04
5 . 6 0 10.00 2 1.334
4 . 8 4 8.15 90,90,90 2 1.70
5 8
58/181
0 . 9 3 2 73.3 23.8
621542
7*2/l
7*2/l
4 8 2
6 8 9
941
18.8 4 1.13 381695
7.00
7.05
4
4
1.104
1.070
1581593
175
1771548
1601664
155/318
9*2/l
3*2/l
3*2/l
7 8 3
5 9 4
7 7 5
5.2 > 2601329 2*4/l 9 6
1118
6 0 2 1 4
9 6
140 7 4 5
391695
4 6 7.74
14* l/l
2*7/2
2*4/l
10* l/l
8*1/l 7 8 3
1410
6 8 6
1165
1098
4 8 2
4 8 2
29.81727
29.31799
3211167
9*2/l 4 8 2
36/180
34/181
351447
4*1/l 4 4 6
50/1328
8* l/l 4 4 6
8.8/1328 8 * l/l 4 4 6
4*1/l 1096
128 53.6 1269
HO/173
180/148
1.371 2 0 3
1.39
32.21271 4* l/l
23.01343 4* l/l
4* l/l
4*1/l
19.5
4t l/l
3 4 4
3 7 8
6 8 9
1094
1195
3 4 3
172
4* l/l
4* l/l
3 7 8
6 8 9
References page VI- 159
VI/56 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 10. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm j) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b e Angl es Z CQdAll. Am0rph.O (cla kJ/mol a (n *p/q) Refs.
-, 3,3-bisethoxymethyl-
(174.24) Hex
-, 3,3-bishydroxymethyl-
(86.13) M0n0
-, 2,2-bistrifluoromethyl-
(194.08) Ortho
-, 3-rert-butyl-
(114.19)
-, 3,3-diethyl-
I. (114.19) M o n o
M o n o
I I . Ortho
-, 3,3-dimethyl-
I. (86.13)
I I .
Ortho
M o n o
I I I . ortho
-, 3-ethyl-3-methyl-
(100.16) Ortho
D2-4
5.24 5.24
11.85 10.39
10.63 8.00
c2-2
D2-5
13.33 5.71
2 0 . 3 6 5.58
C2h-5 8.93 7.48
D2-5 15.60 5 . 1 4
D2-2 18.46 5.66
-, 3-methyl-3-hydroxymethyl
(86.13) M o n o
Poly(oxymethylene) [formaldehyde]
I. (30.03) Rho
RhO
Rho
Rho
Ortho
C3-2
or c3-3
D6h-1
11. Ortho
I I I . Ortho
(at 14 kbar)
Poly(p-phenylene oxide)
(92.10) Ortho
D2-4
D2h-14
-, 2,6-dimethoxy-
(152.15)
-, 2,6-dimethyl-
(120.15)
Tet
6.46 6? 1.25?
4.79 y=90
8.01
4 0 . 9 7 0 4*1/l 1385
4 1.892 4*2/l 921
4.74 y=91.1
6.67
6. 7
2 1.040
4 1.001
4.83
8.35 /3 = 97. 9
6.51
4 1.036
4 0.981
6.57
6. 5
4 0 . 9 6 9
11.69 10.25
4.46 4.46
4.43 4.43
4.471 4.471
4 . 4 7 0 4 . 4 7 0
7.15 4.46
4 . 7 0 y = 89. 4
17.30
4 1.016
9 1.506
17.25 9 1.531
17.39 9 1.491
56.00 2 9 1.492
17.30 1 8 1.501
4.767 7 . 6 6 0 3.563 4 1.533
4.57 7.41 3.49 4 1.688
8.07 5.54 9. 12 4 1.408
8.45 6.02 y=91
11.92 11.92 17.10 1 6 1.314
-, 2,6-diphenyl-
I. (244.29) Tet D4-4 12.51
Poly(m-phenyleneoxy-2-cyano-1,3-phenylene oxide)
(209.20) Mono C2h-5 8.62
Poly(propionaldehyde)
(58.08) Tet C4h-6 17.52
-, 3-methoxycarbonyl-
(116.12)
-, 3-cyano-
(83.09) Tri 9.44
12.51 17.08 8 1.214
13.07 9.03 p=99 4 1.383
17.52 4.78 1 6 1.052
4 . 5 6
5.32 4.95 y=102 2 1.135
1 2 5
83/1271
7 7 5. 0 1358
4711271
1 0 0
8 0
6 4
7511328
80/ 1394
6 6
5611328
0.927 6 0
1.25 181
1.32/640 198/217
1781329
2151964
2001455
9.41 4*2/l? 1209
4* l/l 1097
10.46 4*1/l 1298
4*2/l 1299
4*2/l 1097
10.04 4*2/l 1298
47/44? 4 * l/l
8*1/l
9.211328
4*2/l
7.411328
4*2/l 1299
6.28 4*2/l 1300
4* l/l
7.45191 2 * 915
6.66/186 2*9/5
I.371343 2 * 915
10.0/628 2 * 915
9.8/1121 *29/16
5.65/964 2 * 9/
1.215
11.67
2*2/l
2*2/l
1.27 2 9 8
2621773
2 8 7 3. 2 5* 7 9 3
2 6 1
212/411
3 0 7
2621484
4841201
340 2
12.21201 5 *4/l 5 7
8*1/l 1427
1851329
1 5 0
2*4/l 9 2
2* 7 0 4
1 7 6 2*2/l 2 4 0
7.831173 5 *2/l 4 8 7
5.861524 5 *
3.8/471 5*4/l
5.95
5.01484
5.731972
5.081574
5.381940
5.401598
1095
1095
1095
1385
4 2
134
2 5 8
5 1 3
2 7 0
2 4 9
1195
1344
2 7 0
8 1 7
2 2 6
6 2 1
1200
T/
-
PI
-
P I
-
PI
-
-
P
P
a
b
T
P
P
P
P
P
TABLE 10. contd
Polyhdfides) and Poly(sulfones) VI/57
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm3) Melting Heat of Chai n
poi nt f us i on conf orm.
0 b c Angl es Z crystal. Amorph. a
two
kJ/mol a (n *p/q) Refs.
Poly(propylene oxide)
( 5 8 . 0 8 ) OtThO C2v-9 10.52
or D2-4
Or t ho D2-4 10.51
Or t ho D2-4 10.52
ortho D2-4 10.40
Or t ho D2-4 10.46
-, 3-phenoxy-
(150.18) Or t ho 17.0
4.61 7.16 4
4.69 7.09 4
4.68 7.10 4
4 . 6 4 6.92 4
4 . 6 6 7.03 4
8.2 5.48 4
1.097 13
1.104
1.104
1.155
1.126
0.998/139 75118
751311
721664
131285
SO/1649
8.41498 3 *2/l
8.41377
3*2/ l
3*2/l
8.411649 3 *2/l
3*2/l
8 0 0
41
78
4 4 8
1.30 1.27 215
2101297
2081318
2031833
2031527
3*2/l 2 3 8
9 . 9 0 6.93 4
6.26 6.26 4
8.73 12.07 /3=34.2 4
8.90 12.07 p= 134.2 4
8.89 12.15
8.75 12.25b 8
8.92 12.25 a= 134.5 4
1.418 2 0 0 3*2/l 4 4 5
1.663 3*2/l
1.157
1.112
1.116
1.238
1.095
35
4 3
0.982 601366
37/180
12.61425 5 e 2/l 3 4 8
12.4/600 5 *2/l 4 6 0
14.4 5*2/l 5 9 9
5*2/l 5 3 3
5*2/l 4 0 3
8.199 11.032 1.267
5.55 10.20 2 1.440 3 4 0 lO* l/l
1573
7 4 5
-1 -3 o-chloro-
( 1 8 4 . 6 2 ) Or t ho
-, 3,3,3-trifluoro-
( 1 1 2 . 0 5 ) Or t ho D2-4
Poly(tetrahydrofuran) [tetramethylene oxide]
( 7 2 . 1 1 ) Mono C2h-6
Mono C2h-6
12.6
11.42
5.48
5.59
Or t ho D2-4 1.22
Mono C2h-6 5.61
-, compl ex wi t h:
-1 -1 urea (6 urea: 1.8 EO)
Hex C6-1 8.199
Poly(4,4-thiodiphenylene oxide)
( 2 0 0 . 2 6 ) Ortho 8.16
Poly(trimethylene oxide), see Poly(oxacyclobutane)
The number after the solidus (1) are reference citations.
b The unit cell parameter assignment has been changed from that published so as to make c the fiber axis
TABLE 11. POLY(SULFIDES) AND POLY(SULFONES)
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm j) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. a WY Id/m01 a (n *p/q) Refs.
Polymer of selenium
( 7 8 . 9 6 ) Rh o D3-6 4.355 4 . 3 5 5 4 . 9 4 9 3 4.839
y = 100.75
/3=113 80
2
4
4
9
a=90 12
2.30
2.059
1.413
1.416
1.421
1.079
1.106
4 . 2 8 9
1.92
2191752 5. 201752 1*3/l 751
22111121 6.211121 1195
1*8 2 8 8
Indet. 4 6 9
1 * 1013 192
2 5 0 1195
1301294 134
1131295 4*3/l 4 6 8
1451725
2 1 0 3*2/l 241
190/181 3*2/l 5 0 4
216/1104 14/1104 3*2/l 9 2 2
162 3*3/l 9 0 6
2 1 0 3*3/l 9 0 6
2051694
References page VI- 159
Polymer of sulfur
( 3 2 . 0 6 ) Mono
Or t ho
Mono
C2h-2
c2-1
26.4 12.32
8.11 9.20
17.6 9.25
9 . 2 6
13.8
Poly(ethylene disulfide)
(92.17) 8.8
8.8
Poly(ethylene sulfide)
( 6 0 . 1 1 ) Hex
Or t ho
ortho
-3 rert-butyl-
opt. active
(116.22)
i na c t i ve
RhO
Por t
D2h-6
D2-4
4.92 4.92 6.14
8.50 4.95 6.70
8.508 4.938 6.686
C3-2 16.91 16.91 6.50
C2h-5 16.67 19.27 6.52
VI/58 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 11. contcf
Polymer
tryst
syst.
Space
VP
Unit cell parameters Densi ty (g/ cm 3, Melting Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es z crystal. Amorph. G
WY kJ/mol a (n *p/q) Refs.
-, isopropyl-
i s ot act i c
( 1 0 2 . 2 0 ) OlthO
Poly(ethylene tetrasulfide)
(156.29) Oh0
Mono
Poly(hexamethylene sulfide)
(116.22)
c2v-21 17.92
8.57
8.68
Poly(hexamethylene sulfone)
(148.22) Mono 9.88
Poly(hexamethylenesulfonylpentamethylene sulfone)
(282.42) Mono 9.88
Poly(hexamethylenesulfonyltetramethylene sulfone)
( 2 6 8 . 3 9 ) Mono 9.88
Poly(methylene disulfide)
( 7 8 . 1 5 )
Poly(methylene selenide)
I. (92.99) Hex 5.22
II. Or t ho D2-4 5.37
Poly(methylene sulfide)
( 4 6 . 0 9 ) OlthO 12.7
Hex 5.07
Poly(pentamethylene sulfide)
( 1 0 2 . 2 0 ) Mono C2h-5 9.61
Poly(pentamethylene sulfone)
( 1 3 4 . 1 9 ) Mono 9.88
P~~y(pentnmethylenesulfonyltetr~ethylen sulfone)
( 2 5 4 . 3 6 ) Mono 9.88
Poly@-phenylene sulfide)
(108.16) Ortho D2h-14 8.67
onho 8.68
Or t ho 8.57
Poly(propylene sulfide)
i s ot act i c
( 7 4 . 1 4 ) OrthO D2-4 9.95
Poly(tetradecamethylene sulfide)
I. (228.44) Tii Ci -1 4.81
Poly(tetramethylene sulfide)
I. (88.17) Mono C2h-6 5.73
Poly(thiazy1)
I. (46.07) Mono C2h-5 4.153
Mono C2h-5 4.12
Mono C2h-5 4.15
I. Mono C2h-5 4 . 0 4
Mono C2h-5 4 . 0 4 0
II. Or t ho D2-4 6.25 1
ortho D2-4 4.81
III. Ortho D2-4 9.20
IV. 6 . 8 0
V . 13.92
Poly(trimethylene sulfide)
( 7 4 . 1 4 ) Mono cs-2 5 . 1 6
-, 3,3-dimethyl-
( 1 0 2 . 2 0 )
17.92 7.20 16
5 . 0 4 . 2 7 1
5.03 4.32 y=87 1
4 . 3 2
9. 26 18. 24 p=121.7 8
9. 26 34. 00 b=l21.7 8
9.2615.68 /3= 121.7 4
4.18
5. 22 46. 25 21
9.03 4.27 4
12.0 5.10 16
5. 07 36. 52 17
9.78 7.84 p=131 4
9 . 2 6 7.76 p=121.7 4
9.26 28.33 p=121.7 8
5.61 10.26 4
5.66 10.26 4
5.59 10.33 4
4.89 8.20 4 1.234
9.61 38.8 123.89.106 4 1.058
9.15 13.26 p= 135.7 4 1.206 671181
7.637
7 . 6 4
7.64
7.86
7 . 8 4 9
4 . 8 0 7
6.25
10.72
10.33 4.066 y=120.5 2 1.320
4 . 4 3 9 6
4.43
4 . 4 4
4.436
4.429
4.429
4.43
4.93
5.24
5.81
y=109.7 4 2.308
y=109.5 4 2.328
y=llO 4 2.313
y=lO9 4 2.300
y=109.3 4 2.308
4 2.299
4 2.298
16 2.517
1.174
1.42
1.378
1.387
90.3 19.8
79/181
681295
2 2 0
3*2/l
4* l/l 256
4* l/l 257
4*1/l 134
1322
1.418 2 2 3
7*2/l 39
13*2/l 39
1.460 2 4 6 12*1/l 39
2.971 190
2.983 170
1.575
1.600
3*2/l 4 6 7
2*21/11 4 1 6
2*2/l 4 6 3
2*2/l 2 3 7
2* 1719 331
1.221
1.476
2 6 0
2451181
260/298
651295
2 4 3
1.532 2 4 7
6* l/l 687
6* l/l 39
11*2/l 39
1.440
1.425
1.452 1.319
2 9 5 5*2/l 6 7 7
2901679 5*2/l 1345
31511234 12.1 5*2/l 1575
3 2 0 8.65 1362
3*2/l 515
15*2/l 1422
5*5*2/l 9 6 1
2*2/l 9 1 0
2*2/l 9 1 2
2*2/I 1102
2*2/l 911
2*2/l 9 2 5
2*2/l 925
2*2/l 1102
2* 1102
1103
1103
lOO/Sl
9 0 10.4
19 5.23
4* l/l 9 1 6
1346
1363
The number after the solidus (/) are reference citations.
b The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
TABLE 12. POLY(SACCHARIDES)
Poly(saccharides) VI/59
Polymer
Cryst
syst.
Space
IFouP
Unit cell parameters Densi ty (g/ cm j) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z crystal. Amorph. = (w kJ/mol a (a *p/q) Refs.
PO1y(2,1+-D-fWCtOfUra@
(hemihydrate) OfthO D2-4 16. 70 9. 65 1 4 . 4
( 162. 14)
(monohydrate) O r t h o D2-4 16. 70 9. 80 1 4 . 7
Poly(l,4-~-D-galacto-1,4-~-rbmannose) (1 : 2) [guar galactomannan]
dry 1 3 . 5 8. 66 10.3b
( 486. 42)
16.5% H20 M o n o c2-2 15. 45 8. 65 10.36 y=90
Poly( 1,4-a-D-galactosamine)
anhydride ortho 5 . 2 3 0 . 8 8 . 7
( 161. 16)
Poly( 1,3-b-D-galactosamine-&1,4-P-D-glucuronic acid)
1 2 1. 470 1 6 3 4
I2 1. 492 1 6 3 4
2 1. 34
3*6/l
3*6/l
lO* 6 4 3
6 6 4 3
8 1. 54 5*2/l 1327
1 9 . 6 9*2/l 8 1 9
D2-3 7. 45 17. 81 19. 64 4 9*2/l 1 2 4 2
1 2 . 8 1 2 . 8 2 7 . 4 6 9*3/l 1 2 5 8
D3-6
1 4 . 5 1 4 . 5 2 8 . 8
14. 52 14. 52 28. 32
2 8 . 5
1 6 . 0 2 6 . 0 24.1b
6
6
1 8
9*3/l
9*3/l
9*3/l
9 * 3 / l ?
8 1 9
1241
1 2 5 4
1 1 3 9
03-4 13. 85 13. 85 27. 76 6 9*3/l 1223
18.6b 9*2/l 7 0 5
1 2 . 1 1 4 . 4 2 8 . 5 b
1 2 . 1 9 . 3 2 8 . 5 b
1 4 . 3 1 4 . 3 2 8 . 7
1 3 . 8 1 3 . 8 7 8 . 2
y=93
9? 9*3/l 7 0 5
6? 9*3/l 7 0 5
9? 9*3/l 7 6 9
3 2 9*8/l 7 6 9
Poly(l,4-P-D-glucosamine) [chitosan]
D2-4
D2-4
8 . 9 1 7 . 0 10. 25 b
7. 76 10. 91 10. 30
8. 28 8. 62 10. 43
8. 07 8. 44 10. 34
4 . 4 1 0 . 0 1 0 . 3
8. 24 16. 48 10. 39
1 3 . 8 1 6 . 3 4 0 . 7 a = 96. 5
8 1. 38 5*2/l 1135
4 1. 228 5*2/l 1 1 3 7
4 1. 44 5*2/l 1579
4 1. 520 5*2/l 1 5 8 0
2 1. 18 5*2/l 1 1 3 7
8 1. 517 5*2/l 1 1 3 8
48? 1. 412 5*8/5 1581
D2-4 4. 76 18. 85 10. 28 b 4 1. 463 5*2/l 6 5 2
D2-4 4. 69 19. 13 10. 43 4 1. 442 5*2/l 6 6 9
D2-3 9. 25 19. 25 10. 46 b 8 1. 449 5*2/l 1135
D2-4 4. 74 18. 86 10. 32 4 1. 463 5*2/l 1 2 2 2
c2-2
c2-2
c2-2
c2-2
c2-2
c2-2
4. 85 9. 26 10. 38
4. 82 3 6 . 7 10. 33
4. 80 9. 83 10. 32
4 . 1 1 0 . 5 1 0 . 3
9. 32 22. 15 10.176
4 . 8 1 0 . 5 10.4b
4 . 8 1 1 . 1 10.46
2 1. 460 5*2/l 178
8 1. 477 5*2/l 1 1 3 6
2 1. 495 5*2/l 1253
2 1. 39 5*2/l 6 5 3
8 1. 400 5*2/l 6 7 0
2 1. 41 5*2/l 7 7 8
2 1. 44 5*2/l 7 7 8
9. 67 2 1 . 1 10.4b
4. 78 2 3 . 3 lO.lb
4 . 7 2 8 . 4 10.36
y=97.5
y=ll2
p=90
y=97
y=97
y=99.5
y=94
y=90
8
4
6 1. 47
5*2/l 7 7 8
5*2/l 7 7 8
5*2/l 7 7 9
9.2 23 10.36 8 5+2/l 1135
-, N-acetyl- [chondroitin]
-9 -1 4-sulfate
free acid O r t h o
( 459. 38)
-9 -3 -3 as Ca salt
7 H2O/unit Ortho
( 497. 44) Hex
-, -3 -3 as Na salt
I. (@ 93% RH) Hex
10 Hz0 Hex
( 503. 34)
II. ortho
-1 -3 -1 as K salt
( 535. 57) Hex
-1 -1 6-sulfate
free acid
( 459. 38)
-9 -3 -3 as Na salt
I . ( 503. 34) ortho
o r Mo n o
RhO
II. Te t
I . ( 161. 16) oltho
O r t h o
ortho
(anhydrous) O r t h o
II.
III. O r t h o
IV. M o n o
-, N-acetyl- [chitin]
a O r t h o
( 203. 19) ortho
ortho
ortho
P
cc-phase
(anhydrous) M o n o
O r t h o
M o n o
(hemihydrate) M o n o
( monohydr at e) ortho
M o n o
(dihydrate) M o n o
P-phase (hydrated)
I. M o n o
II. M o n o
Y
M o n o
-9 -1 ni t r a t e
ortho
References page VI-159
VI/60 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 12. contd
Polymer
Cryst
SYSt.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Melting Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. WY kJ/mol a (n *p/q) Refs.
Poly( 1,3-P-D-glucosamine-al?-1.4~P-D-glucuronic acid)
-, N-acetyl- [hyaluronic acid]
(379.32)
I I .
-, -3 as Na salt
(401.30)
dry
wet
-, -, as K salt
(417.41)
I I I .
K salt
K salt
I V .
Na salt
Na salt
Ca salt
Ca salt
v.
Na salt
dry Ca salt
wet Ca salt
VI .
Na salt
VII.
f ree aci d
Poly( 1.3~cc-D-glucose)
Ortho
Tet
Tet
ortbo
Ortho
Tet
ortho
ortho
Tet
He x
He x
He x
He x
He x
He x
He x
ortho
M o n o
D4-8
D2-4
D4-10
D2-4
11. 4 9. 8 33. 7
9. 9 9 . 9 33. 9
9.89 9.89 33.94
11.53 9.89 33.86
11. 0 9 . 9 33. 0
17.14 17.14 3 2 . 8 0
11.73 9.25 35.42
10. 4 9 . 0 37. 1
9.96 9.96 37.87
11. 7 11. 7 28. 5
11.70 11.70 28.50
15. 4 15. 4 28. 5
20. 4 20. 4 28. 5
18. 7 18. 7 28. 5
IS.32 18.32 2 8 . 4 7
20.93 20.93 2 8 . 3 0
34. 4 11. 7 28. 5
19. 6
Doubl e
a
16
8
1.42 9*4/l 7 1 0
1.60 9*4/l 7 6 9
1.61 9*4/l 1227
1.50 18*2/l 1227
1.54 9*4/l 7 1 1
1.55 9*4/l 1225
1.50 18*2/l 1226
D4-8
8 1.60 9*4/l 7 1 1
8 1.54 9*4/l 1 2 2 4
D3-6
D3-6
1.50
1.40
1.43
1.53
9*3/l
9*3/l
9*3/l
9*3/l
6 5 9
1 2 5 6
6 5 9
6 5 9
D3-3
D3-3
1 8 1.58 9*3/l 6 5 9
1 8 1.57 9*3/l 1257
1 8 1.46 9*3/l 1 2 5 7
2 4 1.58 9*3/l 6 5 9
9*2/l 6 5 9
5.81 10. 0 8.35 y=96 2 1.116 4*2/l 1 1 3 0
D2-4
5.02 9.63 8.35 2 1.630 4*2/l 1 1 3 0
4.57 8.65 8.35 2 1.631 4*2/l 1 1 3 0
16.46 9.55 8.44 8 1.623 4*2/l 1131
C6-6
C6-6
Tri pl e
Tri pl e
1.530
I . 5 5 0
c3-1
14.41 14.41 5.87
14.38 14.38 5.82
26. 4 16. 4 22.65
17.01 17.01 2 2 . 7 0
15.56 15.56 18.78
Tri pl e
Tri pl e
6
6
1 4
2 8
18
1.473
1.476
4*6/ l 1 1 3 2
4*6/l 1168
4*7/l 1133
4*7/l 1168
4*6/l 1132
D2-4
C6-2
11. 0 19. 0 22.38 1 2 1.228 4*6/l 1 1 4 0
10.99 10.99 22.91 6 1.198 4*6/l 1 5 8 2
11.49 20.13 18.60 1 2 1.335 4*6/ l 1140
11.90 17.70 10.52
21.24 11.72 10.68
16. 0 9 . 2 10.6b
12. 0 16.25 10.48
15. 6 9 . 0 10.6
18.33 15.87 10.41
18.50 18.50 10.40
15. 9 18. 2 10. 4
y = 123.48
D2-1
5*6/l
5*6/l
5*2/l
y = 96. 5
1 2 1.580
1 2 1.457
8 1.38
1 2 1.591
8 1.61
1 2 1.422
1 2 1.397
1 2 1.55
5*4/ l
5*6/l
5*6/l
5*6/t
1146
1347
6 4 4
1145
6 4 5
1143
1144
1 2 1 9
V-A. anhydrous (monohydrate)
(dehydrate) Ortho D2-4
OldlO D2-4
OlthO D2-4
12.92 2 2 . 4 0 7.95
12.97 2 2 . 4 6 7.91
13. 0 22. 5 7.90
13. 2 23. 3
1 2
12
1 2
1 2
1 2
1.560
1.558
1.554
5*6/l 8 4 3
5*6/l 1243
5*6/ l 2 0
5*6/l 6 4 7
D2-4 13.61 23.60 8.01
D2-4 13.65 2 3 . 7 0 8.05
1.535 5*6/l 1244
1.516 5*6/l 2 0
I. (native) M o n o
(162.14)
II. (dihydrate) Ortho
III. (dry) Ortho
I V . ortho
Poly( 1 ,?i-P-D-ghJCOSC) [curdlan]
(anhydrous) He x
(162.14) He x
(hydrate) ortho
He x
(dihydrate) He x
-, triacetate [pachyman]
I. (288.25) ortho
He x
I I . Ortho
Poly(l,4-U-D-glucose) [amylose]
A. (162.14) ortho
(3 Hz/4 8.) M o n o
B. Ortho
(anhydrous) M o n o
(monohydrate) Ortho
(tri hydrate?) Ortho
(trihydrate) He x
(tetrahydrate?) Ortho
V-H. hydrate (dihydrate?)
oltho
Ortho
TABLE 12. confd
Poly(saccharides) VI/61
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm ) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. a (C) kJ/mol (n *p/q) Ref s.
OlthO
Phex
-, triacetate
I. (288.25) Ortho
I I . ortllo
-> tributyrate
(372.42) OlthO
-> triethyl-
1. (246.30) ortho
Ortho
3. ortho
-> -, complexes with:
chl orof orm
(1:2) Ortho
(1 : 1) Ptet
dichlorometbane
(1:2) Ortho
(1: 1) Ptet
nitromethane
(1 : 1) Ptet
-3
triisobutyrate
(372.42) Ortho
-7 trimethyl-
(204.22) Ortho
-, -, complexes with
chl orof orm
(1 : 1) ortbo
dicloromethane
(1: 1) Ptet
-, tripropionate
(330.34) Ortho
-, trivalerate
(414.50) Ortho
D2-4 13. 7
14.94
10.87
2 9 . 0 4
2 2 . 0 4
D2-4
D2-4
D2-4
16.13
15.36
D2-4 16.76
14.70
D2-4 16.52
14.70
14.70
32.38
D2-4 17.24
D2-4 14.57
02-4 13.92
Poly( 1,4-cc-D-glucose), compl exes wi th:
-, alcohols
butanol
W-4
W-W
I-naphthol
-, DMSO
(8 DMSOkell)
Ortho D2-4 27. 0
o r t b o D2-4 13.20
Ortho D2-4 13.70
Tet D4-4 22. 9
Tet
Ptet
Ortho
(1:2)
-, fatty acids
-, hydroxides
C(NHd3OH
LiOH
NaOH
K O H
NH40H
C S OH
-, i odi ne
(204.44)
(1 I/ 3 resi dues)
-, potassium salts
dry bromide
formate
iodide
wet (10% HzO)
acetate
bicarbonate
Ptet
ortbo
Ortho
He x
Tet D4-8 10. 2
Tet D4-8 10. 2
Tet D4-8 10. 5
Tet D4-8 10. 8
Tet D4-8 10. 8
D2-4
D2-4
19.17
19.21
30.23
D2-4 18.87
D2-4 13. 0
D2-4
13. 1
12. 1
12. 3
12. 7
12. 7
12. 4
12.97
20.26
23.44
23. 8 8.05
14.94 7.93
18.83 52.33
20.97 3 4 . 0 0
38.18 18.45
15.48
11.66 15.48
12.18 15.48
14.28 16.02
14.70 15.48
13.95 16.02
14.70 15.48
14.70 15.48
32.38 16.10
8.704 15.64
13.28 15.96
13.92 15.80
35.10 18.46
27.85 18.80
26. 4
27.00 7.92
25.80 8.10
22. 9 7. 8
19.17 24.39
19.21 8.12
28.18 7.91
18.87 7.99
23. 0 8.05
22. 6 9 . 0
22. 6 8. 8
22. 6 8. 9
2 2 . 6 9 . 0
22.6 9.0
22. 6 8. 9
12.97 7.91
10. 2 16. 4
10. 2 16. 4
10. 5 15. 9
10. 8 16. 1
10. 8 15. 8
1 2 1.504 5*6/l 6 4 6
7 1.503 5*7/l 6 6 8
2 8 1.251 5 * 1413 6 4 8
5 4 1.248 5+9/2 1301
3 0 1.195 5*5/l 1301
8 1.124
8 1.130
5*4/l
5*4/l
5*4/l
1 1 4 2
1221
1 2 2 0
8 1.267
8 1.215
5*4/l
5*4/l
1 1 4 2
1 1 4 2
8 1.192 5*4/l 1 1 4 2
8 1.099 5*4/l 1 1 4 2
8 1.147 5*4/l 1 1 4 2
3 2 1.172 5*4/l 1301
8 1.156 5*4/l 8 2 0
8 1.392 5*4/l 1 3 0 2
8 1.255 5*4/l 1 3 0 2
3 0 1.254 5*5/l 1301
2 0 1.122 5*5/l 1301
2 4 5*6/l 1 1 5 6
1 2 5*6/l 1 2 4 6
1 2 5*6/l 1 2 4 6
1 6 5*8/l 1 2 4 7
3 6 5*18/ 6 4 9
1 2 5*6/l 6 6 7
1 4 5*7/l 1 2 4 5
1 2 5*6/l 1 2 4 8
1 2 5*6/l 6 4 6
1 2
1 2
1 2
1 2
1 2
1 2
6 1.77
6 5 0
6 5 0
6 5 0
650
6 5 0
6 5 0
6 5 1
5*4/l
5*4/l
5*4/l
8
8
5*4/l
5*4/l
6 6 1
6 6 1
6 6 1
6 6 1
6 6 1
References page VI- 159
VI/ 62 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 12. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
n b c Angl es . ? Cryst al . Amorph. ((3 kJ/mol (n *p/q) Refs.
bromide Tet D4-8
formate Tet D4-8
iodide Tet D4-8
atm. dried
acetate Ortho
propionate Ortho
Poly(l,4-P-D-glucose) [ cel l ul ose]
I. (162.14) M o n o
M o n o
M o n o
10. 7 10. 7 16. 1
10. 8 10. 8 16. 1
10. 7 10. 7 16. 1
5*4/l
5*4/l
5*4/l
6 6 1
6 6 1
6 6 1
11. 0 18. 1 17. 9 1 6 6 6 1
11. 4 18. 0 17. 6 1 6 6 6 1
M o n o
M o n o
Tri
M o n o c2-2
c2-2
M o n o
M o n o
Tli
M o n o
M o n o
c2-2
Cl - l
c2-2
c2-2
M o n o
M o n o
M o n o
c2-2
c2-2
c2-2
c2-2
M o n o
M o n o c2-2
y=96 4 1.59
y=96.7 4 1.625
y=98 1 6 1.543
y=96.4 4 1.635
y= 1.59 8 1.598
y=98 1 6 1.585
90,58,96 4 1.624
,9= 97 16 1.628
y = 96. 5 4 1.643
?=97.0 16 1.629
y=97.6 4 1.629
117,113,81 2 1.586
y=97.3 4 1.601
y=l18 4 1.592
y=117.2 4 1.623
y=117.3 4 1.630
y = 99. 4 4 1.610
y= 116.6 4 1.612
y=117 16 1.625
y==117.3 4 1.624
y=98.6 2 1.629
y=116.33 4 1.611
y= 1 1 6 4 1.479
y=117 16 1.617
y= 116.8 4 1.605
y= 122 4 1.61
y= 122.4 4 1.547
y=122 4 1.597
r=90 4 1.612
M o n o
Ortho
M o n o
M o n o
8.35 7. 9 10.3 b
8.20 7.90 10.36
16.78 15.88 10.58 b
8.171 7.846 10.346
10.85 12.08 10.3b
16.78 15.88 10.3b
9.41 8.15 10.34
16.34 15.72 10.38
7.78 8.20 10.346
16.43 15.70 10.33
8.34 7.71 10.37
6.74 5.93 10.36
8.01 8.17 10.36
8.14 9.14 10.3 b
8.02 9.03 10.36
7.917 9.083 10.34b
8.97 7.31 10.34b
8.02 8.99 10.36 b
15. 7 18. 4 10.3b
9.09 7.96 10.31
4 . 4 6 7.25 10.346
7.94 9.12 10.306
9.04 9.63 10.34
15.92 18.22 10.31
8.00 9.05 10.38
7.74 9. 9 10.3 b
10.25 7.78 10.34
7.78 9.92 10.30b
8.12 7.99 10.36
7. 9 10.36
8.068 7.946 10.3b
8.01 8.12 10.34
8.10 8.16 10.3 b
8.12 7.99 10.36
y=90 4 1.63
4 1.601
y= 101.7 4 1.615
r=90 4 1.612
5*2/l 2 2
5*2/l 9 8
5*2/l 1249
5*2/l 2 8
5*2/l 7 0 9
5*2/l 8 0 5
5*2/l 841
5*2/l 8 5 2
5*2/l 1149
5*2/l 1 2 5 0
5*2/l 1576
5*2/l 1577
5*2/l 1577
5*2/l 2 2
5*2/l 9 8
5*2/l 2 8
5*2/l 7 0 8
5*2/l 8 4 2
5*2/l 8 8 4
5*2/l 8 8 9
5*2/l 1150
5*2/l 1151
5*2/l 1152
5*2/l 1303
5*2/l 1578
5*2/l 2 8
5+2/l 8 9 0
5*2/l 1151
5*2/l 9 8
5*2/l 2 3 9
5*2/l 2 8
5*2/l 1153
5*2/t 9 8
5*2/l 2 1 8
13. 9 8. 0 2 4
Port c2-2 8.83 25.28 10.29 8 1.377 5*2/l 1445
M o n o 9.57 8.72 10.35 Y= 122.0 4 1.552 5*2/l 1 4 4 6
Ortho
Port
c2-2
D2-4
c2-2
44. 3 13.45
23.63 6.27
24.68 11.52
24. 5 11.56
24. 6 11. 4
10.47 1 6 1.228 306/l 14 5*2/l
10.43 4 1.239 5*2/l
10.54 8 1.278 5*2/l
10.43 8 1.296 5*2/l
1148
9 3 8
9 6 2
4
1251
-3 -, nitromethane complex
Tet
-> tributyrate
(372.41) Ortho
21.15 21.15 41.36 1252
31. 3 25. 6 10.36 1 6 1.192 207/118 12.6/118 5*2/l
206/46
1148
Ortho 28. 6 16. 7 15.25 6 1.105
116/117 13.0/117 5*
5*3/l 1148
(a)
CP)
I I .
(monohydrate)
I I I .
I V .
X.
-, dinitrate
(252.14)
-, sodium
I. (1 : 1 : 2)
(238.17)
IV. (2:2: 1)
(171.15)
-, triacetate
I. (288.25)
11.
dry
-3 tricaprylate
(540.74)
-, tricarbanilate
(519.51)
TABLE 12. contd
Poly(saccharides) M/63
Polymer
tryst
syst.
Space
group
Unit cell Parameters Density (g/cm3) Melting Heat of Chai n
Point f us i on conf orm.
a b c
Angl es Z Crystal. Amorph. 0 (w kJ/mol (n *p/q) Refs.
(4 MEK/residue)
-, triethyl-
(246.30) Chtho
-1 trimethyl-
I. (204.22) Chtho
Port c2-2
I I .
-, trinitmte
(297.13) Ortho
ortho
-, tripropionate
(330.34) Ortho
-, 2.44-nitrate
Poly( 1,4+r+glucose), compl exes wi th:
-, dimethyl-1,3-propanediamine
(1:2) M o n o
-1 ethylenediamine
I. (1 : 1) M o n o c2-2
(1:2)
-, heptamethylenediamine
(1 : 2)
-, hexamethylenediamine
(1:2)
-, hydrazine
II. (1 : 1) M o n o c2-2
(1:2)
-7
octamethylenediamine
(1:2)
-, pentamethylenediamine
(1 : 2)
-, NaOWHzO
II. (1 : 1) He x
-3 trimethylenediamine
(1 : 2)
Poly( 1,6-a-D-glucose) [dextran]
(162.14) M o n o c2-2
(high temp. )
Poly( 1,4-a+guluronic acid)
(176.12) ortho D2-4
(monohydrate) oltho D2-4
Poly(l,3-a-Dmannose)
(dihydrate) M o n o c2-2
(162.14)
Poly( 1,4+3-D-mannose)
I. (162.14)
ortho D2-4
ortho
I I . M o n o
( 4 HzO/cell) O r t h o D2-8
-, triacetate
(288.25)
-9
trimethyl-
OldlO
Poly( 1.4~p-o-mannuronic acid)
(176.12) ortho D2-4
Poly(l,3+-Dxylose) [xylan]
(132.12) He x
(monohydrate) He x C6-4
Poly(l,4-B-D-xylose) [hardwood xylan]
I. dry He x
(132.12)
15.64 27.09 15. 0 1 8 1.158
4 . 6 4 4 3 . 2 10.43 8 1.298
4 . 6 4 4 3 . 2 10.42 8 1.299
12.25 9 . 0 25.4
9 . 0 14. 6 25. 4
31. 6 22. 1 15. 0
11. 0 15. 4
33.64 3 0 . 4 0 10.26 *
12.87 9.52 10.35
12. 2 12. 3 10.3 *
18. 4 17. 4 (lo)*
17. 2 15. 9 10.36
9.37 19.88 10.39
9.68 9.96 (lo)*
19. 1 17. 9 (lo)*
16. 6 15. 3 10.1*
10. 0 10. 0 15. 1
10.26 1 2 7 0
9 . 2 2 9 . 2 2 7.78 0=91.3 4 1.631 5*2/l 1 1 2 9
7.75 10.6 8.7b
8. 6 10.74 8.72*
11.29 18.12 8.40
7.21 8.82 10.27b 4 1.65 5*2/l 6 3 6
8.92 7.21 10.21 4 1.640 5*2/l 1141
8.87 7.29 10.19 4 1.634 5*2/l 1355
18. 8 18. 7 10.26 y= 122.5 16 1.43 5*2/l 6 3 6
8.91 16.46 10. 3 8 1.505 5*2/l 1583
15.24
4.75 40. 1 10.30 8 1.383
7.58 8.58 10.35 * 4 1.738
13. 7 13. 7 5.85* 6 1.384
15. 4 15. 4 6.12 6 1.190
8. 8 8. 8 14.85 * 6 1.32 5*3/l 6 7 1
1 0 1.762
1 0 1.48
2 4 1.257
7=32.74 1 6
y=118.8 4
y=43.23 4
y=29.23 4
y=32.35 4
y=120 8
y=54.80 4
y=28.52 4
y=32.92 4
6
1.00
1.328
1.394
1.20
1.226
1.539
1.59
1.21
1.259
1.677
1.64
1.60
1.560
5*3/l
5*2/l
5*2/l
5*3/l
697177 3.8- 5*5/1
700/81 6.3177 5*5/2
2341144 5*3/l
617181 5.65181
5*2/l
5*2/l
5*2/l
5*2/l
5*2/l
5*2/l
5*2/l
5+2/l
5*2/l
5*3/l
5*2/l
5*2/l
4*2/l
5*3/l
5*2/l
5*2/l
4*
1148
1 1 3 6
1 1 4 8
1 1 4 8
2 4
1147
1148
1 3 4 8
1255
1 1 5 4
1 2 7 0
1 2 7 0
1 2 7 0
1 1 5 4
1 2 7 0
1 2 7 0
1 2 7 0
1155
6 7 4
6 7 3
1 3 5 6
6 7 2
1 3 0 4
6 7 3
6 5 4
7 8 8
References page VI- 159
VI/64 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 12. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm3) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. a cva kJ/mol a (n *p/q) Refs.
(monohydrate)
(150.13)
(dihydrate)
(168.15)
II.
-, diacetate
(216.19)
Hex D3db 9.16 9.16 14.85 6 1.386 5*3/l 671
Phex Cl-l 9.16 9.16 14.84 y= 120 6 1.387 5*3/l 6 5 5
Hex 9.64 9.64 14.95 6 1.392 5*3/l 671
Or t ho 11.5 14.4 1134
Mono c2-2 7.64 12.44 10.31 y=85 4 1.471 5*2/l 6 5 6
G The number after the solidus (/) are reference citations.
b The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
TABLE 13. OTHER POLYMERS
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Melting Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph. a
WY
kJ/mol (n *p/q) Refs.
Polyaniline, see Poly@-phenylene amine)
Poly(barium sebacate)
( 3 3 7 . 5 8 ) Tet 8.04 8.04
Poly(barium suberate)
( 3 0 9 . 5 2 ) Tet 7.88 7.88
Poly(4,4-biphenylenedioxy 4,4-diphenylene ketone) [PEDEK]
( 3 6 4 . 4 0 ) Or t ho 7.72 5.94
Poly[4,4-biphenylenedioxy)-diphenylene-m-phenylene diketone]
(468.51) Or t ho 7.85 6.05
Poly(cadmium sebacate)
(312.64) Tet 10.16 10.16
Poly(cadmium suberate)
( 2 8 4 . 5 8 ) Tet 8.32 8.32
Poly(calcium sebacate)
( 2 4 0 . 3 2 ) Tet 8.20 8.20
Poly(calcium suberate)
( 2 1 2 . 2 6 ) Tet 7.72 7.72
Poly(carbon monoxide-&ethylene) [Poly(propanone-l)]
rx Or t ho D26-16 6.91 5.12
( 5 6 . 0 6 )
P Or t ho D2h-16 7.97 4.76
( at 140 C) Or t ho D2h-16 8.24 4 . 7 4
15.24
11.53
37.5
47.7
15.59
12.16
15.59
12.16
7.60
7.57
7.58
4
4
A 1.407 4 2 5 1596
4
4
4
4
4
4
4 1.296 193
4 1.256 1586
Poly[4,4-(carbonyldiphenylenedioxy)-diphenylene p-phenylene diketone]
215 repeat Or t ho
( 1 9 8 . 6 1 )
Poly(decamethylene amine)
-, N,N-dimetbyl-
-> -9
salt with (Ionene)
FeCl4 Hex
SbF6 Hex
Poly(dimethy1 ketene)
I. (ketone)
bO.09)
Or t ho
P
II. (ester)
( 1 4 0 . 1 8 )
Poly(ethylene amine)
anhydrate Or t ho
( 4 3 . 0 7 )
hemihydrate Mono
( 5 2 . 0 8 )
sesquihydrate Mono
( 7 0 . 0 9 )
7.74 6.04 10.05 2 1.404 1439
9.71 9.71 11.04 2 1.548 1405
9.71 9.71 11.04 2 1.548 1405
C2v-9 12.85 6.53 8.80 8
8.8
4 . 4 0
1.261 4 3 2
179
4 5 6
D2h-24 29.8 17.2 4.79 Doubl e 4 0
C2h-6 10.89 9.52 7.31 p=127.6 8
C2h-6 11.55 9.93 7.36 p=104.5 8
2.276 1186
2.871 1186
1.374 1594
1.290 1186
2.246 1186
1.523 1186
1.945 1186
1.383 1586
1.165 1107
1.152 1108
1.139 1106
TABLE 13. contd
Other Pol ymers VI/65
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es 7. Ct-ptd. Amorph.a WY kJ/mol u (n *p/q) Refs.
dihydrate
( 7 9 . 1 0 )
-, N-benzoyl-
( 1 4 7 . 1 8 )
Mono CZh-6 13.26 4.61
-3 -, p-chloro-
( 1 8 1 . 6 2 ) Tli
-, N-butyryl-
( 1 1 3 . 1 6 )
-3 -3 4-(4methylthiophenoxy)-
( 2 5 1 . 3 4 ) Tri
-, N-heptanoyl-
( 1 5 5 . 2 4 ) Tri
-, N-hexanoyl-
( 1 4 1 . 2 1 ) Tri
-, N-isobutyryl-
( 1 1 3 . 1 6 )
-, N-isovaleryl-
( 1 2 7 . 1 9 ) Tri
-, N-octanoyl-
(169.27) Tri
-, N-p-toluoyl-
( 1 6 1 . 2 0 ) Tti
-, N-valeryl-
( 1 2 7 . 1 9 ) TIi
Poly(ethylene amine), complexes with:
-, acetic acid (1 : 1)
( 1 0 3 . 1 2 ) Mono C2h-2
-, HCI (1: 1)
( 7 9 . 5 3 ) Pt et
-, oxalic acid and water (2 : 1: 2)
( 1 0 5 . 0 9 ) Or t ho D2h-7
Poly(etbylisocyanide)
-, a-phenyl-
( 1 3 1 . 1 8 ) Phex
Poly(germylene)
-, di-n-hexyl-
( 2 4 2 . 9 3 ) Ortho
Poly(germoxane)
-, phthalocyaninato-
( 6 0 1 . 1 2 ) Tet C4h-1
-, -3 iodine complex (1 : 1.12)
Tet D4h-2
Poly(hexamethylene amine)
-, N,N-diethyl-
-3 -1 salt with (Ionene)
ZnBr4 Tet
-, N,N-dimethyl-
-, -, salt with (Ionene)
BF4
Hex
CdL, Tet
CF303 Hex
FeCl4 Hex
HgI4
Tet
PF6 Hex
SbF b Hex
ZnBr4 Tet
Zncll Tet
ZnI4 Tet
Poly(hydroxymethylene)
(30.03)
Poly(l-hydroxytrimetbylene)
(58.08)
4 . 7 4 14.8 6.55 88,86,99
4.35 24.0
5 . 0 17.7
4 . 9 15.9
4.7 13.0
5.03 19.9
4 . 8 4 14.8
4 . 7 14.4
5.76 6.20
5.06 5 . 0 6
6.65 10.05
14.92 14.92
15.65 2 1 . 4 6
13.27 13.27
13.96 13.96
9.81 9.81 13.88
7.54 7 . 5 4 11.95
9.78 9.78 13.75
7.90 7.90 13.06
8.04 8.04 13.10
9.82 9.82 13.54
7.75 7.75 11.96
7.90 7 . 9 0 12.58
9.52 9.52 13.46
9.36 9 . 3 6 13.07
9.64 9.64 13.89
7.36 p= 101.0
12.7 90.90.90
6 . 4 85,62,98
6 . 4 87,64,95
6.4
6 . 4 80.82.88
6.3 91,60,97
6.61 91,78,99
6 . 4 86,73,97
7.39 y=95
7.57
7.32
10.33 93,90,118
4 . 0 6
3.53
6 . 9 6
2.5
6.89
4
2
4
2
2
2
2
2
2
2
2
4
10
4
1
2
4
2
4
2
2
4
2
2
4
4
4
1.190
1.334
1.259
2101747
2851747
1551747
105
1.06
1.06
1.11
1.04
1.172
1.03
1751747
1751747
2101147
2101747
1651747
2601747
1721747
1.302 135
1.362 26511423
1.427 2 4 0
1.078
1.183
1.606
1.820
1.734
1.214
2.213
1.305
1.476
2.454
1.458
1.807
1.746
1.345
2.134
276
261
207
2 2 0
2 4 2
233
2 3 5
233
3*2/l 1106
3*2/l
3*
7 4 6
3*4/l
3*2/l
3*2/l
3*
7 3 9
7 4 6
7 4 6
7 4 6
3*2/l
3*2/l
3*2/l
3+2/l
7 4 6
7 4 6
7 4 6
7 4 6
3*2/l
3*2/l
3*2/l
1392
1366
1428
8 6 3
1635
1205
1*2/l
3*
3 3 8
7 5 8
References page VI- 159
VI/66 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 13. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Melting Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es 7. Cryst al . Amorph.
WY
kJ/mol c1 (a *p/q) Refs.
Poly(lead sebacate)
(407.44) Tet 7.73 1.73 17.42 4
Poly(lead saberate)
(379.38) Tet 7.64 7 . 6 4 13.66 4
Poly(magnesium sebacate)
(224.54) Tet 8.26 8.26 13.11 4
Poly(magnesium suberate)
(196.49) Tet 8.76 8.76 11.23 4
Poly(manganese sebacate)
(255.17) Tet 7.92 7.92 14.56 4
Poly(manganese suberate)
(227.12) Tet 7.52 7.52 11.83 4
Poly(6-mercaptocaproic acid)
(130.21) 17. 8
Poly(octamethylene-5,5-dibenzimidazole)
(344.46) 2 1
Poly(2,5-octamethylene-1,3,4-triazole)
-, l-amino- (triazole)
(194.28) 25. 5
Poly(oxybisdimethylsilylene)
I I . ( 102. 24) ort ho 8.66 11.94 3. 9 2
III. ortho 7.92 13.72 3. 9 2
Poly(4,4-oxydiphenylene 4,4-biphenylene di ketone) [PEKDK]
(376.41) Ortho 7.64 6.09 3 8 . 0 0 4
Poly(4,4-oxydiphenylene ketone) [PEK]
(196.20) Ortho 7.63 5.96 10. 0 2
Ortho D2h-4 7.65 5.97 10.09 2
Ortho 7.76 6 . 0 0 10.01 2
Poly(4,4-oxydiphenylene m-phenylene diketone) [PEKK(I)]
(300.31) Oh0 7.66 6.11 15.76 2
Poly(4,4-oxydiphenylene p-phenylene diketone) [PEKK]
I. 2/3 repeat Ortho 7.69 6 . 0 6 10.16 2
(200.21) Ortho 7.67 6 . 0 6 10.08 2
II. Ortho 4.17 11.34 10.08 2
ortho 3.93 5.75 10.16 1
Ortho 4 . 2 11. 3 10. 1 2
Poly[(4,4-oxydiphenylene p-phenylene diketone)-&(4,4-oxydiphenylene m-phenylene diketone)]
I. (600.62) Ortho 7.78 6 . 1 0 31.13 2
II. Ortho 4.17 11.08 31.13 2
III. Ortho 6.41 6 . 1 0 35.04 2
Poly(p-phenylene ami ne) [ ani l i ne]
-, emeraldine base
I I . ( 181. 22) ort ho 7.80 5.75 10.05 2
Oh0 11.34 5.75 7 . 5 6 2
-7 -1 complex with doecylbenzenesulfonate
ortho D2h-13 11.78 17.91 7.16 2
-, emeraldine salt (HCl)
I. (217.68) Port 4. 3 5. 9 9 . 6 1
II. ortho 7 . 0 8. 6 10. 4 2
Poly[4,4-(p-phenylenedioxy)-diphenylene di ketone]
213 repeat ortho D2h-14 9.96 4.78 10. 7 2
(210.88)
Poly[4,4-@-phenylenedioxy)-diphenylene ketone] [PEEK]
213 repeat Ortho 7.75 5.86 10. 0 2
(192.20) ortho D2h-14 7.75 5.89 9.883 2
ortho D2h-14 7.78 1 5.922 10.06 2
ortho D2h-14 7.83 5.94 9 . 8 6 2
M o n o 7.767 5.911 9.878 2
Ortho 7.76 5.89 9.95 2
full repeat ortho D2h-14 7.88 5.94 30.50 4
(288.30) oltho D2h-14 7.83 5.94 29.58 4
(at 291C) Ortho 8.048 5.915 9.856 2
2 . 6 0 0 13* l/l 1186
3.160 11* l/l
1.667 13* l/l
1.514 11* l/l
1.856 13* l/l 1186
2.255 11*1/l 1 1 8 6
1 0 6 7+2/l 4 2 8
18* l/l 4 7 0
258/610 11*2/l 6 1 0
0.80
0.84
5 2 3* l/l
3*1/l
1618
1618
1.413 19*2/l
1.433 1.272 361 lO* l/l 1113
1.414 3 6 7 1 1 1 1 7 lO* l/l 1 2 7 4
1.398 3 6 5 lO* l/l 1 4 3 9
1.352 14* l/l 1 5 9 2
1.404
1.419
1.395
1.448
1.39
3 8 5
lO* l/l
lO* l/l
lO* l/l
lO* l/l
lO* l/l
1.350 29* l/l 1597
1.387 29* l/I 1597
1.456 29* l/l 1597
1.335 lO* l/l 1 6 1 2
1.221 lO* l/l 1613
1.114 lO* l/l 1613
1.48 lO* l/l 1 6 1 2
1.15 lO* l/l 1 6 1 2
1.375 lO* l/l 1 4 4 4
1.405
1.415
1.378
1.392
1.407
1.404
1.341
1.392
1.401
1.347
1.265 3 3 5
384/1117
1.264
lO* l/l
lO* l/l
lO* l/l
lO* l/l
lO* l/l
lO* l/l
15*2/l
15*2/l
3 3 5
33811383 4611383
3 5 1 5 8 9
1.263 3 9 5 37. 5
lO* l/l
1113
1 1 1 4
1115
1305
1438
1 4 3 9
1 1 9 4
1305
1 1 1 6
1438
TABLE 13. contd
Other Polymers VI/67
Polymer
Cryst
syst.
Space
group
Unit cell parameters Density (g/cm3) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es 2. Cryst al . Amorph. (C) kJ/mol (n *p/q) Ref s.
-1 methyl- (dioxy)
( 302. 33)
Poly[4,4-(p-phenylenedioxy)-diphenylene 4,4-oxydiphenylene diketone] [PEEKEK]
2/5 repeat O r t h o 1. 19 5. 94 9. 96
( 193. 80)
Poly[4,4-@-phenylenedioxy)-diphenylene m-phenylene diketone] [PEEKmK]
( 392. 41) O r t h o 7. 71 6. 05 3 9 . 9
O r t h o D2h-14 1. 741 6 . 0 8 6 19. 87
Poly[4,4-@-phenylenedioxy)-diphenylene p-phenylene diketone] [PEEKK]
l/2 repeat O r t h o
(196.20) ortho
Poly(p-phenylene disiloxyanylene)
-, tetramethyl-
(208.41) Tet
Tet D4-8
Poly(phosphazene)
-1 bis(@naphthoxy)-
( 331. 31)
-, bis(4-n-butylphenyl)azophenoxyethoxy-
(639.74) Ortho
-, bis(2,2,3,3,4,4,4-heptafluorobutoxy).
(443.08) Ortho
-, bis(2,2,3,3,3-pentafluoropropoxy).
7. 80
7. 19
9. 08
9. 02
2 2 . 4
3 5 . 7
21
I . ( 343. 06) M o n o
II. O r t h o
-, bis(phenoxy)-
G!
( 231. 19) M o n o
Y
6 P h e x
-3 -3 di-m-bromo-
tl M o n o
( 388. 98)
Y O r t h o
-> -, di-p-bromo
Y
O r t h o
( 388. 98)
-, -, di-m-chloro-
cl. M o n o
( at 180C) P h e x
( 300. 08)
-, -3 di-p-chloro-
Y O r t h o
( 300. 08) O r t h o
( at 180C) P h e x
-3 -1 di-2,4-dichloro-
( 368. 97) M o n o
-, -1 di-3,4-dimethyl-
( 287. 30) P o r t
O r t h o
-1 -3
di-p-ethyl-
( 287. 30) M o n o
-3 -> di-m-fluoro-
c( M o n o
( 267. 17)
Y
ortho
-3 -1
di-p-fluoro-
cl M o n o
( 267. 17)
P
M o n o
20. 75 15. 22 4 . 1 4 y = 44. 6 4 2. 168 2*2/l 1 6 1 0
23. 96 10. 77 4. 64 4 1. 903 2*2/l 1 6 1 0
1 6 . 6 1 3 . 8
1 9 . 2 1 1 . 5
1 2 . 9 1 2 . 9
4 . 9
9. 70 y=83
9. 70
390/909
8 1. 392 2*4/l
8 1. 434 2*4/l
5 5 2
1 3 1 4
1 3 1 4
1 3 1 4
2 3 . 7 1 0 . 0 4. 85 y=86
4. 85
4 2. 253 3 2 0 2*2/l 1 6 0 7
2 3 . 1 1 1 . 0 4 2. 043 2*2/l 1607
2 1 . 7 1 2 . 9 4 . 9 0 4 1. 884 4 2 0 2*2/l 1607
2 3 . 8 1 0 . 3
1 4 . 2 1 4 . 2
4. 85 y=86 4 1. 808 2 9 0 2*2/l 1 6 0 7
2* 8 7 0
D2-4 13. 08 20. 23 4 . 9 0 4 1. 537
2 0 . 5 1 3 . 1 4 . 8 0 4 1. 546
4051553
3 9 0
360/1387
2*2/l 8 2 2
2*2/l 1 6 0 7
1 4 . 2 1 4 . 2 2% 8 7 0
2 1 . 6 1 6 . 5 4. 86 y=94
9. 85
9. 98
4 1. 418 2101553 2*2/l 1185
c2-2
D2h-14
c2-2
15. 85
2 0 . 5
3 0 . 1
2 6 . 2
19. 43
1 4 . 9
8 1. 258 2*4/l 1111
8 1. 252 4*2/l 1 6 0 0
2 2 . 1 9. 88 y= 111. 5
4. 85 y=86
4. 85
1 6 1. 248 4*2/l 1604
2 0 . 1 8
8
1. 393
1. 410
1. 430
1. 490
2 6 0 2*2/l
212/l
2*2/l
2*2/l
1607
2 5 . 1 2 0 . 2 1607
2 6 . 4 1 9 . 2 4. 91 y=86
4 . 9 0 y=77
8 36511387 1 3 6 0
1 8 . 9 1 3 . 2 4 1 3 0 6
6. 01 10. 01 2 1. 388
6. 025 10. 08 2 1. 378
3 6 0 IO* l/l 1 4 3 9
lo* l/l 1 6 4 0
9. 08 15. 38 4 1. 092 0.985/787 1481225 18.21225 7*2/l 115
9. 02 15. 43 4 1. 103 1601787 11.31787 1*2/l 8 9 7
1 3 . 9 y=93 1387
17. 85 9. 85 8 1. 354 2+4/21 1 4 4 2
12. 85 9. 48 8 1. 79 4*2/l 1611
2 1. 396 3 4 0 lO* l/l 1 4 3 9
4 1. 400 19*2/l 1593
2 1. 3911 19* l/l 1 6 4 0
1. 348 2 2 . 3 1588
References page VI-159
VI /68 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 13. contd
Polymer
Cryst
syst.
Space
group
Unit cell parameters Densi ty (g/ cm 3, Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
la b c Angl es Z crystal. Amorph.
WY
kJ/mol (II *p/q) Refs.
Y
ortho
He x
Ortho
-3 -, di-p-isopropyl-
a M o n o c2-2
(315.35)
P
M o n o
Ortho D2-4
-, -1 di-p-methoxy-
a Ortho
(291.24)
P
M o n o
Y
Ortho
6
-, -1 di-p-methyl-
(259.24) Ortho
ortho D2h-15
-. ->
di-p-phenyl-
(383.39) oltbo C2v-9
-, bis(2,2,3,3-tetrafluoropropoxy)-
I. (307.08) M o n o
-, bis(2,2,2-trifluoroethoxy)-
u ortho
(243.04)
P
M o n o
M o n o
Y
Ortho
Ortho
6 He x
-, dichloro-
(115.89) Ortho
ortbo
Ortho
M o n o
-, difluoro-
a Ortho
(83.04) Ortho
P
Ortho
-, dimethyl-
u Ortho
(75.05) Ortho
M o n o
P
-, diphenyl-
u ortho
(199.19) M o n o
P
Y
OI l hO
6 He x
CZv-9
C2h-5
c2v-12
C2h-5
Poly( 1,4-piperidinediyl-trimethylene)
-, 2,6-dioxo-
(153.18) Tri
Poly(siloxane)
-, diethyl-
U- l M o n o
(at 193K)
(102.21)
w- 2 M o n o
(at 230 K)
P- 1
Tet
27. 3 19. 5
13. 5 13. 5
2 6 . 4 19. 2
4.75 8 1.404
4.85 8 1.444 3 7 0
2*2/l
2*
2*2/l
1387
1306
1607
24.55 19.56 5.56 y= 101. 0
9 . 8 0 y = 109. 2
9.92
6 1.199 2*3/l 1307
33.24 22.69
31. 4 11. 4
1 6 1.200
8 1.180 1 2 0
2*4/l 1307
4*2/l 1606
23. 9 17. 9 9.83 1 2 1.380 4*2/l 1605
24. 7 19. 8 9.83 y=102
22. 1 20. 1 9.63
14. 4 14. 4 y=120
1 2 1.234 4*2/l
1 2 1.357 4*2/l
1605
1605
1605
14.52 18.62 4.87 4 1.308
28. 9 18. 6 9.95 1 6 1.288
41711387 2*2/l 1110
4*2/l 1598
4 1 . 8 18. 3 9.57 1 6 1.391 2 0 5
3981553
2*4/l 1349
24. 4 9.96 4 2.018 2*2/l 1609
10.16 9.35 2 1.748 2401553 2*2/l
10.03 9.37
10.17 9 . 2 6
2 0 . 6 0 9 . 4 0
20.64 9 . 2 9
11.90 11.90
4 . 9 6 y=123
4 . 8 6
4 . 8
4 . 8 6 y=91
4 . 8 6 y=91
4 . 8 6
4 . 8 6
4 . 8 6
2 1.767
2 1.764
4 1.715
4 1.732
3? 2.031?
2*2/l
2*2/l
2*2/l
2*2/l
2*2/l
1185
5 5 2
1112
1608
1217
1608
1217
12.72 11.07
12.99 11.11
13.01 11.09
5.98 12.99
8 2.222
8 2.168
8 2.169
4 2 . 1 6 8
1.91 2*2/l 5 6
2*2/l 1109
2*2/l 1109
2*2/l 1326
21.43 5.83
11.75 11.25
8.69 5.38
4.92 b
4.92
4 . 9 2
4 . 9 2 p= 111. 7
6.49
6.49
4 . 8 6
1 2 2.041 2*3/l 1218
1 2 1.929 2*3/l 1218
4 2.427 2*2/l 1218
13. 9 5.98
13.90 5.98
6 . 3 4 5 13.80
4. 9
4.73
4 . 8 8 7 ,O = 110.4
5.85
4 1.22
8 1.268
4 1.2427
1 4 6 1 1 3 8 7
143/1350
1 4 6
7 6
2*2/l
2*2/l
2*2/l
1349
1599
1603
9. 9 12. 5
10. 1 10. 1
19. 9 10. 5
12. 8 12. 8
9. 8
9.95 y=lOl
12. 5
9.95
4 1.09 4*2/l
4 1.328 4*2/l
8 1.273 4*2/l
1601
1602
1602
1602
1602
9.64 11.32 8 1.326 2 8 1 7*2/l 481
14.15 8.75
15.80 98.98.114
4 . 7 2 y = 29. 8
4 . 7 5 y = 29.66
4.72
1.169 0.99 2*2/l 1266
14.59 8 . 9 0
7.83 7.83
1.112
1.173
7
7 1.74
2*2/l
2*2/l
1266
1196
1266
TABLE 13. contd
Other Pol ymers VI /69
Polymer
Cryst
syst.
Space
WOP
Unit cell parameters Density (g/cm3) Melting Heat of Chain
point fusion conform.
a b e Angles Z CrystaI. Amorph.a
WY kJ /mol (n *p/q) Refs.
(at 193 K)
P-2
(at 233 K)
mesomorphic
(at 290 K)
-, dimethyl-
( 74. 16)
Tet
M0n0
M o n o
-, diphenyl-
I. (198.30)
I I .
-, dipropyl-
(130.26)
Tet
ortho
M o n o
Tet
c2-1
C4- 2
-3 pentaphenyl-p-toluyltri- (averaged)
( 202. 77) OtthO
-, phenyl-p-toluyl-
(212.32) Ortho
-, phthalocyaninato-
( 556. 62) ortho D2h-26
-, -, bromine complex (1 : 1.12)
Tet D4h-2
-3 -3 iodine complex (1 : 1.12)
Poly(silylene)
-9
n-butyl-n-pentyl-
I. (156.34)
II. (at 100C)
-, di-n-butyl-
I. (142.32)
I I .
-, di-n-decyl-
I. (310.64)
I I .
-, di-n-dodecyl-
I. (366.75)
I I .
-, diethyl-
(86.21)
(at - 20C)
(at WC)
-, di-n-heptyl-
I. (226.48)
I I .
-, di-n-hexyl-
I. (RT)
(198.43)
I I .
-, dimethyl-
(58.16)
(at 160C)
-, di-n-nonyl-
I. (282.59)
I I .
-, di-n-octyl-
I. (254.53)
I I .
I I I .
Tet D4h-2
OtthO
Hex
OtThO
Phex
ortho
Phex
Ortho
Phex
OlthO
ortho
ortho
Ortho
Phex
M o n o
OIlhO
M o n o
Phex
C2v- 9
M o n o
He x
Ortho
Phex
ortho
ortho
Phex
7 . 9 0 7 . 9 0
14.75 8.89
13. 0 7.75
10. 2 10. 2
2 0 . 1 0 10.51
2 1 . 3 3 9.91
9.52 9.52
2 1 . 0 6 10.53
2 1 . 0 4 10.86
13.80 2 7 . 5 9
13.97 13.97
13.97 13.97
13.23 2 2 . 9 2
13. 4 13. 4
12.84 22.24
13. 3 13. 3
21. 4 24. 9
19. 1 19. 1
22. 0 25. 8
20. 8 20. 8
11.08 12.10
10. 9 11. 6
10. 7 12. 4
14.68 27.38
16. 2 16. 2
13.75 2 1 . 8 2
13.76 2 3 . 8 6
15. 5 15. 5
12.18 8.00
7 . 7 9 7 . 7 9
20. 5 25. 1
18. 4 18. 4
16. 4 26. 4
20. 1 2 1 . 7
17. 9 17. 9
4 . 7 2 2 1.152
4 . 8 8 y=31.24
8.3b y=120
9 . 9
10.24
20. 3 y = 108. 9
9 . 4 0
2 1.023
171518 2.641518 2 *2/l 1 2 6 6
1 7 2.15 1 1 9 6
51 2+2/l 1 2 6 6
6 1.02 0. 98 -401517 2.721517 2*3/l
-401631
1 9 7
4
8
1.279
1.218
1 6
2*4/l
2301907 8. 01907 2*4/ l
1.300 4*2/l
7 4 3.03 2*4/l
148 5. 8
206/1260
1 6 5 6
1275
4 1.016 5 1 8
1 1 9 5
10.36 8 1.172 1 2 7 5
9.97 8 1.238 1275
6 . 6 6 4 1.458 1 2 0 5
6 . 6 0 2 1.666 1 2 0 6
6 . 6 0 2 1.802
2*4/l
2*4/l
2*2/l
2*2/l
2*2/l 1 2 0 6
13.88 1 4 0 . 8 6 4 1*7/3 1 6 1 4
1 6 1 4
13. 9 1 4 0.828 1*7/ 3 1 3 9 6
1617
7. 8 8 0.99 4* l/l 1617
1 6 1 7
7 . 8 8 1.10 4*1/l 1 6 1 7
1 6 1 7
3.99 4 1.070
3.86 4 1.173
3.87 4 1.115
4.02 4 0.93 1
1*2/l
1*2/l
1*2/l
1*2/l
1 4 0 0
1 6 3 2
1 6 3 2
1 4 1 4
1 6 1 7
4 . 0 7 y=88
3.99
4 . 0 0
4 1.080
4 1.006
1*2/l
1*2/l
1 3 0 9
1615
1 3 0 8
1 6 1 7
3.88 y=91 4 1.022 38711416 1*2/l 1413
3.88 2 0 . 9 4 7 1*2/l 1 4 1 3
7. 8 8 0.94 4* l/l 1617
1 6 1 7
4 . 0 4 0.98
7 . 8 8 0 . 9 9
1*2/l
4* l/l
1 6 1 7
1 6 1 7
1 6 1 7
References page VI-159
VI/70 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
TABLE 13. contd
Polymer
tryst
syst.
Space
group
Unit cell parameters Density (gb2m3) Mel ti ng Heat of Chai n
poi nt f us i on conf orm.
a b c Angl es Z Cryst al . Amorph.a WY kJ/mol (n *p/q) Ref s.
-, di-n-pentyl-
I. (170.37) Phex
Mono
II. Hex
III. ortho
-, diphenyl-
(182.30) Pt et
-, di-n-propyl-
(114.26) Tet
-, di-n-tetradecyl-
(422.86) Or t ho
Ortho
-, di-n-undecyl-
I. (338.79) Or t ho
II. Phex
-3 n-hexyl-n-heptyl-
I. (212.45) ortho
II. Phex
-> methyl-n-propyl-
( 8 6 . 2 1 ) Or t ho
-1 n-pentyl-n-hexyl-
I. (184.40) Mono
II. Phex
-1 n-propyl-n-pentyl-
(142.32) Hex
Poly(stannous sebacate)
(318.92) Tet
Poly(stannous suberate)
(290.87) Tet
Poly(stannyloxane)
-, phthalocyaninato-
(647.22) Tet C4h-1
Poly(styrene-&carbon monoxide)
i s ot act i c
(132.16) Mono c2-2
syndiotactic
Mono C2h-5
Mono C2h-5
-, p-fluoro-
-3 -> syndiotactic
(150.15) Mono C2h-5
-1 m-met hyl -
- , -3 syndiotactic
( 1 4 6 . 1 9 ) Mono C2h-5
-1 p-methyl-
-1 -3 s yndi ot act i c
( 1 4 6 . 1 9 ) Mono C2h-5
Poly(zinc sebacate)
( 2 6 5 . 6 0 ) Tet
Poly(zinc suberate)
( 2 3 7 . 5 5 ) Tet
13.76 23.83
13.9 24.5
13.8
13.9
13.8
y=120 14
y= 120 14
4
1.011
0 . 9 6 6
14.3 14.3
13.7 21.4 4 . 0 0.96
22.96 22.96 7.02 16 1.309
9.80 9.80 3.99 2 0 . 9 9 0
29.78 21.37 7.84
21.5 29.5 7 . 9
8 1.126
8 1.12
21.6 25.0
20.5 20.5
7.8 8 1.07
14.1 25.0
15.3 15.3
4 . 0 1.00
9.6 13.1 4 . 0 1.14
14.7 25.4
14.9 14.9
4 . 0
4
4
y=120 4
4
4
1
y=llO 2
0.95
12.2 12.2
8.92 8.92 13.62 1.955
7.78 7.78 11.53 2.768
12.81 12.81 3.82 1.714 2* l/l 1205
8.367 5.47 7.5746 1.347 3*2/l 1469
15.5 6.15 1.56 /3=105 4 1.261
15.20 6.166 7.59 /3= 102.5 4 1.264
15.59 6.168 7.551 /3= 98.8 4 1.3900
16.14 6.816 7 . 5 8 0 D= 100.3 4 1.1835
35.54 6.262 7.536 /3= 9 6 . 0 8
13.25 4
10.69 4
1.1642
7.92 7.92
8.68 8.68
2.122
1.959
>221
1*7/3
1*7/3
1 *l/3
1*2/l
1*4/l
1*2/l
4* l/l
4t l/l
4*1/l
4* l/l
1*2/l
1*2/l
13* l/l
11*1/l
3*2/l
1.200 3*2/l
1.306 3*2/l
1.150 3*2/l
1.133 3*2/l
13* l/l
11* l/l
1414
1616
1325
1616
1616
927
1414
1617
1617
1617
1617
1617
1617
1617
1617
1614
1467
1468
1468
1468
1468
a The number after the solidus (/) are reference citations.
b The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
C. MELTING POINTS OF POLYMERS
Melting Points of Polymers VI/71
In the following table of melting points, entries are
alphabetical according to the basic structure of the polymer,
ignoring substituents. Substituted polymers are listed
alphabetically (according to the substituent) under the
entry for the unsubstituted polymer. The molecular
weight is that of the chemical repeat (the constitutional
base unit) in the polymer. Melting points (in C) are taken
from the reference cited. Melting points are presented in
this table only for those polymers without (as yet) available
crystallographic data: an asterisk (*) in the reference
column signifies that the relevant melting point data is
contained within the Crystallographic Data table of
Section B.
Polymer
Mol ecul ar Melting
wei ght point Refs.
Cellulose, see Poly (1,4-P-o-glucose)
Poly(acetaldehyde)
-, 2,2,2-trichloro-
Poly(acrylamide)
-, N-docosyl-
-1 N-dodecyl-
-3 N-hexadecyl-
-, N-isopropyl-
-, N-octadecyl-
N-tetradecyl-
&y(acrylic acid)
-, ally1 ester
-, butyl ester
-3 set-butyl ester
-1 rerr-butyl ester
-, decyl ester
-,
-
1.1 -dihydropenhtoro-
-> docosyl ester
-, dodecyl ester
-, hexadecyl ester
-1 isobutyl ester
-7 isopropyl ester
-, octadecyl ester
-1 octyl ester
-, -, 1, l-dihydropertluoro-
tetradecyl ester
Gly (acrylonitrile)
-7 u-ethyl-
-, cr-isopropyl-
-, a-propyl-
Poly(2,2-adipamidodibenzoic isophtbalic anhydride)
Poly(4,4-adipamidodibenzoic isophthalic anhydride)
Poly(2,2-adipamidodibenzoic terephthalic anhydride)
Poly(4,4-adipamidodibenzoic terephthalic anhydride)
Poly(adipic anhydride)
Poly(adipoy1 dithionisophthaloyldihydrazide)
Poly(adipoy1 ethylenediurea)
Poly(adipoy1 octamethylenediurea)
Poly(adipoy1 pentamethylenediurea)
Poly@-alanine), see poly(3-aminopropionic acid)
Poly(allene)
-, tetrafluoro-
Poly(allylbenzene), see Poly(propene), 3-phenyl-
Poly(2-aminoacetic acid), see Poly(glycine)
Poly(m-aminobenzoic acid)
Poly(p-aminobenzoic acid)
Poly(3-aminobutyric acid)
Poly(4-aminobutyric acid)
Poly( lo-aminocapric acid)
Poly(6-aminocaproic acid) [caprolactam]
-,
o-(-)-3-methyl-
-, 6-methyl-
71.08
379.67
239.40
295.51
323.56
267.46
72.06
128.17 47
212.33
554.15
380.66
240.39
296.50
324.55
184.28
454.14
268.44
81.12
95.14
95.14
514.49
514.49
5 14.49
5 14.49
128.13
336.43
256.26
340.42
298.34
119.12 425 735
127.19
68
- 8
45
68 1906
1 8 1906
100 1898
72 1906
1 2 1906
43 1906
56 1906
3 5 1898
32 1906
200
310
210
225
273
235
285
8 5
98
77
280
241
290
222
*
1906
1906
1906
*
401
*
436
436
436
1 8 7 1
1 8 7 1
1 8 7 1
1 8 7 1
1840
1 8 4 1
1564
1889
402
402
402
*
185 402
References page VI-l 59
VI/72 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly(6-aminocaproic acid-a/t- 1 1-aminoundecanoic acid)
Poly(S-aminocaprylic acid)
Poly(3-aminocyclobutylene)-propionic acid)
-, 2,2-dimethyl-
Poly(4-aminocyclohexyleneacetic acid)
Poly(aminodihexamethylene suberamide)
Poly(aminoditrimethylene oxamide
-, N-methyl
Poly(22-aminodocosanoic acid)
Poly(7-aminoenanthic acid)
-, (R)-3-methyl-
-, (S)-4-methyl-
-, (R)-Smethyl-
-, (R)-6-methyl-
-, N-methyl-
PolyIp-(aminoethylene)-phenyleneacetic acid]
Poly[p-(aminoethylene)phenylenebutyric acid]
Poly[p-(aminoethylene)-phenylenepropionic acid]
Poly[p-(aminoethylene)-phenylenevaleric acid]
Poly(2-aminoethylenesulfonic acid)
Poly(l7-aminoheptadecanoic acid)
Poly(aminoformic acid)
-, N- butyl-
-, ->
2-methyl-
-, N-phenyl-
Poly@-aminohydrocinnamic acid)
Poly( 12-aminolauric acid)
iv-methyl-
&y[(3-aminomethylene)-cyclohexyleneacetic acid]
-, 1,3-dimethyl-
Poly[p-(aminomethylene)-phenyleneacetic acid]
PolyIp-(aminomethylene)-phenylenebutyric acid]
Poly[p-(aminomethylene)phenylenepropionic acid]
Poly[p-(aminomethylene)-phenylenevaleric acid]
Poly(6-amino-4-oxacaproic acid)
-, 3,5-dimethyl-
Poly(5-amino-3-oxavaleric acid)
Poly(9-aminopelargonic acid)
Poly(3-aminopropionic acid) [p-alanine]
-, 2-butyl-2-methyl-
->
2,2-dimethyl
-, 2,3-dimethyl-
erythro
threo
-, 3,3-dimethyl-
-, 2-ethyl-2-methyl-
-, N-isopropyl-
-, N-met hyl -
-, 3-methyl-, see Poly(3-aminobutyric acid)
-1
2-methyl-2-propyl-
-, N-phenyl-
Poly( 18.aminostearic acid)
Poly(2-aminotetrahydropyran-6-carboxylic acid)
Poly( 13-amino-l I-thiatridecanoic acid)
Poly( 13-amino-12-thiatridecanoic acid)
Poly(6-aminothiocaproic acid)
Poly(7-aminothioenanthic acid)
Poly(a-aminotoluic acid)
Poly(l3-aminotridecanoic acid)
Poly(3-aminotrimethylenesulfonic acid)
Poly( 1 I-aminoundecanoic acid)
-, N-allyl-
-, N-ethyl-
125.17
153.22 358
139.20 400
353.55 160
185.23
199.25 202
337.59 1 4 5
141.21
161.20
189.26
175.23
203.28
107.13
267.46
43.02
113.16
119.12
147.18
211.35
153.22
181.28
147.18
175.23
161.20
189.26
115.13
143.19
101.10
99.13
99.13
113.16
85.11
147.18 205
229.38 150
229.38 150
129.22 120
143.25 235
133.15 300
211.35 1 8 3
107.15 260
223.36 350
212.36 - 3 0
65
283
224
382
275
275
150
220
275
310
360
52
297 1816
355 402
267 402
300 402
233 402
210
1 4 8
405
355
296
130
225
202
*
*
1816
402
402
2 9 1
1 7 7
*
*
*
*
*
1828
402
402
402
402
1938
292
*
1909
528
402
1 9 1 1
*
1929
1902
402
*
*
*
*
503
503
503
*
1869
1863
1869
*
*
1869
*
1
402
402
402
402
444
1 7 7
1932
*
402
402
Melting Points of Polymers VI/73
Polymer
Molecular Melting
wei ght point Refs.
-, 2-metbyl-
-, N-methyl-
-, N-phenyl-
-, N-piperazinyl-
Poly(S-aminovaleric acid)
Poly(L-aspartic acid)
a-isobutyl ester
&y(azelaic anhydride)
Poly(azelaoy1 oxalodihydrazide)
Poly(benzaldehyde-alt-dimethylketene)
-, p-chloro-
-, p-met hoxy-
-, m-nitro-
Poly(benzylidenethiodecamethylene sulfide)
Poly(benzylidenethiohexamethylene sulfide)
-, p-met hoxy-
Poly(benzylviny1 ether)
Poly(4,4-biphenyldicarboxaldehyde)
Poly(4,4-biphenylene adi pami de)
Poly(4,4-biphenylene adipate)
Poly(4,4-biphenylene carbodiimine)
-, 3,3-dimethoxy-
Poly(4,4-biphenylene-4,4-dibenzylidenimino adipate)
-, 3 ,3 -dimethoxy-
Poly(4,4-biphenylene-4,4-dibenzylidenimino sebacate)
-, 3 ,3 -dimethoxy
Poly[4,4-(4,4-biphenylenedioxy)-diphenylene carbonate]
Poly(4,4-biphenylenedioxy 4,4-diphenylene ketone)
Poly(4,4-biphenylene disiloxanylenedipropionamide)
-, tetramethyl- (Si)
Poly[4,4-(2,2-2,2-biphenylenedithiazole)-oxy-p-phenylene]
Poly[4,4-(2,2-2,2-biphenylenedithiazole)-~-phenylene]
Poly(4,4-biphenylene ditbiolisophthalate)
Poly(4,4-biphenylene dithiolterephthalate)
Poly(4,4-biphenylenegermylene)
Poly(biphenylene 3,3,4,4-oxydiphenylenetetracarboximide)
Poly(4,4-biphenylene pyromellitimide)
Poly(4,4-biphenylene sebacami de)
Poly(4,4-biphenylene terephthalamide)
-, 3,3-dimethyl-
-1 -, N,N-dietbyl-
-, N,N-dietbyl-
&y(4,4-biphenylene terephthalate)
-, 2,2-dipropyl-
Poly[4,4-biphenylene 4,4-(thiodiphenylene)-dioxy-3,3,4,4-diphenylenete~ac~boximide]
Poly(l,3-butadiene), 1,2-
Poly( 1,3-butadiene), 1,4-
-, 2-tert-butyl
-, 2-chloro- [chloroprene]
-, 2,3-dimethyl-
-, l-methoxy-
trans-
-, 2-metbyl- [isoprene]
-, -1 hydrochlorinated
-, 2-methylacetoxy-
-, 2-propyl-
Poly(l,S-butadiene( 1,4-)-alt-methacrylonitrile]
-, 1,1,4,4-tetradeutero-
Poly [ 1,3-butadiene( 1,4-)-&t-methyl methacrylate]
Poly(butadiene oxide)
Poly(butenamer)
I.
II.
Poly( 1-butene)
-, 4-cyclohexyl-
197.32 130
197.32 80
259.39 - 30
267.42 142
115.09
170.21 54
270.29 260
176.22 290
210.66 260
206.24 240
221.21 240
294.52 1 3 5
238.42 1 1 5
268.44 130
210.23
294.35
296.32
192.22
220.27
502.57
562.62
558.68
618.73
396.40
250
400
300
> 300
190
220
230
250
370.56
426.66
486.61
394.5 1
348.44
348.44
224.79
300
240
250
340
> 460
295
350.46
314.34
342.40
398.5 1
370.45
400.47
658.68
435
500
440
254
316
350
483
84.12
121.18
125.22
154.21
70.09
54.09
138.25
402
402
402
402
*
*
1823
402
1817
1817
1817
1817
1923
1923
1923
*
1 8 0 1
402
1 9 0 1
1907
1907
1893
1893
1915
*
402
1810
1810
1922
1922
1777
*
*
402
402
402
1870
1870
*
1 9 0 1
1 7 7 1
*
*
*
*
*
118 1803
*
*
*
*
75 1825
56 1849
74 1809
210
150
170
138
1864
1864
*
282
328
References page VI-159
VII74 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Polymer
Mol ecul ar Melting
wei ght point Refs.
-, 4-n-n-diisopropylamino-
-, 3,3-dimethyl-
-, 3-methyl-
-, 3-methyl- (1,3-via hydride shift)
-, 3-phenyl-
-, 4-phenyl-
-, 4-o-tolyl-
-, 4-p-tolyl-
-, 4,4,4-trifluoro-
-, 3-trifluoromethyl-
4-trimethylsilyl-
i&y(2-butene-all-ethylene)
Poly(2-butene 4-octenediamide)
tram-, trans-
Poly(2-butene oxide)
-, 2-methyl-
Poly(2-butene sulfide)
cis-
trans-
Poly(Z-butenylene hexamethylenediurethane)
cis-
trans-
Poly(4,4-butylidenediphenylene carbonate)
Poly[4,4-(2,2-butylidene)-diphenylene carbonate]
Poly(butylviny1 ether)
-, 2-methyl-
Poly(sec-butylvinyl ether), see Poly(propylviny1 ether), methyl-
Poly(teri-butylvinyl ether)
Poly(butyraldehyde)
Poly(caprolactam), see Poly(6-aminocaproic acid)
Poly(caprylaldehyde)
Poly(carbon monoxide-alt-ethylene) [ketone]
Poly[m-(carboxyphenoxy)-acetic anhydride]
Poly[p-(carboxyphenoxy)-acetic anhydride]
-, 3-bromo-
Poly(chloroprene), see Poly(l,3-butadiene), chloro-
Poly(chlorotrifluoroethylene-al&ethylene)
Poly( 1,3-cyclobutylene)
-, l-cyano-
Poly( 1,3-cyclobutylene carbonate)
-, 2,2,4,4-tetramethyl-
Poly( 1,3-cyclobutyleneoxymethylene oxide)
-, 2,2,4,4-tetramethyl-
Poly( 1,2-cycloheptylene-alt-ethylene)
Poly( 1 ,Cpoly- 1,3-cyclohexadiene)
trans-
Poly(cyclohexene oxide)
Poly( 1,3-cyclohexylene adipamide)
cis-
trans-
Poly( 1,4-cyclohexylene adipamide)
Poly( 1,4-cyclohexylene adipate)
Poly(l,3-cyclohexylene azelamide)
cis-
trans-
Poly( 1,Ccyclohexylene 3,3 -dibenzamide)
Poly( 1,3-cyclohexylenedimethylene adipamide)
Poly( 1,4-cyclohexylenedimethylene adipamide)
cis-
155.28 315
84.16 260
191
282
*
132.21 360 90
146.23 239
146.23 196
110.08 263
124.11 300
1 8 7
1 8 7
1 8 1 3
1 8 1 3
*
222.29
301 657
*
1879 86.13
88.17
196
156 548
192 548
256.30
136
177
170
222
402
402
438
438
*
268.31
268.31
*
*
*
329
*
128.22 35
178.14
178.14
257.04
134
179
1565
1565
*
*
54.09
114.10
110.12
80.13
98.14
224.30
380 221
126 527
170 402
300 402
400 402 224.30
266.38
125 402
300 402
390 402 320.39
252.36
246
225
345
342
347
385
1878
385
1806
1878
*
Poly( 1,4+yclohexylenedimethylene adipate)
Melting Points of Polymers VI/75
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly( 1,4-cyclohexylenedimethylene azelamide)
cis-
trans-
Poly( 1,4-cyclohexylenedimethylene azelate)
cis-
trans-
Poly( 1,4-cyclohexylenedimethylene
1,4-cyclohexylenedicarboxylate)
cis-, trans-
trans-, trans-
Poly( 1,4-cyclohexylenedimethylene dithiol- 1,4-cyclohexylenedicarboxylate)
trans-, trans-
Poly( 1,4-cyclohexylenedimethylene dodecanediamide)
cis-
trans-
Poly( 1,4-cyclohexylenedimethylene dodecanedioate)
cis-
trans-
Poly[ 1,4-cyclohexylenedimethylene (ethylenedithio)-diethylenediurethane]
trans-
Poly( 1,4-cyclohexylenedimethylene glutaramide)
cis-
trans-
Poly( 1,4-cyclohexylenedimethylene glutarate)
trans-
Poly [ 1,4-cyclohexylenedimethylene (hexamethylenedithio)-diethylenediurethane]
trans-
Poly(l,4-cyclohexylenedimethylene isophthalamide)
trans-
Poly(l,4-cyclohexylenedimethylene isophthalate)
trans-
Poly( 1,4-cyclohexylenedimethylene 2,6-naphthalate)
cis-
trans-
Poly( 1,4-cyclohexylenedimethylene octamethylenediurethane)
trans-
Poly( 1,4-cyclohexylenedimethylene oxalate)
trans-
Poly( 1,4-cyclohexylenedimethylene)-oxymetbylene oxide)
trans-
Poly [ 1,4-cylohexylenedimethylene (pentamethylenedithio)-diethylenediurethane]
trans-
Poly( 1,4-cyclohexylenedimethylene p-phenylenediacetate)
cis-
Poly( 1,4-cyclohexylenedimethylene pimelamide)
cis-
trans-
Poly( 1,4-cyclohexylenedimethylene pimelate)
trans-
Poly( 1,4-cyclohexylenedimethylene sebacamide)
cis-
trans-
Poly( 1,4-cyclohexylenedimethylene sebacate)
cis-
trans-
Poly( 1,4-cyclohexylenedimethylene suberamide)
cis-
trans-
294.44
296.41
280.36
312.49
336.52
338.49
376.53
238.33
240.30
432.64
272.35
274.32
324.38
340.46
198.22
156.22
418.61
302.37
266.38
268.35
308.47
3 10.43
280.41
1 9 5 385
275 385
4 1
50
547
547
205 547
246 547
310 1922
215 385
190 1878
278 385
280 1878
46 547
8 5 547
1 2 1 1897
1 6 7 385
290 385
50 547
124 1897
310 385
1 9 7 547
287 547
3 4 1 547
160 402
160 291
215 547
78 369
86 1945
102 1897
55 547
1 9 1 385
293 385
42 547
208 385
200 1878
300 385
296 1878
292 1769
50 547
78 547
215 385
311 385
References page VI-159
VI/76 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly( 1,4-cyclohexylenedimethylene suberate)
cis-
trans-
Poly( 1,4-cyclohexylenedimethylene succinate)
Poly( 1,4-cyclohexylenedimethylene terephthalate)
Poly[ 1,4-cyclohexylenedimetbylene (tetramethylenedithio)-diethylenediurethane]
trans-
Poly[ 1,4-cyclohexylenedimethylene (trimethylenedithio)-diethylenediurethane]
trans-
Poly[(l,4-cyclohexylenedioxy)-ditrimethylene adipamide]
Poly[(l,4-cyclohexylenedioxy)-ditrimethylene 4,4-(ethylenedioxy)-dibenzamide]
Poly[(l,4-cyclohexylenedioxy)-ditrimethylene 4,4-(hexamethylenedioxy)-dibenzamide]
Poly [( 1,4-cyclohexylenedioxy)-ditrimethylene oxamide]
Poly[(l,4-cyclohexylenedioxy)-ditrimethylene 4,4-(oxydiethylenedioxy)-dibenzamide]
Poly[( 1,4-cyclohexylenedioxy)-ditrimethylene @-phenylenedioxy)-diacetamide]
Poly [( 1,4-cyclohexylenedioxy)-ditrimethylene terephthalamide
Poly[(l,4-cyclohexylenedioxy)-ditrimethylene 4,4-(tetramethylenedioxy)-dibenzamide]
Poly( 1,4-cyclohexylene dithiolsuccinate)
trans-
Poly[ 1 ,Ccyclohexylene (ethylenedithio)-diethylenediurethane]
trans-
Poly[ 1 ,Ccyclohexylene (hexamethylenedithio)-diethylene-diurethane]
trans-
Poly( 1 ,Ccyclohexylene 3,3 -methylenedibenzamide)
Poly( 1 ,Ccyclohexylene octamethylenediurethane)
trans-
Poly( 1,4-cyclohexyleneoxymethylene oxide)
trans-
Poly[ 1 ,Ccyclohexylene (pentamethylenedithio)-diethylene-diurethane]
trans-
Poly( 1,3-cyclohexylene sebacamide)
cis-
trans-
Poly( 1,4-cyclohexylene sebacate)
Poly( 1,4-cyclohexylene suberate)
trans-
Poly( 1 ,Zcyclohexylene sulfide)
Poly( 1,3-cyclohexylene sulfide)
Poly( 1,2-cyclohexylene sulfone)
Poly(l,3-cyclohexylene sulfone)
Poly[l,4-cyclohexylene (tetramethylenedithio)-diethylene-diurethane]
trans-
Poly[l,4-cyclohexylene (trimethylenedithio)-diethylene-diurethane]
trans-
Poly( 1 ,Ccylclohexylene urethane)
Poly(cyclohexylidenedimethylene oxide)
-, 3,4-dihydro-
-3 -9 4-methyl-
-, 4-methyl-
Poly(4,4cyclohexylidenediphenylene carbonate)
-, 2,2-dimethyl-
-, 3,3,5,5-tetrachloro-
Poly(cyclohexylidenethiohexamethylene sulfide)
Poly(l,2-cyclopentylene-alt-ethylene)
Poly( 1,3-cyclopentylene-alt-methylene) [ 1,5-hexadiene]
Poly(4,4-cyclopentylidenediphenylene carbonate)
Poly(cyclopropylene cyclopropylenedicarboxamide)
Poly[cyclopropylene (cyclopropylenedicarboxoyl)-diurethane]
trans-, trans-
Poly(cyclopropylenedimethylene cyclopropylenedicarboxamide)
Poly(cyclopropylenedimethylene cyclopropylenediurethane)
cis-
trans-
282.38
50
96
404.58
129 1 8 9 7
390.56
340.46
496.60
552.71
284.36
540.66
420.5 1
360.45
524.66
230.35
1 0 5 1897
196 402
250 402
215 402
246 402
1 2 5 402
160 402
384 402
224 402
302 1922
348.48
214 1897
404.58
334.42
312.41
128.17
390.56
280.41
204 1897
174 402
255 633
255 402
221 291
209 369
189
120
290
254.33
114.21
114.21
146.21
146.21
376.53
1 8 1 1174
130 1917
139 1917
284 1917
309 1917
214 1897
362.50
141.17
126.20
124.18
138.21
140.23
294.35
322.40
427.09
230.44
280.32
166.18
254.20
194.23
226.23
:
202
l 355
152
102
1 5 5
1 6 5
260
200
270
75
250
285
245 1865
220 1865
1 7 5 1865
210 1865
402
402
*
1897
444
1935
1935
1935
1935
438
1915
540
1923
*
*
438
1865
Melting Points of Polymers VI/77
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly(cyclopropylenedimethylene hexamethylenediurethane)
cis-
trans-
Poly(cyclopropylenedimethylene isophthalamide)
Poly(cyclopropylenedimethylene isophthalate)
Poly[cyclopropylenedimethylene 4,4-(methylenediphenylene)-diurethane]
cis-
trans-
Poly(cyclopropylenedimethylene piperazinediurethane)
cis-
trans-
Poly(cyclopropylenedimethylene sebacami de)
Poly(cyclopropylenedimethylene terephthalate)
Poly(cyclopropylenedimethylene toluylenediurethane)
cis-
trans-
Poly(cyclopropylene hexamethylenediurea)
Poly(cyclopropylene isophthalamide)
Poly(cyclopropylene piperazinediurea)
Poly(cyclopropylene sebacami de)
Poly(cyclopropylidenedimethylene oxide)
Poly(decamethylene)
-, 1,2-dichloro-
trans-
Poly(decamethylene adipamide)
Poly(decamethylene adipate)
-, 3-methyl- (diacid)
Poly[decamethylene N,N-adipolyldi(6aminocaproate)]
Poly(decamethylene adipoyldiurethane)
Poly(decamethyleneaminohexamethylene amine)
Poly(decamethylene azelamide)
Poly(decamethylene azelate)
Poly(decamethylene 4,4-biphenylenediurethane)
-, 3,3-dimethyl- (diisocyanate)
Poly(decamethylene carbonate)
Poly(decamethylene m-carboxycarbanilate)
Poly(decamethylene p-carboxycarbanilate)
Poly[decamethylene (decamethylenedisulfonyl)-dicaproamide]
Poly(decamethylene decamethylenediurethane)
210.33
230.27
232.24
352.39
240.26
266.38
232.24
276.29
240.3 1
202.21
210.24
238.33
84.12
140.27
209.16
298.42 - 2
510.72 137
370.45 164
254.46 102
410.51
438.57
200.28
319.40
319.40
634.98
398.59
Poly(decamethylene 2,2-dibenzoate) 380.48
Poly(decamethylene 3,3-dibenzoate) 380.48
Poly(decamethylene 4,4-dibenzoate) 380.48
Poly[(decamethylenedioxy)-dihexamethylene oxide] 356.59
Poly[4,4-(4,4-(decamethy1enedioxy)-diphenylenedioxy)-~pheny1ene terephthalate] 672.78
Poly[4,4-(decamethylenedioxy)-diphenyleneoxy-p-xylylene oxide] 460.62
Poly[3,3-(decamethylenedioxy)-diphenylene terephthalate] 488.58
Poly[4,4-(decamethylenedioxy)~diphenylene terephthalate] 488.58
-, dichloro- (dial) 557.47
Poly(4,4-decamethylenediphenylene carbonate) 352.47
Poly(4,4-decamethylenedipiperazine sebacami de)
Poly(decamethylene disiloxanylenedipropionamide)
tetramethyl- (silicone)
ioly(decamethylene disulfide)
358.63
414.74
204.39
Poly(decamethylenedithioethylene disulfide) 296.56
Poly(decamethylenedithiohexamethylene disulfide) 352.67
Poly(decamethylene dithioladipate) 316.53
Poly(decamethylene dithiolsebacate) 372.63
Poly(decamethylene dithiolterephthalate) 336.52
Poly(decamethylenedithiotetramethylene disulfide) 324.62
Poly(decamethylene docosanediamide) 506.86
Poly(decamethylene dodecamethylenediurea) 424.67
120 1860
1 6 5 1860
220 1865
100 1860
230 1860
290 1860
70 1860
100 1860
223 1865
130 1860
170 1860
200 1860
180 1865
250 1865
260 1865
220 1865
45 1935
47 1925
*
*
1796
1792
402
1829
*
*
219
55
127
158
207
1 4 5
142
- 3
90
132
68
242
211
108
259
160
110
150
633
1820
1 8 9 1
1 8 9 1
402
291
634
1552
1552
1552
542
1773
1789
1773
1773
1773
1915
1174
*
50 402
45 1868
65 725
80 1837
46 1784
75 1922
103 1922
201 1922
56 1837
58 1784
169 454
190 634
References page VI-159
VI/78 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly(decamethylene phosphinylidenedipropionamide)
-, met hyl - ( P)
Poly(decamethylene phthalamide)
Poly(decamethylene pimelate)
Poly(decamethylene dodecanediamide)
Poly[decamethylene NJ-dodecanedioyldi(p-aminobenzoate)]
Poly(decamethylene eicosanediamide)
Poly[decamethylene 4,4-(ethylenedioxy)-dibenzoate]
Poly[decamethylene 4,4-(ethylenediphenylene)-dioxydiacetamide]
Poly(decamethylene NJ-ethylenediterephthalamate)
Poly(decamethylene 4,4-ethylidenedibenzamide)
Poly(decamethylene fumaramide)
-, 2,3-dimethyl- (diacid)
trans-
methyl- (diacid)
Poly(decamethylene 2,5-furandicarboxamide)
Poly(decamethylene 2,5-furandipropionamide)
Poly(decamethylene glutaramide)
3-carboxyl- (diacid)
&ly(decamethylene glutarate)
Poly[decamethylene (hexamethylenedisulfonyl)-dicapromide]
Poly(decamethylene NJ-hexamethylenediterephthalamate)
Poly(decamethylene hexamethylenediurea)
Poly(decamethylene hexamethylenediurethane)
Poly(decamethylene 3-hexenedioate)
Poly(decamethylene isophthalamide)
Poly(decamethylene isophthalate)
Poly[decamethylene 4,4-(isopropylidenediphenylene)-dioxy-diacetamide]
Poly(decamethylene malonamide)
-, dodecyl- (diacid)
Poly(decamethylene malonate)
Poly(decamethylene 3,3-methylenedibenzamide)
Poly(decamethylene 4,4-methylenedibenzamide)
Poly(decamethylene 4,4-methylenediphenylenediurea)
Poly(decamethylene 4,4-methylenediphenylenediurethane)
Poly[decamethylene (methylene-2,5-furan)-dicarboxamide]
Poly[decamethylene (methylene-2,5-tetrahydrofuran)-dicarboxamide]
Poly[decamethylene octadecamethylenediurea)
Poly(decamethylene ocatadecanediamide)
Poly[decamethylene octadecanedioate)
Poly[decamethylene octamethylenediurea)
Poly[decamethylene octamethylenediurethane)
Poly(decamethylene 4-octenediamide)
Poly(decamethylene 4-octenedioate)
Poly(2,5-decamethylene-1,3,4-oxadiazole)
Poly(decamethylene oxalate)
Poly(decamethylene oxamide)
Poly(decamethylene oxamide-alt-decamethylene sebacamide)
Poly(decamethylene oxide)
Poly(decamethylene oxydiacetate)
Poly(decamethyleneoxymethylene oxide)
Poly(decamethyleneoxy-p-phenylene oxide)
Poly[decamethylene (pentamethylenedisulfonyl)-dicaproamide]
Poly(decamethylene NJ/-pentamethylenediterephthalamate)
Poly(decamethylene p-phenylenediacetamide)
Poly[decamethylene @-phenylenedioxy)-diacetamide] 362.47
Poly(decamethylene p-phenylenedipropionamide) 358.53
Poly(decamethylene 3,3-phosphinylidenedibenzamide) 426.50
-, methyl- (P) 440.52
330.41
302.42
298.42
366.59
606.80
478.80
440.54
466.62
494.59
406.57
252.36
280.41
266.38
292.38
348.49
268.40
312.41
578.87
550.70
340.5 1
302.42
304.39
480.65
240.35
408.67
242.32
392.54
392.54
422.57
306.41 1 1 1
310.44 8 5
508.84 172
450.75 170
368.57 2 0 1
370.53 146
208.30 100
226.32
564.86
272.34
186.30
248.37
564.84
536.67
330.47
1 1 5 1 8 6 8
66 764
1 9 1 244
192 454
1 7 1 1 7 9 2
1 7 1 244
1 3 5 290
220 402
277 7 8 1
150 402
50 402
267 1 9 3 1
166 1 9 3 1
130 1 9 0 5
140 402
70
218
235
210
216
186
36
1 0 5
402
*
402
7 8 1
402
634
*
*
1 8 6 8
1794
402
1 2 3
34
6 5
100
246
1774
764
402
402
634
*
402
402
634
454
*
634
402
*
1 9 2 1
*
229
252
290
231
291
743
402
1 7 8 1
*
64 1798
57 695
< 100 1 8 6 8
223 402
205 7 8 1
242 2 9 1
265 454
1 8 8 402
265 402
271 454
1 5 5 402
Polymer
Melting Points of Polymers
Molecular Melting
wei ght point
VI/79
Refs.
Poly(decamethylene 4,4-phosphinylidenedibenzamide)
-, methyl- (P)
-, phenyl- (P)
Poly(decametbylene 2,4-pyridinedicarboxamide)
Poly(decamethylene 2,Spyridinedicarboxamide)
Poly(decamethylene 2,6-pyridinedicarboxamide)
-, 1,4-dihydro-4-oxo-
Poly(decametbylene 3,Spyridinedicarboxamide)
Poly(decamethylene pyromelltimide)
-, 3-bromo- (imide)
Poly(decamethylene sebacamide)
Poly(decamethylene sebacate)
Poly(decamethylene sebacoyldiurethane)
Poly(decamethylene suberamide)
Poly(decamethylene suberate)
Poly(decamethylene succinamide)
Poly(decamethylene succinate)
D- 1,2-dihydroxy- (diacid)
Poly(decamethylene sulfide)
Poly(decamethylene sulfonyldivalerate)
Poly(decamethylene terephthalamide)
Poly(decamethylene terephthalate)
Poly[decamethylene N,N-terephthaloyldi(6-aminocaproate)]
Poly(decametbylene tetradecametbylenediurea)
Poly(decametbylene tetradecanediamide)
Poly(decamethylene 2,5tetrahydrofurandipropionamide)
Poly[decamethylene (tetramethylenedisulfonyl)-dicaproamide
Poly(decamethylene N,N-tetramethylenediterephthalamate)
Poly(decamethylene tetramethylenediuretane)
Poly(decamethylene thiodivalerate)
Poly(decamethylenethiohexamethylene sulfide)
Poly(decamethylene 2,Sthiophenedicarboxamide)
Poly(2,5-decamethylene-1,3,4-triazole)
l-amino- (triazole)
Poly (decamethy lenetridecanediamide)
Poly(decamethylene NJ-trimetbylenediterephthalamate)
Poly(decamethylene urea)
Poly(decamethylene p-xylylenediurea)
Poly(decamethylene p-xylylenediurethane)
Poly(decenamer)
Poly( 1-decene)
Poly(decylviny1 ether)
Poly[2,7-( 1,6-diazanthrylene)-4,4 -biphenylene]
-, 4,9-diphenyl-
Poly[2,8-(1,9-diazanthrylene)-4,4-biphenylene]
- 4,6-diphenyl
Poly[2,7-(1,6-diazanthrylene)-4,4-oxydiphenylene]
4,9-diphenyl-
~oly[2,8-(1,9-diazanthrylene)-4,4-oxydiphenylene]
4&diphenyl-
Poly(dimethy1 ketene)
Poly(di-1,4-naphthyleneoxyethylene oxide)
Poly(di-1,4-naphthyleneoxyheptamethylene oxide)
Poly(di-1,4-naphthyleneoxyhexamethylene oxide)
Poly(di- 1,4-naphthyleneoxypentamethylene oxide)
Poly(di-1,4naphthyleneoxytetramethylene oxide)
Poly(di-1,4-naphthyleneoxytrimethylene oxide)
Poly( 1,4-dioxanylene-2,Sdimetbylene adipamide)
trans-
Poly(l,4-dioxanylene-2,5-dimethylene sebacami de)
trans-
426.50
440.52
502.59
303.41
303.41
303.41
319.41
303.41
433.30 291
426.55
310.48
288.34
172.33
404.56
302.42
530.7 1
452.73
394.64
352.52
1 550.81
522.64
314.43
372.56
288.55
308.44
207.32
222.34
380.62
508.61
198.31
360.50
362.47
184.32
330.39
482.58
330.39
482.52
346.39
498.58
346.39
498.58
312.37
382.50
368.48
354.45
340.42
326.40
256.30
312.41
186
192
190
232
200
137
210
1 5 3
217
208
66
78
9 1
1 0 1
276
1 6 6
180
189
1 7 8
236
261
1 7 1
57
78
250
402
402
1905
1905
1905
1905
1905
*
1267
*
*
402
244
291
*
*
*
609
1819
1 8 1
1797
1868
*
1792
634
2
402
402
781
633
767
1819
1905
242
1 7 5
222
200
1 9 7
210
260
147
7
610
339
781
402
634
291
634
634
*
*
1900
498 1778
513 1778
490 1778
502
291
239
280
196
324
278
1778
*
1787
1787
1787
1787
1787
1787
291 1769
262 1769
References page VI-159
VI/80 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Mol ecul ar Melting
Polymer wei ght point Refs.
Poly( 1, 3-dioxolane), see Poly(ethyleneoxymethylene oxide)
Poly( 1,3-dioxopane), see Poly(methyleneoxytetramethylene oxide)
Poly(dithiodiethylene sebacamide)
Poly(4,4-dithiodiphenylene hexamethylenediurea)
Poly(divinylbenza1)
-, 2-methyl-
-, 4-methyl-
Poly(divinylfurfura1)
Poly( 1-docosene)
Poly(dodecamethylene)
-, 1,2-dichloro-
trans-
-, l-methyl-
Poly(dodecamethylene adipamide)
Poly(dodecamethylene adipate)
Poly[dodecamethylene NJ-adipoyldi(6-aminocaproate)]
Poly(dodecamethylene 4,4-biphenylenediurethane)
-, 3,3-dimethyl- (diisocyanate)
Poly(dodecamethylene decamethylenediurethane)
Poly[4,4-(dodecamethylenedioxy)-diphenyleneoxy-~-xylylene oxide]
Poly(dodecamethylene docosanediamide)
Poly(dodecamethylene NJ-dodecamethylenediterephthalamate)
Poly(dodecamethylene dodecamethylenediurethane)
Poly(dodecamethylene dodecanediamide)
Poly[dodecamethylene N,N-dodecanedioyldi(p-aminobenzoate)]
Poly(dodecamethylene N,N-ethylenediterephthalamate)
Poly(dodecamethylene NJ-hexamethylenediterephtbalamate)
Poly(dodecamethylene hexamethylenediurea)
Poly(dodecamethylene hexamethylenediurethane)
Poly(dodecamethylene 3-hexenedioate)
Poly(dodecamethylene 4,4-methylenediphenylenediurea)
Poly(dodecametbylene 4,4-metbylenediphenylenediurethane)
Poly(dodecamethylene 1,4,5,8-naphthalenetetracarboximide)
Poly(dodecamethylene octadecanediamide)
Poly(dodecamethylene 4-octenedioate)
Poly(dodecamethylene oxamide)
Poly(dodecamethylene oxamide-alt-dodecamethylene sebacamide)
Poly(dodecamethylene NJ-pentamethylenediterephthalamate)
Poly(dodecamethylene p-phenylenediacetamide)
Poly(dodecamethylene p-phenylenedipropionamide)
Poly(dodecamethylene phosphinylidenedipropionamide)
-, met hyl - ( P)
Poly(dodecamethylene pyromellitimide)
-, 3-bromo- (imide)
Poly(dodecamethylene sebacamide)
Poly(dodecamethylene suberate)
Poly(dodecamethylene succinamide)
Poly(dodecamethylene terephthalamide)
Poly[dodecamethylene N,N-terephthaloyldi(6-aminocaproate)]
Poly(dodecamethylene NJ-tetramethylenediterephthalamate)
Poly(dodecamethylene N,N-trimethylenediterephthalamate)
Poly(dodecamethylene p-xylylenediurea)
Poly(dodecamethylene p-xylylenediurethane)
Poly(dodecanedioic anhydride)
Poly(dodecenamer)
Poly( 1-dodecene)
Poly(dodecylviny1 ether)
Poly(eicosamethylene adipate)
-, 3-methyl- (diacid)
Poly(eicosamethylene azelate)
Poly(eicosamethylene 3,3-dibenzoate)
Poly(eicosamethylene 4,4-dibenzoate)
318.49 155
416.56 262
176.22 100
190.24 95
190.24 1 1 5
166.18 1 4 5
168.32
237.21
182.35
310.48
538.77
438.57
466.62
426.64
488.67
534.92
454.70
394.64
634.86
522.64
578.75
368.57
370.53
450.63 240
452.59 164
478.80 167
620.96
564.72
358.53
386.58
358.46
461.36 238
330.47
558.76
550.70
536.67
388.56
390.52
212.29
212.38 30
424.67 87
438.69 60
466.75 87
520.76 9 1
520.76 1 1 5
40
30
210
230
134
219
133
207
164
128
1 8 3
167
264
231
205
238
139
217
206
256
263
296
301
1 6 3
258
216
258
178
8 7
*
*
402
402
1 8 3 0
1 8 3 0
1 8 3 0
1 8 3 0
*
1925
1 9 2 6
3 3 9
544
*
1 7 9 2
402
634
1 7 8 9
454
*
6 3 3
454
1 7 9 2
7 8 1
7 8 1
634
1 8 9 2
634
*
634
634
*
454
*
*
1781
7 8 1
454
454
*
*
1267
*
*
*
454
5 4 4
1 7 9 2
781
781
6 3 4
6 3 4
1823
*
*
1900
1 7 9 0
1 7 9 6
1 7 9 0
1 5 5 2
1 5 5 2
Melting Points of Polymers VI/81
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly(eicosamethylene glutarate) 410.64
-, 3-@-nitrophenyl)- (diacid) 531.74
Poly(eicosamethylene isophthalate) 444.66
Poly(eicosamethylene malonate) 382.58
Poly(eicosamethylene oxalate)
Poly(eicosamethylene oxydiacetate)
Poly(eicosamethylene phthalate)
Poly(eicosamethylene pimelate)
Poly(eicosamethylene sebacate)
Poly(eicosamethylene suberate)
Poly(eicosamethylene succinate)
Poly(eicosamethylene sulfonyldivalerate)
Poly(eicosamethylene terephthalate)
Poly(eicosamethylene thiodivalerate)
Poly(enanthaldehyde, see Poly(heptaldehyde)
Poly(epichlorohydrin), see Poly(ethylene oxide), chloromethyl-
Poly(ethylene)
-, chlorotrifluoro-
-, 1-butoxy-2-methyl-
cis- (erythro-di-isotactic)
fans- (threo-di-isotactic)
-, I-tert-butoxy-2-methyl-
cis- (erythro-di-isotactic)
-, 1-et hoxy-Zmet hoxy-
trans-
-, 1-ethoxy-2-methyl-
cis- (erythro-di-isotactic)
tram- (threo-di-isotactic)
-, isobutoxy-2-methyl-
-, 1-isopropoxy-2-methyl-
cis- (erythro-di-isotactic)
trans- (threo-di-isotactic)
-, I-methoxy-2-methyl-
cis- or tram- (threo-di-isotactic)
-, I-methyl-2-propoxy-
trans-
-, tetrafluoro-
-, trifluoro-
Poly(ethylene adi pami de)
Poly(ethylene adipamide-all-ethylene oxamide)
Poly(ethylene adipate)
-, methyl- (diol)
Poly[ethylene N,N-adipoyldi(6-aminocaproate)]
Poly(ethylene adipoyldiurethane)
Poly(ethylene amine)
-, N-acetyl-
-, N-benzoyl-
-3 -, p-chloro-
-, N-butyryl-
-3 -, 4-(4-methylthiophenyoxy)-
-, N-cyclohexanecarbonyl-
-, N-dodecanoyl-
-, N-heptanoyl-
-, N-hexanoyl-
-, N-isobutyryl-
-, N-isovaleryl-
-, N-2-naphthoyl-
-, N-octadecanoyl-
-, N-octanoyl-
-, N-perfluorooctanoyl-
368.56
412.61
444.66
438.69
480.78
452.72
396.61
544.83
444.66
512.84
114.19
114.19
102.13
86.13
100.16
72.11
100.16
170.21
284.32
186.21
398.50
258.23
85.11
153.22 285
225.38 1 5 5
197.24 258
309.54 1 4 5
439.12 245
80
46
49
69
69
90
89
52
84
92
8 8
89
1 1 7
1 1 3
79
100
100
> 250
217
1 9 1
207
230
243
204
211
230
287
210
168
310
D359
- 20
1 6 3
210
200
1790
1796
1794
1868
1790
1790
1798
1794
1790
1790
1790
1790
1797
1794
767
*
*
*
*
1880
1880
1880
1 4 1
1880
1880
1804
1 4 1
*
1880
1880
1880
1804
1 4 1
1804
*
*
402
1 7 8 1
*
765
1792
402
*
747
*
*
*
*
747
747
*
*
*
*
747
747
*
747
References page VI- 159
VI/82 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Polymer
Mol ecul ar Melting
wei ght point Refs.
-7 N-perfluoropropionyl-
-, N-pivaloyl-
-, N-P-toluoyl-
-, N-valeryl-
Poly(ethylene azelamide-&-ethylene oxamide)
Poly(ethylene azelate)
-, methyl- (diol)
Poly(4,4-ethylenebiphenylene)
Poly[ethylene p-(carboxyphenoxy)-acetate]
Poly[etbylene p-(carboxyphenoxy)-butyrate]
Poly[ethylene p-(carboxyphenoxy)-caproate]
Poly[ethylene p-(carboxyphenoxy)-heptanoate]
Poly[ethylene p-(carboxyphenoxy)-undecanoate]
Poly[ethylene p-(carboxyphenoxy)-valerate]
Poly[ethylene p-(carboxyphenylene)-acetamide]
Poly(ethylene 1,4-cyclohexylenedicarboxylate)
cis-
trans-
Poly(ethylene cyclopropylenedicarboxamide)
trans-
Poly(ethylene decamethylenediurethane)
Poly(ethylene 2,2-dibenzoate)
-, methyl- (diol)
Poly(ethylene 3,3-dibenzoate)
-, methyl- (diol)
Poly(ethylene 4,4-dibenzoate)
-, methyl- (diol)
Poly(4,4-ethylenedibenzoic anhydride)
Poly(4,4-etbylenedicyclohexylene dodecanediamide)
Poly(4,4-ethylenedicyclohexylene sebacami de)
Poly[3,3 -(ethylenedioxy)-dibenzoic anhydride]
Poly[4,4-(etbylenedioxy)-dibenzoic anhydride]
-, 3,3-dimethoxy- 344.32
Poly[4,4-(ethylenedioxy)-dibenzoic isophthalic anhydride] 432.38
Poly[4,4-(ethylenedioxy)-dibenzoic phthalic anhydride] 432.38
Poly[4,4-(ethylenedioxy)-dibenzoic terephthalic anhydride] 432.38
Poly[(ethylenedioxy)-diethylene adipamide] 258.32
Poly[(ethylenedioxy)-diethylene adipate]
Poly[(ethylenedioxy)-diethylene azelate]
Poly[(ethylenedioxy)-diethylene 2,2-dibenzoate]
Poly[(ethylenedioxy)-dietbylene 3,3-dibenzoate]
Poly[(ethylenedioxy)-diethylene 4,4-dibenzoate]
Poly[4,4-(ethylenedioxydietylenedioxy)-diphenylene 3,3,4,4-(carbonyldiphenylene)tetracarboximide]
Poly[3,4-(ethylenedioxydiethylenedioxy)-diphenylene 3,3,4,4-(oxydiphenylene)tetracarboximide]
Poly[(ethylenedioxy)-diethylene glutarate]
Poly[(ethylenedioxy)-dietbylene isophthalate]
Poly[(ethylenedioxy)-diethylene malonate]
Poly[(ethylenedioxy)-dietbylene oxalate]
Poly[(ethylenedioxy)-diethylene pimelate]
Poly [(ethylenedioxy)-diethylene 1,4-piperazinediacetamide]
Poly[(ethylenedioxy)-diethylene sebacate]
260.29
302.37
356.37
356.37
356.37
616.58
246.26
280.28
218.21
204.18
274.32
3 14.39
316.39
Poly[(ethylenedioxy)-diethylene suberate]
Poly[(ethylenedioxy)-diethylene succinate]
Poly[(ethylenedioxy)-diethylene sulfonyldivalerate
Poly[(ethylenedioxy)-diethylene terephtbalate]
Poly[(ethylenedioxy)-diethylene thiodivalerate]
Poly[(ethylenedioxy)-diethylene undecanediamide]
-, 6-hydroxy- (diacid)
Poly[4,4-(ethylenedioxy)-diphenylene 3,3,4,4-(carbonyLdiphenylene)-tetracarboximide]
Poly[3,4-(ethylenedioxy)-diphenylene 3,3,4,4-(oxy-diphenylene)-tetracarboximide]
Poly[(ethylenedioxy)-ditrimethylene adipamide]
189.08 216
127.19 320
326.40 343
228.29
180.25
222.20
250.25
278.30
292.33
348.44
264.28
204.23
198.22
154.17
268.27 130
282.30 55
268.27 122
282.30 97
282.30
252.27
418.66
390.61
284.27
284.27
288.34
232.23
348.39
280.28
348.46
328.45
344.45
528.48
286.37 180
1 7 8 1
*
- 3 8 765
> 550 1 1 8 7
140 290
85 290
45 290
55 290
65 290
55 290
221 1904
<30 1912
120 1912
350 1860
*
1654
1552
1552
1552
*
140
340
316
333
237
208
215
222
220
140
1 8 5
209
160
190
- 30
- 4 0
4 1
46
93
405
1552
1854
1926
1926
1854
1854
1565
1872
1855
1 8 7 1
1872
1 8 7 1
2 9 1
402
765
765
1552
1552
1552
1808
*
- 28 765
65 1794
- 28 765
- 10 765
- 37 765
115 291
29 696
35 767
- 3 6 765
- 18 765
27 1797
65 1794
- 3 7 767
156
470
402
1 8 0 8
*
1791
Melting Points of Polymers VI/83
Polymer
Poly[(ethylenedioxy)-ditrimethylene azelamide]
Poly[(ethylenedioxy)-ditrimethylene sebacamide]
Poly[(ethylenedioxy)-ditrimethylene terephthalamide]
Poly(4,4-ethylenediphenylene adipamide)
Poly(4,4-ethylenediphenylene carbonate)
Poly(4,4-(ethylenediphenylene)-methylene]
Poly(4,4-ethylenediphenylene sebacami de)
Poly(ethylene disiloxanylenedipropionamide)
tetramethyl- (silicone)
&y(ethylene disulfide)
Poly[(ethylenedisulfonyl)-diacetic anhydride]
Poly[(ethylenedisulfonyl)-dipropionic anhydride]
Poly[4,4-(2,2-ethylenedithiazole)-p-phenylene]
Poly[(ethylenedithio)-diacetic anhydride]
Poly[(ethylenedithio)-dipropionic anhydride]
Poly(ethylenedithiohexamethylene disulfide)
Poly(ethylene dithioladipate) 204.3 1
Poly(ethylene dithiolisophthalate) 224.30
Poly(ethylene dithiol-2$pyridinedicarboxylate) 252.29
Poly(ethylene dithiolterephthalate) 224.29
Poly(ethylene dithionisophthalate) 224.29
Poly(ethylene dithiotetramethylene disulfide) 212.40
Poly(ethylene N,N-dodecamethylenediterephthalamate)
Poly(ethylene dodecanediamide)
Poly[ethylene NJ-dodecanedioyldi(p-aminobenzoate)]
Poly[ethylene (ethylenediamino)-dipropionamide]
-, N,N-diisopropyl-, N,N-dimethyl-
Poly(ethylene 4,4-ethylenedibenzoate)
254.37 261
494.59 242
228.30
340.51 102
296.32 212
> 320
202.21 1 6 8
328.32 1 4 1
Poly[ethylene (ethylenedioxy)-diacetamide]
Poly[ethylene 3,3-(ethylenedioxy)-dibenzoate]
Poly[ethylene 4,4-(ethylenedioxy)-dibenzoate]
-, 3.3.dimethoxy-
Poly[ethylene 4,4-(ethylenedioxydimethylene)-dibenzoate]
Poly[ethylene 4,4-(ethylenediphenylene)-diurethane]
Poly[ethylene 4,4-(ethylenedithio)-dibenzoate]
Poly[ethylene (ethylenedithio)-diethylenediurethane]
Poly(ethylene fumaramide)
Poly(ethylene glutarate)
-1 methyl- (diol)
- , 3-(p-nitro)-
Poly(ethylene 2$hexadienediamide)
Poly(ethylene 4,4-hexamethylenedibenzoate)
Poly[ethylene (hexamethylenedithio)-diethylene-diurethane]
Poly(ethylene hexamethylenediurea)
Poly(ethylene hexamethylenediurethane)
Poly(ethylene isophthalate)
-, methyl- (diol)
Poly(ethylene N,N-lysyldiurea)
methyl ester
&ly(ethylene 4,4-methylenedibenzoate)
Poly[ethylene 4,4-(methylenediphenylene).diurethane]
Poly(ethylene l$naphthalate)
Poly(ethylene 2$naphthalate)
Poly(ethylene 2,7naphthalate)
Poiy(ethylene nonamethylenediurethane)
Poly(ethylene oxalate)
Poly(ethylene oxamide-&ethylene sebacamide)
Poly(ethylene oxamide-&ethylene suberamide)
Poly(ethylene oxide)
-, l,l-bischloromethyl-
Mol ecul ar Melting
wei ght point
328.45
342.48
306.36
322.41
240.26
194.28
378.52
246.42
302.52
130 1 7 9 1
160 1 7 9 1
240 1 7 9 1
400 402
300 438
255 1187
360 402
55
256.24
284.30
270.37
192.25
220.30
240.56
1 8 5
255
265
8 3
75
102
1 0 7
1 2 5
1 8 5
280
340
80
96
8 8
388.37 210
356.38 1 3 5
360.44
294.38
140.14
158.15
172.18
279.25
166.18
352.43
350.49
228.30
190
1 6 8
50
- 1 8
76
6 1
160
130
293
240
402
*
1856
1856
1810
1 5 6 5
1565
1837
1784
1922
1922
1922
1922
1889
1837
1784
*
244
1792
1875
1566
1654
1894
1 1 1
*
1914
1174
*
291
1897
402
206.20 8 7
258.28
272.30 160
282.30 220
> 320
765
1796
402
1174
1897
1892
1768
*
*
1794
242.23 230
242.23 270
340.42 323
312.37 348
141.00 1 8 0
1768
2 9 1
1654
*
2 9 1
*
1 9 1 1
*
*
1 7 8 1
1 7 8 1
*
1816
References page VI- 159
Refs.
VI/84 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Polymer
Mol ecul ar Melting
wei ght point Refs.
-, bromomethyl- [epibromohydrin]
-, rert-butyl-
-, chloromethyl- [epichlorohydrin]
-, 1,2-dichloromethyl-
cis-
trans-
-, fluoromethyl- [epifluorohydrin]
-1 isopropyl-
-1 neopentyl-
-, p-nitrophenol complex
-,
resorcinol complex
-, tetrafluoro-
-3 tetramethyl-
urea compl ex
&y (ethy lene-p-oxybenzoate)
-, m-chloro-
-, o-chloro-
-, m-mehthyl-
o-methyl-
poly(ethylene oxydiacetate)
-, methyl- (diol)
Poly(ethylene 4,4-oxydibenzoate)
Poly[ethylene 4,4-(oxydiethylene)-dioxydibenzoate]
-, 3,3-dimethoxy-
Poly[ethylene 4,4-oxydimethylene)-di-2-(1,3-dioxolanelate]
Poly(ethyleneoxymethylene oxide) [ 1,3-dioxolane]
Poly(ethylene p-oxyphenyleneacetate)
Poly(ethyleneoxy-p-phenylene oxide)
Poly[ethylene 4,4-(pentamethylenedioxy)-dibenzoate]
Poly[ethylene (pentamethylenedithio)-diethylenediurethane]
Poly(ethylene p-phenylenediacetate)
Poly(ethylene m-phenylenedisulfonamide)
Poly(ethylene phthalamide)
Poly(ethylene phthalate)
-, methyl- (diol)
Poly(ethylene pimelate)
methyl- (diol)
&y(ethylene 1,4-piperazinedicarboxylate)
Poly(ethylene 1,4-piperazinedipropionamide)
-, N,N-diisopropyl-
Poly(ethylene 1,4-piperazinedipropionate)
Poly(ethylene sebacami de)
Poly(ethylene sebacate)
-, methyl (diol)
Poly(ethylene sebacoyldiurea)
Poly(ethylene sebacoyldiurethane)
Poly(ethylene suberate)
-, methyl- (diol)
Poly(ethylene succinate)
-, methyl- (diol)
Poly(ethylene sulfide)
tert-butyl-
&y(ethylene 4,4-sulfonyldibenzamide)
Poly(ethylene sulfonyldivalerate)
-, methyl- (diol)
Poly(ethylene L-tartaramide)
-, di-O-methyl-
Poly(ethylene terephthalamide)
-, N,N-dimethyl-
Poly(ethylene terephthalate)
-, chloro- (diacid)
136.98 112
141.00
76.07
235
1 4 5
68
114.19 82
116.02 42
100.16 300
198.61
198.61
178.19
178.19
160.13
174.15
284.27
372.37
432.42
500.63
178.19
136.15
370.40
336.46
220.22
262.30
190.20
192.17
206.20
200.24 - 3 0
254.33
338.50
256.30
226.32
242.32 - 26
312.37 228
314.34 1 9 8
214.26
158.15
330.36
292.35
306.38
174.16
190.20 455
218.26 379
226.62 92
285
153
292
1 5 7
20
2 1
152
134
118
1 9
172
270
150
126
1 0 7
137
182
250
104
50
D231
210
93
276
254
280
- 3 4
0
380
86
68
1 8 0 9
*
*
1 7 7 9
1 7 7 9
1 1 9
*
527
*
*
1 8 5 8
664
*
*
1 1 7 4
1174
1174
1174
1 7 9 8
1 7 9 8
2 9 1
1939
1 9 1 4
7 9 7
*
1 8 4 1
1 8 6 8
1912
1 8 9 7
325
3 4 1
1384
1 8 3 3
1 6 5 4
1 7 9 4
*
765
*
1 8 7 5
1 8 7 5
1 8 7 5
244
2 9 1
402
*
765
402
402
*
765
*
765
*
*
1 8 3 5
1 7 9 7
1797
*
829
829
*
1 9 1 3
Melting Points of Polymers VI/85
Polymer
Mol ecul ar Melting
wei ght point Refs.
-, 2,5-dichloro-
-, 2,5-dimethyl-
-, methyl- (diacid)
-, methyl- (diol)
Poly[ethylene N,N-terephthaloyldi(6-aminocaproate)]
Poly(ethylene 2,5-tetrahydrofurandipropionamide)
Poly(ethylene 4,4-tetramethylenedibenzoate)
Poly[ethylene 3,3-(tetramethylenedioxy)-dibenzoate]
Poly[ethylene 4,4-(tetramethylenedioxy)-dibenzoate]
-, 3,3-dimethoxy-
Poly[ethylene 4,4-(tetramethylenediphenylene)-diurethane]
Poly[ethylene (tetramethylenedithio)-diethylene-diurethane]
Poly[ethylene 2,4,8,10-tetraoxa-3,9-spiro(5.5)hendecane-dicaprylate]
Poly(ethylene 4,4-thiodibenzoate)
Poly(ethylene thiodienanthamide)
Poly(ethylene thiodivaleramide)
Poly(ethylene thiodivalerate)
-, methyl- (diol)
Poly(ethylenethiohexamethylene sulfide)
Poly(ethylenethiotetramethylene sulfide)
Poly(2,5-ethylene-1,3,4-triazole)
-, l-amino- (triazole)
Poly[ethylene 4,4-(trimethylenedioxy)-dibenzoate]
-, 3,3-dimethoxy-
Poly[ethylene 4,4-(trimethylenediphenylene)-diurethane]
Poly(ethylene NJ-trimethylenediterephthalamate)
Poly(ethylene urea)
Poly(ethylidene)
Poly(4,4-ethylidenediphenylene carbonate)
-, phenyl-
Poly(ethylidene p-phenylene)
Poly(ethylviny1 ether)
-, 2-chloro-
-, 2-methoxy-
-, 2,2,2-trifluoro-
Poly(formaldehyde), see Poly(oxymethylene)
Poly(2,5-furandipropionic anhydride)
Poly(furfural-alt-dimethylketene)
Poly(l,4-P-o-glucose) [cellulose]
-, triacetate
-, tributyrate
-, tricaprate
-, tricaproate
-, tricaprylate
-3 triheptylate
-, trilaurate
-, trimyristate
-, trinitrate
-, tripalmitate
-, tripropionate
-, trivalerate
-, 2.44-nitrate
Poly(glycine)
Poly(glycolic acid), see Poly(2-hydroxyacetic acid)
Poly(glycyl-12aminododecanoic acid)
Poly( 1,3-heptadiene), 1,4-
-, fr-methyl-
truns-
isotactic
-, 6-methyl-
Poly(heptaldehyde)
Poly(heptamethylene)
-, 1,2-dichloro-
truns-
Poly(heptamethylene adipamide)
261.06
220.22
206.20
206.20
418.49
240.30
324.38
356.37
356.37
416.43
354.41
322.44
470.60
300.33
3 14.49
,258.38
260.35
274.38
176.34
148.29
95.10
110.12
342.35
403.00
340.38
396.40
86.09
240.26
316.36
104.15
72.11
106.55
102.13
126.08
194.19
166.18
162.14
624.90
456.58
498.66
709.06
793.22
877.38
414.50
110.20
98.19
167.08
1 6 5 1913
180 1913
70 1913
1 1 1 1794
204 1792
218 402
170 291
100 1 1 1
252 1 8 4 1
1 1 7 1914
274 414
126 1897
8 5 797
200 291
210 402
220 402
28 1797
- 34 767
86 1819
89 1 8 1
360
190
1 0 5
207
205
400
195
230
205
86
150
73
128
67
180
610
1912
1914
414
781
402
*
438
438
1876
114
114
114
114
*
1565
1817
88
94
88
9 1
106
1 0 5
122
*
*
144
144
*
144
144
144
*
144
*
144
*
*
*
*
*
180 1896
*
*
53 1925
*
References page VI- 159
VI/86 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Mol ecul ar Melting
wei ght point Refs.
Polymer
Poly(heptamethylene azelamide)
Poly[4,4-(heptamethylenedioxy)-diphenyleneoxy-p-xylylene oxide]
Poly(heptamethylene disulfide)
Poly(heptamethylene NJ-ethylenediterephthalamate)
Poly(heptamethylene NJ-hexamethylenediterephthalamate)
Poly(heptamethylene hexamethylenediurea)
Poly(heptamethylene malonamide)
dodecyl- (diacid)
Poly[heptamethylene 4,4-(methylenediphenylene)diurethane]
Poly(heptamethylene 4-octenediamide)
tram- I.
II.
Poly(heptamethylene oxamide-alt-heptamethylene sebacamide)
Poly(heptamethylene N,N-pentamethylenediterephthalamate)
Poly(heptamethylene p-phenylenediacetamide)
Poly(heptamethylene pimelamide)
Poly(heptamethylene sebacamide)
Poly(heptamethylene sebacate)
Poly(heptamethylene suberamide)
Poly(heptamethylene 4,4-sulfonyldibenzamide)
4,4-dimethyl-
Poly(heptamethylene terephthalamide)
418.54
162.31
452.5 1
508.61
298.43
198.26
366.59
201 1 7 8 9
130 1 8 6 8
215 7 8 1
227 7 8 1
243 1892
1 4 7
266.38
6 5 7
651
1781
7 8 1
402
*
261
249
248
199
234
480.69
494.59
288.39
400.49
428.55
260.34
268 1 8 3 5
328 1 1 7 5
330 8 2 8
341 8 2 9
Poly(heptamethylene terephthalate)
Poly(heptamethylene 2,5-tetrahydrofurandipropionamide)
Poly(heptamethylene N,N-tetramethylenediterephthalamate)
Poly(2,5-heptamethylene-1,3,4-triazole)
-, l-amino-
Poly(heptamethylene NJ-trimethylenediterephthalamate)
Poly(heptametylene undecanediamide)
Poly(heptenamer)
Poly( 1 -heptene)
-, 6,6-dimethyl-
5-methyl-
&y[4,4-heptylidene)-diphenylene carbonate]
Poly(hexadecamethylene adipate)
Poly(hexadecamethylene decamethylenediurethane)
Poly(hexadecamethylene hexamethylenediurethane)
Poly(hexadecamethylene 3-hexenedioate)
Poly(hexadecamethylene 4,4-(methylenediphenylene)-diurethane]
Poly(hexadecamethylene 4-octenedioate)
Poly(hexadecamethylene suberate)
Poly(hexadecamethylene p-xylylenediurethane)
Poly(l-hexadecene)
Poly( 1,5-hexadiene), see Poly(cyclopentylene-alt-methylene)
Poly( 1,3-hexadiene), 1,4-
5-methyl-
Poly(2,4-hexadiene), 2,5-
2,5-dimethyl-
kly(2,4-hexadienedioic acid), 2,5-
diisopropyl ester
&y(2,4-hexadienoic acid), 2,5-
-, 6-amino-
Poly(2,Chexadiyne adipate)
Poly(2,4-hexadiynediol), 2,5-
1,6-bis(p-methoxyphenylsulfonyl)-
&y(2,4-hexadiyne hexamethylenediurethane)
Poly[2,Chexadiyne (4,4-methylenediphenylene)-diurethane]
Poly(hexafluoroisobutylene-alt-vinylidene fluoride)
Poly(hexamethylene adipamide)
-3 2,5-dihydroxy- (diacid)
-,
N,N-dimethyl-
-, 3-methyl- (diacid)
1 4 8 402
269 7 8 1
310.44
480.56
165.24
180.26
466.53
3 10.48
237 610
222 7 8 1
1 9 5 2
126.24 1 0 4 282
3 10.39 200 438
482.75 128 634
426.64 134 634
634
*
508.70 152
446.63 168 634
*
142.11
112.13
130 1 7 8 2 220.22
110.11
278.31 149
360.37 150
1 7 8 2
1 7 8 2
*
258.32
254.31
240.35
163 402
75 402
216 2 9 1
230 1 8 5 9
Melting Points of Polymers VI/g7
Polymer
Mol ecul ar Melting
wei ght point Refs.
-, 3-methyl- (diamine)
n-methyl-
&y(hexamethylene adipamide-alt-hexamethylene oxamide)
Poly(hexamethylene adipate)
Poly[hexamethylene N,N-adipoyldi(6-aminocaproate)]
Poly(hexamethylene adipoyldiurethane)
Poly(hexamethylene azelamide)
Poly(hexamethylene azelamide-al?-hexamethylene oxamide)
Poly(hexamethylene azelate)
Poly(hexamethylene carbonate)
Poly(hexamethylene m-carboxycarbanilate)
Poly[hexamethylene p-(carboxyphenoxy)-acetate]
Poly[hexametbylene p-(carboxyphenoxy)-caproate]
Poly[hexamethylene p-(carboxyphenoxy)-undecanoate]
Poly[hexamethylene p-(carboxyphenoxy)-valerate]
Poly[hexamethylene p-(carboxyphenylene)-acetamide]
Poly(bexamethylene 1,2-cyclohexylenediacetamide)
Poly(hexamethylene 1,2-cyclohexylenedicarboxamide)
frans-
Poly(hexamethylene 1,3-cyclohexylenedicarboxamide)
tram-
Poly(hexamethylene 1,4-cyclohexylenedicarboxamide)
trans-
Poly(hexamethylene 1,4-cyclohexylenedicarboxylate)
trans-
Poly(hexamethylene cyclopropylenedicarboxamide)
cis-
144.17
263.29
278.30
334.41
404.55
320.38
260.34
280.41
252.36
252.36
252.36
254.33
210.28
-, -,
N,N-dibutyl
-, -, N,N-diethyl-
-, -. N,N-diisopropyl-
-, N,N-dimethyl-
iily(hexamethylene glutarate)
Poly[hexamethylene (hexamethylenedioxy)-dipropionamide]
Poly[hexamethylene 4,4-(hexamethylenedisulfonyl)-dibenzoate]
Poly[hexamethylene (hexamethylenedisulfonyl)-dicaproamide]
Poly(hexamethylene N,N-hexamethylenediterephthalamate)
Poly[hexamethylene (hexamethylenedithio)-diethylene-diurethane]
Poly(hexamethylene hexamethylenediurethane)
Poly(hexamethylene 3-hexenedioate)
Poly(hexamethylene isophthalamide)
432.45
376.34
404.40
348.29
214.26
342.48
536.66
522.76
406.60 106
246.3 1
-, Qert-butyl- (diacid) 302.42
Poly(hexamethylene isophthalate) 248.28
Poly(hexamethylene 4,4-isopropylidenedibenzamide)
Poly(hexamethylene 4,4-ketodibenzamide)
Poly(hexamethylene ketodipropionamide)
Poly(hexamethylene N,N-lysyldiurea)
methyl ester
iAly(hexamethylene malonamide)
-, butyl- (diacid)
364.49
350.42
254.33
314.38
328.41
240.35
-, decyl- (diacid) 324.5 1
-, dimethyl- (diacid) 212.19
-, dodecyl- (diacid) 352.56
-, heptadecyl- (diacid) 422.70
-, heptyl- (diacid) 282.43
-, hexadecyl- (diacid) 408.67
-, hexyl- (diacid) 268.40
-, nonyl- (diacid) 310.48
240.35 180
240.35 1 4 5
396.53 268
454.6 1 147
314.34 206
438.61
270.37
291
291
1 7 8 1
*
1792
402
*
254 1 7 8 1
53 539
55 764
60 1820
96 1 8 9 1
50 290
60 290
72 290
60 290
227 1904
255 402
242 402
312 402
360 402
120 1174
180
20
5
20
30
34
1 0 5
186
222
1860
402
402
402
402
764
402
1174
402
*
1897
*
*
220 402
200 828
210 402
140 1 1 1
80 1794
180 402
350 402
180 402
180 1768
*
1 6 1 1783
160 1774
1 3 3 1783
134 1774
117 402
134 1783
132 1774
166 1774
1 3 5 1774
164 1783
160 1774
145 1783
144 1774
137 1774
References page VI- 159
VI/88 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Mol ecul ar Melting
Polymer wei ght point Refs.
-> octadecyl- (diacid)
-3
octyl- (diacid)
-,
pentadecyl- (diacid)
394. 64
-3
pentyl- (diacid) 254. 37
-1 propyl- (diacid)
226. 32
-,
tetradecyl- (diacid)
380. 62
-, tridecyl- (diacid)
undecyl- (diacid)
&y(hexamethylene 3,3-methylenedibenzamide)
Poly(hexamethylene 4,4-methylenediphenylene)
Poly[hexamethylene 4,4-(methylenediphenylene)-dioxy-diacetamide]
Poly[hexamethylene 4,4-(methylenediphenylene)-diurea]
-, 3,3-dimethyl-
-9 -3 N,N-diethyl-
-, N,N-dipropyl-
&ly[hexamethylene 4,4-(methylenediphenylene)-diurethane]
Poly[hexamethylene (methylene-2,5-furan)-dicarboxamide]
Poly[hexamethylene (p-methylenephenoxy)~diacetamide]
Poly[hexamethylene (p-methylenephenylene)-diacetamide]
Poly[hexamethylene (methylene-2,5-tetrahydrofuran)-dicarboxamide]
Poly(hexamethylene naphthalenedicarboxamide)
Poly(hexamethylene nonamethylenediurea)
Poly(hexamethylene octadecamethylenediurea)
Poly(hexamethylene octadecanediamide)
-, 9,10-dihydroxy-
N,N-dimethyl-
&y(hexamethylene octamethylenedithiourea)
Poly(hexamethylene octamethylenediurea)
Poly(hexamethylene octamethylenediurethane)
Poly(hexamethylene 4-octenediamide)
Poly(hexamethylene 4-octenedioate)
Poly(hexamethylene 5-oxadodecanediamide)
Poly(hexamethylene 6-oxaheptadecanediamide)
Poly(hexamethylene 5-oxahexadecanediamide)
Poly(hexamethylene oxalate)
Poly(hexamethylene oxamide)
-, 3-oxypropyl-
Poly(hexamethylene oxamide-alt-hexamethylene pimelamide)
Poly(hexamethylene oxamide-alt-hexamethylene sebacamide)
Poly(hexamethylene oxamide-alt-hexamethylene suberamide)
Poly(hexamethylene 6-oxapentadecanediamide)
Poly(hexamethylene 5-oxasebacami de)
Poly(hexamethylene 5-oxatetradecanediamide)
Poly(hexamethylene 5-oxaundecanediamide)
Poly(hexamethylene oxide)
Poly(hexamethylene oxydiacetamide)
Poly(hexamethylene oxydiacetate) 216. 23
Poly(hexamethylene 4,4-oxydibenzoate)
Poly(hexamethylene oxydibutyramide)
Poly(hexamethylene oxydicaproamide)
Poly(hexamethylene oxydienanthamide)
Poly[hexamethylene 4,4-(oxydimethylene)-di-2-(1,3-dioxolane)-cap~lamide]
Poly(hexamethylene oxydipelarqonamide)
Poly[hexamethylene 4,4-(oxydiphenylene)-dioxydiacetamide]
Poly(hexamethylene 3,3,4,4-oxydiphenylenetetracarboximide)
Poly(hexamethyelene oxydivaleramide)
Poly(hexamethyleneoxymethylene oxide)
340. 38
270. 31
326. 48
354. 53
554. 77
410. 64
398. 46
298. 43 180
436. 12
296. 45
366. 59
338. 54
336. 44
336. 44
396. 49
366. 46
394. 52
450. 63
478. 68
250. 30
304. 39
283. 39
254. 33
298. 39
326. 48
452. 73
394. 64
426. 64
422. 70
344. 58
312. 46
342. 48
312. 45 149
382. 59 160
368. 56 159
228. 29 240
410. 56 259
452. 64 257
424. 58 260
354. 53 154
284. 40 160
340. 51 155
298. 43 152
214.26
167
163
133
131
164
151
163
152
148
133
133
113
132
174
250
290
120
90
115
220
226
204
78
200
243
192
192
172
52
160
239
253
255
153
1 4 3
172
5 1
78
74
187
175
170
145
158
220
1783
1714
1783
1774
1714
1774
1774
1783
1774
1114
1774
402
402
402
402
402
402
402
*
402
402
1202
1202
402
402
1892
634
454
402
1877
402
634
1892
402
633
*
*
1847
1847
1847
*
*
402
1781
1781
1781
1847
1847
1847
1847
*
402
1894
1798
1791
1939
1847
1847
1847
197
1847
402
*
1847
I
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Melting Points of Polymers VI/89
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly(hexamethyleneoxy-p-phenylene oxide) 192.26
Poly[hexamethylene (pentamethylenedisulfonyl)-dicaproamide] 508.73
Poly(hexamethylene N,N-pentamethylenediterephthalamate) 480.56
Poly[hexametbylene (pentamethylenedithio)-diethylene-diurethane] 392.57
Poly(hexamethylene pentamethylenediurea) 270.38
Poly[hexamethylene (p-phenoxy)-diacetamide] 290.36
Poly(hexamethylene m-phenylenediacetamide) 274.36
Poly(hexamethylene p-phenylenediacetamide) 274.36
Poly(hexamethylene 3,3-p-phenylenedibutyramide) 330.47
-, 3,3-dimethyl- (diacid) 358.52
Poly[hexamethylene (p-phenylenedioxy)-diacetamide] 306.36
Poly(hexamethylene p-phenylenedipropionamide) 302.42
-, 3-methyl- (diacid)
Poly(hexamethylene m-phenylenedisulfonamide)
Poly(hexamethylene m-phenylenediurea)
-, 4-methyl- (diisocyanate)
Poly(hexamethylene 3,3-phosphinylidenedibenzamide)
-, methyl- (P)
Poly(hexamethylene 4,4-phosphinylidenedibenzamide)
-, hydroxy- (P)
-, methyl- (P)
-, phenyl- (P)
Poly(hexamethylene phthalamide)
Poly(hexamethylene phthalate)
Poly(hexamethylene pimelamide)
316.44
276.34
290.37
370.39
384.42
370.39
386.39
384.42
445.48
246.31
248.28
240.35
Poly(hexamethylene pimelate) 242.32
Poly(hexamethylene 1,4-piperazinediacetamide) 282.39
Poly(hexamethylene N,N-piperazinediterephthalamate) 464.52
Poly[hexamethylene (1,4-piperazinedithio)-dicarboxylate] 322.44
Poly(hexametbylene piperazinediurea) 254.33
Poly(hexamethylene propylenediurea)
racemi c
Poly(hexamethylene 4(H)-pyran-2,6-dicarboxamide)
-, 4-0x0- (diacid)
Poly(hexamethylene 2,3-pyrazoledicarboxamide)
Poly(hexamethylene 2,4-pyrazoledicarboxamide)
Poly(hexamethylene 2,3-pyridinedicarboxamide)
Poly(hexamethylene 2,4-pyridinedicarboxamide)
Poly(hexamethylene 2,5-pyridinedicarboxamide)
Poly(hexamethylene 2,6-pyridinedicarboxamide)
-, 1,4-dihydro-4-oxo-
Poly(hexamethylene 3,4-pyridinedicarboxamide)
Poly(hexamethylene 3,5-pyridinedicarboxamide)
-, 2,6-dimethyl- (diacid)
Poly(hexamethylene pyromellitimide)
Poly(hexamethylene 2,5-pyrroledipropionamide)
-, l-methyl- (diacid)
Poly(hexametbylene 2,5-pyrrolidinedipropionamide)
-, l-methyl- (diacid)
Poly(hexamethylene 5-pyrrolidonylidenedipropionamide)
Poly(hexamethylene sebacamide)
-, 3-methyl- (diamine)
Poly(hexamethylene sebacate)
Poly(hexamethylene sebacoyldiurethane)
Poly(hexamethylene 4,4-silylenedibenzamide)
-, dimethyl- (Si)
Poly(hexamethylene suberami de)
270.33
250.30
264.28
238.29
238.29
247.30
247.30
247.30
247.30
263.30
247.30
247.30
275.35
291.40
305.42
295.43
309.45
295.40
296.46
370.45
352.51
380.56
170
226
238
98
251
86
180
182
300
196
1 9 3
237
239
290
295
298
300
227
1868
402
781
1897
1892
402
1202
402
454
1895
1895
402
1202
291
402
1202
1895
1895
*
235 402
172 402
245 402
213 402
231 402
150 1833
2 1794
228 244
202 339
50 539
5 5 764
168 291
255 1174
144 1934
245 402
265 1838
230 1768
77
140
271
1 0 3
220
272
220
178
1 0 1
257
140
1905
1 9 0 5
1 9 0 5
1905
1905
1905
1905
1 9 0 5
1905
1905
1905
*
180
200
250
1 5 3
1 5 8
190
402
402
402
*
402
1
402
402
*
References page VI- 159
VI/90 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly(hexamethylene suberate)
Poly[hexamethylene N,N-suberoyldi(p-aminobenzoate)]
Poly(hexamethylene succinamide)
Poly(hexamethylene succinate)
Poly(hexamethylene sulfide)
Poly(hexamethylene sulfone)
Poly(hexamethylene 4,4-sulfonyldibenzamide)
Poly(hexamethylene 4,4-sulfonyldibenzoate)
Poly[hexamethylene 4,4-(sulfonyldimethylene)-dibenzoate]
Poly(hexamethylene sulfonyldivaleramide)
Poly(hexamethylene sulfonyldivalerate)
Poly(hexamethylenesulfonylpentamethylene sulfone)
Poly(hexamethylenesulfonyltetramethylene sulfone)
Poly(hexamethylene L-tartaramide)
-, di-O-methyl-
Poly(hexamethylene terephthalamide)
494.59 250
200.23 57
386.46 310
388.44 280
416.49 252
346.49 215
348.46 92
230.26
-, 2,5-dihydroxy- (diacid)
-, 2,5-dimethyl- (diacid)
-9
iV,N-dimethyl-
methyl- (diacid)
&y(hexamethylene terephthalate)
Poly[hexamethylene NJ-terephthaloyldi(6-aminocaproate)]
Poly(hexamethylene tetradecamethylenediurea)
Poly(hexamethylene tetradecanediamide)
Poly(hexamethylene 2,5-tetrahydrofurandipropionamide)
Poly[hexamethylene (tetramethylenedioxy)-dipropionamide]
Poly[hexamethylene (tetramethylenedisulfonyl)-dicaproamide]
Poly(hexamethylene N,N-tetramethylenediterephthalamate)
Poly[hexamethylene (tetramethylenedithio)-diethylene-diurethane]
Poly(hexamethylene tetramethylenediurea)
Poly[hexamethylene 2,4,8,1O-tetraoxa-3,9-spiro(5.5)hendecane-dicaprylamide]
Poly(hexamethylene 4,4-tetrasiloxanylenedibenzamide)
tetramethyl-tetraphenyl- (Si)
Poly(hexamethylene thiodibutyramide)
Poly(hexamethylene thiodienanthamide)
Poly(hexamethylene thiodipropionamide)
278.31 334
274.36 143
274.36 260
260.34 248
474.60
396.62
338.54
296.41
314.43
494.70
466.53
378.55
256.35
524.74
490.81
847.28
286.43
370.60
258.38
Poly(hexamethylene thiodivaleramide) 314.49
Poly(hexamethylene thiodivalerate)
Poly[hexamethylenethio-4,4-(methylenediphenylene)-diethylene sulfide]
Poly(hexamethylenethiopentamethylene sulfide)
Poly(hexamethylene 2,5-thiophenediacetamide)
Poly(hexamethylene 2.5~thiophenedicarboxamide)
Poly(hexamethylene 2,5-thiophenedipropionamide)
316.46
370.61
218.42
280.39
252.33
308.44
Poly(hexamethylenethiotetramethylene sulfide) 204.39
Poly(hexamethylenethioundecamethylene sulfide)
Poly(hexamethylene thiourea)
Poly(2,5-hexamethylene-1,3,4-triazole)
l-amino- (triazole)
Poly[hexamethylene 4,4-(trimethylenediphenylene)-dioxy-diacetamide]
Poly[hexamethylene(tmethylenedisulfonyl)-diimino-dicaproamide]
Poly(hexamethylene N,N-trimethylenediterephthalamate)
Poly(hexamethylene trimethylenediurea)
Poly(hexamethylene undecanediamide)
-, 6-hydroxy- (diacid)
Poly(hexamethylene urea)
Poly(hexamethylene 4,4-vinylenedibenzamide)
methyl- (diacid)
Poly[hexamethylene 4,4-(p-xylylenedisulfonyl)-dibutyrate]
Poly[hexamethylene N,N-p-xylylenediterephthalamate)
Poly(hexamethylene p-xylylenediurea)
Poly(hexamethylene p-xylylenediurethane)
302.59
158.26
151.21
166.23
424.54
446.59
452.5 1
242.32
296.46
312.45
348.44
362.47
488.61
514.58
304.39
306.36
305
*
*
1 8 3 5
1174
1174
402
1797
*
*
*
*
402
402
829
402
*
177 1792
198 634
209 2
182 402
110 402
241 402
290 781
120 1897
283 1892
186 797
140 402
200 2 9 1
170 402
216 1859
219 402
180 402
1 8 5 1853
46 767
88 1819
65 1819
230 1 9 0 5
315 1905
232 402
210 1 9 0 5
67 1819
75 181
78 1923
160 402
275 610
80 402
1 8 5 402
256 7 8 1
266 1892
1 6 5 402
*
160 402
196 1174
285 1174
306 634
209 634
Melting Points of Polymers VI/91
Polymer
Poly(l,3,Shexatriene), 1,6-
Poly(hexenamer)
Poly(l-hexene)
-, 4,4-dimethyl-
-, 4-ethyl-
-, 3-methyl-
-, 4-met hyl
-, Smethyl-
Poly[4,4-(2,2-hexylidene)-diphenylene carbonate]
Poly(hydrazo adi pami de)
Poly(hydrazo azelamide)
Poly(hydrazo docosanediamide)
Poly(hydrazo dodecanediamide)
Poly(hydrazo glutaramide)
Poly(hydrazo pimelamide)
Poly(hydrazo sebacamide)
Poly(hydrazo suberami de)
Poly(hydrazo succinamide)
Poly(hydrazo thiodivaleramide)
Poly(2-hydroxyacetic acid) [glycolic acid]
-, diethyl-
-, dimethyl-
&y(m-hydroxybenzoic isopropyl- acid)
Poly(p-hydroxybenzoic acid)
-, 3,5-di-terr-butyl-
-, 3-n-propyl-
Poly(4,4-hydroxybibenzoic acid)
Poly(3-hydroxy-3-butenoic acid)
Poly(3-hydroxybutyric acid)
Poly( lo-hydroxycapric acid)
Poly(6-hydroxycaproic acid)
Poly[S-hydroxy-2-(1,3-dioxane)-caprylic acid]
Poly(7-hydroxyenanthic acid)
-, 4-methyl- (R + )
Poly[4-hydroxymethylene-2-(1,3-dioxolane)-caprylic acid]
Poly[S-hydroxymethylene-5-methyl-2-( 1,3-dioxane)-caprylic acid]
Poly(S-hydroxy-3.oxavaleric acid)
Poly[(p-hydroxyphenylene)-acetic acid]
Poly[3-(p-hydroxyphenylene)-propenoic acid]
trans-
Poly(2-hydroxypropionic acid) [lactic acid]
Poly(3-hydroxypropionic acid) [propiolactone]
-, 2,2-bischloromethyl-
-, 3-chloromethyl-
-, 2,2-dibutyl-
-, 3-dichloromethyl-
-, 2,2-diethyl-
-, 2,2-dimethyl- [pivalolactone]
-, 3-ethyl- [3-hydroxyvaleric acid]
-3 -> 1,l -dichloro-
-, 2-ethyl-2-methyl-
-, 3-isopropyl-
-, 2-methyl-
-, 3-methyl-, see Poly(3-hydroxybutyric acid)
-, 2-methyl-2-propyl-
Poly[4-hydroxytetramethylene-2-( 1,3-dioxolane)-caprylic acid]
cis-
Mol ecul ar
wei ght
80.13
82.15
112.22
112.22
98.19
296.36
142.16
184.24
366.59
226.32
128.13
156.18
198.27
170.21
114.10
230.33
114.14
86.09
100.12 120.11
232.32
128.17
142.20
256.34
102.09
134.13
146.14
169.01
184.28
169.01
270.37
Melting
point
250
6 1
350
234
285
200
320
237
210
242
140
260
260
275
360
180
200
190
205 176
480
36
8 1
89
280
313
302
245
235
2 3
Refs.
1848
439
*
90
632
441
*
*
438
402
402
402
402
402
402
402
402
402
402
*
1928
1174
1 9 3 0 1 7 9 9
*
1814
*
*
*
*
*
*
*
1836
*
797
305
1174
1943
*
*
1174
*
1174
*
*
*
*
1199
*
*
*
*
*
797
Irans-
Poly(3-hydroxyvaleric acid), see poly(hydroxypropionic acid), 3-ethyl-
Poly(S-hydroxyvaleric acid)
-, 2,3,4-trimethoxy-
Poly(2-imino-1,3-dithiapentamethylene)
-, N-ethyl-
23 797
*
100.12 55 1844
5 3 305
190.20 138 305
119.20
147.25 68 1927
References page VI-159
VI/92 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Mol ecul ar Melting
Polymer wei ght point Refs.
-, N- met hyl -
-, N-phenyl-
-, -209.32
Poly(isobutene)
Poly(isobutylene oxide)
Poly(isobutylene sulfide)
Poly(4,4-isobutylidenediphenylene carbonate)
Poly(isobutylviny1 ether)
Poly(isobutyraldehyde)
Poly(isophthalaldehyde)
Poly(isophthalic anhydride)
Poly[isophthalic 2,2-(isophthaloyldiamino)-dibenzoic anhydride]
Poly[isophthalic (4,4-isopropylidenediphenylenedioxy)~diacetic anhydride]
Poly[isophthalic 4,4-(methylenedioxy)-dibenzoic anhydride]
-, 3,3-dimethoxy-
Poly[isophthalic (p-phenylenedioxy)-diacetic anhydride]
Poly[isophthalic 2,2-(terephthaloyldiamino)-dibenzoic anhydride]
Poly[isophthalic 4,4-(tetramethylenedioxy)-dibenzoic anhydride]
Poly[isophthalic 4,4-(trimethylenedioxy)-dibenzoic anhydride]
-, 3,3-dimethoxy-
Poly[isophthaloyl (m-carboxyphenoxyacetyl)-dihydrazide]
Poly[isophthaloyl (m-carboxyphenoxybutyryl)-dihydrazide]
Poly[isophthaloyl (m-carboxyphenoxycapryl)-dihydrazide]
Poly[isophthaloyl (m-carboxyphenoxypropionyl)-dihydrazide]
Poly[2,2-(isophthaloyldiamino)-dibenzoic terephthalic anhydride]
Poly(isophthaloy1 dithionisophthaloyldihydrazide)
Poly(isoprene), see Poly(l,3-butadiene), 2-methyl-
Poly(isopropcnylmethy1 ketone)
Poly(4,4-isopropylidenedibenzoic anhydride)
133.23 89
195.30 128
89 1927
88.17 187
268.31 180
134.13
148.12
534.48
474.46
418.36
478.41
356.29
534.48
460.44
446.41
506.46
354.32
382.38
410.43
368.35
534.48
356.42
266.30
Poly[isopropylidenedimetbylene, 4,4-(methylenediphenylene)-diurethane]
Poly[isopropylidenedimethylene (1,4-piperazinedithio)-dicarboxylate]
2,5-dimethyl-
Poly(4,4-isopropylidenediphenylene adipate)
-, 3,3,5,5-tetrachloro-
Poly(4,4-isopropylidenediphenylene carbonate)
-, 3,3-dichloro-
354.41
306.40
334.45
338.40
323.18
-7 3,3 -diisopropyl- 338.45
-, 3,3-dimethyl-
282.34
-, 3,3,5,.5-tetrabromo- 569.87
-, 3,3,5,5-tetrachloro- 392.06
Poly(4,4-isopropylidenediphenylene cyclopropylene-dicarboxylate)
cis-
trans-
-, l-methyl- (diacid)
trans-
-, 3-methyl- (diacid)
trans-
Poly[(4,4-isopropylidenediphenylenedioxy)-diacetic anhydride]
Poly[(4,4-isoproylidenediphenylenedioxy)-diacetic p-phenylenedioxydiacetic anhydride]
Poly[(4,4-isopropylidenediphenylenedioxy)-diacetic 4-pyridinedicarboxylic anhydride]
Poly[(4,4-isopropylidenediphenylenedioxy)-diacetic terephthalic anhydride]
Poly(4,4-isopropylidenediphenylene dithioladipate)
Poly(4,4-isopropylidenediphenylene dithiol-1,3-cyclohexylenedicarboxylate)
Poly(4,4-isopropylidenediphenylene dithionisophthalate)
Poly(4,4-isopropylidenediphenylene hexametbylenediurethane)
Poly(4,4-isopropylidenediphenylene isophthalamide)
Poly(4,4-isopropylidenediphenylene mal onat e)
Poly(4,4-isopropylidenediphenylene 4,4-(methylenediphenylene)-diuretbane)
Poly(4,4-isopropylidenediphenylene 1,4-piperazinedipropionate)
Poly(isopropylidene oxide)
Poly(isopropylidene sulfide)
322.36
336.39
336.39
326.35
502.52
475.45
474.47
370.53
396.57
390.52
396.49
356.42
296.32
478.55
422.52
74.14
1927
1 9 2 7
80
259
259
65
*
*
548
438
*
*
1801
1 5 6 5
1871
1 8 7 1
228
297
291
100
1 6 5
216
1 2 5
265
249
238
264
324
1 8 7 1
1 8 7 1
1 8 7 1
1 8 7 1
1 8 7 1
1 8 7 1
1833
1 8 3 3
1 8 3 3
1 8 3 3
1 8 7 1
1889
*
235
240
190
*
1854
1855
402
1 3 5
210 540
230 736
110 1 9 1 5
170 540
260 540
267 736
260 540
275 736
130 1860
180 1860
90 1860
130
202
230
120
270
198
220
152
130
424
96
193
1 4 5
1860
1 8 5 5
1872
1872
1 8 7 1
1922
1922
1889
402
1886
1868
402
1875
*
125 1882
124 1800
Melting Points of Polymers VI/93
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly(isopropylviny1 ether)
Poly(ketone), see Poly(carbon monoxide-alt-ethylene)
Poly(lactic acid), see Poly(2-hydroxypropionic acid)
Poly(N,N-lysyl nonamethylenediurea)
methyl ester
Poly(N,N-lysyl pentamethylenediurea)
methyl ester
Poly(N,N-lysyl propylenediurea)
356.47
370.49
300.36
314.38
272.30
-, methyl ester
racemi c
Poly(N,N-lysyl tetramethylenediurea)
methyl ester
&y(N,N-lysyl trimetbylenediurea)
methyl ester
&y(N,N-lysylurea)
methyl ester
&y(2-mercaptoacetic acid)
-, 2-methyl-
Poly(6-mercaptocaproic acid)
-, 4-methyl-
Poly(3-mercaptopropionic acid)
-1 2-phthalimido-
-, 2-(p-toluenesulfonamido)-
Poly(methacrylic acid)
-7 tert-butyl ester
isotactic
syndiotactic
-, hexadecyl ester
-7
methyl ester
octadecyl ester
Poly(methacrylonitrile)
Poly(methylene) (see also Poly(ethylene))
-, diphenyl-
-, di-p-tolyl-
Poly(methylene adipamide)
Poly(4,4-methylenedibenzoic anhydride)
Poly[4,4-(methylenedioxy)~dibenzoic anhydride]
Poly[4,4-(methylenedioxy)-dibenzoic terephthalic anhydride]
-, 3,3-dimethoxy-
Poly(4,4-methylenediphenylene adi pami de)
-, 3,3-dimethyl- (diamine)
-, -1 N,N-dibutyl-
-, -, N,N-diethyl-
-> -3 N,N-dihexyl-
-, -,
N,N-diisoamyl-
-9 -, N,N-diisopropyl-
-, N,N-diethyl-
-, N,N-dimethyl-
Poly(4,4-methylenediphenylene adipate)
Poly(4,4-methylenediphenylene azelamide)
286.33
286.33
300.36
272.30
286.33
172.18
186.21
74.10
88.13
144.24
88.13
233.24
257.33
86.09
142.12
310.52
14.03
166.22
194.28
238.24
270.24
418.36
478.41
308.38
336.44
448.65
392.54
504.76
476.70
420.60
364.49
336.44
310.35
350.46
-, N,N-diethyl- 406.57
-, N,N-dimethyl- 378.52
Poly(4,4-methylenediphenylene carbonate)
-, 3,3-dimethyl- 254.29
-, diphenyl- 378.43
-, phenyl- 302.33
Poly[4,4-(methylenediphenylene)-diethylene sulfide] 254.39
Poly(4,4-methylenediphenylene disiloxanylenedipropionamide) 384.58
-, tetramethyl- (Si) 440.69
-, 3,3-dimethyl- (diamine) 454.72
~~ly[3,3-(4,4-methylenediphenylene-N,N-disuccinimidediyl)-imino-4,4- methylenediphenylene amine] 556.62
Poly(4,4-methylenediphenylene dodecanediamide)
Poly(4,4-methylenediphenylene isophthalamide) 328.37
1 8 5 1768
115 1768
175 1768
185 1768
205 1768
1 7 5
169
152
1768
1922
1922
*
62 1922
1 4 5 1922
260 1922
250 1922
104
165
22
1 8 5 1
1 8 5 1
1900
*
*
*
220
180
1 8 3 1
1831
*
332 1854
220 1854
267
356
326
57
79
45
45
6 1
62
120
140
275
268
290
41
58
1 8 7 1
402
402
402
402
402
402
402
402
402
1 9 0 1
402
1443
1946
402
402
*
250 736
230 540
215 438
108 1819
90
265
295
416
402
402
1876
*
1886
References page VI-159
VI / 94 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Mol ecul ar Melting
Polymer wei ght point Refs.
Poly(4,4-methylenediphenylene octadecamethylenediurea)
Poly(4,4-methylenediphenylene octamethylenediurea)
Poly(4,4-methylenediphenylene oxide)
Poly(4,4-methylenediphenylene m-phenylenediurea)
3,3-dimethyl-, 4-methyl-
&ly(4,4-methylenediphenylene pyromellitimide)
Poly(4,4-methylenediphenylene sebacami de)
-3 N,N-diethyl
-7
3,3-dimethyl- (diamine)
N,N-dimethyl-
&y(4,4-methylenediphenylene terephthalamide)
-9
N,N-dibutyl-
N,N-diethyl-
13,3-dimethyl- (diamine)
-, -3
N,N-dibutyl-
-3 -3
N,N-diethyl-
-1 -3 N,N-dimethyl-
-3 -9
N,N-dipropyl-
-,
N,N-dimethyl-
N,N-dipropyl-
Poly(4,4-methylenediphenylene tetradecamethylenediurea)
Poly(N,N-methylenediterephthalamic anhydride)
Poly(methyleneoxynonamethylene oxide)
Poly(methyleneoxyoctadecamethylene oxide)
Poly(methylene oxypentamethylene oxide)
Poly(methyleneoxytetradecamethylene oxide)
Poly(methyleneoxytetramethylene oxide) [1,3-dioxopane]
Poly(methylene p-phenylene)
-, 2,5-dimethyl-
wmethyl-
Poly(methylene sebacami de)
Poly(methylene selenide)
Poly(methylene sulfide)
-, difluoro-
Poly(methylenethiotetramethylene sulfide)
Poly(methylviny1 ether)
Poly( 1,5-naphthalene-4,4-dibenzylidenimino isophthalate)
3 ,3 -dimethoxy-
&y(l,5-naphthalene-4,4-dibenzylidenimino sebacate)
-, 3 ,3 -dimethoxy-
Poly(l,S-naphthalene-4,4-dibenzylidenimino terephthalate)
-, 3,3-dimethoxy-
Poly(neopentylviny1 ether)
Poly(nonamethylene adipamide)
Poly(nonamethylene azelamide)
Poly(nonamethylene azelate)
Poly[4,4-(nonamethylenedioxy)-diphenyleneoxy-p-xylylene ox
Poly(nonamethylene disiloxanylenedipropionamide)
-, diethyl-dimethyl- (Si)
tetraethyl- (Si)
&y(nonamethylene disulfide)
Poly(nonamethylenedithiotetramethylene disulfide)
Poly(nonamethylene N,N-ethylenediterephthalamate)
Poly(nonamethylene N,N-hexamethylene diterephthalamate)
Poly(nonamethylene hexamethylenediurethane)
Poly(nonamethylene malonamide)
-, dodecyl- (diacid)
Poly[nonamethylene 4,4-methylenediphenylenediurethane]
Poly(nonamethylene 4-octenediamide)
truns- II.
Poly(2,5-nonamethlene-1,3,4-oxadiazole)
Poly(nonamethylene oxamide-alt-nonamethylene sebacamide)
534. 79 225
394. 52 263
358. 40
400. 48
364. 49
420. 60
392. 54
392. 54
328. 37
440. 59
384. 48
356. 42
468. 64
412. 53
384. 48
440. 59
356. 42
412. 53
478. 68
324. 29
172. 21
298. 51
242. 40 69
118.18
82. 07 35
134. 26 73
496. 52
556. 58
532. 64
592. 69
496. 52
556. 58
268. 40 205
242 1818
.ide] 446. 59
344. 60
428. 16
456. 82
190. 36
310. 59
480. 56
536. 67
394. 64 127
294. 44
194. 28
536. 80
634
634
*
307
280
270
32
227
55
420
195
182
380
159
178
229
190
264
156
229
330
55
72
300
402
*
402
1443
402
402
402
402
1870
1 8 7 0
402
1870
1870
1870
1870
1870
1870
634
1565
695
695
*
695
*
*
144
*
*
*
*
1842
181
*
220 1893
180 1893
230 1893
*
339
200
*
*
1789
1 0
1 0
55
60
48
261
219
402
402
1868
725
1784
781
781
*
*
1774
*
248 651
82 1921
234 1781
Melting Points of Polymers M/95
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly(nonamethylene oxide)
Poly(nonamethylene N,iV-pentamethylenediterephthalamate)
Poly(nonamethylene 3,3 -phosphinylidenedibenzamide)
-, methyl- (P)
Poly(nonamethylene 4,4-phosphinylidenedibenzamide)
-, methyl- (P)
-, phenyl- (P)
Poly(nonamethylene pimelamide)
Poly(nonmethylene pyromellitimide)
-, 3-bromo- (imide)
Poly(nonamethylene sebacamide)
Poly(nonamethylene terephthalate)
Poly(nonamethylene 2,5-tetrahydrofurandipropionamide)
Poly(nonamethylene N,N-tetramethylenediterephthalamate)
Poly(nonamethylene tridecanediamide)
Poly(nonamethylene NJ-trimethylenediterephthalamate)
Poly(nonamethylene undecanediamide)
Poly(nonamethylene urea)
Poly( 1-nonene)
Poly[4,4-(2,2-nonylidene)-diphenylene carbonate]
Poly(norbomene), see Poly( I-vinylene-3-cyclopentylene)
Poly(octadecamethylene docosanediamide)
Poly(octadecamethylene dodecanediamide)
Poly(octadecamethylene 4,4-(ethylenedixy)-dibenzoate]
Poly(octadecamethylene octadecanediamide)
Poly(octadecamethylene p-phenylenediacetamide)
Poly(octadecamethylene p-phenylenedipropionamide)
Poly(octadecamethylene sebacamide)
Poly(octadecamethylene terephthalamide)
Poly(octadecamethylene terephtbalate)
Poly(octadecamethylene p-xylylenediurea)
Poly(octadecametbylene anhydride)
Poly( I-octadecene)
Poly( 1,3-octadiene), 1,4-
Poly(octamethylene)
-, l-methyl-
Poly(octamethylene adipamide)
Poly(octamethylene adipate)
Poly[octamethylene NJ-adipoyldi(6-aminocaproate)]
Poly(octamethylene azelamide)
Poly(octamethylene 4,4-biphenylenedicarboxylate)
Poly(octamethylene decamethylenediurethane)
Poly[4,4-(octamethylenedicarbonyl)-diphenylene carbonate]
Poly[4,4-(octamethylenedioxy)-diphenyleneoxy-~-xylylene oxide]
Poly(octamethylene disiloxanylenedipropionamide)
-,tetramethyl- (Si)
Poly(octamethylene disulfide)
Poly[4,4-(2,2-octamethylenedithiazole)-p-phenylene]
Poly(octamethylenedithiotetramethylene disulfide)
Poly(octamethylene docosanediamide)
Poly(octamethylene dodecanediamide)
Poly(octamethylene dodecanedioate)
Poly[octamethylene NJ-dodecanedioyldi@-aminobenzoate)]
Poly(octamethylene eicosanediamide)
Poly(octamethylene NJ-ethylenediterephthalamate)
Poly(octamethylene 2,Sfurandicarboxamide)
Poly(octamethylene NJ-hexamethylenediterephthalamate)
Poly(octamethylene hexamethylenediurethane)
Poly(octamethylene 3-hexenedioate)
522.64
412.47
426.50
412.47
426.50
488.57
282.43
419.27
324.51
338.49
508.61
366.59
494.59
338.54
184.28
126.24
338.47
619.08 146
478.80 170
552.77 122
562.97 152
442.69 225
470.74 232
450.75 1 7 1
414.63 255
416.60 116
472.72 226
296.45 95
112.22
254.37
482.66 140
352.43
370.53
380.44
432.56
330.58
386.68
176.34
354.53
296.56
478.80
338.54
340.50
578.15
450.75
466.53
264.32
522.64
194 781
1 4 1 402
167
179
196
402
402
2
*
287
176
202
1267
339
402
*
149
259
1 8 3
211
196
220
1 9
22
190
402
781
2
781
2
1776
250
872
438
*
454
454
290
454
454
454
454
454
290
634
1823
*
*
*
250
235
254
244
291
544
1
1792
*
197 1174
137 634
175 1174
220 1789
95
58
164
45
175
202
200
194
73
188
179
282
1 2 5
238
402
725
1810
1784
454
244
454
291
291
1792
244
781
1905
781
*
*
*
References page VI- 159
VI/96 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Mol ecul ar Melting
wei ght point Refs.
Polymer
Poly(octamethylene isophthalamide)
Poly(octamethylene malonamide)
-, dodecyl- (diacid)
Poly[octamethylene 4,4-(methylenediphenylene)-diurethane]
Poly(octamethylene octadecanediamide)
Poly(octamethylene octamethylenedithiourea)
Poly(octamethylene octamethylenediurethane)
Poly(octamethylene 4-octenediamide)
trans-
Poly(octamethylene 4-octenedioate)
Poly(2,5-octamethylene-1,3,4-oxadiazole)
274.36 186 1 8 6 8
380.62 125 1774
179 454
190 402
144 402
422.70
372.63
342.48
280.41
256 657
*
1 9 2 1
1 8 6 2
743
1781
*
180.25 110
100
276
244
198.27
508.75
Poly(octamethylene oxamide)
Poly(octamethylene oxamide-alt-octamethylene sebacamide)
Poly(octamethylene oxide)
Poly(octamethylene 3,3,4,4-oxydiphenylenetetracarboximide)
Poly(octamethylene N,N,-pentamethylenediterephthalamate)
Poly(octamethylene p-phenylenediacetamide)
Poly(octamethylene p-phenylenedipropionamide)
Poly(octamethylene 3,3-phosphinylidenedibenzamide)
-, methyl- (P)
Poly(octamethylene 4,4-phosphinylidenedibenzamide)
-, methyl- (P)
- phenyl- (P)
Poly(octamethylene phthalamide)
Poly(octamethylene 2,4-pyridinedicarboxamide)
Poly(octamethylene 2,5-pyridinedicarboxamide)
Poly(octamethylene 2,6-pyridinedicarboxamide)
1,4-dihydro-4-oxo-
iAly(octamethylene 3,5-pyridinedicarboxiamide)
Poly(octamethylene pyromellitimide)
-, 3-bromo- (imide)
Poly(octamethylene sebacamide)
508.61
302.42
330.47
398.44
412.47
398.44
412.47
474.54
274.36
275.35
275.35
275.35
291.35
275.35
207 7 8 1
280 454
289 454
158 402
172 402
202 402
123 1 8 6 8
190 1 9 0 5
232 1 9 0 5
192 1 9 0 5
86 1 9 0 5
214 1 9 0 5
405.25
3 10.48
320 1 2 6 7
207 1 5 3
206 454
210 244
212 402
Poly(octamethylene sebacoyldiurea)
Poly(octamethylene suberamide)
Poly(octamethylene suberate)
Poly(octamethylene succinamide)
Poly(octamethylene L-tartaramide)
diGmethyl-
&y(octamethylene terephthalamide)
Poly(octamethylene terephthalate)
Poly[octamethylene N,N-terephthaloyldi(6-aminocaproate)]
Poly(octamethylene tetradecanediamide)
Poly(octamethylene 2,5-tetrahydrofurandipropionamide)
Poly(octamethylene N,N-tetramethylenediterephthalamate)
Poly(octamethylene tetramethylenedithiourea)
Poly(octamethylene 2,5-thiophenedicarboxamide)
Poly(2,5-octamethylene-1,3,4-triazole)
-, l-amino- (triazole)
Poly(octamethylene N,N-trimethylenediterephthalamate)
Poly(octamethylene urea)
Poly(octamethylene p-xylylenediurea)
Poly(octamethylene p-xylylenediurethane)
Poly(octenamer)
Poly( 1 -0ctene)
Poly(oxacyclobutane) [trimethylene oxide]
-, 3,3-bisazidomethyl-
-, 3,3-bisbromomethyl-
-, 3,3-bischloromethyl-
-, 3,3-bisethoxymethyl-
-, 3,3-bisfluoromethyl-
-, 3,3-bishydroxymethyl-
-, 3,3-bisiodomethyl-
396.53
258.32
167 1 7 9 2
196 2
180 402
276 7 8 1
160 402
304 1 9 0 5
502.65
366.59
324.46
494.59
316.53
280.39
179.27
194.28
480.56
170.26
332.45
334.42
258 610
231 7 8 1
260 2 9 1
278 634
196 634
*
1 8 0 7 243.93 220
122.12 135 1 8 0 5
118.13 D280 1271
337.93 290 1 8 0 7
Melting Points of Polymers VI/97
Polymer
Mol ecul ar Melting
wei ght point Refs.
-, 3-tert-butyl-
-, 3,3-diethyl-
-, 3,3-dimethyl-
-, 3-hydroxy-
Poly(oxybisdimethylsilylene)
Poly(4,4-oxydibenzoic anhydride)
Poly(oxydiethylene adipate)
Poly(oxydiethylene azelate)
Poly(oxydiethylene 2,2-dibenzoate)
Poly(oxydiethylene 3,3 -dibenzoate)
Poly(oxydiethylene 4,4-dibenzoate)
Poly[(oxydiethylene)-dioxydibenzoic anhydride]
Poly[4,4-(oxydiethylenedioxydiethylenedioxy)-diphenylene 3,3,4,4-(carbonyldiphenylene)-
tetracarboximide]
Poly[4,4-(oxydiethylenedioxy)-diphenylene 3,3,4,4-(carbonyldiphenylene)-tetracarboximide]
Poly[3,4-(oxydiethylenedioxy)-diphenylene] 3,3,4,4-(oxydiphenylene)-tetracarboximide]
Poly(oxydiethylene 4,4-ethylenedibenzoate)
Poly(oxydiethylene glutarate)
Poly(oxydiethylene hexamethylenediurethane)
Poly(oxydiethylene isophthalate)
Poly(oxydiethylene malonate)
Poly(oxydiethylene 4,4-methylenedibenzoate)
Poly(oxydiethylene oxalate)
Poly(oxydiethylene oxydiacetate)
Poly[(oxydiethylene)-oxy-p-phenylene oxide]
Poly(oxydiethylene phthalate)
Poly(oxydiethylene pimelate)
Poly(oxydiethylene sebacate)
Poly(oxydiethylene suberate)
Poly(oxydiethylene succinate)
Poly(oxydiethylene sulfonyldivalerate)
Poly(oxydiethylene terephthalate)
Poly(oxydiethylene thiodivalerate)
Poly[(oxydimethylenedioxy)-dibenzoic anhydride]
Poly(oxydipentamethylene Soxadodecanediamide)
Poly(oxydipentamethylene 6-oxadodecanediamide)
Poly(oxydipentamethylene 6-oxaheptadecanediamide)
Poly(oxydipentamethylene Soxahexadecanediamide)
Poly(oxydipentamethylene 6-oxapentadecanediamide)
Poly(oxydipentamethylene 5-oxasebacamide)
Poly(oxydipentamethylene Soxatetradecanediamide)
Poly(oxydipentamethylene 6-oxatridecanediamide)
Poly(oxydipentamethylene Soxaundecanediamide)
Poly(oxydipentamethylene oxydibutyramide)
Poly(oxydipentamethylene oxydicaproamide)
Poly(oxydipentamethylene oxydienanthamide)
Poly(oxydipentamethylene oxydipelargonamide)
Poly(oxydipentamethylene oxydivaleramide)
Poly(3,4-oxydiphenylene adi pami de)
Poly(4,4-oxydiphenylene adi pami de)
Poly(3,4-oxydiphenylene azelamide)
Poly(4,4-oxydiphenylene azelamide)
Poly(4,4-oxydiphenylene carbonate)
Poly(4,4-oxydiphenylene4,4-dibenzylidenimino adipate)
-, 3 ,3 -dimethoxy-
Poly(4,4-oxydiphenylene-4,4-dibenzylidenimino isophthalate)
-, 3,3-dimethoxy-
Poly(4,4-oxydiphenylene-4,4-dibenzylidenimino sebacate)
-, 3,3-dimethoxy-
Poly(4,4((4,4-oxydiphenylene)-dioxy-diphenylene pyromellitimide)
Poly(2,2-(4,4-oxydiphenylene-4,4-diquinoline)-4,4-biphenylene)
-, 3,3-diphenyl-
Poly(4,4-oxydiphenylenedithiodecamethylene disulfide)
Poly(4,4-oxydiphenylenedithioethylene disulfide)
Poly(4,4-oxydiphenylenedithiotetramethylene disulfide)
74.08 166 1944
*
240.21 296 1854
216.23 - 24 765
258.3 1 0 696
312.32 95 1654
312.32 75 1552
312.32 170 1654
328.32 190 1854
660.64 360 1808
572.53 402 1808
*
340.38 1 0 5
202.2 1 - 2 2
274.32 120
236.22 90
174.15 - 1 1
326.35 1 4 5
160.13 1 0
204.18 6
180.20 136
236.22 11
230.26 - 2 6
1654
765
633
1654
765
1654
765
1798
1868
1794
765
*
244.29 3 5
188.18 - 8
304.34 66
765
765
1797
*
304.40
300.27
384.56
384.56
454.70
440.67
426.64
356.51
412.61
398.59
370.53
342.48
398.59
426.64
482.75
370.53
3 10.35
310.35
352.43
352.43
228.20
518.57
578.62
538.56
598.61
574.68
634.73
- 3 5 767
192 1854
102 1847
100 1847
1 2 8 1847
122 1847
1 1 7 1847
1 2 7 1847
1 1 8 1847
106 1847
1 0 8 1847
138 1847
128 1847
129 1847
129 1847
134 1847
225 1832
360 1832
150 1832
300 1832
235 540
1 3 5 1 8 9 3
1 8 5 1893
140 1893
*
574.68 475 1778
726.88 500 1778
436.70 80 1837
324.49 1 5 8 1837
352.54 94 1837
*
*
*
References page VI- 159
VI/98 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Mol ecul ar Melting
Polymer wei ght point Refs.
Poly(3,4-oxydiphenylene dodecanediamide)
Poly(4,4-oxydiphenylene dodecanediamide)
Poly(4,4-oxydiphenylene ketone)
Poly(4,4-oxydiphenylene 3,3,4,4-oxydiphenylene-tetacarboximide)
Poly(4,4-oxydiphenylene m-phenylenediketone)
-, 2,2-diethyl-
-, 2,6-diisopropyl-
-, 2-ethyl-2-isopropyl-
-, 2-isopropyl-2-methyl-
Poly(4,4-oxydiphenylene p-phenylenediketone)
-, 2-isopropyl-2-methyl-
Poly(3,4-oxydiphenylene pimelamide)
Poly(4,4-oxydiphenylene pimelamide)
Poly(4,4-oxydiphenylene pyromellitimide)
Poly(3,4-oxydiphenylene sebacami de)
Poly(4,4-oxydiphenylene sebacami de)
Poly(3,4-oxydiphenylene suberamide)
Poly(4,4-oxydiphenylene suberamide)
Poly(3,4-oxydiphenylene undecanediamide)
Poly(4,4-oxydiphenylene undecanediamide)
Poly[2,2-(6,6-oxydiquinoline)-4,4-biphenylene]
-, 4,4-diphenyl-
-, 3,3,4,4-tetraphenyl-
Poly[2,2-(6,6-oxydiquinoline)-4,4-oxydiphenylene]
-, 4,4-diphenyl-
-, 3,3,4,4-tetraphenyl-
Poly[2,2-(6,6-oxydiquinoline)-p-phenylene]
-, 4,4-diphenyl-
-, 3,3,4,4-tetraphenyl-
Poly(oxydisilyleneditrimethylene pyromellitimide)
-, tetramethyl- (Si)
Poly(oxyditetramethylene hexamethylenediurethane)
Poly(oxyditrimethylene adipamide)
Poly(oxyditrimethylene terephthalamide)
Poly(oxymethylene) [formaldehyde]
Poly( I-pentadecene)
Poly( 1,3-pentadiene), 1,2-
4-methyl-
Poly(l,3-pentadiene), 1,4-
-, 2-methyl-
Poly(pentamethylene)
-, l,Zdichloro-
t r ans-
Poly(pnetamethylene adipamide)
-, (L)-l-carboxy- (diamine)
-, (L-l-carboxy- (diamine)
-, 2,2,3,3,4,4-hexafluoro- (diamine)
-, -1 N,N-dibutyl-
-9 -1 N,N-diethyl-
-9 -1 N,N-diisopropyl-
-, N,N-dimethyl-
&y(pentamethylene adipamide-alt-pentamethylene oxamide)
Poly(pentamethylene adipate)
-, 2,2,3,3,4,4-hexafluoro- (diamine)
Poly(pentamethylene azelamide)
Poly(pentamethylene azelamide-alt-pentamethylene oxamide)
Poly(pentamethylene azelate)
Poly(pentamethylene carbonate) 130.14
Poly(pentamethylene m-carboxycarbanilate) 249.27
Poly(pentamethylene p-carboxycarbanilate) 249.27
394.52 150
394.52 290
300.31
356.42
384.48
370.45
356.42
300.31
356.42
324.38
324.38
366.46
366.46
338.41
338.41
380.49
380.49
422.49
574.68
726.88
438.49
590.68
742.88
346.39
498.58
650.78
374.50
430.61
330.42
242.32
262.31
210.40 54
70.14
139.02
212.29
256.30
512.60
320.24
432.45
376.34
404.40
348.29
368.48
214.26
322.20
410.56
256.34
1832
1832
*
*
242 1 7 6 7
1 8 5 1 7 6 7
228 1 7 6 7
220 1 7 6 7
262
170
315
165
310
1 7 5
310
140
270
1 7 6 7
1 8 3 2
1832
*
1832
1832
1832
1832
1832
1832
480 1778
480 1778
448 1778
476 1778
455 1778
475 1778
210
124
190
213
281
1 3 6 1
633
291
1775
1775
*
872
*
75 1 9 2 5
223 339
225 402
251 1852
258 1818
113 1883
102 1883
1 5
20
35
30
281
40
34
402
402
402
402
1 7 8 1
1120
1933
*
268 1 7 8 1
4 1 696
50 1120
46 1820
80 1 8 9 1
160 1 8 9 1
Melting Points of Polymers VI/99
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly[pentamethylene p-(carboxyphenylene)-acetamide]
Poly[pentamethylene (cyclopropylenedicarboxoyl)-diurethane]
trans-
Poly(pentamethylene cyclopropylenediurethane)
Poly[pentamethylene (decamethylenedisulfonyl)-dicaproamide]
Poly(pentamethylene 2,2-dibenzoate)
Poly(pentamethylene 3,3 -dibenzoate)
Poly(pentamethylene 4,4-dibenzoate)
Poly(4,4-pentamethylenedibenzoic anhydride)
Poly[3,3-(pentamethylenedioxy)-dibenzoic anhydride]
Poly[4,4-(pentamethylenedioxy)-dibenzoic anhydride]
Poly[(pentamethylenedioxy)-didecamethylene oxide]
Poly[(pentamethylenedioxy)-dihexamethylene oxide]
Poly(pentamethylene disulfide)
Poly(pentamethylene dithiolisophthalate)
Poly(pentamethylene dithiolterephthalate)
Poly(pentamethylene dodecanedioate)
Poly(pentamethylene N,N-ethylenbediterephthalamate)
Poly[pentamethylene (ethylenedithio)-diethylenediuethane]
Poly(pentamethylene glutaramide)
Poly(pentamethylene glutarate)
Poly[pentamethylene (hexamethylenedisulfonyl).dicaproamide]
Poly(pentamethylene NJ-hexamethylenediterephthalamate)
Poly[pentamethylene (hexamethylenedithio)-diethylene-diurethane]
Poly(pentamethylene hexamethylenediurethane)
Poly(pentamethylene isophthalate)
Poly(pentamethylene malonamide)
-, dodecyl- (diacid)
Poly[pentamethyIene 4,4-(methylenediphenylene)-diurethane]
Poly(pentamethylene octadecanediamide)
Poly(pentamethylene 4-octenediamide)
tram- II.
Poly(pentamethylene oxalate)
Poly(pentamethylene oxamide-alt-pentametylene pimelamide)
Poly(pentamethylene oxamide-alt-pentamethylene sebacamide)
Poly(pentamethylene oxamide-alt-pentamethylene suberamide)
Poly(pentamethylene oxydiacetamide)
Poly(pentamethylene oxydiacetate)
Poly(pentamethylene 4,4-oxydibenzoate)
Poly(pentamethyleneoxy-p-phenylene oxide)
Poly[pentamethylene (pentamethylenedisulfonyl)-dicaproamide]
Poly(pentamethylene N,N-pentamethylenediterephthalamate)
Poly[pentamethylene (pentamethylenedithio)-diethylene-diurethane]
Poly(pentamethylene m-phenylenedisulfonamide)
Poly(pentamethylene phthalate)
Poly(pentamethylene pimelamide)
Poly(pentamethylene pimelate)
Poly(pentamethylene sebacamide)
Poly(pentamethylene sebacate)
Poly(pentamethylene sebacoyldiurea)
Poly(pentamethylene suberamide)
Poly(pentamethylene suberate)
Poly(pentamethylene succinate)
Poly(pentamethylene sulfide)
Poly(pentamethylene sulfone)
Poly(pentamethylene sulfonyldivalerate)
Poly(pentamethylenesulfonyltetramethylene sulfone)
Poly(pentamethylene terephthalamide)
Poly(pentamethylene terephthalate)
Poly(pentamethylene tetradecanediamide)
Poly(pentamethylene 2,Stetrahydrofurandipropionamide)
Poly(pentamethylene N,N-tetramethylenediterephthalamate)
Poly(pentamethylene (tetramethylenedithio)-diethylene-diurethane]
Poly(pentamethylene thiodivalerate)
246.31
284.21
228.25
564.84
310.35
3 10.35
3 10.35
294.35
326.35
326.35
398.67
286.46
134.26
266.38
266.38
298.42
424.45
336.46
200.23 2 5
508.73 210
480.56 255
392.57 94
234.25 82
338.54 208
380.62
238.33
158.15
382.50
424.58
396.53
200.24
202.21
326.35
178.23
494.70
466.53
378.55
304.38
234.25
268.40
270.37
354.45
240.35
242.32
186.21
334.43 86
324.5 1 178
282.38 1 5 3
452.5 1 284
364.52 95
302.43 42
216 1904
250
170
202
1 3
60
170
118
176
188
72
46
44
1 7 5
232
60
312
130
1865
1865
402
1552
1552
15.52
1854
1854
1854
542
542
295
1922
1922
1792
781
1897
*
1 6 7
1120
402
781
1897
*
1794
*
1774
*
339
258
54
273
258
273
130
33
70
164
212
198
87
160
9
657
1120
1 7 8 1
1 7 8 1
1 7 8 1
291
1798
1939
1868
402
7 8 1
1897
1384
1794
*
1 9 5
5 1
57
205
202
46
35
*
339
696
1120
402
339
1120
1120
*
*
1797
*
*
*
339
402
781
1897
761
References page VI- 159
VI / 100
Polymer
CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Mol ecul ar Melting
wei ght point Refs.
Poly(pentamethylenethiotetramethylene sulfide)
Poly(2,5-pentamethylene-1,3,4-triazole)
-, l-amino-
Poly(pentamethylene tridecanediamide)
Poly(pentamethylene N,N-trimethylenediterephthalamate)
Poly(pentamethylene undecamethylenediurethane)
Poly(pentamethylene undecanediamide)
Poly(pentamethylene urethane)
Poly(pentenamer)
Poly( 1-pentene)
-, 5-cyclohexyl-
-, 5-diisobutylamino-
-, 5-diisopropylamino-
190.37
137.19
152.20
310.48
438.48
342.48
282.43
152.28
-1
4,4-dimethyl-
-, 3-ethyl-
-, 3-methyl-
98.19
-,
4-methyl-
-, 5,5,5-trifluoro-
-, rl-trifluoromethyl-
-, 5-trimethylsilyl-
Poly[4,4-(2,2-pentylidene)-diphenylene carbonate]
4-methyl-
Poly[4,4-(3,3-pentylidene)-diphenylene carbonate]
-, 2,4-dimethyl-
Poly[4,4-perfluorodiphenyleneoxyperfluoropentamethylene
-, 1,1,5,5-tetrahydro- (pent amet hyl ene)
Poly(m-phenylene)
Poly@-phenylene)
Poly(m-phenylene adipamide)
124.11
138.13
oxide)
282.34
296.37
282.34
310.39
578.16
506.19
218.26
-, 3-methyl- (diamine)
Poly(o-phenylene adipamide)
Poly(m-phenylene adipamide)
Poly(p-phenylene azelamide)
Poly(p-phenylene azelate)
Poly@-phenylene m-carboranedicarboxylate)
Poly(p-phenylene cyclobutylene)
dipyridyl-
Poly(p-phenylene cyclobutylenedicarboxamide)
Poly(p-phenylene cyclobutylenedicarboxylic acid)
-, dibutyl ester
-1 -,
dicyano-
-,
diethyl ester
-, -1 dicyano-
-, diisopropyl ester
232.28
218.26
260.34
262.3 1
130.19
216.24
218.21
330.42
380.44
-. -7
dicyano-
-, dimethyl ester
324.34
302.37
352.39
-, -,
dicyano-
-, diphenyl ester
-, dipropyl ester
-, dicyano-
Poly(m-phenylene cyclopropylenedi(carboxylate)
cis-
trans-
Poly(p-phenylene cyclopropylenedicarboxylate)
cis-
trans-
Poly(p-phenylenediacetic anhydride)
296.28
302.37
204.18
204.18
176.17
Poly(m-phenylene-3,3-dibenzamido isophthalamide) 476.49
Poly(m-phenylene-4,4-dibenzamido isophthalamide) 476.49
Poly(p-phenylene-3,3-dibenzamido isophthalamide) 476.49
Poly@-phenylene-4,4-dibenzamido isophthalamide) 476.49
Poly(m-phenylene-3,3-dibenzamido terephthalamide) 476.49
Poly(m-phenylene-4,4-dibenzamido terephtbalamide) 476.49
65 1860
1 0 5 1860
160 1860
280 1860
92 1 5 6 5
152 1 8 5 5
410 1788
450 1788
475 1788
490 1788
460 1788
467 1788
67 181
260 610
176 339
235 7 8 1
123 633
176 2 9 1
*
*
*
1 2 3 328
*
*
*
425 632
*
*
225 1 8 1 3
255 1 8 1 3
*
220 438
220 438
1 9 5 1 9 1 5
220 1 9 1 5
145 1908
*
*
296 402
344 828
225 402
179 1868
*
345 828
1 3 5 1174
*
*
405 723
330 723
*
340 723
320 723
320 723
*
290 723
*
*
Melting Points of Polymers VI / 101
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly@-phenylene-3,3-dibenzamido terephthalamide) 476.49
Poly(p-phenylene-4,4-dibenzamido terephthalamide) 476.49
Poly(p-phenylene-4,4-dibenzylidenimino adipate) 426.47
-, 3 ,3 -dimethoxy- 486.52
Poly(p-phenylene-4,4-dibenzylidenimino isophthalate) 446.46
-, 3 ,3 -dimethoxy- 506.52
Poly@-phenylene-4,4-dibenzylidenimino sebacate) 482.58
-, 3 ,3 -dimethoxy- 542.63
Poly@-phenylenediethylene adipamide) 274.36
Poly(p-phenylenediethylene azelamide) 316.44
Poly@-phenylenediethylene docosanediamide) 498.80
Poly(p-phenylenediethylene dodecanediamide) 358.53
Poly@-phenylenediethylene heptadecanediamide) 428.66
Poly(p-phenylenediethylene hexadecanediamide) 414.63
Poly(p-phenylenediethylene octadecanediamide) 442.69
Poly(p-phenylenediethylene octamethylenediurethane)
362.47
Poly@-phenylenediethylene pentadecanediamide) 400.61
Poly(p-phenylenediethylene m-phenylenediacetamide) 322.41
Poly[p-phenylenediethylene 3,3-@-phenylene)-dipropionate] 352.43
Poly(p-phenylenediethylene sebacami de) 330.47
Poly@-phenylenediethylene terephthalate) 296.32
Poly(p-phenylenediethylene tetradecanediamide) 386.58
Poly(p-phenylenediethylene thiodicaproamide) 390.58
Poly@-phenylenediethylene thiodienanthamide) 418.64
Poly(p-phenylenediethylene thiodipelargonamide) 474.75
Poly(p-phenylenediethylene thiodiundecanoamide) 530.86
Poly(p-phenylenediethylene thiodivaleramide) 362.53
Poly(p-phenylenedietylene tridecanediamide) 372.55
Poly(p-phenylenediethylene undecandiamide) 344.50
Poly[(m-phenylenedioxy)-diacetic anhydride] 208.17
Poly[@-phenylenedioxy)-diacetic anhydride] 208.17
Poly[(p-phenylenedioxy)-diacetic 3,4-pyridinedicarboxylic anhydride] 357.27
Poly[(p-phenylenedioxy)-diacetic terephthalic anhydride] 356.29
Poly[(p-phenylenedioxy)-diacetic 4,4-(trimethylenedioxy)-dibenzoic anhydride] 506.46
Poly[@-phenylenedioxy)-diethylene octamethylenediurethane] 394.47
Poly[4,4-(p-phenylenedioxy)-diphenylene carbonate]
Poly[4,4-(p-phenylenedioxy)-diphenylene ketone]
Poly[4,4-(p-phenylenedioxy)-diphenylene 3,3,4,4-(p-phenylenedioxy)-diphenylenete~ac~boximide]
Poly(p-phenylenedipentamethylene terephthalate)
Poly(p-phenylenedipropionic anhydride)
Poly(p-phenylene disiloxanylene)
-, tetramethyl- (Si)
Poly(m-phenylene disiloxanylenedipropionamide)
-, 4-methyl- (diamine)
-7 -3 diethyl-dimethyl- (Si)
-, -3 tetraethyl- (Si)
-1 -, tetramethyl- (Si)
-, tetraethyl- (Si)
-, tetramethyl- (Si)
Poly(o-phenylene disiloxanylenedipropionamide)
-, diethyl-diemthyl- (Si)
-, tetraethyl- (Si)
-, tetramethyl- (Si)
Poly@-phenylene disiloxanylenedipropionamide)
-, diethyl-dimethyl- (Si)
-, tetraethyl- (Si)
-, tetramethyl- (Si)
320.30
658.62
380.48
204.22
152.30
294.46
308.49
392.65
420.70
364.59
406.67
350.57
294.46
378.62
406.67
350.57
294.46
378.62
406.67
350.57
480 1788
555 1788
1 3 5 1893
230 1893
120
310
250
290
230
280
249
258
248
212
212
248
222
219
285
285
300
330
267
251
234
222
207
252
262
275
130
1 5 8
152
160
312
324
260
212
212
215
1893
402
402
454
454
454
454
454
454
402
291
454
402
1174
1 8 4 1
402
454
1 8 8 1
454
1824
1824
1824
1824
1824
454
454
1565
1855
1565
1872
1872
1 8 7 1
1872
633
402
1915
*
660 1018
116 1 8 8 1
92 1565
*
50 402
90 402
70 402
70 402
90 402
40 402
40 402
40 402
300 402
290 402
300 402
References page VI-l 59
VI / 102 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Polymer
Molecular Melting
wei ght point Refs.
Poly(p-phenyleneditetramethylene terephthalate) 352.43
Poly[4,4-(2,2-m-phenylenedithiazole)-oxy-p-diphenylene] 410.51
Poly[(p-phenylenedithio)-dipropionic anhydride] 268.34
Poly(p-phenyleneditrimethylene hexamethylenediurethane) 362.47
Poly(p-phenyleneditrimethylene terephthalate)
Poly@-phenyleneethylene adi pami de)
-, l,l-dimethyl- (diamine)
Poly[p-phenylene 4,4-(ethylenedioxy)-dibenzoate]
-, methyl- (diol)
Poly@phenyleneethylene sebacami de)
1 , l-dimethyl- (diamine)
&y(p-phenyleneethylene succinamide)
-, 1,l -dimethyl- (diamine)
Poly(p-phenyleneethylene terephthalamide)
-, 1 , l-dimethyl- (diamine)
Poly(p-phenylene glutaramide)
Poly(m-phenylene hexamethylenediurethane)
Poly@-phenylene hexamethylenediurethane)
Poly(m-phenylene isophthalamide)
Poly(p-phenylene isophthalamide)
Poly(m-phenylene isophthalate)
Poly(p-phenylene isophthalate)
Poly(p-phenylene mal onat e)
Poly(p-phenylene oxide)
-, 2,6-dimethoxy-
-, 2,6-dimethyl-
2,6-diphenyl-
ioly@-phenyleneoxytrimethylene oxide)
Poly(m-phenylene 3,3-phosphinylidenedibenzamide)
-, methyl- (P)
-, 4-methyl- (diamine)
&y(m-phenylene 4,4-phosphinylidenedibenzamide)
-, methyl- (P)
-1 -1 4-methyl- (diamine)
-, phenyl- (P)
-, 4-methyl- (diamine)
Poly(o-phenylene 3,3-phosphinylidenedibenzamide)
-, met hyl - ( P)
Poly(o-phenylene 4,4-phosphinylidenedibenzamide)
-, met hyl - ( P)
-, phenyl- (P)
Poly@-phenylene 3,3-phosphinylidenedibenzamide)
-, methyl- (P)
Poly(p-phenylene 4,4-phosphinylidenedibenzamide)
-, methyl- (P)
-, phenyl- (P)
Poly(p-phenylene pimelamide)
Poly@-phenylene 1,4-piperazinedipropionate)
methyl- (diacid)
&y(m-phenylene sebacami de)
3-methyl- (diamine)
ioly(o-phenylene sebacami de)
Poly@-phenylene sebacami de)
Poly(m-phenylene suberamide)
Poly(o-phenylene suberamide)
Poly(p-phenylene suberamide)
Poly(m-phenylene succinate)
Poly(p-phenylene succinate)
Poly(p-phenylene sulfide)
-, 2-methyl-
Poly(p-phenylene sulfonate)
Poly(m-phenylene terephthalamide)
324.38
246.31
274.36
376.37
390.39
302.42
330.47
218.26
246.31
266.30
294.35
204.23
278.31
278.31
238.25
240.21
178.14
150.18
362.32
376.35
390.38
362.32
376.35
390.38
438.42
452.45
362.32
376.35
362.32
376.35
438.42
362.32
376.35
362.32
376.35
438.42
304.35 189
318.37 164
288.39 200
274.36 1 2 5
246.31 150
192.17 260
192.17 300
122.18 100
156.16 276
217 1881
220 1 1 7 4
340 1 8 1 0
5 5 1565
50 1 8 5 7
158 6 3 3
240 2 9 1
162 1881
235 1 8 0 2
316
205 1 8 0 2
250 1 8 0 2
360
398
150
150
1 8 0 2
8 2 8
402
402
*
748
1 8 3 7
*
1 8 6 8
*
*
*
*
1 8 6 8
245
233
244
402
402
340 402
252 402
340 402
280 402
1 8 1 402
1 9 3 402
207 402
264 402
340
340
402
402
*
1 8 7 5
1 8 7 5
*
402
1 8 6 8
*
*
1 8 6 8
*
1 1 7 4
1841
*
679
1785
*
Melting Points of Polymers VI / 103
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly(p-phenylene terephthalamide)
Poly(p-phenylene terephthalate)
-, ierr-butyl- (diol)
-, phenyl- (diol)
Poly[p-phenylene 4,4-(tetramethylene dioxy)-dibenzoate]
methyl- (diol)
Polyb-phenylene 4,4-(thiodiphenylene)-dioxy-3,3,4,4-
diphenylenetetracarboximide]
Poly(m-phenylene urea)
-, 4-methyl-
Poly(phosphazene)
-, bis-@naphthoxy-
-, bis-phenoxy-
-9 -1 di-m-bromo-
-I -, di-p-bromo-
-, -3 di-m-chloro-
-, -3 di-p-chloro-
-, -, di-2,4-dichloro-
-, -1 di-m-fluoro-
-3 -1 di-p-fluoro-
-1 -1 di-isopropyl-
-3 -3 di-p-phenyl-
-1 -, di-m-trifluoromethyl-
-, ,bis-2,2,2-trifluoroethoxy-
-, dimethyl-
Poly(phosphinideneditrimethylene adipamide)
octyl-
&y(pimelic anhydride)
Poly(piperazine adipamide)
-, 3-methyl- (diacid)
Poly(piperazine azelamide)
Poly(piperazine cyclopropylenedicarboxamide)
trans-
-9 l-methyl- (diacid)
trans-
-, 3-methyl- (diacid)
trans-
Poly[(piperazinedicarbamoyl)-dithiohexamethylene disulfide]
Poly[(piperazinedicarbamoyl)-dithiotetramethylene disulfide]
Poly( 1,4-piperazinediethylene hexamethylenediurethane)
Poly( 1,4-piperazinediethylene sulfone)
Poly[piperazine (ethylenediamino)-dipropionamide]
-> N,N-diisopropyl-
N,N-diemthyl-
Poly[piperazine (ethylenedixoy)-diacetamide]
Poly(piperazine isophthalamide)
-, 2,5dimethyl- (diamine)
methyl- (diamine)
&y(piperazine 4-octenediamide)
Poly(piperazine oxydiacetamide)
Poly(piperazine phthalamide)
->
2,5dimethyl- (diamine)
methyl- (diamine)
Poly (piperazine 1,4-piperazinedipropionamide)
-> methyl- (diacid)
methyl- (diamine)
kly(piperazine sebacami de)
Poly(piperazine suberamide)
Poly(piperazine terephthalamide)
-, 2,5-dimethyl- (diamine)
methyl- (diamine)
Poly[piperazine (trimethylenedithio)-dipropionamide]
Poly( 1,4-piperidinediyltrimethylene)
-, 2,6-dioxo-
296.32 444
404.42
418.45
582.59
134.14
148.16
47.00
331.31
367.19 330
258.30
370.52
142.15
210.28
238.33
180.21
212
426
284
> 350
1 3 5
55
*
300
148
330
194.23
130
194.23
352.54
324.49
342.44
204.29
254.33
338.50
282.39
228.25
216.24
244.28
230.27
184.20 258
216.24 325
244.29 >350
230.27 350
280.37 D270
294.40 218
294.40 217
224.30
216.24
244.29
230.27
302.45
125.22
280 1860
196 1793
204 1793
1 6 5 291
200 1875
97
1 1 3
1 6 5
340
315
280
300 402
350 1833
380 402
350 1833
350 1833
100 402
*
*
1375
*
1375
1 7 7 1
402
553
*
*
*
*
*
*
*
*
*
*
553
*
*
1859
1823
402
402
1860
1860
1875
1875
1894
1833
1833
1833
*
1894
1 8 3 3
1833
1 8 3 3
1 8 7 5
1 8 7 5
1875
*
*
References page VI- 159
VI / 104 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly( 1 ,Cpiperidene urethane)
Poly(pivalolactone), see Poly(3-hydroxypropionic acid), 2,2-dimethyl-
Poly(propene)
-, 3-cyclohexyl-
-, 3-cyclopentyl-
-, hexafluoro-
-, 3-phenyl- [allylbenzene]
-1 -, 2,5-dimethyl-
-, -, 3,4-dimethyl-
-, -, 3,5-dimethyl-
-, 3-silyl-
-, 3-m-tolyl-
-, 3-o-tolyl-
-, 3-p-tolyl-
-, 3-trimethylsilyl-
Poly(propiolactone), see Poly(3-hydroxypropionic acid)
Poly(propionaldehyde)
-, 3-cyano-
-, 3-methoxycarbonyl-
Poly(propylene oxalate)
Poly(propylene oxide)
-, 2-chloromethyl-
127.14
146.23
146.23
146.23
132.21
132.21
132.21
130.10
106.55
-, 3-(l-naphthoxy)-
-, 3-(2-naphthoxy)-
-, 3-phenoxy-
-> -, o-chloro-
-, -1 p-chloro-
-9 -, dimethyl-
-, -1 o-isopropyl-
-, -, p-methoxy-
-, -7 m-met hyl -
-, -9 o-methyl-
-3 -1 p-methyl-
-1 -1 o-phenyl-
-, 2,4,6-trichloro-
&y(propylene 4,4-sulfonyldibenzamide)
Poly(propylidene)
Poly(propylviny1 ether)
-, l-methyl-
Poly(2,5-pyrazinecyclobutylene)
-, 2,4-diphenyl-
Poly(2,5-pyrroledipropionic anhydride)
-, N-methyl-
Poly(2,6-quinoline)
-, 4-phenyl-
Poly(sebacic anhydride)
Poly(sebacoy1 dithionisophthaloyldihydrazide)
Poly(selenium)
Poly(siloxane)
-, diethyl-
-, dimethyl-
-, diphenyl-
-, dipropyl-
Poly(silylene)
-, dimethyl-
200.24
200.24
184.62
178.23
192.26
180.20
164.20
164.20
164.20
226.28
253.51
344.38
42.08
86.13
132.16
193.20
207.223
1127.2
203.24
184.24
392.54
46.10
28.09
-, diphenyl-
Poly[4,4-(silylenediphenylene)-dimethylene 4,4-disiloxanylenedibenzamide] 524.80
-, dimethyl- (diamine), tetramethyl- (Si) 608.96
Poly[4,4-(silylenediphenylene)-dimethylene 4,4-silylenedibenzamide] 478.70
-, dimethyl- (diamine), dimethyl- (Si) 550.81
270
338
275
252
180
290
240
180
126
126
235
297
176
192
1 2 5
1 2 8
200
169
1 9 1
212
205
293
130
335
90
444
*
*
*
*
*
*
1 8 7
1 8 7
1 8 7
*
1 8 7
1 8 7
1 8 7
*
*
*
*
*
305
*
1816
593
445
445
*
*
445
8 3 3
8 3 3
4 4 5
8 3 3
445
445
445
833
445
445
1 8 3 5
617
*
*
188
552
80
82
294
1 5 6 5
1 7 7 8
1564
1822
1889
*
1 6 5 402
215 402
Melting Points of Polymers VI / 105
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly[4,4-(silylenediphenylene)-dimethylene 4,4-tetrasiloxanylenedibenzamide]
-, dimethyl- (diamine)
-, tetramethyl-tetraphenyl- (Si)
Poly(4,4-stilbenediyloxyheptamethylene oxide)
a-methyl-
ioly(4,4-stitbenediyloxyhexametbylene oxide)
-, a- met hyl -
Poly(4.4~stilbenediyloxymethylene oxide)
wmet hyl -
Poly(4,4-stilbenediyloxyoctamethylene oxide)
cf-methyl-
ioly(4,4-stilbenediyloxypentamethylene oxide)
a- met hyl -
&y(4,4-stilbenediyloxytetramethylene oxide)
cr-methyl-
&y(4,4-stilbenediyltrimethylene oxide)
wmet hyl -
Gly (styrene)
-, p-tert-butyl-
-> -1 isotactic
-, -. syndiotactic
-, m-chloro-
-, -7 isotactic
-> -,
syndiotactic
-, p-chloro-
-, -1 isotactic
-7 -, syndiotactic
-, 2,4-dimethyl-
-9 -, isotactic
-, 2,5dimethyl-
-, -, isotactic
-, 3,4-dimethyl-
-, isotactic
-, 3,5dimethyl-
-7 -, isotactic
-, o-fluoro-
-1 -, isotactic
-, m-fluoro-
-, -1 isotactic
-, -, syndiotactic
-, p-fluoro-
-> -3 isotactic
-9 -, syndiotactic
-, cl-metbyl-
-3 -, p-isopropyl-
-3 -, -, isotactic
-, -, p- met hyl -
-, -9 -1 isotactic
-> o-methyl-
-1 -1 isotactic
-> -, p-fluoro-
-1 -3 -3 isotactic
-9 m-met hyl -
-, -, isotactic
1: i:methyl- syndiotactic
-3 -, isotactic
-1 -3 syndiotactic
-, p-nitro-
1: p-trifluoroacetyl- -, isotactic
-, -3 isotactic
617.00
645.06
1001.5
308.42
322.45
294.40
308.42
224.46
238.29
322.45
336.48
280.37
294.40
266.34
280.37
252.31
266.34
160.26
138.60
138.60
138.60
138.60
132.21
132.21
132.21
132.21
122.14 250
122.14 275
122.14 322
160.26 203
118.18
149.15 285 1937
200.16 1 7 8 1834
150
93
166
254
114
116
182
1 2 8
310
124
192
1 6 5
299
310
350
330
340
240
290
206
402
1772
1772
1772
1772
1772
1772
1772
*
*
1372
1372
1372
1372
1372
75
74
75
74
75
7 5
*
1910
1372
*
1372
*
888
*
*
*
*
1372
*
*
References page VI- 159
VI / 106
Polymer
CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Mol ecul ar Melting
wei ght point Refs.
-3
p-trimethylsilyl-
-, isotactic
Poly(styrene-&carbon monoxi de)
o-hydroxy-
Poly(styrene oxide)
148.16
120.15
Poly(styrene sulfone)
168.21
Poly(styry1 pyridine-&vinyl pyridine)
286.38
Poly(suberic anhydride)
156.18
Poly(4,4-sulfinyldiphenylene carbonate)
260.26
Poly(4,4-sulfonyldiphenylene carbonate)
276.26
Poly(sulfonyldipropionic anhydride)
192.18
Poly(p-sulfonylphenylene sebacami de)
338.42
Poly(sulfur trioxide)
80.06
Poly(terephthalaldehyde)
134.13
-, 2,5dimethyl-
Poly(terephthalic anhydride)
Poly[terephthalic 2,2-(terephthaloyldiamino)-dibenzoic anhydride]
Poly[terephthalic 4,4-(tetramethylenedioxy)-dibenzoic anhydride]
Poly[terephthalic 4,4-(trimethylenedioxy)-dibenzoic anhydride]
-, 3,3-dimethoxy-
Poly[terephthaloyl (m-carboxyphenoxyacetyl)-dihydrazide]
Poly(terephthaloy1 dithionisophthaloyldihydrazide)
Poly(tetradecamethylene adipate)
Poly(tetradecamethylene docosanediamide)
Poly(tetradecamethylene dodecanediamide)
Poly(tetradecamethylene NJ-ethylenediterephthalamate)
Poly(tetradecamethylene NJ-hexamethylenediterephthalamate)
Poly(tetradecamethylene 3-hexenedioate)
Poly(tetradecamethylene octadecanediamide)
Poly(tetradecamethylene 4-octenedioate)
Poly(tetradecamethylene NJ-pentamethylenediterephthalamate)
Poly(tetradecamethylene p-phenylenediacetamide)
Poly(tetradecamethylene p-phenylenedipropionamide)
Poly(tetradecamethylene sebacamide)
Poly(tetradecamethylene suberate)
Poly(tetradecamethylene terephthalamide)
Poly(tetradecamethylene N,N-tetramethylenediterephthalamate)
Poly(tetradecamethylene N,N-trimethylenediterephthalamate)
Poly(tetradecamethylene p-xylylenediurea)
Poly(tetradecanedioic anhydride)
Poly( 1-tetradecene)
Poly(tetrahydrofuran) [tetramethylene oxide]
Poly(2,5-tetrahydrofurandipropionic anhydride)
Poly(2,Stetrahydropyrroledipropionic anhydride)
-, N-methyl-
Poly(tetramethylene adipamide)
Poly(tetramethylene adipamide-alt-tetramethylene oxamide)
Poly(tetramethylene adipate)
Poly[tetramethylene NJ-adipyldi(6aminocaproate)l
Poly(tetramethylene azelamide)
Poly(tetramethylene azelamide-alt-tetramethylene oxamide)
Poly(tetramethylene azelate)
162.19
534.48 312
460.44 215
446.41 285
506.46 255
354.32 218
356.42 309
562.97 1 5 3
422.70 175
550.70 249
606.80 222
506.36 158
592.78 200
386.58 235
414.63 246
394.64 1 7 5
358.53 265
578.75 248
564.72 208
416.61 248
240.34 9 1
198.22
197.23
211.26
340.42 325
382.50
242.32
Poly(tetramethylene carbonate)
116.12
Poly(tetramethylene m-carboxycarbanilate)
235.24
Poly(tetramethylene p-carboxycarbanilate)
235.24
Poly[tetramethylene p-(carboxyphenylene)-acetamide]
232.28
Poly(tetramethylene 1,4-cyclohexylenediurethane)
256.30
Poly[tetramethylene (cyclopropylenedicarboxoyl)-diurethane]
270.24
Poly(tetramethylene cyclopropylenediurethane)
214.22
Poly[tetramethylene (decamethylenedisulfonyl)~dicapromide]
550.81
1 9 5
149
140
162
215
350
66
250
210
237
117
32
120
240
140
1 3 5
1 0 3
156
300 1 7 8 1
37 325
39 696
5 1 766
59 1820
60 1 8 9 1
186 1 8 9 1
221 1904
260 633
226 1865
180 1 8 6 5
219 402
1 8 8 4
1 8 0 9
318
693
1 9 1 6
1920
1 8 2 3
540
540
1856
1 2 6 7
288
1 8 0 1
1174
1 8 0 1
*
1 8 7 1
1 8 7 1
1 8 7 1
1 8 7 1
1 8 3 3
1889
*
454
454
781
7 8 1
*
454
*
781
454
454
454
*
454
781
781
634
1823
*i
*
1 5 6 5
1 5 6 5
*
1 7 8 1
*
1792
*
Melting Points of Polymers VI / 107
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly(tetramethylene 2,2-dibenzoate) 296.32
Poly(tetramethylene 3,3-dibenzoate) 296.32
Poly(tetramethylene 4,4-dibenzoate) 296.32
Poly(4,4-tetramethylenedibenzoic anhydride) 280.32
Poly[4,4-(tetramethylenedicarbonyl)-diphenylene succinate] 380.40
Poly[3,3-(tetramethylenedioxy)-dibenzoic anhydride] 312.32
Poly[4,4-(tetramethylenedioxy)-dibenzoic anhydride] 312.32
-, 3,3-dimethoxy- 372.37
Poly[(tetramethylenedioxy)-didecamethylene oxide] 384.64
Poly[(tetramethylenedioxy)-dihexamethylene oxide] 272.43
Poly[(tetramethyleneoxy)-ditrimethylene oxamide] 258.32
Poly(tetramethylene disiloxanylenedipropionamide)
-, tetramethyl- (Si)
-, N,N-dimethyl-
&y(tetramethylene disulfide)
Poly[4,4-(2,2-tetramethylenedithiazole)-p-phenylene]
Poly[4,4-(tetramethylenedithio)-dibenzoic anbydride]
Poly(tetramethylene dithiodicarboxylate)
Poly(tetramethylene dithioladipate)
Poly(tetramethylene dithiolisophthalate)
Poly(tetramethylene dithiolsebacate)
Poly(tetramethylene dithiolterephthalate)
Poly(tetramethylene dithionisophthalate)
Poly(tetramethylenedithiotrimethylene disulfide)
Poly(tetramethylene dodecanediamide)
Poly[tetramethylene N,N-dodecanedioyldi(p-aminobenzoate)]
Poly[tetramethylene 4,4-(ethylenedioxy)dibenzoate]
Poly[tetramethylene (ethylenedithio)-diethylenediurethane]
Poly(tetramethylene glutarate)
Poly[tetramethylene (hexamethylenedisulfonyl)-dicaproamide]
Poly(tetramethylene N,N-hexamethylenediterephthalamate)
Poly[tetramethylene (hexamethylenedithio)-diethylene-diurethane]
Poly(tetramethylene hexamethylenediurethane)
-, 1,4-dimethyl- (diol)
Poly(tetramethylene isophthalamide)
Poly(tetramethylene isophthalate)
Poly(tetramethylene malonamide)
-, dodecyl- (diacid)
Poly(tetramethylene malonate)
Poly[tetramethylene 4,4-(methylenediphenylene)-diamino-dith]
Poly[tetramethylene 4,4-(methylenediphenylene)-diurethane]
Poly(tetramethylene nonamethylenediurethane)
Poly(tetramethylene octamethylenediurethane)
Poly(tetramethylene 4-octenediamide)
Poly(tetramethylene oxalate)
Poly(tetramethylene oxamide-alt-tetramethylene pimelamide)
Poly(tetramethylene oxamide-alt-tetramethylene sebacamide)
Poly(tetramethylene oxamide-alt-tetramethylene suberamide)
Poly(tetramethylene oxide), see Poly(tetrahydrofuran)
Poly(tetramethylene oxydiacetate)
Poly(tetramethylene 4,4-oxydibenzoate)
Poly(tetramethylene 3,3,4,4-oxydiphenylenetetracarboximide)
Poly[tetramethylene (pentamethylenedisulfonyl)-dicaproamide]
Poly[tetramethylene (pentamethylenedithio)-diethylene-diurethane]
Poly(tetramethylene pentamethylenediurethane)
Poly(tetramethylene p-phenylenediacetate)
Poly(tetramethylene m-phenylenedisulfonamide)
Poly(tetramethylene 4,4-phosphinylidenedibenzamide)
-, methyl- (P)
-, phenyl- (P)
Poly(tetramethylene phthalate)
274.47
330.58
358.63
120.23
298.42
344.44
208.25
232.36
252.35
288.47
252.35
252.35
226.43
282.43
522.64
356.37
322.44
186.21
494.70
466.53
378.55
286.37 104
218.26 262
324.5 1 201
158.15 - 24
404.50 104
300.40 140
286.37 160
144.13 1 0 5
354.45 301
396.53 290
368.48 310
188.18
312.32
362.34
480.68
364.52
244.29
248.28
290.35
342.34
356.36
418.43
220.22
36 1552
66 1552
280 1566
260 1552
328 1174
263 1854
242 1174
199 1854
204 1854
172 1855
73 542
50 542
160 291
1 6 7 402
120
39
44
250
206
1 1 5
1 2 8
174
98
310
1 1 8
53
245
192
180
1 7 7
38
228
300
1 1 7
402
295
725
1810
1854
1936
1922
1922
1922
1922
1889
1784
1 5 3
1792
290
1897
766
402
781
1897
1
633
828
*
*
1774
766
1934
*
633
633
*
766
1 7 8 1
1 7 8 1
1 7 8 1
*
70 1 7 9 8
8 8 1 939
352 1 0 1 5
232 402
1 1 3 1897
1 5 9 633
6 3 325
215 1384
208 402
230 402
1 8 11794
References page VI- 1.59
VI / 108 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Polymer
Mol ecul ar Melting
wei ght point Refs.
Poly(tetramethylene pimelamide) 212.29
Poly(tetramethylene pimelate)
Poly [tetramethylene (1,4-piperazinedithio)-dicarboxylate]
2,5dimethyl-
ioly(tetramethylene 4,4-propylenedibenzamide)
Poly[tetramethylene 4,4-(propylenedioxy)-dibenzamide]
Poly(tetramethylene sebacamide)
214.26
294.38
322.44
336.44
368.43
254.33
Poly(tetramethylene sebacate)
Poly(tetramethylene suberamide)
Poly(tetramethylene suberate)
Poly(tetramethylene succinamide)
-, N,N-dimethyl-
Poly(tetramethylene succinate)
-, D- 1,2-dimethoxy- (diacid)
Poly(tetramethylene sulfide)
Poly(tetramethylene sulfone)
226.32 250
228.29 56
198.27 1 2 3
232.23 92
120.17
Poly(tetramethylene 4,4-sulfonyldibenzamide)
Poly(tetramethylene sulfonyldivalerate)
Poly(tetramethylene L-tartaramide)
-, di-O-methyl-
Poly(tetramethylene terephthalamide)
358.41
320.40
202.21
218.26
-, N,N-dimethyl-
Poly(tetramethylene terephthalate)
Poly[tetramethylene NJ-terephthaloyldi(6-aminocaproate)]
Poly(tetramethylene 2,5-tetrahydrofurandipropionamide)
Poly[tetramethylene (tetramethylenedithio)-diethylene-diurethane]
Poly(tetramethylene tetramethylenediurethane)
246.3 1
446.54
268.36
350.49
230.26
Poly(tetramethylene tetrathiodicarboxylate] 272.37
Poly(tetramethylene thiodicarboxylate) 176.19
Poly(tetramethylene thioditrimethylenediurethane) 290.38
Poly(tetramethylene thiodivalerate) 288.40
Poly(tetramethylenethiotrimethylene sulfide) 162.32
Poly(tetramethylene thiourea) 130.21
Poly(2,5-tetramethylene-1,3,4-triazole) 123.16
-, l-amino- 138.17
Poly[tetramethylene 1,1-(4,4-trimethylenedipiperdine)-dithiodicarboxylate] 418.61
Poly(tetramethylene N,N-trimethylenediterephthalamate) 424.45
Poly(tetramethylene trithiodicarboxylate) 240.31
Poly(tetramethylene undecamethylenediurethane) 328.45
Poly(tetramethylene undecanediamide) 268.40
Poly(tetramethylene urea)
Poly(tetramethylene p-xylylenediurethane)
Poly(tetramethyl-p-silphenylene siloxane), see Poly(p-phenylene disiloxanylene), tetramethyl-
Poly(3,6,13,16-tetraoxa-8,10-octadecadiyne hexamethylenediurethane)
Poly(3,6,13,16-tetraoxa-8,10-octadecadiyne (4,4-methylenediphenylene)-diurethane)
Poly(thiodiethylene dithioladipate)
Poly(thiodiethylene dithiolterephthalate)
Poly(thiodiethylene hexamethylenediurethane)
Poly(thiodiphenylene carbonate)
Poly(4,4-thiodiphenylene oxide)
Poly(thiodipropionic anhydride)
Poly(thioditetramethylene hexamethylenediurethane)
Poly(2,Qhiophenedipropionic anhydride)
Poly(tridecamethylene iV,N-ethylenediterephthalamate)
Poly(tridecamethylene NJ-hexamethylenediterephthalamate)
Poly(tridecamethylene N,N-pentamethylenediterephthalamate)
Poly(tridecamethylene pyromellitimide)
Poly(tridecamethylene N,N-tetramethylenediterephthalamate)
Poly(tridecamethylene tridecanediamide)
114.15
278.31
454.52 1 3 8
536.58 130
264.43 70
284.42 146
290.38 134
160.19 5 5
346.49 1 2 5
210.25 78
536.67 257
592.78 222
578.75 194
564.72 248
233
238
4 1
188
1 1 3
180
140
254
239
339
402
766
1934
1934
402
402
1 5 3
291
*
291
291
*
402
*
609
*
100 1845
>271 3 9
358 1835
88 1797
436
475
272
829
1940
829
*
190 1792
210 402
119 1897
193 291
193 633
92 1936
90 1936
1 3 3 633
38 767
64 1 8 1
213 402
300
80
1 9 3
66
146
208
208
400
227
610
1934
781
1936
633
339
402
402
634
*
1782
1782
1922
1922
633
*
1857
633
1 5 6 5
781
781
7 8 1
*
7 8 1
*
Melting Points of Polymers VI / 109
Polymer
Molecular Melting
wei ght point Refs.
Poly(tridecamethylene N,N-trimethylenediterephthalamate)
Poly(tridecanedioic anhydride)
Poly( 1-tridecene)
Poly(trimethylene adipamide-alt-trimethylene oxamide)
Poly(trimethylene adipate)
-, 2,2-bisbromomethyl- (diol)
-, 2,2-bischloromethyl- (diol)
-, 2-bromomethyl-2-chloromethyl- (diol)
-, 2,2-diemtbyl- (diol)
Poly(trimethylene adipoyldiuretbane)
2-hydroxy- (diol)
Poly(trimethylene amine)
Poly(trimethylene azelamide-alt-trimethylene oxamide)
Poly(trimethylene azelate)
-, 2,2-dimethyl- (diol)
Poly(poly-trimethylenebiphenylene)
-, u,u,a,u,tl,tl-hexafluoro-
Poly[trimetbylene p-(carboxyphenylene)-acetamide]
Poly(trimethylene 1,4-cyclohexylenedicarboxylate)
trans-
Poly(trimethylene cyclopropylenedicarboxamide)
trans-
Poly(trimethylene cyclopropylenediurethane)
Poly(trimethylene 2,2-dibenzoate)
-, l-methyl- (diol)
Poly(trimetbylene 3,3-dibenzoate)
-, l-methyl- (diol)
Poly(trimethylene 4,4-dibenzoate)
-, l-methyl- (diol)
Poly(4,4-trimetbylenedibenzoic anhydride)
Poly[3,3-(trimethylenedioxy)-dibenzoic anhydride]
Poly[4,4-(trimetbylenedioxy)-dibenzoic anhydride]
-, 3,3-dimethoxy-
Poly[(4,4-trimethylenedipipe~dinediyl)-dicarbamoyldi~io-te~amethy1ene disulfil
Poly(trimethylene disulfide)
Poly(trimethylene dodecanedioate)
Poly[trimethylene (ethylenedithio)-diethylenediurethane]
Poly(trimethylene glutarate)
Poly[trimethylene (hexamethylenedithio)-diethylenediurethane]
Poly(trimethylene hexamethylenediurethane)
-, 2-butyl-2-ethyl- (diol)
-, 2,2-dimethyl- (diol)
-, 2-methyl- (diol)
Poly(trimethylene isophthalate)
-, l-methyl- (diol)
Poly(trimethylene malonate)
-, 2,2-dimethyl- (diol)
Poly[trimethylene 4,4-(methylenediphenylene)-diurethane]
-, 2-butyl-2-ethyl- (diol)
-, 2,2-dietbyl- (diol)
-, 1-ethyl-2-propyl- (diol)
Poly(trimethylene octadecanedioate)
Poly(trimethy1ene octamethylenediurethane)
-, l-methyl- (diol)
Poly(trimethy1ene 4-octenediamide)
trans-
Poly(trimethylene oxalate)
-, 2,2-bischlorometbyl- 227.04
-, 2,2-dimethyl- 158.15
Poly(trimethylene oxamide-alt-trimethylene sebacamide) 368.48
de1
550.70 206
226.32 78
182.35 48
312.37 303
372.05
283.15
327.60
214.26
272.26
288.26
57.10
354.45
120 1874
108 1874
1 1 1 1874
37 609
208
126
290
256.34
194.28
302.20
218.26
212.24
0 609
1 5 5 1780
281 1904
110 1918
168.20
200.19
282.30
296.32
282.30
296.32
282.30
296.32
266.30
298.29
298.29
358.35
448.72
106.20
310
170
78
38
78
87
249
1 3 5
215
1 9 7
267
263
1 7 5
150
67
8 8
308.41 1 5 7
364.52 1 1 5
3 14.43 60
272.35 120
258.32 50
206.20 132
220.22 55
144.13 3 3
172.18 67
410.51 120
382.46 150
396.49 140
272.35
286.37 82 633
82 402
210.28
130.10
271 657
86 678
88 305
89 609
122 1874
1 1 1 609
276 1 7 8 1
781
1823
872
1 7 8 1
*
402
1786
1 7 8 1
*
1860
1865
1552
1552
1552
1552
1552
1552
1854
1854
1854
1872
1855
1793
295
725
*
1897
*
1897
*
402
402
402
1 1 1
1794
609
609
*
402
402
402
*
References page VI- 159
VI / 110 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Polymer
Molecular Melting
wei ght point Refs.
Poly(trimethylene oxamide-alt-trimethylene suberamide)
Poly(trimethylene oxide), see Poly(oxacyclobutane)
Poly(trimethylene-p-oxybenzoate)
340.42 295
178.19 1 8 5
2 11
32
8
90
1 2
58
57
1781
*
1841
327
1798
1798
1939
1897
1918
1384
26
1794
*
*
6 0 9
189 4 0 2
*
242.32 1 7 6 0 9
*
255.10 74
186.21 86
1874
6 0 9
*
130.25 8 5
300 1890
364 1 8 9 0
266 1 8 9 0
303 1917
385 1 8 9 0
298 1835
284 1835
272 1835
35
399
220
1797
8 2 9
8 2 9
*
234.25 140
220.22 87
298.42 66
336.46 1 1 3
274.38 - 3 6
288.40 - 3 6
410.43 235
2 9 1
1794
1792
1897
7 6 7
7 6 7
781
*
296.46 218
474.64 1 9 3
508.61 2 5 1
564.72 217
592.91 2 2 1
550.70 199
169
292
248
1 9 8
70
36
1 5 5
544
1789
781
781
1781
781
*
3 3 9
544
781
781
1823
8 7 2
3 2 9
140
*
*
1885
Poly(trimethylene oxydiacetate)
-, l-methyl- (diol)
Poly(trimethylene 4,4-oxydibenzoate)
Poly[trimethylene (pentamethylenedithio)-diethylene-diurethane]
Poly(trimethylene p-phenylenediacetate)
Poly(trimethylene m-phenylenedisulfonamide)
Poly(trimethylene phthalate)
-, l-methyl- (diol)
Poly(trimethylene pimelate)
Poly(trimethylene sebacate)
-, 2,2-dimethyl- (diol)
Poly(trimethylene sebacoyldiurethane)
-, 2-hydroxy- (diol)
Poly(trimethylene suberate)
-, 2,2-dimethyl- (diol)
Poly(trimethylene succinate)
-, 2,2-bischloromethyl- (diol)
-, 2,2-dimethyl- (diol)
Poly(trimethylene sulfide)
-, 3,3-diethyl-
-, 3,3-dimethyl-
Poly(trimethylene sulfone)
-, 3,3-diethyl-
-, 3,3-dimethyl-
174.15
188.18
298.30
350.49
234.25
276.33
206.20
220.22
270.37
328.36
344.36
106.14
162.25
134.19
-, 3,3-dipentyl-
Poly(trimethylene 4,4-sulfonyldibenzamide)
-, 2,2-dimethyl- (diamine)
-, l-methyl- (diamine)
Poly(trimethylene sulfonyldivalerate)
-, l-methyl- (diol)
Poly(trimethylene terephthalamide)
-, NJ-dimethyl- (diamine)
Poly(trimethylene terephthalate)
-, 2,2-dimethyl-
-, l-methyl- (diol)
Poly(trimethylene tetradecanedioate)
Poly[trimethylene (tetramethylenedithio).diethylene-diurethane]
Poly(trimethylene thiodivalerate)
-, methyl- (diol)
Poly(trimethylene NJ-trimethylenediterephthalamate)
Poly(trimethylene undecanedioate)
Poly(undecamethylene adipamide)
Poly[4,4-(undecamethylenedioxy)-diphenyleneoxy-~-xylylene oxide]
Poly(undecamethylene N,N-ethylenediterephthalamate)
Poly(undecamethylene NJ-hexamethylenediterephthalamate)
Poly(undecamethylene oxamide-alt-undecamethylene sebacamide)
Poly(undecamethylene N,N-pentamethylenediterephthalamate)
Poly(undecamethylene pyromellitimide)
Poly(undecamethylene sebacamide)
Poly(undecamethylene terephthalamide)
Poly(undecamethylene NJ-tetramethylenediterephthalamate)
Poly(undecamethylene NJ-trimethylenediterephthalamate)
Poly(undecanedioic anhydride)
Poly( 1 undecene)
Poly(valeraldehyde)
Poly(viny1 acetate)
-, trifluoro-
Poly(viny1 alcohol)
-, 2-methyl-
246.41
344.38
372.44
358.41
306.38
320.40
204.23
232.28
352.56
316.44
536.67
522.64
198.26
154.30
86.13
86.09
58.08
Melting Points of Polymers VI/111
Polymer
Molecular Melting
wei ght point RefS.
Poly(viny1 benzoate)
-, p-tert-butyl-
Poly(viny1 bromi de)
Poly(vinyl-t-butyl ketone)
Poly(N-vinyl carbazole)
Poly(vinyl chloride)
Poly(vinylcyclobutane)
Poly(vinylcycloheptane)
Poly(vinylcyclohexane)
-1 o-methoxy-
-, 3-methyl-
-, 4-methyl-
Poly(vinylcyclohexene)
Poly(vinylcyclohexy1 ketone)
Poly(vinylcyclopentane)
Poly(vinylcyclopropane)
Poly(N-vinyldiphenylamine)
Poly(l-vinylene-3-cyclopentylene) [norbornene]
Poly(vinyl fluoride)
Poly(vinylidene chloride)
Poly(vinylidene fluoride)
Poly(vinylisopropy1 ketone)
Poly(vinyl laurate)
Poly(vinylmetby1 ketone)
Poly(viny1 my&ate)
Poly( l-vinyl naphthalene)
Poly(viny1 pahnitate)
148.16
204.27 327
150
> 240
140.23 1 9 5
124.23 355
124.23 250
108.18 418
138.21 > 240
195.26 320
98.14 220
226.36 1 6
254.41 28
4 1
46
214
54
52
58
80
1 3 5
183.05 270
270
1 8 3
> 300
350
210
230
500
333
340
70
80
8 1
172
263
282
59
74
79
1 8 5
1 8 2 1
*
1812
1843
*
*
*
*
*
1815
1867
1867
1850
1843
*
*
1 8 1 1
*
*
*
*
1843
1906
*
1888
*
1888
1906
1873
*
1846
1888
1906
546
1187
*
395
*
395
1831
395
1187
*
395
142
1794
*
385
402
325
547
1919
402
385
454
325
547
1919
1820
106 547
1 7 5 1 8 6 1
170 1856
260 1856
112.17
282.47
228.39 Poly(3-vinyl pyrene)
Poly(2;vinylpyridine)
Poly(viny1 stearate) 3 10.52
104.15
132.21
Poly(m-xylylene)
-, 4,6-dimethyl-
Poly(p-xylylene)
-, bromo-
-, chloro-
-, cyano-
-, 2,5-dichloro-
129.16
173.04
-, 2,5-dimethyl-
-1 ethyl-
-. methyl-
-, a,cl,cl,cL-tetrafluoro-
Poly(m-xylylene adi pami de)
Poly(p-xylylene adi pami de)
132.21
118.18
176.11
246.3 1
Poly@-xylylene adipate) 248.28
Poly(m-xylylene azelamide) 288.39
Poly(p-xylylene azelamide) 288.39
Poly(p-xylylene azelate) 290.36
164.16
274.32
168.27
332.34
360.40
Poly(p-xylylene carbonate)
Poly(p-xylylene 1,4-cyclohexylenedicarboxylate)
trans-
Poly@-xylylene disulfide)
Poly[(p-xylylenedisulfonyl)-diacetic anhydride]
Poly[(p-xylylenedisulfonyl)-dipropionic anhydride]
References page VI- 159
VI / 112 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Polymer
Mol ecul ar Melting
wei ght point Ref s .
Poly[@-xylylenedithio)-diacetic anhydride] 268.34
Poly[@-xylylenedithio)-dipropionic anhydride] 296.40
Poly@-xylylene dithioladipate) 280.41
-, 2,3,5,6-tetramethyl- 336.52
Poly(p-xylylene dithiolisophthalate) 300.40
Poly(p-xylylene dithiol-4,4-methylenedibenzoate) 390.52
Poly@-xylylene dithiol-p-phenylenediacetate) 328.45
-, 2,3,5,6-tetramethyl- (dial) 384.56
Poly@-xylylene dithiolsebacate) 336.52
-, 2,3,5,6-tetramethyl- (dial) 392.62
Poly@-xylylene docosanediamide) 470.14
Poly(p-xylylene dodecanediamide) 330.47
Poly(p-xylylene dodecanedioate) 332.44
Poly@-xylylene glutaramide) 232.28
Poly@-xylylene glumrate) 206.20
Poly(p-xylylene heptadecanediamide) 400.61
Poly@-xylylene hexadecanediamide) 386.58
-, N,N-dimethyl- 414.63
Poly(m-xylylene isophthalamide) 266.30
Poly@-xylylene isophtbalamide) 266.30
Poly(p-xylylene isophtbalate) 268.21
Poly(p-xylylene malonamide) 204.23
Poly(p-xylylene octadecanediamide) 414.63
-, N,N-diethyl- 470.74
-, N,N-dimethyl- 442.69
Poly(p-xylyleneoctamethylenediurethane) 334.42
Poly@-xylylene 5-oxadodecanediamide) 332.44
Poly@-xylylene 6-oxadodecanediamide) 332.44
Poly@-xylylene 6-oxaheptadecanediamide) 402.58
Poly(p-xylylene 5-oxahexadecanediamide) 388.55
Poly@-xylylene oxalate) 164.12
Poly(p-xylylene 6-oxapentadecanediamide) 374.52
Poly(p-xylylene 5-oxasebacamide) 304.39
Poly@-xylylene 5-oxatetradecanediamide) 360.50
Poly@-xylylene 6-oxatridecanediamide) 346.47
Poly@-xylylene 5-oxaundecanediamide) 318.42
Poly@-xylylene oxydibutyramide) 290.36
Poly(p-xylylene oxydicaproamide) 346.47
Poly@-xylylene oxydienanthamide) 374.52
Poly(p-xylylene oxydipelargonamide) 430.63
Poly@-xylylene oxydivaleramide) 318.42
Poly@-xylylene pentadecanediamide) 372.55
Poly@-xylylene pphenylenediacetate) 296.32
Poly(p-xylylene phtbalamide) 266.30
Poly(m-xylylene pimelamide) 260.34
Poly(p-xylylene pimelamide) 260.34
Poly(p-xylylene pimelate) 262.30
Poly(m-xylylene sebacami de)
Poly@-xylylene sebacami de)
Poly(p-xylylene sebacate)
Poly(m-xylylene suberamide) 214.36
Poly(p-xylylene suberamide) 274.36
Poly@-xylylene suberate) 276.33
Poly@-xylylene succinamide) 218.26
Poly(p-xylylene succinate) 220.22
Poly(m-xylylene terephthalamide) 266.30
302.42
304.39
88 1565
87 1857
9 1 1565
55 1857
170 1922
255 1922
210 1922
274 1922
262 1922
180
240
225
272
270
94
280
58
239
248
8 5
225
290
100
110
235
242
50
80
168
200
206
223
220
214
217
234
215
207
190
241
243
234
229
215
243
241
146
230
192
284
61
66
193
1922
4 0 2
4 5 4
3 8 5
454
5 4 7
4 0 2
1919
4 5 4
454
1877
4 0 2
3 8 5
5 4 7
4 0 2
402
4 5 4
1877
1877
402
1847
1847
1847
1847
1919
1847
1847
1847
1847
1847
1847
1853
1847
1847
1847
1847
4 5 4
291
402
4 0 2
3 8 5
5 4 7
1919
4 0 2
*
84 325
8 8 1919
93 5 4 7
213 4 0 2
305 385
82 5 4 7
360 4 0 2
1 1 5 547
300 4 0 2
-
Pa
-
P a
PC
PC
PC
PC
PC
PC
PC
P C
P C
PC
-
C
L
C
S
1
E
I
1
t
(
I
I
i
I
,
Appendix: Formula Index to the Tables VI/ 1 1 3
Polymer
Molecular
wei ght
Melting
point Refs.
Poly@xylylene terephthalamide) 266. 30
Poly(p-xylylene terephthalate) 268. 27
Poly(m-xylylene tetradecanediamide) 358. 53
Poly(p-xylylene tetradecanediamide) 358. 53
Poly(p-xylylene thiodicaproamide) 362. 53
Poly(p-xylylene thiodienanthamide) 390. 58
Poly(p-xylylene thiodipelargonamide) 446. 69
Poly@-xylylene thiodiundecanoamide) 502. 80
Poly(p-xylylene thiodivaleramide) 334. 48
Poly(p-xylylene tridecanediamide) 344. 50
Poly(p-xylylene undecanediamide) 316. 44
350 402
242 547
267 1881
192 402
257 454
236 1853
228 1853
214 1824
200 1824
242 1853
247 454
264 454
D. APPENDIX: FORMULA INDEX TO THE TABLES
As the number of crystallizable polymers and their
complexity increased, it became necessary to devise a
simple, reasonably unambiguous scheme to relate
polymer structure to the specific name given to that
polymer.
Some time ago, the compiler designed a shorthand
notation to represent the structure of linear polymers which
has proved to be useful. This scheme requires one to write
the line formula for the constitutional base unit (without
concern for priority or direction rules) and to count the
groups/atoms comprising the unit in a specified order. In a
sense, this scheme is analogous to the Chemical Abstracts
Formula Index, but emphasizes groups commonly occuring
in linear organic polymers rather than atoms exclusively.
This scheme has the additional advantage of ensuring that
data for a given polymer are not entered in the tables under
differing polymer names.
The rules of this scheme are simple - count the number
of groups/atoms in the constitutional base unit in the
following order:
1 . -CHz - (methylene as such, but not the -CH2- portion
of a -CHs group).
2. -CO- (carbonyls).
3. -C6H4- (disubstituted benzenes; phenylenes; mono-
substituted benzenes with the fifth proton counted under
point 5 below).
4 . Carbon atoms not already counted (as in -CHs, -CH=,
-C6H3=, etc.).
5. Protons (-H) not already counted (as in -CH3, -NH-,
etc.).
6. Oxygen atoms (exclusive of those in carbonyls).
7. Nitrogen atoms.
8. Sulfur atoms.
9. Other atoms (F, Cl, Br, Si, etc.).
The string of nine integers thus generated, arranged in the
above order, is the required structure code. By looking up
this code in the Formula Index Table one can find the narne
under which the polymer in question appears in the data
tables or, alternatively, by its absence, that no data has been
found for the polymer in question. The Formula Index
Table is arranged in ascending order of the structural code
in columns 2-10 with the assigned polymer name in
column 1. Note that some very long, complicated names
have been truncated. This should cause little difficulty in
the use of this table. Examples of the application of this
scheme are shown below.
Experience has shown that this scheme generates unique
codes for the vast majority of linear polymers capable of
crystallizing. Where two or more polymers do have the
same structural code, the choice of correct name is usually
obvious from the structure. Of course, certain classes of
polymers do tend to generate many members all having
a single code - for example, all of the condensation
poly(amides) having a given total number of methylene
groups and differing only in the proportioning of these
between the diol and diacid constituents. Again, no
ambiguities arise.
An advantage of this structural coding scheme is its
adaptability to electronic data processing equipment. The
logical step beyond this scheme could be a strict sequential
notation detailing each group and its position (similar to
the ACS-IUPAC Nomenclature Recommendation) in a
short-hand notation for conciseness and for computer
compatibility.
References page VI- 159
VI / 1 1 4 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Exampl es *
Structure
F
-CH2-CH-
J3
0
F F
1.0.0.7.4.0.0.0.2
-NH-(CH2)3-CO- 5.1.0.0.1.0.1.0.0 Poly(6-aminocaproic acid)
Poly(styrene)
Poly(p-fluorostyrene)
Poly(35difluorostyrene)
In the hrst example, there is one methylene, one phenylene,
one carbon atom not otherwise counted (in -CH=), and
two protons not otherwise counted (one in -CH= and one
in -ChHdH-). In the second example, the fluorine atom
replaces a proton from the substituted benzene ring - no
other change in code occurs. In the third example, the
tisubstituted benzene ring is removed from category 3 (-
C6H4-) and is placed in category 4 (carbon atoms not
otherwise counted) as 6 carbon atoms and in category 5
(protons) as 3 protons. In the last example, there are five
methylene groups, one carbonyl, no other carbons, one
proton (from -NH-), no uncounted oxygens, and one
nitrogen. The approximately 2700 entries in the Formula
Index Table were generated in a similar fashion.
Constitutional Base Unit
Poly- CH2 CO
C6H4
C H 0 N SX
0 0 0 0 0 0 0 0 0 0
Selenium 0 0 0 0 0 0 0 0 1
Silylene 0 0 0 0 0 0 0 0 1
Sulfur 0 0 0 0 0 0 0 1 0
Dichlorophosphazene 0 0 0 0 0 0 1 0 3
Thiazyl 0 0 0 0 0 0 1 1 0
Difluorophosphazene 0 0 0 0 0 1 0 0 3
Sulfur trioxide 0 0 0 0 0 3 0 1 0
Phosphazene 0 0 0 0 2 0 1 0 1
Germoxane 0 0 0 0 2 1 0 0 1
Siloxane 0 0 0 0 2 1 0 0 1
Stannyloxane 0 0 0 0 2 1 0 0 1
Difluoromethylene sulfide 0 0 0 1 0 0 0 1 2
Hydroxymethylene 0 0 0 1 2 1 0 0 0
Difluoroacetylene 0 0 0 2 0 0 0 0 2
Chlorotrifluoroethylene 0 0 0 2 0 0 0 0 4
Tetrafluoroetbylene 0 0 0 2 0 0 0 0 4
Tetrafluoroethylene oxide 0 0 0 2 0 1 0 0 4
Trifluoroethylene 0 0 0 2 1 0 0 0 3
2,2,2-Trichloroacetaldehyde 0 0 0 2 1 1 0 0 3
Acetylene 0 0 0 2 2 0 0 0 0
2,2-Dichloroacetaldehyde 0 0 0 2 2 1 0 0 2
Ethylidene 0 0 0 2 4 0 0 0 0
Acetaldehyde 0 0 0 2 4 1 0 0 0
Dimethylsilylene 0 0 0 2 6 0 0 0 1
Dimethylphosphazene 0 0 0 2 6 0 1 0 1
Dimethylsiloxane 0 0 0 2 6 1 0 0 1
Oxybisdimethylsilylene 0 0 0 2 6 1 0 0 2
* Periods (.) are used to delineate the structural code integers generated.
Appendi x: Formul a I ndex to the Tabl es VI / 115
Constitutional Base Unit
Poly- CHz
C O CSH4 C H 0 N SX
Tetrafluoroallene 0 0 0 3 0 0 0 0 4
Hexafluoropropene 0 0 0 3 0 0 0 0 6
lsopropylidene sulfide 0 0 0 3 6 0 0 1 0
Isopropylidene oxide 0 0 0 3 6 1 0 0 0
2-Methylvinylalcohol 0 0 0 3 6 1 0 0 0
1,3-Butadiyne, 1,4- 0 0 0 4 2 0 0 0 0
2,5-Thiophene 0 0 0 4 2 0 0 1 0
2-Butene sulfide 0 0 0 4 8 0 0 1 0
2-Butene oxide 0 0 0 4 8 1 0 0 0
Isobutyraldehyde 0 0 0 4 8 1 0 0 0
1-Methoxy-2-methylethylene 0 0 0 4 8 1 0 0 0
3-Methyl-2,Sthiophene 0 0 0 5 4 0 0 1 0
2-Methyl-2-butene oxide 0 0 0 5 1 0 1 0 0 0
2,4-Hexadiyne, 2,5- 0 0 0 6 6 0 0 0 0
2,4-Hexadiene, 2,5- 0 0 0 6 10 0 0 0 0
I-Isopropoxy-2-methyethylene 0 0 0 6 1 2 1 0 0 0
Tetramethylethylene oxide 0 0 0 6 1 2 1 0 0 0
2,6-Benzothiazole 0 0 0 I 3 0 1 1 0
2,5-Benzoxazole 0 0 0 7 3 1 1 0 0
2-Methyl-p-phenylene sulfide 0 0 0 7 6 0 0 1 0
I-terr-Butoxy-2-methylethylene 0 0 0 7 1 4 1 0 0 0
Tetrafluoro-p-xylylene 0 0 0 8 4 0 0 0 4
2,2-Bithiophene 0 0 0 8 4 0 0 2 0
2,6-Dimethyl- 1,4-phenylene oxide 0 0 0 8 8 1 0 0 0
2,6-Dimethoxy- 1 ,Cphenylene oxide 0 0 0 8 8 3 0 0 0
2,5-Dimethyl-2,4-hexadiene, 2,5- 0 0 0 8 1 4 0 0 0 0
2,6-Quinoline 0 0 0 9 5 0 1 0 0
Terthiophene 0 0 0 1 2 6 0 0 3 0
Bis(2,4-dichlorophenoxy)phosphazene 0 0 0 1 2 6 2 1 0 5
3,3-Dimethoxy-4,4-biphenylene carbodiimine 0 0 0 1 5 1 2 0 2 0 0
Bis(3,4-dimethylphenoxy)phosphazene 0 0 0 1 6 1 8 2 1 0 1
4,4-Perfluorodiphenyleneoxypertluoropentamethylene oxide 0 0 0 1 7 0 2 0 0 8
Bis-B-naphthoxyphosphazene 0 0 0 20 1 4 2 1 0 1
m-Phenylene 0 0 1 0 0 0 0 0 0
p-Phenylene 0 0 1 0 0 0 0 0 0
p-Phenylene sulfide 0 0 1 0 0 0 0 1 0
p-Phenylene oxide 0 0 1 0 0 1 0 0 0
p-Phenylene sulfonate 0 0 1 0 0 3 0 1 0
Phenylenedisiloxanylene 0 0 1 0 4 1 0 0 2
p-Phenylene- 1,3 $oxadiazole 0 0 1 2 0 1 2 0 0
p-Phenylenevinylene 0 0 1 2 2 0 0 0 0
8-Nitrostyrene 0 0 1 2 3 2 1 0 0
Ethylidene p-phenylene 0 0 1 2 4 0 0 0 0
cc-Methylmethylene-p-phenylene 0 0 1 2 4 0 0 0 0
a-Phenylethylisocyanide 0 0 1 3 5 0 1 0 0
p-Phenylene tetramethyldisiloxanylene 0 0 1 4 1 2 1 0 0 2
m-Phenyleneoxy-2-cyano-1,3-phenylene oxide 0 0 1 7 3 2 1 0 0
p-Phenylenebenzobisthiazole 0 0 1 8 2 0 2 2 0
p-Phenylenebenzobisoxazole 0 0 1 8 2 2 2 0 0
4-Phenyl-2,6-quinoline 0 0 1 9 5 0 1 0 0
( p-Phenylenedipyridyl)cyclobutylene 0 0 1 1 4 1 2 0 2 0 0
6,6-Oxydiquinolene-p-phenylene 0 0 1 1 8 1 0 1 2 0 0
4,4-Biphenylenegermylene 0 0 2 0 0 0 0 0 1
4,4-Thiodiphenylene oxide 0 0 2 0 0 1 0 1 0
Bis(m-bromophenoxy)phosphazene 0 0 2 0 0 2 1 0 3
Bis(p-bromophenoxy)phosphazene 0 0 2 0 0 2 1 0 3
Bis(m-chlorophenoxy)phosphazene 0 0 2 0 0 2 1 0 3
Bis@-chlorophenoxy)phosphazene 0 0 2 0 0 2 1 0 3
Bis(m-fluorophenoxy)phosphazene 0 0 2 0 0 2 1 0 3
Bis(p-fluorophenoxy)phosphazene 0 0 2 0 0 2 1 0 3
p-Phenylene amine, emeraldine base 0 0 2 0 1 0 2 0 0
Diphenylsilylene 0 0 2 0 2 0 0 0 1
Diphenylphosphazene 0 0 2 0 2 0 1 0 1
Diphenylsiloxane 0 0 2 0 2 1 0 0 1
Bisphenoxyphosphazene 0 0 2 0 2 2 1 0 1
References page VI-159
VI / 116 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHz c o C6H4 C H 0 N s x
4,4-Biphenylene carbodiimine 0 0 2 1 0 0 2 0 0
Diphenylmethylene 0 0 2 1 2 0 0 0 0
Phenyl-p-toluylsiloxane 0 0 2 1 4 1 0 0 1
Bis(m-trifluoromethylphenoxy)phosphazene 0 0 2 2 0 2 1 0 I
Bis(p-methylphenoxy)phosphazene 0 0 2 2 6 2 1 0 1
Bis(p-methoxyphenoxy)phosphazene 0 0 2 2 6 4 1 0 1
Hexafluorotrimethylenebiphenylene 0 0 2 3 0 0 0 0 6
Di-p-tolylmethylene 0 0 2 3 6 0 0 0 0
2,6-Diphenyl- 1,4-phenylene oxide 0 0 2 6 4 1 0 0 0
Bis(p-isopropylphenoxy)phosphazene 0 0 2 6 1 4 2 1 0 1
2,5-Pyrazine-2,4-diphenylcyclobutylene 0 0 2 8 8 0 2 0 0
1,6-Diazanthrylene-4,4-biphenylene 0 0 2 1 2 6 0 2 0 0
1,9-Diazanthrylene-4,4 -biphenylene 0 0 2 1 2 6 0 2 0 0
l,6-Diazanthrylene-4,4 -oxydiphenylene 0 0 2 1 2 6 1 2 0 0
1,9-Diazanthrylene-4,4-oxydiphenylene 0 0 2 1 2 6 1 2 0 0
6,6-Oxydiquinoline-4,4-biphenylene 0 0 2 1 8 1 0 1 2 0 0
6,6-Oxydiquinoline-4,4-oxydiphenylene 0 0 2 1 8 1 0 2 2 0 0
4,4-Isopropylidenediphenylene dithionisophthalate 0 0 3 5 6 2 0 2 0
2,2-Biphenylenedithiazole-p-phenylene 0 0 3 6 2 0 2 2 0
m-Phenylenedithiazole-oxy-p-diphenylene 0 0 3 6 2 1 2 2 0
4,4-Diphenyl-2,2-(6,6-oxydiquinolene)-p-phenylene 0 0 3 1 8 1 0 1 2 0 0
Bis(p-phenylphenoxy)phosphazene 0 0 4 0 2 2 1 0 1
2,2-Biphenylenedithiazole-oxy-p-diphenylene 0 0 4 6 2 1 2 2 0
Phthalocyaninatogermoxane 0 0 4 8 0 1 8 0 1
Phthalocyaninatosiloxane 0 0 4 8 0 1 8 0 1
Phthalocyaninatostannyloxane 0 0 4 8 0 1 8 0 1
4,6-Diphenyl-2,8-(1,9-diazanthrylene)-4,4-biphenylene 0 0 4 1 2 6 0 2 0 0
4,9-Diphenyl-2,7-(1,6-diazanthrylene)-4,4-biphenylene 0 0 4 1 2 6 0 2 0 0
4,6-Diphenyl-2,8-( 1,9-diazanthrylene)-4,4-oxydiphenylene 0 0 4 1 2 6 1 2 0 0
4,9-Diphenyl-2,7-(1,6-diazanthrylene)-4,4-oxydiphenylene 0 0 4 1 2 6 1 2 0 0
2,2-Biphenylene 6,6-bis(4-phenylquinoline) 0 0 4 1 8 1 0 0 2 0 0
4,4-Diphenyl-2,2-(6,6-oxydiquinoline)-4,4-biphenylene 0 0 4 1 8 1 0 1 2 0 0
4,4-Oxydiphenylene-4,4-diquinoline-4,4-biphenylene 0 0 4 1 8 1 0 1 2 0 0
4,4-Diphenyl-2,2-(6,6-oxydiquinoline)-4,4-oxydiphenylene 0 0 4 1 8 1 0 2 2 0 0
Tetraphenyl-2,2-(6,6-oxydiquinolene)-p-phenylene 0 0 5 1 8 1 0 1 2 0 0
Pentaphenyl-p-toluyltrisiloxane 0 0 6 1 8 3 0 0 3
3,3-Diphenyl-2,2-(4,4-oxydiphenylene-4,4-diquinoline)-biphenylene 0 0 6 1 8 1 0 1 2 0 0
Tetraphenyl-2,2-(6,6-oxydiquinoline)-4,4-biphenylene 0 0 6 1 8 1 0 1 2 0 0
Te~aphenyl-2,2-(6,6-oxydiquinoline)-4,4-oxydiphenylene 0 0 6 1 8 1 0 2 2 0 0
Aminoformic acid 0 1 0 0 1 0 1 0 0
2-Mercapto-2-methylacetic acid 0 1 0 2 4 0 0 1 0
2-Hydroxypropionic acid (lactic acid) 0 1 0 2 4 1 0 0 0
Alanine 0 1 0 2 5 0 1 0 0
3-Amino-2-butenoic acid 0 1 0 3 5 0 1 0 0
Dimethyl ketene (ketone) I. 0 1 0 3 6 0 0 0 0
Dimethyl-2-hydroxyacetic acid 0 1 0 3 6 1 0 0 0
2-Aminoisobutyric acid 0 1 0 3 7 0 1 0 0
Isopropylhydroxyacetic acid 0 1 0 4 8 1 0 0 0
2,3-Dimethyl-3-aminopropionic acid 0 1 0 4 9 0 1 0 0
Valine 0 1 0 4 9 0 1 0 0
2,cHexadienoic acid, 2,5- 0 1 0 5 8 1 0 0 0
a-L-Guluronic acid, 1,4- 0 1 0 5 8 5 0 0 0
j3-D-Mannuronic acid, 1,4- 0 1 0 5 8 5 0 0 0
Methyl-2,4-hexadienoate, 2,5- 0 1 0 6 1 0 1 0 0 0
4-Methyl-1,3-phenyleneurea 0 1 0 7 8 0 2 0 0
Dimethyl ketene (ester) II. 0 1 0 7 1 2 1 0 0 0
Furfural-a&-dimethylketene 0 1 0 8 1 0 2 0 0 0
Isopropyl-2,4-hexadienoate, 2,5- 0 1 0 8 1 4 1 0 0 0
Tetramethylcyclobutylene carbonate 0 1 0 8 1 4 2 0 0 0
5-Bromo-6-hydroxy-2-naphthoic acid 0 1 0 1 0 5 1 0 0 1
2,6-Hydroxynaphthoic acid 0 1 0 1 0 6 1 0 0 0
Di-tert-butyl-4-hydroxybenzoic acid 0 1 0 1 4 20 1 0 0 0
4,4-Isopropylidene-3,3,5,5-tetrabromodiphenylene carbonate 0 1 0 1 5 1 0 2 0 0 4
4,4-Isopropylidene-3,3,5,5-tetrachlorodiphenylene carbonate 0 1 0 1 5 1 0 2 0 0 4
4,4-Isopropylidene-3,3-dichlorodiphenylene carbonate 0 1 0 1 5 1 2 2 0 0 2
Appendix: Formula Index to the Tables VI / 117
Constitutional Base Unit
Poly-
CH2
C O C&H, C II 0 N s x
4,4-Isopropylidene-3,3-dimethyldiphenylene carbonate 0 1 0 1 7 1 8 2 0 0 0
4,4-Cyclohexylidene-3,3,5,5-tetrachlorodiphenylene carbonate 0 1 0 1 8 9 2 0 0 4
4,4-Isopropylidene-3,3-diisopropyldiphenylene carbonate 0 1 0 2 1 26 2 0 0 0
m-Hydroxybenzoic acid 0 1 1 0 0 1 0 0 0
p-Hydroxybenzoic acid 0 1 1 0 0 1 0 0 0
m-Aminobenzoic acid 0 1 1 0 1 0 1 0 0
p-Aminobenzoic acid 0 1 1 0 1 0 1 0 0
N-Phenylaminoformic acid 0 1 1 0 1 0 1 0 0
m-Phenylene urea 0 1 1 0 2 0 2 0 0
3-Cp-Hydroxyphenylene)-propenoic acid 0 1 1 2 2 1 0 0 0
5-Phenyl-2,4-pentadienoic acid, 2,5- 0 1 1 4 6 1 0 0 0
p-Chlorobenzaldehyde-alt-dimethylketene 0 1 1 4 7 1 0 0 1
m-Nitrobenzaldehyde-alt-dimethylketene 0 1 1 4 7 3 1 0 0
Benzaldehyde-alt-dimethylketene 0 1 1 4 8 1 0 0 0
2,5-Methyl-5-phenyl-2,4-pentadienoate 0 1 1 5 8 1 0 0 0
p-Methoxybenzaldehyde-co-dimethylketene 0 1 1 5 1 0 2 0 0 0
3-Bromo-4,4-hydroxybibenzoic acid 0 1 1 6 3 1 0 0 1
4,4-Hydroxybibenzoic acid 0 1 2 0 0 1 0 0 0
4,4-Oxydiphenylene ketone 0 1 2 0 0 1 0 0 0
4,4-Thiodiphenylene carbonate 0 1 2 0 0 2 0 1 0
4,4-Oxydiphenylene carbonate 0 1 2 0 0 3 0 0 0
4,4-Sulfinyldiphenylene carbonate 0 1 2 0 0 3 0 1 0
4,4-Sulfonyldiphenylene carbonate 0 1 2 0 0 4 0 1 0
4,4-Ethylidenediphenylene carbonate 0 1 2 2 4 2 0 0 0
4,4-Isopropylidenediphenylene carbonate 0 1 2 3 6 2 0 0 0
4,4-Isobutylidenediphenylene carbonate 0 1 2 4 8 2 0 0 0
4,4-(Methyl-p-phenylenedioxy)-diphenylene ketone 0 1 2 7 6 2 0 0 0
4,4-(2,4-Dimethyl-3,3-pentylidene)diphenylene carbonate 0 1 2 7 1 4 2 0 0 0
@-Phenylenedioxy)diphenylene ketone 0 1 3 0 0 2 0 0 0
@-Phenylenedioxy)diphenylene carbonate 0 1 3 0 0 4 0 0 0
4,4-(Phenylmetbylene)diphenylene carbonate 0 1 3 1 2 2 0 0 0
4,4-Phenylethylidenediphenylene carbonate 0 1 3 2 4 2 0 0 0
4,4-Biphenylenedioxy 4,4-phenylene ketone 0 1 4 0 0 2 0 0 0
4,4-Biphenylenedioxy-diphenylene carbonate 0 1 4 0 0 4 0 0 0
4,4-(Diphenylmethylenekliphenylene carbonate 0 1 4 1 2 2 0 0 0
2,4-Hexadienedioic acid, 2,5- 0 2 0 4 6 2 0 0 0
Alanylvaline 0 2 0 6 1 4 0 2 0 0
2,5-Diisopropyl-2,4-hexadienedioate 0 2 0 1 0 1 8 2 0 0 0
2-Fluoro-p-phenylene 2-fluoroterephthalamide 0 2 0 1 2 8 0 2 0 2
2,6-Naphthalene-2,4cyclobutylenedicarboxylic acid 0 2 0 1 4 1 2 2 0 0 0
2,6-Naphthalene-2,4-bisdichlorophenylcyclobutylenedic~~xylate 0 2 0 26 1 6 2 0 0 4
Isophthalic anhydride 0 2 1 0 0 1 0 0 0
Terephthalic anhydride 0 2 1 0 0 1 0 0 0
p-Xylylene oxalate 0 2 1 0 0 2 0 0 0
p-Phenylene m-carboranedicarboxylate 0 2 1 2 10 2 0 0 1 0
p-Phenylene 2,5-thiopheneamide 0 2 1 4 4 0 2 1 0
2,5Pyrimidine terephthalamide 0 2 1 4 4 0 4 0 0
p-Phenylene cyclobutylenedicarboxylic acid 0 2 1 4 6 2 0 0 0
p-Phenylene cyclobutylenedicarboxamide 0 2 1 4 8 0 2 0 0
Chloro-p-phenylene Terephthalate 0 2 1 6 3 2 0 0 1
p-Phenylene dimethylcyclobutylenedicarboxylate 0 2 1 6 10 2 0 0 0
4-Methyl-m-phenylene terephthalamide 0 2 1 7 8 0 2 0 0
p-Phenylene dicyanodimethylcyclobutylenedicarboxylate 0 2 1 8 8 2 2 0 0
fert-butyl-p-phenylene terephthalate 0 2 1 1 0 1 2 2 0 0 0
p-Phenylene diisopropylcyclobutylenedicarboxylate 0 2 1 1 0 1 8 2 0 0 0
p-Phenylene dicyanodiisopropylcyclobutylenedicarboxylate 0 2 1 1 2 1 6 2 2 0 0
3,3-Dimethyl-4,4-biphenylene terephtbalamide 0 2 1 1 4 1 4 0 2 0 0
2-Isopropyl-2-methyl-4,4-oxydiphenylene m-phenylenediketone 0 2 1 1 6 1 6 1 0 0 0
2-Isopropyl-2-methyl-4,4-oxydiphenylene p-phenylenediketone 0 2 1 1 6 1 6 1 0 0 0
1,5-Naphthalene-4,4-(dimethoxy)dibenzylidenimino isophthalate 0 2 1 26 20 4 2 0 0
1,5-Naphthalene-4,4-(dimethoxy)dibenzylidenimino terephthalate 0 2 1 26 20 4 2 0 0
4,4-Oxydibenzoic anhydride 0 2 2 0 0 2 0 0 0
m-Phenylene terephtbalate 0 2 2 0 0 2 0 0 0
m-Phenylene isophthalate 0 2 2 0 0 2 0 0 0
p-Phenylene isophthalate 0 2 2 0 0 2 0 0 0
References page VI- 159
VI / 118 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CH2 c o CsH4 C H 0 N s x
m-Phenylene terephthalate 0 2 2 0 0 2 0 0 0
p-Phenylene terephthalate 0 2 2 0 0 2 0 0 0
m-Phenylene isophthalamide 0 2 2 0 2 0 2 0 0
p-Phenylene isophthalamide 0 2 2 0 2 0 2 0 0
p-Phenylene phthalamide 0 2 2 0 2 0 2 0 0
m-Phenylene terephthalamide 0 2 2 0 2 0 2 0 0
p-Phenylene terephthalamide 0 2 2 0 2 0 2 0 0
lsophthaloyl (dithionisophthaloyl)dihydrazide 0 2 2 2 4 0 4 2 0
Terephthaloyl dithionisophthaloyldihydrazide 0 2 2 2 4 0 4 2 0
4,4-lsopropylidenedibenzoic anhydride 0 2 2 3 6 1 0 0 0
p-Phenylene phenylthioterephthalate 0 2 2 6 4 0 0 2 0
Phenyl-p-phenylene terephthalate 0 2 2 6 4 2 0 0 0
4,4-lsopropylidenediphenylene 3-methylcyclopropylenedicarboxylate 0 2 2 7 1 2 2 0 0 0
4-Methyl-1,3-phenylene 3,3-methylphosphinylidenedibenzamide 0 2 2 8 11 1 2 0 1
4-Methyl-1,3-phenylene 4,4-methylphosphinylidenedibenzamide 0 2 2 8 11 1 2 0 1
2,6-Diisopropyl-4,4-oxydiphenylene m-phenylenediketone 0 2 2 1 2 1 6 1 0 0 0
p-Phenylene-4,4-(dimethoxy)dibenzylidenimino isophthalate 0 2 2 1 6 1 4 4 2 0 0
4,4-Biphenylene dithiolisophthalate 0 2 3 0 0 0 0 2 0
4,4-Biphenylene dithiolterephthalate 0 2 3 0 0 0 0 2 0
4,4-Oxydiphenylene m-phenyl ene diketone 0 2 3 0 0 1 0 0 0
4,4-Oxydiphenylene m-phenylene ketone 0 2 3 0 0 1 0 0 0
4,4-Oxydiphenylene p-phenylene diketone 0 2 3 0 0 1 0 0 0
4,4-Biphenylene terephthalate 0 2 3 0 0 2 0 0 0
(p-Phenylenedioxy)diphenylene diketone 0 2 3 0 0 2 0 0 0
4,4-Biphenylene terephthalamide 0 2 3 0 2 0 2 0 0
4,4-Sulfonyldiphenylene terephthalamide 0 2 3 0 2 2 1 1 0
m-Phenylene 3,3-phosphinylidenedibenzamide 0 2 3 0 3 1 2 0 1
o-Phenylene 3,3-phosphinylidenedibenzamide 0 2 3 0 3 1 2 0 1
p-Phenylene 3,3-phosphinylidenedibenzamide 0 2 3 0 3 1 2 0 1
m-Phenylene 4,4-phosphinylidenedibenzamide 0 2 3 0 3 1 2 0 1
o-Phenylene 4,4-phosphinylidenedibenzamide 0 2 3 0 3 1 2 0 1
p-Phenylene 4,4-phosphinylidenedibenzamide 0 2 3 0 3 1 2 0 1
m-Phenylene 3,3-(methylphosphinylidene)dibenzamide 0 2 3 I 5 1 2 0 1
o-Phenylene 3,3-(methylphosphinylidene)dibenzamide 0 2 3 1 5 1 2 0 1
p-Phenylene 3,3-(methylphosphinylidene)dibenzamide 0 2 3 1 5 1 2 0 1
m-Phenylene 4,4-(methylphosphinylidene)dibenzamide 0 2 3 1 5 1 2 0 1
a-Phenylene 4,4-(methylphosphinylidene)dibenzamide 0 2 3 1 5 1 2 0 1
p-Phenylene 4,4-(methylphosphinylidene)dibenzamide 0 2 3 1 5 1 2 0 1
4,4-lsopropylidenediphenylene isophthalamide 0 2 3 3 8 0 2 0 0
p-Phenylene diphenylcyclobutylenedicarboxylate 0 2 3 4 6 2 0 0 0
4-Methyl- 1,3-phenylene 4,4 -phenylphosphinylidenedibenzamide 0 2 3 7 9 1 2 0 1
1,5-Naphthalene-4,4-dibenzylidenimino isophthalate 0 2 3 1 2 8 2 2 0 0
1,5-Naphthalene-4,4-dibenzylidenimino terephthalate 0 2 3 1 2 8 2 2 0 0
4,4-Oxydiphenylene-4,4-(dimethoxy)dibenzylidenimino isophthalate 0 2 3 1 6 1 4 5 2 0 0
4,4-Oxydiphenylene 4,4-biphenylene diketone 0 2 4 0 0 1 0 0 0
4,4-Biphenylene 4,4-biphenylenedicarboxylate 0 2 4 0 0 2 0 0 0
(4,4-Phenylenedioxy)diphenylene m-phenyl ene diketone 0 2 4 0 0 2 0 0 0
(4,4-Phenylenedioxy)diphenylene p-phenylene diketone 0 2 4 0 0 2 0 0 0
m-Phenylene 4,4-(phenylphosphinylidene)dibenzamide 0 2 4 0 3 1 2 0 1
o-Phenylene 4,4-(phenylphosphinylidene)dibenzamide 0 2 4 0 3 1 2 0 1
p-Phenylene 4,4-(phenylphosphinylidene)dibenzamide 0 2 4 0 3 1 2 0 1
p-Phenylene-4,4-dibenzylidenimino isophthalate 0 2 4 2 2 2 2 0 0
4,4-Biphenylenedioxy-diphenylene m-phenyl ene diketone 0 2 5 0 0 2 0 0 0
(p-Phenylenedioxy)diphenylene oxydiphenylenediketone 0 2 5 0 0 3 0 0 0
4,4-Oxydiphenylene-4,4-dibenzylidenimino isophthalate 0 2 5 2 2 3 2 0 0
3,8-Phenanthridinonediyl terephthalamide 0 3 1 1 2 9 0 3 0 0
3,4-Carbonyldiphenylene terephthalate 0 3 3 0 0 2 0 0 0
4,4-Benzanilidylene terephthalamide 0 3 3 0 3 0 3 0 0
4,4-(Carbonyldiphenylenedioxy)-diphenylene-~-phenylene diketone 0 3 5 0 0 2 0 0 0
Alanylalanylalanylvaline 0 4 0 1 0 24 0 4 0 0
Alanylalanylvalylvaline 0 4 0 1 2 28 0 4 0 0
3,3-Bis(trifluoromethyl)biphenylene 3,3,4,4-biphenylenetetracarboximide 0 4 0 26 1 2 0 2 0 6
3,3-Dimethyl-4,4-biphenylene 3,3,4,4-biphenylenetetracarboximide 0 4 0 26 1 8 0 2 0 0
m-Phenylene pyromellitimide 0 4 1 6 2 0 2 0 0
p-Phenylene pyromellitimide 0 4 1 6 2 0 2 0 0
Appendi x: Formul a I ndex to the Tabl es VI / 119
Constitutional Base Unit
Poly-
CHz C O CsH4 C H 0 N SX
p-Phenylene 1,4-pyromellitamide
p-Phenylene 3,3,4,4-oxydiphenylenetetracarboximide
p-Phenylene 4,4-oxy(3,3-dicarboxy)dibenzamide
4,4-Biphenylene pyromellitimide
4,4-Thiodiphenylene pyromellitimide
3,4-Oxydiphenylene pyromellitimide
4,4-Oxydiphenylene pyromellitimide
4,4-Biphenylene 1,4-pyromellitimide
4,4-Oxydiphenylene 1 ,Cpyromellitimide
4,4-Biphenylene 3,3 ,4,4-biphenylenetetracarboximide
4,4-Biphenylene 3,3,4,4-oxydiphenylenetetracarboximide
3,4-Oxydiphenylene 3,3,4,4-biphenylenetetracarboximide
4,4-Oxydiphenylene 3,3,4,4-oxydiphenylenetetracarboximide
4,4-Biphenylene 4,4-oxy(3,3-dicarboxy)dibenzamide
4,4-Benzobisthiazole-diphenylene pyromellitimide
p-Terphenylene pyromellitimide
(m-Phenylenedioxy)diphenylene pyromellitimide
@-Phenylenedioxy)diphenylene pyromellitimide
(m-Phenylenedioxy)diphenylene 1 ,Cpyromellitamide
@-Phenylenedioxy)diphenylene 1,Cpyromellitamide
p-Phenylene thiodiphenylenedioxy-diphenylenetetracarboximide
@-Phenylenedioxy)diphenylene oxydiphenylenetetracarboximide
@-Phenylenedioxy)diphenylene 4,4-oxy(3,3-dicarboxy)dibenzamide
p-Phenylene 4,4-dibenzoxyterephthalate
m-Phenylene-3,3-dibenzamido isophthalamide
p-Phenylene-3,3 -dibenzamido isophthalamide
m-Phenylene-4,4-dibenzamido isophthalamide
p-Phenylene-4,4-dibenzamido isophthalamide
m-Phenylene-3,3-dibenzamido terephthalamide
p-Phenylene-3,3-dibenzamido terephthalamide
m-Phenylene-4,4-dibenzamido terephthalamide
p-Phenylene-4,4-dibenzamido terephthalamide
4,4-Biphenylenedioxy-3,3-diphenylene pyromellitimide
(0xydiphenylenedioxy)diphenylene pyromellitimide
4,4-Biphenylene thiodiphenylenedioxydiphenylenetetracarboximide
(p-Phenylenedioxy)diphenylene p-phenylenedioxydiphenylenetetracarboximide
(p-Phenylenedioxy)diphenylenedioxydiphenylene pyromellitimide
4,4-Carbonyldiphenylene pyromellitimide
4,4-Biphenylene 3,3,4,4-carbonyldiphenylenetetracarboximide
4,4-Biphenylene 4,4-carbonyl(3,3-dicarboxy)dibenzamide
4,4-(1sophthaloyldiamino)diphenylene pyromellitimide
4,4-(Terephthaloyldiamino)diphenylene pyromellitimide
4,4-Thiodiphenylene p-phenyleneditrimellitatediimide
4,4-Oxydiphenylene p-phenyleneditrimellitatediimide
4,4-(1sophthaloyldiamino)diphenylene oxydiphenylenetetracarboximide
4,4-Oxydiphenylene 5,5-(p-phenylene)ditrimellitatediamide
Isophthalic 2,2-(isophthaloyldiamino)dibenzoic anhydride
Isophthalic 2,2-(terephthaloyldiamino)dibenzoic anhydride
2,2-(1sophthaloyldiamino)dibenzoic terephthalic anhydride
Terephthalic 2,2-(terephthaloyldiamino)dibenzoic anhydride
Terephthaloyldihydrazodi (p-aminobenzoyl) terephthalamide
(p-Phenylenedioxy)diphenylene p-phenyleneditrimellitatediimide
(0xydiphenylenedioxy)diphenylene p-phenyleneditrimellitatediimide
(p-Phenylenedioxy)diphenylenedioxydiphenylene p-phenyleneditrimellitamide
Isophthaloyldiphenylenedioxdiphenylene carbonyldiphenylenetetracarboximide
4,4-(1sophthaloyldiamino)diphenylene p-phenyleneditrimellitatediimide
4,4-(Terephthaloyldiamino)diphenylene p-phenyleneditrimellitate
1
Methylene
Methylene selenide
Methylene sulfide
Methylene disulfide
Oxymethylene
Vinylidene bromide
Vinylidene chloride
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4 1 6 6 2 2 0 0
4 1 1 2 6 1 2 0 0
4 1 1 2 10 3 2 0 0
4 2 6 2 0 2 0 0
4 2 6 2 0 2 1 0
4 2 6 2 1 2 0 0
4 2 6 2 1 2 0 0
4 2 6 6 2 2 0 0
4 2 6 6 3 2 0 0
4 2 1 2 6 0 2 0 0
4 2 1 2 6 1 2 0 0
4 2 1 2 6 1 2 0 0
4 2 1 2 6 2 2 0 0
4 2 1 2 1 0 3 2 0 0
4 2 14 4 0 4 2 0
4 3 6 2 0 2 0 0
4 3 6 2 2 2 0 0
4 3 6 2 2 2 0 0
4 3 6 6 4 2 0 0
4 3 6 6 4 2 0 0
4 3 1 2 6 2 2 1 0
4 3 1 2 6 3 2 0 0
4 3 1 2 1 0 5 2 0 0
4 4 0 0 4 0 0 0
4 4 0 4 0 4 0 0
4 4 0 4 0 4 0 0
4 4 0 4 0 4 0 0
4 4 0 4 0 4 0 0
4 4 0 4 0 4 0 0
4 4 0 4 0 4 0 0
4 4 0 4 0 4 0 0
4 4 0 4 0 4 0 0
4 4 6 2 2 2 0 0
4 4 6 2 3 2 0 0
4 4 1 2 6 2 2 1 0
4 4 1 2 6 4 2 0 0
4 5 6 2 4 2 0 0
5 2 6 2 0 2 0 0
5 2 1 2 6 0 2 0 0
5 2 1 2 1 0 2 2 0 0
6 3 6 4 0 4 0 0
6 3 6 4 0 4 0 0
6 3 1 2 6 2 2 1 0
6 3 1 2 6 3 2 0 0
6 3 1 2 8 1 4 0 0
6 3 1 2 1 0 5 2 0 0
6 4 0 2 2 2 0 0
6 4 0 2 2 2 0 0
6 4 0 2 2 2 0 0
6 4 0 2 2 2 0 0
6 4 0 6 0 6 0 0
6 4 1 2 6 4 2 0 0
6 5 1 2 6 5 2 0 0
6 6 1 2 6 6 2 0 0
I 5 1 2 6 2 2 0 0
8 4 1 2 8 2 4 0 0
8 4 1 2 8 2 4 0 0
0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 1
0 0 0 0 0 0 1 0
0 0 0 0 0 0 2 0
0 0 0 0 1 0 0 0
0 0 1 0 0 0 0 2
0 0 1 0 0 0 0 2
References page VI- 159
VI / 120 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CH2 C O C4H4 C H 0 N s x
Vinylidene fluoride
Vinyl bromide
Vinyl chloride
Vinyl fluoride
2-Chloroacetaldehyde
Vinyl alcohol
Acrylonitrile
3,3,3-Trifluoropropylene oxide
Ethyl isocyanide
Propene
Propylidene
Propylene sulfide
Methyl vinyl ether
Propionaldehyde
Propylene oxide
Methacrylonitrile
Isobutene
Isobutylene sulfide
Isobutylene oxide
a-Methylvinylmethyl ether
I-Cyano-1,3-butadiene, 1,4-
3-Trifluoromethyl-1-butene
1,3-Pentadiene, 1,2-
1,3-Pentadiene, 1,4-
1-Methoxy-1,3-butadiene, 1,4-
fi-D-XylOSe, l,L%(xylan)
P-D-XylOSe, l,C(hardwood xylan)
3-Methyl-1-butene
Isopropylethylene sulfide
1-Ethoxy-2-methylethylene
Isopropylethylene oxide
Isopropylvinyl ether
Isovaleraldehyde
1-Ethoxy-2-methoxyethylene
8-o-Glucotrinitrate, 1,4-
8-D-Glucodinitrate, 1,4-
cc-Isopropylacrylonitrile
4-Methyl-1,3-pentadiene, 1,2-
2-Methyl- 1,3-pentadiene, 1,4-
3-Methyl- 1,3-pentadiene, 1,4-
a-D-Glucose, 1,3-
P-o-Glucose, 1,3- (curdlan)
cc-D-Glucose, 1,4- (amyl ose)
8-D-Glucose, 1,4- (cellulose)
a-o-Glucose, 1,6- (dextran)
a-o-Mannose, 1,3-
8-o-Mannose, 1,4-
1-Chloro-2-isobutoxyethylene
cc-D-Galactosamine, 1,4-
8-D-Clucosamine, 1,4- (chitosan)
3,3-Dimethyl-1-butene
tert-Butylethylene sulfide
tert-Butylethylene oxide
tert-Butylvinyl ether
2-Vinyl pyridine
5-Methyl-1,3-hexadiene, 1,4-
1-Isobutoxy-2-methylethylene
1,4-Tetradeuterobutadiene-alt-methacrylonitrile
Methylene 3,5-toluene
Methylene 2,6-diamino-3,5-toluene
p-Fluoro-o-methylstyrene
Methylene 2,5-dimethyl-p-phenylene
Tetramethylcyclobutyleneoxymethylene oxide
cr-D-Trimethylglucose, 1,4-
8-o-Trimethylglucose, 1,4-
1
1
1
1
1
1
1
1
1
1
1
1
0 0 1 0 0 0 0 2
0 0 1 1 0 0 0 1
0 0 1 1 0 0 0 1
0 0 1 1 0 0 0 1
0 0 1 1 1 0 0 1
0 0 1 2 1 0 0 0
0 0 2 1 0 1 0 0
0 0 2 1 1 0 0 3
0 0 2 3 0 1 0 0
0 0 2 4 0 0 0 0
0 0 2 4 0 0 0 0
0 0 2 4 0 0 1 0
0 0 2 4 1 0 0 0
0 0 2 4 1 0 0 0
0 0 2 4 1 0 0 0
0 0 3 3 0 1 0 0
0 0 3 6 0 0 0 0
0 0 3 6 0 0 1 0
0 0 3 6 1 0 0 0
0 0 3 6 1 0 0 0
0 0 4 3 0 1 0 0
0 0 4 5 0 0 0 3
0 0 4 6 0 0 0 0
0 0 4 56 0 0 0 0
0 0 4 56 1 0 0 0
0 0 4 6 4 0 0 0
0 0 4 6 4 0 0 0
0 0 4 8 0 0 0 0
0 0 4 8 0 0 1 0
0 0 4 8 1 0 0 0
0 0 4 8 1 0 0 0
0 0 4 8 1 0 0 0
0 0 4 8 1 0 0 0
0 0 4 8 2 0 0 0
0 0 5 5 1 3 0 0
0 0 5 6 9 2 0 0
0 0 5 7 0 1 0 0
0 0 5 8 0 0 0 0
0 0 5 8 0 0 0 0
0 0 5 8 0 0 0 0
0 0 5 8 5 0 0 0
0 0 5 8 5 0 0 0
0 0 5 8 5 0 0 0
0 0 5 8 5 0 0 0
0 0 5 8 5 0 0 0
0 0 5 8 5 0 0 0
0 0 5 8 5 0 0 0
0 0 5 9 1 0 0 1
0 0 5 9 4 1 0 0
0 0 5 9 4 1 0 0
0 0 5 1 0 0 0 0 0
0 0 5 1 0 0 0 1 0
0 0 5 1 0 1 0 0 0
0 0 5 10 1 0 0 0
0 0 6 5 0 1 0 0
0 0 6 1 0 0 0 0 0
0 0 6 1 2 1 0 0 0
0 0 I 5 0 1 0 4
0 0 I 6 0 0 0 0
0 0 I 8 0 2 0 0
0 0 8 7 0 0 0 1
0 0 8 8 0 0 0 0
0 0 8 14 2 0 0 0
0 0 8 1 4 5 0 0 0
0 0 8 1 4 5 0 0 0
C
P
i
2.
2 .
3.
3 .
1.
3.
Iv
m
P
m
O-
P
SI
SI
SI
Ct.
m
O-
P-
N
P-
3-
P-
t e
P-
St
4,
N.
N.
4,
u-
l-
2-
2-
Gl
Tl
At
Vi
A<
C!
Se
3-
Vi
3-
Vi
3- .
Mt
2-I
Vi
37
291
3-
1%
2,:
Mt
2,:
3,:
Hi
Hi
6-l
Vi
Isc
Isc
3-l
Appendix: Formula Index to the Tables VI / 121
Constitutional Base Unit
Poly-
CHz
C O CSH4 C H 0 N s x
P-D-Trimethylmannose, 1,4- 1 0 0 8 1 4 5 0 0 0
2,4-Dimethylstyrene 1 0 0 9 1 0 0 0 0 0
2.5Dimethylstyrene 1 0 0 9 1 0 0 0 0 0
3,CDimethylstyrene 1 0 0 9 1 0 0 0 0 0
3,5-Dimethylstyrene 1 0 0 9 1 0 0 0 0 0
l-Vinyl naphthalene 1 0 0 11 8 0 0 0 0
3-Viny1 pyrene 1 0 0 1 7 1 0 0 0 0 0
Methyl-alt-p-phenylene 1 0 1 0 0 0 0 0 0
m-Chlorostyrene 1 0 1 1 1 0 0 0 1
p-Chlorostyrene 1 0 1 1 1 0 0 0 1
m-Fluorostyrene 1 0 1 1 1 0 0 0 1
o-Fluorostyrene 1 0 1 1 1 0 0 0 1
p-Fluorostyrene 1 0 1 1 1 0 0 0 1
Styrene 1 0 1 1 2 0 0 0 0
Styrene oxide 1 0 1 1 2 1 0 0 0
Styrene sulfone 1 0 1 1 2 2 0 1 0
wMethylstyrene 1 0 1 2 4 0 0 0 0
m-Methylstyrene 1 0 1 2 4 0 0 0 0
o-Methylstyrene 1 0 1 2 4 0 0 0 0
p-Methylstyrene 1 0 1 2 4 0 0 0 0
N-Phenyl-2-imino-1,3-dithia-4-methylpentamethylene 1 0 1 3 5 0 1 2 0
p-Methyl-a-methylstyrene 1 0 1 3 6 0 0 0 0
3-Phenyl- 1 -butene 1 0 1 3 6 0 0 0 0
p-Trimethylsilylstyrene 1 0 1 4 1 0 0 0 0 1
tert-Butylstyrene 1 0 1 5 1 0 0 0 0 0
p-Isopropyl-cr-methylstyrene 1 0 1 5 1 0 0 0 0 0
Styryl pyridine-alt-vinyl pyridine 1 0 1 1 3 1 2 0 2 0 0
4,4-Methylenediphenylene oxide 1 0 2 0 0 1 0 0 0
N-Vinyl carbazole 1 0 2 1 1 0 1 0 0
N-Vinyl diphenylamine 1 0 2 1 3 0 1 0 0
4,4-Stilbenediyloxymethylene oxide 1 0 2 2 2 2 0 0 0
cl-methyl-4,4-stilbenediyloxymethylene oxide 1 0 2 3 4 2 0 0 0
I-N-Carbazoyl-1,3-pentadiynol 1 0 2 4 1 1 0 1 0 0
2-Mercaptoacetic acid 1 1 0 0 0 0 0 1 0
2-Hydroxyacetic acid (glycolic acid) 1 1 0 0 0 1 0 0 0
Glycine 1 1 0 0 1 0 1 0 0
Thiolacrylic acid 1 1 0 1 2 0 0 1 0
Acrylic acid 1 1 0 1 2 1 0 0 0
Vinyl formate 1 1 0 1 2 1 0 0 0
Acrylamide 1 1 0 1 3 0 1 0 0
Cysteine 1 1 0 1 3 0 1 1 0
Serine 1 1 0 1 3 1 1 0 0
3-Trichloromethyl-3-hydroxypropionic acid 1 1 0 2 1 1 0 0 3
Viny1 trifluoroacetate 1 1 0 2 1 1 0 0 3
3-Dichloromethyl-3-hydroxypropionic acid 1 1 0 2 2 1 0 0 2
Vinylmethyl ketone 1 1 0 2 4 0 0 0 0
3-Hydroxybutyric acid 1 1 0 2 4 1 0 0 0
Methacrylic acid 1 1 0 2 4 1 0 0 0
2-Methyl-3-hydroxypropionic acid 1 1 0 2 4 1 0 0 0
Vinyl acetate 1 1 0 2 4 1 0 0 0
3-Aminobutyric acid 1 1 0 2 5 0 1 0 0
2,4-Pentadienoic acid, 2,5- 1 1 0 3 4 1 0 0 0
3-Dichloroethyl-3-hydroxypropionic acid 1 1 0 3 4 1 0 0 2
Isopropenylmethyl ketone 1 1 0 3 6 0 0 0 0
2,2-Dimethyl-3-hydroxypropionic acid 1 1 0 3 6 1 0 0 0
Methylmethacrylate 1 1 0 3 6 1 0 0 0
2,2-Dimethyl-3-aminopropionic acid 1 1 0 3 7 0 1 0 0
3,3-Dimethyl-3-aminopropionic acid 1 1 0 3 7 0 1 0 0
Histidine 1 1 0 4 5 0 3 0 0
Histidine hydrochloride 1 1 0 4 6 0 3 0 1
6-Amino-2,4-hexadienoic acid, 2,5- 1 1 0 4 7 1 1 0 0
Vinyl isopropyl ketone 1 1 0 4 8 0 0 0 0
Isopropyl thiolacrylate 1 1 0 4 8 0 0 1 0
Isopropyl acrylate 1 1 0 4 8 1 0 0 0
3-Isopropyl-3-hydroxypropionic acid 1 1 0 4 8 1 0 0 0
References page VI- 159
VI / 122 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHz C O C6H4 C H 0 N s x
6-Amino-2,4-hexadienoic acid hydrochloride, 2,5- 1 1 0 4 8 1 1 0 1
Isoleucine 1 1 0 4 9 0 1 0 0
N-Isopropyl acrylamide 1 1 0 4 9 0 1 0 0
Leucine 1 1 0 4 9 0 1 0 0
Vinyl-ret?-butyl ketone 1 1 0 5 1 0 0 0 0 0
tert-Butyl acrylate 1 1 0 5 1 0 1 0 0 0
Ethyl-2,4-hexadienoate, 2,5- 1 1 0 6 1 0 1 0 0 0
N-P-D-Acetylglucosamine, 1,4- (chitin) 1 1 0 6 11 4 1 0 0
ter&Butylmethacrylate 1 1 0 6 1 2 1 0 0 0
2,3,4-trimethoxy-5-hydroxyvaleric acid 1 1 0 6 1 2 4 0 0 0
2,5-Dimethylterephthalaldehyde 1 1 0 8 8 1 0 0 0
Isobutyl-2,4-hexadienoate, 2,5- 1 1 0 8 1 4 1 0 0 0
B-D-Galactosamine-aZt-1,4-fi-o-glucuronic acid, 1,3- 1 1 0 1 0 1 7 9 1 0 0
@Clucosamine-aZr- 1 ,4-P-n-glucuronic acid, 1,3- 1 1 0 1 0 1 7 9 1 0 0
3,3-Dimethyl-4,4-methylenediphenylene carbonate 1 1 0 1 4 1 2 2 0 0 0
(p-Hydroxyphenylene)acetic acid 1 1 1 0 0 1 0 0 0
Isophthalaldehyde 1 1 1 0 0 1 0 0 0
Terephthalaldehyde 1 1 1 0 0 1 0 0 0
cc-Amino-p-toluic acid 1 1 1 0 1 0 1 0 0
p-Fl uorost yrene-&carbon monoxi de 1 1 1 1 1 0 0 0 1
Styrene-al&carbon monoxide 1 1 1 1 2 0 0 0 0
o-Hydroxystyrene-alt-carbon monoxide 1
1 1 1 2 1 0 0 0
Vinyl benzoate 1 1 1 1 2 1 0 0 0
Phenylalanine 1 1 1 1 3 0 1 0 0
Tyrosine 1 1 1 1 3 1 1 0 0
p-Trifluoroacetylstyrene 1 1 1 2 1 0 0 0 3
m-Methylstyrene-al&carbon monoxide 1 1 1 2 4 0 0 0 0
p-Met hyl st yrene-&carbon monoxi de 1 1 1 2 4 0 0 0 0
3-Mercapto-2-@-toluenesulfonamide)propionic acid 1 1 1 2 5 2 1 2 0
Vinyl-p-rert-butylbenzoate 1 1 1 5 1 0 1 0 0 0
4,4-Biphenyldicarboxaldehyde 1 1 2 0 0 1 0 0 0
4,4-Methylenediphenyl carbonate 1 1 2 0 0 2 0 0 0
4,4-Methylenediphenylene urea 1 1 2 0 2 0 2 0 0
4,4-Butylidenediphenylene carbonate 1 1 2 3 6 2 0 0 0
4,4-(Methyl-2,2-pentylidene)diphenylene carbonate 1 1 2 5 1 0 2 0 0 0
Aspartic acid 1 2 0 1 3 1 1 0 0
Propylene oxalate 1 2 0 2 4 2 0 0 0
O-Acetylserine 1 2 0 2 5 1 1 0 0
Alanylglycine 1 2 0 2 6 0 2 0 0
(3-Bromo-4-carboxyphenoxy)acetic anhydride 1 2 0 6 3 2 0 0 1
8-DXylodiacetate, 1,4- 1 2 0 6 1 0 4 0 0 0
N-P-D-Acetylgalactosamine-alt- 1 ,4-P-n-glucuronic acid, 1,3- 1 2 0 11 1 9 9 1 0 0
N-l%-Acetylglucosamine-alt- 1,4-fi-D-ghCurOniC acid, 1,3- 1 2 0 11 1 9 9 1 0 0
N-l3-n-Acetylgalactosamine-4-sulfate-alt- 1 ,4-P-o-glucuronic acid 1 2 0 11 1 9 1 2 1 1 0
~-~-D-Acetylgalactosamine-6-sulfate-uZ~-l,4-~-D-glUCUrOniC acid 1 2 0 11 1 9 1 2 1 1 0
3,3-Dimethyl-4,4-methylenediphenylene methyl-1,3-phenylenediurea 1 2 0 2 1 22 0 4 0 0
(m-Carboxyphenoxy)acetic anhydride 1 2 1 0 0 2 0 0 0
@-Carboxyphenoxy)acetic anhydride 1 2 1 0 0 2 0 0 0
p-Phenylene malonate 1 2 1 0 0 2 0 0 0
p-Carboxyphenylacrylate 1 2 1 1 2 2 0 0 0
m-Phenylene cyclopropylenedicarboxylate 1 2 1 2 2 2 0 0 0
p-Phenylene cyclopropylenedicarboxylate 1 2 1 2 2 2 0 0 0
Cyclopropylene isophthalamide 1 2 1 2 4 0 2 0 0
Methylethylene isophthalate 1 2 1 2 4 2 0 0 0
Methylethylene phthalate 1 2 1 2 4 2 0 0 0
Methylethylene terephthalate 1 2 1 2 4 2 0 0 0
3,3-Dimethyl-4,4-methylenediphenylene terephtbalamide 1 2 1 1 4 1 4 0 2 0 0
2-ethyl-2-Isopropyl-4,4-oxydiphenylene m-phenylenediketone 1 2 1 1 6 1 6 1 0 0 0
N,N-Dimetbyl-4,4-(dimethylmethylene)diphenylene terephthalamide 1 2 1 1 6 1 8 0 2 0 0
4,4-Methylenedibenzoic anhydride 1 2 2 0 0 1 0 0 0
4,4-(Methylenedioxy)dibenzoic anhydride 1 2 2 0 0 3 0 0 0
Methylethylene 2,2-dibenzoate 1 2 2 2 4 2 0 0 0
Methyletbylene 3,3 -dibenzoate 1 2 2 2 4 2 0 0 0
Methylethylene 4,4-dibenzoate 1 2 2 2 4 2 0 0 0
Propylene 4,4-sulfonyldibenzamide 1 2 2 2 6 2 2 1 0
C
P
4
P
4
4
4
4
4
hi
4.
A
P
cl
i
;:
P,
2:
2:
I s
4 ,
N
I s
Tl
4,
I s
4,
2
El
El
El
El
El
El
2-
El
A
2-
BI
Cl
Fl
l-
3-
3-
2,:
Cl
T e
Bi
2-
4,
2,:
2,:
3-t
1,:
1,:
1,:
Cl
2,!
BL
1,:
N-
2-l
1- l
B u
Et1
Appendix: Formula Index to the Tables VI / 123
Constitutional Base Unit
Poly- CH2 C O CSH4 C H 0 N s x
4,4-Isopropylidenediphenylene mal onat e 1 2 2 3 6 2 0 0 0
p-Phenylene( l,l-dimethyl)ethylene terephthalamide 1 2 2 3 8 0 2 0 0
4,4-Isopropylidenediphenylene cyclopropylenedicarboxylate 1 2 2 5 8 2 0 0 0
4,4-Isopropylidenediphenylene I-methylcyclopropylenedicarboxylate 1 2 2 6 1 0 2 0 0 0
4,4-Methylenediphenylene isophthalamide 1 2 3 0 2 0 2 0 0
4,4-Methylenediphenylene terephthalamide 1 2 3 0 2 0 2 0 0
4,4-Methylenediphenylene m-phenylenediurea 1 2 3 0 4 0 4 0 0
N,N-Dimethyl-4,4-methylenediphenylene terephthalamide 1 2 3 2 6 0 2 0 0
4,4-Isopropylidenediphenylene (methylenediphenylene)diurethane 1 2 4 3 8 2 2 0 0
Alanylalanylglycine 1 3 0 4 1 2 0 3 0 0
f!-D-Glucotriacetate, 1,3- 1 3 0 8 1 4 5 0 0 0
cx-o-Glucotriacetate, 1,4- 1 3 0 8 1 4 5 0 0 0
B-D-Glucotriacetate, 1,4- 1 3 0 8 1 4 5 0 0 0
B-D-Mannotriacetate, 1,4- 1 3 0 8 1 4 5 0 0 0
cr-o-Glucotriisobutyrate, 1,4- 1 3 0 1 4 26 5 0 0 0
3-Mercapto-2-phthalimidopropionic acid 1 3 1 1 1 0 1 1 0
8-o-Glucotricarbanilate, 1,4- 1 3 3 5 11 5 3 0 0
2,7-Fluorenylene pyromellitimide 1 4 0 1 8 8 0 2 0 0
2,7-Fluorenylene 1,4-pyromellitamide 1 4 0 1 8 1 2 2 2 0 0
Isophthalic 4,4-methylenedioxy-3,3-dimethoxydibenzoic anhydride 1 4 1 1 4 1 2 6 0 0 0
4,4-(Methylenedioxy)-3,3-dimethoxydibenzoic terephthalic anhydride 1 4 1 1 4 1 2 6 0 0 0
NJ-Methylenediterephthalamic anhydride 1 4 2 0 2 1 2 0 0
Isophthaloyl (m-carboxyphenoxyacetyl)dihydrazide 1 4 2 0 4 1 4 0 0
Terephthaloyl (m-carboxyphenoxyacetyl)dihydrazide 1 4 2 0 4 1 4 0 0
4,4-Methylenediphenylene pyromellitimide 1 4 2 6 2 0 2 0 0
Isophthalic 4,4-(methylenedioxy)dibenzoic anhydride 1 4 3 0 0 4 0 0 0
4,4-(Methylenedioxy)dibenzoic terephthalic anhydride 1 4 3 0 0 4 0 0 0
2 2 0 0 0 0 0 0 0 0
Ethylene 2 0 0 0 0 0 0 0 0
Ethylene sulfide 2 0 0 0 0 0 0 1 0
Ethylene disulfide 2 0 0 0 0 0 0 2 0
Ethylene tetrasulfide 2 0 0 0 0 0 0 4 0
Ethylene oxide 2 0 0 0 0 1 0 0 0
Ethylene amine 2 0 0 0 1 0 1 0 0
2-Aminoethylenesulfonic acid 2 0 0 0 1 2 1 1 0
Ethyleneamine-HCl complex 2 0 0 0 2 0 1 0 1
Allene 2 0 0 1 0 0 0 0 0
2-Imino-1,3-dithiapentamethylene 2 0 0 1 1 0 1 2 0
Bromomethylethylene oxide 2 0 0 1 1 1 0 0 1
Chloromethylethylene oxide (epichlorohydrin) 2 0 0 1 1 1 0 0 1
Fluoromethylethylene oxide 2 0 0 1 1 1 0 0 1
1-Hydroxytrimethylene 2 0 0 1 2 1 0 0 0
3-Hydroxyoxacyclobutane 2 0 0 1 2 2 0 0 0
3-Silylpropene 2 0 0 1 4 0 0 0 1
2,3-Dichloro-1,3-butadiene, 1,4- 2 0 0 2 0 0 0 0 2
Chlorotrifluoroethylene-&ethylene 2 0 0 2 0 0 0 0 4
Tetrafluoroethylene-&-ethylene 2 0 0 2 0 0 0 0 4
Bis(2,2,2-trifluoroethoxy)phosphazene 2 0 0 2 0 2 1 0 7
2-Chloro-1,3-butadiene, 1,4- (chloroprene) 2 0 0 2 1 0 0 0 1
4,4,4-Trifluoro-l-butene 2 0 0 2 1 0 0 0 3
2,5-Ethylene- 1,3,4-triazole 2 0 0 2 1 0 3 0 0
2,2,2-Trifluoroethylvinyl ether 2 0 0 2 1 1 0 0 3
3-Cyanopropionaldehyde 2 0 0 2 1 1 1 0 0
1,3-Butadiene, 1,2- 2 0 0 2 2 0 0 0 0
1,3-Butadiene, 1,4- 2 0 0 2 2 0 0 0 0
1,3-Cyclobutylene 2 0 0 2 2 0 0 0 0
Chlorinated 1,3-butadiene, 1,4- 2 0 0 2 2 0 0 0 2
2,5-Ethylene-1-amino-1,3,4-triazole 2 0 0 2 2 0 4 0 0
Butadiene oxide 2 0 0 2 2 1 0 0 0
1,2-Dichloromethylethylene oxide 2 0 0 2 2 1 0 0 2
N-Methyl-2-imino-1,3-dithiapentamethylene 2 0 0 2 3 0 1 2 0
2-Chloromethylpropylene oxide 2 0 0 2 3 1 0 0 1
I-Butene 2 0 0 2 4 0 0 0 0
Butyraldehyde 2 0 0 2 4 1 0 0 0
Ethylvinyl ether 2 0 0 2 4 1 0 0 0
References page VI-159
VI / 124 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly- CH2 c o CljH4 C H 0 N s x
Diethylsilylene 2
Ethylsilylethylene 2
Methyl-n-propylsilylene
2
Diethylsiloxane 2
2,2-Bistrifluoromethyloxacyclobutane 2
1-Cyano-1,3-cyclobutylene
2
3-Chloro-2-methyl-1,3-butadiene, 1,4- 2
a-Ethylacrylonitrile
2
2-Methyl-1,3-butadiene, 1,4- (isoprene)
2
3-Methyl-l-butene, 1,3- 2
3,3-Dimethyltrimethylene sulfide
2
3,3-Dimethyloxacyclobutane 2
3,3-Dimethyltrimethylene sulfone 2
Hexafluoroisobutylene-alt-vinylidene fluoride
2
Bis(2,2,3,3,3-pentafluoropropoxy)phosphazene
2
2,4-Hexadiyne-1,6-diol, 2,5- 2
Bis(2,2,3,3-tetrafluoropropoxy)phosphazene
2
1,3-Cyclohexadiene, 1,4- 2
1,3,5-Hexatriene, 1,6- 2
4-Trifluoromethyl-1-pentene 2
2,3-Dimethyl-1,3-butadiene, 1,4-
2
1,3-Hexadiene, 1,4- 2
P-D-Pructofuran 2
2-Butene-&ethylene
2
3-Methyl- 1 -pentene 2
4-Methyl- 1 -pentene 2
1,4-Diethyl-2,3-azabutadiene, 1,4-
2
Isobutylvinyl ether 2
1-Methyl-2-propoxyethylene 2
1-Methylpropylvinyl ether
2
3-Trimethylsilylpropene 2
4,4-Dimethyl-1-pentene 2
3-tert-Butyloxacylobutane 2
Neopentylethylene oxide 2
Neopentylvinyl ether 2
Bis(2,2,3,3,4,4,4-heptafluorobutoxy)phosphazene 2
2,5-Dichloro-p-xylyene 2
2,4,6-Octatriynediol, 2,5- 2
Bromo-p-xylylene 2
Chloro-p-xylylene 2
2,5Pyrazinecyclobutylene 2
2-rert-Butyl- 1,3-butadiene, 1,4- 2
5-Methyl-1,3-heptadiene, 1,4- 2
6-Methyl-1,3-heptadiene, 1,4- 2
Cyano-p-xylylene 2
2,4,6-Trichloro-3-phenoxypropylene oxide 2
Methyl-p-xylylene 2
Divinyl furfural 2
4,6-Dimethyl-m-xylyene 2
2,5-Dimethyl-p-xylyene 2
2,5-Dimethyl-3-phenylpropene 2
3,4-Dimethyl-3-phenylpropene
2
3,5-Dimethyl-3-phenylpropene 2
Isopropyl-p-xylylene 2
2,6-Dimethyl-3-phenoxypropylene oxide
2
3-(l-Naphthoxy)propylene oxide 2
3-(2-Naphthoxy)propylene oxide 2
4,4-perfluorodiphenyleneoxytetrahydroperylene oxide
2
Di- 1,4-naphthaleneoxyethylene oxide 2
m-Xylylene 2
p-Xylylene
2
p-Xylylene disulfide 2
Ethyleneoxy-p-phenylene oxide 2
Ethylene m-phenylenedisulfonamide
2
N-Phenyl-2-imino-1.3-dithiapentamethylene 2
0 0 2 6 0 0 0 1
0 0 2 6 0 0 0 1
0 0 2 6 0 0 0 1
0 0 2 6 1 0 0 1
0 0 3 0 1 0 0 6
0 0 3 1 0 1 0 0
0 0 3 3 0 0 0 1
0 0 3 3 0 1 0 0
0 0 3 4 0 0 0 0
0 0 3 6 0 0 0 0
0 0 3 6 0 0 1 0
0 0 3 6 1 0 0 0
0 0 3 6 2 0 1 0
0 0 4 0 0 0 0 8
0 0 4 0 2 1 0 11
0 0 4 2 2 0 0 0
0 0 4 2 2 1 0 9
0 0 4 4 0 0 0 0
0 0 4 4 0 0 0 0
0 0 4 5 0 0 0 3
0 0 4 6 0 0 0 0
0 0 4 6 0 0 0 0
0 0 4 6 5 0 0 0
0 0 4 8 0 0 0 0
0 0 4 8 0 0 0 0
0 0 4 8 0 0 0 0
0 0 4 8 0 2 0 0
0 0 4 8 1 0 0 0
0 0 4 8 1 0 0 0
0 0 4 8 1 0 0 0
0 0 4 1 0 0 0 0 1
0 0 5 1 0 0 0 0 0
0 0 5 1 0 1 0 0 0
0 0 5 1 0 1 0 0 0
0 0 5 1 0 1 0 0 0
0 0 6 0 2 1 0 15
0 0 6 2 0 0 0 2
0 0 6 2 2 0 0 0
0 0 6 3 0 0 0 1
0 0 6 3 0 0 0 1
0 0 6 4 0 2 0 0
0 0 6 1 0 0 0 0 0
0 0 6 1 0 0 0 0 0
0 0 6 1 0 0 0 0 0
0 0 I 3 0 1 0 0
0 0 I 3 2 0 0 3
0 0 7 6 0 0 0 0
0 0 7 6 3 0 0 0
0 0 8 8 0 0 0 0
0 0 8 8 0 0 0 0
0 0 9 1 0 0 0 0 0
0 0 9 1 0 0 0 0 0
0 0 9 1 0 0 0 0 0
0 0 9 1 0 0 0 0 0
0 0 9 1 0 2 0 0 0
0 0 11 8 2 0 0 0
0 0 11 8 2 0 0 0
0 0 1 5 0 2 0 0 4
0 0 20 1 2 2 0 0 0
0 1 0 0 0 0 0 0
0 1 0 0 0 0 0 0
0 1 0 0 0 0 2 0
0 1 0 0 2 0 0 0
0 1 0 2 4 2 2 0
0 1 1 1 0 1 2 0
Appendix: Formula Index to the Tables VI / 125
Constitutional Base Unit
Poly- 332 C O CsH4 C H 0 N s x
o-Chloro-3-phenoxypropylene oxide 2 0 1 1 1 2 0 0 1
p-Chloro-3-phenoxypropylene oxide 2 0 1 1 1 2 0 0 1
3-Phenylpropene (allylbenzene) 2 0 1 1 2 0 0 0 0
Benzylvinyl ether 2 0 1 1 2 1 0 0 0
3-Phenoxypropylene oxide 2 0 1 1 2 2 0 0 0
Ethylene dithionisophthalate 2 0 1 2 0 2 0 2 0
p-Phenylenecyclobutylene 2 0 1 2 2 0 0 0 0
3-m-Tolylpropene 2 0 1 2 4 0 0 0 0
3-o-Tolylpropene 2 0 1 2 4 0 0 0 0
3-p-Tolylpropene 2 0 1 2 4 0 0 0 0
m-Methyl-3-phenoxypropylene oxide 2 0 1 2 4 2 0 0 0
o-Methyl-3-phenoxypropylene oxide 2 0 1 2 4 2 0 0 0
p-Methyl-3-phenoxypropylene oxide 2 0 1 2 4 2 0 0 0
p-Methoxy-3-phenoxypropylene oxide 2 0 1 2 4 3 0 0 0
Divinylbenzal 2 0 1 3 4 2 0 0 0
2-Methyldivinylbenzal 2 0 1 4 6 2 0 0 0
4-Methyldivinylbenzal 2 0 1 4 6 2 0 0 0
o-Isopropyl-3-phenoxypropylene oxide 2 0 1 4 8 2 0 0 0
2,2-Ethylenedithiazole-p-phenylene 2 0 1 6 2 0 2 2 0
4,4-Ethylenebiphenylene 2 0 2 0 0 0 0 0 0
4,4-(0xydiphenylene)dithioethylene disulfide 2 0 2 0 0 1 0 4 0
o-Phenyl-3-phenoxypropylene oxide 2 0 2 1 2 2 0 0 0
Bis(p-ethylphenoxy)phosphazene 2 0 2 2 6 2 1 0 1
1,6-Bis(p-fluorophenylsulfonyl)-2,4-hexadiynediol, 2,5- 2 0 2 4 0 6 0 2 2
4,4-Isopropylidenediphenyleneoxy(2-hydrmethylene oxide 2 0 2 4 8 3 0 0 0
l-@-Toluylsulfonyl)-6-(p-fluorobenzylsulfonyl)-hexadiyne~ol 2 0 2 5 3 6 0 2 1
1,6-Bis(p-toluylsulfonyl)-2,4-hexadiynediol, 2,5- 2 0 2 6 6 6 0 2 0
1,6-Bis(p-methoxyphenylsufonyl)-2,4-hexadiynediol, 2,5- 2 0 2 6 6 8 0 2 0
1,6-Di(N-carbazoyl)-2,4-hexadiyne, 2,5- 2 0 4 4 0 0 2 0 0
Carbon monoxide-&ethylene 2 1 0 0 0 0 0 0 0
3-Mercaptopropionic acid 2 1 0 0 0 0 0 1 0
3-Hydroxypropionic acid (propiolactone) 2 1 0 0 0 1 0 0 0
3-Aminopropionic acid (B-alanine) 2 1 0 0 1 0 1 0 0
Ethylene urea 2 1 0 0 2 0 2 0 0
Ethyleneamine-oxalic acid-water complex (2 : 1 : 2) 2 1 0 0 3 2 1 0 0
3-Hydroxy-3-butenoic acid 2 1 0 1 0 1 0 0 0
3-chloromethyl-3-hydroxypropionic acid 2 1 0 1 1 1 0 0 1
N-Acetylethylene amine 2 1 0 1 3 0 1 0 0
N-Methyl-3-aminopropionic acid 2 1 0 1 3 0 1 0 0
2,4-Diaminobutyric acid 2 1 0 1 4 0 2 0 0
Ethyleneamine-acetic acid complex (1 : 1) 2 1 0 1 5 1 1 0 0
N-(Perfluoropropionyl)etbylene amine 2 1 0 2 0 0 1 0 5
1,3-Cyclobutylene carbonate 2 1 0 2 2 2 0 0 0
Hydroxyproline 2 1 0 2 3 1 1 0 0
3-Ethyl-3-hydroxypropionic acid 2 1 0 2 4 1 0 0 0
3-Methoxycarbonylpropionaldehyde 2 1 0 2 4 2 0 0 0
Methionine 2 1 0 2 5 0 1 1 0
Diethyl-2-hydroxyacetic acid 2 1 0 3 6 1 0 0 0
2-Ethyl-2-methyl-3-hydroxypropionic acid 2 1 0 3 6 1 0 0 0
2-Ethyl-2-methyl-3-aminopropionic acid 2 1 0 3 7 0 1 0 0
N-Isobutyrylethylene amine 2 1 0 3 I 0 1 0 0
N-Isopropyl-3-aminopropionic acid 2 1 0 3 7 0 1 0 0
2-Methyl-N-butylaminofonnic acid 2 1 0 3 7 0 1 0 0
see-butylthiolacrylate 2 1 0 4 8 0 0 1 0
Isobutylthiolacrylate 2 1 0 4 8 0 0 1 0
see-butyl acrylate 2 1 0 4 8 1 0 0 0
Isobutyl acrylate 2 1 0 4 8 1 0 0 0
N-Pivaloylethylene amine 2 1 0 4 9 0 1 0 0
3,5-Dimethyl-6-amino-4-oxacaproic acid 2 1 0 4 9 1 1 0 0
Ethylene m-chloro-p-oxybenzoate 2 1 0 6 3 2 0 0 1
Ethylene-o-chloro-p-oxybenzoate 2 1 0 6 3 2 0 0 1
N-(Perlluorooctanoyl)ethylene amine 2 1 0 1 0 0 1 0 5
3-n-Propylhydroxybenzoic acid 2 1 0 7 6 1 0 0 0
Ethylene m-methyl-p-oxybenzoate 2 1 0 7 6 2 0 0 0
Ethylene o-methyl-p-oxybenzoate 2 1 0 7 6 2 0 0 0
References page VI- 159
VI / 126 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly- CHz
C O CsH4 C H 0 N s x
1,l -Dihydroperlluorooctyl acrylate 2 1 0 8 1 1 0 0 5
Isoamyl-2,4-hexadienoate, 2,5- 2 1 0 8 1 4 1 0 0 0
1,l -DihydroperlIuorodecyl acrylate 2 1 0 1 0 1 1 0 0 9
N-2-Naphthoylethylene amine 2 1 0 1 0 7 0 1 0 0
N-(p-Chlorobenzoyl)ethylene amine 2 1 1 0 0 0 1 0 1
Ethylene-p-oxybenzoate
2 1 1 0 0 2 0 0 0
p-Xylylene carbonate 2 1 1 0 0 2 0 0 0
p-Aminohydrocinnamic acid 2 1 1 0 1 0 1 0 0
p-(Aminomethylene)phenyleneacetic acid 2 1 1 0 1 0 1 0 0
N-Benzoylethylene amine 2 1 1 0 1 0 1 0 0
N-Phenyl-3-aminopropionic acid 2 1 1 0 1 0 1 0 0
N-(p-Toluoyl)ethylene amine 2 1 1 1 3 0 1 0 0
S-Benzylthiocysteine 2 1 1 1 3 0 1 2 0
l-Benzylhistidine 2 1 1 4 5 0 3 0 0
4,4-Ethylenediphenylene carbonate 2 1 2 0 0 2 0 0 0
4,4-Butylidenediphenylene carbonate 2 1 2 2 4 2 0 0 0
4,4-Pentylidenediphenylene carbonate 2 1 2 3 6 2 0 0 0
Ethylene oxalate 2 2 0 0 0 2 0 0 0
Hydrazo succinamide 2 2 0 0 2 0 2 0 0
Methylene malonamide 2 2 0 0 2 0 2 0 0
Glutamic acid 2 2 0 1 3 1 1 0 0
Glutamine 2 2 0 1 4 0 2 0 0
Ethylene fumaramide 2 2 0 2 4 0 2 0 0
Ethylasparate 2 2 0 2 5 1 1 0 0
Methyl glutamate 2 2 0 2 5 1 1 0 0
4-Methyloxycarbonyl-4-aminobutyric acid 2 2 0 2 5 1 1 0 0
Alanyl-3-aminopropionic acid 2 2 0 2 6 0 2 0 0
Ethylene -L-tartaramide 2 2 0 2 6 2 2 0 0
O-Acetylhydroxyproline 2 2 0 3 5 1 1 0 0
2,2-dimethyltrimethylene oxalate 2 2 0 3 6 2 0 0 0
Ethylene 2,5-furandicarboxylate 2 2 0 4 2 3 0 0 0
Cyclopropylene cyclopropylenedicarboxamide 2 2 0 4 6 0 2 0 0
Ethylene 2,4-hexadienediamide 2 2 0 4 6 0 2 0 0
Isobutyl aspartate 2 2 0 4 9 1 1 0 0
Ethylene di-O-methyl-t.-tartaramide 2 2 0 4 1 0 2 2 0 0
Ethylene dithiol-2,5-pyridinedicarboxylate 2 2 0 5 3 0 1 2 0
Ethylene 2$dichloroterephthalate 2 2 0 6 2 2 0 0 2
Ethylene chloroterephthalate 2 2 0 6 3 2 0 0 1
Ethylene methylterephthalate 2 2 0 7 6 2 0 0 0
Ethylene 2,5-dimethylterephthalate 2 2 0 8 8 2 0 0 0
Ethylene 1,5-naphthalate 2 2 0 1 0 6 2 0 0 0
Ethylene 2,6-naphthalate 2 2 0 1 0 6 2 0 0 0
Ethylene 2,7-naphthalate 2 2 0 1 0 6 2 0 0 0
4,4-Ethylenedioxy-3,3-dimethoxydibenzoic anhydride 2 2 0 1 4 1 2 5 0 0 0
2,5-Dimethylterephthalaldehyde 2 2 0 1 6 1 6 2 0 0 0
Ethylene dithiolisophthalate 2 2 1 0 0 0 0 2 0
Ethylene dithiolterephthalate 2 2 1 0 0 0 0 2 0
p-Phenylenediacetic anhydride 2 2 1 0 0 1 0 0 0
Ethylene isophthalate 2 2 1 0 0 2 0 0 0
Ethylene phthalate 2 2 1 0 0 2 0 0 0
Ethylene terephthalate 2 2 1 0 0 2 0 0 0
m-Phenylene succinate 2 2 1 0 0 2 0 0 0
p-Phenylene succinate 2 2 1 0 0 2 0 0 0
(m-Phenylenedioxy)diacetic anhydride 2 2 1 0 0 3 0 0 0
(p-Phenylenedioxy)diacetic anhydride 2 2 1 0 0 3 0 0 0
Ethylene phthalamide 2 2 1 0 2 0 2 0 0
Ethylene terephthalamide 2 2 1 0 2 0 2 0 0
p-Chlorobenzylasparate 2 2 1 1 2 1 1 0 1
Benzyl aspartate 2 2 1 1 3 1 1 0 0
S-Benzyloxycarbonylcysteine 2 2 1 1 3 1 1 1 0
1 -Methyltrimethylene isophthalate 2 2 1 2 4 2 0 0 0
1-Methyltrimethylene phthalate 2 2 1 2 4 2 0 0 0
1-Methyltrimethylene terephthalate 2 2 1 2 4 2 0 0 0
Methylbenzyl aspartate 2 2 1 2 5 1 1 0 0
NJ-Dimethylethylene terephthalamide 2 2 1 2 6 0 2 0 0
c
P
2
2
2
9
t
r
?
1
1
I
1
1
1
1
1
1
1
Appendi x: Formul a I ndex to the Tabl es VI/127
Constitutional Base Unit
Poly- CHZ co C4H4 C H 0 N SX
2,2-Dimethyltrimethylene terephthalate 2 2 1 3 6 2 0 0 0
2,5-Dimethylpiperazine isophtbalamide 2 2 1 4 8 0 2 0 0
2,5-Dimethylpiperazine phthalamide 2 2 1 4 8 0 2 0 0
2,5-Dimethylpiperazine terephthalamide 2 2 1 4 8 0 2 0 0
p-Phenylene dietbylcyclobutylenedicarboxylate 2 2 1 6 1 0 2 0 0 0
p-Phenylene dicyanodiethylcyclobutylenedicarboxylate 2 2 1 8 8 2 2 0 0
2,2-Diethyl-4,4-oxydiphenylene m-phenylenediketone 2 2 1 1 4 1 2 1 0 0 0
N,N-Diethyl-3,3-dimetbylbiphenylene terephthalamide 2 2 1 1 6 1 8 0 2 0 0
p-Xylylene dithiolisophtbalate 2 2 2 0 0 0 0 2 0
4,4-Ethylenedibenzoic anhydride 2 2 2 0 0 1 0 0 0
Ethylene 2,2-dibenzoate 2 2 2 0 0 2 0 0 0
Ethylene 3,3 -dibenzoate 2 2 2 0 0 2 0 0 0
Ethylene 4,4-dibenzoate 2 2 2 0 0 2 0 0 0
Isophthalaldehyde 2 2 2 0 0 2 0 0 0
Terephthalaldehyde 2 2 2 0 0 2 0 0 0
p-Xylylene isophthalate
2 2 2 0 0 2 0 0 0
p-Xylylene terephthalate 2 2 2 0 0 2 0 0 0
Ethylene 4,4-thiodibenzoate 2 2 2 0 0 2 0 1 0
3,3 -(Ethylenedioxy)dibenzoic anhydride 2 2 2 0 0 3 0 0 0
4,4-(Ethylenedioxy)dibenzoic anhydride
2 2 2 0 0 3 0 0 0
Ethylene 4,4-oxydibenzoate 2 2 2 0 0 3 0 0 0
4,4-(0xydimethylene)dioxydibenzoic anhydride 2 2 2 0 0 4 0 0 0
p-Phenyleneethylene terephthalamide
2 2 2 0 2 0 2 0 0
m-Xylylene isophthalamide 2 2 2 0 2 0 2 0 0
p-Xylylene isophthalamide 2 2 2 0 2 0 2 0 0
p-Xylylene phthalamide
2 2 2 0 2 0 2 0 0
m-Xylylene terephthalamide 2 2 2 0 2 0 2 0 0
p-Xylylene terephthalamide 2 2 2 0 2 0 2 0 0
Ethylene 4,4-sulfonyldibenzamide
2 2 2 0 2 2 2 1 0
O-Benzyloxycarbonyltyrosine 2 2 2 1 3 2 1 0 0
1-Methyltrimethylene 2,2-dibenzoate 2 2 2 2 4 2 0 0 0
1-Methyltrimethylene 3,3-dibenzoate 2 2 2 2 4 2 0 0 0
1-Methyltrimethylene 4,4-dibenzoate 2 2 2 2 4 2 0 0 0
I-Methyltrimethylene 4,4-sulfonyldibenzamide
2 2 2 2 6 2 2 1 0
(4,4-1sopropylidenediphenylene)dioxydiacetic anhydride
2 2 2 3 6 3 0 0 0
2,2-Dimethyltrimethylene sulfonyldibenzamide 2 2 2 3 8 2 2 1 0
1,6-Bis(phenylurethane)-2,4-hexadiynediol, 2,5- 2 2 2 4 4 2 2 0 0
l,&Bis(phenylurethane)-2,4,6-octatriynediol, 2,5-
2 2 2 6 4 2 2 0 0
Methyl-p-phenylene 4,4-ethylenedioxydibenzoate 2 2 2 1 6 4 0 0 0
p-Phenylene 4,4-(etbylenedioxy)dibenzoate
2 2 3 0 0 4 0 0 0
N,N-Diethylbiphenylene terephthalamide
2 2 3 2 6 0 2 0 0
4,4-Biphenyldicarboxaldehyde 2 2 4 0 0 2 0 0 0
4,4-(Silylenediphenylene)dimethylene 4,4-silylenedibenzamide
2 2 4 0 6 0 2 0 2
4,4-(Silylenediphenyleneklimethylene 4,4-disiloxanylenedibenzamide
2 2 4 0 8 1 2 0 3
4,4-(Silylenediphenylene)dimethylene 4,4-tetrasiloxanylenedibenzamide 2 2 4 0 1 2 3 2 0 5
4,4-Dimethylsilylenediphenylenedimethylene tetrasiloxanylenedibenzamide 2 2 4 2 1 6 3 2 0 5
4,4-Dimethylsilylenediphenylenedimethylene dimethylsilylenedibenzamide
2 2 4 4 1 4 1 2 0 2
4,4-Dimethylsilylenediphenylenedimethylene tetramethyldisiloxanylenedi 2 2 4 6 20 1 2 0 3
4,4-Dimethylsilylenediphenylenedimethylene tetramethyltetraphenyltetra
2 2 8 6 20 3 2 0 5
Alanylglycylglycine
2 3 0 2 7 0 3 0 0
Alanyl(phenylalanyl)glycine) 2 3 1 3 9 0 3 0 0
Cyclopropylene (cyclopropylenedicarboxoyl)diurethane 2 4 0 4 6 2 2 0 0
@-Phenylenedioxy)diacetic 3,4-pyridinedicarboxylic anhydride
2 4 1 5 3 4 1 0 0
Isophthalic (p-phenylenedioxykliacetic anhydride 2 4 2 0 0 4 0 0 0
@-Phenylenedioxy)diacetic terephthalic anhydride 2 4 2 0 0 4 0 0 0
Isophthaloyl (m-carboxyphenoxypropionyl)dihydrazide
2 4 2 0 4 1 4 0 0
4,4-(Isopropylidenediphenyleneklioxydiacetic pyridinedicarboxylic anhydride 2 4 2 8 9 4 1 0 0
3,4-(Ethylenedioxy)diphenylene 3,3 ,4,4-Oxydiphenylenetetracarboximide 2 4 2 1 2 6 3 2 0 0
4,4-(Ethylenedioxy)dibenzoic isophthalic anhydride
2 4 3 0 0 4 0 0 0
4,4-(Ethylenedioxy)dibenzoic phthalic anhydride 2 4 3 0 0 4 0 0 0
4,4-(Ethylenedioxy)dibenzoic terephthalic anhydride 2 4 3 0 0 4 0 0 0
Isophthalic (isopropylidenediphenylene)diacetic anhydride
2 4 3 3 6 4 0 0 0
4,4-(Isopropylidenediphenylene(dioxydiacetic terephthalic anhydride 2 4 3 3 6 4 0 0 0
4,4-(Ethylenedioxy)diphenylene carbonyldiphenylenetetracarboximide 2 5 2 1 2 4 2 2 0 0
Neopentylene-4,4-diphenylene 3,3,4,4-carbonyldiphenylenetetracarbox
2 5 2 1 5 1 2 2 2 0 0
References page VI-159
VI / 128 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHz
C O CsH4 C H 0 N s x
3 3 0 0 0 0 0 0 0 0
Trimethylene sulfide 3 0 0 0 0 0 0 1 0
Trimethylene disulfide 3 0 0 0 0 0 0 2 0
Oxacyclobutane (trimethylene oxide) 3 0 0 0 0 1 0 0 0
Ethyleneoxymethylene oxide (dioxolane) 3 0 0 0 0 2 0 0 0
Trimethylene sulfone 3 0 0 0 0 2 0 1 0
Trimethylene amine 3 0 0 0 1 0 1 0 0
3-Aminotrimethylenesulfonic acid 3 0 0 0 1 2 0 1 0
l,l-Bischloromethylethylene oxide 3 0 0 1 0 1 0 0 2
2-Chloroethylvinylether 3 0 0 1 1 1 0 0 1
5,5,5-Trifluoro-1-pentene 3 0 0 2 1 0 0 0 3
Pent enamer 3 0 0 2 2 0 0 0 0
Vinyl cyclopropane 3 0 0 2 2 0 0 0 0
1,2-Dichloropentamethylene 3 0 0 2 2 0 0 0 2
1,3-Cyclobutyleneoxymethylene oxide 3 0 0 2 2 2 0 0 0
Hydrochlorinated 2-methyl- 1,3-butadiene, 1,4- 3 0 0 2 3 0 0 0 1
N-Ethyl-2-imino- 1,3-dithiapentamethylene 3 0 0 2 3 0 1 2 0
1-Pentene 3 0 0 2 4 0 0 0 0
Propene-&-ethylene 3 0 0 2 4 0 0 0 0
3-Methyl-3-hydroxymethyloxacyclobutane 3 0 0 2 4 1 0 0 0
Propylvinyl ether 3 0 0 2 4 1 0 0 0
Valeraldehyde 3 0 0 2 4 1 0 0 0
2-Methoxyethylvinyl ether 3 0 0 2 4 2 0 0 0
a-Propylacrylonitrile 3 0 0 3 3 0 1 0 0
1-Butoxy-2-chloroethylene 3 0 0 3 5 1 0 0 1
3-Ethyl-3-methyloxacyclobutane 3 0 0 3 6 1 0 0 0
1-Vinylene-3-cyclopentylene 3 0 0 4 4 0 0 0 0
1,3-Heptadiene, 1,4- 3 0 0 4 6 0 0 0 0
3-Ethyl-1-pentene 3 0 0 4 8 0 0 0 0
3-Methyl-l -hexene 3 0 0 4 8 0 0 0 0
4-Methyl- 1 -hexene 3 0 0 4 8 0 0 0 0
.5-Methyl-1-hexene 3 0 0 4 8 0 0 0 0
I-Butoxy-2-methylethylene 3 0 0 4 8 1 0 0 0
2-Methylbutylvinyl ether 3 0 0 4 8 1 0 0 0
4-Trimethylsilylbutene 3 0 0 4 1 0 0 0 0 1
1,4-Butadiene-alt-methacrylonitrile 3 0 0 5 5 0 1 0 0
4,CDimethyl-1-hexene 3 0 0 5 1 0 0 0 0 0
Ethyl-p-xylylene 3 0 0 I 6 0 0 0 0
4-Diisopropylamino-1-butene 3 0 0 I 1 5 0 1 0 0
B-D-Galacto- 1,4-p-D-mannose, 1,4- (1 : 2) (guar gallactomannan) 3 0 0 15 24 5 0 0 0
Di- 1,4-naphthaleneoxytrimethylene oxide 3 0 0 20 1 2 2 0 0 0
p-Phenyleneoxytrimethylene oxide 3 0 1 0 0 2 0 0 0
Trimethylene m-phenylenedisulfonamide 3 0 1 0 2 4 2 2 0
4-Phenyl-1-butene 3 0 1 1 2 0 0 0 0
4-o-Tolyl-1-butene 3 0 1 2 4 0 0 0 0
4-p-Tolyl-1-butene 3 0 1 2 4 0 0 0 0
4,4-(Ethylenediphenylene)methylene 3 0 2 0 0 0 0 0 0
Trimethylene biphenylene 3 0 2 0 0 0 0 0 0
4,4-Stilbenediyloxytrimethylene oxide 3 0 2 2 2 2 0 0 0
a-Methyl-4,4-stilbenediyloxytrimethylene oxide 3 0 2 3 4 2 0 0 0
4,4-lsopropylidenediphenyleneoxytrimethylene oxide 3 0 2 3 6 2 0 0 0
5-Hydroxy-3-oxavaleric acid 3 1 0 0 0 2 0 0 0
4-Aminobutyric acid 3 1 0 0 1 0 1 0 0
5-Amino-3-oxavaleric acid 3 1 0 0 1 1 1 0 0
2,2-Bischloromethyl-3-hydroxypropionic acid 3 1 0 1 0 1 0 0 2
Proline 3 1 0 1 1 0 1 0 0
N-Butylaminoformic acid 3 1 0 1 3 0 1 0 0
Omithine 3 1 0 1 4 0 2 0 0
Omithine hydrobromide 3 1 0 1 5 0 2 0 1
Ally1 acrylate 3 1 0 2 2 1 0 0 0
2-Aminocyclopentylenecarboxy acid 3 1 0 2 3 0 1 0 0
2$Aminotetrahydropyran carboxylic acid 3 1 0 2 3 1 1 0 0
Propylthiolacrylate 3 1 0 2 4 0 0 1 0
Arginine 3 1 0 2 6 0 4 0 0
Arginine hydrochloride 3 1 0 2 7 0 4 0 1
-
C
P
-
2
2
2
A
2
t:
E
E
T
P
P
2
4
?
C
F
E
h
I!
E
;
/
2
C
4
1
1
1
P
E
E
P
1
P
n
c
P
F
P
P
E
4
E
P
P
C
(
(
n
P
P
P
I;
P
4
E
1
1
1
?
4
1
E
Appendi x: Formul a I ndex to the Tabl es VI / 129
Constitutional Base Unit
Poly- CHz C O CaH4 C H 0 N s x
2-Methylacetoxy- 1,3-butadiene 3 1 0 3 4 1 0 0 0
2,2-Diethyl-3-hydroxypropionic acid 3 1 0 3 6 1 0 0 0
2-Methyl-2-propyl-3-hydroxpropionic acid 3 1 0 3 6 1 0 0 0
N-Isovalerylethylene amine 3 1 0 3 I 0 1 0 0
2-Methyl-2-propyl-3-aminopropionic acid 3 1 0 3 I 0 1 0 0
1,4-Butadiene-air-methyl methacrylate 3 1 0 5 8 1 0 0 0
(2,2-Dimethyl-3-aminocyclobutylene)propionic acid 3 1 0 5 9 0 1 0 0
Butyl-2,4-hexadienoate, 2,.5- 3 1 0 6 1 0 1 0 0 0
Ethylene p-oxyphenyleneacetate 3 1 1 0 0 2 0 0 0
Trimethylene p-oxybenzoate 3 1 1 0 0 2 0 0 0
p-(Aminoethylene)phenyleneacetic acid 3 1 1 0 1 0 1 0 0
p-(Aminomethylene)phenylenepropionic acid 3 1 1 0 1 0 1 0 0
2,.5-Butyl-5-phenyl-2,4-pentadienoate 3 1 1 5 8 1 0 0 0
4,4-Hexylidenediphenylene carbonate 3 1 2 3 6 2 0 0 0
Trimethylene oxalate 3 2 0 0 0 2 0 0 0
Glycyl-3-aminopropionic acid 3 2 0 0 2 0 2 0 0
Hydrazo glutaramide 3 2 0 0 2 0 2 0 0
Ethylene cyclopropylenedicarboxamide 3 2 0 2 4 0 2 0 0
Methylethylene succinate 3 2 0 2 4 2 0 0 0
Methylethylene oxydiacetate 3 2 0 2 4 3 0 0 0
Ethyl glutamate 3 2 0 2 5 1 1 0 0
n-Propyl aspartate 3 2 0 2 5 1 1 0 0
2-Methoxyethyl aspartate 3 2 0 2 5 2 1 0 0
Alanyl-4-aminobutyric acid 3 2 0 2 6 0 2 0 0
2,2-Dimethyltrimethylene mal onat e 3 2 0 3 6 2 0 0 0
Cyclopropylenedimethylene toluylenediurethane 3 2 0 9 1 0 2 2 0 0
4,4-Trimethylenedioxy-3,3-dimethoxydibenzoic anhydride 3 2 0 1 4 1 2 5 0 0 0
Trimethylene isophthalate 3 2 1 0 0 2 0 0 0
Trimethylene phthalate 3 2 1 0 0 2 0 0 0
Trimethylene terephthalate 3 2 1 0 0 2 0 0 0
p-Xylylene glutarate 3 2 1 0 0 2 0 0 0
Ethylene p-(carboxyphenoxy)acetate 3 2 1 0 0 3 0 0 0
Ethylene-p-(carboxyphenylene)acetamide 3 2 1 0 2 0 2 0 0
p-Phenylene glutaramide 3 2 1 0 2 0 2 0 0
Trimethylene terephthalamide 3 2 1 0 2 0 2 0 0
p-Xylylene malonamide 3 2 1 0 2 0 2 0 0
m-Chlorobenzylglutamate 3 2 1 1 2 1 1 0 1
o-Chlorobenzylglutamate 3 2 1 1 2 1 1 0 1
p-Chlorobenzylglutamate 3 2 1 1 2 1 1 0 1
N-(p-Bromobenzoyl)-L-ornithine 3 2 1 1 3 0 2 0 1
N-@-Chlorobenzoyl)-L-omithine 3 2 1 1 3 0 2 0 1
N-(p-Fluorobenzoyl)-L-omithine 3 2 1 1 3 0 2 0 1
Benzyl glutamate 3 2 1 1 3 1 1 0 0
4-Benzyloxycarbonyl-4-aminobutyric acid 3 2 1 1 3 1 1 0 0
Phenethylasparate 3 2 1 1 3 1 1 0 0
N-Benzoyl-L-omithine 3 2 1 1 4 0 2 0 0
N-Benzyloxycarbonyl-2,4-diaminobutyric acid 3 2 1 1 4 1 2 0 0
Cyclopropylenedimethylene isophthalate 3 2 1 2 2 2 0 0 0
Cyclopropylenedimethylene terephthalate 3 2 1 2 2 2 0 0 0
Cyclopropylenedimethylene isophthalamide 3 2 1 2 4 0 2 0 0
Methylpiperazine isophthalamide 3 2 1 2 4 0 2 0 0
Methylpiperazine phthalamide 3 2 1 2 4 0 2 0 0
Methylpiperazine terephthalamide 3 2 1 2 4 0 2 0 0
N,N-Dimethyltrimethylene terephthalamide 3 2 1 2 6 0 2 0 0
p-Phenylene( 1,l -dimethyl)ethylene succinamide 3 2 1 3 8 0 2 0 0
N,N-Diethyl-3,3-dimethyl(methylenediphenylene) terephthalamide 3 2 1 1 6 1 8 0 2 0 0
4,4-Trimethylenedibenzoic anhydride 3 2 2 0 0 1 0 0 0
Ethylene 4,4-methylenedibenzoate 3 2 2 0 0 2 0 0 0
Trimethylene 2,2-dibenzoate 3 2 2 0 0 2 0 0 0
Trimethylene 3,3-dibenzoate 3 2 2 0 0 2 0 0 0
Trimethylene 4,4-dibenzoate 3 2 2 0 0 2 0 0 0
3,3-(Trimethylenedioxy)dibenzoic anhydride 3 2 2 0 0 3 0 0 0
4,4-(Trimethylenedioxy)dibenzoic anhydride 3 2 2 0 0 3 0 0 0
Trimethylene 4,4-oxydibenzoate 3 2
Ethylene 4,4-(methylenediphenylene)diurethane
2 0 0 3 0 0 0
3 2 2 0 2 2 2 0 0
References page VI-159
VI / 130 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
(332
c o CaH4 C H 0 N s x
Tri met hyl ene 4,4-sulfonyldibenzamide
Isopropylidenedimethylene methylenediphenylenediurethane
4,4-Diphenyleneglutarate-butadiyne, 1,4-
2,4-Hexadiyne (4,4-methylenediphenylene)diurethane
p-Xylylene dithiol-4,4-methylenedibenzoate
N,N-Diethyhmethylenediphenylene) terephthalamide
Alanylglycylglycylglycine
Alanylglutamylglycine
Isophthalic 4,4-trimethylenedioxy-3,3-dimethoxydibenzoic
anhydride
Terephthalic 4,4-trimethylenedioxy-3,3 -dimethoxydibenzoic
anhydride
Isophthaloyl (m-carboxyphenoxybutyryl)dihydrazide
Isophthalic 4,4-(trimethylenedioxy)dibenzoic anhydride
Terephthalic 4,4-(trimethylenedioxy)dibenzoic anhydride
4
Tetramethylene sulfide
Tetramethylene disulfide
Tetrahydrofuran (tetramethylene oxide)
Tetramethylene sulfone
3,3-Bisazidomethyloxacylobutane
cyclopropylidenedimethylene oxide
3,3-Bisbromomethyloxacyclobutane
3,3-Bischloromethyloxacyclobutane
3,3-Bisfluoromethyloxacyclobutane
3,3-Bisiodomethyloxacyclobutane
Tetramethylene thiourea
3,3-Bishydroxyoxacyclobutane
5Hydroxy- 1 -pentene
3,3-Bishydroxymethyloxacyclobutane
W&no- 1 -pentene
2,5-Tetramethylene-1,3,4-triazole
1,3-Cyclopenylene-altmethylene
Vinyl cyclobutane
1,2-Cyclohexylene sulfide
1,3-Cyclohexylene sulfide
2,5-Tetramethylene-I-amino-1,3,4-triazole
1,2-Cyclohexene oxide
1,2-Cyclohexylene sulfone
1,3-Cyclohexylene sulfone
1-Hexene
n-Butylvinyl ether
Di-n-propylsilylene
Di-n-propylsiloxane
2-Propyl-1,3-butadiene, 1,4-
3,3-Diethyltrimethylene sulfide
3,3-Diethyloxacyclobutane
3,3-Diethyltrimethylene sulfone
1,3-Octadiene, 1,4-
4-Ethyl- 1 -hexene
5-Methyl-1-heptene
5-Trimethylsilyl-1-pentene
6,6-Dimethyl-1-heptene
5-Diisopropylamino-1-pentene
a-o-Triethylglucose, 1,4-
P-o-Triethylglucose, 1,4-
Di- 1,4-naphthaleneoxytetramethylene oxide
Oxydiethyleneoxy-p-phenylene oxide
Tet ramet hyl ene m-phenyl enedi sul fonai de
Tetramethylene dithionisophthalate
2,2-Tetramethylenedithiazole-p-phenylene
4,4-(0xydiphenylene)dithiotetramethylene disulfide
4,4-Stilbenediyloxytetramethylene oxide
a-Methyl-4,4-stilbenediyloxytetramethylene oxide
5-Hydroxyvaleric acid
3
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
2
2
2
2
2
2
4
4
4
4
4
4
4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
2
2
2
2
3
3
0
0
1
1
2
3
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
2
2
2
0
0 2 2 2
3 8 2 2
4 0 2 0
4 2 2 2
0 0 0 0
2 6 0 2
2 8 0 4
3 9 1 3
1 4 1 2 6 0
1 4 1 2 6 0
0 4 1 4
0 0 4 0
0 0 4 0
0 0 0 0
0 0 0 0
0 0 0 0
0 0 1 0
0 0 2 0
1 0 0 6
1 0 1 0
1 0 1 0
1 0 1 0
1 0 1 0
1 0 1 0
1 2 0 2
1 2 1 0
1 2 1 0
1 2 3 0
1 3 0 1
2 1 0 3
2 2 0 0
2 2 0 0
2 2 0 0
2 2 0 0
2 2 0 4
2 2 1 0
2 2 2 0
2 2 2 0
2 4 0 0
2 4 1 0
2 6 0 0
2 6 1 0
3 4 0 0
3 6 0 0
3 6 1 0
3 6 2 0
4 6 0 0
4 8 0 0
4 8 0 0
4 1 0 0 0
5 1 0 0 0
7 1 5 0 1
8 1 4 5 0
8 1 4 5 0
20 1 2 2 0
0 0 3 0
0 2 4 2
2 0 2 0
6 2 0 2
0 0 1 0
2 2 2 0
3 4 2 0
0 0 1 0
-
Tl
5-
6-
TC
1,
iv
L1
Ll
L!
3-
1
61
Bl
3-
6-
2-s
3-1
P-1
P-l
4/
4,
Ac
TE:
Et1
Tel
Tri
T e
Te
Tel
Tel
Et1
ox
Sul
(Et
HY
M e
22
2-c
N5-
NJ
Ttil
M e
TtiI
l-Iv
?l-B
n-PI
Ala]
Met
Tetr
2,2-
2, 5-
2,5-.
2,5-j
cyc.
Pipe
Cycl
Tetr;
D-M
Tetn
N-M
1,6-I
3-M(
4-Mt
Isop
Appendix: Formula Index to the Tables VI / 131
Constitutional Base Unit
Poly-
CHz
C O C6H4 C H 0 N s x
Tetramethylene carbonate 4 1 0 0 0 2 0 0 0
5Aminovaleric acid 4 1 0 0 1 0 1 0 0
6-Amino-4-oxacaproic acid 4 1 0 0 1 1 1 0 0
Tetramethylene urea 4 1 0 0 2 0 2 0 0
1,4-Piperidine urethane 4 1 0 1 1 1 1 0 0
N-Butyrylethylene amine 4 1 0 1 3 0 1 0 0
Lysine 4 1 0 1 4 0 2 0 0
Lysine hydrobromide 4 1 0 1 5 0 2 0 1
Lysine hydrochloride 4 1 0 1 5 0 2 0 1
3Aminocyclobutylenepropionic acid 4 1 0 2 3 0 1 0 0
1 ,CCyclohexylene urethane 4 1 0 2 3 1 1 0 0
6-Mercapto-4-methylcaproic acid 4 1 0 2 4 0 0 1 0
Butyl acrylate 4 1 0 2 4 1 0 0 0
3-Methyl-6-aminocaproic acid 4 1 0 2 5 0 1 0 0
6-Methyl-6-aminocaproic acid 4 1 0 2 5 0 1 0 0
2-n-Butyl-2-methyl-3-aminopropionic acid 4 1 0 3 I 0 1 0 0
3-n-Pentylhydroxybenzoic acid 4 1 0 I 6 1 0 0 0
p-(Aminoethylene)phenylenepropionic acid 4 1 1 0 1 0 1 0 0
p-(Aminomethylene)phenylenebutyric acid 4 1 1 0 1 0 1 0 0
4,4-Cyclopentylidenediphenylene carbonate 4 1 2 1 0 2 0 0 0
4,4-Heptylidenediphenylene carbonate 4 1 2 3 6 2 0 0 0
Adipic anhydride 4 2 0 0 0 1 0 0 0
Thiodipropionic anhydride 4 2 0 0 0 1 0 1 0
(Ethylenedithio)diacetic anhydride 4 2 0 0 0 1 0 2 0
Ethylene succinate 4 2 0 0 0 2 0 0 0
Tetramethylene oxalate 4 2 0 0 0 2 0 0 0
Trimethylene malonate 4 2 0 0 0 2 0 0 0
Tetramethylene thiodicarboxylate 4 2 0 0 0 2 0 1 0
Tetramethylene dithiodicarboxylate 4 2 0 0 0 2 0 2 0
Tetramethylene Trithiodicarboxylate 4 2 0 0 0 2 0 3 0
Tetramethylene tetrathiodicarboxylate 4 2 0 0 0 2 0 4 0
Ethylene oxydiacetate 4 2 0 0 0 3 0 0 0
Oxydiethylene oxalate 4 2 0 0 0 3 0 0 0
Sulfonyldipropionic anhydride 4 2 0 0 0 3 0 1 0
(Ethylenedisulfonyl)diacetic anhydride 4 2 0 0 0 5 0 2 0
Hydrazo adipamide 4 2 0 0 2 0 2 0 0
Methylene glutaramide 4 2 0 0 2 0 2 0 0
2,2-Bischloromethyltrimethylene oxalate 4 2 0 1 0 2 0 0 2
2-Chloroethylglutamate 4 2 0 1 2 1 1 0 1
NS-(2-Hydroxyethyl)glutamine 4 2 0 1 4 1 2 0 0
N,N-Lysylurea 4 2 0 1 4 1 2 0 0
Trimethylene cyclopropylenedicarboxamide 4 2 0 2 4 0 2 0 0
Methylethylene glutarate 4 2 0 2 4 2 0 0 0
Trimethylene cyclopropylenediurethane 4 2 0 2 4 2 2 0 0
1-Methyltrimethylene oxydiacetate 4 2 0 2 4 3 0 0 0
n-Butyl aspartate 4 2 0 2 5 1 1 0 0
n-Propylglutamate 4 2 0 2 5 1 1 0 0
Alanyl-Saminovaleric acid 4 2 0 2 6 0 2 0 0
Methyl-N,N-lysylurea 4 2 0 2 6 1 2 0 0
Tetramethylene-L-tartaramide 4 2 0 2 6 2 2 0 0
2,2-Dimethyltrimethylene succinate 4 2 0 3 6 2 0 0 0
2,SThiophenedipropionic anhydride 4 2 0 4 2 1 0 1 0
2,5-Furandipropionic anhydride 4 a 0 4 2 2 0 0 0
2,5Pyrroledipropionic anhydride 4 2 0 4 3 1 1 0 0
Cyclopropylenedimethylene cyclopropylenedicarboxamide 4 2 0 4 6 0 2 0 0
Piperazine (3-methylcyclopropylene)dicarboxamide 4 2 0 4 6 0 2 0 0
Cyclopropylenedimethylene cyclopropylenediurethane 4 2 0 4 6 2 2 0 0
Tet ramet hyl ene 1,2-dimethoxysuccinate 4 2 0 4 8 4 0 0 0
D-Methionyl-L-methionine 4 2 0 4 1 0 0 2 2 0
Tetramethylene di-O-methyl+tartaramide 4 2 0 4 1 0 2 2 0 0
N-Methyl-2,5-pyrroledipropionic anhydride 4 2 0 5 5 1 1 0 0
1,6-Bis(ethylurethane)-2,4-hexadiynediol, 2,5- 4 2 0 6 8 2 2 0 0
3-Methyl-m-phenylene adipamide 4 2 0 7 8 0 2 0 0
I-Methyl-m-phenylene disiloxanylenedipropionamide 4 2 0 7 1 2 1 2 0 2
Isopropylidenedimethylene dimethylpiperazinedithiodicarboxylate 4 2 0 I 1 4 2 2 2 0
References page VI- 159
VI / 132 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly- CHz
C O C6H,, C H 0 N s x
4-Methyl-1,3-phenylene tetramethyldisiloxanylenedipropionamide 4
4,4-Tetramethylenedioxy-3,3-dimethoxydibenzoic anhydride 4
Ethylene 3,3-dimethoxy-4,4-(ethylenedioxy)dibenzoate 4
4,4-Tetrachloroisopropylidenediphenylene adipate 4
3,3-Dimethylmethylenediphenylene tetramethyldisiloxanylenedipropionamide 4
Tetramethylene dithiolisophthiate 4
Tetramethylene dithiolterephthalate 4
Thiodiethylene dithiolterephthalate 4
Piperazine isophthalamide 4
Piperazine phthalamide 4
Piperazine terephthalamide 4
p-Phenylenedipropionic anhydride 4
(p-Phenylenedithio)dipropionic anhydride 4
(p-Xylylenedithio)diacetic anhydride 4
Ethylene p-phenylenediacetate 4
p-Phenylene adipate 4
Tetramethylene isophthalate 4
Tetramethylene phthalate 4
Tetramethylene terephthalate 4
p-Xylylene succinate 4
Oxydiethylene isophtbalate 4
Oxydiethylene phthalate 4
Oxydiethylene terephtbalate 4
(p-Xylylenedisulfonyl)diacetic anhydride 4
Tetramethylene m-carboxycarbanilate 4
Tetramethylene p-carboxycarbanilate 4
m-Phenylene adipamide 4
o-Phenylene adipamide 4
p-Phenylene adipamide 4
p-Phenyleneethylene succinamide 4
Tetramethylene isophthalamide 4
Tetramethylene terephthalamide 4
Trimethylene p-(carboxyphenylene)acetamide 4
p-Xylylene succinamide 4
m-Phenylene disiloxanylenedipropionamide 4
o-Phenylene disiloxanylenedipropionamide 4
p-Phenylene disiloxanylenedipropionamide 4
Ethylene 3-@-nitro)glutarate 4
Phenylpropyl-L-aspartate 4
Phenethylglutamate 4
N-benzyloxycarbonylomithine 4
Adipoyl dithionisophthaloyldihydrazide 4
NJ-Dimetbyltetramethylene terephthalamide 4
2-Methylpentametbylene terephthalamide 4
m-Phenylene (tetramethyldisiloxanylene)dipropionamide 4
o-Phenylene (tetramethyldisiloxanylene)dipropionamide 4
p-Phenylene (tetramethyldisiloxanylene)dipropionamide 4
p-Phenylene dipropylcyclobutylenedicarboxylate 4
p-Phenylene dicyanodipropylcyclobutylenedicarboxylate 4
Tetramethyl-p-xylylene dithiol-p-phenylenediacetate 4
2,2-Dipropyl-4,4-biphenylene terephtbalate 4
p-Phenylene-4,4-(3,3-dimethoxy)dibenzylidenimino adipate 4
p-Xylylene dithiol-p-phenylenediacetate 4
4,4-Tetramethylenedibenzoic anhydride 4
4,4-(Tetramethylenedithio)dibenzoic anhydride 4
4,4-Biphenylene adipate 4
Ethylene 4,4-ethylenedibenzoate 4
p-Phenylenedietbylene terephthalate 4
Tet ramet hyl ene 2,2-dibenzoate 4
Tet ramet hyl ene 3,3-dibenzoate 4
Tetramethylene 4,4-dibenzoate 4
p-Xylylene p-phenylenediacetate 4
Ethylene 4,4-(ethylenedithio)diben.zoate 4
Oxydiethylene 2,2-dibenzoate 4
Oxydiethylene 3,3 -dibenzoate 4
2 0 11 20 1 2 0 2
2 0 1 4 1 2 5 0 0 0
2 0 1 4 1 2 6 0 0 0
2 0 1 5 1 0 2 0 0 4
2 0 1 8 26 1 2 0 2
2 1 0 0 0 0 2 0
2 1 0 0 0 0 2 0
2 1 0 0 0 0 3 0
2 1 0 0 0 2 0 0
2 1 0 0 0 2 0 0
2 1 0 0 0 2 0 0
2 1 0 0 1 0 0 0
2 1 0 0 1 0 2 0
2 1 0 0 1 0 2 0
2 1 0 0 2 0 0 0
2 1 0 0 2 0 0 0
2 1 0 0 2 0 0 0
2 1 0 0 2 0 0 0
2 1 0 0 2 0 0 0
2 1 0 0 2 0 0 0
2 1 0 0 3 0 0 0
2 1 0 0 3 0 0 0
2 1 0 0 3 0 0 0
2 1 0 0 5 0 2 0
2 1 0 1 2 1 0 0
2 1 0 1 2 1 0 0
2 1 0 2 0 2 0 0
2 1 0 2 0 2 0 0
2 1 0 2 0 2 0 0
2 1 0 2 0 2 0 0
2 1 0 2 0 2 0 0
2 1 0 2 0 2 0 0
2 1 0 2 0 2 0 0
2 1 0 2 0 2 0 0
2 1 0 6 1 2 0 2
2 1 0 6 1 2 0 2
2 1 0 6 1 2 0 2
2 1 1 1 4 1 0 0
2 1 1 2 1 1 0 0
2 1 1 3 1 1 0 0
2 1 1 4 1 2 0 0
2 1 2 4 0 4 2 0
2 1 2 6 0 2 0 0
2 1 2 6 0 2 0 0
2 1 4 1 4 1 2 0 2
2 1 4 1 4 1 2 0 2
2 1 4 1 4 1 2 0 2
2 1 6 1 0 2 0 0 0
2 1 8 8 2 2 0 0
2 1 1 0 1 2 0 0 2 0
2 1 1 4 1 2 2 0 0 0
2 1 1 6 1 4 4 2 0 0
2 2 0 0 0 0 2 0
2 2 0 0 1 0 0 0
2 2 0 0 1 0 2 0
2 2 0 0 2 0 0 0
2 2 0 0 2 0 0 0
2 2 0 0 2 0 0 0
2 2 0 0 2 0 0 0
2 2 0 0 2 0 0 0
2 2 0 0 2 0 0 0
2 2 0 0 2 0 0 0
2 2 0 0 2 0 2 0
2 2 0 0 3 0 0 0
2 2 0 0 3 0 0 0
Appendix: Formula Index to the Tables VI 1133
Constitutional Base Unit
Poly-
CHz c o CsH4 C H 0 N s x
Oxydiethylene 4,4-dibenzoate
3,3-(Tetramethylenedioxy)dibenzoic anhydride
4,4-(Tetramethylenedioxy)dibenzoic anhydride
Tetramethylene 4,4-oxydibenzoate
Ethylene 3,3-(ethylenedioxy)dibenzoate
Ethylene 4,4-(ethylenedioxy)dibenzoate
(0xydiethylenedioxy)dibenzoic anbydride
4,4-Biphenylene adi pami de
3,4-Oxydiphenylene adi pami de
4,4-Oxydiphenylene adi pami de
Ethylene 4,4-(ethylenediphenylene)diurethan
Trimethylene 4,4-(methylenediphenylene)diurethan
Tetramethylene 4,4-sulfonyldibenzamide
Tetramethylene 4,4-phosphinylidenedibenzamide
4,4-Biphenylene disiloxanylenedipropionamide
Tetramethylene 4,4-(methylphosphinylidene)dibenzamide
1,4-Cyclohexylene 3,3-dibenzamide
Cyclopropylenedimethylene 4,4-methylenediphenylenediurethane
4,4-Isopropylidenediphenylene dithioladipate
4,4-Isopropylidenediphenylene adipate
Piperazine 2,cdiphenyL 1,3-cyclobutylenedicarboxamide
4,4-Biphenylene (tetramethyldisiloxanylene)dipropionamide
4,4-Isopropylidenediphenylene dithiol- 1,3-cyclohexylenedicarboxylate
Methyl p-phenylene 4,4-tetramethylenedioxydibenzoate
4,4-Biphenylene-4,4-(dimethoxy)dibenzylidenimino adipate
4,4-Oxydiphenylene-4,4-(dimethoxy)dibenzylidenimino adipate
p-Phenylene 4,4-tetramethylenedioxydibenzoate
Tetramethylene 4,4-(phenylphosphinylidene)dibenzamide
p-Phenylene-4,4-dibenzylidenimino adipate
4,4-Biphenylene-4,4-dibenzylidenimino adipate
4,4-Oxydiphenylene-4,4-dibenzylidenimino adipate
Alanylglycylproline
Alanylprolylglycine
a-D-Glucotripropionate, 1,4-
fl-D-Glucotripropionate, 1,4-
Alanyl(ethylglutamyl)glycine
Tetramethylene 3,3,4,4-oxydiphenylenetetracarboximide
Trimethylene NJ-malonyldi@-aminobenzoate)
3,4-Oxydiethylenedioxydiphenylene 3,3,4,4-oxydiphenylenetetra-
carboximide
Isophthalic 4,4-(tetramethylenedioxy)dibenzoic anhydride
Terephthalic 4,4-(tetramethylenedioxy)dibenzoic anhydride
Tetramethylene (4,4-terephthaloyldioxy)~dibenzoate
4,4-(1sopropylidenediphenylene)dioxydiacetic p-phenylenedioxydiacetic an
Methylenediphenylenedisuccinimidediyliminome~ylene~phenylene~ine
4,4-(0xydiphenylenedioxy)diphenylene carbonyldiphenylenetetra-
carboximide
Alanylglycylalanylglycylserylglycine
2,2-Adipamidodibenzoic isophthalic anhydride
4,4-Adipamidodibenzoic isophthalic anhydride
2,2-Adipamidodibenzoic terephthalic anhydride
4,4-Adipamidodibenzoic terephthalic anhydride
5
Pentamethylene
Pentamethylene sulfide
Methylenethiotetramethylene sulfide
Pentamethylene disulfide
Methyleneoxytetramethylene oxide
Pentamethylene sulfone
6-Aminothiocaproic acid
2,5-Pentamethylene-1,3,4-triazole
1,2-Cyclopentylene-&-ethylene
Heptenamer
Vinyl cyclopentane
1,2-Dichloroheptamethylene
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
4
4
4
4
6
6
6
6
6
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
4
4
0
0
0
0
0
0
2
2
3
3
3
3
4
2
0
3
3
3
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 2
0 2
0 2
0 2
0 2
0 2
0 3
0 6
1 5
2 4
2 4
3 6
3 6
4 6
4 1 4
5 8
I 6
1 6 1 4
1 6 1 4
0 0
0 3
2 2
2 2
2 2
3 I
3 I
8 1 4
8 1 4
4 11
1 2 6
0 2
1 2 6
0
0
0
3
2
1 2
5
0
0
0
0
0
0
0
0
0
0
0
1
2
2
2
2
2
1 6
2
2
2
2
0
0
0
0
0
0
0
1
1
2
2
2
2
3
3
3
3
4
4
4
0
1
1
2
2
2
1
1
1
0
2
0
2
0
1
0
4
4
5
4
1
2
2
3
0
0
5
5
1
1
2
4
4
4
4
4
0
3
1
2
2
2
2
0
0
0
0
0
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
2
2
2
2
2
2
2
2
2
0
0
2
2
0
0
2
2
0
2
2
2
2
3
3
0
0
3
2
2
2
6
2
2
2
2
0
0
0
0
0
0
0
1
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
2
0
0
0
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
2
2
0
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
2
1
0
0
0
0
0
2
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
References page VI- 159
VI / 134 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHz
C O C6H4 C H 0 N s x
2,5-Pentamethylene- 1 -amino- 1,3,4-triazole 5 0 0 2 2 0 4 0 0
1,4-Cyclohexyleneoxymethylene oxide 5 0 0 2 2 2 0 0 0
1 -Heptene 5 0 0 2 4 0 0 0 0
n-Heptaldehyde 5 0 0 2 4 1 0 0 0
Vinyl cyclohexene 5 0 0 3 2 0 0 0 0
3,4-Dihydrocyclohexylidenedimethylene oxide 5 0 0 3 2 1 0 0 0
1 ,%Nonadiyne, 1,9- 5 0 0 4 0 0 0 0 0
3,4-Dihydro-4-methylcyclohexylidenedimethylene oxide 5 0 0 4 4 1 0 0 0
3-Methylvinyl cyclohexane 5 0 0 4 6 0 0 0 0
4-Methylvinyl cyclohexane 5 0 0 4 6 0 0 0 0
2-Methoxyvinyl cyclohexane 5 0 0 4 6 1 0 0 0
3-Hexyl-2,5-thiophene 5 0 0 5 4 0 0 1 0
Di- 1,4-naphthaleneoxypentamethylene oxide 5 0 0 20 1 2 2 0 0 0
Pentamethyleneoxy-p-phenylene oxide 5 0 1 0 0 2 0 0 0
Pentamethylene m-phenylenedisulfonamide 5 0 1 0 2 4 2 2 0
4,4-(Methylenediphenylene)diethylene sulfide 5 0 2 0 0 0 0 1 0
4,4-Stilbenediyloxypentamethylene oxide 5 0 2 2 2 2 0 0 0
cc-methyl-4,4-stilbenediyloxypentamethylene oxide 5 0 2 3 4 2 0 0 0
6-Mercaptocaproic acid 5 1 0 0 0 0 0 1 0
6-Hydroxycaproic acid 5 1 0 0 0 1 0 0 0
Pentamethylene carbonate 5 1 0 0 0 2 0 0 0
6-Aminocaproic acid (caprolactam) 5 1 0 0 1 0 1 0 0
Pentamethylene urethane 5 1 0 0 1 1 1 0 0
N-Valerylethylene amine 5 1 0 1 3 0 1 0 0
4-Aminocyclohexyleneacetic acid 5 1 0 2 3 0 1 0 0
4-Methyl-7-hydroxyenanthic acid 5 1 0 2 4 1 0 0 0
3-Methyl-7-aminoenanthic acid 5 1 0 2 5 0 1 0 0
4-Methyl-7-aminoenanthic acid 5 1 0 2 5 0 1 0 0
5-Methyl-7-aminoenanthic acid 5 1 0 2 5 0 1 0 0
6-Methyl-7-aminoenanthic acid 5 1 0 2 5 0 1 0 0
3-n-Hexylhydroxybenzoic acid 5 1 0 7 6 1 0 0 0
4,4-Cyclohexylidene-2,2-dimethyldiphenylene carbonate 5 1 0 15 1 2 2 0 0 0
p-(Aminoethylene)phenylenebutyric acid 5 1 1 0 1 0 1 0 0
p-(Aminomethylene)phenylenevaleric acid 5 1 1 0 1 0 1 0 0
N-4-(Methylthiophenoxy)butyrylethylene amine 5 1 1 1 3 1 1 1 0
4,4-Cyclohexylidenediphenylene carbonate 5 1 2 1 0 2 0 0 0
Pimelic anhydride 5 2 0 0 0 1 0 0 0
Ethylene glutarate 5 2 0 0 0 2 0 0 0
Pentamethylene oxalate 5 2 0 0 0 2 0 0 0
Tetramethylene malonate 5 2 0 0 0 2 0 0 0
Trimethylene succinate 5 2 0 0 0 2 0 0 0
Oxydiethylene malonate 5 2 0 0 0 3 0 0 0
Trimethylene oxydiacetate 5 2 0 0 0 3 0 0 0
Hydrazo pimelamide 5 2 0 0 2 0 2 0 0
Methylene adipamide 5 2 0 0 2 0 2 0 0
Tetramethylene malonamide 5 2 0 0 2 0 2 0 0
(2,6-Dioxo-1,4-piperidinediyl)trimethylene 5 2 0 1 1 0 1 0 0
N5-(3-Hydroxypropyl)glutamine 5 2 0 1 4 1 2 0 0
Piperazine cyclopropylenedicarboxamide 5 2 0 2 2 0 2 0 0
Cyclopropylene piperazinediurea 5 2 0 2 4 0 4 0 0
Methylethylene adipate 5 2 0 2 4 2 0 0 0
Tetramethylene cyclopropylenediurethane 5 2 0 2 4 2 2 0 0
n-Butylglutamate 5 2 0 2 5 1 1 0 0
Alanyl-6-Aminocaproic acid 5 2 0 2 6 0 2 0 0
Piperazine (1-methylcyclopropylene)dicarboxamide 5 2 0 3 4 0 2 0 0
Ethylene 3,3-dimethoxy-4,4-(trimethylenedioxy)dibenzoate 5 2 0 1 4 1 2 6 0 0 0
3,3-Dimethyl-4,4-methylenediphenylene adi pami de 5 2 0 1 4 1 4 0 2 0 0
N,N-Diisopropyl-3,3 -dimethyl-methylenediphenylene adipamide 5 2 0 20 2 6 0 2 0 0
Pentamethylene dithiolisophthalate 5 2 1 0 0 0 0 2 0
Pentamethylene dithiolterephthalate 5 2 1 0 0 0 0 2 0
Pentamethylene isophthalate 5 2 1 0 0 2 0 0 0
Pentamethylene phthalate 5 2 1 0 0 2 0 0 0
Pentamethylene terephthalate 5 2 1 0 0 2 0 0 0
Trimethylene p-phenylenediacetate 5 2 1 0 0 2 0 0 0
Ethylene p-(carboxyphenoxy)butyrate 5 2 1 0 0 3 0 0 0
Constitutional Base Unit
Poly-
Appendix: Formula index to the Tables VI / 13.5
CHz
C O CaH4 C H 0 N s x
Pentamethylene m-carboxycarbanilate 5 2 1 0 1 2 1 0 0
Pentamethylene p-carboxycarbanilate 5 2 1 0 1 2 1 0 0
Pentamethylene terephthalamide 5 2 1 0 2 0 2 0 0
p-Phenylene pimelamide 5 2 1 0 2 0 2 0 0
Tetramethylene p-(carboxyphenylene)acetamide 5 2 1 0 2 0 2 0 0
p-Xylylene glutaramide 5 2 1 0 2 0 2 0 0
3-Phenylpropylglutamate 5 2 1 1 3 1 1 0 0
N-Benzyloxycarbonyllysine 5 2 1 1 4 1 2 0 0
p-Phenylene( 1,l -dimethyl)ethylene adipamide 5 2 1 3 8 0 2 0 0
N,N-Dipropylmethylene-4,4-dimethyldiphenylene terephthalamide 5 2 1 1 6 1 8 0 2 0 0
4,4-Pentamethylenedibenzoic anhydride 5 2 2 0 0 1 0 0 0
4,4-Methylenediphenylene adipate 5 2 2 0 0 2 0 0 0
Pentamethylene 2,2-dibenzoate 5 2 2 0 0 2 0 0 0
Pentamethylene 3,3-dibenzoate 5 2 2 0 0 2 0 0 0
Pentamethylene 4,4-dibenzoate 5 2 2 0 0 2 0 0 0
Oxydiethylene 4,4-methylenedibenzoate 5 2 2 0 0 3 0 0 0
3,3 -(Pentamethylenedioxy)dibenzoic anhydride 5 2 2 0 0 3 0 0 0
4,4-(Pentamethylenedioxy)dibenzoic anhydride 5 2 2 0 0 3 0 0 0
Pentamethylene 4,4-oxydibenzoate 5 2 2 0 0 3 0 0 0
Ethylene 4,4-(trimethylenedioxy)dibenzoate 5 2 2 0 0 4 0 0 0
4,4-Methylenediphenylene adipamide 5 2 2 0 2 0 2 0 0
3,4-Oxydiphenylene pimelamide 5 2 2 0 2 1 2 0 0
4,4-Oxydiphenylene pimelamide 5 2 2 0 2 1 2 0 0
Ethylene 4,4-(trimethylenediphenylene)diurethane 5 2 2 0 2 2 2 0 0
Tetramethylene 4,4-(methylenediphenylene)diurethane 5 2 2 0 2 2 2 0 0
Tetramethylene methylenediphenylenediaminodithiodicarboxylate 5 2 2 0 2 2 2 2 0
4,4-Methylenediphenylene disiloxanylenedipropionamide 5 2 2 0 6 1 2 0 2
1,4-Cyclohexylene 3,3-methylenedibenzamide 5 2 2 2 4 0 2 0 0
N,N-Dimethyl-4,4-methylenediphenylene adi pami de 5 2 2 2 6 0 2 0 0
Tetramethylene 4,4-propylenedibenzamide 5 2 2 2 6 0 2 0 0
Tetramethylene 4,4-(propylenedioxy)dibenzamide 5 2 2 2 6 2 2 0 0
2,2-Diethyltrimethylene 4,4-(methylenediphenylene)diurethane 5 2 2 3 8 2 2 0 0
I-Ethyl-2-propyltrimethylene (methylenediphenylene)diurethane 5 2 2 4 1 0 2 2 0 0
4,4-Methylenediphenylene tetramethyldisiloxanylenedipropionamide 5 2 2 4 1 4 1 2 0 2
N,N-Dipropyl-4,4-methylenediphenylene terephthalamide 5 2 3 2 6 0 2 0 0
Glycyl-3-aminopropionic acid-3aminopropionic acid 5 3 0 0 3 0 3 0 0
Glycylglycylproline 5 3 0 1 3 0 3 0 0
N,N-Lysyl propylenediurea 5 3 0 3 1 0 1 4 0 0
Methyl-N,N-lysyl propylenediurea 5 3 0 4 1 2 1 4 0 0
Tetramethylene (cyclopropylenedicarboxoyl)diurethane 5 4 0 2 4 2 2 0 0
Ethylene N,N-trimethylenediterephthalamate 5 4 2 0 2 2 2 0 0
Isophthaloyl (m-carboxyphenoxycapryl)dihydrazide 5 4 2 0 4 1 4 0 0
@-Phenylenedioxy)diacetic trimethylenedioxydibenzoic anhydride 5 4 3 0 0 6 0 0 0
6 6 0 0 0 0 0 0 0 0
Hexamethylene sulfide 6 0 0 0 0 0 0 1 0
Ethylenethiotetramethylene sulfide 6 0 0 0 0 0 0 2 0
Hexamethylene disulfide 6 0 0 0 0 0 0 2 0
(Ethylenedithio)tetramethylene disulfide 6 0 0 0 0 0 0 4 0
hexamethylene oxide 6 0 0 0 0 1 0 0 0
Methyleneoxypentamethylene oxide 6 0 0 0 0 2 0 0 0
Hexamethylene sulfone 6 0 0 0 0 2 0 1 0
Hexamethylene amine 6 0 0 0 1 0 1 0 0
7-Aminothioenanthic acid 6 0 0 1 1 0 1 1 0
Hexamethylene thiourea 6 0 0 1 2 0 2 1 0
2,SHexamethylene- 1,3,4-triazole 6 0 0 2 1 0 3 0 0
3-Cyclopentylpropene 6 0 0 2 2 0 0 0 0
Octenamer 6 0 0 2 2 0 0 0 0
Vinyl cyclohexane 6 0 0 2 2 0 0 0 0
2,5-Hexamethylene-1-amino-1,3,4-triazole 6 0 0 2 2 0 4 0 0
1-Octene 6 0 0 2 4 0 0 0 0
Caprylaldehyde 6 0 0 2 4 1 0 0 0
Di-n-butylsilylene 6 0 0 2 6 0 0 0 1
n-Propyl-n-pentylsilylene 6 0 0 2 6 0 0 0 1
4-Methylcyclohexylidenedimethylene oxide 6 0 0 3 4 1 0 0 0
3,3-Bisethoxymethyloxacyclobutane 6 0 0 3 6 3 0 0 0
References page VI- 159
VI / 136 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CH2 C O CsH4 C H 0 N s x
5-Diisobutylamino-1-pentene 6 0 0 7 1 5 0 1 0 0
Di- 1,4naphthaleneoxyhexamethylene oxide 6 0 0 20 1 2 2 0 0 0
Hexamethyleneoxy-p-phenylene oxide 6 0 1 0 0 2 0 0 0
Hexamethylene m-phenylenedisulfonamide
6 0 1 0 2 4 2 2 0
Benzylidenethiohexamethylene sulfide 6 0 1 1 2 0 0 2 0
Hexamethylene dithioterephthalamide 6 0 1 2 2 0 2 2 0
p-Methoxybenzylidenethiohexamethylene sulfide
6 0 1 2 4 1 0 2 0
4,4-Stilbenediyloxyhexamethylene oxide 6 0 2 2 2 2 0 0 0
cc-Methyl-4,4-stilbenediyloxyhexamethylene oxide 6 0 2 3 4 2 0 0 0
7-Hydroxyenanthic acid
6 1 0 0 0 1 0 0 0
Hexamethylene carbonate 6 1 0 0 0 2 0 0 0
7-Aminoenanthic acid 6 1 0 0 1 0 1 0 0
Hexamethylene urea
6 1 0 0 2 0 2 0 0
N-Hexanoylethylene amine 6 1 0 1 3 0 1 0 0
N-Methyl-7-aminoenanthic acid 6 1 0 1 3 0 1 0 0
Vinylcyclohexyl ketone 6 1 0 2 2 0 0 0 0
(3-Aminomethylene)cyclohexyleneacetic acid 6 1 0 2 3 0 1 0 0
(l,3-Dimethyl-3-aminomethylene)cyclohexyleneacetic acid 6 1 0 4 7 0 1 0 0
p-(Aminoethylene)phenylenevaleric acid
6 1 1 0 1 0 1 0 0
4,4-Nonylidenediphenylene carbonate 6 1 2 3 6 2 0 0 0
Ethylene dithioladipate 6 2 0 0 0 0 0 2 0
Suberic anhydride
6 2 0 0 0 1 0 0 0
(Ethylenedithio)dipropionic anhydride 6 2 0 0 0 1 0 2 0
Piperazine oxydiacetamide 6 2 0 0 0 1 2 0 0
Ethylene adipate
6 2 0 0 0 2 0 0 0
Hexamethylene oxalate 6 2 0 0 0 2 0 0 0
Tetramethylene succinate 6 2 0 0 0 2 0 0 0
Trimethylene glutarate
6 2 0 0 0 2 0 0 0
Barium suberate 6 2 0 0 0 2 0 0 1
Cadmi um suberat e 6 2 0 0 0 2 0 0 1
Calcium suberate 6 2 0 0 0 2 0 0 1
Lead suberate 6 2 0 0 0 2 0 0 1
Magnesium suberate 6 2 0 0 0 2 0 0 1
Manganese suberate 6 2 0 0 0 2 0 0 1
Stannous suberate 6 2 0 0 0 2 0 0 1
Zinc suberate 6 2 0 0 0 2 0 0 1
Hexamethylene dithiodicarboxylate
6 2 0 0 0 2 0 2 0
Ethylene 1,4-piperazinedicwboxylate 6 2 0 0 0 2 2 0 0
Oxydiethylene succinate 6 2 0 0 0 3 0 0 0
Tetramethylene oxydiacetate 6 2 0 0 0 3 0 0 0
(Ethylenedioxy)diethylene oxalate 6 2 0 0 0 4 0 0 0
Oxydiethylene oxydiacetate 6 2 0 0 0 4 0 0 0
(Ethylenedisulfonyl)dipropionic anhydride
6 2 0 0 0 5 0 2 0
Ethylene adipamide 6 2 0 0 2 0 2 0 0
Glycyl-6-aminocaproic acid 6 2 0 0 2 0 2 0 0
Hexamet hyl ene oxamide
6 2 0 0 2 0 2 0 0
Hydrazo suberamide 6 2 0 0 2 0 2 0 0
Methylene pimelamide 6 2 0 0 2 0 2 0 0
Pentamethylene malonamide
6 2 0 0 2 0 2 0 0
Tetramethylene succinamide 6 2 0 0 2 0 2 0 0
Ethylene (ethylenedioxy)diacetamide 6 2 0 0 2 2 2 0 0
Aminoditrimethylene oxamide
6 2 0 0 3 0 3 0 0
Ethylene disiloxanylenedipropionamide 6 2 0 0 6 1 2 0 2
2,2-Bischloromethyltrimethylene succinate 6 2 0 1 0 2 0 0 2
NS-(4-Hydroxybutyl)glutamine
6 2 0 1 4 1 2 0 0
(Methylamino)ditrimethylene oxamide 6 2 0 1 5 0 3 0 0
1 ,CCyclohexylene dithiolsuccinate 6 2 0 2 2 0 0 2 0
Piperazine 1,3-cyclobutylenedicarboxamide 6 2 0 2 2 0 2 0 0
1,4-Cyclohexylenedimethylene oxalate 6 2 0 2 2 2 0 0 0
Ethylene 1,4-cyclohexylenedicarboxylate 6 2 0 2 2 2 0 0 0
Hexamethylene fumarate 6 2 0 2 2 2 0 0 0
2,5-Tetrahydrofurandipropionic anhydride 6 2 0 2 2 2 0 0 0
2,5-Tetrahydropyrroledipropionic anhydride 6 2 0 2 3 1 1 0 0
Methylethylene pimelate
6 2 0 2 4 2 0 0 0
Pentamethylene cyclopropylenediurethane 6 2 0 2 4 2 2 0 0
Appendi x: Formul a I ndex to the Tabl es VI / 137
Constitutional Base Unit
Poly- CH2 C O ChH4 C H 0 N s x
n-Amylglutamate 6 2 0 2 5 1 1 0 0
N,N-Dimethyltetramethylene succinamide 6 2 0 2 6 0 2 0 0
Hexamet hyl ene L-tartaramide 6 2 0 2 6 2 2 0 0
Hexafluoropentamethylene adipate 6 2 0 3 0 2 0 0 6
Hexafluoropentamethylene adipamide 6 2 0 3 2 0 2 0 6
Hexamethylene perfluoroglutaramide 6 2 0 3 2 0 2 0 6
N-Methyl-2,5-tetrahydropymoledipropionic anhydride 6 2 0 3 5 1 1 0 0
2,2-Dimethyltrimethylene adipate 6 2 0 3 6 2 0 0 0
lsopropylidenedimethylene piperazinedithiodicarboxylate 6 2 0 3 6 2 2 2 0
Hexamet hyl ene 2,2-dimethylmalonamide 6 2 0 3 8 0 2 0 0
2,4-Hexadiyne adipate 6 2 0 4 0 2 0 0 0
Hexamet hyl ene 2,5-thiophenedicarboxamide 6 2 0 4 4 0 2 1 0
Hexamet hyl ene 2,5-furandicarboxamide 6 2 0 4 4 1 2 0 0
2-Butene 4-octenediamide 6 2 0 4 6 0 2 0 0
Hexamet hyl ene (3-methylcyclopropylene)dicarboxamide 6 2 0 4 8 0 2 0 0
Hexamethylene di-O-methyl-L-tartaramide 6 2 0 4 1 0 2 2 0 0
Tetramethylene (2,5-dimethylpiperazine)dithiodicarboxylate 6 2 0 4 1 0 2 2 2 0
Ethylene (Tetramethyldisiloxanylene)dipropionamide 6 2 0 4 1 4 1 2 0 2
Hexamet hyl ene 2,3-pyridinedicarboxamide 6 2 0 5 5 0 3 0 0
Hexamethylene 2,4-pyridinedicarboxamide 6 2 0 5 5 0 3 0 0
Hexamet hyl ene 2,5-pyridinedicarboxamide 6 2 0 5 5 0 3 0 0
Hexamethylene 2,6-pyridinedicarboxamide 6 2 0 5 5 0 3 0 0
Hexamethylene 3,4-pyridinedicarboxamide 6 2 0 5 5 0 3 0 0
Hexamet hyl ene 3,5-pyridinedicarboxamide 6 2 0 5 5 0 3 0 0
NJ-Dimethyl(hexafluoropentamethylene) adipamide 6 2 0 5 6 0 2 0 6
NJ-Dimethylhexamethylene perfluoroglutaramide 6 2 0 5 6 0 2 0 6
Hexamethylene 2,5-dihydroxyterephthalamide 6 2 0 6 6 2 2 0 0
Hexamethylene methylterephthalamide 6 2 0 I 8 0 2 0 0
Hexamethylene 2,6-dimethyl-3,5-pyridinedicarboxamide 6 2 0 I 9 0 3 0 0
Hexamethylene 4-methyl-1,3-phenylenediurea 6 2 0 I 1 0 0 4 0 0
Hexamethylene 2,5-dimethylterephthalamide 6 2 0 8 1 0 0 2 0 0
N,N-Diisopropyl(hexafluoropentamethylene) adipamide 6 2 0 9 1 4 0 2 0 6
NJ-Diisopropylhexamethylene perfluoroglutaramide 6 2 0 9 1 4 0 2 0 6
Tetramethyl-p-xylylene dithioladipate 6 2 0 1 0 1 2 0 0 2 0
Hexamethylene 5-tert-butylisophthalamide 6 2 0 1 0 1 4 0 2 0 0
4-Methylphenylene diethyldimethyldisiloxanylenedipropionamide 6 2 0 11 20 1 2 0 2
1,4-Cyclohexylenedimethylene 2,6-naphthalate 6 2 0 1 2 8 2 0 0 0
Ethylene 3,3-dimethoxy-4,4-(tetramethylenedioxy)dibenzoate 6 2 0 1 4 1 2 6 0 0 0
Ethylene 3,3-dimethoxy-4,4-(oxydiethylene)dioxydibenzoate 6 2 0 1 4 1 2 7 0 0 0
Hexamethylene dithiolisophthalate 6 2 1 0 0 0 0 2 0
Hexamethylene dithiolterephthalate 6 2 1 0 0 0 0 2 0
p-Xylylene dithioladipate 6 2 1 0 0 0 0 2 0
(p-Xylylenedithio)dipropionic anhydride 6 2 1 0 0 1 0 2 0
Hexamethylene isophthalate 6 2 1 0 0 2 0 0 0
Hexamethylene phthalate 6 2 1 0 0 2 0 0 0
Hexamethylene terephthalate 6 2 1 0 0 2 0 0 0
Tetramethylene p-phenylenediacetate 6 2 1 0 0 2 0 0 0
p-Xylylene adipate 6 2 1 0 0 2 0 0 0
Ethylene p-(carboxyphenoxy)valerate 6 2 1 0 0 3 0 0 0
(Ethylenedioxy)diethylene isophthalate 6 2 1 0 0 4 0 0 0
(Ethylenedioxy)diethylene terephthalate 6 2 1 0 0 4 0 0 0
@-Xylylenedisulfonyl)dipropionic anhydride 6 2 1 0 0 5 0 2 0
Hexamethylene m-carboxycarbanilate 6 2 1 0 1 2 1 0 0
Hexamethylene isophthalamide 6 2 1 0 2 0 2 0 0
Hexamethylene phthalamide 6 2 1 0 2 0 2 0 0
Hexamethylene terephthalamide 6 2 1 0 2 0 2 0 0
Pentamethylene p-(carboxyphenylene)acetamide 6 2 1 0 2 0 2 0 0
p-Phenyleneethylene adipamide 6 2 1 0 2 0 2 0 0
m-Phenylene suberamide 6 2 1 0 2 0 2 0 0
o-Phenylene suberamide 6 2 1 0 2 0 2 0 0
p-Phenylene suberamide 6 2 1 0 2 0 2 0 0
m-Xylylene adipamide 6 2 1 0 2 0 2 0 0
p-Xylylene adipamide 6 2 1 0 2 0 2 0 0
Oxyditrimethylene terephthalamide 6 2 1 0 2 1 2 0 0
m-Phenylene hexamethylenediurethane 6 2 1 0 2 2 2 0 0
References page VI- 159
VI / 138 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHz
C O CSH4 C H 0 N s x
p-Phenylene hexamethylenediurethane 6 2 1 0 2 2 2 0 0
Tetramethylene p-xylylenediurethane 6 2 1 0 2 2 2 0 0
Hexamethylene m-phenylenediurea 6 2 1 0 4 0 4 0 0
1,4-Cyclohexylenedimethylene isophthalate 6 2 1 2 2 2 0 0 0
1,4Cyclohexylenedimethylene terephthalate 6 2 1 2 2 2 0 0 0
p- Xyl yl ene 1,4-cyclohexylenedicarboxylate 6 2 1 2 2 2 0 0 0
1,4-Cyclohexylenedimethylene isophthalamide 6 2 1 2 4 0 2 0 0
N,N-Dimethylhexamethylene terephthalamide 6 2 1 2 6 0 2 0 0
Hexamethylene naphtbalenedicarboxamide 6 2 1 4 6 0 2 0 0
o-Phenylene (diethyldimethyldisiloxanylene)dipropionamide 6 2 1 4 1 4 1 2 0 2
p-Phenylene (diethyldimethyldisiloxanylene)dipropionamide 6 2 1 4 1 4 1 2 0 2
p-Phenylene dibutylcyclobutylenedicarboxylate 6 2 1 6 1 0 2 0 0 0
p-Phenylene dicyanodibutylcyclobutylenedicarboxylate 6 2 1 8 8 2 2 0 0
4,4-Hexamethylenedibenzoic anhydride 6 2 2 0 0 1 0 0 0
Ethylene 4,4-tetramethylenedibenzoate 6 2 2 0 0 2 0 0 0
Hexamet byl ene 2,2-dibenzoate 6 2 2 0 0 2 0 0 0
Hexamet byl ene 3,3-dibenzoate 6 2 2 0 0 2 0 0 0
Hexamet hyl ene 4,4-dibenzoate 6 2 2 0 0 2 0 0 0
p-Phenyleneditrimethylene terephthalate 6 2 2 0 0 2 0 0 0
Hexamethylene dithiol-4,4-sulfonyldibenzoate 6 2 2 0 0 2 0 3 0
3,3-(Hexamethylenedioxy)dibenzoic anhydride 6 2 2 0 0 3 0 0 0
4,4-(Hexamethylenedioxy)dibenzoic anhydride 6 2 2 0 0 3 0 0 0
Hexamet hyl ene 4,4-oxydibenzoate 6 2 2 0 0 3 0 0 0
Oxydiethylene 4,4-ethylenedibenzoate 6 2 2 0 0 3 0 0 0
(Ethylenedioxy)diethylene 2,2-dibenzoate 6 2 2 0 0 4 0 0 0
(Ethylenedioxy)diethylene 3,3-dibenzoate 6 2 2 0 0 4 0 0 0
(Ethylenedioxy)diethylene 4,4-dibenzoate 6 2 2 0 0 4 0 0 0
Ethylene 4,4-(ethylenedioxydimethylene)dibenzoate 6 2 2 0 0 4 0 0 0
Ethylene 3,3-(tetramethylenedioxy)dibenzoate 6 2 2 0 0 4 0 0 0
Ethylene 4,4-(tetramethylenedioxy)dibenzoate 6 2 2 0 0 4 0 0 0
Tetramethylene 4,4-(ethylenedioxy)dibenzoate 6 2 2 0 0 4 0 0 0
Hexamethylene 4,4-sulfonyldibenzoate 6 2 2 0 0 4 0 1 0
Ethylene 4,4-(oxydiethylene)dioxydibenzoate 6 2 2 0 0 5 0 0 0
4,4-Ethylenediphenylene adi pami de 6 2 2 0 2 0 2 0 0
Hexametbylene 3,3 -dibenzamide 6 2 2 0 2 0 2 0 0
Hexamethylene 3,4-dibenzamide 6 2 2 0 2 0 2 0 0
Hexamethylene 4,4-dibenzamide 6 2 2 0 2 0 2 0 0
Hexamethylene 2,2-dibenzamide 6 2 2 0 2 0 2 0 0
p-Phenylenediethylene m-phenylenediacetamide 6 2 2 0 2 0 2 0 0
3,4-Oxydiphenylene suberamide 6 2 2 0 2 1 2 0 0
4,4-Oxydiphenylene suberami de 6 2 2 0 2 1 2 0 0
Ethylene 4,4-(tetramethylenediphenylene)diurethane 6 2 2 0 2 2 2 0 0
Pentamethylene 4,4-(methylenediphenylene)diurethane 6 2 2 0 2 2 2 0 0
Hexamet byl ene 4,4-sulfonyldibenzamide 6 2 2 0 2 2 2 1 0
Hexamet hyl ene 3,3-phosphinylidenedibenzamide 6 2 2 0 3 1 2 0 1
Hexamet hyl ene 4,4-phosphinylidenedibenzamide 6 2 2 0 3 1 2 0 1
Hexamet hyl ene 4,4-(hydroxyphosphinylidene)dibenzamide 6 2 2 0 3 2 2 0 1
Hexamet hyl ene 4,4-silylenedibenzamide 6 2 2 0 4 0 2 0 1
4,4-Dithiodiphenylene hexamethylenediurea 6 2 2 0 4 0 4 2 0
Hexamet hyl ene 4,4-disiloxanylenedibenzamide 6 2 2 0 6 1 2 0 2
Hexamet hyl ene 4,4-tetrasiloxanylenedibenzamide 6 2 2 0 1 0 3 2 0 4
Hexamet hyl ene 3,3-(methylphosphinylidene)dibenzamide 6 2 2 1 5 1 2 0 1
Hexamet byl ene 4,4-(methylphosphinylidene)dibenzamide 6 2 2 1 5 1 2 0 1
Hexamet hyl ene 4,4-vinylenedibenzamide 6 2 2 2 4 0 2 0 0
2-Ethylhexamethylene dithiol-4,4-sulfonyldibenzoate 6 2 2 2 4 2 0 3 0
Hexamet hyl ene 4,4-ethylidenedibenzamide 6 2 2 2 6 0 2 0 0
Hexamet hyl ene 4,4-(dimethylsilylene)dibenzamide 6 2 2 2 8 0 2 0 1
Hexamet hyl ene 4,4-(methylvinylene)dibenzamide 6 2 2 3 6 0 2 0 0
Hexamet hyl ene 4,4-isopropylidenedibenzamide 6 2 2 3 8 0 2 0 0
4,4-Isopropylidenediphenylene hexamethylenediurethane 6 2 2 3 8 2 2 0 0
4,4-Dimethylheptamethylene sulfonyldibenzamide 6 2 2 3 8 2 2 1 0
Hexamet hyl ene 4,4-(tetramethyldisiloxanylene)dibenzamide 6 2 2 4 1 4 1 2 0 2
Hexamet hyl ene 4,4-(phenylphosphinylidene)dibenzamide 6 2 3 0 2 1 2 0 1
Hexamethylene tetramethyltetraphenyltetrasiloxanylenedibenzamide 6 2 6 4 1 4 3 2 0 4
Ethylene N,N-lysyldiurea 6 3 0 1 6 1 4 0 0
-
C C
PC
-
Et
G
H
H
0
H
E
A
2.
P
H
C
I
F
4
I
1
I
Appendix: Formula Index to the Tables VI / 139
Constitutional Base Unit
Poly-
CHz C O CaH.q C H 0 N s x
Ethylene methyl-NJ-lysyldiurea 6 3 0 2 8 1 4 0 0
Glycylprolylhydroxyproline 6 3 0 3 5 1 3 0 0
Hexamet hyl ene 4-oxo-4(H)-pyran-2,6-dicarboxamide 6 3 0 4 4 1 2 0 0
Hexamet hyl ene 1,4-dihydro-4-oxo-2,6-pyridinedicarboxamide 6 3 0 4 5 0 3 0 0
(Phenylglycyl)prolylproline 6 3 1 3 5 0 3 0 0
Hexamet hyl ene 4,4-ketodibenzamide 6 3 2 0 2 0 2 0 0
Ethylene adipoyldiurethane 6 4 0 0 2 2 2 0 0
Adipoyl ethylenediurea 6 4 0 0 4 0 4 0 0
2-Hydroxytrimethylene adipoyldiurethane 6 4 0 1 4 3 2 0 0
Pentamethylene (cyclopropylenedicarboxoyl)diurethane 6 4 0 2 4 2 2 0 0
Hexamethylene pyromellitimide 6 4 0 6 2 0 2 0 0
Oxydisilyleneditrimethylene pyromellitimide 6 4 0 6 6 1 2 0 2
Tetramethyloxydisilyleneditrimethylene pyromellitimide 6 4 0 1 0 1 4 1 2 0 2
Hexamet hyl ene 3,3,4,4-(oxydiphenylene)tetracarboximide 6 4 0 1 2 6 1 2 0 0
4,4-(Tetramethylenedicarbonyl)diphenylene succinate 6 4 2 0 0 2 0 0 0
Trimethylene N,N-glutaryldif&aminobenzoate) 6 4 2 0 2 2 2 0 0
Trimethylene NJ-trimethylenediterephthalamate 6 4 2 0 2 2 2 0 0
n-Benzylglutamyl-L-benzylglutamate 6 4 2 2 6 2 2 0 0
3,4-Ethylenedioxydiethylenedioxydiphenylene 3,34,4-oxydiphenylenetet 6 4 2 1 2 6 5 2 0 0
4,4-(Ethylenedioxydiethylenedioxy)diphenylene carbonyldiphenylenetetrac 6 5 2 1 2 4 4 2 0 0
Alanylglycylalanylglycylalanylglycylglutamylglycine 6 9 0 7 22 1 8 0 0
I 7 0 0 0 0 0 0 0 0
Heptamethylene 7 0 0 0 0 0 0 0 0
Heptamethylene disulfide 7 0 0 0 0 0 0 2 0
Tetramethylenethiotrimethylene sulfide 7 0 0 0 0 0 0 2 0
(Tetramethylenedithio)trimethylene disulfide 7 0 0 0 0 0 0 4 0
Hexamethyleneoxymethylene oxide 7 0 0 0 0 2 0 0 0
Cyclohexylidenedimethylene oxide 7 0 0 1 0 1 0 0 0
1,4-Piperidinediyltrimethylene 7 0 0 1 1 0 1 0 0
2,5-Heptamethylene-1,3,4-triazole 7 0 0 2 1 0 3 0 0
1,2Cycloheptylene-&ethylene 7 0 0 2 2 0 0 0 0
3-Cyclohexylpropene 7 0 0 2 2 0 0 0 0
Vinyl cycloheptane 7 0 0 2 2 0 0 0 0
2,5-Heptamethylene-1-amino-1,3,4-triazole 7 0 0 2 2 0 4 0 0
1,4-Cyclohexylenedimethyleneoxymethylene oxide 7 0 0 2 2 2 0 0 0
1 -Methyloctamethylene 7 0 0 2 4 0 0 0 0
1 -Nonene 7 0 0 2 4 0 0 0 0
n-Nonaldehyde 7 0 0 2 4 1 0 0 0
n-Butyl-n-pentylsilylene 7 0 0 2 6 0 0 0 1
3-Octyl-2,5-thiophene 7 0 0 5 4 0 0 1 0
Di- 1,4-naphthaleneoxyheptamethylene oxide 7 0 0 20 1 2 2 0 0 0
3-(4-0ctylphenyl)thiophene 7 0 1 5 4 0 0 1 0
4,4-Ethylene-3-methyldiphenyleneoxypentamethylene oxide 7 0 1 7 6 2 0 0 0
4,4-Stilbenediyloxyheptamethylene oxide 7 0 2 2 2 2 0 0 0
a-Methyl-4,4-stilbenediyloxyheptamethylene oxide 7 0 2 3 4 2 0 0 0
8-Aminocaprylic acid 7 1 0 0 1 0 1 0 0
Heptamethylene urea 7 1 0 0 2 0 2 0 0
N-Cyclohexanecarbonylethylene amine 7 1 0 1 1 0 1 0 0
N-Heptanoylethylene amine 7 1 0 1 3 0 1 0 0
2,2-Dibutyl-3-hydroxypropionic acid 7 1 0 3 6 1 0 0 0
A&-Dibutylacrylamide 7 1 0 3 7 0 1 0 0
Biphenyloxyhexamethylene acrylate 7 1 2 1 2 2 0 0 0
Azelaic anhydride 7 2 0 0 0 1 0 0 0
Ethylene pimelate 7 2 0 0 0 2 0 0 0
Pentamethylene succinate 7 2 0 0 0 2 0 0 0
Tetramethylene glutarate 7 2 0 0 0 2 0 0 0
Trimethylene adipate 7 2 0 0 0 2 0 0 0
Oxydiethylene glutarate 7 2 0 0 0 3 0 0 0
Pentamethylene oxydiacetate 7 2 0 0 0 3 0 0 0
(Ethylenedioxy)diethylene malonate 7 2 0 0 0 4 0 0 0
Hexamethylene malonamide 7 2 0 0 2 0 2 0 0
Hydrazo azelamide 7 2 0 0 2 0 2 0 0
Methylene suberamide 7 2 0 0 2 0 2 0 0
Pentamethylene oxydiacetamide 7 2 0 0 2 1 2 0 0
Tetramethylene trimethylenediurethane 7 2 0 0 2 2 2 0 0
References page VI-159
VI / 140 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHz c o CsH4 C H 0 N SX
Tri met hyl ene 1,4-cyclohexylenedicarboxylate 7 2 0 2 2 2 0 0 0
Cyclopropylenedimethylene piperazinediurethane 7 2 0 2 2 2 2 0 0
Hexamethylene cyclopropylenedicarboxamide 7 2 0 2 4 0 2 0 0
Piperazine 3-methyladipamide I 2 0 2 4 0 2 0 0
Trimethylene 4-octenediamide I 2 0 2 4 0 2 0 0
Hexamethylene 2,3-pyrazoledicarboxamide I 2 0 2 4 0 4 0 0
Hexamethylene 2,4-pyrazoledicarboxamide 7 2 0 2 4 0 4 0 0
Methylethylene suberate 7 2 0 2 4 2 0 0 0
n-Hexylglutamate 7 2 0 2 5 1 1 0 0
Cyclopropylene hexamethylenediurea 7 2 0 2 6 0 4 0 0
3-Oxypropylhexamethylene oxamide 7 2 0 2 6 1 2 0 0
Hexamet hyl ene (l-methylcyclopropylene)dicarboxamide 7 2 0 3 6 0 2 0 0
Hexamet hyl ene (methylene-2,5&rran)dicarboxamide 7 2 0 4 4 1 2 0 0
Hexamethylene 4(H)-pyran-2,6-dicarboxamide 7 2 0 4 4 1 2 0 0
Hexamet hyl ene 3,3-dimethyl-4,4-methylenediphenylenediurea 7 2 0 1 4 1 6 0 4 0 0
N,N-diethyl-3,3-dimethyl-4,4-methylenediphenylene adi pami de I 2 0 1 6 1 8 0 2 0 0
Heptamethylene terephthalate I 2 1 0 0 2 0 0 0
p-Phenylene azelate I 2 1 0 0 2 0 0 0
p-Xylylene pimelate I 2 1 0 0 2 0 0 0
Ethylene p-(carboxyphenoxy)caproate 7 2 1 0 0 3 0 0 0
Hexamet hyl ene p-(carboxyphenoxy)acetate 7 2 1 0 0 3 0 0 0
Heptamethylene terephthalamide 7 2 1 0 2 0 2 0 0
Hexamethylene p-(carboxyphenylene)acetamide 7 2 1 0 2 0 2 0 0
p-Phenylene azelamide 7 2 1 0 2 0 2 0 0
m-Xylylene pimelamide I 2 1 0 2 0 2 0 0
p-Xylylene pimelamide 7 2 1 0 2 0 2 0 0
p-Phenylene (methyl- 1,4-piperazine)dipropionate I 2 1 2 4 2 2 0 0
IV&-Dibutyl-4,4-(dimethylmethylene)diphenylene terephthalamide I 2 1 1 6 1 8 0 2 0 0
Ethylene 4,4-(pentamethylenedioxy)dibenzoate 7 2 2 0 0 4 0 0 0
Hexamet hyl ene 3,3-methylenedibenzamide 7 2 2 0 2 0 2 0 0
Hexamet hyl ene 4,4-methylenedibenzamide 7 2 2 0 2 0 2 0 0
3,4-Oxydiphenylene azelamide 7 2 2 0 2 1 2 0 0
4,4-Oxydiphenylene azelamide I 2 2 0 2 1 2 0 0
Hexamet hyl ene 4,4-(methylenediphenylene)diurethane 7 2 2 0 2 2 2 0 0
Heptamethylene 4,4-sulfonyldibenzamide I 2 2 0 2 2 2 1 0
Hexamet hyl ene 4,4-(methylenediphenylene)diurea I 2 2 0 4 0 4 0 0
IV&-Diethyl(methylenediphenylene) adipamide 7 2 2 2 6 0 2 0 0
2-Butyl-2-ethyltrimethylene methylenediphenylenediurethane 7 2 2 3 8 2 2 0 0
NJ/-Dibutyl(methylenediphenylene) terephthalamide 7 2 3 2 6 0 2 0 0
A&-Lysyl trimethylenediurea 7 3 0 1 6 1 4 0 0
Glycylprolylproline 7 3 0 2 3 0 3 0 0
Hexamethylene propylenediurea 7 3 0 2 8 0 4 0 0
Methyl-N,N-lysyl trimethylenediurea 7 3 0 2 8 1 4 0 0
a-D-Glucotributyrate, 1,4- I 3 0 8 1 4 5 0 0 0
8-n-Glucotributyrate, 1,4- I 3 0 8 1 4 5 0 0 0
Trimethylene adipoyldiurethane 7 4 0 0 2 2 2 0 0
Azelaoyl oxalodihydrazide 7 4 0 0 4 0 4 0 0
Pentamethylene N,N-ethylenediterephthalamate 7 4 2 0 2 2 2 0 0
Tetramethylene NJ-trimethylenediterephthalamate 7 4 2 0 2 2 2 0 0
Trimethylene N,N-adipoyldi(p-benzoate) I 4 2 0 2 2 2 0 0
Heptamethylene (4,4-terephthaloyldioxy)dibenzoate 7 4 3 0 0 4 0 0 0
8 8 0 0 0 0 0 0 0 0
Octamethylene 8 0 0 0 0 0 0 0 0
Ethylenethiohexamethylene sulfide 8 0 0 0 0 0 0 2 0
Octamethylene disulfide 8 0 0 0 0 0 0 2 0
(Ethylenedithio)hexamethylene disulfide 8 0 0 0 0 0 0 4 0
Octamethylene oxide 8 0 0 0 0 1 0 0 0
1,4-Piperazinediethylene sulfone 8 0 0 0 0 2 2 1 0
2,5-Octamethylene-1,3,4-oxadiazole 8 0 0 2 0 1 2 0 0
2,5-Octamethylene-1,3,4-triazole 8 0 0 2 1 0 3 0 0
4-Cyclohexyl- 1 -butene 8 0 0 2 2 0 0 0 0
Decenamer 8 0 0 2 2 0 0 0 0
1,2-Dichlorodecamethylene 8 0 0 2 2 0 0 0 2
2,5-Octamethylene-1-amino-1,3,4-triazole 8 0 0 2 2 0 4 0 0
1-Decene 8 0 0 2 4 0 0 0 0
-
C o
P O
-
Di
Ll
5,;
oc
F
27,
4/
U-I
131
9->
OC
N-
oc
T e
Tt
Pi]
(P
Se
Et
Ht
Pe
T e
Tr
Br
Cl
Cl
Lt
M
M
St
Zi
Pi
H I
0:
(E
HI
HI
H:
01
Pf
Tc
H
H
El
Tt
Et
Tf
El
El
Tr
2,
2,
2,
Pi
1,
1,
H
1,
1,
Z
E
Iv
2.
1 .
H
T
Appendix: Formula Index to the Tables VI / 141
Constitutional Base Unit
Poly- CH2
C O CsH4 C H 0 N s x
Di-n-pentylsilylene 8 0 0 2 6
l,lI-Dodecadiyne, 1,12- 8 0 0 4 0
5,7-Dodecadiynediol, $8 8 0 0 4 2
Octamethylene 5,5-dibenzimidazole 8 0 0 1 4 8
2,2-Octamethylenedithiazole-p-phenylene 8 0 1 6 2
4,4-Stilbenediyloxyoctamethylene oxide 8 0 2 2 2
a-methyl-4,4-stilbenediyloxyoctamethylene oxide 8 0 2 3 4
1,12-Bis(p-toluylsulfonyl)-5,7-dodecadiynediol, 5,8- 8 0 2 6 6
9Aminopelargonic acid 8 1 0 0 1
Octamethylene urea 8 1 0 0 2
N-Octanoylethylene amine 8 1 0 1 3
Octyl acrylate 8 1 0 2 4
Tetramethylene dithioladipate 8 2 0 0 0
Thiodiethylene dithioladipate 8 2 0 0 0
Piperazine adipamide 8 2 0 0 0
(Piperazinedicarbamoy1)dithiotetramethylene disulfide 8 2 0 0 0
Sebacic anhydride 8 2 0 0 0
Ethylene suberate 8 2 0 0 0
Hexamethylene succinate 8 2 0 0 0
Pentamethylene glutarate 8 2 0 0 0
Tetramethylene adipate 8 2 0 0 0
Trimethylene pimelate 8 2 0 0 0
Barium sebacate 8 2 0 0 0
Cadmi um sebacat e 8 2 0 0 0
Calcium sebacate 8 2 0 0 0
Lead sebacate 8 2 0 0 0
Magnesium sebacate 8 2 0 0 0
Manganese sebacate 8 2 0 0 0
Stannous sebacate 8 2 0 0 0
Zinc sebacate 8 2 0 0 0
Piperazine (ethylenedioxy)diacetamide 8 2 0 0 0
Hexamethylene oxydiacetate 8 2 0 0 0
Oxydiethylene adipate 8 2 0 0 0
(Ethylenedioxy)diethylene succinate 8 2 0 0 0
Heptamethylene malonamide 8 2 0 0 2
Hexamethylene succinamide 8 2 0 0 2
Hydrazo sebacamide 8 2 0 0 2
Octamethylene oxamide 8 2 0 0 2
Pentamethylene glutaramide 8 2 0 0 2
Tetramethylene adipamide 8 2 0 0 2
Hydrazo thiodivaleramide 8 2 0 0 2
Hexamethylene oxydiacetamide 8 2 0 0 2
Ethylene hexamethylenediuirethane 8 2 0 0 2
Tetramethylene tetramethylenediuretbane 8 2 0 0 2
Ethylene (ethylenedithio)diethylenediurethane 8 2 0 0 2
Tetramethylene (1,4-piperazinedithio)dicarboxylate 8 2 0 0 2
Ethylene (ethylenediamino)dipropionamide 8 2 0 0 4
Ethylene hexamethylenediurea 8 2 0 0 4
Tetramethylene disiloxanylenedipropionamide 8 2 0 0 6
2,2-Bisbromomethyltrimethylene adipate 8 2 0 1 0
2,2-Bischloromethyltrimethylene adipate 8 2 0 1 0
2,2-(Bromomethylchloromethyl)trimethylene adipate 8 2 0 1 0
Piperazine 4-octenediamide 8 2 0 2 2
1,4-Cyclohexylene adipate 8 2 0 2 2
1,4-Cyclohexylenedimethylene succinate 8 2 0 2 2
Hexametbylene 3-hexenedioate 8 2 0 2 2
1,3Cyclohexylene adi pami de 8 2 0 2 4
1,4-Cyclohexylene adi pami de 8 2 0 2 4
Tetramethylene 4-octenediamide 8 2 0 2 4
Ethylene 2,5-tetrahydrofurandipropionamide 8 2 0 2 4
Methylethylene azelate 8 2 0 2 4
2-Butenylene hexamethylenediurethane 8 2 0 2 4
1,4-Dioxanylene-2,5-dimethylene adi pami de 8 2 0 2 4
Hexamet hyl ene 1,4-dioxanylene-2,5dicarboxamide 8 2 0 2 4
Tet ramet hyl ene 1,4-cyclohexylenediurethane 8 2 0 2 4
0
0
2
0
0
2
2
6
0
0
0
1
0
0
0
0
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
4
0
0
0
0
0
0
0
1
2
2
2
2
0
0
1
2
2
2
0
2
2
2
0
0
0
1
2
2
2
2
2
0
0
0
4
2
0
0
0
1
2
1
0
0
0
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
0
0
0
2
2
2
2
2
2
2
2
2
2
2
2
4
4
2
0
0
0
2
0
0
0
2
2
2
2
0
2
2
2
2
0
0
0
0
2
0
0
2
0
0
0
0
2
3
0
4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
References page VI- 159
VI / 142 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHz C O C6H4 C H
Hexamethylene propylmalonamide 8 2 0 2 6
Hexamethylene 2,5-dihydroxyadipamide 8 2 0 2 6
2-Methltrimethylene hexamethylenediurethane 8 2 0 2 6
Octamethylene L-tartaramide 8 2 0 2 6
2,2-Dimethyltrimethylene suberate 8 2 0 3 6
2,2-Dimethyltrimethylene hexamethylenediurethane 8 2 0 3 8
2,CHexadiyne hexamethylene diurethane 8 2 0 4 2
Hexamet hyl ene 2,5-thiophenediacetamide 8 2 0 4 4
Octamethylene 2,Uhiophenedicarboxamide 8 2 0 4 4
Octamethylene 2,5-furandicarboxamide 8 2 0 4 4
1,4-Dimethyltetramethylene hexamethylenediurethane 8 2 0 4 1 0
Octamethylene di-O-methyl-L-tartaramide 8 2 0 4 1 0
Tetramethylene tetramethyldisiloxanylenedipropionamide 8 2 0 4 14
Octamethylene 2,4-pyridinedicarboxamide 8 2 0 5 5
Octamethylene 2Jpyridinedicarboxamide 8 2 0 5 5
Octamethylene 2,6-pyridinedicarboxamide 8 2 0 5 5
Oct amet hyl ene 3,5-pyridinedicarboxamide 8 2 0 5 5
NJ-Diethyl(hexafluoropentamethylene) adi pami de 8 2 0 5 6
N,N-Diethylhexamethyelne perfluoroglutaramide 8 2 0 5 6
NJ-Dimethyltetramethylene tetramethyldisiloxanylenedipropionamide 8 2 0 6 1 8
3-Methyl-m-phenylene sebacamide 8 2 0 I 8
NJ-Diisopropylethylene dimethyl(ethylenediamino)dipropionamide 8 2 0 8 20
4-Methyl-l$phenylene tetraethyldisiloxanylenedipropionamide 8 2 0 11 20
1,5-Naphthalene-4,4-(dimethoxy)dibenzylidenimino sebacate 8 2 0 26 20
Hexamethylene dithiol-p-phenylenediacetate 8 2 1 0 0
Octamethylene terephthalate 8 2 1 0 0
p-Xylylene suberate 8 2 1 0 0
p-Phenylene 1,4-piperazinedipropionate 8 2 1 0 0
Ethylene p-(carboxyphenoxy)heptanoate 8 2 1 0 0
Hexamethylene m-phenylenediacetamide 8 2 1 0 2
Hexamethylene p-phenylenediacetamide 8 2 1 0 2
Octamethylene isophthalamide 8 2 1 0 2
Octamethylene phthalamide 8 2 1 0 2
Octamethylene terephthalamide 8 2 1 0 2
p-Phenylenediethylene adipamide 8 2 1 0 2
m-Phenylene sebacamide 8 2 1 0 2
o-Phenylene sebacamide 8 2 1 0 2
p-Phenylene sebacamide 8 2 1 0 2
m-Xylylene suberamide 8 2 1 0 2
p-Xylylene suberamide 8 2 1 0 2
Hexamethylene p-phenoxydiacetamide 8 2 1 0 2
p-Xylylene oxydibutyramide 8 2 1 0 2
(Ethylenedioxy)ditrimethylene terephthalamide 8 2 1 0 2
Hexamet hyl ene (p-phenylenedioxy)diacetamide 8 2 1 0 2
Hexamethylene p-xylylenediurethane 8 2 1 0 2
p-Sulfonylphenylene sebacamide 8 2 1 0 2
Hexamethylene p-xylylenediurea 8 2 1 0 4
1,4Cyclohexylenedimethylene pphenylenediacetate 8 2 1 2 2
Sebacoyl dithionisophthaloyldihydrazide 8 2 1 2 4
Hexamet hyl ene 3,3-p-phenylenedibutyramide 8 2 1 4 1 0
m-Phenylene (tetraethyldisiloxanylene)dipropionamide 8 2 1 4 1 4
o-Phenylene (tetraethyldisiloxanylene)dipropionamide 8 2 1 4 1 4
p-Phenylene (tetraethyldisiloxanylene)dipropionamide 8 2 1 4 1 4
Hexamet hyl ene 3,3-dimethyl-3,3$phenylenedibutyramide 8 2 1 6 1 4
p-Phenylene-4,4-(3,3-dimethoxy)dibenzylidenimino sebacate 8 2 1 1 6 1 4
Ethylene 4,4-hexamethylenedibenzoate 8 2 2 0 0
4,4-Hexamethylenediphenylenesuccinate 8 2 2 0 0
Octamethylene 4,4-biphenylenedicarboxylate 8 2 2 0 0
p-Phenylenediethylene 3,3-(p-phenylene)dipropionate 8 2 2 0 0
p-Phenyleneditetramethylene terephthalate 8 2 2 0 0
Hexamet hyl ene 4,4-(ethylenedioxy)dibenzoate 8 2 2 0 0
Hexamet hyl ene 4,4-(sulfonyldimethylene)dibenzoate 8 2 2 0 0
4,4-Biphenylene sebacamide 8 2 2 0 2
4,4-Methylenediphenylene azelamide 8 2 2 0 2
3,4-Oxydiphenylene sebacamide 8 2 2 0 2
0
-
0
2
2
2
2
2
2
0
0
1
2
2
1
0
0
0
0
0
0
1
0
0
1
4
0
2
2
2
3
0
0
0
0
0
0
0
0
0
0
0
1
1
2
2
2
2
0
2
0
0
1
1
1
0
4
2
2
2
2
2
4
4
0
0
1
2 0 0
2 0 0
2 0 0
2 0 0
0 0 0
2 0 0
2 0 0
2 1 0
2 1 0
2 0 0
2 0 0
2 0 0
2 0 2
3 0 0
3 0 0
3 0 0
3 0 0
2 0 6
2 0 6
2 0 2
2 0 0
4 0 0
2 0 2
2 0 0
0 2 0
0 0 0
0 0 0
2 0 0
0 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 0 0
2 1 0
4 0 0
0 0 0
4 2 0
2 0 0
2 0 2
2 0 2
2 0 2
2 0 0
2 0 0
0 0 0
0 0 0
0 0 0
0 0 0
0 0 0
0 0 0
0 1 0
2 0 0
2 0 0
2 0 0
(
I

1
1
(
(
(
(
P
4
I
I
4
4
(
I
4
4
1
F
P
C
I
4
E
C
(
(
1
E
1
4
I
:
4
P
E
P
E
2
<
;
li
3
4
4
4
1
1
I-
5
4
2
4
3
L
E
f:
P
I
1
i
h
h
Appendi x: Formul a i ndex to the Tabl es VI / 143
Constitutional Base Unit
Poly- CHz c o CsH4 C H 0 N s x
4,4-Oxydiphenylene sebacamide 8
Heptamethylene 4,4-(methylenediphenylene)diurethane 8
Hexamet hyl ene 4,4-(oxydiphenylene)dioxydiacetamide 8
Octamethylene 3,3-phosphinylidenedibenzamide 8
Octamethylene 4,4-phosphinylidenedibenzamide 8
Octamethylene 3,3-(methylphosphinylidene)dibenzamide 8
Octamethylene 4,4-(methylphosphinylidene)dibenzamide 8
N,N-Diemthyl-4,4-methylenediphenylene azelamide 8
4,4-Isopropylidenediphenylene 1,4-piperazinedipropionate 8
1,12-Bis(phenylurethane)-5,7-dodecadiynediol, 5,8- 8
1,5-Naphthalene-4,4-dibenzylidenimino sebacate 8
4,4-Biphenylene-4,4-(dimethoxy)dibenzylidenimino sebacate 8
4,4-Oxydiphenylene-4,4-(dimethoxy)dibenzylidenimino sebacate 8
Octamethylene 4,4-(phenylphosphinylidene)dibenzamide 8
p-Phenylene-4,4,4-dibenzylidenimino sebacate 8
4,4-Biphenylene-4,4dibezylidenimino sebacate 8
4,4-Oxydiphenylene-4,4-dibenzylidenimino sebacate 8
l-l-Carboxypentamethylene adi pami de 8
N,N-Lysyl tetramethylenediurea 8
Methyl-N,N-lysyl tetramethylenediurea 8
Oct amet hyl ene 1,4-dihydro-4-oxo-2,6-pyridinedicarboxamide 8
Lysyllysylvaline 8
4,4-(0ctamethylenedicarbonyl)diphenylene carbonate 8
Ethylene adipamide-&-ethylene oxamide 8
Octamethylene bromopyromellitimide 8
Octamethylene pyromellitimide 8
Oct amet hyl ene 3,3,4,4-oxydiphenylenetetracarboximide 8
Hexamet hyl ene N,N-ethylenediterephthlamate 8
Pentamethylene N,N-trimethylenediterephthalamate 8
Hexamet hyl ene N,N-@-xylylene)diterephthalamate 8
4,4-(Oxydiethyleneoxydiethylenedioxy)diphenylene carbonyldiphenylenet 8
Alanylalanylglycylprolylprolylglycine 8
Alanylglycylalanylpro1ylglycylproline 8
(Alanylglycyl)4-glutamylglycine 8
9 9
Nonamethylene disulfide 9
Pentamethylenethiotetramethylenesulfide 9
Nonamethylene oxide 9
Pentamethylenesulfonyltetramethylene sulfone 9
2,5-Nonamethylene-1,3,4-oxadiazole 9
5-Cyclohexyl-1-pentene 9
1 -Undecene 9
n-Pentyl-n-hexylsilylene 9
3-Decylthiophene 9
4,4-Methylenedicyclohexylenethiourea 9
4,4-Ethylene-3-methyldiphenyleneoxyheptamethylene oxide 9
4,4-Heptamethylenedioxydiphenyleneoxy p-xylylene oxide 9
lo-Hydroxycapric acid 9
lo-Aminocapric acid 9
Nonamethylene urea 9
5-Hydroxy-2-( 1,3-dioxane)caprylic acid 9
4-Hydroxymethylene-2-(1,3-dioxolane)caprylic acid 9
2-Methyl- 1 1-aminoundecanoic acid 9
4,4-Methylenedicyclohexyleneurea 9
3-n-Decylhydroxybenzoic acid 9
Undecanedioic anhydride 9
Ethylene azelate 9
Hexamethylene glutarate 9
Pentamethylene adipate 9
Tetramethylene pimelate 9
Trimethylene suberate 9
Oxydiethylene pimelate 9
(Ethylenedioxy)diethylene glutarate 9
hexamethylene glutaramide 9
Methylene sebacamide 9
2 2 0 2
2 2 0 2
2 2 0 2
2 2 0 3
2 2 0 3
2 2 1 5
2 2 1 5
2 2 2 6
2 2 3 6
2 2 4 4
2 2 1 2 8
2 2 1 6 1 4
2 2 1 6 1 4
2 3 0 3
2 3 2 2
2 4 2 2
2 4 2 2
3 0 1 4
3 0 1 6
3 0 2 8
3 0 4 5
3 0 6 1 7
3 2 0 0
4 0 0 4
4 0 6 1
4 0 6 2
4 0 1 2 6
4 2 0 2
4 2 0 2
4 3 0 2
5 2 1 2 4
6 0 6 1 4
6 0 6 1 4
? 0 9 26
0 0 0 0
0 0 0 0
0 0 0 0
0 0 0 0
0 0 0 0
0 0 2 0
0 0 2 2
0 0 2 4
0 0 2 6
0 0 5 4
0 0 5 6
0 1 7 6
0 3 0 0
1 0 0 0
1 0 0 1
1 0 0 2
1 0 2 2
1 0 2 2
1 0 2 5
1 0 4 6
1 0 7 6
2 0 0 0
2 0 0 0
2 0 0 0
2 0 0 0
2 0 0 0
2 0 0 0
2 0 0 0
2 0 0 0
2 0 0 2
2 0 0 2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
4
4
3
5
0
4
2
2
2
2
2
2
2
6
6
1 0
0
0
0
0
0
2
0
0
0
0
2
0
0
0
1
2
0
0
1
2
0
0
0
0
0
0
0
0
0
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
0
2
0
0
0
0
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
References page VI- 159
VI / 1 4 4 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly- (332 C O C6H, C H 0 N s x
Octamethylene malonamide 9 2 0 0 2 0 2 0 0
Pentamethylene adipamide 9 2 0 0 2 0 2 0 0
Tetramethylene pimelamide 9 2 0 0 2 0 2 0 0
Hexamethylene trimethylenediurethane 9 2 0 0 2 2 2 0 0
Tetramethylene pentamethylenediurethane 9 2 0 0 2 2 2 0 0
Trimethylene hexamethylenediurethane 9 2 0 0 2 2 2 0 0
Trimethylene (ethylenedithio)diethylenediuretbane 9 2 0 0 2 2 2 2 0
Hexamethylene trimethylenediurea 9 2 0 0 4 0 4 0 0
1,4-Cyclohexylenedimetbylene glutarate 9 2 0 2 2 2 0 0 0
1,4Cyclohexylenedimethylene glutaramide 9 2 0 2 4 0 2 0 0
Cyclopropylene sebacamide 9 2 0 2 4 0 2 0 0
Pentamethylene 4-octenediamide 9 2 0 2 4 0 2 0 0
Hexamet hyl ene (methylene-2,5-tetrahydrofuran)dicarboxamide 9 2 0 2 4 1 2 0 0
Methylethylene sebacate 9 2 0 2 4 2 0 0 0
Methylethylene thiodivalerate 9 2 0 2 4 2 0 1 0
Cyclopropylenedimetbylene hexamethylenediuretbane 9 2 0 2 4 2 2 0 0
Methylethylene sulfonyldivalerate 9 2 0 2 4 4 0 1 0
n-Octylglutamate 9 2 0 2 5 1 1 0 0
Hexamethylene 2-butylmalonamide 9 2 0 2 6 0 2 0 0
Hexamethylene 3-methyladipamide 9 2 0 2 6 0 2 0 0
3-Methylehexamethylene adipamide 9 2 0 2 6 0 2 0 0
2,2-Dimethyltrimetbylene azelate 9 2 0 3 6 2 0 0 0
3,3-Dimethyl-4,4-methylenediphenylene sebacami de 9 2 0 14 14 0 2 0 0
Hexamet hyl ene (diethyldimethyl)methylenediphenylenediurea 9 2 0 1 6 20 0 4 0 0
N,N-Diisoamyl-3,3-diemthyl-4,4-methylenediphenylene adi pami de 9 2 0 20 26 0 2 0 0
Nonamethylene terephthalate 9 2 1 0 0 2 0 0 0
p-Xylylene azelate 9 2 1 0 0 2 0 0 0
Heptamethylene p-Phenylenediacetamide 9 2 1 0 2 0 2 0 0
Hexamet hyel ene (p-methylenephenylene)-diacetamide 9 2 1 0 2 0 2 0 0
m-Xylylene azelamide 9 2 1 0 2 0 2 0 0
p-Xylylene azelamide 9 2 1 0 2 0 2 0 0
Hexamethylene (methylene-p-phenoxy)diacetamide 9 2 1 0 2 1 2 0 0
p-Xylylene 5-oxasebacamide 9 2 1 0 2 1 2 0 0
Hexamet hyl ene 3-Methyl-3,3-p-phenylenedipropionamide 9 2 1 2 6 0 2 0 0
p-Phenylene( 1, 1-dimethyl)ethylene sebacamide 9 2 1 3 8 0 2 0 0
4,4-Methylenediphenylene sebacamide 9 2 2 0 2 0 2 0 0
3,4-Oxydiphenylene undecanediamide 9 2 2 0 2 1 2 0 0
4,4-Oxydiphenylene undecanediamide 9 2 2 0 2 1 2 0 0
Hexamet hyl ene 4,4-(methylenediphenylene)dioxydiacetamide 9 2 2 0 2 2 2 0 0
Octamethylene 4,4-(methylenediphenylene)diurethane 9 2 2 0 2 2 2 0 0
Nonamethylene 3,3-phosphinylidenedibenzamide 9 2 2 0 3 1 2 0 1
Nonamet hyl ene 4,4-phosphinylidenedibenzamide 9 2 2 0 3 1 2 0 1
4,4-Methylenediphenylene octamethylenediurea 9 2 2 0 4 0 4 0 0
Nonamethylene 3,3-(methylphosphinylidene)dibenzamide 9 2 2 1 5 1 2 0 1
Nonamethylene 4,4-(metbylphosphinylidene)dibenzamide 9 2 2 1 5 1 2 0 1
N,N-Dimethyl-4,4-methylenediphenylene sebacami de 9 2 2 2 6 0 2 0 0
Nonamethylene 4,4-(phenylphosphinylidene)dibenzamide 9 2 3 0 3 1 2 0 1
N,N-Lysyl pentamethylenediurea 9 3 0 1 6 1 4 0 0
Methyl-N,N-lysyl pentamethylenediurea 9 3 0 2 8 1 4 0 0
Adipoyl Pentamethylenediurea 9 4 0 0 4 0 4 0 0
Nonamethylene bromopyromellitimide 9 4 0 6 1 0 2 0 1
Nonamethylene pyromellitimide 9 4 0 6 2 0 2 0 0
Nonamethylene 3,3,4,4-oxydiphenylenetetracarboximide 9 4 0 1 2 6 1 2 0 0
Ethylene N,N-azelaoyldi(p-aminobenzoate) 9 4 2 0 2 2 2 0 0
Heptamethylene N,N-ethylenediterephtbalamate 9 4 2 0 2 2 2 0 0
Hexamethylene N,N-trimethylenediterephthalamate 9 4 2 0 2 2 2 0 0
Pentamethylene N,N-tetramethylenediterephtblalamate 9 4 2 0 2 2 2 0 0
10 1 0 0 0 0 0 0 0 0 0
Decamethylene 1 0 0 0 0 0 0 0 0 0
Decamethylene sulfide 1 0 0 0 0 0 0 0 1 0
Decamethylene disulfide 1 0 0 0 0 0 0 0 2 0
Hexamethylenethiotetramethylene sulfide 1 0 0 0 0 0 0 0 2 0
(Hexamethylenedithio)tetramethylene disulfide 1 0 0 0 0 0 0 0 4 0
Decamethylene oxide 1 0 0 0 0 0 1 0 0 0
Methyleneoxynonamethylene oxide 1 0 0 0 0 0 2 0 0 0
t
1
1
1
r

c
I
1
1
P

i
1
1
i
1

1
1
1
1
1
,
Appendix: Formula Index to the Tables VI / 145
Constitutional Base Unit
Poly- CHz
C O CsH4 C H 0 N s x
Hexamethylenesulfonyltetramethyloene sulfone 1 0 0 0 0 0 4 0 2 0
Decamethylene amine 10 0 0 0 1 0 1 0 0
2,5-Decamethylene-1,3,4-oxadiazole 1 0 0 0 2 0 1 2 0 0
2,5-Decamethylene-1,3,Ctriazole 1 0 0 0 2 1 0 3 0 0
Dodecenamer 1 0 0 0 2 2 0 0 0 0
1,2-Dichlorododecamethylene 1 0 0 0 2 2 0 0 0 2
2,5-Decamethylene-1-amino-1,3,4-triazole 1 0 0 0 2 2 0 4 0 0
I-Dodecene 1 0 0 0 2 4 0 0 0 0
Decylvinyl ether 1 0 0 0 2 4 1 0 0 0
Di-n-hexylgermylene 1 0 0 0 2 6 0 0 0 1
Di-n-hexylsilyene 1 0 0 0 2 6 0 0 0 1
3,3-Dipentyltrimethylene sulfone 1 0 0 0 3 6 2 0 1 0
3,3-Dihexyl-2,2-bithiophene 1 0 0 0 1 0 8 0 0 2 0
Decamethyleneoxy-p-phenylene oxide 1 0 0 1 0 0 2 0 0 0
Benzylidenethiodecamethylene sulfide 10 0 1 1 2 0 0 2 0
4,4-(0xydiphenylene)dithiodecamethylene disulfide 1 0 0 2 0 0 1 0 4 0
4,4-Octamethylenedioxydiphenyleneoxy-p-xylylene oxide 1 0 0 3 0 0 4 0 0 0
Bis-(Butylphenyl)azophenoxyethoxy phosphazene 1 0 0 4 2 6 4 5 0 1
Decamethylene carbonate 1 0 1 0 0 0 2 0 0 0
1 I-Aminoundecanoic acid 1 0 1 0 0 1 0 1 0 0
Decamethylene urea 1 0 1 0 0 2 0 2 0 0
N-Methyl- 1 1-aminoundecanoic acid 1 0 1 0 1 3 0 1 0 0
Decyl acrylate 1 0 1 0 2 4 1 0 0 0
5-Hydroxymethylene-5-methyl-2-(1,3-dioxane)caprylic acid 1 0 1 0 3 4 3 0 0 0
N-Phenyl-1 1-aminoundecanoic acid 1 0 1 1 0 2 0 1 0 0
4,4-decamethylenediphenylene carbonate 1 0 1 2 0 0 2 0 0 0
Hexamethylene dithioladipate 10 2 0 0 0 0 0 2 0
Piperazine suberamide 1 0 2 0 0 0 0 2 0 0
(Piperazinedicarbamoyl)dithiohexamethylene disulfide 1 0 2 0 0 0 0 2 4 0
Dodecanedioic anhydtide 1 0 2 0 0 0 1 0 0 0
Decamethylene oxalate 1 0 2 0 0 0 2 0 0 0
Ethylene sebacate 1 0 2 0 0 0 2 0 0 0
Hexamethylene adipate 1 0 2 0 0 0 2 0 0 0
Pentamethylene pimelate 1 0 2 0 0 0 2 0 0 0
Tetramethylene suberate 1 0 2 0 0 0 2 0 0 0
Trimethylene azelate 1 0 2 0 0 0 2 0 0 0
Ethylene thiodivalerate 1 0 2 0 0 0 2 0 1 0
Ethylene 1,4-piperazinedipropionate 1 0 2 0 0 0 2 2 0 0
Oxydiethylene suberate 1 0 2 0 0 0 3 0 0 0
(Ethylenedioxy)diethylene adipate 1 0 2 0 0 0 4 0 0 0
Ethylene sulfonyldivalerate 1 0 2 0 0 0 4 0 1 0
Decamethylene oxamide 1 0 2 0 0 0 0 2 0 0
Ethylene sebacamide 1 0 2 0 0 2 0 2 0 0
Hexamethylene adipamide 1 0 2 0 0 2 0 2 0 0
Hydrazo dodecanediamide 1 0 2 0 0 2 0 2 0 0
Nonamethylene malonamide 1 0 2 0 0 2 0 2 0 0
Octamethylene succinamide 1 0 2 0 0 2 0 2 0 0
Pentamethylene pimelamide 1 0 2 0 0 2 0 2 0 0
Tetramethylene suberamide 1 0 2 0 0 2 0 2 0 0
Ethylene thiodivaleramide 1 0 2 0 0 2 0 2 1 0
Hexamethylene thiodipropionamide 1 0 2 0 0 2 0 2 1 0
(Hexamethylenedicarbamoyl)dithiotetramethylene disulfide 1 0 2 0 0 2 0 2 4 0
Ethylene 1,4-piperazinedipropionamide 1 0 2 0 0 2 0 4 0 0
Hexamethylene piperazinediurea 1 0 2 0 0 2 0 4 0 0
Piperazine (ethylenediamino)dipropionamide 1 0 2 0 0 2 0 4 0 0
Oxyditrimethylene adipamide 1 0 2 0 0 2 1 2 0 0
(Ethylenedioxy)diethylene adipamide 1 0 2 0 0 2 2 2 0 0
Hexamethylene (ethylenedioxy)diacetamide 1 0 2 0 0 2 2 2 0 0
(Tetramethylenedioxy)ditrimethylene oxamide 1 0 2 0 0 2 2 2 0 0
Tetramethylene Hexamethylenediurethane 1 0 2 0 0 2 2 2 0 0
Tetramethylene (thioditrimethylene)diurethane 1 0 2 0 0 2 2 2 1 0
Thiodiethylene hexamethylenediurethane 1 0 2 0 0 2 2 2 1 0
Ethylene (tetramethylenedithio)diethylenediurethane 1 0 2 0 0 2 2 2 2 0
Hexamethylene (1,4-piperazinedithio)dicarboxylate 1 0 2 0 0 2 2 2 2 0
Tetramethylene (ethylenedithio)diethylenediurethane 1 0 2 0 0 2 2 2 2 0
References page VI- 159
VI / 146 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CH2 C O CsH4 C H 0 N s x
Oxydiethylene hexamethylenediurethane 1 0 2 0 0 2 3 2 0 0
Phosphinideneditrimethylene adipamide 1 0 2 0 0 3 0 2 0 1
Hexamethylene tetramethylenediurea 1 0 2 0 0 4 0 4 0 0
Hexamethylene disiloxanylenedipropionamide 1 0 2 0 0 6 1 2 0 2
N-Methylhexamethylene adi pami de 1 0 2 0 1 4 0 2 0 0
Hexamethylene dithiol- 1,4-cyclohexylenedicarboxylate 1 0 2 0 2 2 0 0 2 0
1,4-Cyclohexylenedimethylene adipate 1 0 2 0 2 2 2 0 0 0
1,4-Cyclohexylene suberate 1 0 2 0 2 2 2 0 0 0
Hexamet hyl ene 1,4-cyclohexylenedicarboxylate 1 0 2 0 2 2 2 0 0 0
hexamethylene 4-octenedioate 1 0 2 0 2 2 2 0 0 0
Octamethylene 3-hexenedioate 1 0 2 0 2 2 2 0 0 0
1,3-cyclohexylenedimethylene adi pami de 1 0 2 0 2 4 0 2 0 0
Decamethylene fumaramide 1 0 2 0 2 4 0 2 0 0
Hexamet hyl ene 1,4-cyclohexylenedicarboxamide 1 0 2 0 2 4 0 2 0 0
Hexamet hyl ene 1,2-cyclohexylenedicarboxamide 1 0 2 0 2 4 0 2 0 0
Hexamethylene 1,3-cyclohexylenedicarboxamide 1 0 2 0 2 4 0 2 0 0
Hexamethylene 4-octenediamide 1 0 2 0 2 4 0 2 0 0
Tetramethylene 2,Stetrahydrofurandipropionamide 1 0 2 0 2 4 1 2 0 0
I-Methyltrimethylene thiodivalerate 1 0 2 0 2 4 2 0 1 0
(1,4-Cyclohexylenedioxy)ditrimethylene oxamide 1 0 2 0 2 4 2 2 0 0
Hexamet hyl ene 1,4-dioxanylene-2,Sdiacetamide 1 0 2 0 2 4 2 2 0 0
1,4-Cyclohexylene (ethylenedithio)diethylenediurethane 1 0 2 0 2 4 2 2 2 0
Decamet hyl ene 1,2-dihydroxysuccinate 1 0 2 0 2 4 4 0 0 0
I-Methyltrimethylene sulfonyldivalerate 1 0 2 0 2 4 4 0 1 0
Alanyl-1 1-Aminoundecanoic acid 1 0 2 0 2 6 0 2 0 0
N-N-Dimethylhexamethylene adi pami de 1 0 2 0 2 6 0 2 0 0
Hexamethylene pentylmalonamide 1 0 2 0 2 6 0 2 0 0
Piperazine N,N-dimethyl(ethylenediamino)dipropionamide 1 0 2 0 2 6 0 4 0 0
1 -Methyltrimethylene octamethylenediurethane 1 0 2 0 2 6 2 2 0 0
Decamethylene methylfumaramide 1 0 2 0 3 6 0 2 0 0
2,2-Dimethyltrimethylene sebacate 1 0 2 0 3 6 2 0 0 0
1,4-Cyclohexylenedimethylene dithiol- 1,4-cyclohexylenedicarboxylate 1 0 2 0 4 4 0 0 2 0
Decamet hyl ene 2,5-thiophenedicarboxamide 1 0 2 0 4 4 0 2 1 0
Hexamet hyl ene 2,Sthiophenedipropionamide 1 0 2 0 4 4 0 2 1 0
Decamet hyl ene 2,5-furandicarboxamide 1 0 2 0 4 4 1 2 0 0
Hexamet hyl ene 2,5-furandipropionamide 1 0 2 0 4 4 1 2 0 0
1,4-Cyclohexylenedimethylene 1,4-Cyclohexylenedicarboxylate 1 0 2 0 4 4 2 0 0 0
Hexamet hyl ene 2,5-pyrroledipropionamide 1 0 2 0 4 5 0 3 0 0
Decamet hyl ene 2,3dimethylfumaramide 10 2 0 4 8 0 2 0 0
Hexamet hyl ene (tetramethyldisiloxanylene)dipropionamide 1 0 2 0 4 1 4 1 2 0 2
Decamet hyl ene 2,4-pyridine di carboxami de 1 0 2 0 5 5 0 3 0 0
Decamet hyl ene 2,5-pyridine di carboxami de 1 0 2 0 5 5 0 3 0 0
Decamet hyl ene 2,6-pyridine di carboxami de 1 0 2 0 5 5 0 3 0 0
Decamethylene 3,5-pyridine dicarboxamide 1 0 2 0 5 5 0 3 0 0
Hexamet hyl ene (N-methyl-2,5-pyrrole)dipropionamide 1 0 2 0 5 7 0 3 0 0
1,12-Bis(ethylurethane)-5,7-dodecadiynediol, 5,8- 1 0 2 0 6 8 2 2 0 0
NJ-diisopropylethylene 1,4-piperazinedipropionamide 1 0 2 0 6 1 4 0 4 0 0
Piperazine N,N-diisopropyl(ethylenediamino)dipropionamide 1 0 2 0 6 1 4 0 4 0 0
Tetramethyl-p-xylylenedithiol sebacate 1 0 2 0 1 0 1 2 0 0 2 0
Decamethylene 3,3-dimethyl-4,4-biphenylenediurethane 1 0 2 0 1 4 1 4 2 2 0 0
Decamethylene dithiolterephthalate 1 0 2 1 0 0 0 0 2 0
p-Xylylene dithiolsebacate 1 0 2 1 0 0 0 0 2 0
Decamethylene isophthalate 1 0 2 1 0 0 2 0 0 0
Decamethylene terephthalate 1 0 2 1 0 0 2 0 0 0
p-Xylylene sebacate 1 0 2 1 0 0 2 0 0 0
Hexamethylene p-(carboxyphenoxy)valerate 1 0 2 1 0 0 3 0 0 0
Decamethylene m-carboxycarbanilate 1 0 2 1 0 1 2 1 0 0
Decamethylene p-carboxycarbanilate 1 0 2 1 0 1 2 1 0 0
Decamethylene isophthalamide 1 0 2 1 0 2 0 2 0 0
Decamethylene phthalamide 1 0 2 1 0 2 0 2 0 0
Decamethylene terephthalamide 1 0 2 1 0 2 0 2 0 0
Hexamet hyl ene 3,3 -p-phenylenedipropionamide 1 0 2 1 0 2 0 2 0 0
Octamethylene p-phenylenediacetamide 1 0 2 1 0 2 0 2 0 0
p-Phenylene dodecanediamide 1 0 2 1 0 2 0 2 0 0
p-Phenyleneethylene sebacamide 1 0 2 1 0 2 0 2 0 0
Appendix: Formula Index to the Tables VI 1147
Constitutional Base Unit
Poly-
332
C O CsH4 C H 0 N s x
m-Xylylene sebacamide 1 0 2 1 0 2
p-Xylylene sebacamide 1 0 2 1 0 2
p-Xylylene thiodivaleramide 1 0 2 1 0 2
p-Xylylene 5-oxaundecanediamide 1 0 2 1 0 2
p-Xylylene oxydivaleramide 1 0 2 1 0 2
Octamethylene p-xylylenediurethane 1 0 2 1 0 2
p-Xylylene octamethylenediurethane 1 0 2 1 0 2
Octamethylene p-xylylenediurea 1 0 2 1 0 4
(1,4-Cyclohexylenedioxy)ditrimethylene terephthalamide 1 0 2 1 2 4
4,4-(Decamethylenedioxy)dichlorodiphenylene terephthalate 1 0 2 1 12 6
Decamethylene 2,2-dibenzoate 1 0 2 2 0 0
Decamethylene 3,3-debenzoate 1 0 2 2 0 0
Decamethylene 4,4-debenzoate 1 0 2 2 0 0
p-Phenylenedipentamethylene terephthalate 1 0 2 2 0 0
4,4-Ethylenediphenylene sebacamide 1 0 2 2 0 2
3,4-Oxydiphenylene dodecanediamide 1 0 2 2 0 2
4,4-Oxydiphenylene dodecanediamide 1 0 2 2 0 2
Decamethylene 4,4-biphenylenediurethane 1 0 2 2 0 2
Hexamethylene 4,4-(ethylenediphenylene)dioxydiacetamide 1 0 2 2 0 2
Nonamethylene 4,4-(methylenediphenylene)diurethane 1 0 2 2 0 2
Decamethylene 3,3-phosphinylidenedibenzamide 1 0 2 2 0 3
Decamethylene 4,4-phosphinylidenedibenzamide 1 0 2 2 0 3
Decamethylene 3,3-(methylphosphinylidene)dibenzamide 1 0 2 2 1 5
Decamethylene 4,4-(methylphosphinylidene)dibenzamide 1 0 2 2 1 5
4,4-Vinylenediphenylene dodecanedioate 1 0 2 2 2 2
Decamethylene 4,4-ethylidenedibenzamide 1 0 2 2 2 6
NJ-Diethyl(methylenediphenylene)azelamide 1 0 2 2 2 6
4.4.Methylvinylene)diphenylene dodecanedioate 1 0 2 2 3 4
3,3 -(Decamethylenedioxy)diphenylene terephthalate 1 0 2 3 0 0
4,4-(Decamethylenedioxy)diphenylene terephthalate 1 0 2 3 0 0
Decamethylene 4,4-(phenylphosphinylidene)dibenzamide 1 0 2 3 0 3
(Decamethylenedioxy)diphenylenedioxydiphenylene terephthalate 1 0 2 5 0 0
Hexamethylene ketodipropionamide 1 0 3 0 0 2
Hexamethylene NJ-lysyldiurea 1 0 3 0 1 6
Hexamethylene methyl-NJ-lysyldiurea 1 0 3 0 2 8
Decamethylene 1,4-dihydro-4-oxo-2$pyridinedicarboxamide 1 0 3 0 4 5
cc-D-Glucotrivalerate, 1,4- 1 0 3 0 8 14
P-D-Glucotrivalerate, 1,4- 1 0 3 0 8 14
Ethylene sebacoyldiurethane 1 0 4 0 0 2
Hexamethylene adipoyldiurethane 1 0 4 0 0 2
Ethylene oxamide-&t-ethylene suberamide 1 0 4 0 0 4
Ethylene sebacoyldiurea 1 0 4 0 0 4
Trimethylene adipamide-alt-trimethylene oxamide 1 0 4 0 0 4
2-Hydroxytrimethylene sebacoyldiurethane 1 0 4 0 1 4
Decamethylene bromopyromellitimide 1 0 4 0 6 1
Decamethylene pyromellitimide 1 0 4 0 6 2
Decamethylene 3,3,4,4-oxydiphenylenetetracarboximide 1 0 4 0 12 6
Hexamethylene N,N-piperazinediterephthalamate 1 0 4 2 0 0
Heptamethylene N,N-trimethylenediterephthalamate 1 0 4 2 0 2
Hexamethylene NJ-tetramethylenediterephthalamate 1 0 4 2 0 2
Octamethylene NJ-ethylenediterephthalamate 1 0 4 2 0 2
Pentamethylene N,N-pentamethylenediterephthalamate 1 0 4 2 0 2
Tetramethylene NJ-hexamethylenediterephthalamate 1 0 4 2 0 2
Trimethylene N,N-azelaoyldi(p-aminobenzoate) 1 0 4 2 0 2
Decamethylene 4,4-terephthaloyldioxydibenzoate 1 0 4 3 0 0
(Benzyloxycarbonyllysyl)(benzyloxycarbonyllysyl)valine 1 0 5 2 6 17
Alanylglycyl)S-glutamylglycine 1 0 ? 0 11 30
11 11 0 0 0 0
Hexamethylenethiopentamethylene sulfide 11 0 0 0 0
Decamethyleneoxymethylene oxide 11 0 0 0 0
Hexamethylenesulfonylpentamethylenesulfone 11 0 0 0 0
Cyclohexylidenethiohexamethylene sulfide 11 0 0 1 0
1-Methyldodecamethylene 11 0 0 2 4
LTridecene 11 0 0 2 4
n-Hexyl-n-heptylsilylene 11 0 0 2 6
0
0
0
1
1
2
2
0
2
4
2
2
2
2
0
1
1
2
2
2
1
1
1
1
2
0
0
2
4
4
1
6
0
1
1
0
5
5
2
2
0
0
0
3
0
0
1
2
2
2
2
2
2
2
4
2
1
0
0
2
4
0
0
0
0
2
2
2
2
2
2
2
4
2
0
0
0
0
0
2
2
2
2
2
2
2
2
2
2
0
2
2
0
0
0
2
0
2
4
4
3
0
0
2
2
4
4
4
2
2
2
2
2
2
2
2
2
2
2
0
5
12
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
0
2
2
0
0
0
0
0
0
0
0
0
0
0
0
2
0
0
0
0
0
0
0
0
0
0
1
1
1
1
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
References page VI- 159
VI / 1 4 8 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHz C O C6H4 C H 0 N s x
3-Dodecyl-2,5-thiophene 11 0 0 5 4 0 0 1 0
4,4-Ethylene-3-methyldiphenyleneoxynonamethylene oxide 11 0 1 7 6 2 0 0 0
Hexamethylenethio-4,4-methylenediphenylenediethylenesulfide 11 0 2 0 0 0 0 2 0
4,4-Nonamethylenedioxydiphenyleneoxy p-xylylene oxide 11 0 3 0 0 4 0 0 0
12.Aminolauric acid 11 1 0 0 1 0 1 0 0
13-Amino- 11 -thiatridecanoic acid 11 1 0 0 1 0 1 1 0
13-Amino-12-thiatridecanoic acid 11 1 0 0 1 0 1 1 0
N-Methyl-12-aminolamic acid 11 1 0 1 3 0 1 0 0
N-Ethyl-l I-aminoundecanoic acid 11 1 0 1 4 0 1 0 0
Vinyl laurate 11 1 0 2 4 1 0 0 0
Hexamethylene dithiolpimelate 11 2 0 0 0 0 0 2 0
Piperazine azelamide 11 2 0 0 0 0 2 0 0
Piperazine (trimethylenedithio)dipropionamide 11 2 0 0 0 0 2 2 0
Tridecanedioic anhydrlde 11 2 0 0 0 1 0 0 0
Decamethylene malonate 11 2 0 0 0 2 0 0 0
Hexamethylene pimelate 11 2 0 0 0 2 0 0 0
Pentamethylene suberate 11 2 0 0 0 2 0 0 0
Tetramethylene azelate 11 2 0 0 0 2 0 0 0
Trimethylene sebacate 11 2 0 0 0 2 0 0 0
Trimethylene thiodivalerate 11 2 0 0 0 2 0 1 0
Oxydiethylene azelate 11 2 0 0 0 3 0 0 0
(Ethylenedioxy)diethylene pimelate 11 2 0 0 0 4 0 0 0
Trimethylene sulfonyldivalerate 11 2 0 0 0 4 0 1 0
Decamet hyl ene mal onami de 11 2 0 0 2 0 2 0 0
Glycyl- 1 1-aminoundecanoic acid 11 2 0 0 2 0 2 0 0
Heptamethylene adipamide 11 2 0 0 2 0 2 0 0
Hexamet hyl ene pi mel ami de 11 2 0 0 2 0 2 0 0
Methylene dodecanediamide 11 2 0 0 2 0 2 0 0
Pentamethylene suberamide 11 2 0 0 2 0 2 0 0
Tetramethylene azelamide 11 2 0 0 2 0 2 0 0
Ethylene nonamethylenediurethane 11 2 0 0 2 2 2 0 0
Pentamethylene hexamethylenediurethane 11 2 0 0 2 2 2 0 0
Trimethylene octamethylenediurethane 11 2 0 0 2 2 2 0 0
Ethylene (pentamethylenedithio)diethylenediurethane 11 2 0 0 2 2 2 2 0
Pentamethylene (ethylenedithio)diethylenediurethane 11 2 0 0 2 2 2 2 0
Trimethylene (tetamethylenedithio)diethylenediurethane 11 2 0 0 2 2 2 2 0
Hexamethylene pentamethylenediurea 11 2 0 0 4 0 4 0 0
1,4-Cyclohexylenedimethylene pi mel at e 11 2 0 2 2 2 0 0 0
1,3-Cyclohexylene azelamide 11 2 0 2 4 0 2 0 0
1,4-Cyclohexylenedimethylene pimelamide 11 2 0 2 4 0 2 0 0
Cyclopropylenedimethylene sebacamide 11 2 0 2 4 0 2 0 0
Heptamethylene 4-octenediamide 11 2 0 2 4 0 2 0 0
Methylpiperazine 1,4-piperazinedipropionamide 11 2 0 2 4 0 4 0 0
Piperazine (methyl- 1,4-piperazine)dipropionamide 11 2 0 2 4 0 4 0 0
Pentamethylene 2,5-tetrahydrofurandipropionamide 11 2 0 2 4 1 2 0 0
1,4-Cyclohexylene (trimethylenedithio)diethylenediurethane 11 2 0 2 4 2 2 2 0
Hexamethylene 2-hexylmalonamide 11 2 0 2 6 0 2 0 0
2-Butyl-2-etbyltrimethylene hexamethylenediurethane 11 2 0 3 8 2 2 0 0
Decamet hyl ene (methylene-2,Sfuran)dicarboxamide 11 2 0 4 4 1 2 0 0
N,N-dibutyI-3,3-dimethyl-4,4-methylenediphenylene adipamide 11 2 0 1 6 18 0 2 0 0
N,N-dipropylhexamethylene dimethylmethylenediphenylenediurea 11 2 0 1 6 20 0 4 0 0
Hexamethylene (diemthyldipropyl)methylenediphenylenediurea 11 2 0 1 6 20 0 4 0 0
Hexamet hyl ene p-(carboxyphenoxy)caproate 11 2 1 0 0 3 0 0 0
p-Phenylenediethylene azelamide 11 2 1 0 2 0 2 0 0
Undecamethylene terephthalamide 11 2 1 0 2 0 2 0 0
p-Xylylene undecanediamide 11 2 1 0 2 0 2 0 0
p- Xyl yl ene 5-oxadodecanediamide 11 2 1 0 2 1 2 0 0
p- Xyl yl ene 6oxadodecanediamide 11 2 1 0 2 1 2 0 0
Decamet hyl ene 3,3-methylenedibenzamide 11 2 2 0 2 0 2 0 0
Decamet hyl ene 4,4-methylenedibenzamide 11 2 2 0 2 0 2 0 0
4,4-Methylenediphenylene dodecanediamide 11 2 2 0 2 0 2 0 0
Decamethylene 4,4-(methylenediphenylene)diurethane 11 2 2 0 2 2 2 0 0
Hexamet hyl ene 4,4-(trimethylenediphenylene)dioxydiacetamide 11 2 2 0 2 2 2 0 0
Decamethylene 4,4-(methylenediphenylene)diurea 11 2 2 0 4 0 4 0 0
N,N-diethyl(methylenediphenylene) sebacamide 11 2 2 2 6 0 2 0 0
-
Cl
P C
-
Tt
TI
El
U
H
H
N
C
P
?
?
P
1?
1
I
(
(
I
1
C
I
I
4
I
I
I
L
1
1
r
Appendix: Formula index to the Tables VI / 149
Constitutional Base Unit
Poly-
332 c o C6H4 C H 0 N s x
Tetraoxa-8,10-octadecadiyne (4,4-methylenediphenylene)diurethane 11 2 2 4 2 6 2 0 0
Trimethylene sebacoyldiurethane 11 4 0 0 2 2 2 0 0
Ethylene azelamide-all-ethylene oxamide 11 4 0 0 4 0 4 0 0
Undecamethylene pyromellitimide 11 4 0 6 2 0 2 0 0
Heptamethylene N,N-tetramethylenediterephthalamate 11 4 2 0 2 2 2 0 0
Hexamet hyl ene N,N-pentamethylenediterephthalamate 11 4 2 0 2 2 2 0 0
Nonmethylene N,N-ethylenediterephthalamate 11 4 2 0 2 2 2 0 0
Octamethylene N,N-trimethylenediterephthalamate 11 4 2 0 2 2 2 0 0
Pentamethylene N,N-hexamthylenediterephthalamate 11 4 2 0 2 2 2 0 0
Tetramethylene N,N-azelaoyldi(p- aminobenzoate) 11 4 2 0 2 2 2 0 0
Trimethylene N,N-sebacoyldi(p-aminobenzoate) 11 4 2 0 2 2 2 0 0
Alanylglycylprolylprolylglycylproline 11 6 0 5 1 0 0 6 0 0
Alanylprolylglycy1prolylpro1ylglycine 11 6 0 5 1 0 0 6 0 0
1 2 1 2 0 0 0 0 0 0 0 0
Dodecamethylene 1 2 0 0 0 0 0 0 0 0
(Decamethylenedithio)ethylene disulfide 1 2 0 0 0 0 0 0 4 0
(0ctamethylenedithio)tetramethylene disulfide 1 2 0 0 0 0 0 0 4 0
Dodecamethylene oxide 1 2 0 0 0 0 1 0 0 0
I-Tetradecene 1 2 0 0 2 4 0 0 0 0
Octamethylene tetramethylenedithiourea 1 2 0 0 2 4 0 4 2 0
Dodecylvinyl ether 1 2 0 0 2 4 1 0 0 0
Di-n-heptylsilylene 1 2 0 0 2 6 0 0 0 1
4,4-decamethylenedioxydiphenyleneoxy p-xylylene oxide 1 2 0 3 0 0 4 0 0 0
13-Aminotridecanoic acid 1 2 1 0 0 1 0 1 0 0
N-Allyl- 11 -aminoundecanoic acid 1 2 1 0 1 1 0 1 0 0
N-Dodecanoylethylene amine 1 2 1 0 1 3 0 1 0 0
4-Hydroxytetramethyelne-2-( 1,3-dioxolane)caprylic acid 1 2 1 0 2 2 3 0 0 0
Dodecyl acrylate 1 2 1 0 2 4 1 0 0 0
n-Dodecyl acrylamide 1 2 1 0 2 5 0 1 0 0
Hexamethylene dithiolsuberate 1 2 2 0 0 0 0 0 2 0
Tetramethylene dithiolsebacate 1 2 2 0 0 0 0 0 2 0
Piperazine sebacamide 1 2 2 0 0 0 0 2 0 0
Piperazine 1,4-piperazinedipropionamide 1 2 2 0 0 0 0 4 0 0
Tetradecanedioic anhydride 1 2 2 0 0 0 1 0 0 0
Decamethylene succinate 1 2 2 0 0 0 2 0 0 0
Hexamethylene suberate 1 2 2 0 0 0 2 0 0 0
Octamethylene adipate 1 2 2 0 0 0 2 0 0 0
Pentamethylene azelate 1 2 2 0 0 0 2 0 0 0
Tetramethylene sebacate 1 2 2 0 0 0 2 0 0 0
Trimethylene undecanedioate 1 2 2 0 0 0 2 0 0 0
Tetramethylene thiodivalerate 1 2 2 0 0 0 2 0 1 0
Decamethylene oxydiacetate 1 2 2 0 0 0 3 0 0 0
Oxydiethylene sebacate 1 2 2 0 0 0 3 0 0 0
Oxydiethylene thiodivalerate 1 2 2 0 0 0 3 0 1 0
(Ethylenedioxy)diethylene suberate 1 2 2 0 0 0 4 0 0 0
Tetramethylene sulfonyldivalerate 1 2 2 0 0 0 4 0 1 0
Oxydiethylene sulfonyldivalerate 1 2 2 0 0 0 5 0 0 0
Decamethylene succinamide 1 2 2 0 0 2 0 2 0 0
Dodecamethylene oxamide 1 2 2 0 0 2 0 2 0 0
Ethylene doecanediamide 1 2 2 0 0 2 0 2 0 0
Glycyl-12-aminododecanoic acid 1 2 2 0 0 2 0 2 0 0
Heptamethylene pimelamide 1 2 2 0 0 2 0 2 0 0
Hexamethylene suberamide 1 2 2 0 0 2 0 2 0 0
Octamethylene adipamide 1 2 2 0 0 2 0 2 0 0
Pentamethylene azelamide 1 2 2 0 0 2 0 2 0 0
Tetramethylene sebacamide 1 2 2 0 0 2 0 2 0 0
Hexamethylene thiodibutyramide 1 2 2 0 0 2 0 2 1 0
Dithiodiethylene sebacamide 1 2 2 0 0 2 0 2 2 0
(Hexamethylenedicarbamoyl)dithiohexamethylene disulfide 1 2 2 0 0 2 0 2 4 0
Hexamet hyl ene 1,4-piperazinediacetamide 1 2 2 0 0 2 0 4 0 0
Hexamethylene oxydibutyramide 1 2 2 0 0 2 1 2 0 0
Ethylene decamethylenediurethane 1 2 2 0 0 2 2 2 0 0
(Ethylenedioxy)ditrimethylene adipamide 1 2 2 0 0 2 2 2 0 0
Hexamethylene hexamethylenediurethane 1 2 2 0 0 2 2 2 0 0
Tetramethylene octamethylenediurethane 1 2 2 0 0 2 2 2 0 0
References page VI-159
VI / 150 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHz
C O C6H4 C H 0 N s x
Ethylene (hexamethylenedithio)diethylenediurethane 1 2
Hexamethylene (ethylenedithio)diethylenediurethane 1 2
Tetramethylene (tetramethylenedithio)diethylenediurethane 1 2
Triemthylene (pentamethylenedithio)diethylenediurethane 1 2
(Ethylenedioxy)diethylene 1,4-piperazinediacetamide 1 2
Octamethylene disiloxanylenedipropionamide 1 2
1,4-Cyclohexylenedimethylene suberate 1 2
1,4-Cyclohexylene sebacate 1 2
Decamethylene 3-hexenedioate 1 2
Octamethylene 4-octenedioate 1 2
1,3Cyclohexylenedimethylene suberami de 1 2
1,4-Cyclohexylenedimethylene suberami de 1 2
1,3-Cyclohexylene sebacami de 1 2
Hexamet hyl ene 1,2-cyclohexylenediacetamide 1 2
Octamethylene 4-octenediamide 1 2
Hexamet hyl ene 2,Stetrahydrofurandipropionamide 1 2
1,4-Cyclohexylene octamethylenediurethane 1 2
l$Dioxanylene-2,Sdimethylene sebacami de 1 2
1,4-Cyclohexylenedimethylene ethylenedithiodiethylenediurethane 1 2
1,4-Cyclohexylene (tetramethylenedithio)diethylenediurethane 1 2
Hexamt hyl ene 2,5-pyrrolidinedipropionamide 1 2
Hexamethylene heptylmalonamide 1 2
Hexamet hyl ene (N-methyl-2,5-pyrrolidine)dipropionamide 1 2
Hexamethylene (diethyldimethyldisiloxanylene)dipropionamid 1 2
Octamethylene (tetramethyldisiloxanylene)dipropionamide 1 2
NJ-Dibutyl(hexafluoropentamethylene) adipamide 1 2
NJ-Dibutylhexamethylene perfluoroglutaramide 1 2
Dodecamethylene 3,3-dimethyl-4,4-biphenylenediurethane 1 2
p-Xylylene Dodecanedioate 1 2
Ethylene p-(carboxyphenoxy)undecanoate 1 2
Decamethylene p-phenylenediacetamide 1 2
Dodecamethylene terephthalamide 1 2
Ocatmethylene p-phenylenedipropionamide 1 2
p-Phenylenediethylene sebacamide 1 2
p-Xylylene dodecanediamide 1 2
p-Phenylenediethylene thiodivaleramide 1 2
p-Xylylene thiodicaproamide 1 2
p-Xylylene 6-oxatridecanediamide 1 2
p-Xylylene oxydicaproamide 1 2
Decamethylene (p-phenylenedioxy)diacetamide 1 2
Decamethylene p-xylylenediurethane 1 2
p-Phenylenediethylene octamethylenediurethane 1 2
p-Phenyleneditrimethylene hexamethylenediurethane 1 2
(p-Phenylenedioxy)diethylene octamethylenediurethane 1 2
Decamethylene p-xylylenediurea 1 2
(1,4-Cyclohexylenedixoy)ditrimethylene p-phenylenedioxydiacetamide 1 2
Decamethylene 4,4-(ethylenedioxy)dibenzoate 1 2
Hexamethylene 4,4-(hexamethylenedisulfonyl)dibenzoate 1 2
Dodecamethylene 4,4-biphenylenediurethane 1 2
4,4-(Ethylenedioxydiphenylene)ditrimethylene adipamide 1 2
(1,4-Cyclohexylenedioxy)ditrimethylene ethylenedioxydibenzamide 1 2
Decamethylene isopropylidenedi-p-phenylenedioxydiacetamide 1 2
6-Aminocaproyl-5-aminovaleryl-3-aminopropionic acid 1 2
3-Aminopropyl-5-aminovaleryl-6-aminocaproic acid 1 2
Hexamet hyl ene 5-pyrrolidonylidenedipropionamide 1 2
Decamethylene 3-carboxylglutaramide 1 2
Adipoyl octamethylenediurea 1 2
Ethylene oxamide-&ethylene sebacamide 1 2
Tetramethylene adipamide-alt-tetramethylene oxamide 1 2
Trimethylene oxamide-a/t-trimethylene suberamide 1 2
Dodecamethylene bromopyromellitimide 1 2
Dodecamethylene pyromellitimide 1 2
Dodecamet hyl ene 1,4,5,%naphthalenetetracarboximide 1 2
Ethylene N,N-terephthaloyldi(6-aminocaproate) 1 2
Decamet hyl ene N,N-ethylenediterephthalamate 1 2
2 0 0 2 2 2 2
2 0 0 2 2 2 2
2 0 0 2 2 2 2
2 0 0 2 2 2 2
2 0 0 2 2 4 0
2 0 0 6 1 2 0
2 0 2 2 2 0 0
2 0 2 2 2 0 0
2 0 2 2 2 0 0
2 0 2 2 2 0 0
2 0 2 4 0 2 0
2 0 2 4 0 2 0
2 0 2 4 0 2 0
2 0 2 4 0 2 0
2 0 2 4 0 2 0
2 0 2 4 1 2 0
2 0 2 4 2 2 0
2 0 2 4 2 2 0
2 0 2 4 2 2 2
2 0 2 4 2 2 2
2 0 2 5 0 3 0
2 0 2 6 0 2 0
2 0 3 7 0 3 0
2 0 4 1 4 1 2 0
2 0 4 1 4 1 2 0
2 0 5 6 0 2 0
2 0 5 6 0 2 0
2 0 1 4 1 4 2 2 0
2 1 0 0 2 0 0
2 1 0 0 3 0 0
2 1 0 2 0 2 0
2 1 0 2 0 2 0
2 1 0 2 0 2 0
2 1 0 2 0 2 0
2 1 0 2 0 2 0
2 1 0 2 0 2 1
2 1 0 2 0 2 1
2 1 0 2 1 2 0
2 1 0 2 1 2 0
2 1 0 2 2 2 0
2 1 0 2 2 2 0
2 1 0 2 2 2 0
2 1 0 2 2 2 0
2 1 0 2 4 2 0
2 1 0 4 0 4 0
2 1 2 4 4 2 0
2 2 0 0 4 0 0
2 2 0 0 6 0 2
2 2 0 2 2 2 0
2 2 0 2 2 2 0
2 2 2 4 4 2 0
2 2 3 8 2 2 0
3 0 0 3 0 3 0
3 0 0 3 0 3 0
3 0 1 3 0 2 0
3 0 1 4 1 2 0
4 0 0 4 0 4 0
4 0 0 4 0 4 0
4 0 0 4 0 4 0
4 0 0 4 0 4 0
4 0 6 1 0 2 0
4 0 6 2 0 2 0
4 0 1 0 4 0 2 0
4 1 0 2 2 2 0
4 2 0 2 2 2 0
0
0
0
0
0
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
6
6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
Appendix: Formula Index to the Tables VI / 151
Constitutional Base Unit
Poly-
CH2
C O CsH4 C H 0 N s x
Ethylene NJ-dodecanedioyldi(p-aminobenzoate)
Heptamethylene N,N-pentamethylenediterephthalamate
Hexamet hyl ene N,N-hexamethylenediterephthalamate
Hexamet hyl ene N,N-suberoyldi@-aminobenzoate)
Nonamethylene N,N-glutaryldi@-aminobenzoate)
Nonamethylene N,N-trimethylenediterephthalamate
Octamethylene N,N-tetramethylenediterephthalamate
(Alanylglycyl)6-glutamylglycine
:Ii onamethylenedithio)tetramethylene disulfide
1-Pentadecene
3-Tetradecyl-2,Sthiophene
4,4-Ethylene-3-methyldiphenyleneoxyundecamethylene oxide
4,4-Undecamethylenedioxydiphenyleneoxy p-xylylene oxide
Vinyl my&ate
Hexamethylene dithiolazelate
Decamethylene glutarate
Hexamethylene azelate
Pentamethylene sebacate
Trimethylene dodecandioate
Pentametbylene thiodivalerate
(Ethylenedioxy)diethylene azelate
Pentamethylene sulfonyldivalerate
Deamet hyl ene glutaramide
Dodecamethylene malonamide
Heptamethylene suberamide
Hexamet hyl ene azel ami de
Nonamethylene adipamide
Pentamethylene sebacamide
Tetramethylene undecanediamide
Hexamet hyl ene Soxasebacamide
Heptamethylene hexamethylenediurethane
Tetramethylene nonamethylenediurethane
Pentamethylene (tetramethylenedithio)diethylenediurethane
Tetramethylene (pentamethylenedithio)diethylenediurethane
Trimethylene (hexamethylenedithio)diethylenediurethane
Heptamethylene hexamethylenediurea
Nonamethylene disiloxanylenedipropionamide
1,4-Cyclohexylenedimethylene azelate
1,4-Cyclohexylenedimethylene azelamide
Nonamethylene 4-octenediamide
Decamet hyl ene (methylene-2,5-tetrahydrofuran)dicarboxamide
Heptamethylene 2,5tetrahydrofurandipropionamide
Decamethylene 3-methyladipate
1,4Cyclohexylenedimethylene trimethylenedithiodiethylenediurethane
1,4-Cyclohexylene (pentamethylenedithio)diethylenediurethane
Dodecyl glutamate
Hexamethylene 2-octylmalonamide
3-Methylhexamethylene sebacamide
Tetramethylene 4,4-methylenedicyclohexylenediurethane
p-Phenylenediethylene undecanediamide
p-Xylylene tridecanediamide
p-Xylylene 5-oxatetradecanediamide
Dodecamethylene 4,4-(methylenediphenylene)diurethane
Dodecamethylene 4,4-(methylenediphenylene)diurea
NJ-Lysyl nonamethylenediurea
Methyl-NJ-lysyl nonamethylenediurea
b-n-Glucotricaproate, 1,4-
Pentamethylene sebacoyldiurea
Tetramethylene oxamide-a&-tetramethylene pimelamide
Trimethylene azelamide-alt-trimethylene oxamide
Tridecamethylene pyromellitimide
Decamethylene NJ-trimethylenediterephthalamate
Heptamethylene NJ-hexamethylenediterephthalamate
Nonamethylene NJ-adipoyldi(p-aminobenzoate)
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1 2
1 3
1 3
1 3
1 3
1 3
13
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
13
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
13
1 3
13
13
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
13
13
13
13
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
1 3
13
4
4
4
4
4
4
4
?
0
0
0
0
0
0
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
4
4
4
4
4
4
4
2
2
2
2
2
2
2
0
0
0
0
0
1
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
2
2
0
0
0
0
0
0
0
2
2
2
0 2
0 2
0 2
0 2
0 2
0 2
0 2
1 3 34
0 0
0 0
2 4
5 4
I 6
0 0
2 4
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 2
0 2
0 2
0 2
0 2
0 2
0 2
0 2
0 2
0 2
0 2
0 2
0 2
0 4
0 6
2 2
2 4
2 4
2 4
2 4
2 4
2 4
2 4
2 5
2 6
2 6
4 6
0 2
0 2
0 2
0 2
0 4
1 6
2 8
8 1 4
0 4
0 4
0 4
6 2
0 2
0 2
0 2
2
2
2
2
2
2
2
1
0
0
0
0
2
4
1
0
2
2
2
2
2
4
4
0
0
0
0
0
0
0
1
2
2
2
2
2
0
1
2
0
0
1
1
2
2
2
1
0
0
2
0
0
1
2
0
1
1
5
0
0
0
0
2
2
2
2
2
2
2
2
2
2
1 4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
2
2
2
2
2
2
2
2
2
2
2
4
2
0
2
2
2
2
0
2
2
1
2
2
2
2
2
2
2
4
4
4
0
4
4
4
2
2
2
2
0
0
0
0
0
0
0
0
0
4
0
1
0
0
0
2
0
0
0
0
1
0
1
0
0
0
0
0
0
0
0
0
0
2
2
2
0
0
0
0
0
0
0
0
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
References page VI- 1.59
VI / 152 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHZ C O CaH4 C H 0 N s x
Nonamethylene NJ-tetramethylenediterephthalamate 1 3 4 2 0 2 2 2 0 0
Octamethylene NJ-pentamethylenediterephthalamate 1 3 4 2 0 2 2 2 0 0
Undecamet hyl ene NJ-ethylenediterephthalamate 1 3 4 2 0 2 2 2 0 0
14 1 4 0 0 0 0 0 0 0 0
Tetradecamethylene sulfide 1 4 0 0 0 0 0 0 1 0
(Decamethyleneditbio)tetramethylene disulfide 14 0 0 0 0 0 0 4 0
(Hexamethylenedithio)ocatamethylene disulfide 1 4 0 0 0 0 0 0 4 0
1-Hexadecene 1 4 0 0 2 4 0 0 0 0
Hexamethylene octamethylenedithiourea 1 4 0 0 2 4 0 4 2 0
Di-n-octylsilylene 1 4 0 0 2 6 0 0 0 1
3,3-Dioctyl-2,2-bithiophene 1 4 0 0 1 0 8 0 0 2 0
3,3-Dioctyl-2,2:5,2-terthiophene 1 4 0 0 1 4 1 0 0 0 3 0
4,4-Dodecametbylenedioxydiphenyleneoxy p-xylylene oxide 1 4 0 3 0 0 4 0 0 0
N-Piperazinyl-1 1-aminoundecanoic acid 14 1 0 0 1 0 3 0 0
Tetradecyl acrylate 1 4 1 0 2 4 1 0 0 0
n-Tetradecyl acrylamide 1 4 1 0 2 5 0 1 0 0
Decamethylene dithioladipate 1 4 2 0 0 0 0 0 2 0
Hexamethylene dithiolsebacate 1 4 2 0 0 0 0 0 2 0
Decamethylene adipate 1 4 2 0 0 0 2 0 0 0
Hexametbylene sebacate 1 4 2 0 0 0 2 0 0 0
Octamethylene suberate 1 4 2 0 0 0 2 0 0 0
Hexamethylene thiodivalerate 14 2 0 0 0 2 0 1 0
(Ethylenedioxy)diethylene sebacate 1 4 2 0 0 0 4 0 0 0
(Ethylenedioxy)diethylene thiodivalerate 1 4 2 0 0 0 4 0 1 0
Hexamethylene sulfonyldivalerate 1 4 2 0 0 0 4 0 1 0
(Etbylenedioxy)diethylene sulfonyldivalerate 1 4 2 0 0 0 6 0 0 0
Decamethylene adipamide 1 4 2 0 0 2 0 2 0 0
Dodecamethylene succinamide 1 4 2 0 0 2 0 2 0 0
Heptamethylene azelamide 1 4 2 0 0 2 0 2 0 0
Hexamet hyl ene sebacami de 14 2 0 0 2 0 2 0 0
Nonamethylene pimelamide 1 4 2 0 0 2 0 2 0 0
Octamethylene suberamide 1 4 2 0 0 2 0 2 0 0
Pentamethylene undercanediamide 1 4 2 0 0 2 0 2 0 0
Tetramethylene dodecanediamide 1 4 2 0 0 2 0 2 0 0
Ethylene thiodienanthamide 1 4 2 0 0 2 0 2 1 0
Hexamethylene thiodivaleramide 1 4 2 0 0 2 0 2 1 0
Hexamethylene 5-oxaundecanediamide 1 4 2 0 0 2 1 2 0 0
Hexamethylene oxydivaleramide 1 4 2 0 0 2 1 2 0 0
Decamethylene tetramethylenediurethane 1 4 2 0 0 2 2 2 0 0
Hexamethylene (tetramethylenedioxy)dipropionamide 1 4 2 0 0 2 2 2 0 0
Octamethylene hexamethylenediurethane 1 4 2 0 0 2 2 2 0 0
Hexamethylene sulfonyldivaleramide 1 4 2 0 0 2 2 2 1 0
Thioditetramethylene hexamethylenediurethane 1 4 2 0 0 2 2 2 1 0
Hexamethylene (tetramethylenedithio)diethylenediurethane 1 4 2 0 0 2 2 2 2 0
Pentamethylene (pentamethylenedithio)diethylenediurethane 1 4 2 0 0 2 2 2 2 0
Tetramethylene (hexamethylenedithio)diethylenediurethane 1 4 2 0 0 2 2 2 2 0
1,4-Piperazinediethylene hexamethylenediurethane 1 4 2 0 0 2 2 4 0 0
Oxyditetramethylene hexamethylenediurethane 1 4 2 0 0 2 3 2 0 0
Decamethylene phosphinylidenedipropionamide 1 4 2 0 0 3 1 2 0 1
Hexamethylene octamethylenediurea 1 4 2 0 0 4 0 4 0 0
Decamethylene disiloxanylenedipropionamide 1 4 2 0 0 6 1 2 0 2
Hexamethylene 6-hydroxyundecanediamide 1 4 2 0 1 4 1 2 0 0
(Ethylenedioxy)diethylene 6-hydroxyundecanediamide 1 4 2 0 1 4 3 2 0 0
Decamethylene (methylphosphinylidene)dipropionamide 14 2 0 1 5 1 2 0 1
1,4Cyclohexylenedimethylene sebacate 1 4 2 0 2 2 2 0 0 0
Decamethylene 4-octenedioate 1 4 2 0 2 2 2 0 0 0
Dodecamethylene 3-hexenedioate 1 4 2 0 2 2 2 0 0 0
1,4-Cyclohexylenedimethylene sebacamide 1 4 2 0 2 4 0 2 0 0
Decamethylene 4-octenediamide 1 4 2 0 2 4 0 2 0 0
Octamethylene 2,5-tetrahydrofurandipropionamide 1 4 2 0 2 4 1 2 0 0
1,4-Cyclohexylenedimethylene octamethylenediurethane 1 4 2 0 2 4 2 2 0 0
(1,4-Cyclohexylenedioxy)ditrimethylene adi pami de 1 4 2 0 2 4 2 2 0 0
1,4-Cyclohexylenedimethylene tetramethylenedithiodiethylenediuretbane 1 4 2 0 2 4 2 2 2 0
1,4-Cyclohexylene (hexamethylenedithio)diethylenediurethane 1 4 2 0 2 4 2 2 2 0
Hexamethylene nonylmalonamide 1 4 2 0 2 6 0 2 0 0
I
4
I
F
k
I
I
P
1
n
P
P
P
P
P
c
c
E
(1
D
H
PI
I;
T
l-
D
D
E
N
0
Tl
Tl
U
If
(f
M
3-
V
DI
HI
Pc
Tr
6-
HI
H I
01
UI
g
(E
Nc
Nc
Te
H e
P e
H e
4,L
NC
1,4
Te
He
Tel
494
Appendix: Formula Index to the Tables VI / 153
Constitutional Base Unit
Poly-
CH2 c o CfjH4 C H 0 N s x
Hexamethylene octamethylenediurethane
Decamethylene 2,5-Furandipropionamide
4,4-Methylenedicyclohexylene pimelamide
Decamethylene (tetramethyldisiloxanylene)dipropionamide
Hexamethylene (tetraethyldisiloxanylene)dipropionamide
Hexamethylene 4,4-( p-xylylenedisulfonyl)dibutyrate
Decamethylene p-phenylenedipropionamide
Dodecamethylene p-phenylenediacetamide
p-Phenylenediethylene dodecanediamide
Tetradecamethylene terephthalamide
m-Xylylene tetradecanediamide
p-Xylylene tetradecanediamide
p-Phenylenediethylene thiodicaproamide
p-Xylylene thiodienanthamide
p-Xylylene 6-oxapentadecanediamide
p-Xylylene oxydienanthamide
Dodecamethylene p-xylylenediurethane
Dodecamethylene p-xylylenediurea
Decamet hyl ene 4,4-(ethylenediphenylene)dioxydiacetamide
(1,4-Cyclohexylenedioxy)ditrimethylene tetramethylenedioxydibenzamide
(1,4-Cyclohexylenedioxy)ditrimethylene oxydiethylenedioxydibenzamide
Decamethylene adipoyldiurethan
Hexamethylene sebacoyldiurethane
Pentamethylene adipamide-alt-pentamethylene oxamide
Tetramethylene oxamide-a/t-tetramethylene suberamide
Trimethylene oxamide-air-trimethylene sebacamide
Tetramethylene NJ-terephthaloyldi(6-aminocaproate)
Decamet hyl ene NJ-tetramethylenediterephthalamate
Dodecamethylene N,N-ethylenediterephthalamate
Ethylene NJ-dodecamethylenediterephthalamate
Nonamethylene NJ-pentamethylenediterephthalamate
Octamethylene N,N-hexamethylenediterephthalamate
Tetramethylene N,N-dodecanedioyldi(p-aminobenzoate)
Trimethylene N,N-tridecanedioyldi(p-aminobenzoate)
Undecamethylene N,N-trimethylenediterephthalamate
ti examethylenedithionronamethylene disulfide
Methyleneoxytetradecamethylene oxide
3-Hexadecyl-2,5-thiophene
Vinyl palmitate
Decamethylene pimelate
Heptamethylene sebacate
Pentamethylene dodecanedioate
Trimethylene tetradecanedioate
6-Aminocaproic acid-& 1 I-aminoundecanoic acid
Heptamethylene sebacamide
Hexamethylene undecanediamide
Octamethylene azelamide
Undecamethylene adipamide
Hexamet hyl ene Soxadodecanediamide
(Ethylenedioxy)diethylene undecanediamide
(Ethylenedioxy)ditrimethylene azelamide
Nonamethylene hexamethylenediurethane
Nonamethylene hexamethylenediurethane
Tetramethylene undecamethylenediurethane
Hexamethylene (pentamethylenedithio)diethylenediurethane
Pentamethylene (hexamethylenedithio)diethylenediurethane
Hexamethylene nonamethylenediurea
4,4-(Trimethylenedipiperidenediyl)dicarbamoyldithiotetramethylene disul
Nonamethylene 2,5-tetrahydrofurandipropionamide
1,4-Cyclohexylenedimethylene pentamethylenedithiodiethylenediurethane
Tetramethylene (trimethylenedipiperidene)dithiodicarboxylate
Hexamethylene 2-decylmalonamide
Tetramethylene dodecylmalonamide
4,4-Methylenedicyclohexylene suberami de
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 4
1 5
15
1 5
15
1 5
15
1 5
15
15
1 5
15
1 5
15
1 5
15
1 5
15
1 5
15
1 5
1 5
1 5
15
1 5
15
1 5
1 5
1 5
1 5
1 5
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
4
4
4
4
4
4
4
4
4
4
4
4
4
4
0
0
0
0
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
0
0
0
0
0
1
2
2
2
2
2
2
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
4
4
4
4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
5
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
2
2
2
2
4
6
4
6
1 4
1 4
0
2
2
2
2
2
2
2
2
2
2
2
4
2
4
4
2
2
4
4
4
2
2
2
2
2
2
2
2
2
0
0
0
4
4
0
0
0
0
2
2
2
2
2
2
2
2
2
2
2
2
2
4
2
4
4
4
6
6
6
2
1
0
1
1
6
0
0
0
0
0
0
0
0
1
1
2
0
2
4
5
2
2
0
0
0
2
2
2
2
2
2
2
2
2
0
0
2
0
1
2
2
2
2
0
0
0
0
0
1
2
2
2
2
2
2
2
0
0
1
2
2
0
0
0
2
2
2
2
2
0
2
2
2
2
2
2
2
2
2
2
2
4
2
2
2
2
2
4
4
4
2
2
2
2
2
2
2
2
2
0
0
0
0
0
0
0
0
0
2
2
2
2
2
2
2
2
2
2
2
2
2
4
2
2
2
2
2
2
2
0
0
0
0
0
2
0
0
0
0
0
0
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
0
4
0
2
2
0
0
0
0
0
0
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
References page VI-159
VI / 154 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHz
C O C6H4 C H 0 N s x
Nonamethylene (diethyldimethyldisiloxanylene)dipropionamide
N,N-dihexyl-3,3-dimethyl-4,4-methylenediphenylene adi pami de
p-Phenylenediethylene tridecanediamide
p-Xylylene pentadecanediamide
p-Xylylene 5-oxahexadecanediamide
4,4Methylenediphenylene tetradecamethylenediurea
Pentamethylene oxamide-alt-Pentamethylene pimelamide
Tetramethylene azelamide-alt-tetramethylene oxamide
Decamet hyl ene N,N-pentamethylenediterephthalamate
Dodecamethylene NJ-trimethylenediterephthalamate
Nonamethylene NJ-hexamethylenediterephthalamate
Tridecamethylene NJ-ethylenediterephthalamate
Undecamethylene N,N-tetramethylenediterephthalamate
;I?ecamethylenethio)hexamethylene sulfide
(Decamethylenedithio)hexamethylene disulfide
(Tetramethylenedioxy)dihexamethylene oxide
Decamet hyl eneami nohexamet hyl ene ami ne
I-Octadecene
Octamethylene octamethylenedithiourea
Di-n-nonylsilylene
Tetracosatetrayne
17-Aminoheptadecanoic acid
Hexadecyl acrylate
n-Hexadecyl acrylamide
Hexadecyl methacrylate
Octadecanedioic anhydride
Decamethylene suberate
Dodecamethylene adipate
Nonamethylene azelate
Decamethylene suberamide
Dodecamethylene adipamide
Heptamethylene undecanediamide
Hexamethylene dodecanediamide
donamethylene azelamide
Octamethylene sebacamide
Pentamethylene tridecanediamide
Hexamethylene oxydicaproamide
Decamethylene hexamethylenediurethane
(Ethylenedioxy)ditrimethylene sebacamide
Hexamethylene decamethylenediurethane
Hexamethylene (hexamethylenedioxy)dipropionamide
Octamethylene octamethylenediurethane
Oxydipentamethylene oxydibutyramide
Pentamethylene undecamethylenediurethane
Hexamethylene (hexamethylenedithio)diethylenediurethane
Dodecamethylene phosphinylidenedipropionamide
Decamethylene hexamethylenediurea
Dodecamethylene (methylphosphinylidene)dipropionamide
1,4-Cyclohexylenedimethylene dodecanedioate
Dodecamethylene 4-octenedioate
Tetradecamethylene 3-hexenedioate
1,3-Cyclohexylenedimethylene dodecanediamide
Decamet hyl ene 2,5-tetrahydrofurandipropionamide
1,4-Cyclohexylenedimethylene hexamethylenedithiodiethylenediurethane
Hexamethylene undecylmalonamide
Pentamethylene dodecylmalonamide
Tetraoxa-8, lo-octadecadiyne hexamethylenediurethane
4,4-Bicyclohexylene sebacate
4,4-Methylenedicyclohexylene azelamide
Hexamethylene p-(carboxyphenoxy)undecanoate
Dodecamethylene p-phenylenedipropionamide
p-Phenylenediethylene tetradecanediamide
Tetradecamethylene p-phenylenediacetamide
p-Xylylene hexadecanediamide
1 5 2 0 4 14 1 2 0 2
15 2 0 L6 18 0 2 0 0
1.5 2 1 0 2 0 2 0 0
1 5 2 1 0 2 0 2 0 0
1 5 2 1 0 2 1 2 0 0
15 2 2 0 4 0 4 0 0
15 4 0 0 4 0 4 0 0
15 4 0 0 4 0 4 0 0
15 4 2 0 2 2 2 0 0
15 4 2 0 2 2 2 0 0
15 4 2 0 2 2 2 0 0
15 4 2 0 2 2 2 0 0
15 4 2 0 2 2 2 0 0
16 0 0 0 0 0 0 0 0
16 0 0 0 0 0 0 2 0
16 0 0 0 0 0 0 4 0
16 0 0 0 0 3 0 0 0
16 0 0 0 2 0 2 0 0
16 0 0 2 4 0 0 0 0
16 0 0 2 4 0 4 2 0
16 0 0 2 6 0 0 0 1
16 0 0 8 2 0 0 0 0
16 1 0 0 1 0 1 0 0
16 1 0 2 4 1 0 0 0
16 1 0 2 5 0 1 0 0
16 1 0 3 6 1 0 0 0
16 2 0 0 0 1 0 0 0
16 2 0 0 0 2 0 0 0
16 2 0 0 0 2 0 0 0
16 2 0 0 0 2 0 0 0
16 2 0 0 2 0 2 0 0
16 2 0 0 2 0 2 0 0
16 2 0 0 2 0 2 0 0
16 2 0 0 2 0 2 0 0
16 2 0 0 2 0 2 0 0
16 2 0 0 2 0 2 0 0
16 2 0 0 2 0 2 0 0
16 2 0 0 2 1 2 0 0
16 2 0 0 2 2 2 0 0
16 2 0 0 2 2 2 0 0
16 2 0 0 2 2 2 0 0
16 2 0 0 2 2 2 0 0
16 2 0 0 2 2 2 0 0
16 2 0 0 2 2 2 0 0
16 2 0 0 2 2 2 0 0
16 2 0 0 2 2 2 2 0
16 2 0 0 3 1 2 0 1
16 2 0 0 4 0 4 0 0
16 2 0 1 5 1 2 0 1
16 2 0 2 2 2 0 0 0
16 2 0 2 2 2 0 0 0
16 2 0 2 2 2 0 0 0
16 2 0 2 4 0 2 0 0
16 2 0 2 4 1 2 0 0
16 2 0 2 4 2 2 2 0
16 2 0 2 6 0 2 0 0
16 2 0 2 6 0 2 0 0
16 2 0 4 2 6 2 0 0
16 2 0 4 4 2 0 0 0
16 2 0 4 6 0 2 0 0
16 2 1 0 0 3 0 0 0
16 2 1 0 2 0 2 0 0
16 2 1 0 2 0 2 0 0
16 2 1 0 2 0 2 0 0
16 2 1 0 2 0 2 0 0
-
C
P
-
P
P-
7
;
P
E
H
C
P
I
1
E
1
lz
E
t
h
P
7
7
L
L
1
H
( 1
1
t
I:
I:
PI
P
E
C
0
b
4
4
h
P
P
H
H
P
c
n
T
7
T
L
1,
c
3
A
C
C
C
c
c
D
0
T
D
D
D
Appendi x: Formul a I ndex to the Tabl es VI / 155
Constitutional Base Unit
Poly-
CHz
C O CsH4 C H 0 N s x
p-Phenylenediethylene thiodienanthamide
p-Xylylene 6-oxaheptadecanediamide
Tetradecamethylene p-xylylenediurea
MN-Dimethyl-p-xylylene hexadecanediamide
(1,4-Cyclohexylenedioxy)ditrimethylene hexamethylenedioxydibenzamide
fi-o-Glucotriheptylate, 1,4-
Ethylene NJ-adipoyldi(6-aminocaproate)
Hexamethylene adipamide-alt-hexamethylene oxamide
Octamethylene sebacoyldiurea
Pentamethylene oxamide-a/t-pentamethylene suberamide
Tetramethylene oxamide-alt-tetramethylene sebacamide
1,12-Bis(n-Butoxycaonylmethylurethane)-5,7-dodecadiynediol
Hexamethylene N,N-terephthaloyldi(6-aminocaproate)
Decamethylene N,N-hexamethylenediterephthalamate
Dodecamethylene NJ-tetramethylenediterephthalamate
Ethylene NJ-hexadecanedioyldi(p-aminobenzoate)
Hexamethylene N,N-dodecanedioyldi(p-aminobenzoate)
Nonamethylene NJ-azelaoyldi(p-aminobenzoate)
Pentamethylene N,N-tridecanedioyldi(p-aminobenzoate)
Tetradecamethylene N,N-ethylenediterephthalamate
Tridecamethylene N,N-trimethylenediterephthalamate
Undecamethylene iV,N-pentamethylenediterephthalamate
L- 1 -0rboxypentamethylene adipamide
17
Hexamethylenethioundecamethylene sulfide
(Pentamethylenedioxy)dihexamethylene oxide
1SAminostearic acid
Vinyl stearate
Decamethylene azelate
Decamethylene azelamide
Nonamethylene sebacamide
Pentamethylene tetradecanediamide
Hexamet hyl ene 5-oxatetradecanediamide
Oxydipentamethylene 5-oxasebacamide
(0ctylphosphinidene)ditrimethylene adi pami de
Hexamet hyl ene 2-dodecylmalonamide
4,4-Bicyclohexylene undecanedioate
4,4-Methylenedicyclohexylene sebacamide
Nonamethylene (tetraethyldisiloxanylene)dipropionamide
p-Phenylenediethylene pentadecanediamide
p-Xylylene heptadecanediamide
Hexadecamet hyl ene 4,4-(methylenediphenylene)diurethane
Hexamet hyl ene oxamide-air-hexamethylene pimelamide
Pentamethylene azelamide-alt-pentamethylene oxamide
Dodecamethylene N,N-pentamethylenediterephthalamate
Nonamethylene N,N-sebacoyldi(p-aminobenzoate)
Tetradecamethylene NJ-trimethylenediterephthalamate
Tridecamethylene MN-tetramethylenediterephthalamate
Trimethylene MN-hexadecanedioyldi(p-aminobenzoate)
Undecamethylene MN-hexamethylenediterephthalamate
1 8
Di-n-decylsilylene
3,3-Didecyl-2,2-bithiophene
N-octadecanoylethylene amine
Octadecyl acrylate
Octadecyl acrylamide
Octadecyl methacrylate
Decamethylene dithiolsebacate
Decamethylene sebacate
Dodecamethylen suberate
Octamethylene dodecanedioate
Tetradecamethylene adipate
Decamethylene thiodivalerate
Decamethylene sulfonyldivalerate
Decamethylene sebacamide
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
1 6
11
1 7
1 7
1 7
1 7
1 7
1 7
1 7
1 7
1 7
1 7
1 7
1 7
1 7
1 7
1 7
1 7
1 7
1 7
11
1 7
1 7
1 7
1 7
1 7
1 7
1 7
1 8
1 8
1 8
1 8
18
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
2
2
2
2
2
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
6
0
0
0
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
4
4
4
4
4
4
4
4
0
0
0
1
1
1
1
2
2
2
2
2
2
2
2
1
1
1
1
2
0
0
0
0
0
0
0
1
2
2
2
2
2
2
2
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
2
0
0
2
2
2
2
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
8
0
0
0
0
0
6
0
0
0
0
0
0
0
0
0
0
2
0
0
0
0
2
0
0
0
0
0
0
1
2
4
4
4
0
0
0
0
0
0
0
0
0
0
0
0
2
1 0
1
2
2
3
0
0
0
0
0
0
0
0
-
2
2
4
6
4
1 4
2
4
4
4
4
8
2
2
2
2
2
2
2
2
2
2
8
0
0
0
1
4
0
2
2
2
2
2
5
6
4
6
1 4
2
2
2
4
4
2
2
2
2
2
2
0
6
8
3
4
5
6
0
0
0
0
0
0
0
2
0
1
0
0
4
5
2
0
0
0
0
4
2
2
2
2
2
2
2
2
2
2
2
0
0
3
0
1
2
0
0
0
1
2
0
0
2
0
1
0
0
2
0
0
2
2
2
2
2
2
0
0
0
0
1
0
1
0
2
2
2
2
2
4
0
2
2
4
2
2
0
2
4
4
4
4
2
2
2
2
2
2
2
2
2
2
2
4
0
0
0
1
0
0
2
2
2
2
2
2
2
0
2
2
2
2
2
4
4
2
2
2
2
2
2
0
0
0
1
0
1
0
0
0
0
0
0
0
0
2
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
0
0
0
0
2
0
0
0
0
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
2
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
References page VI-159
VI / 156 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHz
C O CsH4 C H 0 N s x
Hexamethylene tetradecanediamide
Nonamethylene undecanediamide
Octamethylene dodecanediamide
Hexametbylene tbiodienanthamide
Hexamet hyl ene 6-oxapentadecanediamide
Hexamethylene oxydienanthamide
Decamethylene octamethylenediurethane
Dodecamethylene hexamethylenediurethane
Octamethylene decamethylenediurethane
Oxydipentamethylene 5-oxaundecanediamide
Oxydiepentamethylene oxydivaleramide
Aminodihexamethylene suberamide
Decamethylene octamethylenediurea
Dodecamethylene hexamethylenediurea
Hexadecamethylene 3-hexenedioate
Tetradecamethylene 4-octenedioate
Heptamethylene dodecylmalonamide
Hexamet hyl ene tridecylmalonamide
4,4-Ethylenedicyclohexylene sebacamide
4,4-Methylenedicyclohexylene undecanediamide
Octadecamethylene terephthalate
Octadecamethylene terephthalamide
p-Phenylenediethylene hexadecanediamide
Tetradecamethylene p-phenylenedipropionamide
p-Xylylene octadecanediamide
p-Xylylene thiodipelargonamide
p-Xylylene oxydipelargonamide
Hexadecametbylene p-xylylenediurethane
NJ-Dimethyl-p-xylylene octadecanediamide
Decamethylene sebacoyldiurethane
Tetramethylene N,N-adipoyldi(6-aminocaproate)
Hexametbylene oxamide-air-hexamethylene suberamide
Pentamethylene oxamide-al&pentamethylene sebacamide
Octamethylene NJ-terephthaloyldi(6aminocaproate)
Dodecamethylene IV,N-hexamethylenediterephthalamate
Hexamethylene NJ-dodecamethylenediterephthalamate
Octamethylene NJ-dodecanedioyldi(p-aminobenzoate)
Tetradecamethylene MN-tetrametbylenediterephthalamate
Tetramethylene NJ-hexadecanedioyldi(p-aminobenzoate)
Tridecametbylene MN-pentametbylenediterephtbalamate
19
Methyleneoxyoctadecamethylene oxide
10,12-Pentacosadiynoic acid, 10,13-
Trimethylene octadecanedioate
Undecamethylene sebacamide
Hexamet hyl ene Soxahexadecanediamide
Oxydipentamethylene 5-oxadodecanediamide
Oxydipentamethylene 6-oxadodecanediamide
Tet ramet hyl ene (pentamethylenedisulfonyl)dicaproamide
Hexametbylene (trimethylenedisulfonyl)diaminodicaproamide
Hexamet hyl ene 2-tetradecylmalonamide
Octamethylene dodecylmalonamide
4,4-Methylenedicyclohexylene dodecanediamide
p-Phenylenediethylene heptadecanediamide
4,4-Metbylenediphenylene octadecamethylenediurea
P-D-Glucotricaprylate, 1,4-
Hexamethylene azelamide-alt-hexamethylene oxamide
Pentamethylene NJ-hexadecanedioyldi(p-aminobenzoate)
Tetradecametbylene N,N-pentamethylenediterephthalamate
Tridecamethylene WV-hexamethylenediterephthalamate
20
1-Docosene
Di-n-undecylsilylene
Eicosamethylene oxalate
Hexadecametbylene adipate
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 8
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
1 9
20
20
20
20
20
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
2
2
4
4
0
0
0
0
0
0
0
0
2
0
0
0
0
0
0
0
0
0
0
0
0
0
5
0
0
0
0
0
0
0
2
2
4
0
0
8
0
0
0
0
0
2
2
0
0
2
2
2
2
2
2
2
2
2
2
2
3
4
4
2
2
6
6
6
6
0
2
2
2
2
2
2
2
6
2
2
4
4
2
2
2
2
2
2
2
0
0
2
0
2
2
2
2
2
4
6
6
6
2
4
1 4
4
2
2
2
0
4
6
0
0
(
I
1
I
I
f
P
(
1
I
(
(
1
F
1
F
E
F
P
F
E
E
4
4
E
E
E
c
P
P
C
A
E
E
C
I-
F
I-
L:
I:
h
7
2
2
11
E
c
P
0
H
PI
D
H
4 .
N
2 :
(1
D
D
N
E
H
E
D
D
H
TI
-
Appendix: Formula Index to the Tables VI / 157
Constitutional Base Unit
Poly-
CHz C O CsH4 C H 0 N S
Tetradecamethylene suberate
Decamethylene dodecandiamide
Dodecamethylene sebacamide
Hydrazo docosanediamide
Nonamethylene tridecanediamide
Octamethylene tetradecanediamide
Hexamet hyl ene 6-oxaheptadecanediamide
Decamethylene decamethylenediurethane
Oxydipentamethylene 6-oxatridecanediamide
Oxydipentamethylene oxydicaproamide
Hexamethylene (tetramethylenedisulfonyl)dicaproamide
Pentamethylene (pentamethylenedisulfonyl)dicaproamide
Tetramethylene (hexamethylenedisulfonyl)dicaproamide
Hexamethylene tetradecamethylenediurea
Hexadecamethylene 4-octenedioate
Hexamethylene pentadecylmalonamide
Nonamethylene dodecylmalonamide
Hexamet hyl ene 9,10-dihydroxyoctadecanediamide
Ethylene tetraoxa-3,9-spiro(5S)hendecanedicaprylate
Ethylene 4,4-(oxydimethylene)di-2-(1,3-dioxolane)cap~late
4,4-Ethylenedicyclohexylene dodecanediamide
4,4-Methylenedicyclohexylene tridecanediamide
Eicosamethylene isophthalate
Eicosamethylene phthalate
Eicosamethylene terephthalate
Octadecamethylene p-phenylenediacetamide
p-Phenylenediethylene octadecanediamide
p-Phenylenediethylene thiodipelargonamide
Octadecamethylene p-xylylenediurea
N,N-Diethyl-p-xylylene octadecanediamide
Eicosamethylene 3,3 -dibenzoate
Eicosamethylene 4,4-dibenzoate
Octadecamethylene 4,4-(ethylenedioxy)dibenzoate
Hexamethylene NJ-adipoyldi(6-aminocaproate)
Hexamethylenedi(6.hydroxycaproamide) adipate
Hexamet hyl ene oxamide-alt-hexamethylene sebacami de
Decamet hyl ene NJ-terephthaloyldi(6-aminocaproate)
Decamet hyl ene NJ-dodecanedioyldi@-aminobenzoate)
Nonamethylene NJ-tridecanedioyldi@-aminobenzoate)
Tetradecamethylene NJ-hexamethylenediterephthalamate
2 1
22-Aminodocosanoic acid
10,12-Heptacosadiynoic acid, 10,13-
Eicosamethylene malonate
Decamethylene tridecanediamide
Pentamethylene octadecanediamide
Oxydipentamethylene 5-Oxatetradecanediamide
Hexamethylene (pentamethylenedisulfonyl)dicaproamide
Pentamethylene (hexamethylenedisulfonyl)dicaproamide
Decamethylene dodecylmalonamide
Hexamethylene 2-hexadecylmalonamide
4,4-Methylenedicyclohexylene tetradecanediamide
Nonamethylene NJ-tetradecanedioyldi(p-aminobenzoate)
22
(Decamethylenedioxy)dihexamethylene oxide
Di-n-dodecylsilylene
Docosyl acrylate
N-Docosyl acrylamide
Eicosamethylene succinate
Hexadecamethylene suberate
Eicosamethylene oxydiacetate
Decamethylene tetradecanediamide
Dodecamethylene dodecanediamide
Hexamethylene octadecanediamide
Tetradecamethylene sebacamide
0 0 2 0 0
0 2 0 2 0
0 2 0 2 0
0 2 0 2 0
0 2 0 2 0
0 2 0 2 0
0 2 1 2 0
0 2 2 2 0
0 2 2 2 0
0 2 2 2 0
0 2 4 2 2
0 2 4 2 2
0 2 4 2 2
0 4 0 4 0
2 2 2 0 0
2 6 0 2 0
2 6 0 2 0
2 6 2 2 0
3 2 6 0 0
4 4 7 0 0
4 6 0 2 0
4 6 0 2 0
0 0 2 0 0
0 0 2 0 0
0 0 2 0 0
0 2 0 2 0
0 2 0 2 0
0 2 0 2 1
0 4 0 4 0
2 6 0 2 0
0 0 2 0 0
0 0 2 0 0
0 0 4 0 0
0 2 2 2 0
0 2 2 2 0
0 4 0 4 0
0 2 2 2 0
0 2 2 2 0
0 2 2 2 0
0 2 2 2 0
0 0 0 0 0
0 1 0 1 0
5 2 1 0 0
0 0 2 0 0
0 2 0 2 0
0 2 0 2 0
0 2 2 2 0
0 2 4 2 2
0 2 4 2 2
2 6 0 2 0
2 6 0 2 0
4 6 0 2 0
0 2 2 2 0
0 0 0 0 0
0 0 3 0 0
2 6 0 0 0
2 4 1 0 0
2 5 0 1 0
0 0 2 0 0
0 0 2 0 0
0 0 3 0 0
0 2 0 2 0
0 2 0 2 0
0 2 0 2 0
0 2 0 2 0
X
-
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
References page VI- 159
VI / 158 CRYSTALLOGRAPHIC DATA AND MELTING POINTS FOR VARIOUS POLYMERS
Constitutional Base Unit
Poly-
CHz C O CGH, C H 0 N s x
Hexamethylene oxydipelargonamide 22 2 0 0 2 1 2 0 0
Dodecamethylene decamethylenediurethane 22 2 0 0 2 2 2 0 0
Hexadecamethylene hexamethylenediurethane 22 2 0 0 2 2 2 0 0
Oxydipentamethylene 6-oxapentadecanediamide 22 2 0 0 2 2 2 0 0
Oxydipentamethylene oxydienanthamide 22 2 0 0 2 2 2 0 0
Hexamethylene (hexamethylenedisulfonyl)dicaproamide 22 2 0 0 2 4 2 2 0
Decamethylene dodecamethylenediurea 22 2 0 0 4 0 4 0 0
NJ-Dimethylhexamethylene octadecanediamide 22 2 0 2 6 0 2 0 0
Hexamethylene heptadecylmalonamide 22 2 0 2 6 0 2 0 0
Octadecamethylene p-phenylenedipropionamide 22 2 1 0 2 0 2 0 0
p-Xylylene docosanediamide 22 2 1 0 2 0 2 0 0
p-Xylylene thiodiundecanoamide 22 2 1 0 2 0 2 1 0
Eicosamethylene 3-@-nitrophenyl)glutarate 22 2 1 1 1 4 1 0 0
Octamethylene NJ-adipoyldi(6-aminocaproate) 22 4 0 0 2 2 2 0 0
Heptamethylene oxamide-alt-heptamethylene sebacamide 22 4 0 0 4 0 4 0 0
Hexamet hyl ene oxamide-alt-hexamethylene sebacami de 22 4 0 0 4 0 4 0 0
Dodecamethylene N,N-terephthaloyldi(6-aminocaproate) 22 4 1 0 2 2 2 0 0
Dodecamet hyl ene N,N-dodecanedioyldi(p-aminobenzoate) 22 4 2 0 2 2 2 0 0
23 23 0 0 0 0 0 0 0 0
10,12-Nonacosadiynoic acid, 10,13- 23 1 0 5 2 1 0 0 0
Eicosamethylene glutarate 23 2 0 0 0 2 0 0 0
Oxydipentamethylene Soxahexadecanediamide 23 2 0 0 2 2 2 0 0
Eicosamethylene 3-methyladipate 23 2 0 2 4 2 0 0 0
Hexamethylene 2-octadecylmalonamide 2 3 2 0 2 6 0 2 0 0
Nonamethylene NJ-hexadecanedioyldi(p-aminobenzoate) 23 4 2 0 2 2 2 0 0
24 24 0 0 0 0 0 0 0 0
(Tetramethylenedioxy)didecamethylene oxide 24 0 0 0 0 3 0 0 0
Eicosamethylene adipate 24 2 0 0 0 2 0 0 0
Hexamethylene eicosanediamide 24 2 0 0 2 0 2 0 0
Octamethylene octadecanediamide 24 2 0 0 2 0 2 0 0
Tetradecamethylene dodecanediamide 24 2 0 0 2 0 2 0 0
Tridecamethylene tridecanediamide 24 2 0 0 2 0 2 0 0
Dodecamethylene dodecamethylenediurethane 24 2 0 0 2 2 2 0 0
Oxydipentamethylene 6-oxaheptadecanediamide 24 2 0 0 2 2 2 0 0
Decamethylene (tetramethylenedisulfonyl)dicaproamide 24 2 0 0 2 4 2 2 0
Tetramethylene (decamethylenedisulfonyl)dicaproamide 24 2 0 0 2 4 2 2 0
Oxydiethylenedioxydiethylenedioxydiethylene hexamethylenediurethane 24 2 0 0 2 I 2 0 0
Decamethylene tetradecamethylenediurea 24 2 0 0 4 0 4 0 0
Hexamethylene octadecamethylenediurea 24 2 0 0 4 0 4 0 0
Hexamet hyl ene tetraoxa-3,9-spiro(5.5)hendecanedicaprylamide 24 2 0 3 4 4 2 0 0
Hexamet hyl ene 4,4-(oxydimethylene)di-dioxolanecaprylamide 24 2 0 4 6 5 2 0 0
p-Phenylenediethylene docosanediamide 24 2 1 0 2 0 2 0 0
p-Phenylenediethylene thiodiundecanoamide 24 2 1 0 2 0 2 1 0
Decamethylene NJ-adipoyldi(6-aminocaproate) 24 4 0 0 2 2 2 0 0
Octamethylene oxamide-alt-octamethylene sebacamide 24 4 0 0 4 0 4 0 0
Dodecamethylene NJ-dodecamethylenediterephthalamate 24 4 2 0 2 2 2 0 0
25 25 0 0 0 0 0 0 0 0
(Pentamethylenedioxy)didecamethylene oxide 25 0 0 0 0 3 0 0 0
Eicosamethylene pimelate 2 5 2 0 0 0 2 0 0 0
Decamethylene (pentamethylenedisulfonyl)dicaproamide 2 5 2 0 0 2 4 2 2 0
Pentamethylene (decamethylenedisulfonyl)dicaproamide 2 5 2 0 0 2 4 2 2 0
P-D-Glucotricaprate 25 3 0 8 1 4 5 0 0 0
26 26 0 0 0 0 0 0 0 0
(Hexamethylenedioxy)didecamethylene oxide 26 0 0 0 0 3 0 0 0
Di-n-tetradecylsilylene 26 0 0 2 6 0 0 0 1
4,4-Decamethylenedipiperazine sebacamide 26 2 0 0 0 0 4 0 0
Decamethylene octadecanedioate 26 2 0 0 0 2 0 0 0
Eicosamethylene suberate 26 2 0 0 0 2 0 0 0
Decamethylene octadecanediamide 26 2 0 0 2 0 2 0 0
Hexamethylene docosanediamide 26 2 0 0 2 0 2 0 0
Octadecamethylene sebacamide 26 2 0 0 2 0 2 0 0
Octamethylene eicosanediamide 26 2 0 0 2 0 2 0 0
Hexadecamethylene decamethylenediurethane 26 2 0 0 2 2 2 0 0
Oxydipentamethylene oxydipelargonamide 26 2 0 0 2 2 2 0 0
Decamethylene (hexamethylenedisulfonyl)dicaproamide 26 2 0 0 2 4 2 2 0
References VI / 159
Constitutional Base Unit
Poly-
CHz C O CSH4 C H 0 N s x
Hexamethylene (decamethylenedisulfonyl)dicaproamide 26 2 0 0 2 4 2 2 0
Dodecamethylene NJ-adipoyldi(6-aminocaproate) 26 4 0 0 2 2 2 0 0
Nonamethylene oxamide-alt-nonamethylene sebacamide 26 4 0 0 4 0 4 0 0
2 7 27 0 0 0 0 0 0 0 0
Eicosamethylene azelate 27 2 d 0 0 2 0 0 0
2 8 28 0 0 0 0 0 0 0 0
Eicosamethylene sebacate 28 2 0 0 2 0 0 0 0
Eicosamethylene thiodivalerate 28 2 0 0 0 2 0 1 0
Eicosamethylene sulfonyldivalerate 28 2 0 0 0 4 0 1 0
Decamethylene eicosanediamide 28 2 0 0 2 0 2 0 0
Dodecamethylene octadecanediamide 28 2 0 0 2 0 2 0 0
Octamecamethylene dodecanediamide 28 2 0 0 2 0 2 0 0
Octamethylene docosanediamide 28 2 0 0 2 0 2 0 0
Decamethylene octadecamethylenediurea 28 2 0 0 4 0 4 0 0
Decamethylene oxamide-alt-decamethylene sebacamide 28 4 0 0 4 0 4 0 0
3 0 30 0 0 0 0 0 0 0 0
Decamethylene docosanediamide 30 2 0 0 2 0 2 0 0
Tetradecamethylene octadecanediamide 30 2 0 0 2 0 2 0 0
Decamethylene (decamethylenedisulfonyl)dicaproamide 30 2 0 0 2 4 2 2 0
p-Phenylene 2,5-di-n-hexadecyloxyterephthalate 30 2 1 8 8 4 0 0 0
Undecamethylene oxamide-alt-undecamethylene sebacamide 30 4 0 0 4 0 4 0 0
@Ghtcotritaurate 3 1 3 0 8 1 4 5 0 0 0
Dodecamethylene docosanediamide 32 2 0 0 2 0 2 0 0
Dodecamethylene oxamide-air-dodecamethylene sebacamide 32 4 0 0 4 0 4 0 0
Octadecamethylene octadecanediamide 34 2 0 0 2 0 2 0 0
Tetradecamethylene docosanediamide 34 2 0 0 2 0 2 0 0
P-D-Glucotrimyristate 37 3 0 8 1 4 5 0 0 0
Octadecamethylene docosanediamide 38 2 0 0 2 0 2 0 0
P-o-Glucotripalmitate 43 3 0 8 1 4 5 0 0 0
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1944. E. J. Vandenberg, J. Polym. Sci., Polym. Chem. Ed., 23,915
(1985).
1945. E. Riande, J. Guzman, E. Siaz, Polymer, 22, 465
(1981).
1946. K. Onder, A. T. Chen, Polym. Eng. Sci., 25, 942 (1985).
A.
B.
C.
D.
E.
F.
Glass Transition Temperatures of Polymers
Rodney J . Andrews, Eric A. Grulke
Chemical and Materials Engineering, University of Kentucky, Lexington, KY 40506-0046, USA
A. Introduction
1. Example of a Property Change at T,
2. Ts: A Non-Equilibrium Transition
B. T, Measurement Methods
1. Data Interpretation
2. Oscillating Load Methods
C. Other Factors Affecting T,
1. Structure
2 . Crystallinity/Crosslinking
3. Di l uent s
4. Mol ecul ar Wei ght
5. Thermal History
6. Pressure
D. Estimation Methods for the Glass
Transition Temperature
E. Classification, Nomenclature, and
Abbreviations
1. Naming Conventions
2. Abbreviations
F. Tables of Glass Transition Temperatures of
Pol ymer s
VI-I 94
VI-1 94
VI-1 95
VI-1 95
VI-1 95
VI-1 96
VI-l 96
VI-1 96
VI-1 96
VI-I 97
VI-1 97
VI-I 97
VI-1 97
VI-1 97
VI-1 97
VI-1 98
VI-l 98
VI-1 98
Table 1. Main-Chain Acyclic Carbon Polymers VI-1 98
1 .l. Poly(acrylics) and
Poly(methacrylics) VI-1 98
1 .l .I. Poly(acrylic acid) and
Polyfacrylic acid esters) VI-1 98
1 .1.2. Poly(acrylamides) V I - 2 0 1
1 .1.3. Polyfmethacrylic acid)
and Polyfmethacrylic
aci d est ers) VI-201
1 .I .4. Poly(methacrylamides) VI-205
1 .1.5. Other w and P-Substituted
Poly(acrylics) and
Poly(methacrylics) VI-205
1.2. Poly(alkenes) VI-205
1.3. Polyfdienes) VI-207
1.4. Poly(styrenes) VI-209
1.5. Polyfvinyl alcohol) and
Poly(vinyl ketones) VI-21 2
1.6. Poly(vinyl esters) VI-21 3
1.7. Poly(vinyl ethers) and
Poly(vinyl thioethers) VI-214
1.8. Poly(vinyl halides) and
Polyfvinyl nitriles) VI-21 5
1.9. Others VI-21 6
Table 2. Main-Chain Carbocyclic Polymers VI-2 18
2.1. Poly(phenylenes) VI-21 8
2.2. Others VI-2 18
Table 3. Main-Chain Acyclic Heteroatom
Polymers VI-21 9
3.1. Main-Chain -C-O-C Polymers VI-21 9
3 . 1 .l. Poly(anhydrides) V I - 2 1 9
3 . 1 . 2 . Polyfcarbonates) V I - 2 1 9
3.1.3. Polyfesters) VI-221
3.1.4. Polytether ketones) VI-226
3.1.5. Polyfoxides) VI-226
3 . 1 . 6 . Polyfurethanes) V I - 2 2 9
3.2. Main-Chain 0-Heteroatom
Pol ymer s VI-231
3. 2. 1. Ni t roso-pol ymers VI -231
3 . 2 . 2 . Poly(siloxanes) V I - 2 3 1
3 . 2 . 3 . Polyfsulfonates) V I - 2 3 3
3.3. Main-Chain -C-(S),-C- and
-C-S-N- Pol ymers VI-233
3.3.1. Polyfsulfides) VI-233
3.3.2. Polyfsulfones) and
Poly(sulfonamides) VI-234
3 . 3 . 3 . Poly(thioesters) V I - 2 3 5
3. 4. Mai n-Chai n -C-N-C
Pol ymer s VI-235
3.4.1. Polyfamides) VI-235
3.4.2. Polyfanilines) VI-241
3.4.3. Polyimides VI-241
3.4.4. Poly(imines) VI-241
3.4.5. Polyfureas) VI-242
3.5. Polyfphosphazenes) VI-242
3.6. Polyfsilanes) and
Polyfsilazanes) VI-243
Table 4. Main-Chain Heterocyclic Polymers VI-243
4.1. Carbohydrates VI-243
4.2. Liquid Crystals VI-244
4.3. Natural Polymers VI-244
4.4. Polyfacetals) VI-244
VI / 193
VI / 194 CLASS TRANSITION TEMPERATURES OF POLYMERS
4 . 5 . Polyfanhydrides)
4 . 6 . Polyfbenzimidazoles)
4 . 7 . Poly(benzothiazinopheno-
thiazines)
4 . 8 . Polyfbenzothiazoles)
4 . 9 . Poly(benzoxazines)
4.10. Poly(benzoxazoles)
4. 11. Polyfcarboranes)
4.12. Polyfdibenzofurans)
4.13. Polyfdioxoisoindolines)
4.14. Polyffluoresceins)
4.15. Polyffuran tetracarboxylic
acid diimides)
4.16. Polyfoxabicyclononanes)
4.17. Polyfoxadiazoles)
4.18. Polyfoxindoles)
4.19. Polyfoxoisoindolines)
4.20. Polyfphthalazines)
4. 21. Polyfphthalides)
4. 22. Polyfpiperazines)
4.23. Poly(piperidines)
4. 24. Poly(pyrazinoquinoxalines)
4.25. Poly(pyrazoles)
4. 26. Polyfpyridazines)
4. 27. Polyfpyridines)
4.28. Poly(pyromellitimides)
4. 29. Polyfpyrrolidines)
4. 30. Polyfquinones)
4. 31. Polyfquinoxalines)
4. 32. Polykriazines)
4. 33. Polyftriazoles)
Tabl e 5. Copolymers
C. Ref erences
A. INTRODUCTION
VI-244
VI-245
VI-245
VI-245
VI-245
VI-245
VI-245
VI-246
VI-246
VI-247
VI-247
VI-247
VI-248
VI-248
W-248
VI-248
VI-248
VI-248
VI-249
VI-249
VI-249
VI-249
VI-249
VI-249
VI-250
VI-250
VI-250
VI-252
VI-252
W-252
VI-253
Amorphous (noncrystalline) polymeric solids are either
glasses or rubbers. A glassy polymer lacks long range order,
and is below the temperature at which molecular motions
take place on the time scale of the experiment. A rubbery
polymer is above the temperature at which molecular
motions take place on the time scale of the experiment. The
glass transition temperature, T,, is the critical temperature
that separates glassy behavior from rubbery behavior. Many
amorphous solids, including polymers, organic liquids,
biomaterials, some metals and alloys, and inorganic oxide
glasses, exhibit glass transition temperatures.
The dramatic change in the local movement of polymer
chains at T, leads to large changes in a host of physical
properties. These properties include density, specific heat,
mechanical modulus, mechanical energy absorption, dielec-
tric coefficients, acoustical properties, viscosity, and the
rate of gas or liquid diffusion through the polymer, to name
a few. Any of these properties can be used, at least in a
crude manner, to determine T,.
Temperature
Fi gure 1.
1 . Example of a Property Change at Tg
A classic method for determining T, is dilatometry, in
which the specific volume of the polymer is measured as a
function of temperature. Figure 1 compares the specific
volume vs. temperature curves for two idealized samples: a
100% amorphous material and a 100% crystalline material.
Both materials follow the same path as their liquids are
cooled from the melt. At the melting temperature, T,, the
crystallizing material orders into its crystal habit and
exhibits a discontinuous decrease in specific volume. Below
T,, this solid has a reduction in specific volume with
decreasing temperature, but the slope of this line, the
volumetric thermal expansion coefficient, is less than the
slope of the liquid line.
The amorphous material does not crystallize as the
temperature falls below T,, but continues to contract with a
thermal expansion coefficient similar to the molten liquid: it
acts as a supercooled liquid. At T,, large-scale molecular
motion (often considered to be the movement of 20-50
carbon atoms along a chain) becomes greatly reduced, the
chain segments no longer rearrange rapidly in experimental
time, and further cooling does not result in a similar volume
change. Below T,, the thermal expansion coefficient is
similar to that of the crystalline solid. T, can be defined as
the temperature at the intersection of the two line segments.
The specific volume is not discontinuous at T,, as would be
the case for the melting point, but the slope dV/dT, is.
Therefore, T, is sometimes referred to as a second-order
transition, as compared to the melting point, which is a
first-order transition. Both the primary property, specific
volume, and its differential, the volumetric thermal
expansion coefficient, change at T, and can be used to
identify the event.
Most polymer samples are either completely amorphous
or partially crystalline. Figure 2 shows the specific volume
vs. temperature curve for a semicrystalline polymer. The
crystallizable fraction becomes ordered as it cools to T,.
Below the melting point, the amorphous material
continues to contract as though it were a subcooled liquid,
while the crystalline portion has a smaller thermal
Fi gure 2.
Temperature
/
L i q u i d
Crystallization
volume change
expansion coefficient and contributes less to the volumetric
decrease. Rapid amorphous phase motion stops at the glass
transition temperature, and both solid components have
similar thermal expansion coefficients below this tempera-
ture.
2 . Tg: A Non-Equilibrium Transition
The glass transition temperature is not a fundamental
thermodynamic property like the melting point because it is
not thermodynamically stable, it is not defined by state
variables, and its measurement is highly dependent on the
time scale of the experiment used to determine its value.
For example, experiments in which temperature or a
deforming force is changed rapidly give higher T, values
than experiments in which conditions are changed slowly.
Sample age and history affect the measurements as well.
The thermodynamic transition issue has been studied by
a number of researchers. Staverman (1210) and Breuer and
Rehage (1211) have concluded that T, is not a true second-
order transition because the glassy state is not completely
defined by the normal state variables, p, Vand i? Ehrenfest
(1212) derived the following relationship that should hold
for a true second-order transition:
g T,V(T,)Aa A&
dT
dp - AC, = z
where T, is the glass transition temperature, p is the
pressure, V(T,) is the molar volume at T,, Ao is the
thermal expansion coefficient difference (rubber to glass) at
T,, AC,, is the molar heat capacity difference, and AK. is
the compressibility difference. Available data for a number
of polymer systems show large deviations from the above
equation for well-studied polymers, including polystyrene
(121 l), poly(isobutylene), poly(viny1 acetate), poly(viny1
chloride) and poly(methy1 methacrylate) (1213,1214). The
glass transition temperature is thought to be a kinetically
controlled phenomenon ( 12 15 - 12 18).
T, Measurement Methods VI / 195
6. T, MEASUREMENT METHODS
The classical method of mercury dilatometer requires
moderate amounts of sample, and time to permit thermal
equilibrium to be achieved. Instruments that are easier to
use and require only milligram quantities of sample are the
thermal mechanical analyzer (TMA), the dynamic mechan-
ical analyzer (DMA), and the differential scanning
calorimeter (DSC). A TMA deforms a sample under a
static load as the temperature is changed. At very low loads,
it measures the specific volume change of the sample. A
DMA measures the response of the material to an
oscillating deformation. A DSC measures the change in
sample enthalpy with time, dH/dt, for a known temperature
program, dT/dt. The ratio of these two quantities gives
dH/dT (also the specific heat capacity), which is a
derivative measurement for T,. (Experimental heat capacity
curves of amorphous and semicrystalline polymers are
given in the Heat Capacity chapter of this Handbook.) DSC
is the most commonly used method for measuring the glass
transition temperature of non-crosslinked polymers. All of
these instruments can be interfaced to computers for data
acquisition, test control, data reduction, and analysis.
The interpretation of T, data can be controversial
(1069-1071). The rate at which the sample is cooled or
heated will affect the result. If the specific volume
experiment of Fig. 2 was repeated for various cooling
rates, T, would occur at lower temperatures as the cooling
rate is lowered, the transition region would become sharper,
and a denser polymer would be produced. When a sample is
allowed to remain below its glass transition temperature
over a long period of time (aging), its density will increase.
This process is called annealing; the rate of densification
increases with annealing temperature.
1. Data Interpretation
The previous history of a sample will affect the measure-
ment of T,, unless the materials memory is erased by
heating it well above the transition. The sample is heated
well above its expected T,, cooled to the original
temperature, and reheated along a temperature profile to
find the glass transition temperature of the material with
minimal history. Some information can be inferred from the
first heat, including residual stresses in the material, the
presence of low-boiling diluents, etc.
The process of heating a polymer solid to find T, often
gives a curve similar to Fig. 1 and will produce a melt with
the same density as that of the cooling experiment.
However, in heating experiments, chain motions dominate
the change in properties, and sudden property changes can
occur near the transition temperature. At temperatures
much higher than T,, the property response once again
becomes linear with temperature. In DSC measurements,
sudden expansions can lead to an endothermic peak past the
T,. This endothermic peak has also been called enthalpy
overshoot, and is thought to relate to the difference between
the rate of temperature increase and the rate of increase of
References page VI - 253
VI / 196 CLASS TRANSITION TEMPERATURES OF POLYMERS
chain mobility around T,. The size of this overshoot
depends on the annealing of the sample and the heating
rate.
In a direct property measurement experiment (Fig. 1 is
an example), it is common practice to ignore the kinetic
effects of the transition region and to define T, as the
intersection of the two straight lines. For this case, the same
T, is found both on heating and cooling at a given polymer
density. In an experiment that measures the differential of a
property (DSC for example), integrating the curve gives the
change in enthalpy from before to after the transition
region, to which the simple intersection method of Fig. 1
can be applied, giving a T, that is independent of heating
rate (1079-1081). This method is well-known with
inorganic glasses.
In DSC experiments, T, is usually determined either by
the onset point, the intersection of the initial straight line
and the transition region straight line, or by the midpoint of
the transition region (inflection point). The integration
methods T, is the same as the midpoint T, if there is no
endotherm, and is closer to the onset T, if there is an
endotherm. Moreover, it is common to measure T, upon
heating without any mention of previous thermal history or
the heating rate. Because of these practices, the T, values
reported in this article should be considered as approximate
by the reader. Authors reporting T, should describe the
thermal history of their measurements and also consider the
integration method of determining T,.
The classical methods of T, measurement discussed
previously can be quite insensitive for some polymers, e.g.,
highly crosslinked polymers. A penetration probe, on the
other hand, is very sensitive and can determine T, even on a
thin film. But this method depends on the force of the
penetrator and does not measure T, in a fundamental way.
Softening temperature methods are popular and are part of
various ASTM standards.
2. Oscillating load Methods
The measurement of the material response to an oscillating
load gives a direct measure of the samples modulus. The
measurement of the lag of the material response (phase
shift) to the mechanical forcing function gives a measure of
the damping, or loss factor, of the sample. This last quantity
is called the tan S peak value. Dielectric thermal analysis is
done by using an oscillating electric field as the forcing
function. At T,, there is often an order of magnitude change
in the modulus and a large maximum in tan S. This a-
transition is distinguished from other thermal transitions (p,
y, etc.) by being the most dominant and occurring at the
highest temperature. An onset point, a midpoint, or a
change in modulus by a certain amount have all been used
to mark the glass transition temperature. The tan 6
maximum clearly specifies a thermal transition. However,
it is necessary to independently determine that it is a glass
transition and not another of the many transitions that
appear in oscillating deformation methods. A classical T,
measured at a low programmed temperature rate (1 deg/
. *
min) may correspond to a tan S measurement at a low
frequency of measurement (1 Hz). The loading rate of a
DMA experiment is the oscillating frequency, and T,
increases with frequency (analogous to the increase in T,
with heating rate in a DSC experiment). It is possible to
measure a tan S maximum at constant temperature while the
frequency is being scanned and there is an inverse
relationship between temperature and frequency. Even at
a reasonably low frequency (10 Hz), a tan S T, can easily be
20-30C greater than a classical one.
C. OTHER FACTORS AFFECTING Tg
Though the factors that govern T, have been known for
some years, there is still a wide variation in values for
particular polymers. Polymer T,s are sensitive to para-
meters which may or may not have been evaluated by the
authors. Published values should be reviewed considering
all the factors which affect T,. The main factors affecting
T, values are polymer structure, sample crystallinity,
diluent types and concentrations, molecular weight dis-
tributions, previous thermal history of the sample, and
system pressure. More detailed treatments are given in
reviews (6,48,49,1241-1249).
1. Structure
Within families of similar polymers, increasing chain
stiffness and interchain cohesion increase the glass transi-
tion temperature. Copolymers may have one or multiple
T,s, depending on the ordering of monomers along the
chain. The glass transition temperatures of copolymers may
be higher, lower, or in between those of the homopolymers
of their comonomers.
Most polymer structures are idealized and presumed
from the characteristics of the reactants rather than proven
by chemical and structural analysis. Structural uncertainties
can arise both from the multiplicity of chemical reactions
occurring during polymerization (especially those taken to
high conversions), downstream processing, and from the
structure of the reactants themselves. For example, a
polymer with an asymmetric in-chain tetravalent atom can
produce several stereoregular forms.
Alternatively, a polymer containing a residual double
bond in the repeating unit could be in a cis, or tram
conformation. Polymers of 1,3-dienes can have various
combinations of cis, tram, 1,2- or 1,4-structures. Variations
in these structural features can greatly effect the T, values.
Despite these uncertainties, the data are often useful if they
can be regarded as pertaining to a polymer with
reproducible properties.
2 . Crystallinity/Crosslinking
Some workers suggest that the presence of crystallinity
does not appreciably affect T,. However, steric constraints
imposed by crystalline regions on neighbouring amorphous
polymer segments might result in an increase in T, because
Estimation Methods for the Glass Transition Temperature VI / 197
of the reduced mobility of these segments. In samples with
crystallinity and moderate fractions of high molecular
weight chains, tie molecules (long chains that have
segments in more than one crystallite) provide physical
crosslinking and increase T,.
Some polymer families, such as the methacrylates and
a-chloroacrylates, show high dependencies of T, on
tacticity. Intermolecular bonding can affect T, either by
increasing the cohesive energy of chain segments, or by
decreasing the backbone degrees of freedom of chain
segments. This last concept has been used (1240) to aid
group contribution models.
As crystallinity increases, polymer T,s may be little
affected (50), may increase (5152) (at least for isothermal
crystallization (53)) or may decrease (51,54). T, values
selected in this work are the highest quoted on the sample
with the lowest degree of crystallinity, other factors being
equal.
In general, the presence of crosslinks in a sample
increases its T, relative to an uncrosslinked sample. This
effect can be independent of the chemical composition of
the crosslinking agent, caused by the restricted motion of
chain segments near crosslinking sites. However, the
crosslinking agent can behave similarly to a second
monomer, inducing either an increase or a decrease in T,
due to the copolymer effect.
3. Diluents
Much of the variation in published T, data is caused by the
use of impure samples. Common impurities are unpolymer-
ized monomer, low molecular weight polymer, solvents,
and water. Great care should be taken to remove such
impurities. Their presence in small concentrations can lead
to a shift (48,98-103) in T, of over 40C and sometimes
the occurrence of diluent transitions, for example water
peaks. Preferred values are from publications that describe
the precautions taken to exclude diluents and the residual
levels of these diluents. Few references contain this
information and most values should be regarded as only
provisional.
4. Molecular Weight
The T, of a homopolymer generally increases with
increasing molecular weight up to a limiting value, known
as the limiting or persistent T, value (48,104,105). The
reverse may hold for polymers with particular end-groups
(106), or where crystallinity decreases with increasing
molecular weight (107). For some polymers, T,s are
independent of molecular weight (108).
Many data, especially on condensation polymers, are for
polymers of rather low molecular weight and it seems likely
that higher T, values would be obtained if higher molecular
weight samples were tested. Many polymers are not
properly characterized with respect to molecular weight
and few have reported molecular weight distributions. In
many cases, the only measure of molecular weight is a
viscosity value, which itself can be very dependent on
solvent-polymer interactions and, to some extent on the
temperature. Usually, the highest viscosities and the highest
molecular weight polymers are associated with the most
reliable data.
The classical model for the effect of molecular weight on
T, is (1219-1226)
T,=T;-$
n
This model suggests that the glass transition temperature
reaches a limiting value when the number average molecular
weight of the polymer is large. Cowie and Toporowski
(1220) have shown that there is no further increase in T,
when the molecular weight is above a critical value, which
is similar to the critical molecular weight for viscosity.
5. Thermal History
We have previously discussed in detail how thermal history
(cooling rate, annealing time, and temperature), as well as
the method of T, measurement affects the reported T,.
6. Pressure
Increasing pressure increases T, in a linear relationship. A
simple model is (Refs. 1227-1230)
T&J = Tg(O) + SP
where Tg@) is the glass transition temperature as a function
of pressure, p is pressure, and s is the linear pressure
coefficient. This coefficient is 0.2K/MPa for flexible
aliphatic chains, and 0.55 K/MPa for semirigid aromatic
chains (1231- 1233). The effect of pressure on T, can be
important in some processing applications, such as injection
molding. A different method for modeling the effect of
temperature takes into account pVT data near T, (1235-
1237), giving an equation that includes the bulk modulus of
the polymer glass.
D. ESTIMATION METHODS FOR THE CLASS
TRANSITION TEMPERATURE
Several researchers have developed group contribution
methods for correlating polymer properties, including the
glass transition temperature (1238- 1240). These techni-
ques emphasize quantitative modeling of the various effects
of polymer structure on T,, and are a valuable aid to
interpreting experimental data and estimating glass transi-
tion temperatures for new materials.
E. CLASSIFICATION, NOMENCLATURE,
AND ABBREVIATIONS
Over 10000 papers contain glass transition data (43). This
section of Polymer Handbook represents a fraction of these
References page VI - 253
VI / 198 GLASS TRANSITION TEMPERATURES OF POLYMERS
data. Most of the data in the tables are for linear propylene is used in naming polymers instead of l-
homopolymers. In general, the polymers contain no methylethylene which could be preferred.
additives or diluents, and are thought to have low or no Polymer names are tabulated in alphabetical order within
branching. each subsection, but
Polymers are subdivided into principle classes by the
composition of their repeating chain segment: acyclic
carbon polymers, carbocyclic polymers, acyclic heteroatom
polymers, heterocyclic polymers, and copolymers. All
entries are placed in the most senior class their structure
commands (109,110) and appear in only one class. The
subclasses and their entries are organized in alphabetical
order.
1. prefixes like set-, tert-, including designated atoms
and the numbers showing locations of substituents are
ignored except as secondary and tertiary indicators of
order. For example, poly(ethylene 2,6-naphthalate)
appears before poly(ethylene 1,4-terephthalate);
poly(4-p-anisoylstyrene) appears before poly(4-ben-
zoylstyrene).
1. Naming Conventions
With the exception of common polymers with accepted
trivial names, the polymers are named substantially
according to the ACS recommendations for polymer
nomenclature (110) in conjunction with IUPAC rules
(109); less common polymers are cross-referenced
from the trivial to the systematic name. Systematic names
are not given for all the polymers in order to save space.
Substitutive nomenclature is generally used for simple
radicals, but for long combinations of radicals replace-
ment nomenclature has been used to provide a much
shorter name (as for some fluorocrylates with ether side
chains).
2. multiplying prefixes for various substituents, such as
dimethyl or trimethyl, are observed in alphabetical
ordering rather than being grouped together as in the
3rd edition of this Handbook.
3. the locations of substituents in otherwise identical
polymers are taken as tertiary indicators of order: the
numbers are arranged in increasing order at the first
point of difference. Thus, 2,3,8- comes before 2,4,1-.
When sequences of radicals have repeated, the repeating
sequence has been written once and prefixed di, tri,
etc. as appropriate, for example, di(oxyethylene) for the
sequence -O-CH2-CH2-O-CH2-CH2-. Note that the
diradical di(oxyethylene) must be distinguished from the
diradical dioxyethylene which has the structure, -O-O-
CH2-CH2-, and also the diradical ethylenedioxy which
has the structure, -0-CH2-CH2-O- (IUPAC rule
C205.2). The principle underlying the last-named diradical
has not generally been extended to the naming of polymers
in this section, i.e., diradicals of structure -X-Y -X- are
not named YdiX, with the exception of alkanedioyl
diradicals, because of the difficulty of locating indexed
polymer names in which the diradicals are not named from
left to right. Many polymers are derivatives of the diradical
propylene -CH(CHs)-CH2-; the substituted diradical
Comments may include information as to the instrument of
measurement and, whenever possible, information regard-
ing the method of DSC measurement (e.g., onset),
conditions of measurement, thermal history, and whether
measurements were made as a function of a particular
variable such as molecular weight (f(MW)).
2. Abbreviations
HR
CR
OCR
XP
TH
DSC
TMA
DTA
DMA
E
Mdpt
Intg
Heating rate
Cooling rate
Zero cooling rate
Extrapolate
Thermal history
Differential scanning calorimeter
Thermal mechanical analyzer
Differential thermal analysis
Dynamic mechanical analyzer
Molecular weight
Function of a variable
Midpoint
Integration
F. TABLES OF GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 1. MAIN-CHAIN ACYCLIC CARBON POLYMERS
Polymer CAS No. T, WI
Remarks Refs.
1.1. POLY(ACRYLICS) AND POLY(METHACRYLICS)
1.1.1. POLY(ACRYLIC ACID) AND POLY(ACRYLIC ACID ESTERS)
Poly(acrylic acid) 9003-01-4 379 720,811-818
348 1 2 9 3
Poly(l-adamantyl acrylate) 426 1401,1349
Poly(adamanty1 crotonate) 507 1349
Poly(adamanty1 sorbate) 388 1349
Poly(benzy1 acrylate) 279 746,1447
Tb
-
PC
-
PC
PC
PC
PC
PC
P C
PC
P C
P C
P C
PC
PC
PC
PC
PC
PC
PC
P C
P
P
I -
F
E
I
I
I
I
I
I
I
1
1
1
1
TABLE 1. contd
Poly(acrylics) and Poly(methacryiics)
Polymer CAS No. T, (K)
Remarks Refs.
Poly(4-biphenylyl acrylate)
Poly(4-butoxycarbonylphenyl acrylate)
Poly(buty1 acrylate)
Poly(sec-butyl acrylate) conventional
syndiotactic
isotactic
Poly(terr-butyl acrylate)
Poly(2-terr-butylphenyl acrylate)
Poly(4-tert-butylphenyl acrylate)
Poly(cesium acrylate)
Poly[3-chloro-2,2-bis(chloromethyl)propyl acrylate]
Poly(2-chlorophenyl acrylate)
Poly(4-chlorophenyl acrylate)
Poly(2,4-dichlorophenyl acrylate)
Poly(4-cyanobenzyl acrylate)
Poly(2-cyanobutyl acrylate)
Poly(2-cyanoisobutyl acrylate)
Poly(4-cyanobutyl acrylate)
Poly(2-cyanoethyl acrylate)
Poly(2-cyanoheptyl acrylate)
Poly(2-cyanohexyl acrylate)
Poly(cyanomethy1 acrylate)
Poly(2-cyanomethyl acrylate)
Poly(S-cyano-3-oxapentyl acrylate)
Poly(4-cyanophenyl acrylate)
Poly(2-cyanoisopropyl acrylate)
Poly(4-cyano-3-thiabutyl acrylate)
Poly(6-cyano-3-thiahexyl acrylate)
Poly(6-cyano-4-thiahexyl acrylate)
Poly(8-cyano-7-thiaoctyl acrylate)
Poly(S-cyano-3-thiapentyl acrylate)
Poly(cyclododecy1 acrylate)
Poly(cyclohexy1 acrylate) conventional
syndiotactic
isotactic
Poly(l,2:3,4-di-O-isopropylidene-a-~galactopyranos-
60~1 acrylate)
Poly(3,5dimethyladamantyl acrylate)
Poly(3,5-dimethyladamantyl crotonate)
Poly(3-dimethylaminophenyl acrylate)
Poly( 1,3-dimethylbutyl acrylate)
Poly[2,2-difluoro-2-(2-heptafluorotetrahydrofuranyl)
ethyl acrylate]
Poly(dodecy1 acrylate)
Poly(2-ethoxycarbonylphenyl acrylate)
Poly(3-ethoxycarbonylphenyl acrylate)
Poly(4-ethoxycarbonylphenyl acrylate)
Poly(2-ethoxyethyl acrylate)
Poly(3-ethoxypropyl acrylate)
Poly(ethy1 acrylate) conventional
syndiotactic
isotactic
9003-49-O
25 154-80-7
26809-38- 1
25067-30-5
26936-29-8
26877-39-4
25931-02-6
56710-66-8
9003-32- 1
N 383
286
219
224
251
253
253
250
380, 316
346
304
345
344
447
319
326
331
333
317
384-396
324
233-238
277
388
389
358
433
296
250
363
339
249
215
215
214
223
310
292
289
285
371
379
378
432
320
258
275
270
303
297
310
223
218
249
251
249
248
Mechanical method
819
746
1, 23,634,775,
802-822
1 4 0 1
823,824
1 4 0 1
Conflicting data 746,824,825,1401
Extrapolated from DSC data
on water plasticized samples
Dilatomer, 10 deg/min HR,
DTA, flpolymerization)
Dilatomer, 10 deg/min HR
No experimental details
Dilatomer, 10 deg/min HR
DTA
Dilatomer, 10 deg/min HR
Dilatomer, 10 deg/min HR,
DTA, Apolymerization)
No experimental details
No experimental details
Dilatomer, 10 deg/min HR
DSC, onset, HR, 32deglmin
quenched
DSC heating rate; data
corrected (sci)
Brittle point
Brittle temperature
Brittle point
1432
826
826
817
746
746
826
746
746
1088
1089
827
746,820
1090
1092
1093
1087
820
820
746
1 0 9 1
828
828
828
828
828
1086
824
11,842
849,850
1401,1349
1349
746
823
830
821,829
746
746
746
830
830,831
23,634,775
1 4 0 1
820,821,824
832, 833
References page VI - 253
VI / 200 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 1. contd
Polymer CAS No.
T, (K)
Remarks Refs.
Poly(2-ethylbutyl acrylate)
Poly(2-ethylhexyl acrylate)
Poly(ferrocenylethy1 acrylate)
Poly(ferrocenylmethy1 acrylate)
Poly(3-fluoroalkyl a-fluoroacrylate)
Poly(4-fluoroalkyl cr-fluoroacrylate)
Poly(S-fluoroalkyl n-fluoroacrylate)
Poly(%fluoroalkyl a-fluoroacrylate)
Poly( 17-fluoroalkyl a-fluoroacrylate)
Poly(fluoromethy1 acrylate)
Poly(furfuryl acrylate)
Poly( lH, lH-heptafluorobutyl acrylate)
Poly(5,5,6,6,7,7,7-heptafluoro-3-oxaheptyl acrylate)
Poly(2,2,3,3,5,5,5-heptafluoro-4-oxapentyl acrylate)
Poly(heptafluoro-2-propyl acrylate)
Poly(hepty1 acrylate)
Poly(2-heptyl acrylate)
Poly(hexadecy1 acrylate)
Poly(lH,lH,3H-hexafluorobutyl acrylate)
Poly(hexy1 acrylate)
Poly(3-hydroxyalkanoate)
Poly(isobomy1 acrylate) conventional
syndiotactic
isotactic
Poly(isobuty1 acrylate)
Poly(isopropy1 acrylate) conventional
syndiotactic
isotactic
Poly(magnesium acrylate)
Poly(3-methoxybutyl acrylate)
Poly(2-methoxycarbonylphenyl acrylate)
Poly(3-methoxycarbonylphenyl acrylate)
Poly(4-methoxycarbonylphenyl acrylate)
Poly(2-methoxyethyl acrylate)
Poly(4-methoxyphenyl acrylate)
Poly(3-methoxypropyl acrylate)
Poly(methy1 acrylate) conventional
head to tail
head to head
Poly(2-methylbutyl acrylate)
Poly(3-methylbutyl acrylate)
Poly(2-methyl-7-ethyl-4-undecyl acrylate)
Poly(2-methylpentyl acrylate)
Poly(2-naphthyl acrylate)
Poly(neopenty1 acrylate)
Poly( 1 H, l H-nonafluoro-4-oxahexyl acrylate)
Poly( 1 H, 1 H-nonafluoropentyl acrylate)
Poly(nony1 acrylate)
Poly(octy1 acrylate)
Poly(2-octyl acrylate)
Poly( lH,lH,SH-octafluoropentyl acrylate)
Poly(pentabromobenzy1 acrylate)
Poly(pentachloropheny1 acrylate)
Poly(lH,lH-pentadecafluorooctyl acrylate)
Poly( lH,l H-pentafluoropropyl acrylate)
Poly(n-pentyl acrylate)
223
9003-77-4 223
430
470-483
398
368
374
338
388
288
321
243
228
218
278-283
213
235
308
251
216
293
367
369
363
249
230
267-270
271-284
262
673
217
319
311
340
223
324
1 9 8
9003-21-8 283
284
290
282
278
304
241
228
253
235
358
295
224
236
215
184
25266-13-1 208
228
238
453
420
256
247
216
Brittle point
Brittle point
No experimental details
DSC heating rate
Est i mat ed T,
No details on sample
or measurement
Brittle point
Brittle point
Brittle point
Brittle point
Brittle point
8 2 3
8 2 1
834
8 3 5
1 2 6 3
1 2 6 3
1 2 6 3
1 2 6 3
1 2 6 3
8 3 8
1 2 7 9
155,836,837
830
830,837
8 3 9
821,1401
8 2 3
23,821,840,841
836
8 2 3
1401
1451
8 2 4
8 2 3
1 4 0 1
746,823,824
Estimated from copolymer data a43
844
746
746
746
830
826
830
18,22,23,81
Dilatomer 1 0 9 4
1 3 4 3
1401,1432
576,720,775-777
821,824,831,841,
845-848
Brittle point 823,1401
Brittle point 8 2 3
Brittle point 8 2 3
Brittle point 8 2 3
8 2 6
746,1401
8 3 0
8 3 6
Brittle point 821
1401
Brittle point 821,841,1401
Brittle point 8 2 3
8 3 6
1447
7 4 6
Crystalline 8 3 6
8 3 6
1401
T,
-
P
-
P I
P I
P C
P C
P C
PC
PC
PC
P C
P C
P C
P C
P C
P C
P C
PC
PC
PC
PC
PC
PC
P C
P C
P C
P C
1 .
P O
P O
P O
P O
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
PO
Po i
PO1
PO1
PO1
1.1
PO1
PO1
PO1
PO1
PO1
TABLE 1. contd
Poly(acrylics) and Poly(methacrylics)
Polymer CAS No.
T, (K)
Remarks Refs.
Poly(S-pentyl acrylate)
Poly(pheny1 ethyl)acrylate
Poly(pheny1 acrylate)
Poly(potassium acrylate)
Poly(propy1 acrylate)
Poly(sodium acrylate)
Poly(tertura1 acrylate)
Poly(tetradecy1 acrylate)
Poly(7,7,8,8-tetrafluoro-3,6-dioxaoctyl acrylate)
Poly(4,4,5,5-tetrafluoro-3-oxapentyl acrylate)
Poly(3-thiabutyl acrylate)
Poly(4-thiahexyl acrylate)
Poly(S-thiahexyl acrylate)
Poly(S-thiapentyl acrylate)
Poly(4-thiapentyl acrylate)
Poly(m-tolyl acrylate)
Poly(o-tolyl acrylate)
Poly(p-tolyl acrylate)
Poly(2,2,2-trifluoroethyl acrylate)
Poly(5,5,5-trifluoro-3-oxapentyl acrylate)
Poly(3,3,5-trimethylcyclohexyl acrylate)
Poly(lH,IH-ttidecatluoro-4-oxaoctyl acrylate)
Poly( 1 H, 1 H-undecafluorohexyl acrylate)
Poly(lH,lH-undecatluoro-4-oxahexyl acrylate)
Poly(zinc acrylate)
1.1.2. POLY(ACRYLAMIDES)
Poly(acrylamide)
Poly(N-butylacrylamide)
Poly(N-set-butylacrylamide)
Poly(N-reti-butylacrylamide)
Poly(N,N-dibutylacrylamide)
Poly(N,N-diisopropylacrylamide)
Poly(N,N-dimethylacrylamide)
Poly(N-dodecylacrylamide)
Poly(isodecylacrylamide)
Poly(isohexylacrylamide)
Poly(isononylacrylamide)
Poly(isooctylacrylamide)
Poly(N-isopropylacrylamide)
Poly([iV-(l-methylbutyl)acrylamide)
Poly(N-methyl-N-phenylacrylamide)
Poly(morpholylacryamide), [Poly(morpholinocarbonylethylene)]
Poly(N-octadecylactylamide)
Poly(iV-octylacrylamide)
Poly(piperidylacrylamide)
9003-05-8
26793-34-O
25 189-55-3
1.1.3. POLY(METHACRYLIC ACID) AND POLY(METHACRYLIC ACID ESTERS)
Poly(aqlonitrile methacrylate)
Poly(adamanty1 methacrylate)
Poly(benzy1 methacrylate)
Poly(2-bromoethyl methacrylate)
Poly(2-rert-butylaminoethyl methacrylate)
25085-83-o
267
210
330
467
236
228
503
321
297
233
251
213
197
203
202
208
298
325
316
263
235
288
205
234
205
694
438
319
390
401
333
N 393
362
198- 320
313
344
325
339
358, 403
380
- 453
420
162
220
381
383
414
456
4561532
327
325
306
746,823
146
746,826
Extrapolated from data on 817
water plasticized samples
Brittle point 23,592,832,836,
Est i mat ed from
copolymer data
Brittle point; probably
1st order transition
No experimental details
Mechanical method
No experimental details
No experimental details
Softening point, amorphous
Softening point, almost
amorphous
Conflicting data, 198 K more
probable in amorphous
sampl e
No experimental details
No experimental details
No experimental details
No experimental details
Conflicting data
No experimental details
Softening point, amorphous
Mechanical method
DSC heating rate
851, 852
1 4 0 1
817,843
1279
23,821
830
830
8 3 1
8 3 1
8 3 1
8 3 1
8 3 1
826
826
826
836
830
1 4 0 1
830
836
830
1 2 6 1
820
853
820
820
854
854
746
820,853
820
820
820
820
820,855
820
854
9,856
853
853
9,856
1362
849
1349
1 4 0 1
746
746
746,857
References page VI - 253
VI / 202 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 1. contd
Polymer CAS No.
T, 6)
Remarks Refs.
Poly(4-tert-butylcyclohexyl methacrylate) 34903-89-4 356
403-45 1
Poly(buty1 methacrylate) 9003-63-8 293
isotactic
syndiotactic
Poly(sec-butyl methacrylate)
Poly(rerr-butyl met hacryl at e) atactic
syndiotactic
isotactic
Poly(4-reti-butylphenyl methacrylate)
Poly(2-chloroethyl methacrylate)
Poly(2-cyanoethyl methacrylate)
Poly(4-cyanomethylphenyl methacrylate)
Poly(4-cyanophenyl methacrylate)
Poly(cyclobuty1 metbacrylate)
Poly(cyclodecy1 methacrylate)
Poly(cyclododecy1 methacrylate)
Poly(cyclohexy1 met hacryl at e) atactic
isotactic
Poly(cycloocty1 methacrylate)
Poly(cyclooctylmethy1 methacrylate)
Poly(cyclopenty1 methacrylate)
Poly(2-decanhydronapthyl methacrylate)
Poly(decy1 methacrylate)
Poly(diethylaminoethy1 met hacryl at e)
Poly( 1,2:3,4-di-O-isopropylidene-cc-~-galactopyranos-
6-U-y1 methacrylate)
Poly(3,5-dimethyladamantyl methacrylate)
Poly(dimethylaminoethy1 methacrylate)
Poly(3,3-dimethylbutyl methacrylate)
Poly(3,3-dimethyl-2-butyl methacrylate)
Poly(lH,lH,7H-dodecafluoroheptyl methacrylate)
Poly(dodecanidio1 dimethacrylate)
Poly(dodecy1 methacrylate)
Poly(2-ethylhexyl methacrylate)
Poly(ethy1 methacrylate)
atactic
300
307
328
297
294
299
249
328
333
391
395
380
387
280
29696-27-3 371
N 365
364
-401
428
351
331
329
356
25768-50-7 377
406
324
346
326
348
418
203
N 289-297
399
469
467
292
-318
318
-381
381
286
277
208
25719-51-1 263
9003-42-3 -
338
339
352
362
DSC, f(HR)
N 286 to 308 K
298 K elsewhere
Maximum value
Maximum value
1096
1286
22,69,272,695,
720,775,822,824,
847,858-862,
1359,1367
1272
1254
1342
1 4 0 1
1 2 5 5
1 4 1 3
824
1342,1555
746,863,1401
746,847,864
1254
1 4 0 1
DSC, flHR) 1104
Likely to be slightly high 262
746,865
746
746
1 4 0 1
1 4 0 1
1 4 0 1
263,353,820,824
1 4 0 1
1254
847,862
1 4 0 1
1 4 0 1
1 4 0 1
1 4 0 1
23,821,840,846
857
11,842
Temperature reported as 849,850
corrected
1401,1349
746
Vicat softening point 332 K 863
1 4 0 1
Vicat softening poing 396 K 863
1 4 0 1
Mechanical method 876
1 5 2 8
Conflicting data 1,821,858,866,
867
Brittle point 8 2 1
DSC, onset, 16 deg/min HR, 1 0 9 5
quenched, flMW)
Data covers range 22,69,286,352,
320-343 K 353,521,695,821,
824,857,858,860,
862,868-874,
1342,1401,1363,
1545,1432
1315
1552
1254
TA
-
P O
-
P O
P O
P O
P O
P O
P O
P O
P O
P O
P O
P O
P O
P O
P C
P C
P C
PC
PC
PC
PC
PC
PC
PC
PC
PC
PC
PC
PC
TABLE 1. contd
Polymer CAS No.
Poly(acrylics) and Poly(methacrylics) VI / 203
T, (K) Remarks Refs.
isotactic
syndiotactic
Poly(2-ethylsulfinylethyl methacrylate)
Poly(ferrocenylethy1 methacrylate)
Poly(ferrocenylmethy1 methacrylate)
Poly(3-fluoroalkyl methacrylate)
Poly(Cfluoroalky1 methacrylate)
Poly(S-fluoroalkyl methacrylate)
Poly(8fluoroalkyl methactylate)
Poly(l7-fluoroalkyl methacrylate)
Poly(glycidy1 methacrylate)
Poly(lH,lH-heptafluorobutyl methacrylate) syndiotactic
Poly( lH,lH,9H-hexadecafluorononyl methacrylate)
Poly(hexadecy1 methacrylate)
Poly(hexy1 methacrylate)
Poly(2-hydropropyl methacrylate)
80% isotactic
58% syndiotactic
Poly(2-hydropropyl methacrylate)
Poly(2-hydroxyethyl met hacryl at e)
Poly(D,L-isobomyl methactylate)
Poly(isobomy1 met hacryl at e)
Poly(isobuty1 met hacryl at e) random
isotactic
80% syndiotactic, 20% isotactic
Poly(isobuty1 methacrylate)
Poly(isopropy1 met hacryl at e) atactic
isotactic
syndiotactic
Poly(2,3-O-isopropylidene-D,L-glyceritol-l-o-y1
methacrylate)
Poly(magnesium methacrylate)
Poly(methacrylic acid)
Poly(methacrylic anhydride) see Section 4.27
Poly(4-methoxycarbonylphenyl methacrylate)
Poly(methacrylate)
Poly(methy1 methacrylate)
25986-80-5
25087-17-6
25249- 16-5
64114-51-8
9011-15-8
26655-94-7
54193-36-1
9003-21-8
9011-14-7
331
330
344
359
378
348
347
285
339
298
482
N 458-468
355
353
350
320
310
347
336
- 330
258
288
268
273
270
274
328, 359
311
393
349
358
39614641443
383
423
326
281
326
326
337
354
358
300
358
335
- 763
501
379
273
378
with 25% wt. of chromaphore
I-doped polymer
with 25% wt. of chromaphore
II-doped polymer
DSC
No experimental details
DSC heating rate
Mechanical method
Brittle point, sample probably
crystalline-may be T,
DSC
1359
1360
1413
1418
1418
1438
1484
824
847
746
834
835
1263
1263
1263
1 2 6 3
1 2 6 3
1269
1360
875
876
821,866
695,846,
858,877,
1251,1443
1 4 0 1
1484
1416
1413
Conflicting data
DSC, dry Xp
DSC, dry Xp
746,878-880
1098
1199
846,878
1279
1 4 0 1
824
1508
746,821,824
846,881
1 4 0 1
1438
746,824,862
1 4 0 1
Heating rate: 20 K/min 842
Xp value
Xp data from plasticized
samples
843
882
746
1255
1102,1112,1101,
1107,1108
DSC, onset, 16 deg/min HR, 1 1 0 1
quenched, flMW)
Dilatomer, CR 3 deg/h; 1109
creep relaxation, quenched
1432,1315,
1401,1288,1318
References page VI - 253
VI / 204 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 1. contd
Polymer CAS No.
T, W)
Remarks Refs.
319
400
387
atactic
isotactic
syndiotactic
heterotactic
plasticized with 5% dibutylphthalate
plasticized with 10% dibutylphthalate
plasticized with 25% dibutylphthalate
with bis(2-ethylhexyl phthalate)
Poly[(2-nitrosoethyl) methacrylate]
Poly(octadecy1 methacrylate)
Poly(lH,lH,SH-octafluoropentyl methacrylate)
Poly(octy1 methacrylate)
Poly(3-oxabutyl methacrylate)
Poly(3-oxa-5hydroxypentyl methacrylate)
Poly(penty1 methacrylate)
Poly(neopenty1 methacrylate)
Poly(phenethy1 methacrylate)
Poly(pheny1 methacrylate)
Poly(propy1 methacrylate)
391
384
373
390
367
382
423
395
378
379
380
311
323
325
319
373
378
414
403
372
363
355
373
200-398
252-373
328
25639-21-8 173
309
203, 253
253
289
278-280
268
34903-87-2 299-3 12
299
299
383
407
308
308
332
1320,130O
1 3 4 3
1365
Aldrich chemicals 1547
1552
DSC 1 2 7 7
1359,1508,1531
1363,1545
1413,1457
DSC 1489
1533
1254
1106
1,17,22,25-27,
69,78,79,81,190,
201,263,286,287,
317,318,352-354,
400,614,684,698,
720,775,777-119,
789,804,821,824,
846,858,860,862,
880,883-895
1 2 7 1
1 2 5 5
6,122,720,824,
847,884,886,890,
895-901
1 2 5 5
1271
1 4 3 2
1 2 5 4
122,720,824,847,
890,895,896,898,
900,901
1 2 5 6
1 2 5 4
DSC, rapid cooling, 10 deg/min 1103
HR, onset point, Mr
1254
1 2 5 4
1254
DS 1557
PCS 1557
9 0 3
1,720,904
Mechanical method 8 7 6
Conflicting data 23,695,821,840,
846,858
1401
846,857
Mechanical method 880
Brittle point 8 2 1
1401
DSC, flHR) 1 1 0 5
1401
746
353,746,820,847,
863,875,1334
1 2 5 4
Conflicting data, 22,262,272,821,
308-345 K reported 847,857,
858,860,
1 4 3 2
1401
1 2 5 4
Poly(alkenes) VI / 205
TABLE 1. contd
Polymer
CAS No. T, 6)
Remarks Refs.
319
Poly(sodium methacrylate)
-583
Poly(3-tetracyclododecyl methacrylate)
477
Poly(tetradecy1 methacrylate)
201-264
Poly( 1 , l, l-trifluoro-2-propyl methacrylate)
354
Poly(3,3,5trimethylcyclohexyl methacrylate)
398
Poly(3,5,5-trimethylhexyl met hacryl at e)
274
Poly(trimethylsily1 methacrylate) isotactic
3 4 1
syndiotactic
400
Poly(2,3-xylenyl methacrylate)
398
Poly(2,6-xylenyl methacrylate)
440
1.1.4. POLY (METHACRYLAMIDES)
Poly(4-butoxycarbonylphenylmethacrylamide)
401
Poly(N-tert-butylmethactylamide)
433
Poly(4-carboxyphenylmethacrylamide)
473
Poly(4-ethoxycarbonylphenylmethacrylamide)
441
Poly(4-methoxycarbonylphenylmethacrylamide)
453
1.1.5. OTHER X-AND P-SUBSTITUTED POLY(ACRYLICS) AND POLY(METHACRYLICS)
Poly(buty1 butoxycarbonylmethacrylate)
298
Poly(buty1 chloroacrylate)
330
Poly(sec-butyl chloroacrylate)
347
Poly(buty1 cyanoacrylate)
358
Poly(cyclohexy1 chloroacrylate)
387
Poly(dibuty1 itaconate) see Poly(butylbutoxy-
carbonylmethacrylate)
Poly(ethy1 chloroacrylate)
366
10% isotactic
308
100% syndiotactic
404
Poly(ethy1 ethoxycarbonylmethacrylate)
325
Poly(ethy1 ethacrylate)
300
Poly(ethy1 fluoromethacrylate)
316
Poly(hexy1 hexyloxycarbonylmethacrylate)
269
Poly[( l-heptoxycarbonyl-l-
28451-56-1 188, 250
heptoxycarbonylmethylene)ethylene]
Poly(isobuty1 chloroacrylate)
363
Poly(isopropy1 chloroacrylate)
363
Poly[( l-methoxycarbonyl-l-
372
methoxycarbonylmethylene)ethylene]
Poly(methy1 chloroacrylate)
413
Poly(methy1 fi-chloroacrylate)
416
Poly(methy1 fluoroacrylate)
404
Poly(methy1 fluoromethacrylate)
357
Poly(methy1 phenylacrylate) atactic
391
isotactic
397
Poly(propy1 chloroacrylate)
344
1.2. POLY(ALKENES)
Poly(butene-1) see Poly(ethylethylene)
Poly(butylethylene)
Poly(tert-butylethylene)
Poly(cyclohexylethylene) atactic
isotactic
Poly(2-cyclohexylethylene)
9003-28-5
223
337
393
406
313
DSC
Xp value
1413
1484
410547,616
1 4 0 1
Conflicting data
Vicat softening temperature
Heating rate: 15 Wmin
Weak T, for syndiotactic
pol ymer
843
863
1 4 0 1
867
902
1334
1334
Softening point
No experimental details
Softening point
Softening point
Softening point
Vicat softening point
Vicat softening point
Vicat softening point
Vicat softening point
Calculated for infinite M,;
heating rate: 20 K/min
Calculated for infinite M,;
heating rate: 20 Wmin
Intrinsic vicosity only 0.24dL/g
Intrinsic vicosity only 0.24 dL/g
DSC, onset, 20deglmin HR
Vicat softening point
DSC, onset, 20 deg/min HR
Vicat softening point
No measurement details
No details on samples or
measurement
No experimental details
Vicat softening point
Softening point, highly
crystalline sample
Dynami c met hod
Mechanical method
905
820
905
905
905
906
863
863
907
863
832,863,
908,909
906
746
910
906
1110
832,911
832,863
1110
863
820
820,912
820,910
913
832,863
1.272574,
629-633
631
634-639
640
634
References page VI - 253
VI / 206 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 1. contd
Polymer CAS No.
T, (K)
Remarks Refs.
Poly[(cyclohexylmethyl)ethylene]
Poly(3-cyclohexylpropylethylene)
Poly(cyclopentylethylene)
Poly[(cyclopentylmethyl)ethylene]
Poly(decylethylene), poly( 1-decene)
Poly(3,3-dimethylbutylethylene)
Poly(1 ,l-dimethylethylene), poly(isobutane)
25 189-70-2
9003-27-4
Poly(4,4-dimethylpentene-1) see Poly(neopentylethylene)
Poly(4,4-dimethylpentylethylene)
Poly( I,1 -dimethyltetramethylene)
Poly(l,l-dimethyltrimethylene)
Poly(dodecylethylene), poly( 1 -dodecene)
Poly(ethylene)
-c-
-C- and -C-C-
Poly(ethylene) [Poly(methylene)]
Poly(ethy1 ethylene)
Poly( l-ethyl- 1 -methyltetramethylene)
Poly(ethyl-2-propylene)
Poly(furylene ethylene)
Poly(heptylethylene), poly(l-heptene)
Poly( 1-hexene)
Poly(hexyldecylethylene)
Poly(hexylethylene)
Poly(hydroxymethylene)
Poly(isobutylene) see Poly( 1,l -dimethylethylene)
Poly(isobutylethylene)
25067-08-7
9002-88-4
9002-88-4
255 1 l-64-2
25067-06-S
9003-27-4
348
248
348
333
237
326
200
205
1 9 5
202
170- 370
203
1 9 9
313
253
263
241
-
1 9 5
275
190
148
About 148
222-240
1 6 3
248
1 5 5
235-240
249
522
- 250
268
293
226
About 215
328
208-228
407
302
313
300&l
302
573
Mechanical method 634
Softening point, comparative 6 3 1
data reported
Dynami c met hod 634
Mechanical method 634
629,632,641
Softening point 631
1,23,24,58,61,
216,223,695-704
Volumetric measurements 1252
1 2 5 5
1288
1540
1549
1432
Softening point, crystalline 631
sampl e
Dynami c met hod 706
Dynami c met hod 706- 709
629,632,641,1078
1 2 5 5
1254
1 2 8 7
Conflicting interpretations 1,6,16,28,
of data; branch point 61,80,191,
transition at 252 K 223,238,261,
262,272,317,
3 18,344,349,
395,396,469,
521-523,574,
589,592,608,629,
641- 676
DSC,lO/deg/min HR 1080
WLF fit of volume relaxation 1076
1432
1432
489,897,598,574,
694
Calorimeter 1 0 7 3
Wide spread in 1,61,67,273,349,
reported values 395,397,574,629,
632,641,645,646,
677-680
1 5 4 1
DTA heating rate 6 8 1
Dynami c met hod 682
1 4 7 7
Dynami c met hod 629
Calorimeter 1 0 7 2
Dynamic method, 629,641,683
stereoregular sample; may
be first-order transition
Conflicting data 1,574,629,632
DSC, onset, 6 deg/min HR, 1 0 8 5
dry, flwater)
Reported values 1,51,675,684-692
range from 297 to 333 K
1 3 3 0
1 3 5 6
1 4 3 2
1451
T,
-
P
-
P I
PI
PI
PI
PI
F?
PI
PI
PI
P
P
F
F
F
E
E
I
E
P
P
F
F
E
I
I
I
Poly(dienes) VI / 207
TABLE 1. contcf
Polymer CAS No.
T, (K)
Remarks Refs.
Poly(isohexylethylene)
Poly(isopentylethylene)
Poly(isopropylethylene) atactic
isotactic
Poly( l-methyloctamethylene)
Poly(4-methylpentene-1) see Poly(isobutylethylene)
Poly(neopentylethylene)
Poly(nonylethylene)
Poly(octylethylene), poly(l-octene)
Poly(pentene- 1)
Poly(pentylethylene)
Poly(propylene) atactic
isotactic
syndiotactic (c)
Poly(propylethylene)
Poly(propyl-2-propylene)
Poly(tetradecylethylene)
Poly(2,5thienylene ethylene)
Poly( 1,1,2-trimethyltrimethylene)
1.3. POLY(DIENES)
EPDM, mal eat ed
Natural rubber see Poly(isoprene) cis
Neoprene see Poly(l-chloro-l-butenylene)
Poly( 1 -bromo- 1-butenylene)
Poly(butadiene)s see Poly( 1-butylene)s and Poly(vinylethylene)
Poly( 1,2-butadiene)
ionically-terminated
Poly(l,3-butadiene) cis
Poly( 1,4-butadiene)
cis
Poly( 1 -butenylene) cis
239
259
323
361
215
25068-26-2
332
236
255 1 l-67-5 232
238
511
242
9003-07-O -
238
- 260
266
253
267
170- 370
243
263
25085-53-4 -
- 265
212
+.. 265
N 233
300
246
298
353
310
236
241
293
258
273
170- 370
9903-17-2 218
170
164
1 7 1
Softening point 631
Softening point 631
Dynami c met hod 634,641,685,691,
692
Dilatometry; suggested 693
transition crystal/crystal type
Heating rate: 4-8 Wmin 705
Softening point, crystalline 631
sample
632
629,632,641
1356
1541
Dynami c met hod 629
1084
1320
Conflicting data; 1,6,15,80,122,
most values reported 191,223,
range 258 to 270K 261,272,
273,282,318,326,
394-391,469,514,
615,629,632,641,
645,640,659,666,
668,675,677,678,
684,710-726,1255
DSC, onset, AMW) 1082
1271
Light scattering under terminal 1452
mode
Light scattering under 1452
segmental mode
1540
1432
1499
1083
Most values range 238 to 260 K
DSC, onset, quenched, flMW) 1 0 8 1
Most values range 263 to 267 K
Conflicting data 1,272,574,595,
629,630,632,645,
685,727
Dynamic method 682
629,632,641
1477
1471
682
1455
DSC, annealed 1077
1432
1337
1337
1540
1432
1285
DSC, onset, HR 20 deg/min, 1075
quenched
26,61,574-597
References page VI - 253
VI / 208 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 1. contd
Polymer CAS No.
T, W)
Remarks Refs.
Poly(l-butyl-1-butenylene)
Poly( 1 -tert-butyl- 1 -butenylene)
Poly(2-chloro-1,3-butadiene) see Poly(l-chloro-
1-butenylene)
Poly(l-chloro-1-butenylene) cis
tram
Poly(2-chloro-1,4,4-trifluoro-1-butenylene)
Poly(chloroprene)
Poly( 1-decyl- 1-butenylene)
Poly(endo-dicyclopentadiene)
Poly(exo-dicyclopentadiene)
Poly( 1,2-dimethyl-l -butenylene)
Poly( 1 -ethyl- 1 -butenylene)
Poly(l-heptyl-1-butenylene)
Poly(isoprene) cis
9010-98-4
9003-31-0,
104389-31-3
truns 104389-32-4
protonated
Poly(isoprene), gutta percha
Poly(l-isopropyl-1-butenylene)
Poly(4-methoxy-1-hutenylene)
Poly(4-methoxycarbonyl-3-methyl-1-butenylene)
Poly(methy1 sorbate) see Poly(4-methoxycarbonyl-
3-methyl- 1-butenylene)
Poly(norbomene)
Poly(octafluoro-4-methyl-1-butenylene)
Poly( 1 -pentenylene) cis
tram
Poly( 1 -phenyl- 1 -butenylene)
Poly( 1 -propyl- 1 -butenylene)
Poly[5-(1,1,3,3-tetramethyl-1,3-disilabutyl)norbomene]
Poly( 1,4,4-trifluoro-1-butenylene)
Poly(S-trimethylsilylnorbomene)
Poly(vinylethylene) atactic
25038-76-o
9003-17-2
40022-03-5 cis
deuterated
diol
diol (crosslinked)
diol 50%, Poly(propylene oxide) diol 50%
diol 80%, Poly(propylene oxide) diol 20%
high
protonated
PVE- 0
215
192
293
253
233
256
227
220
370
339
262
1 9 7
190
200
203
204
266
206-218
207
215
215
311
221
256
326
304
337-313
270
159
1 8 3
-283
196
297
238
386
269
304-294
258
249fl
261
276
1 7 1
186
205
199
211
213
250
258
264
274
268
261
182
272
Wide spread in
published data
Dynami c met hod
580,583,585-587,
589,594,595,598,
599
600
80,348,601,602
603
1,24,604-611
No experimental details 587
1360
1
1486
1486
576
600,612
80,601
349,388,394,464,
469,574,591,594,
595.613-623
1255,1271
1432,1309
1255
DSC, Mdpt, AHR,TH) 1079
DSC, onset, 20deg/min HR 1074
514,581,589,594,
608,617,624,1329
1495
1 3 2 3
600,601,612
5 9 1
Dynami c met hod 625
1 2 9 5
With increase in spacer length 1 4 0 5
DSC heating rate 9 7
Heating rate: 16 Wmin 626
DTA heating rate 594
Low molecular weight 584
600
1 2 9 5
Slightly crystalline 5 8 7
1295
Published values 585,586,592,597,
range from 245 to 283 K 627,628
With increase in spacer length 1 4 0 5
DSC 1354
1356
Volumetric measurements 1252
1329
,1255
1 4 9 5
1258
1326
1258
1258
DSC 1559
DSC 1559
DSC 1559
DSC 1354,1559
DSC 1354,1559
DSC 1559
1495
1550
1
1
1
P
P
P
P
P
P
P
P
P
PI
P I
P I
PI
PC
PC
Pi
PC
PC
PC
PC
P C
P C
P C
PC
PC
PC
P a
P O
PO
PO
PO
PO
PO
P C
P C
P O
P O
P O
P O
PO
PO
P O
PO
PO
PO
PO
TABLE 1. contd
Polymer CAS No.
T, WI
Poly(styrenes) VI / 209
Remarks Refs.
PVE-5 276 1550
PVE- 11 279 1550
PVE-22 282 1550
PVE-44 285 1550
PVE- 66 287 1550
tram 25038-44-2 215 125.5
1. 4. POLY(STYRENES)
Poly(4-acetylstyrene) 389
Poly(4-p-anisoylstyrene) 376
Poly(4-benzoylstyrene) 371
Poly[(2-benzoyloxymethyl)styrene] 345
Poly[3-(4-biphenylyl)styrene] -471
Poly[4-(4-biphenylyl)styrene] 593
Poly(S-bromo-2-butoxystyrene) 320
Poly(S-bromo-2-ethoxystyrene) 353
Poly(5-bromo-2-isopentyloxystyrene) 310
Poly(S-bromo-2-isopropoxystyrene) 308
Poly(S-bromo-2-methoxystyrene) 359
Poly(S-bromo-2-pentyloxystyrene) 322
Poly(S-bromo-2-propoxystyrene) 327
Poly(4-bromostyrene) 24936-50-3 391
414-430
339
349
< 235
340
< 283
313
N 320
360
279
359
422
26009-55-2 399-404
347
450
386
395
418
387
392
363
2499 l-47-7 383
388- 401
298
393
Poly(2-butoxycarbonylstyrene)
Poly(4-butoxycarbonylstyrene)
Poly(-[(2-butoxyethoxy)methyl]styrene)
Poly(2-butoxymethylstyrene)
Poly(4-butoxymethylstyrene)
Poly[4-(set-butoxymethyl)styrene]
Poly(4-butoxystyrene)
Poly(S-tert-butyl-2-methylstyrene)
Poly(4-butylstyrene)
Poly(4-set-butylstyrene)
Poly(tert-butylstyrene)
Poly(4-ierr-butylstyrene)
Poly(4-butyrylstyrene)
Poly(2-carboxystyrene)
Poly(4-carboxystyrene)
Poly(4-chloro-3-fluorostyrene)
Poly(4-chloro-2-metbylstyrene)
Poly(4-chloro-3-methylstyrene)
Poly(2-chlorostyrene)
Poly(3-chlorostyrene)
Poly(4-chlorostyrene)
Poly(4-cyanostyrene)
Poly(4-decylstyrene)
Poly(2,4-dichlorostyrene)
Poly(2,5-dichlorostyrene)
Poly(2,6-dichlorostyrene)
Poly(3,4-dichlorostyrene)
Poly[4-(2-diethylaminoethoxycarbonyl)styrene
hydrochloride]
Poly(4-diethylcarbamoylstyrene)
Poly(2,5-difluorostyrene)
Poly(2,4-diisopropylstyrene)
Poly(2,5-diisopropylstyrene)
208
406
379
440
401
347
375 Mechanical method 728
314 Softening point 8 3
N 435 Softening point 83
441 Softening point 8 3
Mechanical method 728
Mechanical method 728
Mechanical method 728
Mechanical method 729
Softening point 730
Softening point 730
Mechanical method 731
Mechanical method 731
Mechanical method; 731
low viscosity
Mechanical method 731
Mechanical method 731
Mechanical method; 731
low viscosity
Mechanical method; 731
low viscosity
732-734
DSC, Mdpt, S(TH) 1124
Mechanical method 735
Mechanical method 728
736
Mechanical method 729
736
Dynami c met hod 736
Mechanical method 736,737
732
736,738,739
Softening point 739
1523
DSC, Mdpt, X. 1 deg/min, j(CR) 1122
Mechanical method 728
Mechanical method 742
Mechanical method 728
732
732
732
732
732
83,732-734
DSC, Mdpt, ATH) 1123
1423
Sample thought to be 746
crosslinked
738
732,743
44,732,744
83,569,745
732,744
Mechanical method 728
References page VI - 253
VI / 210 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 1. cont' d
Polvmer
CAS No. T, UQ
Remarks Refs.
Poly(2-dimethylaminocarbonylstyrene)
Poly(4-dimethylaminocarbonylstyrene)
Poly[2-(2-dimethylaminoethoxycarbonyl)styrene]
Poly[4-(2-dimethylaminoethoxycarbonyl)styrene]
Poly[4-(2-dimethylaminoethoxycarbonyl)styrene
hydrochloride]
Poly(2,4-dimethylstyrene)
Poly(2,5dimethylstyrene)
Poly(3,4-dimetbylstyrene)
Poly(3,5dimetbylstyrene)
Poly(4-dodecylstyrene)
Poly(2-ethoxycarbonylstyrene)
Poly(4-ethoxycarbonylstyrene)
Poly[4-(2-ethoxymethyl)styrene]
Poly(2-ethoxymethylstyrene)
Poly(4-ethoxystyrene)
Poly[4-(1-ethylhexyloxymetbyl)styrene]
Poly(Zethylstyrene)
Poly(3-ethylstyrene)
Poly(4-ethylstyrene)
Poly(2-fluoro-5-methylstyrene)
Poly(4-fluorostyrene)
Poly(4-hexadecylstyrene)
Poly(4-hexanoylstyrene)
Poly(2-hexyloxycarbonylstyrene)
Poly(4-hexyloxycarbonylstyrene)
Poly(4-hexyloxymethylstyrene)
Poly(Chexylstyrene)
Poly[4-(4-hydroxybutoxymethyl)styrene]
Poly[4-(2-hydroxybutoxymethyl)styrene]
Poly[4-( 1-hydroxyiminoethyl)styrene]
Poly(4-[( I-hydroxyimino)-2-phenethyllstyrene)
Poly[C(l-hydroxy-3-dimethylaminopropyl)styren~
Poly[4-(1-hydroxy-1-methylbutyl)styrene]
Poly[4-( 1-hydroxy- 1-methylethyl)styrene]
Poly[4-(1-hydroxy-1-methylhexyl)styrene]
Poly[4-(1-hydroxy-1-methylpentyl)styrene]
Poly[4-( 1 -hydroxy- 1-methylpropyl)styrene]
Poly(2-hydroxymethylstyrene)
Poly(3-hydroxymetbylstyrene)
Poly(4-hydroxymethylstyrene)
Poly[C(l-hydroxy-3-morpholinopropyl)styrene]
Poly[4-(l-hydroxy-3-piperidinopropyl)styrene]
Poly(4-hydroxystyrene)
Poly(4-iodostyrene)
Poly(2-isobutoxycarbonylstyrene)
Poly(4-isobutoxycarbonylstyrene)
Poly(2-isopentyloxycarbonylstyrene)
Poly(2-isopentyloxymethylstyrene)
Poly(4-isopentyloxystyrene)
Poly(2Gsopropoxycarbonylstyrene)
Poly(4-isopropoxycarbonylstyrene)
Poly(2-isopropoxymethylstyrene)
Poly(4-isopropylstyrene)
Poly(2-methoxycarbonylstyrene)
Poly(4-metboxycarbonylstyrene)
398
342
313
355
385
416
384
311
221
391
367
213
347
- 359
250
376
- 303
300, <351
384
368
278
339
318
339
253
246
293
319
407
384
:I
316
- 403
- 438
- 364
- 356
- 459
433
398
413
323
327
433
429
400
363
341
351
- 330
419
368
361
306
403
386
Mechanical method;
low viscosity
Mechanical method
Mechanical method
Mechanical method
Mechanical method
DTA heating rate
DTA heating rate
Mechanical method
Mechanical method
Dynami c met hod
Mechanical method;
low viscosity
Mechanical method
Softening point
Softening point
Conflicting data
Mechanical method
Mechanical method
Mechanical method
Mechanical method
Dynami c met hod
Dynami c met hod
Dynami c met hod
Mechanical method
Mechanical method
Mechanical method;
low viscosity
Softening point
Softening point
Softening point
Softening point
Softening point
Dynami c met hod
Mechanical method;
low viscosity
Mechanical method;
low viscosity
Mechanical method
Mechanical method
Mechanical method
Mechanical method;
low viscosity
Mechanical method
Mechanical method
Mechanical method
Mechanical method;
low viscosity
Softening point
Mechanical method;
low viscosity
Mechanical method
742
728
735
128
728
122, 732, 739, 749,
768
732
732
749
738
735
728
736
729
731
136
739
139
736, 738, 739
748
732- 734, 749- 751
738
728
735
728
736
738
736
736
728
728
754
754
754
754
154
754
1
1
1
754
154
1423
133, 734
735
728
735
729
737
735
728
729
739
742
728
T/
-
PI
-
P C
P C
P C
PI
P C
P C
P C
P I
PI
PI
PI
PI
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
F
F
F
F
F
TABLE 1. contd
Poly(styrenes) VI / 211
Polymer CAS No. T, (K) Remarks Refs.
Poly(2-methoxymethylstyrene)
Poly(4-methoxymethylstyrene)
Poly(4-methoxy-2-methylstyrene)
Poly(2-methoxystyrene)
Poly(4-methoxystyrene)
Poly(2-methylaminocarbonylstyrene)
Poly(a-methylstyrene) 25014-31-7
Poly(2-methylstyrene)
Poly(3-methylstyrene)
Poly(4-methylstyrene)
Poly(4-methoxystyrene)
Poly(4-morpholinocarbonylstyrene)
Poly[4-(3-morpholinopropionyl)styrene]
Poly(4-nonadecylstyrene)
Poly(4-nonylstyrene)
Poly(4-octadecylstyrene)
Poly(4-octanoylstyrene)
Poly[4-(octyloxymethyl)styrene]
Poly(2-octyloxystyrene)
Poly(4-octylstyrene)
Poly[4-(pentadexafluoroheptyl)styrene]
Poly(2,3,4,5,6-pentafluorostyrene)
Poly(2-pentyloxycarbonylstyrene)
Poly(2-pentyoxymethylstyrene)
Poly(periIuorostyrene)
Poly(2-phenethyloxymethylstyrene)
Poly(2-phenoxycarbonylstyrene)
Poly(4-phenoxystyrene)
Poly(4-phenylacetylstyrene)
Poly(2-phenylaminocarbonylstyrene)
Poly(4-phenylstyrene)
Poly(4-piperidinocarbonylstyrene)
Poly[4-(3-piperidinopropionyl)styrene]
Poly(4-propionylstyrene)
Poly(2-propoxycarbonylstyrene)
Poly(4-propoxycarbonylstyrene)
Poly(2-propoxymethylstyrene)
Poly(4-propoxymethylstyrene)
Poly(4-propoxystyrene)
Poly(4-propoxysulfonylstyrene) isotactic
Poly(styrene) alkylated
amorphous
crosslinked
deuterated PS
isotactic and atactic
24936-41-2
24936-44-5
9003-53-6
362
350
-358
- 348
N 362
462
293
371-375
453
443
455
409
370
366, 374
382
386
400
314
305
220
305
323
231
286
228
320
378
365
320
467
336
397
7.. 373
351
464
434
387
311
375
381
365
370
295
343
490
356
373
373
378
373
Mechanical method; 729
low viscosity
Dynami c met hod 736
Softening point 755
Softening point 755
Mechanical method 737,755-757
Mechanical method 742
DSC, onset, 20degImin HR 1130
DSC, Mdpt, 20 deglmin HR, 1135
jW-0
1549,1432
1324
DSC 1277
63,732,739,749,755
DTA heating rate 732,739,749,766
Conflicting data 732,739,756,766,767
1423
DSC, Mdpt, 320degImin CR, 1 1140
deg/min HR, j(TH, HR, M,)
Mechanical method 728
Mechanical method 754
1
738
738
Mechanical method 728
Dynamic method 736
769
738
Heating rate 32 K/min, fiTH) 747
Heating rate: 5-20 IUmin 97
Mechanical method 735
Mechanical method 729
Heating rate: 5-20 Wmin 97
Mechanical method; 729
low viscosity
Mechanical method; 742
low viscosity
Softening point 8 3
Mechanical method 728
Mechanical method; 742
low viscosity
Extrapolated to zero rate 763, 770
Mechanical method 728
Mechanical method 754
Mechanical method 728
Mechanical method 735
Mechanical method 728
Mechanical method; 729
low viscosity
Dynamic method 736
Mechanical method 737
DTA heating rate 771
1 5 2 1
1506
1352
1495
9,17,21,22,25,47,51,
57,63,64,72,78,79,188,
190,191,261,263,317,318,
344,350-352,394,397,
399,469,524,569,576,619,
628,630,635,637,640,646,
647,684,699,731-734,
746,750,766,768,
References page VI - 253
VI / 212 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 1. contd
Polymer CAS No. T, (K)
Remarks Refs.
772-810,1125,
1133,1138,1139,1141,
1254,1276,1288,
1308,1318,1324,1423,
1432,1523,1549,1255
p-cyanobenzyl
p-cyanobiphenyl
sulfonated syndiotactic
Poly(4-tetradecylstyrene)
Poly(4-p-toluoylstyrene)
Poly(cr, h, h-trifluorostyrene)
Poly{3-[bis(trimethylsiloxy)boryl]styrene}
Poly{4-[bis(trimethylsiloxy)boryl]styrene}
Poly(2,4,5trimethylstyrene)
Poly(2,4,6&methylstyrene)
Poly(4-[bis(trimethylstannyl)methyl]styrene)
Poly(4-valerylstyrene)
1.5. POLY(VINYL ALCOHOL) AND POLY(VINYL KETONES)
Poly(l-acetyl-1-fluoroethylene)
Poly(benzoylethylene)
Poly(4-bromo-3-methoxybenzoyletbylene)
Poly(4-reti-butylbenzoylethylene)
Poly(4-chlorobenzoylethylene)
Poly(3,4-dimetbylbenzoylethylene)
Poly(4-ethylbenzoylethylene)
Poly(4-isopropylbenzoyletbylene)
Poly(4-methoxybenzoylethylene)
Poly(pheny1 vinyl ketone) see Poly(benzoylethylene)
Poly(4-propylbenzoylethylene)
368
371
371
371- 377
373
376
377
382
364
374
377
378
380
374
400
401
170- 370
365
370
433- 463
237
372
475
308
357
- 409
- 435
413
343
415
314, 347
317
377
310, 362
315
325
336
319
26742- 84- 7
317
DSC
DSC, onset, 16 deglmin HR,
quenched, flMW)
DSC, Mdpt , 20deglmin HR,
AMW
DSC, Intg, AHR, CR, MW)
DSC, Intg, AHR, CR)
Dilatometer, CR 3 deg!h; creep
relaxation, quenched
Dilatometer, 2.5 deg/min CR
DSC, onset, HR 32 deg/min,
quenched
DTA, DSC, onset, 1 deg/min
HR, AHR)
DSC, penetration, onset MP,
zero HR
DSC, Intg, OHR, 10 deg/min
CR
DSC, Mdpt, 1 deg/min X HR,
TH, AMW
DSC, onset, 20deglmin HR
after similar cool, AMW)
DSC, onset, 20deg/min HR
GPC
PCS
NR and SE
DSC
Mechanical method
Heating rate:
5-20K/min; values up to
5 13 K reported
Refractive index
Refractive index
Softening point
Softening point
Mechanical method
Conflicting data
Mechanical data
Conflicting data
Mechanical data
Mechanical data
1489
1126
1129
1143
1144
1148
1145
1132
1147
1146
1142
1128
1149
1130
1271
1284
1309
1319
1433
1437
1530
1530
1540
1253
1253
1322
738
728
83, 97, 114, 752,
753
1136
1136
83
83
1556, 1347
728
923
924, 925
924
925
924, 925
924
924, 925
925
924
925
TABLE 1. contd
Poly(vinyl esters) VI / 213
Polymer CAS No.
T, W) Remarks Refs.
Poly(p-toluoylethylene)
Poly(viny1 alcohol) [Poly(hydroxyethylene)]
1.6. POLY(VINYL ESTERS)
Poly[(2-acetoxybenzoyloxy)ethylene]
Poly(4-acetoxybenzoyloxyetbylene)
Poly(acetoxyethylene) [Poly(vinyl acetate)]
Poly[(l-acetylindazol-3-ylcarbonyloxy)ethylene]
Poly(4-benzoylbutytyloxyethylene)
Poly(benzoyloxyethylene)
Poly(3-bromobenzoyloxyethylene)
Poly(4-bromobenzoyloxyethylene)
Poly[(rert-butoxycarbonylamino)ethylene]
Poly(4-tert-butylbenzoyloxyethylene)
Poly(4-butyryloxybenzoyloxyetbylene)
Poly(2-chlorobenzoyloxyethylene)
Poly(3-chlorobenzoyloxyethylene)
Poly(4-chlorobenzoyloxyethylene)
Poly(cyclohexanoyloxyethylene)
Poly(cyclohexylacetoxyethylene)
Poly(4-cyclohexylbutytyloxyetbylene)
Poly(cyclopentanoyloxyethy1ene)
Poly(cyclopentylacetoxyethylene)
Poly(3,3-dimethyl-3-phenylpropionyloxyethylene)
Poly[(2,2-dimethylvaleryloxy)ethylene]
Poly(4-ethoxybenzoyloxyethylene)
Poly(4-ethylbenzoyloxyetbylene)
Poly(2-ethyl-2-methylpropylene terephthalate)
Poly[(2-ethyl-2,3,3-trimethylbutyryloxy)ethylene]
Poly(formyloxyethylene)
Poly[(heptafluorobutyryloxy)ethylene]
Poly(3-hydroxybutyrate)
344
9002-89-5 358
308
350
333
N 349
9003-20-7 305
302
590
315
304
303
311
313
423
318
344
331
365
393
374
334
335
338
357
349
298
N 263
309
270
293
283
343
326
340
328-338
388
310
306
300
277
278f2
223
924,925
Dynami c met hod 1,191,202,216,
230,261,573,926,
927
From hydrolysis of poly(viny1 1424
acetate)
1498
1513
29,925
29,925
1,9,12,19,22,62,
187,216,223,230,
286,352,354,399,
400,573,593,695,
775,777,792,816,
840,845,888,926,
928,932,1016,
1034-1044,1121,
1302,1320,1288
1432
1317
1339,1516
1513
1255
1437,1468
DSC 1489
Heating rate: 20 K/min-onset 1045
value
DTA heating rate 1046
29,354,755,820,
925,1047,1048
29,925
29,925,1047,1048
DTA heating rate 1049
29,925,1050
29,925
29,925,1048
29,925,1048
29,925,1047,1048
Mechanical method, heating 1043
rate: 3OK/h
Mechanical method, heating 1043
rate: 3Owh
Mechanical method, heating 1043
rate: 3OK/h
Mechanical method, heating 1043
rate: 3OK/h
Mechanical method, heating 1043
rate: 3OK/h
Mechanical method, heating 1043
rate: 3Owh
Mechanical method 1043
29,925
29,925
1532
1532
Mechanical method 1043
N 60% syndiotactic diads 593
50% syndiotactic diads
1 0 5 1
1262
1536
1494
References page VI - 253
VI / 214 CLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 1. contd
Polymer CAS No.
T, (K)
Remarks Refs.
Poly(isonicotinoyloxyethylene) 312
Poly(4-isopropylbenzoyloxyethylene) 342
Poly[(2-isopropyl-2,3-dimethylbutyryloxy)ethylene] 393
Poly[(2-methoxybenzoyloxy)ethylene] 338
Poly[(3-methoxybenzoyloxy)ethylene] -317
Poly[(4-methoxybenzoyloxy)ethylene] 360
Poly[(2-methylbenzoyloxy)ethylene] 321
Poly[(3-methylbenzoyloxy)ethylene] 324
Poly[(4-methylbenzoyloxy)ethylene] 343
Poly[( 1-methylcyclohexanoyloxy)ethylene] 359
Poly(nicotinoyloxyethylene)
Poly(nitratoethylene)
Poly[(3-nitrobenzoyloxy)ethylene]
Poly[(4-nitrobenzoyloxy)ethylene]
Poly(nonadecaAuorodecanoyloxy)ethylene]
Poly[(nonafluorovaleryloxy)ethylene]
Poly(octamethylene p,p-dibenzoate)
Poly[(pentadecafluorooctanyloxy)ethylene]
Poly[(pentafluoropropionyloxy)ethylene]
Poly[(4-phenylbenzoyloxy)ethylene]
Polyl(pivaloyloxyethylene)
Poly[(4-propionyloxybenzoyloxy)ethylene]
Poly(propionyloxyethylene)
Poly[(2,2,3,3-tetramethylvaleryloxy)ethylene]
Poly[(2,2,3,4-tetramethylvaleryloxy)ethylene]
Poly[(2,2,4,4-tetramethylvaleryloxy)ethylene]
Poy[(4-p-toluoylbutyryloxy)ethylene]
Poly(triethylene glycol p,p-dibenzoate)
Poly[(trifluoroacetoxy)ethyIene]
Poly[(3-trimethylsilylbenzoyloxy)ethylene]
Poly[(4-trimethylsilylbenzoyloxy)ethylene]
Poly[(undecafluorocyclohexylcarbonyloxy)ethylene]
Poly[(undecafluorohexanoyloxy)ethylene]
Poly(viny1 acetate) see Poly(acetoxyethylene)
Poly(viny1 formate) see Poly(formyloxyethylene)
Poly(vinyl-4-isopropylbenzoate) see Poly(4-isopropyl
benzoyloxyethylene)
Poly(4-( l l-(vinyloxy)undecyloxy)-4-cyanophenylbenzoate)
Poly(4-( l l-(vinyloxy)undecyloxy)-4-ethoxyphenylbenzoate)
360
307
366
395
253-255
288-293
315
258-263
315
358
359
346
283
363
323
328
313
293
-319, <348
353
408
327
264
9003-20-7
310 1 5 4 8
310 1 5 4 8
1.7. POLY(VINYL ETHERS) AND POLY(VINYL THIOETHERS)
Poly(butoxyethylene)
Poly(sec-butoxyethylene)
Poly(tert-butoxyethylene)
Poly(butylthioethylene)
Poly(buty1 vinyl ether) see Poly(butoxyethylene)
Poly(chlorotrifluoroethylene)
Poly(cyclohexyloxyethylene)
Poly(decyloxyethylene)
218 1,832,866,914-918
217 1 4 3 2
253 866,914
361 1,918
253 8 6 6
9002-83-9 325
354
- 183, 211
Poly(2,2-dimethylbutoxyethylene) 282
Poly( 1,l -difluoro-2-trifluoromethoxyethylene) 263-273
Poly( 1,2-difluoro- 1 -trifluoromethoxyethylene) 263-273
Poly(dodecafluorobutoxyethylene) 263 -273
Poly(ethoxyethylene) 230
Poly[(2-ethylhexyloxy)ethylene]
Poly(ethylthioethylene)
25 104-37-4 240
207
266
From polyvinyl alcohol 29,288,1053
29,925
Mechanical method 1 0 4 3
29,925
29,925
29,757,925,
1047,1048
29,820,925,1048
29,925,1048
29,925,1047,1048
Mechanical method, heating 1 0 4 3
rate: 3OK/h
From polyvinyl alcohol 29,1053
903
29,925
29,925
1051
1 0 5 1
1 5 1 9
1051
1 0 5 1
29,925
Mechanical method 1 0 4 3
29,925
Mechanical method 1 0 4 3
Mechanical method 1 0 4 3
Mechanical method 1 0 4 3
Mechanical method 1 0 4 3
DTA heating rate 1 0 4 6
Annealed 1 5 0 5
Conflicting data 1051,1052
DTA heating rate 1 0 5 4
DTA heating rate 1054,1055
1051
Plasticizer may be present 1051
1 4 7 0
Softening point 918
Conflicting data, 866,914,916,917
independent DSC data
supports higher value
Mechanical method 918
Estimated from copolymer data 451
Estimated from copolymer data 457
T, estimated from copolymer 457
data
1,223,521,573,
832,866,914-920
1 4 3 2
866,915
Viscosity only 0.2 dl/g 8 6 6
TABLE 1. contd
Polymer CAS No.
Poly(vinyl Hal i des) and Pol yvi nyl VI / 215
T, (K)
Remarks Refs.
Poly(2-furyloxirane) 288
Poly[(heptafluoro-2-propoxy)ethylene] - 328-338
Poly(hexafluoromethoxyethylene) 268
Poly(hexyloxyethylene) 199
Poly(isobutoxyethylene) 254
Poly(isopropeny1 methyl ether) see PolyQ-methoxy propylene)
Poly(isopropoxyethylene)
Poly(methoxyethylene)
Poly(2-methoxypropylene)
Poly(methylthioethylene)
Poly(neopentyloxyethylene)
Poly(octyloxyethylene)
Poly(pentyloxyethylene)
Poly(propoxyethylene)
Poly(2,2,2-trifluoroethoxytrifluoroethylene)
Poly[l,l-bis(trifluoromethoxy)difluoroethylene]
Poly(viny1 methyl ether) see Poly(methoxyethylene)
Poly(4-vinyl phenol)
Poly(p-vinyl phenol)
1.8. POLY(VINYL HALIDES) AND POLY(VINYL NITRILES)
Poly( 1-acetoxy-1-cyanoethylene)
Poly(acrylonitrile) [poly(cyanoethylene)]
Poly(chlorotrifluoroethylene) 9002-83-9
Poly( l,l-dichloroethylene), poly(vinylidene chloride)
255
Poly( l , l-dichloro-2-fluoroethylene)
N 320
Poly( 1,2-dichloro- 1,2-difluoroethylene) 350
Poly(l,l-difluoroethylene), poly(vinylidene fluoride)
24937-79-9
-
N 233
223
235
371
200
281
Poly( 1,2-difluoroethylene)
Poly(ethylene), chlorinated
9002-84-O
63231-66-3,
110028-31-4
Poly(hexafluoropropylene) 425
Poly[(heptafluoropropyl)ethylene]
331
9003-09-2
24919-10-2
25014-41-9
DTA heating rate
1419
839
457
866,914-918,1432
1,223,513,832,
866,914,916-918,
920,922
210
261
242
246
228
245
248
251
1 9 1
199
247
340
212
N 424
194
201
224
308
213
NR and SE
GPC
Softening point
DTA heating rate
Poorly defined DTA
endotherms
832,866,914,918
1432
1,223,805,866,
914-918,920,1255
1319
1284
1300
1308
1348
1495,1432
1502
1502
1516
866
866
918
866,914-917
866,915
832,915
457,921
451
429 1457
428 1552
420
398
370
355-413
N 325
313
Heating rate: 8 K/min 255
Dielectric, 1 Hz,flHz) 1113
1,7,26,80,191,
202,393,400,521,
525,516,152,112,
779,787,928-941
1382
By static methods 66,80,191,261,
349,355
By mechanical 396,401,521,647,
methods even at low 893,945-961
frequencies
1,6,62,80,216,521,
524,648,942-944
[q] only 0.035 dl/g 962
Heating rate: 5-20 K/mm, high 97
pressure, radiation synthesis
1118
401,963-970
1 3 2 1
DSC 1333
DTA heating rate 114,457,971
1287
48 wt.% Cl 1325
Heating rate: 5-20 Wmin 97,984,1006
Heating rate: 5-20 Wmin, high 97
pressure, radiation synthesis
References page VI - 253
VI / 216 CLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 1. contd
Polymer CAS No.
T, (K)
Remarks Refi.
Poly(2-iodoethylethylene) 343
Poly(9-iodononylethylene) 267
Poly(3-iodopropylethylene) - 303
Poly(methacrylonitrile) 393
Poly[(pentafluoroethyl)ethylene] 314
Poly(tetradecafluoropentylethylene) 503?
Poly(tetrafluoroethylene) [poly(difluoromethylene)] 9002-84-o
Poly(2,3,3,3-tetrafluoropropylene)
Poly(trifluoroethylene)
Poly(3,3,3-trifluoropropylene)
Poly(viny1 chlorate)
Poly(viny1 chloride) 9002-86-2
chlorinated
with Poly(buty1 methacrylate) (30/70)
with Poly(buty1 methacrylate) (50/50)
with Poly(buty1 methacrylate) (50/50)
with Poly(ethy1 methacrylate) (30/70)
with Poly(ethy1 methactylate) (50/50)
with Poly(ethy1 methacrylate) (50/50)
with Poly(methy1 methacrylate) (30/70)
with Poly(methy1 methacrylate) (50/50)
with Poly(methy1 methacrylate) (50/50)
with Poly(methy1 methacrylate) (80/20)
H-H Poly(viny1 chloride)
68648-82-8
Poly(viny1 fluoride) 24981-14-4
Poly(vinylidene chloride) see Poly(l,l-dichloroethylene) 9002-85- 1
1.9. OTHERS
Poly(l,l-bis[( 1-adamantyloxy)ca.rbonyl]-2-vinylcyclopropane)
Poly(benzylethylene)
390
160, 400
315
304
300
347
-
-
354
366
371
359
357
363
342
353
347
361
408
313
315
323
343
325
343
370
363
366
364
348
352
314
307 1 4 9 2
333 631,634,1056
Dynami c met hod
Dynami c met hod
Dynami c met hod
Heating rate: 5-20 Wmin, high 9 7
pressure, radiation synthesis
Heating rate: 5-20 K/mitt, high 9 7
pressure, radiation synthesis,
value uncertain
1 1 1 7
Much data, some 1,6,66,190,191,
conflicting 253,261,355,256,
296,521,522,641,
651,659,891,893,
914,921,952,
972- 1005
Heating rate: 5-20 Wmin, high 9 7
pressure, radiation synthesis
Quoted value, DTA? 457
97,914,1007,1008
1 2 7 1
1112,1115,1116
Dilatometer, CR 3 deg/h; creep 1119
relaxation, quenched
Increasing syndiotactic
content increases
T, to 371 K
Dekryptonation, f(MW)
DSC, 20 deg/min HR, M,
infinity, onset,
varied annealing
67 wt.% Cl
Semi-IPNs
Blend
Semi-IPNs
Semi-IPNs
Blend
Semi-IPNs
Semi-IPNs
Blend
Semi-IPNs
DSC
DMA
Mechanical method
1,21,52,78,80,
104,188,191,
230,286,349,
353,354,356,
469,608,696,
720,772,777,
787,798,861,
926,942,944,
972,1010-1031
1114
1120
1 3 2 5
1 3 3 5
1432
1398
1255
1288
1489
1325
1359
1359
1359
1359
1359
1359
1359
1359
1359
1446
1 2 9 9
1299
521,1032,1033
TABLE 1. contd
Poly(vinyl halides) and Polyvinylnitriles VI / 217
Polymer CAS No. T, (K) Remarks Refs.
Poly(N-carbazolylethylene) 25067-59-g 500
Poly[dimethylamino(ethoxy)phosphinylethylene]
Poly[dimethylamino(phenoxy)phosphinylethylene]
Poly(4,4-dimethyl-oxazolonylethylene)
Poly(4,4-dimethyl-oxazolonyl-2-propylene)
Poly(2,4-dimethyl-1,3,5-triazinylethylene)
Poly(diphenylphosphinylethylene)
Poly(ferrocenylethylene)
Poly(P-hydroxyvalerate)
Poly(indazol-2-ylethylene)
Poly(isopropy1 benzene) 126
Poly(indene) 473
Poly(3-methyl hexane) 90
Poly(3-methyl pentane) 80
Poly(2-methyl pentane) 76
Poly[(2-methyl-5-pyridyl)ethylene] 403
Poly[(2-methyl-6-pyridyl)ethylene] 365
Poly(l-naphthylethylene) 432
Poly(2-naphthylethylene) 424
Poly(phenethylethylene)
Poly(phenethylmethylethylene)
Poly(l,l-bis(phenoxycarbonyl)-2-vinylcyclopropane)
Poly(phenylacetylene) see Poly(phenylvinylene)
Poly(phenylvinylene)
Poly(phthalimidoethylene)
Poly(2-pyridylethylene)
Poly(4-pyridylethylene)
Poly(N-pyrrolidinylethylene)
Poly(o-terphenyl)
Poly(m-tolylmethylethylene)
Poly(o-tolylmethylethylene)
Poly(p-tolylmethylethylene)
Poly(2,4,6-tribromophenyl acetate)
Poly(viny1 carbazole) see Poly(N-carbazolylethylene)
Poly(vinyltrimethylgermanium)
Poly(vinylpyridine) see Poly(pyridylethylene)
Poly(viny1 pyrrolidine) see Poly(N-pyrrolidinylethylene)
500
357, 423,
481
305
300
365
380, 438
350
453
457-467
257
262
331, 298
283
245
349-357
393
497
377
9017-40-7 415
433
456
9003-39-g 327
359
448
233
243
313
353
338
423
463 Mechanical method 1068
DSC, lOdeg/min HR, X t o 1127
infinite MW
1330
Conflicting values 1,272,573,845
reported
1057
1057
DTA heating rate; low viscosity 1058
Conflicting data 1058,1059
820
1065
DSC heating rate 835
1355
1355
Two values for different 1045
preparations, heating
rate: 20 Wmin
1 2 7 1
1 5 0 1
1 2 7 1
1 2 7 1
1 2 7 1
Mechanical method 1060-1062
Heating rate 20 Wmin 1 0 6 1
Values range from 83,755,
323 to 453 K 763,1063
Extrapolated to zero heating 770
rate
Crystalline sample 631,634,1056,1064
Softening point
Crystalline
No experimental details
Molar concentration 5%
Molar concentration 10%
DSC, onset, Xp to dry
Crystalline sample
Crystalline sample
Crystalline sample
631
1535
1066
820
1061,1062,1067
1061,1062,1272
1305
1305
573
1,4,907
1150
1 2 7 1
1 2 7 1
1056
1056
1056
1269
References page VI - 253
VI / 218 CLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 2. MAIN-CHAIN CARBOCYCLIC POLYMERS
Polymer CAS No. T, WI Remarks Refs.
2.1. POLY(PHENYLENES)
Poly(3,3-biphenylylenehexafluorotrimethylene)
Poly(2-bromo-1,4-phenylene ethylene) 353
Poly(2-chloro- 1,Cphenylene ethylene) 343
Poly(2-cyano-1,4-phenylene ethylene)
Poly(2,5-dichloro-1,Cphenylene ethylene)
363
613
Poly(2,5-dimethyl-1,4-phenylene ethylene) 313
Poly(2-ethyl- 1,4-phenylene ethylene)
Poly(2,3,6,2,3,5-hexaphenyl-
p,p,m,p,p-quinquephenylylenedecamethylene)
298
453
Poly(2,3,6,2,3,5-hexaphenyl-
4, 4-p-quinquephenylylenedecamethylene)
508
324
Poly(2,3,6,2,3,5-hexaphenyl-
p,p,m,p,p, quinquephenylylenehexamethylene)
Poly(2,3,6,2,3,5-hexaphenyl-
4, 4-p-quinquephenylylenehexamethylene)
Poly(2,3,6,2,3,5-hexaphenyl-
p,p,m,p,p-quinquephenylylenetetradecamethylene)
Poly(2,3,6,2,3,5-hexaphenyl-
4,4-p-quinquephenylylenetetradecamethylene)
Poly(2,3,6,2,3,5-hexaphenyl-
p,p,m,p,p-quinquephenylylenetetramethylene)
Poly(2,3,6,2,3,5-hexaphenyl-
4, 4-p-quinquephenylylenetetramethylene)
Poly(2,3,6,2,3,5-hexaphenyl-
p,p,m,p,p-quinquephenylylenetrimethylene)
Poly(2,3,6,2,3,5-hexaphenyl-
4,4-quinquephenylylenetrimethylene)
Poly(2-methyl- 1 ,Cphenylene ethylene) 328
Poly( 1,4-phenylenetrichloroethylene) 433
Poly( 1,4-phenylene ethylene) N 353
Poly( 1,3-phenylenehexafluorotrimethylene) 303
Poly( 1 ,Cphenylene- I-phenylethylene) 428
Poly(trimethyl-phenylene ether) 483
2.2. OTHERS
Poly(acenaphthylene)
Poly(5-chlorononafluoro-1,3-cyclohexylene-
difluoromethylene)
523
433
458
453
478
513
563
25036-01-5 487-618
628-649
420
Heating rate: 32 urnin, ninh only 563
0.05 dllg
Mechanical method
Mechanical method,
heating rate: 1.5 Wmin
Mechanical method
Softening point, no
measurement details
Mechanical method, heating
rate: 1.5 K/min
Mechanical method
Heating rate: 20 Wmin,
structure may contain
more m-links
Heating rate: 20 K/min,
structure may contain
more m-links
Heating rate: 20 Wmin,
structure may contain
more m-links
Heating rate: 20 Wmin,
structure may contain
more m-links
Heating rate: 20 Wmin,
structure may contain
more m-links
Heating rate: 20 Wmin,
structure may contain
more m-links
Heating rate: 20 K/mm,
structure may contain
more m-links
Heating rate: 20 Wmin,
structure may contain
more m-links
Heating rate: 20 K/min,
structure may contain
more m-links
Heating rate: 20 Wmin,
structure may contain
more m-links
Mechanical method,
heating rate: 1 .SK/min
564
300,564,565
564
565
566
564
568
568
568
568
568
568
568
568
568
568
564,565
Polymer contains small amount 5 6 5
of different structure,
mechanical method; heating
rate: 1 .SK/min
Mechanical method, 300,564,
variable data 565,567
Heating rate: 32K/min, 17th only 1 4 8
0.1 dllg
Softening point, no 5 6 5
experimental details
1 4 3 2
Conflicting data 31,83,566,
reported 569-571
DSC, onset, 32 deg/min HR 1151
after cooling from above T,
Heating rate: 5-20 Wmin, high 9 7
pressure, radiation synthesis,
ring structure unproven
TABLE 2. contd
Main- Chain - C- O- C Polymers VI / 219
Polymer CAS No.
T, (K)
Remarks Refs.
Poly(cyclobutene) erythro di-isotactic
erythro di-syndiotactic
Poly(decafluoro-1,3-cyclohexylenedifluoromethylene)
Poly(dodecafluoro-1,3-cycloheptylenedifluoromethylene)
Poly(hexafluoro-1.3-cyclobutylenedifluoromethylene)
Poly(indenylene)
Poly(octafluoro- 1,3-cyclohexylenedifluoromethylene)
Poly( 1,4naphthyleneethylene)
293
273
374?
471?
395
358
390
433
Degree of polymerization 150
Degree of polymerization 15
Heating rate: 5-20 IUmin
Heating rate: 5-20 Wmin, high
pressure, radiation synthesis,
data queried in original paper,
ring structure unproven
Heating rate: 5-20 Wmin, high
pressure, radiation synthesis,
ring structure unproven; [n] only
0.03 dllg
Heating rate: 5-20 Wmin, high
pressure, radiation synthesis,
ring structure unproven
Mechanical method
572
91
97
97
513
97
565
TABLE 3. MAIN-CHAIN ACYCLIC HETEROATOM POLYMERS
Polymer CAS No. T, WI Remarks Refs.
3.1. MAIN-CHAIN -C-O-C- POLYMERS
3.1.1. POLY(ANHYDRIDES)
Poly(oxycarbonyl- 1,4-phenylenehexafluorotrimethylene-
1,4-phenylenecarbonyl)
Poly(oxycarbonyl- 1,4-phenyleneisopropylidene-
1,4-phenylenecarbonyl)
Poly(oxycarbonyl- 1,4-phenylenemethylene-
1,4-phenylenecarbonyl)
Poly(oxycarbonyl-1,4-phenylenepentamethylene-
1,4-phenylenecarbonyl)
Poly(oxycarbonyl- 1,4-phenylenetetramethylene-
1,4-phenylenecarbonyl)
Poly(oxycarbonyl- 1,4-phenylenethiotetramethylenethio-
1,4-phenylenecarbonyl)
Poly(oxyisophthaloy1)
3.1.2. POLY(CARBONATES)
Bisphenol A + 2,2-(fm-biphenyl carboxylate)
Bisphenol A + Carboxylate
Bisphenol A + Terephthalate + Isophthalate 50/50
Bisphenol A of 4,4-(2,2-propylidene)-diphenol
Bisphenol AP + 2,2-(fm-biphenyl carboxylate)
Bisphenol AP + Carboxylate
Bisphenol AP + Terephthalate + Isophthalate
Bisphenol A-based homopoly(forma1)
Bisphenol AF-based homopoly(forma1)
Cyclohexane-bisphenol-poly(carbonate)
Norbanane-bisphenol-poly(carbonate)
Poly( 1,4-cyclohexanecarbonate)
Poly(2-hydroxypropyl ether Bisphenol A)
Polyarylate of Bisphenol A (1 mol), isophthalic acid
(0.5 mol) and terephthalic acid (0.5 mol)
Polyarylate of Bisphenol A (1 mol), isophthalic acid
(0.7 mol) and terephthalic acid (0.3 mol)
Polyarylate of Bisphenol A and isophthalic acid
271
333
395
321
319
319
335
403
421
420
468
313
445
460
516
361
396
458
506
411
370
472
466
451
433
247
247
Amorphous
Crystalline
241
241
241
Dynamic mechanical method 398,444
Elsewhere 367 K
1432
1432
1432
1 4 3 1
1432
1432
1432
1 3 1 1
1 3 1 1
1353
1353
1393
1516
1254
1254
1254
References page VI - 253
VI / 220 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 3. contd
Pol ymer CAS No. T, (K)
Remarks Refs.
Polycarbonate 423
420
Polycarbonate of Bisphenol A see Poly(oxycarbonyloxy- 24936-68-3
1,4-phenyleneisopropylidene-1,Cphenylene)
Poly(2-methoxycyanurate) of Bisphenols F and A
Poly(oxycarbonyloxy-2,6-dibromo-l,Cphenylene-
isopropylidene-3,5-dibromo-1,4-phenylene)
Poly(oxycarbonyloxy-2-chloro-6-methyl-1,4-phenylene-
isopropylidene-3-chloro-5-methyl- 1,4-phenylene)
Poly(oxycarbonyloxy-2-chloro- 1,4-phenylene-
cyclohexylidene-3-chloro-1,4-phenylene)
Poly(oxycarbonyloxy-2-chloro-1,4-phenylene-
isopropylidene-3-chloro-1,Cphenylene)
Poly(oxycarbonyloxy-2-cyclohexyl- 1 ,Cphenylene-
isopropylidene- 1,4-phenylene)
Poly(oxycarbonyloxy-2,6-dichloro-1,4-phenylene-
cyclohexylidene-3,5-dichloro-1,4-phenylene)
Poly(oxycarbonyloxy-2,6-dichloro-1,Cphenylene
isopropylidene-3,5-dichloro-1,4-phenylene)
Poly(oxycarbonyloxyhexamethylene)
Poly(oxycarbonyloxy-2-isopropyl- 1 ,Cphenylene-
isopropylidene- 1 ,Cphenylene)
Poly(oxycarbonyloxy-2-methoxy-1,Cphenylene
isopropylidene- 1 ,Cphenylene)
Poly(oxycarbonyloxy-
2,2,3,3,4,4,5,5-octafluorohexamethylene)
Poly[oxycarbonyloxy-1,3-(2,2,4,4-tetra-
methylcyclobutylene)]
Poly(oxycarbonyloxy-2-methyl-l,Cphenylene-
cyclohexylidene-3-methyl- 1 ,Cphenylene)
Poly(oxycarbonyloxy-2-methyl- 1,4-phenylene-
isopropylidene-3-methyl- 1,4-phenylene)
Poly(oxycarbonyloxy-2-methyl-1,4-
phenyleneisopropylidene-1,4-phenylene)
Poly(oxycarbonyloxy-2-methyl- 1,4-phenylenemethylene-
3-methyl- 1 ,Cphenylene)
Poly[oxycarbonyloxy-4,6-dimethyl-1,2-phenylene-
methylene-3,5-dimethyl-1,2-phenylene]
Poly(oxycarbonyloxy-3-methyl-1,4-phenylenebenzylidene-
2-methyl- 1,4-phenylene)
Poly(oxycarbonyloxy- 1,4-phenylenebenzylidene-
1,4-phenylene)
Poly(oxycarbonyloxy-1,4-phenylene-l,l-butylidene-
1,4-phenylene)
Poly(oxycarbonyloxy- 1,4-phenylene-2,2-butylidene-
1,4-phenylene)
Poly[oxycarbonyloxy-1,4-phenylene(cyano)
phenylmethylene-1,4-phenylene]
Poly(oxycarbonyloxy- 1,4-phenylenecyclohexylidene-
1,4-phenylene)
Poly(oxycarbonyloxy- 1,4-phenylenecyclopentylidene-
1,Cphenylene)
Poly(oxycarbonyloxy-1,4-phenylene-1,3-dichloro-
1,1,3,3-tetrafluoro-2,2-propylidene- 1 ,4-phenylene)
Poly(oxycarbonyloxy-1,4-phenyleneethylidene-
1 ,Cphenylene)
Poly(oxycarbonyloxy-1,4-phenylenefluoren-9-ylidene-
1 ,Cphenylene)
Poly(oxycarbonyloxy-1,4-phenylenehexafluoro-
2,2-propylidene-1,4-phenylene)
Poly(oxycarbonyloxy- 1,3-phenylenehexafluorotrimethylene-
1,3-phenylene)
291 In vacuum of 297 K
418 DSC
420 DSC
433
430
427
443-452
420
405
436
453, 493,
504
230
385
418
232
N 500, <433,
418
408
368, 313,
418, 363-383
413
324
410
Mechanical method, heating
rate: 1 Wmin
Mechanical method, heating
rate: 1 K/min
Mechanical method
Conflicting data
Low molecular weight sample
No experimental details
No experimental details
DTA heating rate
Conflicting data
Mechanical method
Conflicting data
455
394
396
401
411
448
440
456
403
653
449
319
Mechanical method
No experimental details
Mechanical method
DTA heating rate
Heating rate: 10 Wmin
DTA heating rate
1250,1340,1353
1432
1 4 4 2
1 4 4 2
1 4 8 9
1 5 4 6
333,334
3 3 5
3 3 5
334,335
3 3 8
334
334,336,337
3 3 9
3 3 8
3 3 8
3 3 9
340-342
335,343
334-336,343
3 3 8
3 3 5
3 3 8
3 3 5
335,338
344
335,344
3 4 5
334,335,344
334,346
331
344
341
331
148
TI
-
PC
-
PC
PC
PC
PI
TABLE 3. contd
Main-Chain -C-O-C Polymers VI / 221
Polymer CAS No.
T, (K)
Remarks Refs.
Poly(oxycarbonyloxy- 1,4-phenylene-4,4-heptylidene-
1 ,Cphenylene)
Poly(oxycarbonyloxy- 1,4-phenyleneisobutylidene-
1,Cphenylene)
Poly(oxycarbonyloxy-1,4-phenyleneisopropylidene-
1,3-phenyleneisopropylidene- 1 ,Cphenylene)
Poly(oxycarbonyloxy- 1,4-phenyleneisopropylidene-
1,4-phenylene)
24936-68-3
Poly(oxycarbonyloxy-1,4-phenylenemethylene-
1 ,Cphenylene)
Poly[oxycarbonyloxy- 1,4-phenylene
(methyl)phenylmethylene- 1,4-phenylene]
Poly(oxycarbonyloxy-1,4-phenylenecarbonyl-oxycarbonyl-
1,4-phenylene)
Poly(oxycarbonyloxy-1,4-phenylenediphenylmethylene-
1,4-phenylene)
Poly(oxycarbonyloxy-1,4-phenylene-2,2-pentylidene-
1,4-phenylene)
Poly[di(oxyethylene)oxy-1,4-phenylenecarbonyl-
oxycarbonyl- 1 ,Cphenylene]
Poly(oxymethyleneoxy- 1,4-phenylenecarbonyl-
oxycarbonyl- 1,4-phenylene)
Poly[di(oxymethylene)oxy-1,4-phenylenecarbonyl-
oxycarbonyl-1,4-phenylene]
Poly(oxypentamethyleneoxy-1,4-phenylenecarbonyl-
oxycarbonyl- 1,4-phenylene)
Poly(oxy- 1,3-phenylenecarbonyloxycarbonyl-
1,3-phenyleneoxypentamethylene)
Poly(oxy- 1,3-phenylenecarbonyloxycarbonyl-
1,3-phenyleneoxytetramethylene)
3,3,5-trimethyl cyclohexane-1-polycarbonate
Poly(oxytetramethyleneoxy-1,4-phenylenecarbonyl-
oxycarbonyl- 1 ,Cphenylene)
Poly(oxytrimethyleneoxy-1,3-phenylenecarbonyl-
oxycarbonyl- 1,3-phenylene)
Poly(oxytrimethyleneoxy- 1,4-phenylenecarbonyl-
oxycarbonyl-1,4-phenylene)
3.1.3. POLY(ESTERS)
Polyarylate of terephthalic acid
421
422
393
About 417
418
419-420
428
417
421
420
435
420
449
318
394
410
314
357
325
326
334
< 293
508
348
326
368
471 1254
334
344
No experimental details 338
1162
Dielectric 1163
DSC, onset , HR lOdeg/min 1161
78,102,131,145,
230,233,262,263,
287,317-319,321,
335-337, 344,
348- 378
DSC, Mdpt , 1 0 deg/min HR, 1164
TSD, 2 deg/min HR.
Acrystallinity)
1254
1259
1297
DSC 1264
No experimental details 338
No experimental details 338,367
334,336
247
334
334
247
247
Amorphous 247
247
247
247
1353
247
247
247
Poly(bispheno1 A terephthalate) see Poly(oxyterephthaloyloxy-1,4-phenyleneisopropylidene-1,4-phenylene)
Poly(butylene adipate) 223
Poly(butylene isophthalate) 291
Poly(butylene 2,6-naphthalate) 321
Poly(butylene naphthalate) 512
1 3 3 1
1 3 3 1
1542
1461
References page VI - 253
VI / 222 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 3. contd
Polymer CAS No. T, (K)
Remarks Rcfs.
Poly(butylene 1,4-terephthalate)
Poly(butylene terephthalate)
Poly(diethy1 phthalate)
Poly[(l,2-diethoxycarbonyl)ethylene]
Poly[(l,2-dimethoxycarbonyl)ethylene]
Poly(dimethy1 phthalate)
Poly[di(oxyethylene)oxyadipoyl]
Poly[di(oxyethylene)oxyazelaoyl]
Poly[di(oxyethylene)oxydodecanedioyl])
Poly[di(oxyethylene)oxyglutary]
Poly[di(oxyethylene)oxyheptylmalonyl]
Poly[di(oxyethylene)oxymalonyl]
Poly[di(oxyethylene)oxymethylmalonyl]
Poly[di(oxyethylene)oxynonylmalonyl]
Poly[di(oxyethylene)oxyoctadecanedioyl]
Poly[di(oxyethylene)oxyoxalyl]
Poly[di(oxyethylene)oxypentylmalony]
Poly[di(oxyethylene)oxypimeloyl]
Poly[di(oxyethylene)oxypropylmalonyl]
Poly[di(oxyethylene)oxysebacoyl]
Poly[di(oxyethylene)oxysuberoyl]
Poly[di(oxyethylene)oxysuccinyl]
Poly[di(oxy- 1,4-phenylene)oxyisophthaloyl]
Poly[di(oxy-l,4-phenylene)oxy-5-pentyloxyisophthaloyl]
Poly[( 1,2-dipropoxycarbonyl)ethylene]
Poly(oxy-2,6-diphenyl-1,4-phenylenemethylene-
3,5-diphenyl-1,4-phenyleneoxysebacoyl)
Polyesters of 3-phenyl-4,4-biphenyl dicarboxylic acid,
aromatic
Poly(ethylene adipate) see Poly(oxyethyleneoxyadipoy1)
Poly(ethylene naphthalate)
Poly(ethylene 2,6-naphthalate)
Poly(ethylene 2,6-naphthalene-dicarboxylate)
Poly(ethylene 1,4-terephthalate)
Poly(ethylene terephthalate) see
Poly(oxyethyleneoxyterephthaloy1)
Poly(lactic acid)
Poly(oxyadipoyloxy-2,6-dichloro-1,4-phenylene-
isopropylidene-3,5-dichloro-1,4-phenylene)
Poly(oxyadipoyloxy-3,3 ,5,5-tetramethyl-
4,4-biphenylylene)
Poly(oxyadipoyloxydecamethylene)
Poly(oxyadipoyloxy-2,6-dimethyl- 1,4-phenylene
isopropylidene-3,5-dimethyl-1,Cphenylene)
Poly(oxyadipoyloxy- 1,4-phenyleneisopropylidene-
1 $phenylene)
Poly(oxyadipoyloxy-2,6-diphenyl-1,4-phenyleneme~ylene-
3,5-diphenyl-1,4-eylene)
Poly(oxy-2-butenyleneoxysebacoyl) cis
tram
Poly(oxy-5-butyl-1,3-phenyleneoxyisophthaloyl)
Poly(oxy-2-butynyleneoxysebacoyl)
Poly(oxycarbonyl-3,3-biphenylylenecarbonyloxy-
1,4-phenyleneisopropylidene-1,4-phenylene)
Poly(oxycarbonyl- 1 +cyclohexylenecarbonyloxy-
1,4-phenyleneisopropylidene- 1 ,Cphenylene) tram
Poly(oxycarbonyl-1,5-dimethylpentamethylene)
Poly(oxycarbonyl-3-methylpentamethylene)
Poly(oxycarbonyl-2,6-naphthylene-
carbonyloxydecamethylene)
Poly(oxycarbonylpentamethylene)
Poly(oxycarbonyl-1,3-phenyleneoxy-
1,3-phenylenecarbonyloxy-
2,2,3,3,4,4-hexafluoropentamethylene)
499
304
180
286
361
192
227
205
202
226
215
244
244
214
205
265
226
213
235
199
212
244
446
399
262
365
Dilatomer
Dilatomer
1 4 6 1
1 3 3 1
1271
1158
1159
1 2 7 1
Heating rate: 20 Wmin
Heating rate: 20 Wmin
Dilatomer
Heating rate: 8 K/min
96
96
96
96
96
96
96
96
96
96
96
96
96
96
313
313
1160
3 7 1
398-443
24938-31-2
534
398
398
526
25038-59-9
1 4 6 1
1542
1341,1554
1 4 6 1
327
383
381
No measurement details
Heating rate: 8 Wmin
1427
380
217
366 Heating rate: 8 Wmin
96,381
371
341 382
388
232
233
359
246
460 Heating rate: 8 Wmin
384
383,429
386
423 Heating rate: 20 Wmin 42
240 Torsion pendulum 1173
220 Torsion pendulum 1172
287 No measurement details 387
213
293
Torsion pendulum
TABLE 3. contd
Main-Chain -C-O-C Polymers VI / 223
Polymer CAS No. T, WI Remarks Refs.
Poly(oxydibutyltinoxyadipoy1)
Poly(oxydibutyltinoxyfumaroy1)
Poly(oxydibutyltinoxyterephthaloy1)
Poly(oxy-2,6-dimethy1-1,4-phenyleneisopropylidene-
3,5dimethyl- 1,4-phenyleneoxysebacoyl)
Poly(oxy-2,5dimethylterephthaloyloxy-
1,4-phenylenisopropylidene-1,4-phenylene)
Poly(oxyethyleneoxycarbonyl-1,4-cyclohexylenecarbonyl) nuns
Poly(oxyethyleneoxycarbonyl-2,2-dimethyl-
4,4-biphenylylenecarbonyl)
Poly(oxyethyleneoxycarbonyl-1,4-naphthylenecarbonyl)
Poly(oxyethyleneoxycarbonyl- 1 ,%naphthylenecarbonyl)
Poly(oxyethyleneoxycarbonyl-2,6-naphthylenec~bonyl)
Poly(oxyethyleneoxycarbonyl-2,7-naphthylenecarbonyl)
Poly(oxyethyleneoxycarbonyl-l,Cphenylene-
see-butylidene-1,4-phenylenecarbonyl)
Poly(oxyethyleneoxycarbonyl- 1,1,3-trimethylindan-
3,5-ylene-1,4-phenylenecarbonyl)
Poly(oxyethyleneoxyisophthaloy1)
Poly(oxyethyleneoxyterephthaloy1) 25038-59-9
amorphous
Poly(oxy-5-ethyl-1,3-phenyleneoxyisophthaloyl)
Poly(oxyglutaryloxy-
2,2,3,3,4,4-hexafluoropentamethylene)
Poly(oxyglutaryloxy-
2,2,3,3,4,4,5,5-octafluorohexamethylene)
Poly(oxy-3-heptafluoropropylglutaryloxy-
2,2,3,3,4,4-hexafluoropentamethylene)
Poly(oxy-2,2,3,3,4,4-hexafluoropenta-
methyleneoxyadipoyl)
Poly(oxy-2,2,3,3,4,4-hexafluoropentamethyonyl-
3,3 -biphenylylenecarbonyl)
Poly(oxy-2,2,3,3,4,4-hexafluoropenta-
methyleneoxycarbonyl-
1,3-phenylenedecafluoropentamethylene-
1,3-phenylenecarbonyl)
Poly(oxy-2,2,3,3,4,4-hexafluoropentamethyleneoxyc~bonyl-
1,3-phenylenehexafluorotrimethylene-
1,3-phenylenecarbonyl)
Poly(oxy-2,2,3,3,4,4-hexafluoropentamethyleneoxy-
3,6-dithiaoctanedioyl)
Poly(oxy-3-heptafluoropropylglutaryloxy-
2,2,3,3,4,4,5,5-octafluorohexamethylene)
Poly(oxyhexamethyleneoxycarbonyl-
2,6-naphthylenecarbonyl)
Poly(oxy-5-hexyl- 1,3-phenyleneoxyisophthaloyl)
Poly(3-hydroxybutyrate)
Poly(4-hydroxybutyrate)
Poly(oxyisophthaloyloxy-4,4-biphenylylene)
383 Heating rate: 20 Wmin 385
459 Heating rate: 20 K/min 385
588
Heating rate: 20 Wmin 385
318 Heating rate: 8 K/min 371
457
291
346
337
344
351
386
392
N 380
427
324
333-358 Dielectric, Aannealing)
334 DSC, onset, Xp zero HR,
335-350
342
359
355
355-357
337
333-349
395
218-223
218-223
243-248
216
318
301 Heating rate: 32 Wmin; qiti low
N 233
N 248
317
335
233
223
437, 583
Mechanical method
Heating rate: 20 K/min
366
42
391
Amorphous
Crystalline
393
393
387,393
393
165
DTA heating rate 392
393
1166
1165
1168
f(annealing)
DSC, onset, AHR, draw ratio) 1167
1,42,61,78,94,
183,202,233,261,
262,272,319,344,
349,352-354,360,
362,371,381,388,
DSC
Brittle point
Brittle point
Brittle point
Brittle point
Brittle point
No measurement details
NMR
Conflicting data
389,393-418
1169
1254
1338
1432
1383
384
422
422
422
419-423
148
1 4 8
1 4 8
422
422
387
384
1278
1494
131,424
References page VI - 253
VI / 224 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 3. contd
Polymer CAS No. T, (K) Remarks Refs.
Poly(oxyisophthaloyloxy-
2,2,3,3,4,4-hexafluoropentamethylene)
Poly(oxyisophthaloyloxy-2-methyl-1,4-phenylene
isopropylidene-3-methyl-1,Cphenylene)
Poly(oxyisophthaloyloxy-2,6-dimethyl-1,4-phenylene
isopropylidene-3,5-dimethyl-1,4-phenylene)
Poly(oxyisophthaloyloxy-2-methyl-1,4-phenylene
methylene-3-methyl- 1,4-phenylene)
Poly(oxyisophthaloyloxy-2,6-dimethyl- 1,4-phenylene
methylene-3,5-dimethyl- 1 ,Cphenylene)
Poly(oxyisophthaloyloxy-1,4-phenylenebenzylidene-
1,4-phenylene)
Poly(oxyisophthaloyloxy-1,4-phenylenecyclohexylidene-
1,4-phenylene)
Poly(oxyisophthaloyloxy- 1,4-phenyleneisopropylidene-
1,4-phenylene)
Poly(oxyisophthaloyloxy-1,4-phenylenemethylene-
1 ,Cphenylene)
Poly(oxymethylene- 1,4-cyclohexylenemethylene-
oxycarbonyl-truns- 1,4-cyclohexylenecarbonyl)
Poly(oxy-5-methyl- 1,3-phenyleneoxyisophthaloyl)
Poly(oxyneopentyleneoxycarbonyl-
1,4-cyclohexylenecarbonyl) trans
Poly(oxyneopentyleneoxyterephthaloy1)
Poly(oxy-5-nonyl-l,3-phenyleneoxy-2-fluoroisophthaloyl)
Poly(oxy-5-nonyl-1,3-phenyleneoxy-5-fluoroisoph~aloyl)
Poly(oxy-5-nonyl- 1,3-phenyleneoxyisophthaloyl)
Poly(oxy-2,2,3,3,4,4,5,5-octafluorohexame~yleneoxy-
3,6dithiaoctanedioyl)
Poly(oxy-5-octyl-1,3-phenyleneoxyisophthaloyl)
Poly[oxy-5-(pentadecafluoraheptyl)isophthaloyloxy-
2,2,3,3,4,4-hexafluoropentamethylene]
Poly(oxypentamethyleneoxyadipoy1)
Poly(oxypentamethyleneoxycarbonyl-
2,6naphthylenecarbonyl)
Poly(oxypentamethyleneoxyterephthaloy1)
Poly(oxy-5-pentyloxyisophthaloyloxy-4,4-biphenylene)
Poly(oxy-2-pentyloxyisophthaloyloxy-
2,2,3,3,4,4-hexafluoropentamethylene)
Poly(oxy-4-pentyloxyisophthaloyloxy-
2,2,3,3,4,4-hexafluoropentamethylene)
Poly(oxy-5-pentyloxyisophthaloyloxy-
2,2,3,3,4,4-hexafluoropentamethylene)
Poly(oxy-Spentyloxyisophthaloyloxy-
1,4-phenylenemethylene-1,4-phenylene)
Poly(oxy-1,4-phenylenefluoren-9-ylidene-
1,4-phenyleneoxysebacoyl)
Poly(oxy- 1,3-phenylenehexafluorotrimethylene-
1,3-phenyleneoxycarbonyl-1,3-phenylene-
hexafluorotrimethylene-1,3-phenylenecarbonyl)
Poly(oxy- 1,4-phenyleneisopropylidene-
1,4-phenyleneoxycarbonyl- 1,4-phenylene-sec-butylidene-
1,4-phenylenecarbonyl)
Poly(oxy- 1,4-phenyleneisopropylidene-
1,4-phenyleneoxycarbonyl-1,3-phenylene-
hexafluorotrimethylene-1,3-phenylenecarbonyl)
Poly(oxy- 1,4-phenyleneisopropylidene-
1,4-phenyleneoxysebacoyl)
Poly[oxy-l,3-phenyleneoxy-5-(1OH-eicosafluorodecyl)
isophthaloyl)
Poly [oxy- 1,3-phenyleneoxy-
5-(pentadecafluoroheptyl)isophthaloyl]
Poly(oxy- 1,3-phenyleneoxy-2-fluoroisophthaloyl)
298
438
498
418
461
433
400
462
423
325
426
303
341
307
293
304
N 235
314
300
204
311
283
411
290
282
243
383
424
345
N 480
389
280
356
374
393
Heating rate: 32 Wmin; vi&
0.14 dl/g only
Dynami c met hod
Heating rate: 8 Wmin
Mechanical method
Mechanical method
Heating rate: 8 K/min
Heating rate: 20 Wmin
Heating rate: 20 K/min
Heating rate: 20 Wmin
Heating rate: 20 Wmin
Brittle point
145,369,37
Heating rate: 32 K/min; ninh only
0.10 dl/g
Heating rate: 2OK/min; ninh Onl y
0.13
386,425
366
371
369
369
426
1 4 5
1,427
313
42
384
42
42
432
255
384
422
384
386
96
387
411
313
425
425
425
313
347
1 4 8
No measurement details
DTA heating rate
Heating rate: 20 K/mitt
DTA heating rate; l)inh only
0.12dllg
DTA heating rate; niti only
0.25 dllg
DTA heating rate
Heating rate: 10 Wmin
Heating rate: 8 Wmin
Heating rate: 32 Wmin
1 6 5
433
363,371,409
432
432
255
TABLE 3. contd
Main-Chain -C-O-C Polymers VI / 225
Polymer CAS No. T, (K) Remarks Refs.
Poly[oxy- 1,3-phenyleneoxy-
5-(heptafluoropropyl)isophthaloyl]
Poly(oxy- 1,3-phenyleneoxyisophthaloyl)
394
411
Poly(oxy-1,3-phenyleneoxy-5-pentyloxyisoph~aloyl) 269
Poly(oxypimeloyloxy-3,3,5,5-tetramethyl-
4,4-biphenylylene)
Poly(oxypimeloyloxy-2,6-dimethyl-1,4-phenylene-
isopropylidene-3,5-dimethyl-1,Cphenylene)
Poly(oxypimeloyloxy-2,6-diphenyl-1,4-phenylene-
methylene-3,5-diphenyl-1,4-phenylene)
Poly(oxypropyleneoxycarbonyl-2,6-naphthylenecarbonyl)
Poly(oxypropyleneoxyterephthaloy1)
Poly(oxy-5-propyl-1,3-phenyleneoxyisophthaloyl)
Poly(oxyterephthaloyloxy-2-butyl-1,Cphenylene
isopropylidene-3-butyl- 1 ,Cphenylene)
Poly(oxyterephthaloyloxy-2-sec-butyl- 1 ,Cphenylene-
isopropylidene-3-set-butyl-1,Cphenylene)
Poly(oxyterephthloyloxy-2-chloro-1,4-phenylene-
isopropylidene-3-chloro-1,4-phenylene)
Poly(oxyterephthloyloxy-2-isopropyl- 1 ,Cphenylene-
isopropylidene-3-isopropyl-1,Cphenylene)
Poly(oxyterephthaloyloxydecamethylene)
Poly(oxyterephthaloyloxyheptamethylene)
Poly(oxyterephthaloyloxyhexamethylene)
Poly(oxyterephthaloyloxynonamethylene)
Poly(oxyterephthaloyloxyoctamethylene)
Poly(oxyterephthaloyloxypentamethylene)
Poly(oxyterephthaloyloxymethylene-
1,4-cyclohexylenemethylene) 70% truns
Poly(oxyterephthaloyloxy-2-methyl-1,4-phenylene-
isopropylidene-3-methyl- 1,4-phenylene)
369
357
384
361
341
394
433
373 Mechanical method
463 Mechanical method
403
298, 268 Conflicting data
276 DTA heating rate
318, 264 Conflicting data
308, 270 Conflicting data
318 Dynami c met hod
318 Dynami c met hod
358 Heating rate: 20 K/min
- 428 Dilatometric method
Poly(oxyterephthaloyloxy-2,6-dimethyl-1,4-phenylene-
isopropylidene-3,5-dimethyl-1,4-phenylene)
Poly(oxyterephthaloyloxy- 1,4-phenylene)
9,9-anthronylidene- 1 ,Cphenylene)
Poly(oxyterephthaloyloxy- 1,4-phenylenebenzylidene-
1,4-phenylene)
Poly(oxyterephthaloyloxy-1,4-phenylene-
cyclohexylmethylene- 1 ,Cphenylene)
Poly(oxyterephthaloyloxy-1,4-phenylenefluoren-9-ylidene-
1 ,Cphenylene)
Poly(oxyterephthaloyloxy-1,4-phenylene-
hexafluoroisopropylidene- 1,4-phenylene)
Poly(oxyterephthaloyloxy-l,4-phenylene-l,l-indanylidene-
1,4-phenylene)
Poly(oxyterephthaloyloxy-1,4-phenyleneisoproplyidene-
1,4-phenylene)
Poly(oxy-3,3,5,5-tetramethyl-
4,4-biphenylyleneoxysebacoyl)
Poly(oxy-2,2,4,4-tetramethyl-1,3-cyclobutyleneoxyc~bonyl-
funs- 1,4-cyclohexylenecarbonyl)
Poly(oxy-2,2,4,4-tetramethyl-1,3-cyclobutylene
oxyterephthaloyl) 60-68% tram
Poly(oxytetramethyleneoxyadipoy1)
461 Dynami c met hod
498 Heating rate: 8 K/min
570
473
543
654
534
608
478
330
442
457
155
Poly(oxytetramethyleneoxycarbonyl-
1,4-cyclohexylenecarbonyl)
Poly(oxytetramethyleneoxycarbonyl-
2,6-naphthylenecarbonyl)
Poly(oxytrimethyleneoxycarbonyl-
1,4-cyclohexylenecarbonyl) tram
263
349
267
Sample of low qinh
Values range
from 411 to 463 K
Heating rate: 20 K/mm;
l)inh only 0.13
Heating rate: 8 Wmin
Heating rate: 8 Wmin
Heating rate: 8 K/mm
No measurement details
Heating rate: 10 Wmin
No measurement details
Heating rate: 10 Wmin
Softening point
Heating rate: 10 K/mm
DTA heating rate
Heating rate: 8 K/mm
Heating rate: 20 K/min
Heating rate: 20 Wmin
Transition at 194-206 K,
1st order (Ref. 243)
rate: 10 K/min
Heating rate: 20 Wmin
No measurement details
Heating rate: 20 Wmin
434
3 13,384,427,
435-437
313
371
371
371
387
389
384
439
439
439
439
6,403,411
411
6,403,411
6,403,411
403
6,403
42,440
366,439,411
371
347
426
442
347
443
347
363,369,371,382,
427,439,441,443
3 7 1
42
42,319,428
80,96,243
42
387
42
References page VI - 253
VI / 226 CLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 3. contd
1,
-
P
-
P
P
P
F
F
F
I
I
I
1
1
1
1
1
1
1
Polymer CAS No. T, (K)
Remarks Refs.
Poly(oxytrimethyleneoxycarbonyl-
2,6-naphthylenecarbonyl)
Poly(oxytetramethyleneoxysebacoy1)
346 No measurement details
387
T, decreases as intrinsic
viscosity increases
Conflicting data
Heating rate: 8 Wmin
Conflicting data
1,383,429
6,42,403,411
3 7 1
9 6
42,183,403,411
384
384
216
Poly(oxytetramethyleneoxyterephthaloy1)
Poly(oxy-3,3,5,5-tetraphenyl-4,4-biphenylylenesebacoyl)
Poly(oxytrimethyleneoxyadipoy1)
Poly(oxytrimethyleneoxyterephthaloy1)
Poly(oxy-5-tridecyl-1,3-phenyleneoxyisophthaloyl)
Poly(oxy-5-undecyl-1,3-phenyleneoxyisophthaloyl)
Poly(resorcino1 isophthalate) see Poly(oxy-
1,3-phenyleneoxyisophthaloyl)
Poly(trifluoro-chloroethylene)
Poly( 1,4,7-trioxy-3,3,5,5-tetrafluoro-
heptamethylenecarbonyl-1,3-phenylene-
hexafluorotrimethylene- 1,3-phenylenecarbonyl)
Poly(l,4,7-trioxy-3,3,5,5-tetrafluoro-
heptamethyleneisophthaloyl)
Poly(l,4,7-trioxy-3,3,5,5-tetrafluoroheptamethylene-
5-pentyloxyisophthaloyl)
290, 353
371
214
368, 308
291
295
352
303 Heating rate: 32 Wmin
1432
218
301 Heating rate: 32 Wmin; qtnh 0.23 218
only
Heating rate: 321Vmin; [v] only
0.24 dl/g
218
287
3.1.4. POLY(ETHER KETONES)
Biphenylene-ether-ketone
Methyl poly(ary1 ether ether ketone)
Poly(ary1 ether ether ketone)
Poly(ary1 ether ketone)
454 1 3 7 5
418 1551
423 1291
429 1 2 9 1
491 1 4 0 6
495 1 5 0 7
487-543 1 5 2 5
Poly(ary1 ether ketone) of 1,8-bis(4-fluorobenzoyl)
naphthalene and aromatic bisphenols
Poly(ether ether ketone)
420
425
418
430
405
431
428-496
418
473
1 3 4 4
1 4 7 2
1 3 3 2
1 3 3 2
1 2 6 0
1 4 3 2
1 3 8 5
1 3 9 9
1 3 6 8
DSC with 10% crystallinity
DSC with 28% crystallinity
Poly(ether ketone),fluorinated
Poly(phenylene ether ether ketone), isopropyl subs
Poly(phosphene oxide ether ketone)
3.1.5. POLY(OXIDES)
Poly(acetaldehyde) see Poly(oxyethylidene)
Poly[3,3-bis(chloromethyl)oxacyclobutane] see Poly[oxy-2,2-bis(chloromethyl)trimethylene]
Poly( 1,2-dihydroxypropane) 25322-69-4 200
Br-Poly(2,6-dimethyl-1,4-phenylene oxide), linear 481
Poly(2,6-dimethyl-1,4-phenylene oxide) [PPO] see 25134-01-4
Poly(oxy-2,6-dimethyl- 1,4-phenylene)
Poly[di(oxymethylene)oxy- 218
2,2,3,3,4,4-hexafluoropentamethylene]
Poly [di(oxy- 1,4-phenylene)carbonyl- 1,4-phenylene] 433
Poly(epichlorohydrin) see Poly[oxy(chloromethyl)ethylene] 24969-06-o
Poly(ethylene oxide)s see Poly(oxyethylene)s 25322-68-3
Poly(ethylene oxide) 1000 209
Poly(ethylene oxide) 400 210
Poly(ethylene oxide) 600 210
Poly(formaldehyde) see Poly(oxymethylene) 9002-81-7
Poly(methylene oxide) see Poly(oxymethylene)
Poly(4,4-(2,7-napthalenedioxy) dibenzoic acid)
471
1281
1 3 2 6
2 8 5
Mechanical method 1 1 6
1266
1266
1 2 6 6
Poly(oxacyclobutane) see Poly(oxytrimethylene)
Poly(oxetane)s see Poly(oxytrimethylene)s
Poly(oxy-2-acetoxytrimethyleneoxy-2,6-dichloro-
1,4-phenyleneisopropylidene-3,5-dichloro-l,4-phenylene)
Poly(oxy-2-acetoxytrimethyleneoxy- 1,4-pheylene)
373 219
322 219
TABLE 3. contd
Main-Chain -C-O-C Polymers VI / 227
Polymer CAS No. T, (K) Remarks Refs.
Poly(oxy-2-acetoxytmethyleneoxy-l,4-phenylene-l-ethyl-
1,3-cyclohexylene- 1,4-phenylene)
Poly(oxy-2-acetoxytrimethyleneoxy-
1,4-phenyleneisopropylidene-1,4-phenylene)
Poly[oxy-2-acetoxytrimethyleneoxy-
1,4-phenylenemethyl(phenyl)methylene- 1,4-phenylene]
Poly[oxy(allyloxymethyl)ethylene]
Poly(oxy-2-benzoyloxytrimethyleneoxy-
1,4-phenyleneisopropylidene-1,Cphenylene)
Poly[oxy-2-benzoyloxytrimethyleneoxy-
1,4-phenylenemethyl(phenyl)methylene- 1,4-phenylene]
Poly[oxy-2-(2-biphenylyl)-6-phenyl-1,4-phenylene]
Poly[oxy(bromomethyl)ethylene]
Poly(oxybutadiene)
Poly[oxy(butoxymethyl)ethylene]
Poly(oxybutylene)
Poly(oxybutylethylene)
Poly(oxy-tert-butylethylene)
Poly[oxy-2-(4-terr-butylphenyl)-6-phenyl-1,4-phenylene]
Poly[oxy-2-(chloroacetoxy)trimethyleneoxy-
1,4-phenyleneisopropylidene-1,4-phenylene]
Poly[oxy-2-(2-chlorobenzoyloxy)trimethyleneoxy-
1,4-phenyleneisopropylidene- 1,4-phenylene]
Poly[oxy(chloromethyl)ethylene]
Poly[oxy-2,2-bis(chloromethyl)trimethylene]
Poly(oxydecylethylene)
Poly(oxy-2,6-dimethoxy- 1,4-phenylene)
Poly(oxy-1 ,l-dimethylethylene)
Poly(oxy- 1,2,dimethylethylene) truns
Poly[oxy(2,6-dimethyl- ,4-phenylene)]
crosslinked
Poly(oxydiphenoxymethyleneoxy-4,4-biphenylene)
Poly(oxydiphenoxymethyleneoxy-3,3-dimethyl-
4,4-biphenylylene)
Poly(oxydiphenoxymethyleneoxy-1,4-
phenyleneisopropylidene- 1,4-phenylene)
Poly[oxy(ethoxymethyl)ethylene]
Poly(oxy-2-ethyl-2-chloromethyltrimethylene)
Poly(oxyethylene)
with dipivaloyl methane
with neodymium nitrate
Poly(oxyethylethylene)
Poly(oxyethylidene)
Poly[oxy-l-(heptafluoro-2-propoxymethyl)ethylene]
Poly(oxy-2,2,3,3,4,4-hexafluoropentamethyleneoxy-
4,4-octafluorobiphenylylene)
380 219
333 219
383 219
1 9 5 220
338 219
399 219
484 DSC heating rate; low viscosity 2 2 1
259 Heating rate: 20 Wmin 222
198 Structure not given 223,224
194 Heating rate: 10 Wmin 220
1 8 5 1432
203 Heating rate: 10 Wmin 220
308 223,225-227
513 DSC heating rate 221
338 219
339 219
251
248
265
232
440
264
277
25134-01-4
482
483-507
493
483
469
385
398
Heating rate: 20 Wmin 222
1 3 4 5
1,122,230-236
220,223
260
223
223
1156
102,114,202,262,
286-300
DSC,DTA, confused by large 1155
endotherm, ATH, filler)
1254
1276
1326
DSC heating rate 379
DSC heating rate 379
365 DSC heating rate 379
212
- 293
25322-68-3, 232?
9004-74-4
-
-
206
340
1 6 5
373
220
340
222
203
243
253
- 230
314
Dynami c met hod
Conflicting data,
values range
from 158 to 223 K
DTA heating rate
Heating rate: 32 K/min
220
237
107,223,234,
238-244
1 1 5 3
1154
1432,1287
1316
1 2 5 5
1422
1271,1478
1316
1316
220
250,251
1304
258
255
References page VI - 253
VI / 228 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 3. contd
Polymer CAS No. T, (K) Remarks Refs.
Poly(oxy-2,2,3,3,4,4-hexafluoro-
pentamethyleneoxymethylene-
1,4-phenylenemethylene)
Poly(oxyhexylethylene)
Poly[oxy(hexyloxymethyl)ethylene]
Poly(oxy-2-hydroxytrimethyleneoxy-2-chloro-
1,4-phenyleneisopropylidene-3-chloro- 1 ,Cphenylene)
Poly(oxy-2-hydroxytrimethyleneoxy-2,6-dichloro-
1,4-phenyleneisopropylidene3 ,Wichloro- 1 ,Cphenylene)
Poly(oxy-2-hydroxytrimethyleneoxy- 1 ,Cphenylene)
Poly(oxy-2-hydroxytrimethyleneoxy- 1 ,Cphenylene-l-ethyl-
1,4-cyclohexylene- 1,4-phenylene)
Poly(oxy-2-hydroxytrimethyleneoxy-
1,4-phenyleneisobutylidene-1,4-phenylene)
Poly(oxy-2-hydroxytrimethyleneoxy-
1,4-phenyleneisopropylidene- 1,4-phenylene)
Poly(oxy-2-hydroxytrimethyleneoxy- 1 ,rl-phenylene-
5-isopropyl-2-methyl- 1,2-cyclohexylene- 1 ,4-phenylene)
Poly(oxy-2-hydroxytrimethyleneoxy- 1,4-phenylene-l-methyl-
1,4-cyclohexyleneisopropylidene- 1 ,Cphenylene)
Poly(oxy-2-hydroxytrimethyleneoxy-1,4-
phenylenemethylene- 1,4-phenylene)
Poly(oxy-2-hydroxytrimethyleneoxy-l,Cphenylene-
3,3-dimethyl- 1,6-indanylene)
Poly(oxy-2-hydroxytrimethyleneoxy-1,4-phenylene-
1,3,3-trimethyltrimethylene-1,4-phenylene)
Poly(oxy-2-hydroxytrimethyleneoxy-
1,4-phenylenemethyl(phenyl)methylene- 1,4-phenylene)
Poly[oxy(methoxymethyl)ethylene]
Poly(oxymethylene)
Poly(oxypropylene) 25322-69-4
diol
diol-based urethane prepolymer
Poly(oxymethyleneoxy-
2,2,3,3,4,4-hexafluoropentamethylene)
Poly(oxymethyleneoxy-
2,2,3,3,4,4,5,5octafluorohexamethylene)
Poly(oxymethylene-1,3-phenylenemethyleneoxy-
2,2,3,3,4,4-hexafluoropentamethylene)
Poly(oxymethylene- 1 ,Cphenyleneoxy-
1,4-phenylenemethyleneoxy-
2,2,3,3,4,4-hexafluoropentamethylene)
Poly(oxy-2-methyl-6-phenyl-1,4-phenylene)
Poly(oxy- 1-methyltrimethylene)
Poly(oxy-2-methyltrimethylene)
Poly[oxy-2-(1-naphthyl)-6-phenyl-l A-phenylene]
Poly(oxy-3-nitro-1,3-phenyleneoxy-
1,4-phenyleneisopropylidene- 1,4-phenylene)
Poly(oxyoctafluorotetramethylene)
Poly(oxy-1,3-phenylene)
Poly(oxy-1,4-phenylene)
Poly(oxyphenylene) 9041-80-9
Poly(oxy- 1,4-phenylenecarbonyl- 1,4-phenyleneoxy-
1,4-phenyleneisopropylidene-4-methyl- 1 ,Ccyclohexylene-
1 ,Cphenylene)
241 Heating rate: 32 Wmin 256
206
190
358
Heating rate: 10 Wmin 220
220
259
388 259
333 259
413 259
368 259
313 259
448 259
408 259
353 259
393 259
348 259
388 219
211
9002-81-7
1 9 1
Heating rate: 10 Wmin
Values range from
188 to 263 K
200
260
1 8 3
190
205
200
202
225
220 Heating rate: 32 Wmin
220
1152
1,6,68,191,230,
233,238,239,
261- 271
1432
1254
1304
1287
1304
1394
1314
1258
284
220 Heating rate: 32 K/min
238
279 Heating rate: 32 K/min; high
rate effect
284
256
256
428
223
218
507
423
Dynami c met hod
Dynami c met hod
299
281
281
DSC heating rate; low viscosity
Mechanical method
2 2 1
1 1 6
- 208
-318
358
363
493
Heating rate: 10 Wmin
DTA heating rate;
low viscosity
DTA heating rate
Mechanical method
254,257
114,295
288,305-307
1432
1 1 6
TABLE 3. contd
Main-Chain -C-O-C Polymers VI / 229
Polymer CAS No.
T, (W
Remarks Refs.
Poly(oxy- 1,4-phenylenecarbonyl- 1,4-phenyleneoxy-
1,4-phenyleneisopropylidene- 1,4-phenylene)
Poly(oxy- 1,4-phenylene-2,2-dicyanotrimethylene-
1,4-phenylene)
Poly[oxy-l,4-phenylene-(2-cyano)-2-phenyltrimethylene-
1,4-phenylene]
Poly[oxy-1,4-phenylene-2,2-
di(ethoxycarbonyl)trimethylene-1,4-phenylene]
Poly(oxy-l,4-phenylenehexafluoro-2,2-propylidene-
1 ,Cphenyleneoxy- 1,4-phenylenecarbonyl- 1,4-phenylene]
Poly(oxy- 1,4-phenyleneisopropylidene- 1,4-phenyleneoxy-
1,4-phenyleneazo-1 ,Cphenylene)
Poly(oxy- 1,4-phenyleneisopropylidene- l,Cphenyleneoxy-
1,4-phenyleneterephthaloyl- 1 ,Cphenylene)
Poly(oxy-1,4-phenylenemethylenefluoroen-
9-ylidenemethylene-1,Cphenylene)
Poly(oxyphenylethylene)
Poly(oxy-2,6-diphenyl-1,4-phenylene)
Poly [oxy-6-phenyl-2-(3 -o-terphenylyl)- 1 ,4-phenylene]
Poly[oxy-6-phenyl-2-(m-tolyl)-l,Cphenylene]
Poly[oxy-6-phenyl-2-(p-tolyl)-1,4-phenylene]
Poly(oxy-2-propionyloxytrimethyleneoxy-
1,4-phenyleneisopropylidene-1,4-phenylene)
Poly(oxypropylene)
Poly[oxy-1-(2,2,3,3-tetrafluorocyclobutyl)ethylene]
Poly(oxytetrafluoroethylene)
Poly(oxytetramethylene)
Poly(oxy-2,2,2-trichloroethylethylene)
Poly(oxytrimethylene)
Poly(pertluorotrimethylene oxide)
Poly(phenylene oxide)s see Poly(oxyphenylene)s
Poly(tetrahydrofuran) see Poly(oxytetramethylene)
Poly(trihydroxypropane)
Poly [tri(oxy- 1,4-phenylene)carbonyl- 1 ,Cphenylene]
3.1.6. POLY(URETHANES)
Poly(oxy-2-butenylene oxycarbonyliminohexamethylene
iminocarbonyl)
cis-tram
Poly(oxycarbonyliminodecamethylene
iminocarbonyloxyhexadecamethylene)
Poly(oxycarbonyliminohexamethylene
iminocarbonyloxydecamethylene)
Poly(oxycarbonyliminohexamethylene
iminocarbonyloxyhexadecamethylene)
Poly(oxycarbonyliminomethylene-1,4-phenylene
methyleneiminocarbonyloxydecamethylene)
Poly(oxycarbonyliminomethylene-1,Cphenylene
methyleneiminocarbonyloxydodecamethylene)
Poly(oxycarbonyliminomethylene-1,4-phenylene
methyleneiminocarbonyloxyhexadecamethylene)
Poly(oxycarbonylimino-4-methyl-1,3-phenylene
iminocarbonyloxydecamethylene)
Poly(oxycarbonylimino-4-methyl- 1,3-phenylene
iminocarbonyloxynonamethylene)
428
420
416
321
448
448
438
411
313
493
498
485
492
491
331
198
201
248
225
25190- 06- l 189
178
271
195
172
9041- 80- 9
25190- 06- l
341
423
234
228
307
309
312
322
318
320
291
335
Mechanical method
DTA heating rate
Proposed structure; DTA
heating rate
DTA heating rate
Mechanical method
Mechanical method
Mechanical method
Proposed structure; DTA
heating rate
DSC heating rate; low zero HR
DSC heating rate; low viscosity
DSC heating rate; low viscosity
DSC heating rate; low viscosity
Conflicting data
Mechanical method, heating
rate: 2 Wmin
Low molecular weight
No measurement details
Mechanical method
Heating rate: 1 Wmin
Heating rate: 1 K/min
Heating rate: 1 K/min
Heating rate: 1 Wmin
Heating rate: 1 Wmin
Heating rate: 1 Wmin
Heating rate: 10 Wmin
Heating rate: 10 Wmin
116
310
310
310
116
116
116
310
220, 223,
225, 324
464, 130, 471
1157
221
221
221
219
220, 223, 243,
251, 269, 273,
216, 281,
326- 332, 1432
1271
252
253, 254
231,238,243,
272- 278, 1287
1304
229
238, 272, 273,
278- 281, 1287
1287
1271
116
383
429
445
445
445
445
445
445
446
446
References page VI - 253
VI / 230 CLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 3. contd
Polymer CAS No. T, (K)
Remarks Refs.
Poly(oxycarbonylimino-4-methyl- 1,3-phenylene
iminocarbonyloxyoctamethylene)
Poly(oxycarbonylimino-1,4-phenylenemethylene-
1 $phenylene iminocarbonyloxyhexadecamethylene)
Poly(oxydecamethyleneoxycarbonyliminohexamethylene-
iminocarbonyl)
Poly(oxy-2,2-diethyltrimethyleneoxycarbonylimino-
4-methyl-1,3-phenylene iminocarbonyl)
Poly(oxydodecamethyleneoxycarbonyliminodecamethylene
iminocarbonyl)
Poly(oxyethyleneoxycarbonyliminodecamethylene
iminocarbonyl)
Poly(oxyethyleneoxycarbonyliminohexamethylene
iminocarbonyl)
Poly(oxyethyleneoxycarbonyliminononamethylene
iminocarbonyl)
Poly(oxyethyleneoxycarbonylimino-4-methyl-
1,3-phenylene iminocarbonyl)
Poly(oxyethyleneoxycarbonylimino-1,4-phenylene ethylene-
1,4-phenyleneiminocarbonyl)
Poly(oxyethyleneoxycarbonylimino- 1,4-phenylene
methylene- 1,4-phenyleneiminocarbonyl)
Poly(oxyethyleneoxycarbonylimino- 1,4-phenylene
tetramethylene- 1,4-phenyleneiminocarbonyl)
Poly(oxyethyleneoxycarbonylimino- 1,4-phenylene
trimethylene- 1,4-phenyleneiminocarbonyl)
Poly(oxyheptamethyleneoxycarbonyliminohexamethylene
iminocarbonyl)
Poly(oxy-2,2,3,3,4,4-hexafluoropentamethylene
oxycarbonyliminohexamethyleneiminocarbonyl)
Poly(oxy-2,2,3,3,4,4-hexafluoropentamethylene
oxycarbonylimino-2,2,3,3,4,4,5,5-octafluoro
hexamethyleneiminocarbonyl)
Poly(oxydecamethyleneoxycarbonylimino-
1,4-phenylenemethylene-1,4-phenyleneiminocarbonyl)
Poly(oxydodecamethyleneoxycarbonylimino-
1,4-phenylenemethylene-1,4-phenyleneiminocarbonyl)
Poly(oxyheptamethyleneoxycarbonylimino-4-methyl-
1,3-phenyleneiminocarbonyl)
Poly(oxyheptamethyleneoxycarbonylimino-
1,4-phenylenemethylene-l,4-phenyleneiminoc~bonyl)
Poly(oxyhexamethyleneoxycarbonylimino-4-methyl-
1,3-phenyleneiminocarbonyl)
Poly(oxyhexamethyleneoxycarbonliminomethylene-
1,4-phenylenemethyleneiminocarbonyl)
Poly(oxyhexamethyleneoxycarbonylimino-
1,4-phenylenemethylene- 1,4-phenyleneiminocarbonyl)
Poly(oxymethylene-5-tert-butyl-1,3-phenylenemethylene
oxycarbonylimino- 1,4-phenylenemethylene-
1,4-phenyleneiminocarbonyl)
Poly(oxymethylene-1,3-
phenylenemethyleneoxycarbonylimino-
1,4-phenylenemethylene- 1,4-phenyleneiminocarbonyl)
Poly(oxyneopentyleneoxycarbonylimino-4-methyl-
1,3-phenyleneiminocarbonyl)
Poly(oxynonamethyleneoxycarbonyliminohexamethylene
iminocarbonyl)
Poly(oxynonamethyleneoxycarbonylimino-
1,4-phenylenemethylene-1,4-phenyleneiminocarbonyl)
Poly(oxyhexamethyleneoxycarbonyliminohexamethylene
iminocarbonyl)
Poly(oxyhexamethyleneoxycarbonylimino-
2,2,3,3,4,4,5,5-octafluorohexamethyleneiminoc~bonyl)
Poly(oxy-2,2,3,3,4,4,5,5-octafluorohexamethylene
oxycarbonyliminohexamethyleneiminocarbonyl)
337
313
328
213
307
334
329
317
326
390
412, 366
379
347
328
289
298
321 Heating rate: 1 Umin 445,446
316 Heating rate: 1 Wmin 445
334 Heating rate: 10 Wmin 446
357 Heating rate: 10 Wmin 446
305 Heating rate: 10 Wmin 446
329 Heating rate: 1 K/min 445
324 Heating rate: 1 K/min 445,446
387 DTA heating rate 453
379
241 DTA heating rate 448
331 Heating rate: 10 Wmin 446
345 Heating rate: 10 Wmin 446
332 Heating rate: 10 JS/min 446
278 DTA heating rate 451,452
271 DTA heating rate 451,452
Viscosity only 0.20
Heating rate: 10 Wmin
Heating rate: 1 Wmin
Heating rate: 10 Wmin
Heating rate: 1 Wmin
Heating rate: 10 Wmin
Heating rate: 10 Wmin
Conflicting data
Heating rate: 10 Wmin
DTA heating rate
DTA heating rate
446
445
446
448
445
447
446
447
446,448
447
446,447
447
447
446
449
449
453
TABLE 3. contd
Mai n- Chai n 0- Het eroat om Pol ymers VI / 231
Polymer CAS No.
T, (W Remarks Refs.
Poly(oxy-2,2,3,3,4,4,5,5-octafluorohexamethylene
oxycarbonylimino-2,2,3,3,4,4,5,5-octafluoro-
hexamethyleneiminocarbonyl)
Poly(oxyoctamethyleneoxycarbonylimino-
1,4-phenylenemethylene-1,4-phenyleneiminocarbonyl)
Poly(oxypentamethyleneoxycarbony1iminohexamethylene
iminocarbonyl)
Poly(oxypentamethyleneoxycarbonylimino-4-methyl-
1,3-phenyleneiminocarbonyl)
Poly(oxypentamethyleneoxycarbonylimino-
2,2,3,3,4,4,5,5-octafluorohexamethyleneiminocarbonyl)
Poly(oxypentamethyleneoxycarbonylimino-
l,4-phenylenemethylene-1,4-phenyleneiminocarbonyl)
Poly(oxy-2,2,3,3-tetrafluorotetramethylene
oxycarbonyliminohexamethyleneiminocarbonyl)
Poly(oxy-2,2,3,3-tetrafluorotetramethylene
oxycarbonylimino-2,2,3,3,4,4,5,5-octafluoro-
hexamethyleneiminocarbonyl)
Poly(oxytetramethyleneoxycarbonyliminohexamethylene
iminocarbonyl)
Poly(oxytetramethyleneoxycarbonylimino-4-methyl-
1,3-phenyleneiminocarbonyl)
Poly(oxytetramethyleneoxycarbonylimino-
2,2,3,3,4,4,5,5-octafluorohexamethyleneiminocarbonyl)
Poly(oxytetramethyleneoxycarbonylimino-
1,4-phenylenemethylene- 1,4-phenyleneiminocarbonyl)
Poly(oxytrimethyleneoxycarbonyliminohexamethyleneimino
carbonyl)
Poly(oxytrimethyleneoxycarbonylimino-4-methyl-
1,3-phenyleneiminocarbonyl)
Poly(oxytrimethyleneoxycarbonylimino-
1,4-phenylenemethylene- 1,4-phenyleneiminocarbonyl)
3.2. MAIN-CHAIN 0-HETEROATOM POLYMERS
3.2.1. NITROSO-POLYMERS
Poly(2-bromotetrafluoroethyliminotetrafluoroethylene)
Poly(oxy-l,l-difluoroethy1iminotetrafluoroethylene)
Poly(oxytrifluoromethyliminotetrafluoroethylene)
Polymer from trifluoronitrosomethane and
bromotrifluoroethylene
Polymer from trifluoronitrosomethane and
chlorotrifluoroethylene
Polymer from trifluoronitrosomethane and
perfluorobutadiene
Polymer from trifluoronitrosomethane and
1,1,2-trifluorobutadiene
Polymer from trifluoronitrosomethane and trifluoromethyl
trifluorovinyl ether
Polymer from trifluoronitrosomethane and trifluoromethyl
trifluorovinyl sulfide
Polymer from trifluoronitrosomethane and
hexafluoropropylene
3.2.2. POLY(SILOXANES)
Poly(ethylene) - poly(dimethylsiloxane) 50 : 50, linear
Poly(dimethylsiloxane)-1
Poly(dimethylsiloxane)-3
Poly(dimethylsiloxane)-5
Poly(dimethylsiloxane)-7
Poly(dimethylsiloxane) see Poly(oxydimethylsilylene)
Poly[di(oxydimethylsilylene)-
1,4-phenylenedimethylsilylene]
293
352
331. 281
325
306
368
282
311
215, 253,
303, 273, 332
315
306
382
328
345, 213
392
256
238
219
276
248-253
266, 230
218
268
225
264
154
150
150
150
150
9016-00-6
210
DTA heating rate
Heating rate: 10 K/min
Conflicting data
Heating rate: 10 Wmin
DTA heating rate
Heating rate: 10 Wmin
DTA heating rate
DTA heating rate
Conflicting data
Heating rate: 10 Wmin
DTA heating rate
Heating rate: 10 Wmin
Heating rate: 10 Wmin
Conflicting data
Heating rate: 10 K/min
Heating rate: 15 Wmin
No measurement details
Heating rate: 15 K/min
Heating rate: 15 Wmin
conflicting data
No measuremetnt details
DSC heating rate
No measurement details
No measurement details
DSC heating rate
449
446
446,449
446
449
446
450
450
160,261,344,429,
446
446,454
450
446
446
446,448
446
455
456
423,457-462
455,461
423
455,461
456
457
461
456
1327
1320
1320
1320
1320
478
References page VI - 253
VI / 232 CLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 3. contd
Polymer CAS No. T, WI
Remarks Refs.
Poly(disiloxane)
Poly(methylphenylsilylenemethylene)
Poly(oxydimethylsilylene)
269
331
301
9016-00-6 146
Poly(oxydimethylsilylene-
2,4,5,6-tetrafluorophenylenedimethylsilylene)
Poly(oxydimethylsilyleneoxypentylene
oxyisophthaloyloxyneopentylenedimethylsilylene)
Poly(oxydimethylsilyleneoxypentylene
oxyterephthaloyloxyneopentylenedimethylsilylene)
Poly(oxydimethylsilyleneoxydimethylsilylene-
2,4,5,6-tetrafluorophenylenedimethylsilylene)
Poly(oxydimethylsilyleneoxy-1,4-phenylene)
Poly(oxydimethylsilyleneoxy-l,4-phenyleneisopropylidene-
1,4-phenylene)
Poly(oxydimethylsilylene-
1,3-phenylenehexafluorotrimethylene-
1,3-phenylenedimethylsilylene)
Poly(oxydimethylsilylene- 1,3-phenylenetetrafluoroethylene-
1,3-phenylenedimethylsilylene)
Poly(oxydimethylsilylene-1,4-phenyleneoxy-
1,4-phenylenedimethylsilylene)
Poly[oxydi(pentafluorophenyl)silylenedi-
(oxydimethylsilylene)]
Poly(oxydiphenylsilyleneoxydimethylsilylene-
1,4-phenylenedimethylsilylene)
Poly(oxydiphenylsilylene-1,3-phenylene)
Poly[oxymethylchlorotetrafluorophenylsilylenedi-
(oxydimethylsilylene)]
Poly(oxymethylpentafluorophenylsilylene)
129- 150
150
1 4 3
245
221
238
212
363
318
265
271
293
231
N 273
-331
198
248
Poly[oxymethylpentafluorophenylsilylenedi-
(oxydimethylsilylene)]
Poly(oxymethylpentafluorophenylsilyleneoxydimethylsilylene)
190
208
Poly[oxy(methyl)phenylsilylene]
Poly(oxymethyl-3,3,3-trifluoropropylsilylene)
187
< 193
Poly[oxy(methyl)-3,3,3-trifluoropropylsilylene-
3,3-difluoropentamethylene(methyl)-
3,3,3-trifluoropropylsilylene]
Poly[oxy(methyl)-3,3,3-trifluoropropylsilylene
ethyldodecafluorohexamethyleneethylene(methyl)-
3,3,3-trifluoropropylsilylene]
Poly[oxy(methyl)-3,3,3-trifluoropropylsilylene
ethyleneeicosafluorodecamethyleneethylene(methyl)-
3,3,3-trifluoropropylsilylene]
Poly[oxy(methyl)-3,3,3-trifluoropropylsilylene
ethylenehexadecafluorooctamethyleneethylene-(methyl)-
3,3,3-trifluoropropylsilylene]
Poly[oxy(methyl)-3,3,3-trifluoropropylsilylene
ethyleneoctafluorotetramethyleneethylene(methyl)-
3,3,3-trifluoropropylsilylene]
Poly[oxy(methyl)-3,3,3-trifluoropropysilylene-
3,3,4,4-tetrafluorohexamethylene(methyl)-
3,3,3-trifluoropropylsilylene]
Poly[oxy(methyl)phenylsilyleneoxy-1,4-phenylene]
Poly[oxy(methyl)phenylsilyleneoxy
1,4-phenyleneisopropylidene- 1,4-phenylene]
Poly [oxy- 1,3-phenyleneoxy-
5-(triphenylsiloxydimethylsilyl)isophthaloyl]
235
249
262
245
248
246
368
331
376
1 3 1 3
1 3 1 3
1 4 1 7
1,6,223,243,467,
469-474,1478
1 4 7 6
1 2 5 5
1441
463 No measurement details
No measurement details 463
468,476
468.476
Mechanical method
Mechanical method
Heating rate: 32 Wmin
Heating rate: 32 TUrnin;
crystalline samples
Heating rate: 8 Wmin
No experimental details 463
DSC heating rate
DTA heating rate
No experimental details
1 1 4
463
No measurement details; [n]
only 0.2 dllg
No measurement details
463
463
463 No measurement details; [n]
only 0.24 dllg
461
421,423,464,465,
466
466 DSC heating rate
DSC heating rate 466
DSC heating rate 466
466 DSC heating rate
DSC heating rate 466
DSC heating rate 466
Low viscosity
Low viscosity
Heating rate: 32 Wmin
468
468
438
TABLE 3. contd
Main-Chain -C-!&C- and -C-S-N Polymers VI / 233
Polymer CAS No.
T, W
Remarks Refs.
Poly[oxytri(dimethylsilylenoxy)(methyl)phenylsilylene-
1,3-phenylene(methyl)phenylsilylene]
Poly[penta(oxydiethylsilylene)-
1,4-phenylenedimethylsilylene]
Poly[penta(oxydiethylsilylene)- 1,4-phenyleneoxy-
1,4-phenylenedimethylsilylene]
Poly[tetra(oxydimethylsilylene)-1,4-phenyleneoxy-
1,4-phenylenedimethylsilylene]
Poly[tetra(oxydimethylsilylene)-
1,3-phenylenedimethylsilylene]
Poly[tetra(oxydimethylsilylene)-
1,4-phenylenedimethylsilylene]
Poly(tetrasiloxane)
Poly( 1 -trimethylsilyl- l-propane)
Poly[tri(oxydimethylsilylene)oxy(methyl)-
2-phenylethylsilylene]
Poly[tri(oxydimethylsilylene)oxy(methyl)phenylsilylene]
Poly[tri(oxydimethylsilylene)oxy(methyl)trimylsiloxysilylene]
Poly[tri(oxydimethylsilylene)-
1,4-phenylenedimethylsilylene]
Poly[tri(oxydimethylsilylene-1,4-phenyleneoxy)-
1,4-phenylenedimethylsilylene]
Poly(trisiloxane)
231
1 9 3
208
221
1 9 8
201
251
623
1 7 1
201
1 4 8
211
236
281
3.2.3. POLY(SULFONATES)
Poly(4,4-cyclopentylidene diphenylene toluene-
2,4-disulfonate)
Poly(oxysulfonyl-1,3-phenylenecarbonyl-
1,3-phenylenesulfonyloxy-1,4-phenyleneisopropylidene-
1,4-phenylene)
Poly(oxysulfonyl-1,3-phenylenesulfonyloxy-
1,4-phenyleneisoproplyidene- 1,4-phenylene)
407
395
- 385
3.3. MAIN-CHAIN -C-(S),-C- AND -C-S-N- POLYMERS
3.3.1. POLY(SULFlDES)
Poly(dithiodecamethylene)
Poly(dithioethylene)
Poly(dithiohexamethylene)
Poly(dithiomethylene- 1,4-phenylenemethylene)
Poly(dithiopentamethylene)
Poly(oxycarbonyloxy-2-methyl-1,4-phenylenethio-3-methyl-
1,4-phenylene)
Poly(oxycarbonyloxy- 1 ,Cphenylenethio- 1,4-phenylene)
Poly(oxyethylenedithioethylene)
Poly(oxyethylenetetrathioethylene)
Poly(oxymethyleneoxyethylenedithioethylene)
Poly(oxymethyleneoxytetramethylenedithiotetramethylene)
Poly(oxytetramethylenedithiotetramethylene)
Poly(phenylene sulfide)
10% m-phenylene
Poly(p-phenylene sulfide)
Poly(p-phenylene sulfide) + HXlOOO,amorphous LCP
Poly(p-phenylene sulfide) + HX4000, amorphous LCP
Poly(tetrathiodecamethylene)
Poly(tetrathioethylene)
Poly(tetrathiomethylene- 1,4-phenylenemethylene)
Poly[thio-1-(allyloxymethyl)ethylene]
Poly(thiocarbony1 fluoride) see Poly(thiodifluoromethylene)
208
246
199
296
201
340
- 383
220
233
214
1 9 7
1 9 7
359
383
341
353
365
363
445
433
1 9 7
249
276
213
DTA heating rate
DSC heating rate
DTA heating rate
DTA heating rate
DSC heating rate
DSC heating rate
DSC heating rate
DTA heating rate
302
302
302
302
302
302
1313
1538
415
475
475
302
302
1313
Mechanical method
1407
361
Not well defined; mechanical
met hod
361
DTA heating rate
Mechanical method
DTA heating rate
No experimental details
489
248,249
248
249,489
248
338
DTA heating rate
Mechanical method
Under reactants
(diiodobenzene and phenyl
ethylene)
DTA heating rate
DTA heating rate
367
248,249
248
248,249,283
248
248,249
1497
1432
1497
1290
1454
1488
1396
1396
489
248,249
489
220
References page VI - 253
VI / 234 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 3. contd
Polymer
CAS No. T, (K)
Remarks Refs.
Poly(thio- 1,2-cyclohexylene)
Poly(thio-1,3-cyclohexylene)
Poly(thioethylene)
Poly(thiodifluoromethylene)
Poly(thio-2&dimethylene) Poly(thioisobutylene)
Poly(thio-1-ethylethylene)
Poly(thio-2-ethyl-2-methyltrimethylene)
Poly(thiomethylene)
Poly(thio-1-methyltrimethylene)
Poly(thioneopentylene)
Poly(thio- 1,Cphenylene)
24936-67-2
26373-01-3
- 256, N 228
221
223
r-., 253
1 5 5
259
218
N 223
218
214
233
370
Conflicting data
DTA heating rate
DTA, quenched possibly
Interpretation difficult
DTA, quenched
No measurement details
DSC heating rate
Heating rate: 20 Wmin
DSC heating rate
Poly(thiopropylene)
PolyQhiotrimethylene)
Poly(trithiodecamethylene)
Poly(trithiomethylene- 1,4-phenylenemethylene)
Thiokols see Poly(thiomethylene)s
226
N 228
203
291
Conflicting data
DTA heating rate
DTA heating rate
479,480
480
1174
481-483
484-486
1 1 7 5
220
1 6 0
482
490
160,480
305,307,
493,494
220,482,483,
495,496
480,487,488
489
489
3.3.2. POLY(SULFONES) AND POLY(SULFONAMIDES)
Camphorquinone in poly(sulfone)
Poly(ary1 ether sulfone)
Poly [di(oxy-1,4-phenylene)sulfonyl- 1,4-phenylene]
Poly(ether ether sulfone)
Poly(ether sulfone)
Poly(ether sulfone ketone), aromatic
Poly(oxy-2-acetoxytrimethyleneoxy- 1,4-phenylenesulfonyl-
1 ,Cphenylene)
Poly(oxy-4,4-biphenylyleneoxy-1,4-phenylenesulfonyl-
1,4-phenylene)
Poly[oxycarbonyldi(oxy-1,4-phenylene)sulfonyl-
1,4-phenyleneoxy- 1 ,Cphenylene]
Poly(oxycarbonylneopentylenesulfonylneopentylene)
Poly(oxy-2-hydroxytrimethyleneoxy- 1,4-phenylenesulfonyl-
1,4-phenylene)
Poly(oxyneopentylenesulfonylneopentyleneoxyc~bonylimino
hexamethyleneiminocarbonyl)
Poly(oxy-5-pentyloxyisophthaloyloxy-
1,4-phenylenesulfonyl- 1,4-phenylene)
Poly(oxy- 1,4-phenyleneisopropylidene- 1 ,Cphenyleneoxy-
1,4-phenylene-sulfonylmethyliminotetramethylene-
methyliminosulfonyl- 1 ,Cphenylene)
Poly(oxy-LCphenylenesulfinyl-1,4-phenyleneoxy-
1,4-phenylenecarbonyl- 1 ,4-phenylene)
Poly(oxy- 1,4-phenylenesulfinyl- 1,4-phenyleneoxy-
1,4-phenyleneisopropylidene- 1 ,Cphenylene)
Poly(oxy-l,4-phenylenesulfonyl-4,4-biphenylylenesulfonyl-
1,4-phenylene)
Poly(oxy-l,4-phenylenesulfonyl-2,7-naphthylenesulfony1-
1,4-phenylene)
Poly(oxy- 1,4-phenylenesulfonyl- 1,4-phenylene)
458
520
393-433
483
483
498
440-479
403
Mechanical method
1316
1507
1378
1 1 6
1270
1432,1487
1514
219
503 Mechanical method
1 1 6
-478 Mechanical method
323
1 6 0
428
219
303
1 6 0
Heating rate: 20 K/min;
qinh only 0.11
Mechanical method
443
393
1 1 6
478 Mechanical method 1 1 6
438 Mechanical method 1 1 6
533
523
1 8 4
116,184,
314- 316
Calculated T, for
infinite molecular weight:
511K (Ref. 316)
Mechanical method
487
478
1 1 6
508 Mechanical method 1 1 6
Poly(oxy- 1,4-phenylenesulfonyl- 1,4-phenyleneoxy-2-chloro-
1,4-phenyleneisopropylidene-3-chloro-l,Cphenylene)
Poly(oxy- 1,4-phenylenesulfonyl- 1 ,Cphenyleneoxy-
2,6-dimethyl- 1,4-phenyleneisopropylidene-3,5-dimethyl-
1,4-phenylene)
Poly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-
1,4-phenylenecarbonyl- 1 ,Cphenylene)
Poly(oxy- 1,4-phenylenesulfonyl- 1 ,Cphenyleneoxy-
1,4-phenylenecyclohexylidene-1,4-phenylene)
478 Mechanical method 1 1 6
478 Mechanical method 1 1 6
TABLE 3. contd
Main-Chain -C-N-C- Polymers VI / 235
Polymer CAS No. T, W) Remarks Refs.
Poly(oxy-1,4-phenylenesulfonyl- 1,4-phenyleneoxy-
1,4-phenyleneethylidene- 1,3-cyclohexylene- 1,4-phenylene)
Poly(oxy- 1,4-phenylenesulfonyl- 1 ,Cphenyl
(1,4-phenylene)neoxy- 1,4-phenylenehexafluoro
-2,2-propylidene- 1,4-phenylene)
Poly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-
1,4-phenyleneisobutylidene- 1,4-phenylene)
Poly(oxy- 1,4-phenylenesulfonyl- 1,4-phenyleneoxy-
1,4-phenyleneisopropylidene- 1 ,Cphenylene)
Poly(oxy- 1,4-phenylenesulfonyl- 1,4-phenyleneoxy-
1,4-phenylenemethylene- 1 ,Cphenylene)
Poly(oxy- 1,4-phenylenesulfonyl- 1,4-phenyleneoxy-
1,4-phenylenemethylphenylmethylene- 1 ,Cphenylene)
Poly(oxy- 1,4-phenylenesulfonyl- 1,4-phenyleneoxy-
1,4-phenylene-2,2norbomylene- 1,4-phenylene)
Poly(oxy- 1,4-phenylenesulfonyl- l,Cphenyleneoxy-
1,4-phenylenediphenylmethylene- 1,4-phenylene)
Poly(oxy- 1,4-phenylenesulfonyl- 1,4-phenyleneoxy-
1,4-phenylenethio- 1,4-phenylene)
Poly(oxy-1,4-phenylenesulfonyl-
1,4-phenyleneoxyterephthaloyl)
Poly(oxyterephthaloyloxyneopentylene
sulfonylneopentylene)
Poly(oxytetramethyleneoxy- 1,4-phenyleneisopropylidene-
1,4-phenyleneoxy- 1,4-phenylenesulfonyl- 1 ,Cphenyleneoxy
1,4-phenyleneisopropylidene- 1,Cphenylene)
Poly(sulfone)
Polysulfone of Bisphenol A and diphenylene sulfone
Poly(sulfonyl-1,2-cyclohexylene)
Poly(sulfonyl- 1,3-cyclohexylene)
Poly(sulfonylneopentylene)
Poly(sulfonyl- 1,4-phenylenemethylene- 1 ,Cphenylene)
Poly [tri(oxy- 1,4-phenylene)sulfonyl- 1 ,Cphenylene] 453
3.3.3. POLY(THIOESTERS)
Poly(thio-3-methyl-6-oxohexamethylene) 293
Poly(thio- 1 -methyl-3-oxotrimethylene) 285
Poly(thio-6-oxohexamethylene) 292
3.4. MAIN-CHAIN -C-N-C- POLYMERS
3.4.1. POLY(AMIDES)
Nylon
Nylon 3 [Poly(imino- 1 -oxotrimethylene)]
Nylon 4,6 [Poly(iminotetramethyleneiminoadipoyl)]
Nylon 5,6 [Poly(iminopentamethyleneiminoadipoyl)]
Nylon 6 [Poly(imino-1-oxohexamethylene)]
323
384
50327-22-5 316
318
25038-54-4
-
373
313-360
27% crys.
Nylon 6,2 [Poly(iminooxalyliminohexamethylene)]
Nylon 6,6 [Poly(iminoadipoyliminohexamethylene)]
503
478
473
449
453
473
523
503
448
522
378
413
25135-51-7 459
460
459
401
381
386
497
228
326-327
427-432
32131-17-2 = 323
Mechanical method
Mechanical method
Mechanical method
Mechanical method
Mechanical method
Mechanical method
Mechanical method
Mechanical method
Heating rate: 20 Wmin
? DTA heating rate; n low
Mechanical method
Heating rate: 20 Wmin
Heating rate: 20 Wmin
Heating rate: 20 K/min
Heating rate: 40 Wmin
calculated T, at infinite
molecular weight; 5 11 K
Mechanical method
DTA heating rate
DTA heating rate
Crystalline, DTA heating rate
Dynami c met hod
Heating rate: 2 K/min
Dilatomer, dry
Conflicting data,
values -313-325K
DSC, torsion tester, TH
DSC, TMA, DTA, annealed
Conflicting data,
most values about
323 K
116
116
116
102,116,262,
287,316-323
116
116
116
116
116
313
160
116
1320
1432
1254
480
480
160,480
316
116
497
498
499
1320
502
503
504,505
1181,1193
1187
1,75,101,122,
187,191,261,
262,3 18,394,
396,399,416,
506-520
1366
1176
1188
6,75,78,161,
170,171,191,
234,261,262,
272,317,326,
344,381,388,
References page VI - 253
VI / 236 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 3. contd
Polymer CAS No.
T, (K)
Remarks Refs.
21% cry.
Nylon 6,7 [Poly(iminohexamethyleneiminopimeloyl)]
Nylon 6,8 [Poly(iminohexamethyleneiminosuberoyl)]
Nylon 6,9 [Poly(iminohexamethyleneiminoazelaoyl)]
Nylon 6,lO [Poly(iminohexamethyleneiminosebacoyl)]
28757-63-3
9008-66-6
19% cry.
Nylon 6,12 [Poly(iminohexamethyleneiminododecanedioyl)] 24936-74-l
Nylon 7 [Poly(imino-1-oxoheptamethylene)]
Nylon 7,6 [Poly(iminoadipoyhminoheptametbylene)]
Nylon 7,7 [Poly(iminopimeloyliminoheptamethylene)]
Nylon 8 [Poly(imino-1-oxooctamethylene)]
Nylon 8,2 Poly[(iminooxalyliminooctamethylene)]46% crys.
Nylon 8,6 [Poly(iminoadipoyliminooctamethylene)]
Nylon 8,lO [Poly(iminooctamethyleneiminodecanedioyl}]
Nylon 8,12 [Poly(iminoctamethyleneiminododecanedioyl)]
Nylon 8,22 [Poly(iminooctamethyleneiminodocosanedioyl)]
Nylon 9 [Poly(imino-1-oxononamethylene)] 25035-03-4,
25748-72-5
Nylon 9,6 [Poly(iminoadipoyliminononamethylene)]
Nylon 10 [Poly(imino-1-oxodecamethylene)]
Nylon 10,2 54% crys.
Nylon IO,6 [Poly(iminoadipoyliminodecamethylene)]
Nylon 10,lO [Poly(iminosebacoyliminodecametbylene)]
Nylon lo,12 [Poly(iminodecamethyleneiminododecanedioyl)]
Nylon 11 [Poly(imino-1-oxoundecamethylene)] 25035-04-5
19% crys.
Nylon 12 [Poly(imino-1-oxododecamethylene)]
26% crys.
24937-16-4
Nylon 12,2 33% crys.
Nylon 12,18 [Poly(iminododecamethyleneiminooctadecanedioyl)]
Nylon 13 [Poly(imino-1-oxottidecametbylene)]
Nylon 14,18 [Poly(iminotetradecamethyleneiminooctadecanedioyl)]
Nylon 18,18 [Poly(iminooctadecanedioyliminooctadecamethylene)]
Polyamide of 1,7-bis(aminophenoxy)napthalene and
dicarboxylic acid
Polyamide of 2,4-biphenyldiamine
Polyamide of bis(4-carboxyphenyl)phenylphosphene oxide
Poly(amide-sulfonamide)
Poly(N,N-bis(4-amino-4-biphenylene isophthalamide))
Poly(y-benzyl L-glutamate)
Poly(butyliminohexafluoroglutary1
butyliminohexamethylene)
Poly(butylimino-2,2,3,3,4,4-
hexafluoropentamethylenebutyliminoadipoyl)
Poly(s-caprolactam) see Nylon 6 25038-54-4
Poly(3,Cdibenzyl terephthalamide)
Poly[di(oxyethylene)oxycarbonyliminohexayleneimino
carbonyl]
Poly(ethyliminohexafluoroglutarylethyliminohexamethylene)
330- 331
341
331
330
331
323
318
319
-
325
318, 333
328
323
373
359
318
333
323
321
-
319
318
315
330
313
333,319
322
315
316, 365
333-343
-
313-316
314
330-333
323
314
321
323
412-536
521-557
498-527
> 523
498-508
N 288
N 293
283-288
476
518-600
212
+a 218
DSC, torsion tester, TH
Heating rate: 0.5 Wmin
Variable data below
323 K
DSC, torsion tester, TH
Heating rate: 0.5 K/min
Conflicting data
Heating rate: 0.5 Wmin
Penetration, quenched
Penetration, annealed
Heating rate: 2 K/min
Heating rate: 2 Wmin
Dynami c met hod
Dynami c met hod
Estimated
DSC, TMA, anneal ed
Heating rate: 2 Wmin
Conflicting data
Dynami c met hod
DSC, torsion tester, TH
Transitions affected by thermal
history and relaxation effects
DSC, torsion tester, TH
Affected by thermal
history and relaxation
effects
DSC, TMA
Dynami c met hod
Dynami c met hod
Dynami c met hod
Dynami c met hod
Brittle point
Brittle point
Heating rate: l-2 Wmin
Brittle point
394,396,399,
506,510,521,
522-533
1177
1254
492,506
506
5 2 1
75,161,167,191,
399,503,505,506,
528534,535
1178
506,535,536
1183
191,506,537,538
282,492,505,506
506
1184,538
1190
1189
505
505
535
535
1182
506,537,538
504
538
1 1 9 1
505
505,506
535
1 1 8 5
1179
538
1483
1186
1180
75,520,538
1192
535
538
535
535,536
1 4 9 1
1 5 1 1
1 4 4 5
1510
1392
273
539
1 4 0 8
1429
245
TABLE 3. contd
Main-Chain -C-N-C- Polymers VI / 237
Polymer CAS No.
T, (K)
Remarks Refs.
Poly(ethylimino-2,2,3,3,4,4-
hexafluoropentamethyleneethyliminoadipoyl)
Poly(hexamethylene adipamide) see Nylon 6,6
Poly(hydroxyamide ether)
Poly(iminoadipoylimino- 1,4-cyclohexylenemethylene)
1,4-cyclohexylene) 98% tram/tram, 2% cisltrans
Poly(iminoadipoyliminomethylene-2,5-dimethyl-
1,4-phenylenemethylene)
Poly(iminoadipoyliminotrimethylenefluoren-
9-ylidenetrimethylene)
Poly(iminoadipoyliminotrimethyleneisobutylphosphinidene
trimethylene)
Po1y(iminoadipoyliminotrimethy1enemethyliminot~methylen~
Poly(iminoadipoyliminotrimethylenemethylinylidene-
tetramethylene)
Poly(iminoadipoy1iminotrimethylenemethylphosphinylidene
trimethylene)
Poly(iminoadipoyliminotrimethyleneoctylphosphinylidene
trimethylene)
Poly[iminoadipoyliminotrimethylene-
(phenylphosphinidene)trimethylene]
Poly[iminoadipoyliminotrimethylene-
(phenylphosphinylidene)trimethylene]
Poly[imino-5-tert-butylisophthaloylimino-
(2,5dimethylhexamethylene)]
Poly[imino-5-terr-butylisophthaloylimino-
(3,4-dimethylhexamethylene)]
Poly(imino-5-tert-butylisophthaloyliminohexame~ylene)
Poly(imino-5-rerr-butylisophthaloyliminomethylene-
1,4-cyclohexylenemethylene)
Poly(imino-5-rerr-buty1isophthaloyliminomethylene-
1,3-phenylenemethylene)
Poly(imino-5-tert-butylisophtha1oy1iminome~ylene-
1,4-phenylenemethylene)
Poly(iminocarbonyl- 1,3-
adamantylenecarbonyliminohexamethylene)
Poly(iminocarbonyl-2,2-
biphenylylenecarbonyliminotrimethylenefluoroen-
9-ylidenetrimethylene)
Poly(iminocarbonyl- 1,4-cyclohexylenemethylene)
Poly(iminocarbonyl- 1,4-phenylene-
2-oxoethyleneiminohexamethylene)
Poly(imino-1,4-cyclohexylenemethylene-
1,4-cyclohexyleneiminododecanedioyl) 98% fransham,
2% cisltrans
Poly(imino-1,4-cyclohexylenemethylene-
1,4-cyclohexyleneiminosebacoyl) 98% transltrans,
2% cisltrans
Poly(imino-2,2-dimethylpentamethyleneiminoadipoyl)
Poly(imino-2,2-dimethylpentamethyleneiminoazelaoyl)
Poly(imino-2,2-dimethylpentamethyleneiminopimeloyl)
Poly(imino-2,Z
dimethylpentamethyleneiminoterephthaloyl)
Poly(iminoethylene- 1,4-phenyleneethyleneimino-
1,16-dioxohexadecamethylene)
Poly(iminoethylene- 1,4-phenyleneethyleneimino-
1,18-dioxooctadecamethylene)
Poly(iminoethylene-1,4-phenyleneethyleneimino-
1,14-dioxotetradecamethylene)
Poly(iminoethylene- 1,4-phenyleneethyleneimino-
1,l 1-dioxoundecamethylene)
Poly(iminoethylene- 1,4-phenyleneethyleneiminosebacoyl)
Poly(iminoglutarylimino-2,2-dimethylpentamethy1ene)
Poly(iminohexamethyleneiminocarbonyl-
2,2-biphenylenecarbonyl)
293
32131-17-2
363-406
458
343
393
344
:)
278
332
332
285
322
328
422
446
436
509
465
477
N 385
438
466
377
408
417
350
336
344
430
358
348
366
369
378
355
400
Brittle point
T, depends on cisltrans isomer
content
DTA heating rate
Mechanical method, heating
rate: 1 Wmin
DTA heating rate
DTA heating rate
DTA heating rate
DTA heating rate
539
1439
540
303
78,161
492
492
492
492
492
492
492
DTA heating rate
DTA heating rate
DTA heating rate
DTA heating rate
DTA heating rate
DTA heating rate
Values from 378 to 393 K
obtained
Mechanical method, heating
rate: 1 Wmin
453
453
453
453
453
453
255
78,161
DTA heating rate
Heating rate: 20 K/mm
T, depends on cisltrans isomer
content
517
5 4 1
540
T, depends on cisltrans isomer
content
540
DTA heating rate
DTA heating rate
DTA heating rate
DTA heating rate
Dynami c met hod
Dynami c met hod
Dynami c met hod
Dynami c met hod
Dynami c met hod
DTA heating rate
Mechanical method, heating
rate: 1 Wmin
542
542
542
308
536
536
536
536
536
542
78,161
References page VI - 253
VI / 238 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 3. contd
Remarks Refs.
Polymer CAS No. T, (K)
165
Poly(iminohexamethyleneiminocarbonyl-1,4-phenylene-
2,2-butylidene-1,4-phenylenecarbonyl)
Poly(iminohexamethyleneimino-4-methylpimeloyl)
Poly(iminohexamethyleneimino-l-oxotrimethylenefluoren-
421-437
323
395
521
78,161 Mechanical method, heating
rate: 1 Wmin 9-ylidene-3-oxotrimethylene)
Poly(iminohexamethyleneimino-l-oxotrimethylene-
phenylphosphinothioylidene-3-oxotrimethylene)
Poly(iminohexamethyleneimino-l-
oxotrimethylenephenylphosphinylidene-3-oxo~me~ylene)
Poly(iminoisophthaloylimino-4,4-biphenylylene)
Poly(iminoisophthaloylimino-3,4-dimethylhexame~ylene)
Poly(iminoisophthaloylimino-2,2-dimethylpentamethylene)
Poly(iminoisophthaloyliminohexamethylene)
Poly(iminoisophthaloyliminomethylene-
1,4-cyclohexylenemethylene)
Poly(iminoisophthaloyliminomethylene-
1,3-phenylenemethylene)
Poly(iminoisophthaloyliminooctamethylene)
Poly(iminoisophthaloylimino-l,4-phenylenemethylene-
1,4-phenylene)
Poly(iminoisophthaloyliminotrimethylenefluoren-
9-ylidenetrimethylene)
Poly(iminomesaconoyliminodecamethylene)
Poly(iminomesaconoyliminohexamethylene)
Poly(iminomesaconoyliminomethylene-
1 $phenylenemethylene)
Poly(imino-3-methyladipoyliminohexamethylene)
Poly(iminomethylene-Werr-butyl-
1,3-cyclohexylenemethyleneiminoisophthaloyl)
Poly(iminomethylene-5.rerr-butyl-
1,3-phenylenemethyleneiminoadipoyl)
Poly(iminomethylene-5-tert-butyl-
1,3-phenylenemethyleneiminoisophthaloyl)
Poly(iminomethylene-1,3-cyclohexylenemethyleneimino-
5-terr-butylisophthaloyl)
Poly(iminomethylene-
1,3-cyclohexylenemethyleneiminoisophthaloyl)
Poly[iminomethylene(2.5-dimethyl-
1,4-phenylene)methyleneiminosuberoyl]
Poly(iminomethylene-
1,3-phenylenemethyleneiminoadipoyl)
Poly(iminomethylene-
1,3-phenylenemethyleneiminocarbonyl-
2,2-biphenylenecarbonyl)
Poly[iminomethylene-1,4-
phenylenemethyleneiminocarbonyl
(1,3,3-trimethyl-5-oxopentamethyl)]
Poly(iminomethylene-
1,4-phenylenemethyleneiminododecanedioyl)
Poly(iminomethylene-
1,4-phenylenemethyleneiminooctadecanedioyl)
Poly(iminomethylene-1,3-phenylenemethyleneimino-
l-oxotrimethylenefluoren-9-ylidene-3-oxotrimethylene)
Poly(iminomethylene-
1,4-phenylenemethyleneiminopentadecanedioyl)
Poly(iminomethylene-
1,4-phenylenemethyleneiminosebacoyl)
Poly(iminomethylene-
1,4-phenylenemethyleneiminotridecanedioyl)
Poly(iminomethylene-
1,4-phenylenemethyleneiminoundecanedioyl)
Poly(iminomethylene-1,3,3-trimethyl-
1,5-cyclohexyleneiminoadipoyl)
Poly(iminomethylene-1,3,3-trimethyl-
cyclohexyleneiminoterephthaloyl)
316 4 9 2
492 302
311,312
453
308
78,161,255,543
453
558
398
426
390
481
DTA heating rate
DSC heating rate
DTA heating rate
DSC heating rate
78,161,453 438
388
< 500
448
Mechanical method,
heating rate: 1 Wmin
Dynami c met hod
Dynami c met hod
Mechanical method 78,161
Heating rate: 16 Wmin
Heating rate: 16 K/min
Heating rate: 16 Wmin
DTA heating rate
DSC heating rate
347
367
408
492
453
290
482
382 DTA heating rate
DSC heating rate
453
461
413
453
DTA heating rate
453 DSC heating rate
DTA heating rate
303
351
346
18 Mechanical method, heating
rate: 1 Wmin
Mechanical method, heating
rate: 1 Wmin
78
432
3 8 1
398 No experimental details
491,536
378
348 Dynami c met hod
Mechanical method, heating
rate: 1 Wmin
Dynami c met hod
Dynami c met hod
Dynami c met hod
536
78,161
423
363
388
536
536
536
373
380 491.536
No experimental details 3 8 1
433
473 3 8 1 No experimental details
TABLE 3. contd
Polymer CAS No.
T, 6)
Main-Chain -C-N-C- Polymers
Remarks
VI 1239
Refs.
Poly(imino-5-methylisophthaloyliminohexamethylene)
Poly(imino-1-methyl-3-oxotrimethylene)
Poly(imino-1,5-naphthyleneiminoisophthaloyl)
Poly(imino- 1,5-naphthyleneiminoterephthaloyl)
Poly(iminooctamethyleneimino-l-oxoethylene-
1,4-phenylene-2-oxoethylene)
Poly(iminooxalylimino-2,2-dimethylpentamethylene)
Poly(imino- 1 -oxoethylene- 1,4-phenylene-
2-oxoetbyleneiminooctadecamethylene)
Poly(imino-1-oxotrimethylenefluoren-9-ylidene-
3-oxotrimethyleneiminotrimethylenefluoren-
9-ylidenetrimethylene)
Poly(imino- I-oxotrimethylene- 1,4-phenylene-
3-oxotrimethyleneiminododecamethylene)
Poly(imino-1-oxotrimethylene-1,4-phenylene-
3-oxotrimethyleneiminooctadecamethylene)
Poly(iminopentamethyleneiminocarbonyl-1,4-phenylene-
2-oxoethylene)
Poly(iminopentamethyleneiminoterephthaloy1)
Poly(imino-1,3-phenyleneiminocarbonyl-
1,3-adamantylenecarbonyl)
Poly(imino-1,3-phenyleneiminoisophthaloyl)
Poly(imino- 1,4-phenyleneiminoisophthaloyl)
Poly(imino-l,3-phenyleneimino-5-methylisophthaloyl)
Poly(imino- 1,3-phenyleneiminosebacoyl)
Poly(imino- 1,3-phenyleneiminoterephthaloyl)
Poly(imino- 1,4-phenyleneiminoterephthaloyl)
Poly(iminoterephthaloylimino-
4,4-biphenylylene)
Poly(iminoterephthaloylimino-3-ethylhexamethylene)
Poly(iminoterephthaloylimino-3-isopropylhex~e~ylene)
Poly(iminoterephthaloyliminododecamethylene)
Poly(iminoterephthaloyliminoheptamethylene)
Poly(iminoterephthaloyliminohexamethylene)
Poly(iminoterephthaloyliminononamethylene)
Poly(iminoterephthaloyliminomethylene-2.5-dimethyl-
1,4-phenylenemethylene)
Poly(iminoterephthaloylimino-
4$dimethylheptamethylene)
Poly(iminoterephthaloylimino-
1,4,4&methylheptamethylene)
Poly(iminoterephthaloylimino-
2,2,4-trimethylheptamethylene)
Poly(iminoterephthaloylimino-
2,4,4-trimethylheptamethylene)
Poly(iminoterephthaloylimino-1,4-phenylenemethylene-
1,4-phenylene)
Poly[imino(tetrachloroterephthaloyl)iminohexame~ylene~
Poly(iminotetramethyleneiminocarbonyl- 1,4-phenylene-
2,2-butylidene- 1,4-phenylenecarbonyl)
Poly(iminotetramethyleneiminocarbonyl-l,4-phenylene-
2-oxoethylene)
Poly(iminotrimethylenefluoren-9-
ylidenetrimethyleneiminosebacoyl)
Poly(iminotrimethyleneiminocarbonyl- 1,4-phenylene-
2-oxoethylene)
Poly(imino-2,2,4-trimethylpentamethyleneiminoadipoyl)
Poly(isopropyliminohexafluoroglutarylisopropyli~nohexa-
methylene)
Poly(isopropylimino-2,2,3,3,4,4-hexafluoro-
pentamethyleneisopropyliminoadipoyl)
Poly(methyliminohexafluoroglutarylmethyliminohexa-
methylene)
393
369
598
518
383
382
351
438
358
338
316
- 500
580
553
< 500
578
383
<500
618
613
403
416
393
470
413
388
498
425
423
418
421, 432
< 500
71164-49-3 569
446-455
357
358
382
338
- 293
303-308
298- 303
Crystalline; DTA heating rate
DTA heating rate
Heating rate: 10 Wmin
Dynamic method
DTA heating rate
Dyamic met hod
Mechanical method, beating
rate: 1 Wmin
Dynamic method
Dynamic method
Heating rate: 20 Wmin
Dynami c met hod
Heating rate: 32 Wmin
Mechanical method,
heating rate: 2 Wmin
Dynami c met hod
Heating rate: 32 Wmin
Dynami c met hod
Dynami c met hod
Heating rate: 10 Wmin
DTA heating rate
DSC heating rate
DSC heating rate
Dynami c met hod
Dynami c met hod
No experimental details
No experimental details
DTA heating rate
No experimental details
DTA heating rate
DSC heating rate
Two different samples; DSC
heating rate
Dynamic method
DSC, HR 16 deg/min, f(MW)
Heating rate: 20 K/min
Mechanical method, heating
rate: 1 Wmin
Heating rate: 20 Wmin
No measurement details
Brittle point
Brittle point
Brittle point
255
502
312
312
536
542
536
78
536
536
541
518
255
311,518,546
311
255
544
311
311,312
311,312
381
381
543,541
518
381
381
303
381
548
262,381
381
311
1194
1 6 5
541
78, 161
541
381
539
539
539
References page VI - 253
VI f 240 CLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 3. contd
Polymer CAS No. T, (K)
Remarks Refs.
Poly(methylimino-2,2,3,3,4,4-hexafluoro-
pentamethylenemethyliminoadipoyl)
Poly(2-methylpentamethylene terephthalamide) amorphous
crystalline
drawn fiber
Poly( 1,3,4-oxidiazole-amide)
Poly(oxytrimetbyleneiminoadipoy1iminotrimethylene)
Poly(oxy-3-oxotrimetyleneiminomethylene-2,5-dimethyl-
1,4-phenylenemethyleneimino- 1-oxotrimetbylene)
Poly(oxy-5-oxopentamethyleneiminomethylene-
1,4-phenylenemethyleneimino-l-oxopentametbylene)
Poly(oxy-l,4-phenylenecarbonylimino-2,2-dimethyl-
pentamethyleneiminocarbonyl- 1 ,Cphenylene)
Poly(oxy-1,4-phenylenecarbonylimino-
1,4-phenylenesulfonyl- 1,4-phenyleneiminocarbonyl-
1,4-phenylene)
Poly(oxy- 1,4-phenyleneiminoisophthaloylimino-
1,4-phenylene)
Poly(oxy-1,4-phenyleneiminoterephthaloylimino-
1,4-phenylene)
Poly@-phenylene terephthalamide) Kevlar
Poly(N-phenyl-2-hydroxytrimethylene amine)
Poly(phenylquinoxaline-imide-amide)
Poly(sulfonyl-1,3-phenyleneiminoadipoylimino-
1,3-phenylene)
Poly(sulfonyl- 1,3-phenyleneiminoadipoylimino-
1,4-phenylene)
Poly(sulfonyl- 1,3-phenyleneiminoazelaoylimino-
1,3-phenylene)
Poly(sulfonyl-1,4-phenyleneiminoazelaoylimino-
1 ,Cphenylene)
Poly(sulfonyl-1,3-phenyleneiminocarbonyl-
1,4naphthylenecarbonylimino- 1,3-phenylene)
Poly(sulfonyl-1,4-phenyleneiminocarbonyl-
1,4-naphthylenecarbonylimino- 1,4-phenylene)
Poly(sulfonyl- 1,4-phenyleneiminocarbonyl-
1,4-phenylenemethylene- 1,4-phenylenecarbonylimino-
1,4-phenylene)
Poly(sulfonyl-1,3-phenyleneiminododecanedioylimino-
1,3-phenylene)
Poly(sulfonyl-1,4-phenyleneiminododecanedioylimino-
1 ,cphenylene)
Poly(sulfonyl-l,3-phenyleneiminoisophthaloylimino-
1,3-phenylene)
Poly(sulfonyl- 1,4-phenyleneimino-2-methoxy-
isophthaloylimino- 1 ,Cphenylene)
Poly(sulfonyl- 1,4-phenyleneiminopimeloylimino-
1 ,Cphenylene)
Poly(sulfonyl-1,3-phenyleneiminosebacoylimino-
1,3-phenylene)
Poly(sulfonyl- 1,4-phenyleneiminosebacoylimino-
1 ,Cphenylene)
Poly(sulfonyl-1,3-phenyleneiminosuberoylimino-
1,3-phenylene)
Poly(sulfonyl- 1,4-phenyleneiminosuberoylimino-
1,Cphenylene)
Poly(sulfonyl-1,4-phenyleneiminoterephthaloyl-
1,4-phenylenecarbonylimino-1,Cphenylene)
Poly(terephthalamide), pendant ester
Poly(thio- 1 l-oxoundecamethyleneiminoethylene-
1,4-phenyleneetbyleneimino- 1-oxoundecamethylene)
Poly(tbio-3-oxotrimethyleneiminohexamethyleneimino-
I-oxotrimethylene)
298-303
416
424
453
498-545
307
353
343
428
571
463. 554
613
508
343
557- 581
413
467
398
451
<573
<573
< 573
380
433
573-593
568-583
436
385
444
398
453
590
451-490
331
287-300
Brittle point
DTA heating rate
Estimated from copolymer data
DTA heating rate
Softening point
Conflicting data
Heating rate: 10 Wmin
DTA heating rate
DTA heating rate
DTA heating rate
DTA heating rate
Softening point; mechanical
met hod
Softening point; mechanical
met hod
Softening point
DTA heating point
DTA heating point
Softening point; mechanical
met hod
Softening point
DTA heating point
DTA heating point
DTA heating point
DTA heating point
Softening point
Softening point; mechanical
met hod
Dynamic method; low viscosity
539
435
1 4 3 5
1 4 3 5
1 3 8 8
282
303
304
3 0 8
309
130,311,312
311,312
1 4 3 2
1408
1 3 8 9
500,501
500,501
500,501
500,501
3 0 9
3 0 9
3 0 9
500,501
500,501
3 0 9
309
500,501
500,501
500,501
500,501
500,501
309
1 4 6 2
4 9 1
492
Td
-
PC
-
P C
P C
P C
P C
3.1
P C
P C
P C
P C
P C
P C
P C
P C
P C
3.2
Pf
Pk
PC
PC
PC
PC
PC
PC
PC
PC
PC
P C
PI
P I
P I
3.
PI
P I
P I
PI
P I
P I
PI
PI
PI
P
P
P
P
P
P
TABLE 3. contd
Polymer CAS No.
T, 6)
Main-Chain -C-N-C- Polymers VI 1241
Remarks Refs.
Poly(thio-7-oxoheptamethyleneiminomethylene-
1,4-phenylenemethyleneimino-1-oxoheptamethylene)
Poly(thio-5-oxopentamethyleneiminomethylene-
1,4-phenylenemethyleneimino- 1-oxopentamethylene)
Poly(tridecanolactone)
Poly[tri(oxyethylene)oxycarbonyliminohexame~yleneimino
carbonyl]
3.4.2. POLY(ANILINES)
Poly(aniline)
Poly(4-(methacryloyloxy)acetanilide)
Poly(4-(2-methacryloyloxy)ethyloxy)acetanilide)
Poly(4-(6-methacryloyloxy)hexyloxy)acetanilide)
Poly(2-methyl-4-nitro-[N,N-bis(2-hydroxyetyl)]-aniline)
Poly(2-methyl-4-nitrophenylazo)-[N,N-bis(2-hydroxyethyl)]-
aniline)
Poly(4-nitrophenylazo)-[Nslr-bis(2-hydroxye~yl)]-aniline)
Poly([2(4-nitrophenylethylenyl)]-[N,N-bis(2-hydroxyethyl)]-
aniline)
Poly(4-tricyanovinyl-[N,N-bis(2-hydroxye~yl)]-aniline)
3.4.3. POLY(IMIDES)
Phenylethynyl-terminated imide, cured
Phenylethynyl-terminated imide, uncured oligomer (6300 M,)
Poly(imide) of 3,3-bis
[4-(4-aminophenoxy)phenyl]phthalimidime with
bis(trimellitimide)
Poly(ester-amide-imide) of phenyltrimellitimide
Poly(ester imide)
Poly(ether imide)
Poly(bis(p-ethynylphenyl)pyromellitimide)
Poly(4-(4-fluorobenzoyl)-N-(4-hydroxyphenyl)phthalimide)
Poly([4-(N,N-bis(2-hydroxyethyl)amino)-benzylidene]
imidazolidine-2-dione)
Poly(imide)
Poly(imide), di-t-butyl subs
nanofoam
PMR-15
Poly(imides) of 4,4-diaminotriphenylmethane, aromatic
Poly(imide) of 4,4-oxidiphthalic anhydride and 2,2-dimethyl-
4-4-diaminobiphenyl diamine
Poly(methacryl-methyl-imide)
Poly[4,4-oxydiphenylene oxydiphthalimide)
3.4.4. POLY(IMINES)
Poly(acetyliminoethylene)
Poly(acetyliminotrimethylene)
Poly(benzoyliminoethylene)
Poly(benzoyliminotrimethylene)
Poly(butytyliminoethylene)
Poly(dodecanoyliminoethylene)
Poly[(pentadecafluorooctanoylimino)trimethylene]
Poly(heptanoyliminoethylene)
Poly(hexanoyliminoethylene)
Poly(hexanoyliminotrimethylene)
Poly(isobutyryliminoethylene)
Poly(isovaleryliminoethylene)
Poly(3-methoxycarbonylpropyionyliminoethylene)
Poly(2-naphthyliminoethylene)
Poly(octadecanoyliminoethylene)
338
343
237
260
373
471
585
318
371
410
404
394
398
522
491
540-595
373-403
364
473
538
485
>713
570
451
495
515- 571
> 673
613
533-593
571
> 423
543
- 353
N 303
378
345
N 303
N 283
298
- 283
N 283
257
N 303
N 303
304
403
N 283
Dynami c met hod 491
Dynami c met hod 491
1361,1544
246
1298
1526
1526
1526
1280
1280
1280
1280
1280
1458
1458
1493
1467
1534
1432
1376
1254
1303
1558
1280
1432
1373
1372
1453
1466
1434
1397
1448
Mechanical method
Mechanical method; low
viscosity
Mechanical method
Mechanical method
Mechanical method
Mechanical method-apparent T,
Mechanical method
Mechanical method-apparent T,
Mechanical method-apparent T,
Mechanical method
Mechanical method
Mechanical method
Mechanical method
Mechanical method
Mechanical method-apparent T,
549
550
549
550
549
549
550
549
549
550
549
549
551
549
549
References page VI - 253
VI / 242 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 3. contd
Polymer
CAS No. T, W)
Remarks Refs.
Poly(octanoyliminoethylene)
Poly(propionyliminoethylene)
Poly(propionyliminotrimethylene)
Poly(valeryliminoethylene)
3.45. POLY(UREAS)
Poly(di(aminophenyl)acetylene diurea)
Poly(urethane), hemicyanine dye
PU-30
PU-40
PU-50
PU-60
PU-70
Poly(urethane)s, shape-memory
Poly(ureylenemethylene-
1,4-phenylenemethyleneureylenedecamethylene)
Poly(ureylenemethylene-
1,4-phenylenemethyleneureylenehexamethylene)
Poly(ureylenemethylene-
1,4-phenylenemethyleneureyleneoctadecamethylene)
Poly(ureylenemethylene-
1,4-phenylenemethyleneureyleneoctamethylene)
Poly(ureylenemetbylene-
1,4-phenylenemethyleneureylenetetradecamethylene)
Poly(ureylenedecametyleneureylenetetradecamethylene)
Poly(ureylenehexamethyleneureylenedodecamethylene)
Poly(ureylenehexamethyleneureylene-
1,4-phenylenemethylene- 1 ,Cphenylene)
Poly(ureylenehexamethyleneureylenetetradecamethylene)
Poly(ureyleneoctamethyleneureylene-
1,4-phenylenemethylene-1,4-phenylene)
Poly(ureylene- 1,4-phenylenemethylene-
1,4-phenyleneureylenedecamethylene)
Poly(ureylene- 1,4-phenylenemethylene-
1,4-phenyleneureylenedodecamethylene)
Poly(ureylene-1,4-phenylenemethylene-
1,4-phenyleneureyleneoctadecamethylene)
3.5. POLY(PHOSPHAZENES)
Aminoorganosiloxane poly(phosphazene)
Poly[(amino)thionylphosphazene]
Poly[bis(4-benzylphenoxy)phosphazene]
Poly[bis(2,3-bis(2-n-butoxyethoxy)propoxy)phosphazene]
Poly(bis(r-butyl-p-phenoxyphosphazene))
Poly(chloro-2,2,2&ifluoroethoxyphosphazene)
(average structure)
Poly(dichlorophosphazene)
Poly(diethoxyphosphazene)
Poly[bis(dimethylamino)phosphazene]
Poly(dimethoxyphosphazene)
Poly[bis(2,3-dimethoxypropoxy)phosphazene]
Poly[bis(dimethylamino)phosphazene]
Poly(diphenoxyphosphazene)
Poly[bis(ethylamino)phosphazene]
Poly[bis(4-fluorophenoxy)phosphazene]
Poly[bis(lH,lH-pentafluoropropoxy)phosphazene]
Poly[bis(2-methoxyethoxy)phosphazene]
Poly[bis((methoxyethoxy)ethoxy)phosphazene]
26085-02-9
N 283
N 343
281
N 286
508-583
394
233
364
230
356
230
353
232
351
239
346
283-323
328
345
325
3 4 1
327
313
322
328
320
323
319
324
321
190-251
233-355
286
187
323
213
210
189
233
1 9 7
194
269
265
303
259
198, 218
192
189
Mechanical method-apparent T,
Mechanical method
Mechanical method; low
viscosity
Mechanical method
Soft microphase
Hard microphase
Soft microphase
Hard microphase
Soft microphase
Hard microphase
Soft microphase
Hard microphase
Soft microphase
Hard microphase
Heating rate: 1 Wmin
Heating rate: 1 Wmin
Heating rate: 1 Wmin
Heating rate: 1 Wmin
Heating rate: 1 Wmin
Heating rate:
Heating rate:
Heating rate:
Heating rate: 1
Heating rate: 1
549
549
550
549
1 4 2 1
1456
1 2 6 8
1268
1 2 6 8
1268
1268
1268
1 2 6 8
1268
1 2 6 8
1268
1496
445
445
445
445
445
Wmin 445
Wmin 445
Wmin 445
Wmin 445
Wmin 445
Heating rate: 1 Wmin 445
Heating rate: 1 K/min 445
Heating rate: 1 Wmin 445
Heating rate: 20 Wmin;
probably branched structure
DTA heating rate
DTA heating rate
Heating rate: 20 Wmin
DTA heating rate
Dynamic mechanical method
DTA heating rate
DTA heating rate
Heating rate: 20 Wmin
1441
1 4 5 0
1 5 1 8
1 4 2 2
1 2 9 6
552
5 5 3
5 5 3
552
5 5 3
1 4 2 2
554
5 5 3
554
552
551
1 4 2 2
1449,1441
TABLE 3. contd
Main-Chain Heterocyclic Polymers VI 1243
Polymer CAS No. T, (K) Remarks Refs.
Poly[bis(methylphenoxy)phosphazene]
Poly[bis(2-(2.(2-(2-(2-(2.(2-methoxyethoxy)
ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)phosphazene]
Poly[bis(2-(2-(2-(2-(2.(2.methoxyethoxy)
ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)phosphazene]
Poly[bis(2-(2-(2-(2.(2-methoxyethoxy)
ethoxy)ethoxy)ethoxy)ethoxy)phosphazene]
Poly[bis(2-(2.(2-(2-methoxyethoxy)
ethoxy)ethoxy)ethoxy)phosphazene]
Poly[bis(2-(2-(2.methoxyethoxy)
ethoxy)ethoxy)phosphazene]
Poly[bis(2,3-bis(2-(2.(2-methoxyethoxy)
ethoxy)ethoxy)propoxy)phosphazene]
Poly[bis(2-(2-methoxyethoxy)ethoxy)phosphazene]
Poly[bis(2-(2.methoxyethoxy)ethoxy)phosphazene]
Poly[bis(2,3-bis(2-(2-methoxyethoxy)
ethoxy)propoxy)phosphazene]
Poly[bis(2,3-bis(2-methoxyethoxy)propoxy)phosphazene]
Poly(organophosphazene), ethyleneoxy subs
Poly[bis(2,3-bis(2-set-propoxyethoxy)
propoxy)phosphazene]
Poly[bis(phenylamino)phosphazene]
Poly(phosphazene)s
fluorinated
Poly[bis(piperidino)phosphazene]
Poly[bis(trifluoroethoxy)phosphazene]
Poly[bis(2,2,2-trifluoroethoxy)phosphazene]
Poly[bis(3-trifluoromethylphenoxy)phosphazene]
3.6. POLY(SILANES) AND POLY(SILAZANES)
Poly(carbosilazanes)
Poly(di-n-butylsilylenemethylene)
Poly(di-n-hexylsilylenemethylene)
Poly[(4-dimethylaminophenyl)methylsilylenetrimethylene]
Poly[(4-dimethylaminophenyl)phenylsilylenet~methylene]
Poly( l,l-dimethylsilazane)
Poly(dimethylsilylenemethylene)
Poly(dimethylsilylenetrimethylene)
Poly(di-n-pentylsilylenemethylene)
Poly(di-n-propylsilylenemethylene)
Poly(di-p-tolysilylenetrimethylene)
Poly[(methyl)phenylsilylenetrimethylene]
Poly(silethylene)
Poly(silethylene glycol)
Poly(siloxyethylene glycol)
Poly(silylethylene)
Poly(viny1 trimethyl silane)
269 1 4 4 1
198 1422
1 9 7 1422
194 1422
1 9 3 1422
1 9 3 1422
191 1422
189 1422
189 1422
192 1422
192 1422
203-217 1449
196 1422
364
1 6 8
311-367
292
210
203
238
198- 253
243
217
267
325
191
1 7 3
186
203
218
323
311
243
328
204
220-373
>653
378-417
DTA heating rate
Heating rate: 20 Wmin
554
1 4 4 1
1512
554
1 4 4 1
552,555,556
552
No measurement details
Mechanical method
No measurement details
Increases with Si content
1370
1440
1440
558
558
560,561
562
1440
559
1440
1440
558
559
1313
1478
1478
1395
1295
TABLE 4. MAIN-CHAIN HETEROCYCLIC POLYMERS
Polymer CAS No.
T, WI
Remarks Refs.
4. 1. CARBOHYDRATES
Acetoxypropyl cellulose 9004-39- 1 257
Amylose hexanoate (2.9) 315
Amylose triacetate
440
Amylose tributyrate 365
Amylose tripropionate
406
Amylose valerate: (2.8) 330
Cellulose 9004-34-6 243- 433
Heating rate: 5 - 1 0 Wmin
Heating rate: 5- 1 0 K/min
Heating rate: 5- 1 0 Wmin
Heating rate: 5- 1 0 K/min
Heating rate: 5- 1 0 K/min
Conflicting data
1358
1 8 9
1 8 9
1 8 9
189
189
190- 200
References page VI - 253
_i-. -
VI 1244 GLASSTRANSI TI ON TEMPERATURESOF POLYMERS
TABLE 4. contd
Polymer CAS No.
T, (W
Remarks Refs.
Cellulose acetate
Cellulose eicosanoate
Cellulose laurate
Cellulose triacetate
Cellulose tributyrate
Cellulose tridecanoate
Cellulose triheptanoate
Cellulose trihexanoate
Cellulose nitrate
Cellulose tripropionate
Cellulose trivalerate
Cyanoethyl cellulose
Ethyl cellulose
Methyl cellulose
Poly( 1 ,Cbutanediol succinate)
Starch acetate, dry
humi d
Triphenylmethyl cellulose
4.2. LIQUID CRYSTALS
LC Poly(acrylate)
LC Poly(butadiene) +p-nitrostilbene
LC Poly(hydroquinone terephthalate), t-butyl
LC Poly(norborene) +p-nitrostilbene
LC Polylster
4.3. NATURAL POLYMERS
Amorphous silk fibroinchains
Collagen
Gelatin
4.4. POLY(ACETALS)
Poly(l,3-dioxa-4,6cyclohexylenemethylene)
Poly(l,3-dioxa-2-propyl-4,6-cyclohexylenemethylene)
Poly(2-ethyl-l,3-dioxa-4,6-cyclohexylenemethylene)
Poly(2-isopropyl- 1,3-dioxa-4,6-cyclohexylenemethylene)
Poly(2-methyl-1,3-dioxa-4,6-cyclohexylenemethylene)
Poly(viny1 acetal) see Poly(2-methyl-1,3-dioxa-
4,6-cyclohexylenemethylene)
Poly(viny1 butyral) see Poly( 1,3-dioxa-2-propyl-
4,6-cyclohexylenemethylene)
Poly(viny1 pentanal acetal)
4.5. POLY(ANHYDRIDES)
Poly(amide imide) of biphenyltetracarboxylic dianhydride
Poly(3,3,4,4-benzophene tetracarboxylic dianhydride)
Poly(3,3,4,4-biphenyl tetracarboxylic dianhydride)
Poly(2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane
dianhydride)
Poly(methacrylic anhydride)
Poly(3,3,4,4-oxydiphthalic anyhydride)
Poly(pyromellitic dianhydride) Kapton
Poly(N,N,N,N-tetraglycidyl-4-4-diaminodiphenylmetane
hexahydrophthalic anhydride)
Poly(N,N,N,N-tetraglycidyl-4-4-diaminodiphenylmethane
tetrahydrophthalic anhydride)
9012- 09- 3
39320- 16- 6
9004- 70- O
9004- 41- 5
9004- 57- 3
9004- 67- s
63148-65-2
63148-65-2
473
407
367
322- 751
388
321
320
237
326, 339
400
338
453
316
423
346
438- 458
368- 408
426
294
287- 304
458
317- 337
333
453
308
343
378
322
345
329
355
327
493- 563
597
616
597
432
536
635
693
479
457
Conflicting data;
depend on acetate
and water content and
degree of crystallinity
Conflicting data
Dynami c met hod
Dynami c met hod
Dynami c met hod
Vicat softening point
1320
388, 1464
1464
1,21,93,143,188,
191,197,201-214
1, 206, 215
215
215
215
18,21,188,201,
216,217
215
215
1 9 7
1,201
197
1 5 2 7
1 4 6 9
1 4 6 9
197
1463
1405
1480
1405
1499
1364
1498
1498
1, 187
1, 188
1
1
1
1524
1404
1350
1350
1350
186
1350
1350
1320
1381
1381
Ti
-
PC
-
4. 1
P C
PC
P C
P C
P C
P C
PC
4. :
P O
4. 1
P O
PO
4. !
PO
PO
P O
P O
P O
4. 1
P O
P O
P O
I
P O
P O
P O
P O
P O
P O
P O
4. 1
P O
f
P O
PO
PO1
,
TABLE 4. contcf
Mai n-Chai n Heterocycl i c Pol ymers VI 1245
Polymer
4.6. POLY(BENZIMIDAZOLES)
CAS No.
T, (K)
Remarks Refs.
Poly(2,6-benzimidazolediyl-
6,2-benzimidazolediylocatamethylene)
Poly(2,5-benzimidazolediyl-
6,2-benzimidazolediylpentamethyleneimino-
4-diethylamino- 1,3,5-triazinediyliminopentamethylene)
Poly(2,5-benzimidazolediyl-5,2-benzimidazolediyl-
1,3-phenylene)
Poly(2,5-benzimidazolediyl-6,2-benzimidazolediyl-
1,4-phenyleneimino-4-diphenylamino-
1,3,5-triazinediylimino- 1,4-phenylene)
Poly(2,6-benzimidazolediyl-
6,2-benzimidazolediyltrimethylene)
Poly(2,6-benzimidazole-diy1sulfonyl-5,2-benzimidazolediyl-
1,3-phenylene)
Poly(5,5-bibenzimidazole-2,2-biphenylylene)
4.7. POLY(BENZOTHIAZINOPHENOTHIAZINES)
Poly(7,7-[ 1,4-dihydro-(2,3H)benzothiazino
(2,3-b)hexahydro(l,2,3,4H)phenothiazine]diyl)
4.8. POLY(BENZOTHIAZOLES)
Poly(2,6-benzothiazolediyl-
6,2-benzothiazolediyloctamethylene)
Poly(2,6-benzothiazolediyl-6,2-benzothiazolediyl-
1,3-phenylene)
4.9. POLY(BENZOXAZINES)
Polybenzoxazine B-b
Polybenzoxazine B-e
Polybenzoxazine B-ip
Polybenzoxazine B-m
Polybenzoxazine B-p
4.10. POLY(BENZOXAZOLES)
Poly(arylene ether benzoxazole)
Poly(benzoxazole)
Poly(2,6-benzoxazolediyl-6,2-
benzoxazolediyloctamethylene)
Poly(benzoxazole-5,2-diylhexamethylenebenzoxazole-
2,5-diyliminosebacoylimino)
Poly(benzoxazole-5,2-diylhexamethylenebenzoxazole-
2,5-diyliminosuberoylimino)
Poly(benzoxazole-5,2-diyloctamethylenebenzoxazole-
2,5-diyliminoadipoylimino)
Poly(benzoxazole-5,2-diyloctamethylenebenzoxazole-
2,5-diyliminosebacoylimino)
Poly(benzoxazole-5,2-diy1-1,3-phenylenebenzoxazole-
2,5-diyliminosebacoylimino)
Poly(m-phenylene),o,m-2-benzoxazole
Poly(m-phenylene),o,m-5-methyl-2-benzoxazole
4. 11. POLY(CARBORANES)
Poly(CzB~H5-carborany1enedi(dimethy1sily1eneoxy)
dimethylsilylene)
Poly(CzBsH~-carboranylenedimethylsilyleneoxy-
dimethylsilylene)
Poly(C2B loH lo-carboranylenedimethylsilyleneoxy-
dimethylsilylene)
Poly(C 2B loH lo-carboranylenedi(dimethylsilyleneoxy)
dimethylsilylene)
507
463
703
602
548
N 560
663
483
511
768
408
453
413
453
403
>573
328-370
326
359
350
358
366
393
494-523
494-523
< 188
277, 211
298
239
No experimental details
Heating rate: 2 Wmin
112
142
T, increased after storage at
773 K
Heating rate: 2 K/mini vinh O n l y
0.21 dllg
1 4 3
142
No experimental details
DTA heating rate
Mechanical method
112
114
144
Dynamic method 1 1 7
No method
Dynamic method
112
118
1410
1410
1410
1410
1410
1539
1346
No method 112
Heating rate: 20 Wmin 1 1 3
Heating rate: 20 Wmin 1 1 3
Heating rate: 20 K/min 1 1 3
Heating rate: 20 Wmin 113
Heating rate: 20 K/min 1 1 3
1474
1474
Dynami c met hod
Conflicting data
Mechanical method
180
178,179
1 8 1
180- 182
References page VI - 253
VI j 246 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 4. contd
Polymer CAS No. T, (K)
Remarks Refs.
-
PolyGB IOH IO-
carboranylenedi(dimethylsilyleneoxy)dimethy~silylene)
4. 12. POLY(DIBENZOFURANS)
Poly(3,6-dibenzofurandiylsulfonyl)
Poly(3,6-dibenzofurandiylsulfonyl-1,4-phenyleneoxy-
1,4-phenylenesulfonyl)
4.13. POLY(DIOXOISOINDOLINES)
Poly(l,3-dioxoisoindoline-2,5-diylcarbonyl-
1 $dioxoisoindoline-5,2-diyl- 1,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diylcarbonyl-
1,3-dioxoisoindoline-5,2-diyl-
1,3-phenylenedecafluoropentamethylene- 1,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diylcarbonyl-
1,3-dioxoisoindoline-5,2-diyl-
1,3-phenylenehexafluorotrimethylene- 1 Jphenylene)
Poly( 1,3-dioxoisoindoline-2,5-diylcarbonyl-
1,3-dioxoisoindoline-5,2-diyl- 1,4-phenyleneoxy- 1,4-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diylcarbonylimino-
1,4-phenyleneiminocarbonyl- 1,3-dioxoisoindoline-5,2-diyl-
1,4-phenylenesulfonyl- 1,4-phenylene)
Poly( 1,3-dioxoisoindoline-
2,5-diyldodecafluorohexamethylene- 1,3-dioxoisoindoline-
5,2-diyl-1,4-phenyleneoxy- 1,4-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diylhexafluorotrimethylene-
1,3-dioxoisoindoline-5,2-diyl-
1,3-phenylenedecafluoropentamethylene- 1,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diylhexafluorotrimethylene-
1,3-dioxoisoindoline-5,2-diyl-
1,3-phenylenehexafluorotrimethylene- 1,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diylhexafluorotrimethylene-
1,3-dioxoisoindoline-5 $diyl- 1,4-phenylenemethylene-
1,4-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diylhexafluorotrimethylene-
1,3-dioxoisoindoline-5,2-diyl-1,3-phenyleneoxy-
1,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diylhexafluorotrimethylene-
1,3-dioxoisoindoline-5,2-diyl-1,4-phenyleneoxy-
1,4-phenylene)
Poly(l,3-dioxoisoindoline-2,5-
diylhexadecafluorooctamethylene-1,3-dioxoisoindoline-
5,2-diyl-1,4-phenyleneoxy-1,4-phenylene)
Poly(l,3-dioxoisoindoline-2,5-diylhexafluorotrimethylene-
1,3-dioxoisoindoline-5,2-diyl-1,4-phenylenesulfonyl-
1,4-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diyloctafluorotetamethylene-
1,3-dioxoisoindoline-5,2-diyl-
1,3-phenylenedecafluoropentamethylene- 1,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diyloctafluorotetamethylene-
1,3-dioxoisoindoline-5,2-diyl-
1,3-phenylenehexafluorotrimethylene- 1,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diyloctafluorotetamethylene-
1,3-dioxoisoindoline-5,2-diyl-1,4-phenyleneoxy-
1,4-phenylene)
Poly(l,3-dioxoisoindoline-2,5-diyltetradeca-
fluoroheptamethylene- 1,3-dioxoisoindoline-
5,2-diyl-1,3-phenylene-decafluoropentamethylene-
1,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diyltetradeca-
fluoroheptamethylene-1,3-dioxoisoindoline-
5,2-diyl-l$phenylene-hexafluorotrimethylene-
1,3-phenylene)
213 Mechanical method 180- 182
633 1 8 4
563 1 8 4
N 638
533-543
N 393
Dynami c met hod
Softening point; viscosity only
0.11 dl/g
Sample hygroscopic
428,905,437
1 4 8
1 4 9
< 469
641
Heating rate: 32 Wmin
Dynami c met hod
124,125,150
151
458 Heating rate: 32 Wmin 1 5 3
371 Heating rate: 32 Wmin 1 4 8
418 1 4 8
498 Heating rate: 32 Wmin 152
451 Heating rate: 32 Wmin
483
457
533
417 Heating rate: 32 Wmin 1 4 8
432 Heating rate: 32 Wmin 148
485 Heating rate: 32 Wmin 148
385 Heating rate: 32 Wmin 148
406 Heating rate: 32 Wmin 148
Heating rate: 32 Wmin; highly
crystalline
Heating rate: 32 Wmin
1 4 8
148
1 5 2
1 5 4
TABLE 4. contd
Polymer CAS No.
T, (K)
Main-Chain Heterocyclic Polymers
Remarks
VI / 247
Refs.
Poly( 1,3-dioxoisoindoline-2,5-diyltetradeca-
fluoroheptamethylene- 1,3-dioxoisoindoline-
5,2-diyl- 1 ,Cphenyleneoxy- 1,4-phenylene)
Poly(l,3-dioxoisoindoline-2,5-diyloxy-1,3-dioxoisoindoline-
5,2-diyl-1,3-phenylenedecafluoropentamethylene- 1,3-phenylene)
Poly(l,3-dioxoisoindoline-2,5-diyloxy-l,3-dioxoisoindoline-
5,2-diyl- 1,3-phenylenehexafluorotrimethylene- 1,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diyloxy-1,3-dioxoisoindoline-
5,2-diyl- 1,3-phenyleneimino-4-dimethylamino-
1,3,5-triazinediylimino-1,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diyloxy-1,3-dioxoisoindoline-
5,2-diyl- 1,3-phenyleneimino-4-diphenylamino-
1,3,5-triazinediylimino-1,3-phenylene)
Poly(l,3-dioxoisoindoline-2,5-diyloxy-l,3-dioxoisoindoline-
5,2-diyl-1,3-phenyleneimino-4-phenyl-
1,3,5-triazinediylimino-1,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diyloxy- 1,3-dioxoisoindoline-
5,2-diyl-1,3-phenyleneimino-l,3,5-triazinediylimino-l,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diyloxy-1,3-dioxoisoindoline-
5,2-diyl-1,3-phenyleneoxy-1,3-phenylene)
Poly( 1,3-dioxoisoindoline-2,5-diyloxy-1,3-dioxoisoindoline-
5,2-diyl- 1,4-phenyleneoxy- 1 ,Cphenylene)
Poly( 1,3-dioxoisoindoline-2,5-diyloxy- 1,3-dioxoisoindoline-
5,2-diyl-1,4-phenylene-4-pheny1-1,3,5-triazinediyl-
1,4-phenylene)
Poly(l,3-dioxoisoindoline-5,2-diyl-1,4-phenylenesulfonyl-
1,4-phenylene- 1,3-dioxoisoindoline-2,5-diylcarbonylimino-
4,4-biphenylyleneiminocarbonyl)
Poly( 1,3-dioxoisoindoline-5,2-diyl-1,4-phenylenesulfony~-
1,4-phenylene- 1,3-dioxoisoindoline-2,5-diylcarbonylimino-
1,3-phenyleneiminocarbonyl)
Poly(l,3-dioxoisoindoline-5,2-diyl-1,4-phenylenesulfonyl-
1,4-phenylene- 1,3-dioxoisoindoline-2,5-diylcarbonylimino-
1,4-phenylenemethylene- 1,4-phenyleneiminocarbonyl)
Poly( 1,3-dioxoisoindoline-5,2-diyl-l,4-phenylenesulfonyl-
1,4-phenylene-l,3-dioxoisoindoline-2,5-diylcarbonylimino-
1,4-phenyleneoxy- 1,4-phenylene-iminocarbonyl)
Poly(l,3-dioxoisoindoline-5,2-diyl-l,4-phenylenesulfonyl-
1,4-phenylene-l,3-dioxoisoindoline-2,5-diylcarbonylimino-
1,4-phenylenesulfonyl- 1,4-phenyleneiminocarbonyl)
4. 14. POLY(FLUORESCEINS)
Poly(fluorescein-3 ,6-diyloxyisophthaloyloxy)
4.15. POLY(FURAN TETBACARBOXYLIC ACID DIIMIDES)
Poly(4,5,6,8,9,10-hexahydro-1,3,6,8-tetra[3,2-c:4,5-cf]
dipyrrole-2,7[ lH,3H]-diyl-1,4-phenylene-
3-phenylquinoxaline-2,7-diylcarbonyl-
3-phenylquinoxaline-7,2-diyl- 1,4-phenylene)
Poly(4,5,6,8,9,1O-hexahydro-1,3,6,8-tetraoxofuro[3,2-c:4,5-c]
dipyrrole-2,7[ lH,3H]-diyl-1,4-phenylene-
3-phenylquinoxaline-2,7-diyloxy-3-phenylquinoxaline-
7,2-diyl-1,4-phenylene)
Poly(4,5,6,8,9,10-hexahydro-1,3,6,8-tetraoxofuro[3,2-c:4,5-c]
dipyrrole-2,7[ lH,3H]-diyl-1,4-phenylene-
3-phenylquinoxaline-2,7-diyl-3-phenylquinoxaline-
7,2-diyl- 1,4-phenylene)
4. 16. POLY(OXABICYCLONONANES)
Poly[9-oxabicyclo(3,3,1)nonane-2,6-diyloxycarbonylimino-
1,4cyclohexylenemethylene-
1,4-cyclohexyleneiminocarbonyloxy] 53% tram, tram
70% tram, tram
460
393
457
567
563
565
563
480
523
628
643
584
597
583
580
549
528
583
503
494
502
Heating rate: 32 Wmin
Heating rate: 32 K/min
Heating rate: 2 Wmin
Heating rate: 2 Wmin
Heating rate: 2 Wmin
Heating rate: 2 Wmin
Heating rate: 32 Wmin
Heating rate: 2 K/min
Heating rate: 2 K/min
Dynamic method
Dynamic method
Dynamic method
Dynamic method
Dynamic method
Dynamic method
Dynamic method
Dynamic method
1 4 8
148
148
142
142
142
142
148
129
142
1 5 1
1 5 1
1 5 1
1 5 1
1 5 1
1 8 3
1 1 1
1 1 1
111
DTA heating rate 164
164
References page VI - 253
VI / 248 GLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 4. contd
Polymer CAS No. T, (W Remarks Refs.
Poly[9-oxabicyclo(3,3,1)nonane-2,6-diyloxycarbonylimino-
1,4-phenylenemethylene-l,4-phenyleneiminocarbonyloxy]
Poly[9-oxabicyclo(3,3, I)nonane-2$diyloxycarbonyloxy-
1 $phenyleneisopropylidene- 1,4-phenylenecarbonyloxy]
473
461
4.17. POLY(OXADIAZOLES)
Poly(arylene-1,3,4-oxadiazole)
Poly( 1,3,4-oxadiazolediyl- 1,3-phenylene-
1,3,4-oxadiazolediyl-1,4-phenylene)
Poly( 1,3,4-oxadiazolediyl- 1 ,Cphenyleneoxy-
1,4-phenylene)
Poly(l,3,4-oxadiazolediyl- 1,4-phenyleneoxy-
1,4-phenyleneisopropylidene-1,4-phenyleneoxy-
1,4-phenylene)
Poly( 1,3,4-oxadiazolediyl- 1,4-phenylene-
3,3-phthalidylidene- 1,4-phenylene)
Starburst oxadiazole
4.18. POLY(OXINDOLES)
Poly(5,7-dichloro-3,3-oxindolylidene-
1 $phenyleneoxyisophthaloyl-1 ,Cphenylene)
Poly(3,3-oxindolylidene-1,4-phenyleneoxyisophthaloyloxy-
1,4-phenylene)
4. 19. POLY(OXOISOINDOLINES)
Poly(N-methyl-3,3-oxoisoindolylidene-
1,4-phenyleneoxyisophthaloyloxy- 1,4-phenylene)
Poly(N-methyl-3,3-oxoisoindolylidene-
1,4-phenyleneoxyterephthaloyloxy- 1 ,Cphenylene)
Poly(3,3-oxoisoindolylidene-
1,4-phenyleneoxyisophthaloyloxy- 1,4-phenylene)
Poly(3,3-oxoisoindolylidene-1,4-
phenyleneoxyterephthaloyloxy-1,Cphenylene)
4.20. POLY(PHTHALAZINE)
Poly(ary1 ether phthalazine)
Poly(ary1 ether phthalazine), 2-napthalenyl
Poly(ary1 ether phthalazinium)
4.21. POLY(PHTHALIDES)
Poly(3,3-phthalidylidene-l,Cphenyleneoxy-
S-tert-butylisophthaloyloxy-1,4-phenylene)
Poly(3,3-phthalidylidene-1,4-phenyleneoxycarbonyloxy-
1,4-phenylene)
Poly(3,3-phthalidylidene-1,4-phenyleneoxy-
5-chloroisophthaloyloxy- 1,4-phenylene)
Poly(3,3-phthalidylidene-1,4-phenyleneoxyisophthaloyloxy-
1,4-phenylene)
4.22. POLY(PIPERAZINES)
Poly(2,5-dimethyl- 1,4-piperazinediylcarbonyloxyneopentylenesulfonyl-
neopentyleneoxycarbonyl)
Poly(2,5-dimethyl- 1,4-piperazinediylcarbonyloxyneopentylene-
thioneopentyleneoxycarbonyl)
Poly( 1,4-piperazinediyladipoyl)
Poly( 1,4-piperazinediylcarbonyl-
2,2-biphenylylenecarbonyl)
Poly( 1,4-piperazinediylcarbonyloxyethyleneoxycarbonyl)
Poly(l,4-piperazinediylcaonyloxyneopentyleneoxycarbonyl)
Poly( 1,4-piperazinediylcarbonyloxy-9-oxabicylco-
[3,3,l]nonan-2,6-yleneoxycarbonyl)
535- 551
551
513
453
653
370-415
543
529
N 558
-555
598
600
551-603
560-607
570-636
DTA heating rate 164
DTA heating rate
Mechanical method
Mechanical method
Mechanical method
Transition indistinct
Transition indistinct
552
513, 538
586
Conflicting data
591
164
1490
114
1 1 5
116
1460
1460
1479
1 4 5
145,185
14.5
1 4 5
358
313
399
466
333
343
386
160
1 6 0
No experimental details
Mechanical method, heating
rate: 1 Wmin; low viscosity
DTA heating rate
161,162
78,161
1 6 3
1 6 0
1 6 4
TABLE 4. contd
Main-Chain Heterocyclic Polymers VI / 249
Pol ymer CAS No.
T, WI
Remarks Refs.
Poly( 1,4-piperazinediylcarbonyl- 1,4-phenylene-
2,2-butylidene-1,4-phenylenecarbonyl)
Poly( 1,4-piperazinediylisophthaloyl)
Poly( l,Cpiperazinediyl-l-oxotrimethylenefluoren-9-ylidene-
3-oxotrimethylene)
Poly( 1,4-piperazinediylsebacoyl)
492-505
465
418
N 355
Mechanical method, heating
rate: 1 K/min
Mechanical method, heating
rate: 1 Wmin
Rather ill-defined
transition
1 6 5
78,161
78,161
161,166-168
4.23. POLY(PIPERIDINES)
Poly(2,6-dioxopiperidine-1,4-diyltrimethylene) 363 Heating rate: 10 Wmin 172
4. 24. POLY(PYRAZINOQUINOXALINES)
Poly[3,7-diphenylpyrazino(2,3-g)quinoxaline-2,8-diyl-
1,3-phenylene]
Poly[3,7-diphenylpyrazino(2,3-g)quinoxaline-2,8-diyl-
1,4-phenylene]
Poly[pyrazino(2,3-g)quinoxaline-2,8-diyl-l,4-phenylene]
Poly[pyrazino(2.3-g)quinoxaline-2,8-diyl-l,4-phenyleneoxy-
1,4-phenylene]
638
668
665
626
Heating rate: 20 Wmin
Heating rate: 20 Wmin
Heating rate: 20 Wmin
Heating rate: 20 lVmin
119
119
119
119
4.25. POLY(PYRAZOLES)
Poly(arylene ether pyrazole)
Poly( 1,3-pyrazolediyl- 1,3-phenylene-
3,1 -pyrazolediylhexamethylene)
Poly( 1,3-pyrazolediyl- 1,4-phenylene-
3,1 -pyrazolediylhexamethylene)
Poly(l,3-pyrazolediyl- 1,3-phenylene-3,1 -pyrazolediyl-
1,4-phenylene)
Poly( 1,3-pyrazolediyl- 1,4-phenylene-3,1 -pyrazolediyl-
1,4-phenylene)
PoMpyrdd,
p-toluene sulfonated
463-566
343
353
353
373
438
428
DTA heating rate; low viscosity
DTA heating rate; high
crystallinity
DTA heating rate; high
crystallinity
DTA heating rate; high
crystallinity
1390
1 7 5
1 7 5
1 7 5
1 7 5
1328
1529
4.26. POLY(PYRIDAZINES)
Poly(3,6-pyridazinediyloxy-1,4-phenyleneisopropylidene-
1,4-phenyleneoxy)
453 Mechanical method 1 1 6
4.27. POLY(PYRIDINES)
Poly(2,5-pyridinediylcarbonyliminohexamethyleneiminocarbonyl)
Poly(2,3,5-trifluoropyridinediyloxy-
2,2,3,3,4,4-hexafluoropentamethyleneoxy)
322
260 Polymer structure may contain
o-linkage
170
1 6 9
4.28. POLY(PYROMELLITIMIDES)
Poly(5,7-dihydro-1,3,5,7-tetraoxobenzo[l,2-~:4,5-c]
dipyrrole-2,6[1H,3H]-diyl-4,4-dimethylheptamethylene)
Poly(5,7-dihydro-1,3,5,7-tetraoxobenzo[ 1,2-c:4,5-c]
dipyrrole-2,6[1H,3H]-diyl-2,7-fluorenylene)
Poly(5,7-dihydro-1,3,5,7-tetraoxobenzo[l,2-~:4,5-c]
dipyrrole-2,6[1H,3H]diyl-3-methylheptamethylene)
Poly(5,7-dihydro-1,3,5,7-tetraoxobenzo[1,2-~:4,5-c]
dipyrrole-2,6[1H,3H]-diylnonamethylene)
Poly(5,7-dihydro-1,3,5,7-tetraoxobenzo[l,2-~:4,5-c]
dipyrrole-2,6[ lH,3H]-diyl-1,4-phenyleneoxy-
1,4-phenylene)
Poly(5,7-dihydro-1,3,5,7-tetraoxobenzo[l.2-~:4,5-~]
dipyrrole-2,6-[lH,3H]-diyl-1;4-phenylene-
3-phenylquinoxaline-2,7-diylcarbonyl-
3-phenylquinoxaline-7,2-diyl-1,4-phenylene)
Poly(5,7-dihydro-1,3,5,7-tetraoxobenzo[1,2-~:4,5-c]dipyrrol-
2,6[1H,3H]-diyl-1,4-phenylene-3-phenylquinoxaline-
2,7-diyloxy-3-phenylquinoxaline-7,2-diyl-1,4-phenylene)
408
- 623
408
383
Probably
- 773
513
No experimental details 1 2 1
Heating rate: 3 Wmin 120
No experimental details 1 2 1
No experimental details 1 2 1
Conflicting data, 119,120,122-131
transitions from 523 K
upwards reported as T,
Dynamic method, heating rate 1 3 2
5 Wmin
547 Dynamic method, heating rate
5 K/min
132
References page VI - 253
VI / 250 CLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 4. contd
Polymer
CAS No.
T, W)
Remarks Refs.
Poly(5,7-dihydro-1,3,5,7-tetraoxobenzo[l,2-~:4,5-c]
dipyrrole-2,6[1H,3]-diyl-1,4-phenylene-
3-phenylquinoxaline-2,7-diyl-3-phenylquinoxaline-
7,2-diyl- 1,4-phenylene)
Poly(5,7-dihydro-1,3,5,7-tetraoxobenzo[l,2-c:4,5-c]
dipyrrole-2,6[ lH,3H]-diyl- 1 ,Cphenylene-
3-phenylquinoxaline-2,7-diylsulfonyl-3-phenylquinoxaline-
7,2-diyl-1,4-phenylene)
Poly(5,7-dihydro-1,3,5,7-tetraoxobenzo[ 1,2-c:4,5-c]
dipyrrole-2,6[ lH,3H]-diyl-l,Cphenylenethio-
490
459
618
Dynamic method, heating rate
5 Wmin
Dynamic method, heating rate
5 K/mm
Dynami c met hod
132
132
1 2 5
1 $phenylene)
Polv(lN,N(~~,p-oxydiphenylene)pyromellitimeide] see Poly(5,7-dihydro-1,3,5,7-tetraoxobenzo[ 1,2-c:4,5-c]
. .-
dipyrrole:2;6[1H;3H]-diyl-l,4-phenyleneoxy-1,4-phenylene)
4.29. POLY(PYRROLIDINES)
Poly(l-butyl-2,5-diazo-3,4-pyrrolidinediyl)
Poly(l-decyl-2,5-diazo-3,Cpyrrolidinediyl)
Poly(2,5-dioxo-1,3-pyrrolidinediylethylene)
Poly(dodecyl-2,5-diazo-3,4-pyrrolidinediyl)
Poly(l-ethyl-2,5-diazo-3,4-pyrrolidinediyl)
Poly(l-hexadecyl-2,5-diazo-3,4-pyrrolidinediyl)
Poly( 1-hexyl-2,5-diazo-3,4-pyrrolidinediyl)
Poly( 1-octadecyl-2,5-diazo-3,4-pyrrolidinediyl)
Poly(l-octyl-2,5-diazo-3,4-pyrrolidinediyl)
Poly( 1-tetradecyl-2,5-diazo-3,4-pyrrolidinediyl)
4.30. POLY(QUINONES)
Poly(2-actylaminoanthraquinone)
Poly(t-butylhydroquinone)
Poly(methylhydroquinone)
Poly(phenylhydroquinone)
4. 31. POLY(QUINOXALINES)
Poly(3-phenylquinoxaline-2,6-diylcarbonyl-
3-phenylquinoxaline-7,2-diyl- 1,4-phenylene)
Poly(3-phenylquinoxaline-2,7-diylcarbonyl-
3-phenylquinoxaline-7,2-diyl-1,4-phenylene)
Poly(3-phenylquinoxaline-2,7-diylcarbonyl-
3-phenylquinoxaline-7,2-diyl- 1,4-phenylene-
1,3-dioxoisoindoline-2,5-diylcarbonyl-l,3-dioxoisoindoline-
5,2-diyl-1,4-phenylene)
Poly(3-phenylquinoxaline-2,7-diylcarbonyl-
3-phenylquinoxaline-7,2-diyl-l,Cphenyleneoxy-
1,4-phenylene)
Poly(3-phenylquinoxaline-2,6-diyloxy-3-phenylquinoxaline-
6,2-diyl-4,4-biphenylene)
Poly(3-phenylquinoxaline-2,6-diyloxy-3-phenylquinoxaline-
7,2-diyl-1,4-phenylene)
Poly(3-phenylquinoxaline-2,7-diyloxy-3-phenylquinoxaline-
7,2-diyl-1 ,Cphenylene)
Poly(3-phenylquinoxaline-2,7-diyloxy-3-phenylquinoxaline-
7,2-diyl-1,4-phenylene)
Poly(3-phenylquinoxaline-2,7-diyloxy-3-phenylquinoxaline-
7,2-diyl-1,4-phenylene-1,3-dioxoisoindoline-2,5-
diylcarbonyl-1,3-dioxoisoindoline-5,2-diyl- 1,4-phenylene)
Poly(3-phenylquinoxaline-2,6-diyloxy-3-phenylquinoxaline-
6,2-diyl- 1,4-phenyleneoxy- 1 ,Cphenylene)
461
368-370
408
255
523
348
422
348
393-395
351
401
450
426
430
583
595
528
516, 544
683
565
526, 543
571
527
710
DSC, Mdpt , Xp zero HR
DSC, Mdpt, Xp zero HR,
dilatomer
Heating rate: 20 Wmin
Dilatomer
DSC, Mdpt, Xp zero HR
Dilatomer
DSC, Mdpt, Xp zero HR
Dilatomer
DSC, Mdpt, Xp zero HR,
dilatomer
Dilatomer
1196
1196
176,177
1196
1196
1196
1196
1196
1196
1196
1294
1312
1312
1312
Dynami c met hod 1 3 3
Values range from 119,134,135
531 to 651K
Dynamic method, heating rate: 111
5 Wmin
Conflicting data 119,134
Dynami c met hod
Dynami c met hod
Conflicting data possibly
arising from different
rate effects
Dynami c met hod
Dynami c met hod
1 3 6
1 3 3
119,134,137
119,134,137-139
111
Dynami c met hod 1 3 6
TABLE 4. contd
Polymer CAS No.
T, (K)
Mai n-Chai n Heterocycl i c Pol ymers
Remarks
VI / 251
Refs.
Poly(3-phenylquinoxaline-2,6-diyloxy-3-phenylquinoxaline-
7,2-diyl- 1,4-phenyleneoxy-1,4-phenylene)
Poly(3-phenylquinoxaline-2,7-diyloxy-3-phenylquinoxaline-
7,2-diyl-1,4-phenyleneoxy- 1,4-phenylene)
Poly(3-phenylquinoxaline-2,6-diyl-3-phenylquinoxaline-
6,2-diyl-4,4-biphenylylene)
Poly(3-phenylquinoxaline-2,6-diyl-3-phenylquinoxaline-
7,2-diyl-1,4-phenylene)
Poly(3-phenylquinoxaline-2,7-diyl-3-phenylquinoxaline-
7,2-diyl-1,3-phenylene)
Poly(3-phenylquinoxaline-2,7-diyl-3-phenylquinoxaline-
7,2-diyl- 1,4-phenylene)
Poly(3-phenylquinoxaline-2,7-diyl-3-phenylquinoxaline-
7,2-diyl-1,4-phenylene-l,3-dioxoisoindoline-2,5-diylcarbonyl-
1,3-dioxoisoindoline-5,2-diyl- 1,4-phenylene)
Poly(3-phenylquinoxaline-2,6-diyl-3-phenylquinoxaline-
6,2-diyl- 1,4-phenyleneoxy- 1 ,Cphenylene)
Poly(3-phenylquinoxaline-2,6-diyl-3-phenylquinoxaline-
7,2-diyl-1,4-phenyleneoxy-1,4-phenylene)
Poly(3-phenylquinoxaline-2,7-diyl-3-phenylquinoxaline-
7,2-diyl- 1,4-phenyleneoxy- 1,4-phenylene)
Poly(3-phenylquinoxaline-2,6-diylsulfonyl-
3-phenylquinoxaline-7,2-diyl-1,4-phenylene)
Poly(3-phenylquinoxaline-2,7-diylsulfonyl-
3-phenylquinoxaline-7,2-diyl-1,4-phenylene)
Poly(3-phenylquinoxaline-2,7-diylsulfonyl-
3-phenylquinoxaline-7,2-diyl-1,4-phenylene-
1,3-dioxoisoindoline-2,5diylcarbonyl- 1,3-dioxoisiondoline-
5,2-diyl- 1 ,Cphenylene)
Poly(3-phenylquinoxaline-2,7-diylsulfonyl-
3-phenylquinoxaline-7,2-diyl- 1,4-pheyleneoxy-
1,4-phenylene)
Poly(quinoxaline-2,7-diylcarbonylquinoxaline-7,2-diyl-
1,4-phenylene)
Poly(quinoxaline-2,6-diyloxyquinoxaline-6,2-diyl-
4.4.biphenylene)
Poly(quinoxaline-2,7-diyloxyquinoxaline-7,2-diyl-
1,4-phenylene)
Poly(quinoxaline-2,6-diyloxyquinoxaline-6,2-diyl-
1,4-phenyleneoxy- 1,4-phenylene)
Poly(quinoxaline-2,6-diyloxyquinoxaline-7,2-diyl-
1,4-phenyleneoxy- 1 ,Cphenylene)
Poly(quinoxaline-2,6-diylquinoxaline-6,2-diyl-
-4-4-biphenylylene)
Poly[quinoxaline-2,6-diylquinoxaline-6,2-diyl-
di( 1,4-phenyleneoxy) 1,4-phenylene]
Poly[quinoxaline-2,7-diylquinoxaline-7,2-diyl-
di( 1,4-phenyleneoxy)- 1,4-phenylene]
Poly(quinoxaline-2,6-diylquinoxaline-6,2-diyl-
1,4-phenylene)
Poly(quinoxaline-2,7-diylquinoxaline-7,2-diyl-1,4-phenylene)
Poly(quinoxaline-2,6-diylquinoxaline-6,2-diyl-
1,4-phenyleneoxy-4,4 -biphenylyleneoxy- 1 ,Cphenylene)
Poly(quinoxaline-2,6-diylquinoxaline-6,2-diyl-
1 ,Cphenyleneoxy- 1,4-phenylene)
Poly(quinoxaline-2,7-diylquinoxaline-7,2-diyl-
l$phenyleneoxy- 1 ,Cphenylene)
Poly(quinoxaline-2,7-diylquinoxaline-7,2-diyl-p-te~henyl-
4,4-ylene)
Poly[quinoxaline-2,6-diylquinoxaline-6,2-diyl-
tri-( 1,4-phenyleneoxy)- 1,4-phenylene]
Poly[quinoxaline-2,7-diylquinoxaline-7,2-diyl-
tri-( 1,4-phenyleneoxy)- 1 ,Cphenylene]
Poly(quinoxaline-2,7-diylsulfonylquinoxaline-7,2-diyl-
1,4-phenylene)
516
541
677
639-698
593
590-638
533
567
558
561, 533
543
485-618
513
468, 563
591
663
579
655
543
659
468
508
623
649
486
661, 553
580
578
406
489
615
Dynamic method
Dynamic method
Dynamic method
Dynamic method
Conflicting data;
dilatometric T, 638 K
Dynamic method, heating
rate: 5 Wmin
Values range from
558 to 693K
Dynamic method
Conflicting data
Dynami c met hod
Conflicting data
Dynamic method, heating
rate: 5 K/min
Conflicting data
Heating rate: 20 K/min
Dynami c met hod
Heating rate: 20 K/min
Dynamic method
Dynamic method
Dynamic method
Heating rate: 20 K/mm
Dynamic method
Heating rate: 20 K/min
Dynamic method
Dynamic method,
conflicting data
Heating rate: 20 Wmin
Dynami c met hod
Heating rate: 20 K/min
Heating rate: 20 K/min
1 3 3
119,134,137
136
1 3 3
134,137
119,134,139
111
119,134,136,140
1 3 3
119,134
1 3 3
119,134,135
1 1 1
119,134
119
136
119
136
1 3 7
136,141
1 4 1
119
141
119
1 4 1
136,137,141
1 1 9
1 1 9
141
119
1 1 9
References page VI - 253
VI / 252 CLASS TRANSITION TEMPERATURES OF POLYMERS
TABLE 4. contcf
Polymer CAS No.
T, (W
Remarks Refs.
4.32. POLY(TRIAZINES)
Poly(heptafluoropropy1-1,3,5-triazinediyltrimethylene)
Poly[(4-H-octafluorobutyl)-1,3,5-triazinediyltrimethylene]
Poly(pentafluoroetbyl- 1,3,5-triazinediyltrimethylene)
Poly[perfluoro(propyl-1,3,5-triazinediylhex~e~ylene)]
Poly(6-phenyl-1,3,5-triazinediylphenylimino-
1,3,5&iazinediylphenylimino)
Poly(6-phenyl-l,2,4-triazine-5,3-diyl-2,6-pyridinediyl-
6-phenyl-l,2,4-triazine-3,5-diyl-l,4-phenylene)
Poly(6-phenyl-l,2,4-triazine-5,3-diyl-2,6-pyridinediyl-
6-phenyl- 1,2,4-triazine-3,5-diyl- 1,4-phenylenemethylene-
1,4-phenylene)
Poly(6-phenyl-l,2,4-triazine-5,3-diyl-2,6-pyridinediyl-
6-phenyl-l,2,4-triazine-3,5-diyl-l,4-phenyleneoxy-
1 ,Cphenylene)
Poly(2-H-tetrafluoroethyl-1,3,5-triazinediyl~me~ylene)
Poly(l,2,4-triazine-5,3-diyl-2,6-pyridinediyl-1,2,4-triazine-
3,6-diyl- 1,4-phenyleneoxy- 1,Cphenylene)
4.33. POLY(TRIAZOLES)
Poly(Cphenyl- 1,2,4-triazolediyl- 1,3-phenyleneimino-
terephthaloylimino-1,3-phenylene)
Poly(4-phenyl-l,2,4-triazolediyl-l,3-phenylene-4-pheny1-
1,2,4-triazolediyl- 1,4-phenylene)
253-255
253-255
253-255
261
541-552
533
478
488
253-255
496
623
538
No measurement details
No measurement details
No measurement details
DTA heating rate
DTA heating rate
Dynamic method; different
structural isomers may
be present
Dynamic method; different
structural isomers may be
present
Dynamic method; different
structural isomers may be
present
No measurement details
Heating rate: 20 Wmin
DTA heating rate
1 5 5
1 5 5
1 5 5
156
114
157,158
TABLE 5. COPOLYMERS
Polymer CAS No. T, (K) Remarks Refs.
Copolyester (p-hydroxybenzoic acid-isophthalic acid-
hydroquinone) 40 : 30 : 30
Copolyester, aromatic
Copolyester, aromatic
Poly(alkylene p,p-bibenzoate-b-tetrametbylene ether)
Poly(ary1 ether sulfone-b-aryl ether ketone)
Poly(t-butyl methacrylate-co-styrene-co-butadiene-co-
styrene-co-t-butyl methacrylate)
Poly(&-caprolactone-b-1,5-dioxepen-2-one-P-&-caprolactone)
Poly(carbonate-co-butylene terephthalate) 0.5/0.5
Poly(3-carboxyphenyl maleimide-co-styrene)
Poly(Ccarboxypheny1 maleimide-co-styrene)
Poly(2-chloro-1,3-butadiene-co-ethyl methacrylate)
Poly(2-chloro- 1,3-butadiene-co-glycidyl methacrylate)
Poly(chloroprene-co-ethyl methacrylate)
Poly(chloroprene-co-glycidyl methacrylate)
Poly(chloroprene-g-ethyl methacrylate)
Poly(chloroprene-g-glycidyl methacrylate)
Poly(N-cyclohexylmaleimide-alt-isobutene)
Poly(ethylene oxide-b-dimethyl siloxane-b-ethylene oxide)
Poly(ethylene oxide-co-epychloridrine)
Poly(ethylene terephthalate-co-p-hydroxybenzoic acid)
Poly(ethylene-co-methacrylate)
Poly(ethylene-co-metacrylic acid) ionomer
Poly(etby1 methacryate-co-methyl methacrylate, 40 : 60)
Poly(ethy1 methacrylate-co-methyl methacrylate, 30: 70)
Poly(furfury1 acrylate-alt-2-hydroxyethyl met hacryl at e)
50:50
Poly(3-hydroxybutyrate-co-4-hydroxybutyrate)-18
Poly(3-hydroxybutyrate-co-4-hydroxybutyrate)-69
Poly@-hydroxybutyrate-co-hydroxyvalerate)
25 103-74-6
25053-53-6
398-414
403-433
377
205
>473
423
235
363
493
493
238
257
238
256
230
243
465
156
233
333
237
330
377
365
326
269
237
257
1436
1509
1 2 6 9
1 4 8 5
1 4 2 5
1 3 7 7
1 5 1 5
1 3 8 6
1 2 7 3
1 2 7 3
1360
1360
1543,136O
1543,136O
1 3 6 0
1 3 6 0
1 4 6 5
1 5 0 0
1 4 1 5
1 5 1 7
1 3 0 7
DSC 1 2 6 5
1 5 5 2
1 5 5 2
1 2 7 9
NMR 1 4 9 4
NMR 1 4 9 4
1 5 6 0
Re f e r e n c e s VI / 253
TABLE 5. contd
Polymer CAS No.
T, WI
Remarks Refs.
Poly(N-(4-hydroxyphenyl)maleimide-co-allyt~methylsilane)
Poly( 1,4-isoprene-b-styrene)
Poly(L-lactic acid-co-or-maleic acid) O-45 mol%
Poly(maleimide-nlt-p-trimethylsilyl-a-methy~styrene)
Poly(maleimide-alt-p-trimethylsilylstyrene)
Poly(methy1 methacrylate-co-styrene)
Poly(methy1 methacrylate-co-styrene-co-butadiene-co-
styrene-co-methyl methacrylate)
Poly(norbomene-co-ethylene)
Poly(styrene-b-isoprene)
Poly(styrene-b-methylphenylsiloxane) 58% styrene
Poly(styrene-co-acrylonotrile-co-chromium acrylate)
Poly(styrene-co-maleic anhydride)
Poly[styrene-b-(ethylene-co-butylene)-b-styrene]
Poly(N-vinyl carbazole-co-pyrrole)
Poly(viny1 chloride-co-vinyl acetate)
Resorcinol-Bisphenol A copolymer, o-adamantyl
4 9 9 1289
2 8 6 1283
306-329 1412
4 9 9 1324
503 1324
375 1318
4 3 3 1371
4 2 8 1403
3781213 1472
303 1282
3 6 9 1537
381 1348
2 3 3 1 3 2 1
453-413 1328
9003- 22- 9 3 4 2 1359
3 7 3 1369
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VI / 266 GLASS TRANSITION TEMPERATURES OF POLYMERS
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852. P. Weitz, Paint Vam. Prod., 57, 99 (1967).
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855. 0. Smidsrod, J. E. Guillet, Macromolecules, 2, 272 (1969).
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893. A. K. Schulz, J. Chim. Phys., 53, 933 (1956).
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Re f e r e n c e s VI / 267
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VI / 268 CLASS TRANSITION TEMPERATURES OF POLYMERS
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VI / 270 CLASS TRANSITION TEMPERATURES OF POLYMERS
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Rates of Crystallization of Polymers
J. H. Magill
School of Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania, USA
A. Introduction VI-280
1. Background VI-280
1 .l . General Remarks VI-280
1.2. Background VI-280
1.3. Morphological Outline/Growth
Features VI-281
2. General Principles and Techniques Involved
in Crystallization Rate Studies VI-282
2.1. Kinetics of Bulk Transformations VI-282
2.2. Thermodynamic Crystallization
Models VI-284
2.3. Growth Kinetics of Lamellar Structures:
Crystals and Spherulites VI-284
3. Other Significant Aspects of Crystallization VI-286
3.1. Nonisothermal Crystallization
3.2. Crystallization of Blends
3.3. Solvent and Pressure-Induced
Crystallization
3.4. Crystallization of Mesophases
3.5. Flow Induced Crystallization
3.6. Epitaxial Crystallization
3.7. Orientational Crystallization
3.8. Crystallization of Copolymers
3.9. Computer Simulations
B. Tables of Rates of Crystallization of Various
Polymers
1. Rates of Crystal Growth
Table 1. Poly(alkenes), Poly(dienes),
Poly(vinyls)
1.1. Homopolymer Melts
1.2. Solutions
Table 2. Poly(oxides)
2. Rates of Radial Spherulitic Growth
Table 3. Polyfdienes), Polyfalkenes),
Polyfvinyls)
3.1. Homopolymer Melts
3.2. Blends
Table 4. Poly(oxides)
4.1. Homopolymer Melts
VI-286
VI-287
VI-288
VI-288
VI-289
VI-289
VI-289
VI-290
VI-290
VI-291
VI-291
VI-291
VI-291
VI-296
VI-300
VI-304
VI-304
VI-304
VI-31 2
VI-31 5
VI-31 5
4.2. Complexes
4.3. Blends
Table 5. Poly(carbonates)
Table 6. Poly(esters)
6.1. Homopolymer melts
6.2. Blends
6.3. Copolymers
Table 7. Polyfamides)
Table 8. Poly(siloxanes)
8.1. Homopolymer melts
8.2. Copolymers
Table 9. Others
9.1. Homopolymers melts
9.2. lonomers
3. Rates of Bulk Crystallization (Avrami
Constants)
Table 10. Poly(dienes.1, Poly(alkenes),
Poly(vinyls)
10.1. Melts and Solutions
10.2. Blends and Copolymers
Table 11. Polyfoxides)
Table
Table
Table
Table
Table
Table
11 .i. Homopolymer melts
11.2. Blends
2. Poly(carbonates.1
3. Poly(esters)
13.1. Homopolymer melts
13.2. Blends and Copolymers
1 4. Poly(amides)
14.1. Blends of Poly(amides)
1 5. Polyturethanes)
15.1. Blends of Poly(urethanes)
6 . Polyfsiloxanes)
7 . Poly(phosphazenes)
Table 18. Others
Table 19. Composites
19.1. Composites of Blends
C. References
VI-31 8
VI-31 9
VI-326
VI-327
VI-327
VI-329
VI-331
VI-331
VI-334
VI-334
VI-334
VI-336
VI-336
VI-340
VI-341
VI-341
VI-341
VI-353
VI-365
VI-365
VI-371
VI-372
VI-373
VI-373
VI-377
VI-379
VI-382
VI-383
VI-383
VI-384
VI-384
VI-385
VI-389
VI-390
VI-391
VI / 279
VI/280 RATES OF CRYSTALLIZATION OF POLYMERS
A. INTRODUCTION
1 . Background
7.7. General Remarks This chapter is intended to serve
as a useful compendium of crystallization data for many
types of polymers and polymeric systems. Some informa-
tion is also provided on the fundamentals of crystallization
(nucleation and growth) of these materials, with appropriate
references relating to the techniques that are usually
employed to study phase transformation processes in
polymers. Controversial issues on growth and morphology
will be mentioned briefly so that the reader who is new to
this field will gain some perspective on the theoretical and
experimental developments that have evolved over many
decades, although this has little bearing on the numerical
data presented here. This presentation serves not only as a
guide to the data, but as a timely attempt to alert the vigilant
reader to some difficulties, and some intricacies and
problems of polymer crystallization that may be encoun-
tered in the literature (l-5).
The third edition of this Handbook reported the rates of
crystallization for homopolymers (l-5), polymer blends
(6,7), and copolymers (8). This edition updates this
information, adds polymeric mesophases, and factors other
than temperature that effect crystallization behavior. Within
the past decade, crystallization of polymer blends have
become increasingly important industrially. Besides the
property-synergism provided through blending, there is a
further economical incentive to use available materials
rather than attempt to develop new polymers. Solid-state
multiphase systems provide challenging academic research
problems because polymer compatibility, per se, dominates
morphology, whatever the crystallinity content of the
system. The phase transformation depends upon the poly-
mer type, monomer size and placement of the monomer
units comprising the macromolecules (10). Sequence length
and blockiness often feature strongly in determining rates
of crystallization and levels of crystallinity. Related
monotonic changes sometimes occur in physical parameters
such as melting points and glass temperatures, crystal-
linities, and heats of fusion (11). The usefulness of a
material depends upon the magnitude of these parameter
changes. Polymer blending can often provide dispersions
with overall properties that are superior to those of the
respective components in the system, whether they crystal-
lize or not. Blended mixtures frequently phase separate, but
others maintain their morphological and physical integrity
in practical applications (12). Cocrystallization may occur
sometimes if there is lattice matching of the crystal-
lographic chain axis repeat dimension and direction, and
packing in the lateral directions within the crystallites is not
too disruptive. In these circumstances the property changes
may be striking. A fundamental knowledge of the kinetics
of crystallization helps one to modify and improve proper-
ties (15).
The crystallization and morphology of lyotropic and
thermotropic phases have only been developed compara-
tively recently, though liquid crystal polymers were
recognized experimentally (13) and theoretically (14) a
long time ago. The guidelines established for small-
molecule liquid crystals (15) have been helpful for
macromolecules, but they too may be misleading at times,
particularly for polydisperse high-molecular-weight poly-
meric mesophases (16) and where their structural features
are submicroscopic. Kinetic information for liquid crystal
polymer systems is growing but still sparse (17,18).
Synchrotron radiation sources and rapid monitoring tech-
niques (19,20) are now available nationally and intema-
tionally for measuring isothermal and nonisothermal
changes (21) and these simplify the monitoring of in situ
transformations. Spectroscopic procedures (22) are now
more capable than ever for sensing and tracking rapid and
specific motions that have escaped detection by conven-
tional means until the present. In addition to high intensity
X-ray and light (laser) sources (23), deuterium NMR
methods (24) are being used and developed for studying
molecular dynamics, structural, or orientational changes
(25). These new classes of nondestructive experiments are
essential for improving our understanding of polymer
behavior in the condensed state.
7.2. Background Over the years, two parallel themes
describing aspects of crystallization of synthetic polymers
have been developed. The oldest of these (26,27,30) uses a
thermodynamic approach and provides a statistical descrip-
tion of morphology related to polymer crystallization,
morphology, and properties. The other approach (28-29) is
about half a century old and prefers a kinetic description of
the development of lamellar structures that are basic to
nucleation, growth, and stability in this context. Each has its
merits and shortcomings but neither model is a panacea.
Now, there is a consensus over the molecular dimensions
that characterize macromolecules in the condensed state
(4), but controversy remains over the intricacies of crystal-
lization and its role in determining structure-property
relationships. However, with new techniques now available
for surface investigations and data processing, the time may
not be too far away for an atomic view of matter in real
space. For information on this topic, the reader should
consult the current literature (15,31).
Whenever a polymer melt (liquid) or solution is
sufficiently cooled, it may spontaneously crystallize. For
instance, a supersaturated dilute solution produces tiny
single crystals (32). Spherulites are formed from concen-
trated polymer solutions, and these most frequently grow
from the supercooled molten state. These growth patterns
only occur from privileged nuclei, i.e., those that are
capable of growing with a decrease in free energy (i.e.,
enhanced stability) to form ordered structures. If the
supercooled melt (liquid) does not undergo this discontin-
uous transformation, then it is destined to form a glass, a
disordered condensed phase. The crystalline texture and
More appropriately described here as solution-grown crystals.
morphology, as well as degree of crystallinity, depends to
some degree upon experimental conditions (33,34). Sin-
gle crystals are comprised of thin lamellae with diverse
habits. These morphological forms are discussed later in
this article. Lamellae are basic crystal structures, although
their intricate morphology is still open to debate (15,16).
The next steps in the hierarchical level of structure are
many different kinds of spherulites that are polycrystalline.
The exact morphology of these moieties is still unsettled
though they were discovered about a century ago. Several
factors may be involved, namely: (a) monomeric chemical
repeat unit, (b) crystallization temperature, (c) molecular
weight and molecular weight distribution, (d) degree of
branching and crosslinking, (e) tacticity, (f) degree of
supersaturation, and (g) environmental factors (stereoche-
mica1 defects, stress, solvent, impurities, etc.) and so on.
These items are not placed in order of importance.
Morphology is often dictated by other circumstances.
Merely by changing the concentration of polymer in
solution or its solvent, it is often possible to cover the
morphological spectrum of crystalline polymeric forms,
ranging from the monocrystal (formed in very dilute
solution) to spherulites (formed in relatively concentrated
solutions or from the polymer melt) under quiescent
conditions. Other external factors such as pressure or stress
and orientation can also alter the morphology (5).
This article deals mainly with isothermal crystallization
conditions, but kinetic results obtained under constrained
conditions are also listed. These are in the minority but the
literature is growing. Although nonisothermal transforma-
tions (35) dominate in industrial operations, the data are
frequently proprietary and often peculiar to specific process
conditions. For example, molding processes (36) and fiber
extrusion (37) operations create complex crystallization
patterns, but the literature and even patents are still sparse
on kinetic details. Most manufacturing procedures actually
originated in industry. Still, some aspects of the topic have
been examined theoretically (38).
Again, the influences of nucleants or additives on
crystallization behavior have made considerable inroads
in the scientific and patent2 literature (39) but the impor-
tance of shear rates (40,41) on crystallization kinetics is
beginning to receive more attention in the literature (42). In
the field of single crystal growth many new results have
been added to older kinetic data (43,44) tabulated in
previous editions of Polymer Handbook. The most
recent are concerned with the crystallization of oligomers
of polyethylene, polyethylene oxide and so on. Many
aspects of crystallization are reported in some recent
reviews (45,45a,45b) and later in this article.
1.3. Morphological Outline/Growth Features Under
quiescent conditions, most often in very dilute solutions,
and in self-seeding procedures, crystalline lamellae or
single crystals are formed. They are seldom more than
Patents are excluded from this article.
I nt roduct i on: Background VI / 281
85% crystalline even for annealed samples. Within these
crystals, the chain macromolecules are disposed with their
chain axis (c axis) more or less perpendicular to the flat
faces of the thin lamellar crystals. However, angles of
inclination as large as 48 have been reported in polyamides
(5). Lamellar thickness (45-48) is controlled by nucleation/
growth conditions. Electron microscopy (48) and other
studies (49) have shown that crystallization (growth)
proceeds outward from a primary center (a nucleation site)
until growth is arrested or slowed to an imperceptible level
at very low supersaturations. Screw dislocations (50) that
often grow perpendicular to the basal plane of the crystal
have an unusually large Burgers vector (equivalent to the
lamellar thickness). Growth rates perpendicular on the basal
plane of the crystal have not been reported, but a knowledge
of this process should provide a better understanding of
morphology and mechanistic relationships in high polymers
and copolymers as they interrelate to each other and
determine properties.
Crystallization from more concentrated solution(s) or
from the supercooled molten state produces spherulites that
seem to have nucleated similarly, and the high super-
saturations encountered lead to polycrystalline spherical
arrays. These arrays are comprised of radiating platelets or
lamellae (often splayed and branched) in which the polymer
chains are also folded to varying degrees, dependent upon
polymer molecular weight and experimental conditions.
The chains are usually oriented tangentially to their growth
direction. Because of this morphology, most spherulites
show a negative birefringence since the polarizability along
the molecular chain axis is much greater than it is
transverse to it, except in polymers with highly polar side
groups or in hydrogen bonded polyamides. A variety of
textural/optical features are associated with changes in
crystallite orientation. The literature (51,52,5a) is replete
with details of spherulite morphology, but no unique growth
mechanism has been reported. Indeed, one might question
its uniqueness in materials science! It is appropriate to
mention that many classes of other materials also form
spherulites; see for example, sulfur (53) selenium (54),
antimony (55), proteins and carbohydrates (56), graphite
(57) silicates (58), and inorganic (59) and polar and
nonpolar low-molecular-weight organic molecules (60), to
cite some examples. Spherulites are almost ubiquitous
given suitable growth conditions and their forms are
diverse, but it is important to realize that other morpholo-
gical forms exist.
Polygonized structures are produced when spherulites
impinge upon each other, limiting further outward radial
growth. Growth rate is extremely temperature-sensitive and
it is nucleation-controlled but this has been questioned
recently (61). Even so, it is generally agreed that polymer
transformations from solutions and melts are nucleation
controlled. There has been confusion sometimes over the
terms used to describe (a) primary and (b) secondary
processes. Nucleation is termed primary for the onset of
crystallization; the propagation of lamellae/spherulites (i.e.,
growth) is named secondary crystallization. Crystallization
References page VI - 39 1
VI / 282 RATES OF CRYSTALLIZATION OF POLYMERS
that occurs after the radial growth ceases, i.e., filling-in
or densification behavior in spherulites, is sometimes
termed secondary crystallization. However, kineticists often
restrict the term primary crystallization to the nucleation
step (creation) of the phase transformation process, and
secondary is given to that stage in the transformation where
significant deviations from Avrami3 kinetics may take
place. Several in situ experiments have been made with
synchrotron radiation to monitor intricacies of nucleation
and growth with time using WAXS and SAXS modes (62).
During the secondary stage, densification takes place (63)
and improvements in crystallinity have been reported by
dilatometry (64). Even so, it must be recognized that the
density and perfection of a spherulite decreases as it grows
outwards from its center. Changes in crystallite thickness
that may occur with annealing are another matter that is still
unsettled.
The temperature dependencies of spherulitic and crystal
growth rate have been claimed to correspond closely (65)
under comparable conditions of undercooling, but there are
results to the contrary. In monodisperse poly(oxyethylene)
(66) and poly(ethylene)s (67,68), the rate of growth of
single crystals in the melt depends on the crystal thickness,
determined primarily by the undercooling temperature.
Chain ends have been reported to reside sometimes inside
(67) but more often outside (68, 68a) the crystalline core of
low-molecular-weight poly(ethylene)s below 400 CHzs
per molecule4.
2. General Principles and Techniques Involved
in Crystallization Rate Studies
2.1. Kinetics of Bulk Transformations Whenever a
polymer crystallizes, the extent of the phase transformation
depends upon the crystallizing species and the experimental
conditions. High molecular weight polymers do not
crystallize completely (9,69) because of topological con-
straints that lower crystallinity considerably. The classical
isothermal transformation kinetics, initially formulated by
Kolmogorov (70) and Goler et al. (71) were extended later
by the Avrami theory that was initially formulated for
metals and later modified, for example, by Evans (72) and
others, for polymers. The Avrami (73) equation
~9 = exp( -kt)
relates the fraction or amount of uncrystallized material that
remains after time t, during an isothermal transformation to
its growth rate parameter, k, and nucleation parameter, 12.
As formulated by Avrami, crystallization was presumed to
3 The basic concepts in this model are hardly commensurate with the
known crystallization behavior of polymers; see for example, Ref. 5,
p. 250.
4 The most recent in situ synchrotron studies made with monodisperse
n-alkanes (C246H494) have indicated that once folded chains have
considerable ciliated disorder as formed at first, but they undergo a slower
improvement in crystallinity as chains equilibrate (adjust) to twice folded
lamellae of much higher crystallinity (68a).
take place under isovolume conditions. Modifications have
been made to equation (Al) to correct for incomplete
crystallization (74). The mode of nucleation, IZ, is an integer
that varies from 1 to 4, reflecting the geometry and
dimensionality of the growth process, under ideal condi-
tions. The different forms are summarized in the following
table.
AVRAMI EXPONENT AND MORPHOLOGY
Exponent Nucleation Qpe Crystallite Shape
1 Instantaneous Rod Constant
2 Instantaneous Homogeneous Discoid/ Rod Constant
3 Instantaneous Homogeneous Sphere/ Discoid Constant
4 Homogeneous Sphere Constant
There are also classical growth conditions where the
diffusion limited rate proceeds as t I2 and IZ exhibits l/2, 1;
and 2i values. These examples have been addressed in
detail in other texts (31). Still, it is worthwhile pointing out
that other terminology has been used to describe the mode
of nucleation. For example, n = 3 may be termed sporadic
or predetermined in time where the form of growth is
disklike (2D) or spherulitic, respectively. Anyhow, it
happens that in polymer phase transformation the growth
velocity proceeds linearly with time. Now that mesophase
crystallization is receiving more attention (75), rod-like
morphologies with 12 = 1 resemble those found in well-
oriented fibrous homopolymer systems (76). Some non-
integral values of n correspond to heterogeneous transfor-
mations for IZ = 2 and 3. Other values of IZ determined in
kinetic experiments may arise from many factors connected
with the morphological complexity of the polymeric
system. Computer simulations (77-79) have been con-
ducted to model the bulk phase transformation, but the
analysis is seldom free of ambiguity for many reasons,
except in the early stages of crystallization. Note that in a
recent paper, Levine et al. (80) have pointed out that the
Avrami-Kolmogorov isothermal growth equation should
not be applied to nonisothetmal transformations without
proper concern for the microstructural features that are
inherent in the sample itself. Again, they claim that
measurements employing small samples are subject to
error whenever anisotropicity features in this mean field
theory. They obtained a modified equation from extensive
computer simulations. Polymeric materials are likely to be
subjected to these criticisms though they were mainly
concerned with metallic and related systems. Polymers
exhibit more serious side-effects6 such as mixed types of
nucleation (that causes more than one type of spherulite
morphology), nucleation on impurities, severe volume
shrinkage upon crystallization and variations in spherulite
5 In polymer crystallization experiments this situation is never realized,
but large single polymer crystals accompanied by small volume changes,
have been produced in some solid state polymerizations. So far, kinetic
measurements have not been made on these systems.
6These are intrinsic factors that are known to influence the Avrami
exponent.
Introduction: General Principles and Techniques Involved in Crystallization Rate Studies VI / 283
density (crystallinity) within and between the spherulite(s)
all of which may contribute to nonintegral values of n. In
view of these complexities, it is surprising that Avrami II
values are taken seriously in practice, except for making
comparative rate studies. It is even claimed (81) that the
mechanical properties of spherulitic samples may be related
to internal morphological defects, such as tie-molecules,
and even voids created between confined spherulites during
melt crystallization. Laser microbeam and X-ray micro-
diffraction has also been used to examine the internal
morphology of spherulites (82,83). The kinetics of the
embryonic nuclei and subsequent stages of spherulitic
developments (84,85) from a sheaf-like morphology to a
spherical entity (spherulite) have been studied using low-
angle light scattering. Of course, electron microscopy
(86,87) has recorded more detailed morphological changes
at higher resolution, and atomic force microscopy (AIM)
investigations have probed even further in this respect
(88,89,89a).
In principle, any technique that can follow unambigu-
ously the amorphous -+ crystalline transformation with
time, under isothermal or non-isothermal conditions, can
be employed as a bonafide method to detect and monitor the
crystallization rate(s) that occur. Many experimental
techniques exist, such as calorimetry (90), dilatometry
(91), density balance (92) and density gradient (93), light
depolarization (or transmission) technique (94,95) and/or
small-angle light scattering (96) (for average spherulite
growth rate measurements), infrared spectra (97), X-ray
(98), nuclear magnetic resonance (99,102), electrical
resistivity (loo), and small-angle X-ray scattering (lOl),
neutron scattering (103), atomic force microscopy (103a)
and more. The Avrami 6 may involve any property
parameters, Pis, that are relevant in the transformation
time domain. In this respect, specific volume changes are
related to 0 by the equation
0 = @Jo0 - ~t)/(Tx - va) C-42)
Here v,, wuy, and v, correspond to the initial, intermediate,
and final stages of the isothermal crystallization (71,104)
and the other Pis may be similarly incorporated. Wood and
Bekkedahl (104) were the first to show that the overall
isothermal transformation rate of rubber expressed as
(ti&i passes through a maximum as its crystallization
temperature was lowered. It was later shown experimentally
and theoretically that the spherulitic growth rate also
proceeded similarly, as related by Eq. (A3). Simply
expressed (105), k may be written as in Eq. (Al):
k = f(hG)
(-43)
where a is a geometric parameter that is three for
spherulites, and it may take on other values for other
geometrical shapes. Another formulation (106) obtained
experimentally, at constant crystallization temperature, is
k =f[h(MW, t)G(MW, t)]
W)
since it was observed that nucleation rate, I?, and
spherulitic growth rate, G, are each dependent on molecular
weight, molecular weight distribution and time.7
The type of property, P, being monitored (107) depends
upon the amorphous contribution, P,, and crystalline
portion, PC, where each phase can be expressed as a
weight fraction or a volume fraction in the simple two-
phase model expressed as
P=xP,+(l-x)P,
W)
If P is specific volume then a weight fraction x,(w) is
obtained, whereas a volume fraction x,(w) results whenever
the sensing is made (for example) by X-ray or dilatometry.
The relationship then becomes
1 -xc(w) = Pa l-.44
xc(w) 0PC xc(v)
W)
where pa and pC represent the amorphous and crystalline
densities, respectively. This model is an oversimplification
(109) in that it does not allow for the increasing inter-
dependence of the properties of each phase with changes in
crystallinity. Other complications also arise because (i)
crystallinity is molecular weight dependent (9,45,64) and
(ii) for oriented systems, accurate determinations of
crystallinity can be difficult (110,111). It strongly depends
upon morphology.
Bulk crystallization rates are of some practical value in a
relative sense (112) and depend markedly on the concen-
tration of impurity nuclei (of adventitious origin or from
additives or nucleants introduced deliberately for property
or process control). No satisfactory way (other than
counting primary nuclei, i.e., spherulites) exists to quantify
their concentration. Generally, spherulitic growth rate (after
nucleation) is independent of how the spherulite originated
(94,113) (i.e., whether the nucleation is homogeneous,
heterogeneous, or pseudo-homogeneous). On the other
hand, it must also be recognized that bulk transformations
can be greatly influenced by impurities.
Adequate fusion conditions and sample purification
(94,114) must always be established for best results in a
given system to suppress or eliminate adventitious hetero-
geneous nuclei in crystallization. Homogeneous nucleation
is seldom encountered at small undercoolings (115);
although it may be mimicked in the earlier stages of
crystallization (116). Because of these complications, it is
always advisable to combine complementary techniques;
for example, optical microscope studies with dilatometric
or other rate measurement. Reliable nucleation rates
may only be deduced from independent measurements of
70n this account bulk rate measurements are intrinically controlled by
two convoluted independent factors or parameters. Only a unique insight
into interfacial growth mechanisms is obtained from spherulitic or
lamellar (single crystal-like) interfacial tranformations per se from the
polymer melt or solution growth respectively, and not from a composite
of G and N contained in (4) above.
References page VI - 391
VI / 284 RATES OF CRYSTALLIZATION OF POLYMERS
(i) spherulitic growth rate and (ii) nucleation counts made
over relatively long transformation times.
Investigations of liquid-+solid phase transformations
with SAXS and WAXS techniques now employ rotating
anode X-ray (117) or the more intense synchrotron radia-
tion sources for real time kinetic measurements. Normally,
good policy to check samples for radiation damage after
each experiment. Even so, it has been reported that the
development of two or more crystal modifications may be
identified and monitored in situ by synchrotron WAXS and
SAXS investigations (11&l 19). Dilatometry, and/or DSC
measurements for example, may be usefully combined with
SAXS investigations where the absolute integrated scatter-
ing intensity Q was expressed (21) as
Q = K+(l - dbc - ~a) W)
and later modified to read:
Q = KwW - 4>(pc - pa)* w-9
In this equation K is an instrumental constant, pc and pa
being the densities of the crystalline and amorphous
regions, respectively, 4 is the volume fraction crystallinity,
and v, is the spherulitic volume. Note that Q increases with
crystallinity, reaching a maximum around 4 = 0.5 as
Sheldon had shown earlier. Rate profiles for poly(tetra-
methyl-p-silphenylene siloxane) [poly(TMPS)] fractions
(21) of high and low molecular weights differ in some
respects from measurements made by other techniques.
Strangely, changes in Q for relatively long isothermal
transformation times show no signs of the secondary
crystallization often encountered in isothermal dilatometry
for the same high molecular weight samples. Long period
thickening becomes invariant with the time of crystal-
lization in some polymers, but not in poly(ethylene)
(25,117,121). Interestingly, synchrotron SAXS work on
poly(P-hydroxybutyrate) (20) has shown that the long
period is unaltered with time during isothermal crystal-
lization from the melt even though crystals of this polymer
have been found in another study (122) to thicken
isothermally upon annealing. Elsewhere (123) in oriented
poly(ethylene) the long periods are found to0 change
reversibly between 30C (217 A) and 100C (252 A). Upon
cooling of poly(TMPS) fractions, following isothermal
crystallization, under quiescent conditions and reheating
crystallized sample(s), a reversal of the long period,that is
dependent upon molecular weight is observed (21).
Concomitantly, the crystallinity increases upon cooling
specimens from the crystallization temperature to room
temperature (125). More detailed measurements have been
made recently (62) where it was demonstrated that the
increase in the degree of crystallinity by WAXS and SAXS
cannot be correlated with the long period. Clearly, more
investigations of this kind are needed.
2.2. Thermodynamic Crystallization Mode/s Thermo-
dynamic and statistical theories of morphology (124,126)
do not provide rate data but only important crystalline/
amorphous information, i.e., morphological features con-
sistent with thermodynamic quantities predicated to change
with crystallization temperature or undercooling. Kineti-
cally, these models hardly merit a place in this article on
rate measurements except that they do provide information
on the equilibrium crystallite size I, in relation to its
melting temperature T, of the finite crystal, from the
general expression of the form
(A%
that may be simplified for very long chains when the last
term vanishes. In Eq. (A9), x, is the molecular chain length,
R, the gas constant, and AH,, the ideal enthalpy of fusion
per mole of repeat units comprising the crystallites of end
interfacial energy, (TV. Tz = AH/ASo is the thermody-
namic temperature of the infinite crystal with enthalpy and
entropy, AH0 and ASo, respectively. Theories of melting of
polymers have been the subject of much discussion (127)
over the years. For example, the reported thermodynamic
melting temperatures of poly(ethylene) range from 414 to
419 K and from poly(oxyethylene) from 342 to 348 K are in
dispute based upon theory and experiment. At best, Ti is
only reasonably well established for a few well-character-
ized polymers, yet so much morphological, growth kinetics
and structural interpretations are based upon Tz. Only a
fraction (5 70%) of the chains are folded into the end
surfaces of the crystallite (126) but the quality and even the
extent of the re-entry adjacency is still disputed.
The crystal fold surface of poly(ethylene) crystals and
interfaces have been studied more than any other polymer
(126-130). This dispute is likely to continue until the
crystal surface morphology in real space (88,89) can be
resolved and the corresponding surface(s) chemically
analyzed by the newer experimental techniques of the last
decade or more ( 13 1,132,133). It should be realized that the
thermodynamic model, unlike the kinetic one, does not
require a chain-folded nucleus, nor does it provide kinetic
information.
2.3. Growth Kinetics of Lamellar Structures: Crystals
and Spherulites Growth rate depends primarily upon the
degree of undercooling rather than on the crystallization
temperature, but the influence of chemical and physical
structure and molecular weight and molecular weight
distribution are also important factors in linear chain
polymers. Without impurities, growth occurs isothermally
at a constant rate, and the temperature dependence of these
rates are typical of a nucleation controlled process (134),
whatever the model employed to describe it.
Theories for isothermal growth rate-temperature, G(T),
in polymeric and other less complex systems can be
formulated simply by
G(T) = f(T)D(T) (AlO)
Introduction: General Principles and Techniques Involved in Crystallization Rate Studies VI / 285
which is often approximated by
G(T) = g
(All)
It is frequently assumed that the temperature dependence of
the diffusive term D(T) is reciprocally related via the
Stokes-Einstein relationship to the zero shear viscosity
q(T) which is more readily available than D(T). The f(r)
term in equations (AlO) or (Al 1) differentiates between the
growth geometries introduced in various growth rate
models. Different formalisms (l(a),4,15,61,119-121,134-
137) invoking chain folding and diverse nucleus/growth
geometries have been used to simulate crystallization. One
of the most elaborate and widely used kinetic descriptions
is the modified multiparameter model of the original
Hoffman-Lauritzen theory (1). Another salient model is
that to Point (137), who first predicted the correct crystal
thickness temperature up to large undercooling, that is
accordance with experimental evidence (138- 140). Point
and others (137), have disputed some of the basic ideas in
Hoffmans model, that pertain to a stable nucleus and to
surface energy and other related features connected with
growth Regimes that are now postulated to describe
interface roughness and interfacial energy assigned to three
stages of undercooling (see below in text). Points test of
Regime theory (141) questions its validity, though there is
much experimental evidence (142) pro and con for
transitional breaks in growth rate with undercooling.
The matter is still unsettled.
The Hoffman-Lauritzen spherulitic growth rate equation
(Al) is similar in principle to the Becker-Diiring model
(except for the complexions that are invoked to incorporate
chain folding). The basic equation can be represented
formally by
G= Go exp(-g) exp(-g) (A12)
In which Ga is a constant for a given molecular weight,
AE* is the activation barrier to molecular chain transport,
and AG is the free energy barrier to nucleation.
Only valid for spherical molecules, but it has been used indiscriminately.
9 Questions have been posed (61) that challenge the mechanistic nature of
the nucleation processes per se. Recent AFM work has shown (68a) that
growing polymer lamellae at the melt-crystal interface exhibited sporadic
behavior with time, suggesting that stress may be a significant influence.
Interestingly, reports on asymmetric aromatic hydrocarbons (60) have
cited and demonstrated stress related growth behavior at faceted
spherulitic interfaces. In this paper it was stated that this could complicate
growth rate measurements unless proper care was exercised. The
implications of this commonality in the behavior of polymers and small
molecules may lead to further interesting investigations into materials,
generally.
Recently it was reported (144a) that the P-relaxation process is
responsible for nucleation from the quenched state but this seems to be
irrevalent to isothermal crystalliztion that takes place directly from the
supercooled molten state well above the glass transition temperature.
Crystallization from the supercooled melt and from glassy polymers (see
Ref.5, p.258 and elsewhere) and small molecules were investigated (60)
in some detail a long time ago and explained along conventional lines by
the writer.
However, the L-H model differs in several important
macromolecular details that distinguish it from small
molecule morphology. Following the ad hoc assumption
that the first exponential in the crystallization equation
(A12) may be approximated by a Vogel or modified
Williams-Landel-Ferry (WLF) type of terrn,12, Eq. (A12)
becomes
G = Go exp[-R(~y Td q-g] (Al3)
Here To lies at least 30 below the glass transition tempera-
ture T,, at a temperature where growth enabling motions
vanish. A is an activation energy for such segmental
transport, usually - 5 kcal/mol. The nucleation term is
often expressed as
BT
exp -*
1 1
(w
Here the undercooling AT = (TL - T) and Tz is the
melting temperature of the perfect polymer crystal, most
often obtained by extrapolation. The term AT- implies
two-dimensional surface nucleation (growth) but it has been
claimed (143) that a ATp2 dependence provides an equally
valid fit to experimental growth rate data. The geometric
parameter B may be expressed as
B =nbocm,/f Ahfk
W)
where bo is the inter planar distance in the growth direction,
0 and ge are the lateral and end surface (interfacial) free
energy of the growing crystal or lamella13, k is Boltzmanns
constant, and flhf is the heat of fusion of the crystal. The
adjustable parameter f(0 If 5 1) accounts for the tem-
perature dependence of the heat of fusion away from the
melting point. Another fitting parameter $, (0 5 $J 5 1) is
an apportionment factor of the bulk free energy asso-
ciated with nucleation and growth away from the melting
point. This has been troublesome in the past, amounting to
serious discrepancies between theoretical and experimental
values of lamellar thickness, 1, with undercooling and it was
referred to (by Hoffman et al.) as the 81 catastrophe (1).
Now, in a recent paper by Snyder et al., (146), claim to have
resolved this problem. This integer n, (is not to be confused
with the Avrami, IZ, in equation (1)). The Hoffman
parameter, n, is both morphology and growth rate related
and is claimed to coincide with nucleation Regime changes
at the growth front with undercooling in some polymers
ii The writer (60,144) pointed out decades ago that it differed in
magnitude, from the macroscopic viscosity (or fluidity) temperature
dependence by fitting experimental data for asymmetric aromatic
hydrocarbons.
l2 Just recently (145), further considerations of Eq. (A13) concludes that
a better fit to transport data is obtained by compromising the C 1 and
9, parameters in the classical WLF type formulation for transport in the
melt.
I3 This geometry is consistent with many polymer morphological habits.
References page VI - 391
VI / 286 RATES OF CRYSTALLIZATION OF POLYMERS
(1,147,148). It alters for a smooth interface (n = 1) to a
rough one (n = 3); IZ = 2 corresponds to an intermediate
morphology. Several transitions in growth rates (149-
152) are claimed to be consistent with Hoffmans predic-
tions. Before this theory, breaks in the growth rate with
undercooling were assigned to morphological changes, but
now it is accepted by many investigators though the entire
issue is still under discussion.
The concept of reptation14 (7,152(a)) is another process
that has been claimed facilitate chain foldingI of lamellae,
and to circumvent chain entanglements at the melt-crystal
interface during crystallization. Experimental evidence (see
for example 30, 45,69,144,153-155) questions its validity
in interfacial growth kinetics, whenever spherulitic growth
over a wide span of molecular weight fractions is
investigated. For example, the dependence of the interfacial
surface energy of crystallites on molecular weight is
contrary to expectations if reptation was indeed functional.
Clearly, it does not override topological constraints and
multiple nucleation events that suppress chain folding and
seriously diminish sample crystallinity in poly(TMPS) and
polyethylene - see for example (Ref. 155). It is well known
that low molecular weight crystalline fractions are mostly
chain folded and brittle because of the lack of tie-mole-
cules. On the other hand high molecular weight fractions
are tough due to the existence of disordered regions as well
as the presence of tie molecules. Hikosaka (156) has
proposed another kinetic model for crystallization that
simultaneously deals with lateral lamellar growth (chain-
folding) coupled with crystal thickening for extended chain
growth. Hikosaka and co-workers (157) believe this theory
accounts for pressure crystallized polymers (158) and chain
extended polymeric mesophases (159). Now, an all-
encompassing crystallization scenario involving both of
these features is claimed to be relevant in all polymer
transformation kinetics (157). Although interesting, this
model is open to question because other investigations
dealing with in situ real time monitoring of solid phase
transformations (1162) points out that melting per se
precedes chain extension.
Another model termed Molecular Nucleation has been
emphasized by Cheng and Wunderlich (160a) as a
significant factor in the crystallization of PEO fractions
and mixtures but it is not readily amenable to experimental
testing yet, although it has received favorable mention from
Point (159a). So faq all theories of polymer crystallization
and morphological models formulated, do not have & priori
predictive capability whether they invoke chain folding
implicitly or not. The formation of lamellar structures is
I4 A recent review (45b) still insists on this process even though it is
unable to facilitate chain folding in high molecular weight polymers, nor
is it required to account for crystallization behavior below the
entanglement molar mass, MC.
I5 If folding is a consequence of kinetics, it is an inherent surface defect
that compromises the attainment of high degrees of crystallinity even
under the most favorable circumstances. Multiple nucleation and
topological contraints worsens this flawed situation even more as physical
measurements have shown (eg. see situation summary in Ref. 155).
Another publication is in press.
amply backed by electron and X-ray diffraction evidence
(4,47,160) but real surface details are still lacking. Studies
of well-defined oligomers of poly (ethylene) (67,68) and
poly(oxy-ethylene)s (66) support chain folding in short-
chain polymers crystallized from the melt, yet the latest
WAXS and SAXS measurements indicate that there are
conflicting details too (68a,160).At this stage, it appears
that the evidence is insufficient to take a polarized stance on
this problem bearing in mind the balance of existing
evidence and not opinion.
3. Other Significant Aspects of Crystallization
In the preceding sections, some of the following items have
been mentioned, but the writer believes that they deserve
more attention as many of these areas have grown since the
publication of the third edition of this Handbook. For
example, there have been developments in:
(I) Non-isothermal crystallization
(II) Crystallization of blends
(III) Solvent and pressure induced crystallization
(IV) Mesophase crystallization
(V) Flow induced crystallization
(VI) Epitaxial crystallization
(VII) Orientational crystallization from the melts and
solutions
(VIII) Crystallization of copolymers
(IX) Computer simulations
A brief foreword is given by way of introduction in these
important areas. Rate measurements in all of these fields
except for epitaxial crystallization appears in the tabulated
data in this chapter. In some respect, the growth
experienced on a given topic is connected with practical
developments and manufacturing and that often provides
the opportunities for further investigations.
3.7. Nonisothermal Crysfalliza tion This important
aspect of polymer crystallization is responsible for the
morphology and properties of processed polymers that are
crystallizable (ie. polymers, blends, mesophases or any
combination of these ingredients in a plastic product) to
whatever extent. in the developments. There are many
complex events responsible for polymer properties. Several
approaches have been used to gain a better representation
and understanding of non-isothermal crystallization pro-
cesses, since the quality of manufactured plastics goods
depends upon it. Processing induced structures are never
homogeneous even when the materials are thin films or
fibers. Because of their complexity, years ago fundamental
knowledge was gained through experiments, but now
computer modeling has increased in popularity. Several
approaches to this problem exist. The techniques of
Ozawa (162) Nakamura et al. (163) are still popular. In
essence, they have been usually modeled as an extension of
Avrami theory
e(t) = 2 e,(t)
(Al6)
j=l
where the phase change over the crystallization range is
considered to be comprised of many incremental isothermal
parts so that wherej = 1 to k involves all the types of nuclei
(i.e., homogeneous, heterogeneous, pseudo homogeneous,
thermal, athermal and so on). The nucleation rates R(t) and
growth rates G(t) has been patterned as
R(t) =&[f(t)] and G(t) = G[f(t)]
W7)
Simplifying assumptions lead to a more general equation.
After some manipulations, it becomes:
log{ -ln( 1 - x(t)} = log k(T) - n log p
w9
where x(t) is the fraction of material transformed at Tand p
is the cooling rate, k(T) is the cooling rate function and 12 is
the Avrami exponent. From plots of log{-ln[l - x(t)]} VS.
log p a straight line is obtained if Osawas method is valid.
From this plot, k(T) and n respectively can be obtained.
Harnisch and Muschik (164) derived the Avrami
equation from non-isothermal crystallization thermograms
where
x(t) = 1 - exp (-kntn)
(fw
A plot of log {-Zn[l -x(t)]} vs. log t for each cooling rate
is linear, providing the adjustable parameter k, and 12 that
are needed. Two parameters are different from the
isothermal values. Besides this, it is important to realize
that the heat of fusion of the 100% crystalline polymer is
needed for the data analysis.
Ziabicki (165) developed a procedure where he assumed
that crystallization in polymers may be represented by first
order kinetics, i.e.,
; = (1 -x)kT
( AW
wherein overlap of growing moieties is neglected and k(T)
is a temperature dependent rate constant. Plots of rate
constant vs. T is Gaussian-like; so that the kinetic
crystallizability C, may be expressed in terms of D, the
width of the crystallization exotherm at half-height and
kmax equals k at the top of the exotherm
Tltl
C =
J
k(T)dT = (n/ln2) 12k,,D/2
Wl)
Tg
Depending upon the polymer and its crystallizability (fast
vs. slow kinetically), C varies more than three or more
orders of magnitude (polymer to polymer) but kinetic
parameters obtained from Ziabickis method do not always
Introduction: Other Significant Aspects of Crystallization VI/287
compare well with other methods. Except for tests on
blended systems in recent literature (164) others were
reasonable. A generalized theory by Ziabicki (165), con-
taining the thermodynamics and kinetics of phase transi-
tions, while sound in concepts, appears complex and not
readily amenable to testing.
Whenever polymer melts or solutions are sheared (166)
the nucleation rate can often be drastically enhanced so that
the overall transformation rate becomes accelerated, if the
conditions are conducive to crystallization (167,168). If the
external cooling is sufficiently rapid, the level of crystal-
linity may be compromised for instance in molded parts
that may subsequently crystallize slowly (ie. age in storage)
causing serious changes in dimensions that could cause
distortion in the workpiece. Moisture conditioning of
polyamides, for example, is a well practised industrial
procedure that is used to stabilize fibers on-line and as
processed molded parts. Network systems undergo non-
isothermal crystallization or isothermal crystallization
when they are oriented uniaxially (169) or biaxially
(170). Some of them have been analyzed from the view-
point of kinetics and/or thermodynamics as further alluded
to in the next section. Non-isothermal crystallization at
varying cooling rates is representative of actual polymer
processing situations. Integral methods have been devel-
oped (171) for simulating the material fraction of
transformed material under arbitrary cooling rates but the
widespread use of Avrami theory has been criticized (see
Computer Modeling section).
In industrial processes rapid sample cooling and
monitoring has been a problem. Years ago, the writer
introduced the light depolarization intensity method (LDI)
to follow rapid changes taking place on the spin line and
in laboratory tests (94). This procedure is now widely used
and has just been further developed (95) to cope with
average cooling rates as high as 5000Umin. for the
investigation of non isothermal crystallization generally
(i.e., with constant and varying cooling rates) as Spruiell
and coworkers have demonstrated for polyolefins. Over the
years, Janeschitz-Kriegl and coworkers (see for example,
(38)) have investigated the theoretical and experimental
difficulties associated with transport and transformation
processes encountered in polymer crystallization. In recent
papers, they have detailed their findings.
3.2. Crystal l i zati on of s/ends The first polymer blend
was made from two polymeric rubbers in 1846, but polymer
blend technology and a scientific understanding of the
underlying principles controlling the compatibility (or lack
of) in polymer mixtures (alloys as they have been named
recently) has taken place only in the latter part of the
current century. Many blends are non-crystalline but our
interest in this document is focused on the kinetics of phase
transformations of binary and ternary systems that receives
more attention annually. Some of these systems can be very
complicated, often comprised of multiple phases that may
involve homopolymers, copolymers, mesophases and the
like. Polymorphism and even isomorphism may occur
References page VI - 391
VI/288 RATES OF CRYSTALLIZATION OF POLYMERS
because of inherent chemical interactions, imposed tem-
perature and pressure conditions and so on. Despite these
complexities, blends comprise a significant part of indus-
trial production where synergism among materials is often
exploited through various processing techniques.
The lattice theory of Flory-Huggins captures the
essential features of mixing and demixing and the
magnitudes of their corresponding entropic and enthalpic
changes have provided a basis of understanding for some
fifty years ago (172). Since then, experimental practice and
more subtle theoretical developments, including computer
simulations, have advanced our understanding of homo-
polymer and copolymer blends (see for example, Binder
(173)). With mesophases the situation becomes more
complex but it is still beneficial in practical ways. On the
technological side, Utracki (174,175) has provided infor-
mative overviews of the processing science and technology
of blends or alloys in detailed accounts of processing-
morphology-property relationships.
Crystallization always involves phase changes and often
insufficient attention is given to transformation rates that
may correlate strongly with structural and morphological
details. For polymer mixtures/blends and copolymers with
one or more random components, certain generalizations
may be made when they are crystallizable. For instance in
bulk crystallization, the Avrami or a related theory has often
been employed to analyze bulk kinetics in blends to
demonstrate the strong effect of molecular weight and
composition on transformations rates. There is an analogy
here with homopolymers in that crystallization rate is
usually suppressed by the non-crystallizable component(s)
in the system. Consequently transformation curves are
moved to lower temperatures, although their transformation
isothermals are seldom superposable (as they are in most
homopolymer transformations). Spherulitic growth rates are
usually attenuated too and shifted toward lower tempera-
tures as the results compiled in this article show. The
crystallization of blends has been modeled by thermo-
dynamic or kinetic type equations employing computer
simulations.
3.3. Solvent and Pressure-induced Crystallization Di-
luent or solvent in a polymer system, alters its crystal-
lizability and often its crystallinity is enhanced. Solvent-
induced morphological changes (176) may occur and
mechanical properties and deform ability including aging
behavior (177) of systems can be affected so that the topic
is of considerable importance technologically. Plasticizers
(178), nucleants (179), and chain length (180) may
attenuate or sometimes accelerate the phase transformation
kinetics. Several types of investigations and analysis have
been employed. Mandelkern and others have adopted a
thermodynamic approach where the focus is on the overall
Gibbs free energy for nucleus formation, while crystal-
lization kinetics has been investigated by using the Avrami
theory as a basis for detecting mechanistic changes with
time, temperature, and diluent concentration. For spheru-
litic growth kinetics the effect of diluent on morphology
and crystallization kinetics has been formulated (74)
according to
G= Ghenp(&!ko)} exp(eAGii :) (A22)
where AG: is the free energy contribution from the solvent
(diluent), the other terms having been defined before.
Equation (A22) may be modified to take care of crystal
geometry and polymer diluent interaction. These effects are
very marked in many polymers, especially where plastici-
zers that modify physical behavior are involved, as for
instance moisture in polyamides. In these circumstances the
defining parameters A, Gb, Th are altered (usually
decreased in magnitude compared with homopolymers).
In non-compatible polymer blends (18 1) this is often a rare
event, and changes in morphology and crystallization
behavior have not always been documented even when
rates have been measured. Copolymer systems are being
studied more extensively (18 l), and spherulitic growth rates
(181,182) are receiving some attention as later tabulated
results illustrate.
Pressure induced crystallization has been documented
for a few systems (183), poly(ethylenes) (31,46,184) in
especially being the most extensively investigated materials
from a morphological and properties viewpoint. Conforma-
tional constraints are responsible for gauche bond formation
in polyethylene, for example, lead to the formation of the
higher entropy hexagonal phase as a morphological high-
pressure intermediary that is essential to the overall
thermodynamic picture of its melting temperature-pressure
phase diagram. Other kinetics data (185-190) are also
listed in this article. Pressure is a significant processing
parameter. In the past, experimentation was the yard
stick rather than theory for optimization of polymer
processing conditions. Crystallization kinetics made by
dilatometry at small undercoolings (190a) has moved the
focus to the process rather than on the product itself for
nylon 66, polypropylene and poly(ethylene terephthalate).
According to Zoller (190a), the Malkin modification of the
Avrami equation best describes the kinetic data in this
investigation. Other systems such as polypropylene behave
likewise, and PVT modeling studies have been published
(190b,190c).
3.4. Crystallization of Mesophases Although poly-
meric mesophases were discovered more than one century
ago (191), their exploitation has only been developed
within the recent decades. Synthesis, properties and
applications have been the focus of most studies because
of the technological potential of these systems. Now that it
is known that mesophases form supermolecular structures
through self-organization, this discovery has lead research-
ers to investigate the criteria underlying liquid crystalline
formation. The morphology and structure of these polymers
have been the subject of theories (14,192,193) and
experiments (194). Molecular design vis a vis properties
(somewhat analogous to activities in drug chemistry/
-
industry) has become an attractive research topic. The
molecular requirements for liquid crystallinity have been
featured in papers and reviews (19.5) that have also covered
lyotropic and thermotropic phases. Structure in these types
of phases have sometimes been tailored to ease processing
and/or to facilitate or even to reduce rates of crystallization.
Blending has been tackled through processing and model-
ing, including phase separation dynamics (196); yet
crystallization kinetics, despite its importance, has had a
low profile until comparatively recently, kinetic measure-
ments on mesophases are still sparse. Most results known to
the writer, are tabulated in this article. Rate data have been
analyzed along the conventional lines normally used for
homopolymers in Section B. Insufficient research has been
devoted to the development of a new theory and to examine
the influence of crystallization rate on morphology-proces-
sing-property relationships; viscosity and diffusion con-
siderations notwithstanding.
Crystallization of some thermotropic copolymers cannot
be explained on the Flory model (192) through homo-
polymer segregation. However, Windle and coworkers
(197), by means of computer modeling have demonstrated
that 3D ordered regions, described as non-periodic layers
(NPL) are possible. Structurally, NPL crystallites agree
with experimental X-ray observations even when random
intramolecular statistical sequencing exists. This ongoing
project is of interest as the NPL model may also be
explained by a paracrystalline lattice (PCL) model, that
does not require explicit sequence matching (198).
3.5. Flow-Induced Crystallization This topic covers
polymer solutions and melts (199,200) generally and may
be further categorized into
(a) flow induced Poiseuille flow (201),
(b) elongational flow (199),
(c) shear induced transformations (202,203),
and there are others.
Polymers, other than homopolymers (i.e., blends,
copolymers, mesophases) have been listed according to
processing characteristics. Rates of crystallization in these
categories are sparse compared with synthesis, structure,
morphology, properties, processing and even computer
simulation (the latter being a rapidly growing field), with
some information on the factors/forces that modify
behavior. An exception is the work of McHugh and
coworkers (204,205) who have reported the strain induced
crystallization rates of swollen poly(ethylene) networks by
using dynamometry coupled with in situ fiber video-
imaging with birefringence measurements in order to
obtain one dimensional heterogeneous growth rates. How-
ever, the deformation rates encountered in these experi-
ments are much lower than the values encountered in
commercial fiber melt spinning and molding processes.Still,
modeling is now underway to link transient deformation
histories with flow induced shear results (205). These
authors have just developed a continuum model for flow
Introduction: Other Significant Aspects of Crystallization VI / 289
induced crystallization that embodies strain induced
crystallization by employing an irreversible thermodynamic
formalism based upon principles set forth by Beris and
Edwards (206) for describing non equilibrium irreversible
thermodynamics of flowing systems.
The Hoffman has developed a kinetic model for fibrous
crystal growth from solutions (207). It is patterned after the
well established pioneering solution spinning shish-
kebab textures, and properties by Pennings and co-
workers (see for example 208,208a) and others (208b)
especially for UHMWPE and their blends. In this model,
shishs comprise a well-oriented central core fibrils
(N 15-50nm) flanked by chain-folded kebab over-
growths off the core. The shish cores are interconnected
by highly strained amorphous regions. They (core regions)
contain many defects. Here again, the paucity of experi-
mental rate data hampers testing of the theoretical model.
3.6. Epitaxial Crystallization This aspect of crystal-
lization deserves to be mentioned. Polymer-polymer
epitaxy (209-210) involving mutual interactions between
different macromolecules where crystallinity, crystal struc-
ture, lattice matching, molecular conformation and chem-
istry have been considered. The kinetics of epitaxial
processes have been largely ignored despite their plausible
significance in surface bonding that has practical implica-
tions.
Recent experiments (211) have shown that the lamellar
thickness of poly(ethylene), PE, on oriented isotactic
poly(propylene), changes from 16 to 39 nm upon annealing.
This thickening is attributed to dimensional matching and
secondary nucleation with the requirement (212) that the
PE crystal(s) are thinner than the i PP dimension along the
chain-row matching direction. However, no detailed kinetic
measurements were reported on the rate of epitaxial growth
here, or elsewhere in the literature.
3.7. Orientational Crystallization Strain, shear, and
elongational flow under isothermal or nonisothermal
conditions promote crystallization. The problem is of
long-standing commercial importance in fiber manufactur-
ing, injection molding (213) and other important processes.
On the academic side, the problem has been recognized for
a long time, but it has been studied only sporadically until
now (203). Although published data are still sparse, useful
behavioral trends have been established.
Crystallization of cis- 1,4-polybutadiene between rollers
during shearing has been modeled (214) using a novel
procedure in which the influences of shear flow on lateral
heat conduction is approximately avoided. This technique
permits the crystalline layer build-up to be determined as a
function of time, temperature, and shear rates in on-line
processing. The morphology created under these conditions
was studied. This is not an easy kinetic problem to
handle theoretically.
Crystallization in polymer networks has received some
attention (169) since Flory proposed the basic principles
many years ago (215). Gaylord (216) modified this theory
References page VI - 39 1
VI / 290 RATES OF CRYSTALLIZATION OF POLYMERS
for finite chains while others studied and determined the
interrelation between elongation, melting, and crystallinity.
Calculated strain dependence of the melting temperatures
(max), average crystallite sizes and crystallinity extension
ratios, Xs, as high as four for crosslinked rubber networks
have been correlated, but rates of crystallization were not
included in this kind of work that is further addressed by
Negahban in Section IX.
3.8. Crystallization of Copolymers In this category, the
focus has been on morphology and properties though Flory
(2 15) developed an equilibrium thermodynamic description
of the semi crystalline state of these materials almost half a
century ago. Fusion of copolymers is expected to occur
over a wider range of temperature in contrast to
homopolymers. Random and block copolymers have been
studied and melting theories are widely used to describe
them. Whenever one species of a copolymer is crystal-
lizable and is dependent upon its sequence probability, p,
and not on composition, its melting behavior has been
described16. The technological importance of copolymers
has developed over the years, but kinetic descriptions of the
phase changes observed (often multiple) have been mostly
patterned after models for blends that are analogously
related to equation (A22) whenever crystallization
proceeds according to a spherulitic morphology. The non-
crystallizable component(s) affects crystallization para-
meters in accordance with their degree of compatibility
and interfacial transport that often constrains and usually
suppresses growth rate. Even so, the morphological features
that determine the overall crystallization kinetics and
properties do change with molecular weight and co-unit
content and rates have been monitored and analyzed mostly
according to procedures outlined in Section A. Morphology
varies with molecular weight akin to the behavior
encountered in homopolymers. Avrami type transforma-
tions and spherulitic growth rates tabulated in this article
indicate that the time scale of the transformation is strongly
influenced here (more so than it is in blends of the same
composition) for species with similar compositions. Other
copolymers behave similarly even though the range of
molecular weights for these random copolymers of ethylene
is not extensive (216,217). Other kinetic theories of
copolymer crystallization have been formulated (218) and
tested. Modeling of copolymers with short crystallizable
sequences using a Monte Carlo approach (219) has been
aimed to reveal the 3D morphology of A-B type crystallites
such as ethylene-propylene with high propylene content and
low crystallinity. This work shows promise. Goldbeck-
Wood (220,221) has written an informative overview of
I6 Goldbeck-Wood [Polymer 33, 778 (1992)] has developed a new
melting point equation that is comparable with Eq. (A23) (see below) for
copolymer melting point depression, but it predicts a much steeper
dependence on composition than the Flory model which states
1 1
---=--
TM
T?!
ALU lnp
64231
where p is the sequence probalility [P. J. Flory, Trans. Farad Sot., 51, 848
(1955)].
computer simulations where the focus has been on
molecular dynamics and Monte Carlo simulations pertain-
ing to classical lamellar crystallization and 3D models. The
reader should consult the original texts for details.
3.9. Computer Simulations On this topic, there have
been a number of developments that have a kinetics basis,
apparently connected with assumptions used in the Avrami
theory that only provides analytic solutions. In simulations,
the approach has been used to model bulk transformations
for:
(a) volume shrinkage, non-random nucleation and
crystallinity variability (222),
(b) spherulite impingement in two dimensions on SALS
patterns (223),
(c) the morphology of spherulites (thermally and
athermally nucleated) (224) and the implications of
various nucleation modes, as well as density changes
and size distribution effects,
(d) isothermal kinetics in thin films, including the
influence of surface nucleation on morphology
(225,226), and
(e) simulation of crystallization in polymeric compo-
sites in two dimensions with some representation of
the three dimensional situation (227), and for several
other criteria too.
Simulation of phase transformations in these examples
have some predictive capability. For composite systems, the
Avrami model as such, is claimed not to apply because
nucleation is constrained by fiber loading and surface sites.
For instance, factors such as fiber fraction and diameter,
spherulitic growth (normal and transcrystalline) must all
figure in the overall composite morphology.
Another different, but recent approach by Negahban and
coworkers (228-230) to crystallization kinetics involves
modeling:
(a) thermo-mechanical effects that occur during the phase
transformation in simple homogeneous processes,
(b) simulation of the thermo-mechanical effects of
crystallization in non-homogeneous processes and,
(c) developments of models for the prediction and
verification of material responses.
There are other criticisms of the Avrami method here.
Negahban points out that modeling of crystallization
kinetics using Avrami-type equations is incompatible
with the entropy production inequality (i.e., Clausius
Duhem inequality) that is basic to the termination of
crystallization in real situations. Much of his work has
concentrated on the crystallization of rubber (literature
results) with all its ancillary effects/property-wise material
functions that are amenable to simulation. In the same
manner, the kinetic theory of crystallization, based upon
concepts of molecular chain-folding and its related
parametersat the same time recognizing some of the
shortcomings involved. An attempt has been made to keep
Rates of Crystal Growth VI / 291
this section relevant to crystallization kinetics even though
modeling/simulation procedures are becoming widely
applied now, on account of growing availability of
computers. In this regard one of the more recent practical
computer simulations that has been developed for injection
molding,embodies nonisothetmal and stress-induced
crystallization kinetics in poly(phenylenesulfide) during
processing (232). The authors claim to be able to predict
the thermomechanical history and crystallinity develop-
ments in PPS in reasonable agreement with experiment.
Undoubtedly, there will be further developments in this
field,because of its technological and economic relevance.
ADDENDUM
This chapter on Rate of Crystallization of Polymers is
incomplete for several reasons. Sometimes original data
were not available. Where the deconvolution of complex
graphical kinetic scenarios was unnecessarily tedious and
resulted in questionable accuracy, these data were omitted.
However, results are listed for rate plots that could be
deciphered and digitized satisfactorily. Original data
provided directly by authors are included and gratefully
acknowledged by the writer.
B. TABLE OF RATES OF CRYSTALLIZATION OF VARIOUS POLYMERS
1. Rates of Crystal Growth
TABLE 1. POLY(ALKENES), POLY(DIENES), POLY(VINYLS)
Polymer Tf (C) T, (Cl G (NW Remarks Refs.
1.1. HOMOPOLYMER MELTS
Poly(ethylene) oligomers C246 (alkane)
Poly(ethylene) oligomers C294
(monodisperse)
Poly(ethylene) oligomers C246
118 680
119 638
119.6 1 3 7
120 124
120.6 67
121.1 138
121.5 1 0 3
122 138
122.5 142
123.1 159
123.5 103
124.0 75
124.6 67
125.1 25
118 1100
119 840
120 960
1 2 1 530
122 260
123 170
123.5 120
124 20
124.5 2.1
1 2 5 2
126 4
127 4
128 2
129 2
118 4310
119 3000
120 2250
120.5 2430
1 2 1 910
121.8 30
122 60
122.5 100
123 150
124 220
125 230
126 200
1 2 7 130
128 70
Melt crystallization as thin film;
phase contrast hot stage microscopy;
1 /t~,~, transformation rates for
Cl98 follow a similar pattern with T,
Optical and electron microscopy,
melt crystallized banded and
and lamellar spherulites
233
234
234
References page VI - 39 1
VI / 292 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 1. cont' d
Polymer Tt (C) Tc (Cl G (mW Remarks Refs.
Poly(ethylene)
M, = 32000
M, = 119000
Cl98 118
119
120
121.8
122
122.2
122.5
123
123.5
124
1 2 5
125.5
- 45
- 30
- 15
0
1 0
24. 5
39. 5
- 40. 2
- 25. 1
- 18. 2
- 13. 0
0. 2
- 38. 4
- 32. 8
- 26. 3
- 15. 7
4. 2
Poly(isoprene) cis
Poly (isoprene) cis with 2-2.5% rrunr
(a) growth in Hevea
M, / M, =4. 81
M, / M, = 16.93
(a) growth in Natsyn
M, / M, =4. 12
M, / M, = 10. 17
(a) growth in Natsyn
cis with 2-2.5% tram
(a) growth in Hevea
(CL) growth in Natsyn
- 39. 2
- 25. 3
- 19. 4
- 11. 3
- 0. 4
- 39. 3
- 34. 3
- 29. 5
- 25. 2
- 19. 3
- 14. 5
- 9. 6
- 4. 9
0. 6
- 39. 2
- 34. 3
- 29. 7
- 25. 3
- 19. 6
- 14. 4
- 10.1
-5. 1
- 10
- 10
1330
1440
1330
1140
1340
1180
970
1040
1020
980
590
500
3. 2
13
20
800
1000
20000
2oOOOO0
0. 023
0. 125
0. 138
0. 098
0. 019
0.011
0. 020
0. 030
0. 024
0. 006
0.001
0. 027
0. 118
0. 138
0.110
0. 027
0. 007
0. 014
0. 025
0. 034
0. 024
0.010
0.014
0. 009
0. 003
0. 004
0. 007
0. 013
0. 019
0. 016
0. 012
0. 009
0. 005
0. 071
0. 206
0. 370
0. 432
0. 233
0. 069
0. 017
0. 021
0. 123
0. 117
0. 051
0. 036
Crystallization from quenched droplets
upon heating; lamellar thickness over
the same range; 45 5 1 5 75 nm cited;
crystallization measured upon heating
Electron microscopy; thin films
Electron microscopy; thin films
Electron microscopy after staining;
for further details see text
0.0 kbar
0. 5 kbar
0. 7 kbar
1 . O kbar
1.5 kbar
1.7kbar
0.0 kbar
0. 5 kbar
0. 7 kbar
l.Okbar
1.3 kbar
1.5 kbar
234
235
238
238
186
186
186
186
Rates of Crystal Growth VI / 293
TABLE 1. contd
Polymer Tf ("Cl T, (0 G (ds)
Remarks Refs.
(a) growth in Hevea
(CL) growth in Natsyn
Poly(isoprene)cis
M, = 543000
Poly(isoprene)cis (from Hevea rubber)
M, = 313000
Poly(isoprene)cis GR-F u-lamellar
GR- AP a-lamellar
GR- AP P-lamellar
Poly(isoprene)trans-1,4
(low melting crystals) LMF
0 0.009
0.028
0.156
0.698
0.731
0.124
0 0.003
0.006
0.011
0.186
0.141
- 4 2 0.021
- 36.5 0.049
-31 0.068
- 27.3 0.113
- 20.8 0.093
- 16.1 0.065
- 10.6 0.036
- 5.6 0.014
- 2.5 0.013
- 0.9 0.011
1.4 0.0055
3.1 0.005
-41.2 0.040
- 36.5 0.061
- 33.4 0.074
- 31.3 0.082
- 27.1 0.145
-21.1 0.117
- 16.4 0.096
- 15.3 0.091
- 13.2 0.085
- 10.3 0.076
- 8.3 0.070
- 6.0 0.060
-4. 1 0.029
- 1.6 0.0098
- 0.0 0.0046
1.1 0.0038
2.7 0.00335
- 3 6 0.080
- 27.5 0.104
-21.5 0.144
- 16.7 0.114
- 11.8 0.093
- 5.0 0.069
- 35.5 0.063
- 27.0 0.093
- 22.0 0.111
- 16.8 0.094
- 11.7 0.067
- 5.0 0.041
41.7
44.3
46.5
47.5
49.0
41.7
44.3
46.5
47.5
49.0
4.2
2.1
0.95
0.50
0.23
7.0
4.7
2.35
1.90
1.21
(high melting crystals) HMF
0.0 kbar
0.5 kbar
l.Okbar
1.5 kbar
1.7 kbar
2.0 kbar
0.0 kbar
0.5 kbar
l.Okbar
1.5 kbar
2.0 kbar
Electron microscopy of thin films
( N 80.0 nm); growth (lamellar)
arrested by 0~04
186
186
239
Electron microscopy of thin film
( N 80 nm) growth; stained with
0~04; lamellar growth rates reported
239
Electron microscopy with 0~04
staining; u and p spherulitic
morphologies studied in quayle
rubber extracts as (a) fresh
extract GR-F and (b) aged
specimen GR-AP
Optical hot stage microscopy
T, (LMF) = 64C
u, = 23 erg/cm2
(negative spherulites)
T,(HMF) = 74C
ue = 35 erg/cm2
(dendritic spherulites)
240
240
241
2 4 1
References page VI - 391
VI / 294 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 1. contd
Polymer
Tt (Cl T, (Cl G (rim/s)
Remarks Refs.
Poly(isoprene)truns- 1,4
(high molecular weight fraction)
- 10.2 0.096
- 5.3 0.154
- 0. 6 0.42
4.3 0.80
9.9 1.43
14.7 2.08
47.3 1.47
49.3 1.09
51.3 0.77
5 4 0.44
55.3 0.30
6 0 0.052
- 0.7 0.11
4.8 0.22
9.4 0.44
14.7 0.82
19.3 1.38
55.6 1.25
58.6 0.77
60.5 0.55
6 2 0.374
64.3 0.14
68.0 0.079
4.5 0.102
9.8 0.26
14.3 0.49
19.5 0.89
25.6 1.58
57.5 1.29
61.5 0.80
63.5 0.57
66.0 0.31
68.4 0.14
14.2 0.23
19.3 0.44
24.4 0.79
6 8 0.64
68.3 0.46
71.6 0.23
7 6 0.11
29.3 0.104
34.5 0.202
39.5 0.39
44.6 0.69
49.2 1.10
5 4 1.46
59.5 1.75
63.7 1.80
7 0 1.67
7 5 1.17
79.3 0.58
8 2 0.35
84.5 0.206
8 7 0.103
49.3 0.104
5 9 0.44
64.5 0.66
7 4 1.06
79.3 1. 11
84.7 1.01
8 9 0.63
92.5 0.50
94.6 0.27
l oo 0.15
102.7 0.085
Electron microscopy with 0~04 187,242
staining; thin film N 1OOnm thick
spherulitic growth pressure = 1 bar
0.5 kbar 187,242
0.7 kbar 187,242
l . Okbar 187,242
2.0 kbar 187,242
3.0 kbar 187,242
TABLE 1. contd
Polymer Tf (Cl Tc ((3 G mm
Rates of Crystal Growth
Remarks
VI / 295
Refs.
Poly(isoprene)fruns-1,4
(low molecular weight fraction)
59.5
63.1
69.3
74
79.2
8 5
89.7
9 5
100
1 0 3
1 0 5
107.7
- 5. 3
- 0.6
4.4
9.8
14.7
39.4
41.3
44.7
47.1
49.5
51.3
54.0
55.8
4 . 4
9.5
14.5
19.5
2 5
50.5
55.3
57.6
59.5
62.3
9.5
14.8
2 0
2 . 5
51.5
5 6
57.6
6 0
6 1
6 4
14.4
19.4
2 4
29.5
36.6
5 6
57.1
59.8
63.5
6 9
3 5
39.5
45
49.1
54.5
59.8
6 4
IO
7 5
84.1
0.124
0.23
0.38
0.53
0.73
0.90
0.83
0.68 3
0.45
0.254
0.15
0.095
0.099
0.197
0.385
0.630
0.915
1. 81
1.33
0.90
0.62
0.41
0.26
0.12
0.063
0.11
0.19
0.32
0.59
0.98
0.96
0.51
0.33
0.20
0.07 3
0.088
0.22
0.40
0.63
1.08
0.78
0.57
0.42
0.24
0.082
0.089
0.180
0.303
0.57
1.02
0.98
0.83
0.66
0.39
0.16
0.104
0.154
0.31
0.46
0.64
0.79
0.794
0.12
0.46
0.072
3.5 kbar
Pressure. 1 bar
0.5 kbar
0.7 kbar
1 kbar
187,242
187,242
187,242
187,242
181,242
References page VI - 39 1
VI/ 296 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 1. contd
Polymer Tr (Cl Tc (Cl G (Mm
Remarks Refs.
Poly(isoprene)/epoxide cis
loo/O, w/w
95814.2, w/w
90.319.1, w/w
81.8/12.2, w/w
1. 2. SOLUTIONS
Poly(ethylene)
M,=3.1 x 103
M, = 2.9 x lo3
T, = 365. 9 K
Td=361.4 K
34.5
4 0
4 5
5 0
54.5
6 0
6 4
7 0
74.4
8 5
5 9
64.5
7 0
74.5
8 0
84.7
89.5
92.4
94.1
6 7
7 0
74.1
79.5
84.5
89.5
94.5
98.2
99.5
102.7
- 30.2
-20.8
- 2 0
- 10.6
- 5.7
- 30.2
- 24.8
- 20.0
- 15
- 5.1
- 30.2
- 24.8
- 2 0
- 5.7
- 30.2
- 24.8
- 2 0
- 1 5
- 5.7
70.45
72.93
76.10
11.00
74.05
18.25
81.00
83.00
84.00
85.00
86.25
0.096
0.15
0.32
0.48
0.64
0.17
0.82
0.72
0.47
0.085
0.08
0.195
0.33
0.42
0.48
0.40
0.26
0.14
0.052
0.091
0.15
0.18
0.29
0.35
0.36
0.29
0.19
0.14
0.C%2
8.5 x 10-3
30 x 10-3
10 x 10-3
6.3 x 1O-3
4.5 x 10-3
1.8 x 1O-3
2.3 x 1O-3
4.5 x 10-3
2.4 x 1O-3
5.5 x 10-3
0.5 x 10-3
0.75 x 10-3
0.10 x 10-3
0.53 x 10-3
0.12 x 10-3
7.67
6.53
4.41
4.40
5.21
2.93
1.25
0.12
0.62
0.36
0.18
2 kbar 187,242
3 kbar 187,242
3.5 kbar 187,242
2 4 2
2 9 2
2 9 2
2 9 2
Electron microscopy; temperature
control f O.OlC; data for [ 1 101
faces; 0.05 wt.% in xylene;
crystallized from stock
solution prepared at 75C
seeded growth used
4 2
TABLE 1. contd
Rates of Crystal Growth VI/297
Polymer Tr ((3 T, (C) G (mds) Remarks Refs.
M, = 3.1 x 103
M, =2. 9x lo3
T, =365. 9 K
T,, = 367. 4 K
M, = 4.05 x 103
M, =3. 90 x lo3
T, =367. 6 K
Td=371.5K
M, =4. 05 x lo3
M, =3. 90 x lo3
T, =367. 6 K
Td = 371. 5 K
M,=3.1 x lo3
M, =2. 9x lo3
T, =365. 9 K
Td = 367. 4 K
M, =3.1 x lo3
M, =2. 9x lo3
T, =365. 9 K
Td = 367. 4 K
M, =4. 05 x lo3
M, = 3.90 x 103
T, =367. 6 K
T,j = 371. 5 K
68.90 5.77
70.45 5.11
72.10 4.83
74.05 3.98
77.00 2.03
79.80 0.88
81.00 0.71
84.00 0.35
85.00 0.25
86.25 0.13
87.70 0.06
70.85 9.93
74.85 5.41
77.00 3.21
77.50 2.91
78.05 2.18
80.00 1.88
82.00 1.22
83.00 0.72
84.10 0.52
85.00 0.30
86.10 0.24
88.00 0.07
68.90 6.04
69.90 5.80
70.85 4.62
72.10 4.80
74.00 3.01
77.00 1.42
78.05 0.97
80.00 0.79
81.60 0.63
82.40 0.59
85.00 0.26
87.70 0.05
68.90 3.93
69.90 3.57
71.20 2.88
74.05 1.68
74.95 1.27
76.10 1.20
77.00 1. 11
78.40 0.96
80.30 0.54
83.20 0.34
84.00 0.21
86.25 0.10
87.70 0.03
70.45 1.06
71.20 1. 01
72.93 0.89
74.05 0.69
77.00 0.48
78.25 0.47
79.80 0.32
81.00 0.20
83.00 0.17
85.00 0.10
86.40 0.05
68.90 4.43
69.10 4.29
70.85 3.63
73.06 2.71
75.00 1.52
76.00 1.17
Temperature control f O.OlC;
data for [l lo] faces; 0.01 wt.%
in xylene
4 2
Data for [l lo] faces; 0.05 wt.%
in xylene
4 2
Data for [l lo] faces; 0.01 wt.%
in xylene
4 2
Temperature control h O.OlC; data for
[ 1 lo] faces 0.005 wt.% in xylene
4 2
Temperature control f O.OlC; data
for [l lo] faces 0.001 wt.% in xylene
4 2
Data for [l lo] faces; 0.005 wt.%
in xylene
4 2
References page VI - 391
VI / 298 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 1. contd
Polymer Tf (Cl Tc ((2 G (NW
Remarks Refs.
M, =4.05 x 103
M, = 3.90 x 103
T, =367. 6 K
Td=371.5K
M, =6. 75 x lo3
M, = 6.10 x lo3
T, =367. 8 K
Td = 368.4 K
M, >lo4
solution cont. 2.7 x 10m4 wt.%
2.5 x 1O-5 wt.%
4.5 x 10-5 wt.%
8.0 x 10-s wt.%
1.5 x 10-4 wt.%
2.7 x 10m4 wt.%
5.0 x 10-4 wt.%
9.0 x 10-4 wt.%
67
68
69
70
7 1
7 1
71.8
72.6
73.3
74.1
75.4
76.7
77.8
77.8
79.0
79.0
69.0
77.00
78.40
78.90
80.30
82.00
83.20
84.10
85.00
86.70
87.70
69.10
71.00
73.40
75.00
77.00
77.60
78.90
80.00
82.00
82.95
85.00
86.70
75.50
77.80
78.95
81.60
83.60
86.00
88.10
75.50
77.80
81.60
83.60
86.00
88.10
75.50
77.80
78.95
81.60
83.60
86.00
88.10
1 3 3
75
4 1
4 1
29
2 1
1 6
11
6
2.9
1.5
1 . 3 3
0.70
0.58
12.0
20.8
33.3
53.3
75
1 0 5
142
1 . 1 3
0.70
0.67
0.57
0.38
0.28
0.17
0.13
0.06
0.03
1.21
1 . 1 6
0.82
0.58
0.30
0.30
0.22
0.21
0.13
0.12
0.05
0.03
21.60
13.10
11.33
3.33
1 . 0 8
0.25
0.07
11.25
5.55
1 . 0 9
0.36
0.13
0.04
3.40
1.50
0.96
0.35
0.13
0.05
0.02
232
180
1 6 3
1 2 7
1 2 5
102
1 1 3
78
33
8 . 5
20
3 5
6 5
8 7
163
260
488
Data for [l lo] faces; 0.001 wt.%
in xylene
Data for [l 101 faces; 0.05 wt.%
in xylene
Data for [l lo] faces; 0.01 wt.%
in xylene
Data for [l lo] faces; 0.001 wt.%
in xylene
. 9 = 9.6 Growth rates from dilute
8 = 8.0 tetrachloroethylene;
0 = 6.9 single crystal and [ 1 101
0 = 7.0 twins measured, G N C I3
0 = 4.8 without [ 10 0] sectors;
8 = 3.8 G < Gt, enhanced growth
rate where 6 is the angle w.r.t. growth
direction in twinned crystal (see
text figures)
8=10
8-8.5
0=8.5
8 = 8.0
B=7.5
8=7.6
t=7.2
42
42
42
236
TABLE 1. contd
Rates of Crystal Growth VI/299
Polymer Tr V-3 T, V-3 G (mW
Remarks Refs.
2. 5 x 1O-5 wt . %
8.0 x lo-wt.%
2.7 x 10-4 wt.%
9.0 x 10-4 wt.%
4.5 x 10-3 wt . %
8.0 x 1O-5 wt.%
2.7 x 10-4 wt.%
9.0 x 10-4 wt.%
4. 5 x 10-s wt . %
I x 10-s wt.%
1.3 x 10-s wt.%
2. 5 x lo- wt . %
M, = 120000
M, / M, = 1.19
M, =32000
M, / M, = 1.11
M, = 13600
M, I M, = 1.19
73.3 3.5
7.8
15.8
31.7
15
75.4
32
6 1
1 2 3
317
54.5
58.4
61.7
50.0
82
83
84
85
86
86.5
87.2
87.6
87.6
88
88.5
89
89.5
85
85.9
86.1
86.8
85.5
85.9
86.1
86.8
86.9
87.0
87.4
88.2
88.7
89.2
89.6
90.2
90.6
9 1
86.8
87.1
87.8
88.5
89.0
89.5
90
90.3
9 1
91.3
91.7
92.1
92.4
92.8
93
88.3
7.2
78.3
167
15.5
32.5
71.7
43
31
27
28
48
1 0 5
450
340
208
1 2 5
58
5 1
3 5
27
24
1 8
1.3
5.5
2.9
0= 7.3; 0 is oblique angle with .9 = 5.9;
with respect to [l lo] faces; 6=4.8;
see Fig. 3 of text
Growth rates G measured by 246
Dynamic Light Scattering (DLS)
from self-seeded crystals in
p-xylene. G N M, " where
0.6 5 CI < 0.8 for the molecular
weights studied; surface energies
reported as uoe erg2/cm4
530
463
403
260
530
463
403
260
250
214
178
109
76
58
31
28
20
1 3
246
2710
2130
1810
1016
134
570
420
335
213
178
110
80
68
40
3 3
1186
References page VI - 39 1
VI/300 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 1. contd
Polymer Tr ("Cl T, (Cl G mm
Remarks Refs.
Poly( 1-cyanoetbylene); poly(acrylonitrile) 105 5.56 x lo-* Crystallized from propylene 231
M, =668x lo3 1 1 5 7.18 x 10- s carbonate; 0.06 wt./vol%
130 9.84 x lo-* solution 0.25 wt./vol%
solution
140 2.00 x 10-7
155 3.20 x lo-
160 2.89 x 10- s
TABLE 2. POLY(OXIDES)
Polymer Tr (0 Tc (2 G (ds) Remarks Refs.
Poly(oxyethylene)
M, =5. 6x lo4
M,/M, = 1.05
M, = 1.05 x lo5
M, I M, = 1.03
M, = 1.60 x lo5
M, I M, = 1.05
13.5
14.0
14.4
14.9
15.3
15.7
16.4
16.6
17.4
17.7
18.3
18.6
19.6
20.5
21.1
21.6
22.0
22.5
23.6
16.3
17.1
17.6
18.2
18.8
19.1
19.6
20.2
20.7
21.2
21.7
22.1
22.5
23.0
23.5
24.0
24.5
24.9
14.7
15.1
15.7
16.8
17.3
17.8
18.2
18.8
19.2
19.7
20.2
20.7
21.2
22.7
18330
14968
11045
8730
9344
6022
4920
2865
2680
2422
1915
1193
567
252
174
19.4
77.3
9.24
19.4
19060
12722
6692
5658
4782
4000
2980
2912
1625
1013
625
435
221
125
67.8
37.6
16.9
10.9
42570
34983
33865
19745
15070
13178
10060
6486
5480
4184
3089
1990
1327
321
Growth rates made from self-seeded
polymer crystal stocks; dynamic
light scattering measurements;
Tz = 69C; 25.4 erg/cm 5
a, 5 81 erg/cm*; Tp solution
temperatures reported for each
fraction
243
243
243
TABLE 2. contd
Rates of Crystal Growth
Polymer
Tr (C) Tc ((3
Remarks Refs.
23.0
23.5
24.0
24.5
25.0
25.5
M, = 3.25 x 10 16.3
M, / M, = 1.06 17.3
17.6
M = 7.70 x 105
M, / M, = 1.12
Poly(oxyethylene)
M, =3. 5 x lo3
M, f M, < 1.2
18.6
19.2
19.8
20.2
20.8
21.0
22.0
22.6
23.6
24.2
24.6
25.2
25.6
26.0
26.6
16.3
17.8
19.3
19.7
20.2
20.7
21.2
22.1
23.2
23.8
24.1
24.7
25.2
25.6
26.0
26.6
21.2
21.6
28.1
28.6
29.1
69 (15 min) 35.0
39.3
40.0
40.4
41.7
42.0
43.5
4 4
44.4
45.3
46.0
46.4
47.0
48.0
49.0
50.0
51.0
52.0
54.0
55.0
194
117
53.1
48.4
2 3
14.3
40156
31750
24235
18520
13672
11173
10450
7715
6517
5 5 1 4
2 9 0 4
1207
8 6 0
7 5 2
4 6 8
215
159
34.7
54469
36396
20538
15674
14813
10463
8262
4 5 0 0
3682
3220
2025
1639
1056
955
807
5 2 0
3 8 4
2 0 9
134
69.0
19.6
58900
4 8 9 0 0
46800
43700
38000
36300
26300
23400
19900
19500
10700
8910
7 5 9 0
4 6 8 0
24QO
1260
4 3 6
1 4 1
42.7
8.51
Interference optical
microscopy for linear
growth measurements
243
2 4 3
160(a)
References page VI - 39 1
VI / 302 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 2. contd
Polymer Tf V-7 T, ((3
G (rim/s) Remarks Refs.
M, =4. 5 x lo3 69 (15min) 35.0 53700
M, / M, < 1.04
37.0 50100
39.0 47900
39.8 45700
40.4 42600
42.8 33100
42.7 28800
43.4 24800
43.8 23400
45.0 16600
45.8 12900
46.8 9 5 5 0
47.8 5010
49.8 1120
50.8 575
51.8 2 7 5
52.8 1 0 7
53.8 14.8
54.8 4.89
M, =I . 0 x lo3 69 (15 min) 35.0 70800
M, / M, , < 1.2
39.8 60200
40.0 55000
41.2 53700
43.4 43600
44.9 33100
45.0 34700
47.0 21900
49.0 13500
49.4 13800
50.0 9120
51.0 4 8 9 0
52.0 2820
53.0 1580
54.0 871
55.0 3 8 9
56.0 1 4 5
57.0 45.7
58.0 12.6
M, =9. 0x lo3 69 (15 min) 40.1 38900
M, / M, <1. 07
40.8 38900
42.8 32600
43.4 30200
45.8 20400
48.4 11200
48.8 10200
49.6 7 9 4 0
49.6 7 4 1 0
50.8 7410
51.8 1900
52.8 1200
53.8 5 8 9
55.8 2 1 4
56.8 91.2
57.8 38.0
58.8 13.8
59.8 49.0
M, = 20. 0 x lo3 69 (15 min) 40.0 22400
M, / M, < 1.3 42.0 17400
44.4 14500
45.0 13800
46.0 11700
46.3 11000
47.0 9120
48.0 7760
48.4 6 9 2 0
160(a)
160(a)
160(a)
160(a)
TABLE 2. contd
Rates of Crystal Growth VI / 303
Polymer
Tf ((3 Tc (Cl G (mds) Remarks Refs.
M, = 100.0 x 103
M, / M, is unknown
M, =3. 5 x lo3
M, = 100 x 10
Blend with mole fraction of
M, = 100 x lo3 at 0.279 mol
fraction
Poly(oxyethylene)
49.0
50.0
51.0
51.7
52.0
53.0
53.2
54.0
55.0
56.0
57.0
58.0
69 (15min) 39.8
40.0
42.0
43.4
44.0
46.0
47.3
48.0
49.4
51.5
52.0
53.0
53.9
54.0
56.0
57.0
39.5
40.0
45.6
46.8
47.9
48.9
50.0
51.3
51.9
54.4
55.2
45.6
46.8
47.9
48.9
50.0
51.3
51.9
54.4
55.2
3 4
3 6
38.5
40.5
42.7
4 5
46.7
4 8
4 9
50.5
5 1
51.5
52.5
53.5
54.0
56.0
56.6
5250
4 4 7 0
3240
2570
2290
1170
1150
631
2 1 9
97.7
32.4
92.1
26300
24000
19100
19100
19100
17000
15100
10700
7240
3470
2950
2340
1380
1380
7 2 4
3 8 9
35600
27700
17000
12400
10300
6550
3730
2450
1010
221
80.5
14100
7210
4 5 9 0
2310
3470(?)
3 8 4
1 1 3
4 2 4
1 2 5
129628
110640
65120
44545
22615
9183
2952
1052
625
189
83.2
18.8
17.3
17.3
16.0
8.8
6. 0
Interference optical microscopy
160(a)
160(a)
2 4 5
References page VI - 39 1
VI / 304 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 2. contd
Polymer Tf (C) Tc (2
G @m/s) Remarks Refs.
Poly(oxymethyoxyethylene)
M, = 3000
57.1
34
36.3
Poly(oxy- 1,4-phenoxyethylene)
M, = 3000
Poly(oxy-2,2-bischloromethyl-trimethylene) 139
M, = 5.0-10.0 x 103
38.2
40
42.5
45
41
48.6
55.8
55.8
57.2
51.5
52.5
51.4
53.7
55.8
51.2
57.5
28
30
32
34
36
38
39.5
40.3
41.9
43
44
45
46
41
45
60
78
86
95
1 0 5
60
78
86
95
1 0 5
86
95
105
112
1.46
217920
200355
137060
93780
68980
19280
68975
2968
23.1
23.1
8.72
4.15
294
130
31.6
23.1
8.72
4.15
46989
40180
27412
25292
13842
7034
3857
1969
515
1 2 5
25.9
9.90
2.01
1.14
7.000
3.830
2.160
2.160
1.170
0.333
4.500
3.500
2.000
1.500
0.330
3.670
2.830
0.670
0.333
245
In situ synchrotron rate studies;
optical microscopy and DSC
runs made
245
High resolution NMR; experiment
in m-xylene 0.1-0.001 wt.%,
nucleation densities listed
initial concentration
2 x 10m4 g/cm3
244
Initial concentration
5 x 10m4 g/cm3
244
Initial concentration
2 x 10m3 g/cm3
244
2. Rates of Radial Spherulitic Growth
TABLE 3. POLY(DIENES), POLY(ALKENES), POLY(VINYLS)
Polymer Tf (C) Tc (C) G (NW
Remarks Refs.
3.1. HOMOPOLYMER MELTS
Poly( 1-butene) 160 (10 min) 90.0 338.0 Supercooled liquid, form II 249
96.0 168.0
100.0 60.4
105.0 19.6
TABLE 3. contd
Polymer
Tr 0.3 T, (C) G (nmls)
Rates of Radial Spherulitic Growth VI / 305
Remarks Refs.
94% Isotactic Shell Chem. Co.
M, =73x103
M, . , =75Ox lo3
Poly(chlorotrifluoroethylene)
Kel-F NST 300
P0ly(ldifluoroethylene)
Kureha KF- 1100
M, =525x 103; M, =348x lo3
(a)-spherulites
mixed spherulites
(a and Y)
Kynar 88 1
M, =555 x 103; M, =375 x lo3
(c+spherulites
mixed spherulites (u and y)
Poly(ethylene)
Sinclair 2907
95 100
100
94
92
100 23
27
25
23
105 3. 2
3.1
3. 3
3. 3
4.1
180 (5 min) 65
70
80
85
90
95
100
163
169
169
172
180
1 8 5
1 9 1
195
197
170
175
180
185
190
305
277
305
277
277
267
267
270 (10 min)
0
0. 23
0. 46
0. 9
0
0. 23
0. 66
1.0
0
0. 23
0. 5
1.0
2. 2
1192
1082
675
449
244
1 1 1
32. 6
450. 1
440.1
430. 1
360. 1
195.0
110.0
40.0
7. 25
2. 50
406. 7
310.0
216.7
124.2
36. 3
154.7 120
159.5 36. 2
165.3 7. 2
167.2 3. 4
170.2 0. 82
174.0 0. 07
157.5 13.5
161.4 4. 26
165.2 1.68
167.3 0. 86
170.1 0. 39
174.1 0.10
151.6 57. 2
155.7 20. 3
159.9 4.51
162.2 1.60
165.1 0. 33
168.8 0. 03
153.3 6.13
159.3 1.20
162.3 0. 56
165.1 0. 26
167.4 0.12
168.9 0. 07
1 2 3 300
122 500
1 2 1 750
120 1100
119 1700
Parallel plate shearing device;
shear rate (s-l)
Hot stage optical microscopy;
crystallinity values listed
Hot stage microscopy
200
251
121.252
121,252
Hot stage microscopy 253
253
253
253
Spherulitic growth rates by laser light
scattering; at atmospheric pressure
254
References page VI - 39 1
VI / 306 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 3. contcf
Polymer Tf (3 Tc ((3
Remarks Refs.
M, = 3.60 x lo3
M, f M, = 1.13
M, =4. 20x lo3
M, / M, = 1.26
M,=6.15 x 103
M, / M, = 1.09
M, =6. 29 x lo3
M, / M, = 1.17
M, =8. 56x lo3
M- I M- = 1.09
M, =8. 59x lo3
M, / M" =l.ll
M, = 17.0 x lo3
M, / M, = 1.08
M, =266x lo3
M, / M, = 1.81
M, = 210 x lo3
M, / M, = 1.43
M, =500x lo3
M, / M, = 1.60
M, =807x lo3
M, / M, =2. 9
1 5 5
155
118
132
130.9
129.5
128.5
127.7
148.5
147.5
146.5
145.5
144.5
157.5
156.5
155.5
153.5
151.5
169.6
168.6
168.0
166.6
166.2
165.5
118.3
119.6
120.8
122.0
118.9
119.3
121.4
123.7
122.3
123.6
124.2
124.9
122.7
124.0
124.6
125.1
123.5
124.8
125.4
126.1
124.6
125.1
126.0
126.8
125.1
125.7
126.9
127.5
122.7
123.8
125.4
127.7
122.5
126.1
127.4
128.5
124.9
126.2
127.7
128.9
123.1
125.5
2 0 0 0
3 1 0
4 9 0
8 2 0
1170
1410
140
2 0 0
3 7 0
5 9 0
8 2 0
3 0 0
5 2 0
8 1 0
1820
2420
150
3 1 0
5 4 0
9 1 0
1220
1560
2265.2
271.3
24.2
1.44
5350.6
3389.2
70.8
0.35
3043.7
68.9
7.03
0.47
2146.8
87.8
23.5
3.5
11663
575.6
114.8
7.03
1 6 4 1
623.9
52.7
3.90
4 6 7 8
1435
108.8
14.5
80.7
29.0
5.6
0.2
124.3
6.9
1.7
0.5
52.4
1 8 . 1
3.0
0.6
233.0
50.4
Pressure = 0.5 kbar
Pressure = 1 .O kbar 2 5 4
Pressure = 2.0 kbar 2 5 4
Hot stage microscopy; selected
values only listed for axialites
255
255
255
255
255
2 5 5
Hot stage microscopy;
irregular shaped spherulites
255
2 5 5
2 5 5
2 5 5
TABLE 3. contd
Polymer
Tr (Cl T, (C) G (ds)
Rates of Radial Spherulitic Growth
Remarks
VI / 307
Refs.
SRM 1475
M, =74. 4x lo3
M, / M, = 1.12
M, = 18.1 x lo3
M, / M, = 1.39
M, =30. 6x lo3
M, j M, = 1.19
D=OMR*
D=40MR*
D= lOOMR*
M,=19x lo3
M, =4. 0x lo3
M, =7. 0x lo3
M, = 10.0 x lo3
1. 55
2 9 2
192
1 9 3
196
168
153
195
1 9 5
1 9 5
1 9 5
1 9 5
1 9 5
195
1 9 5
200 (20min)
127.5
129.3
125.6
126.3
127.6
128.5
128.9
129.6
130.1
130.6
123.2
124.5
125.2
125.5
125.6
126.7
128.0
128.7
124.7
125.8
126.7
127.1
127.5
128.1
128.5
130.0
120.7
122.9
125.1
127.0
122.4
122.5
118.9
113.1
115.8
117.8
100.0
100.0
101.8
104.0
125.0
126.0
127.0
128.0
81.0
83.0
85.0
88.0
91.0
93.0
95.2
97.0
98.0
92.0
93.0
95.0
97.0
98.0
90.3
92.0
98.0
100.3
8.1
0.7
22.95
13.8
4.86
2.54
1.53
0.41
0.12
0.04
542.1
199.1
108.3
98.2
63.7
1 0 . 1
0.78
0.14
242.33
90.76
48.41
32.68
17.78
5.16
1.59
0.05
1 1 7
103.4
18.2
1.08
88.4
100.4
41.68
291.7
65.0
2.33
71.7
61.68
31.67
7.84
126.7
36.67
16.67
3.33
510.0
256.7
143.4
63.4
215.0
86.7
35.0
14.0
7.84
175.0
101.2
40.01
20.01
11.50
316.7
185.0
12.2
3.33
Hot stage microscopy; axialites
above 129C approx.
Axi al i tes above 125C
approx.
Axialites above 127C
approx.
Hot stage optical microscopy
# CH3/100CH2 =5.3
# CH3/100CH2 =5
# CH3/100CH2 =4.7
CH3/100CH2 =4.5
255
255
2 5 5
2 5 6
2 5 6
2 5 6
2 5 7
2 5 8
2 5 8
258
258
* D: Radiation does; MR: megarad.
References page VI - 39 1
VI / 308 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 3. cont' d
Polymer Tr (C) Tc (Cl
Remarks Refs.
Poly(ethylene)
M, = 5.14 x 103
M, =6. 29 x lo3
M, =i ' . 62x lo3
M, = 10.51 x lo3
M, = 11.74 x lo3
M, = 13.22 x lo3
M, =56. 35 x lo3
M, =68. 57 x lo3
M, =83. 93 x lo3
M, =l 6. 76 x lo3
M, = 134.30 x lo3
M, =276. 00x lo3
M, = 195.00 x lo3
M, =323. 20 x lo3
M, =500. 80 x lo3
Poly(isoprene), unfractionated
cis-Poly(isoprene)
M, = 313 x lo3
M, = 351 x lo3
M, =543x lo3
160 (30min) 121.39
125.12
125.32
127.81
234. 46
128. 65
123.07
121.14
120. 25
126. 30
- 10
0
1 0
- 10
0
8
0
1 0
2 1
25
0
1 0
2 1
25
0
1 0
25
25
29
35
- 40
- 26
- 15
- 12
- 5
- 1
0. 8
1. 8
3. 0
- 40
- 32
- 26
- 20
- 12
- 7. 3
1.0
- 40
- 35
- 30
- 26
- 20
- 15
- 10
- 5
- 2. 2
- 0. 6
1. 4
2. 2
422.1
1.069
93. 39
0. 433
25. 10
0. 371
117. 3
1. 039
196. 3
1. 062
210. 8 x 1O-3
27. 8 x 1O-3
2.11 x 10-s
392. 5 x 1O-3
156.1 x 1O-3
11.9 x 10-s
782. 8 x 1O-3
98. 6 x 1O-3
4. 44 x 10-s
3. 89 x 1O-3
124.2 x 1O-3
554. 2x 1O-3
43. 9 x 10-s
3 5 x 10-s
19.72 x 1O-3
392. 5 x 1O-3
110.6 x 1O-3
554. 2 x 1O-3
175.3 x 10-s
31.1 x 10-s
39. 7 x 10-s
146.1 x 1O-3
92. 5 x 1O-3
82. 2 x 1O-3
55. 6 x 1O-3
9.17 x 10-s
4. 08 x 1O-3
3. 64 x 10-s
2. 92 x 1O-3
33. 3 x 10-s
66. 1 x 10-s
138.9 x 1O-3
100 x 10-s
72. 5 x 1O-3
47. 5 x 10-s
10.0 x 10-s
20. 83 x 1O-3
50. 83 x 1O-3
69. 4 x 1O-3
111.1 x 10-s
91. 2 x 1O-3
64. 4 x 10-s
34. 7 x 10-s
12.8 x 1O-3
13.6 x 1O-3
10.6 x 1O-3
5. 39 x 10-s
5. 0 x 10-s
Fractionated samples;
NBS material SRM 1475
Fractionated samples;
NBS material SRM 1475
Fractionated samples;
NBS material SRM 1475
Fractionated samples;
NBS material SRM 1475
Fractionated samples;
NBS material SRM 1475
Optical microscopy
0. 5 kbar
l.Okbar
1. 5 kbar
2.0 kbar
2. 5 kbar
3.0 kbar
Optical microscopy; rates
I to II at - 8C; lamellar
thickness and surface
energy data are listed
Optical microscopy; rates
I to II at - 8C; lamellar
thickness and surface
energy data are listed
Optical microscopy; rates
I to II at - 8C; lamellar
thickness and surface
energy data are listed
259
259
259
259
259
283
283
283
283
283
283
239, 240
239, 240
239, 240
TABLE 3. contd
Rates of Radial Spherulitic Growth
Polymer Tr (0 T, (Cl G (ds)
Remarks Refs.
M, = 1421 x lo3
cis-Poly(isoprene)
- 4 0
- 35
- 26
- 20
- 8.0
- 4 0
- 3 0
- 26
- 2 0
- 5.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
rrans-Poly(isoprene)
M, = 7.0 x 103
M, = 12.0 x 103
M, = 45.0 x 103
M,=91.0x 103
M, = 165.0 x lo3
M, =400. 0x lo3
M, = 12.0 x lo3
M, =45. 0 x lo3
M, =91.0 x 10
100
100
100
100
100
100
100
100
100
33.6
35.6
37.5
37.6
40.4
43.0
37.6
39.5
43.0
45.6
34.0
38.0
40.0
43.0
46.0
34.0
38.0
40. 0
43.0
46.0
38.0
40.0
43.0
46.0
34.0
38.0
40.0
43.0
46.0
25.8
29.6
33.6
37.6
43.0
26.0
30.0
34.0
38.0
40.0
43.0
26.0
30.0
34.0
38.0
38.20 x 1O-3
51.7 x 10-3
104.2 x 10-j
83.3 x 1O-3
48.4 x 1O-3
11.1 x 10-3
47.2 x 1O-3
61.1 x 1O-3
50.0 x 10-3
6.94 x 1O-3
8.37 x 1O-3
15.74 x 10-3
28.02 x 1O-3
55.37 x 10-3
179.3 x 10-j
783 x 1O-3
118.3 x 1O-3
16.38 x 1O-3
13.60 x 1O-3
72.18
63.01
48.01
53.18
39.01
22.67
44.01
36.01
21.34
14.34
24.67
11.67
9.34
5.67
2.83
16.50
7.92
5.85
3.52
1.71
5.83
4.25
2.10
1.05
14.00
6.67
4.38
2.33
0.95
173.37
111.69
66.68
34.01
9.17
51.01
34.84
16.50
8.17
4.83
1.83
36.01
20.83
11.16
4.33
Optical microscopy; rates
I to II at - 8C; lamellar
thickness and surface
energy data are listed
239,240
Optical microscopy; rates
I to II at - 8C; lamellar
thickness and surface
energy data are listed
239,240
Electron microscopy with 0~04 staining
0.0 kbar 272
0.3 kbar
0.5 kbar
0.8 kbar
1 .O kbar
1.5 kbar
2.0 kbar
2.5 kbar
3.0 kbar
Hot stage optical microscopy 286
Hot stage optical microscopy
Hot stage optical microscopy
Hot stage optical microscopy
Hot stage optical microscopy
Hot stage optical microscopy
286
286
286
286
286
287
287
287
References page VI - 39 1
VI / 310 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 3. contd
Polymer Tf (2 Tc CC)
Remarks Refs.
M,=30x 103
High melting form
b
Low melting form
M,=30x 103
High melting form
Low melting form
Poly(propylene)
40.0
43.0
- 9.5
- 4.6
0.4
5.3
9.5
14.6
47.1
49.4
51.3
53.4
55.4
59.3
-5. 1
0.0
5.5
9.9
14.3
38.3
42.0
45.0
47.5
49.4
51.7
54.2
55.7
29.8
34.6
39.9
45.0
49.6
55.1
59.7
64.1
69.3
74.6
79.4
80.8
84.0
86.3
34.2
39.3
44.7
49.4
54.6
59.4
63.8
69.5
73.2
78.7
84.0
191- 195 125
130
134
138
140
180 (15 min) 122.0
125.0
130.0
135.0
140.0
145.0
2.50
1.17
0.080
0.125
0.401
0.811
1.390
2.067
1.470
1.123
0.775
0.481
0.330
0.134
0.071
0.196
0.383
0.650
0.900
1.791
1.337
0.909
0.624
0.446
0.294
0.169
0.107
0.096
0.213
0.426
0.714
1.086
1.470
1.740
1.800
1.651
1.179
0.589
0.366
0.209
0.114
0.092
0.170
0.323
0.490
0.653
0.785
0.802
0.714
0.465
0.305
0.075
87.52
61.51
28.67
8.668
4.501
300.1
200.1
71.68
26.67
9.835
4.501
Electron microscopy with
0~04 staining; pressure @ 1 bar
1 8 7
Electron microscopy with
0~04 staining; pressure @ 1 bar
1 8 7
Electron microscopy and
0~04 staining; pressure @ 2kbar
187
Electron microscopy and
OsO 4 staining; pressure @ 2 kabr
187
Hot stage optical microscopy 2 6 0
Hot stage optical microscopy 261
TABLE 3. contd
Rates of Radial Spherulitic Growth
Polymer Tf (3 Tc (Cl G @m/s) Remarks Refs.
220
Hostalen PPN 1060F
(Hoechst AG) T, = 180C
T, = 190C
T,=2ooT
M, = 289 x lo3
M,=51 x 10s
(KS10 from Petrochemica Danubia)
(heterotacticlisotacticlsyndiotactic
= 0.145/0.21 l/0.644; from
13C NMR analysis)
Poly( 1-phenylethylene)
M,=60x lo3
M, = 330 x 10s
M, = 185 x lo3
164.6
164.8
165.3
165.8
166.8
167.5
170.1
164.8
167.5
164.8
167.5
270
250
120
1 2 5
1 3 1
1 3 5
120.5
129
1 4 5
1 2 1
132
1 4 5
127.5
130.0
132.5
135.0
138.0
140.0
145.0
130.0
140.0
130.0
140.0
93.2
98.6
104.0
108.7
113.2
122.9
131.8
136.1
145.4
97.4
101.4
104.4
105.4
109.4
113.4
117.4
121.4
125.4
129.4
133.4
137.3
140
1 5 5
177
190
200
210
140
150
170
180
190
120
130
140
150
160
170
180
190
200
210
Hot stage optical microscopy
Pro-fax 65 13E
Pro-fax 6501
Hot stage microscopy;
rate constants also listed;
crystallinity also provided
Optical microscopy; linear
crystallization under unilateral
quench, modeled and
measured; comparisons
made with literature
spherulitic growth rates
Hot stage microscopy
Hot stage optical microscopy
262
263
263
264
264
264
264
265
1 4 9
490.1
216.7
64.68
27.17
480.1
120.0
4.501
408.4
46.67
2.334
116.7
71.7
43.3
26.7
143.3
98.3
45.0
65.0
83.3
63.3
78.3
1733
3363
8531
7505
1794
470.9
69.9
23.1
3.7
122.0
123.7
82.0
71.3
70.3
30.5
26.9
15.6
7.4
4.4
1.7
0.3
0.333
1.500
4.334
3.667
1.667
0.500
0.83
0.333
1.334
334
0.500
0.040
0.162
0.600
1.43
2.50
3.42
3.42
2.50
1.43
0.45
262
268
269
References page VI - 39 1
VI / 312 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 3. contd
Polymer
Tr (Cl T, (Cl G (mW
Remarks Refs.
M, = 1250 x lo3
M, = 1380 x lo3 270
M,=22OOx lo3 260
260
M, = 220 x lo3
M, = 2100 x lo3 250 (30 min)
(Dow Chem. )
Poly(methy1 methacrylate) isotactic 180 (5 min)
M=213 x lo3
(heterotacticlisotactickyndiotactic =5/94/l)
Poly(2-vinyl pyridine) isotactic 230 (1 min)
M, =400 x lo3
1 5 5
170
184
200
210
130
150
170
180
190
112.01
119.62
129.70
150.26
159.22
172.15
179.70
195.06
200.52
113.3
121.9
133.0
143.8
154.9
174.8
180.0
190.6
203.6
203.4
202.4
208.3
212.2
212.5
111.1
123.2
144.7
161.6
180.0
192.2
206.3
215.2
215.2
220.7
90
100
110
120
1 3
100
110
120
130
140
150
160
170
180
3.2. BLENDS
Poly(isoprene)
Bl end of cisltrans
5% tram
20
40
60
40
2.167
4.834
4.501
2.167
0.666
0.333
1.834
4.501
7.502
3.167
0.00454
0.02582
0.1518
1.526
2.532
3.844
3.980
2.529
1.832
0.005
0.040
0.158
0.582
1.343
3.063
3.380
3.063
1.872
1.279
0.821
0.582
0.422
0.611
0.004
0.069
0.498
2.009
3.711
3.529
1.738
0.404
0.355
0.037
0.072
0.018
0.444
0.606
4.80
100
79
413
1524
4163
8574
13058
13565
7707
0.4
1
1.6
2.1
270
268
270
Hot stage microscopy; average
of many literature results
2 7 1
Electron microscopy; thin films
(80- 100 nm) solution cast
and then melt crystallized
272
Hot stage microscopy 273
Hot stage microscopy 274
Hot stage optical
microscopy; other results
in this paper including
crystallinities
Ref. 6, p. 49
TABLE 3. contd
Rates of Radial Spherulitic Growth VI / 313
Polymer
Tr (Cl Tc ((3
G (m/s) Remarks Refs.
80
1 0 0
Poly(ethylene)/isotactic poly(propylene) 125.4
PE: M, = 16.6 x lo3 129.3
M, = 10.2 x lo3 131.2
LPP: M, =307 x lo3 135.1
M, = 15.6 x lo3
137.1
125.6
127.5
129.5
131.4
133.4
135.3
137.3
Poly(propylene)/poly(isobutene)
Med. Mw.
100/O; PP/IIB 121.0
123.0
125.0
127.0
131.0
90/10 121.0
123.0
125.0
127.0
131.0
80120 121.0
123.0
125.0
127.0
131.0
60140 121.0
123.0
125.0
127.0
131.0
High kw.
100/O; PP/PiB: 121.0
123.0
125.0
127.0
131.0
90/10 121.0
123.0
125.0
127.0
131.0
80120 121.0
123.0
125.0
127.0
131.0
60140 121.0
123.0
125.0
127.0
131.0
Poly( 1 -phenylethylene)/poly( 1-phenylethylene); isotactic/atactic polystyrene
GPS, M, = 550 x 103; a-PS, M, = (900-1800) x lo3
i-PS/a-PS; 100/O 140
160
170
180
3.6
7.7
265.4
114.9
71.7
27.3
19.0
267.9
175.4
116.9
74.7
47.9
29.3
20.3
550.0
366.7
250.0
166.7
83.3
400.0
300.0
216.7
150.0
66.7
333.3
266.7
166.7
116.7
33.3
316.7
200.0
150.0
83.3
50.0
550.0
366.7
250.0
166.7
83.3
250.0
166.7
116.7
66.7
33.3
300.0
216.7
133.3
100.0
50.0
316.7
166.7
150.0
100.0
50.0
1.56
3.43
4.27
4.65
Hot stage optical microscopy
growth rates of PP spherulites
in blends of 0, 10, 20,
and 50 wt.%: DSC rates listed
275
Hot stage microscopy
*average values cited for
blends of I-PPILDPE:
100/o
90110
70130
50/150
Hot stage microscopy 6,277
Hot stage microscopy 6,277
Hot stage microscopy 6,277
Hot stage microscopy 6,277
Hot stage microscopy 278
Hot stage microscopy
Hot stage microscopy
Hot stage microscopy 278
276
278
278
279
References page VI - 39 1
VI / 314 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 3. contd
Polymer
Tr ((2 Tc (C)
G (rim/s) Remarks Refs.
80/20
60140
Poly(l-phenylethylene)(polystyrene)/poly(vinyl methyl ether)
M, = 134 x 103; M, =971 x 103
PSlPVMe; 100/O
90/110
80120
Poly(propylene)/poly(propylene) isotactic/atactic
i-PP: M, = 3.07 x 105; M, = 1.56 x lo4
a-PP: M, =2. 4 x lo4
190 3.42
200 1.76
140 1.14
160 2.67
170 3.50
180 3.56
190 2.46
200 0.92
140 0.56
160 1.77
170 2.30
180 2.50
190 1.72
150.0 0.8
180.0 2.5
150.0 1.3
180.0 3.0
150.0 1.5
180.0 3.2
121.3 503
123.4 337
125.4 235
127.4 1 7 5
129.1 1 1 3
131.4 83.3
121.3 433
123.4 308
125.4 218
127.4 132
129.1 97
131.4 67
121.4 392
123.4 263
125.4 180
127.4 130
129.1 70
131.4 50
212.4 358
123.4 247
125.4 163
127.4 1 1 7
129.1 67
131.4 3 3
Poly(propylene)/poly(ethylene); isotactic/linear low density poly(ethylene)
loo/O, wl w 126
90110, w/w 126
80120, w/w 126
50150, w/w 126
180.0
90/l 10, w/w 150.0
180.0
80120, wl w 150.0
180.0
240
243
242
248
2.5
1.3
3.0
1.5
3.2
Hot stage microscopy 277
Hot stage microscopy 277
Hot stage microscopy 277
Interpolated i-PP 280
i-PPIa-PP = 9 : 1 280
i-PPIa-PP = 8 : 2. 280
i-PP:a-PP = 7 : 3.
Hot stage microscopy; 10.5 values are
also listed microscopy
Hot stage microscopy; to.5 values are
also listed microscopy
Hot stage microscopy; to.5 values are
also listed microscopy
279
279
280
2 8 1
282
282
282
TABLE 4. POLY(OXIDES)
Rates of Radial Spherulitic Growth
Polymer
Te (Cl T, CC) G WW Remarks Refs.
4.1. HOMOPOLYMER MELTS
Poly[oxy(l-oxo-2,2-dimethyltrimethylene)]
Poly(pivalolactone); PPVL
Poly(oxy-2,2-bischloromethyltrimethylene) 210 (25 min)
180
1 8 5
190
192.5
195
197.5
200.0
202.5
205.0
207.5
210.0
213.0
215.0
218.0
75
Poly(oxy-2,2-dimethyltrimethylene)
M, =(18.5 x lo3 - 130 x 103)
Poly(oxyethylene)
M, = 5.47 x 103
M, = 12.4 x lo3
M,=33.1 x lo3
M, =45. 0x lo3
80
90
100
110
120
130
140
80 (15 min) 25.2
29.1
33.2
36.8
40.5
42.2
44.0
44.3
42.0
44.2
45.2
47.2
47.2
48.8
51.2
55.2
47.6
48.2
51.0
53.8
56.4
156.0
157.0
158.0
159.8
160.8
163.0
163.9
164.5
166.1
169.1
Poly(oxyethylene); Polyox WRS-205, Union Carbide
M, =920x lo3 120 (45 min)
M, = 1.6 x lo3 100 (min)
M, I M, = 1.6
[q] = 0.062
53.7
54.7
55.7
56.6
57.5
44.8
45.4
45.9
46.5
7.93 x 103
3.60 x lo3
1.37 x 103
7.25 x lo*
3.65 x lo*
1.90 x 102
95.0
40.2
23.5
12.2
6.38
3.88
2.18
0.99
208.4
183.4
150.0
125.0
100.0
66.68
33.34
25.01
2.11
1.38
0.73
0.35
0.14
0.08
0.05
0.04
12769.4
4734.2
2217.1
395.1
11752.3
6034.5
1514.0
55.51
1784.0
1516.9
421.8
94.19
1.60
346.7
180.0
99.19
77.02
56.61
20.84
14.25
4.801
2. 95 1
0.475
352.2
194.3
111.4
54.0
25.5
36.5 x lo3
18.2 x lo3
6.91 x lo3
1.82 x lo3
Spherulitic growth; hot
stage, photographic method;
regime growth; c( phase
308
Hot stage optical microscopy
Hot stage microscopy; average of
several molecular weights cited
289
290
Hot stage optical microscopy 291
Hot stage optical microscopy 291
Hot stage optical microscopy 291
Hot stage optical microscopy 292-294
Hot stage microscopy 11
Hot stage optical microscopy; selected
molecular weights only are listed
295
References page VI - 391
VI / 316 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 4. contd
Polymer
Tr (Cl Tc (f-3 G (ds)
Remarks Refs.
M, =20x 103
M, / M, =1. 2
[ q] =O. 374
M = 4.3 x 103 48.0
M,/M, = 1.07 50.0
51.0
52.0
53.0
54.0
55.0
53.6
55.1
55.9
56.8
57.8
58.7
51.7
52.5
53.6
54.3
55.1
56.8
57.8
59.1
M, =600x lo3
M,/M, = 1.2
[ q] =3. 65
Poly(oxymethylene)
M, =66x 103
Poly(oxymethylene)
M, =2x lo3
137.3
142.1
145.2
147.0
150.0
152.0
153.4
155.0
156.5
29.6
32.6
37.2
40.1
41.8
44.1
48.0
50.4
51.2
M, =3x 103 32.9
36.8
40.4
45.2
47.8
48.5
49.7
51.8
54.5
55.5
M, =4x lo3 34.6
37.7
42.5
45.7
48.3
50.6
52.2
53.3
54.0
54.4
56.9
36.4
M, =6x lo3 41.5
45.7
30.33 x 103
19.33 x 103
6.06 x 103
4.33 x 10s
1.53 x 103
0.55 x 103
0.078 x lo3
40.0 x 103
8.00 x lo3
4.00 x 103
1.67 x lo3
0.433 x 103
0.145 x 103
31.00 x 103
25.50 x lo3
21.83 x lo3
11.67 x lo3
7.80 x lo3
1.67 x lo3
0.233 x lo3
0.163 x lo3
19.82 x lo4
63.83 x IO3
26.80 x lo3
18.37 x lo3
81.50 x lo*
40.08 x lo*
17.58 x lo*
863.3
359.0
84275
51892
17195
3908
841
678
231
1 9
1
86579
50513
21913
3324
319
100
1 7
1 6
6
1
96427
57796
22511
6013
1072
1 2 1
52
1 6
4
2
1
73655
37558
14240
Hot stage optical microscopy; selected
molecular weights
only are listed
Hot stage optical microscopy; selected
molecular weights only are listed
Optical hot stage microscopy;
Regime III crystallization
Melt crystallized; data interpolated
from original plots
Melt crystallized; data interpolated
from original plots
Melt crystallized; data interpolated
from original plots
Melt crystallized; data interpolated
from original plots
295
295
296
296
296
296
TABLE 4. contd
Polymer
Tr (Cl T, (3 G (ds)
Rates of Radial Spherulitic Growth VI / 317
Remarks Refs.
M,=lOx 103
M, =150x 103
Poly(oxymethylene oxyethylene)
M, = 9. 4 x 103
Poly(oxypropylene)
M, =10. 3 x 103
49. 0
51. 9
54. 1
55. 4
57. 2
39. 3
43. 8
47. 0
50. 2
52. 2
55. 4
56. 9
58. 3
59. 6
30. 2
34. 6
39. 1
43. 6
46. 8
49. 8
52. 9
55. 2
57. 6
59. 8
61. 1
80 - 18
- 9. 8
3. 0
8. 5
14. 0
16. 0
17. 0
19. 0
22. 0
25. 0
28. 0
31. 0
34. 0
22. 0
25. 0
28. 0
31. 0
34. 0
120 (2-5 min) 42. 3
46. 3
46. 7
51. 0
40. 5
42. 3
44. 2
46. 3
39. 0
40. 5
42. 3
44. 2
85 45
50
55
38
43
48
120 ( 5 min) 0
5
1 0
1 5
3415
407
43
6
2
57796
29471
15438
5399
1227
109
15
4
1
64372
54765
355
21913
10877
4471
1404
465
74
7
1
1840
3980
4680
5650
5410
2450
2630
1730
385
255
94. 5
29. 1
21
370
240
90
1 0
9
325. 8
132. 5
39. 1
16. 7
165. 8
104. 1
66. 7
73. 3
8. 3
40
33. 3
8. 3
1. 37
0. 175
0.14
1.00
0. 42
0.15
500. 1
746. 8
723. 4
838. 5
Melt crystallized; data interpolated
from original plots
Melt crystallized; data interpolated
from original plots
Hot stage microscopy; 2 crystal
modifications; form I
Form II
Hot stage optical microscopy
Mean isotactic sequence
length = 122
Mean isotactic sequence
length = 14
Optically active hot stage
optical microscopy
296
296
297
291
299
300
301
References page VI - 39 1
VI / 318 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 4. cont' d
Polymer
Tr ((3 Tc V-3
G (rim/s) Remarks Refs.
M = 135 x 103
Poly(oxypropylene) isotactic
M, =86. 0 x lo3
(Dow Chem.)
4.2. COMPLEXES
Poly(oxyethylene)/resorcinol
stoichiometry, 2 : 1 complex
PEO; M, = 6000
PEO; M, = 35000
25
30
35
40
45
50
60
120 (5 min) 25
30
35
40
45
50
55
60
120 (20 min) 45. 3
41. 7
50. 2
52. 6
55. 0
25
30
35
40
45
50
55
60
62
65
67
69. 5
71
72. 3
72. 8
12. 7
25. 1
27. 3
30. 2
32. 5
35
37. 5
40
42. 4
44. 9
47. 5
50
52. 5
54. 1
57. 5
26
30. 3
35
42. 5
47. 2
52.
51. 5
62. 5
67. 4
71. 4
74. 2
78
476. 8
403. 4
240. 0
145. 7
56. 68
23. 50
2. 050
255. 2
157. 5
103. 3
41. 7
23. 6
6. 01
2. 02
0. 467
162. 9
109. 2
63. 2
38. 3
20. 0
3030
4440
7110
10800
15550
21230
27500
33170
34240
32900
31100
22540
16060
11050
720
8047
1490
1740
2430
2740
3320
4020
4950
6020
6530
7490
6950
6230
5200
3270
15990
27680
139700
391110
784000
1459150
2711400
3478600
4145700
3961000
3269600
1928000
Optically active hot stage
optical microscopy
Hot stage optical microscopy;
nucleation rates listed in text
Hot stage optical microscopy;
unbanded spherulites
303
Banded spherulites
Unbanded spherulites 302
TABLE 4. cont' d
Polymer Tf ("C) T, (3 G @m/s)
Rates of Radial Spherulitic Growth VI / 319
Remarks Refs.
Poly(oxyethylene)/resorcinol
stoichometry 2 : 1 complex
4.3. BLENDS
Poly(oxyethylene)/poly[1-(methoxycarbonyl)-l-methylethylene]
M, =20x lo3
PEOFMMA
100/o 80
9515 80
90/10 80
80 1141300
82 481000
82. 5 117200
84. 0 43100
85 14650
25 2160
28 2400
30 3000
32 3580
35. 5 4210
37. 1 4940
42. 4 5670
45. 7 6530
50 7240
54 8020
51. 3 8580
60 8220
62. 5 6310
64 4170
65 3460
66 2660
67 1460
45 15. 34 x lo3
41. 5 17.96
50 20.10
52. 5 24. 0
55 27. 1
57. 5 30. 7
60 32. 8
62. 5 34. 2
65 35. 5
45 4. 35 x 103
41. 5 4.21
50 6. 03
52. 5 7. 14
55 8. 6
57. 5 11. 40
60 12. 51
60 14. 32
49. 0 3333
50. 0 1950
51. 0 1183
52. 0 600
53. 0 333
54. 0 167
55. 0 33
47. 0 3300
48. 0 2300
49. 0 1583
50. 0 1067
51. 0 683
52. 0 433
53. 0 250
54. 0 150
55. 0 33
47. 0 1883
48. 0 916
49. 0 650
50. 0 483
Unbanded spherulites 302
Unbanded spherulites 302
Optical hot stage microscopy;
two spherulitic form of PEO:
u and p; other growth features
were established m-type
P-w
303
303
Hot stage microscopy
Hot stage microscopy
Hot stage microscopy 6
References page VI - 39 1
VI / 320 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 4. contd
Polymer Tr (Cl Tc (Cl G (ds)
Remarks Refs.
51.0
52.0
53.0
54.0
55.0
80120 80 41.0
48.0
49.0
50.0
51.0
52.0
53.0
54.0
IO/30 80 49.0
M, = 116 x IO3 50.0
o/100 51.0
52.0
53.0
Poly(oxyethylene)/Poly[ l-(methoxycarbonyl)-1-methylene] PEO/PMMA
100/o 41.6
M, = 2.0 x 103 49.0
48.5
49.4
49.9
51.4
52.5
53.3
54.2
90/10 46.3
47.3
48.5
49.3
50.4
51.4
52.4
53.4
54.3
80120 46.3
47.3
48.4
49.3
50.5
51.4
52.5
53.4
54.3
IO/30 46.3
47.3
48.2
49.3
50.3
51.4
53.4
Poly(oxyethylene)/poly[ 1-methylcarbonyl)-1-methy(ethylene] M, = 10 x lo3
PEO/PMMA 48.7
100/o 49.7
50.3
53.2
55.5
90/10 47.2
47.8
48.8
50.0
50.8
283
216
116
50
1 7
800
600
367
233
200
100
33
1 7
167
177
100
67
1 7
10189
6793
6203
5333
4771
2386
1094
477.2
252.6
3200
2189
2049
1319
1263
701.8
421.1
252.6
140.4
926.3
729.8
561.4
477.2
449.1
252.6
252.6
84.2
56.1
364.9
280.1
280.7
168.4
140.4
0.0
0.0
2570
1583
1106
1 5 3
0 .
689
536.2
374.5
255.3
187.2
Hot stage microscopy 6
Hot stage microscopy 6
Hot stage microscopy;
homopolymer and blends
278
Hot stage microscopy;
homopolymer and blends
218
Hot stage microscopy;
homopolymer and blends
278
Hot stage microscopy;
homopolymer and blends
278
Hot stage microscopy;
homopolymer and blends
278
Hot stage microscopy;
homopolymer and blends
278
TABLE 4. contd
Rates of Radial Spherulitic Growth VI / 321
Polymer
Tr (C) Tc ((3 G (rim/s) Remarks Refs.
80120
70130
60140
Poly(oxyethylene)/poly([ l-(methoxycarbonyl)-1-methyletbylene]
M,(PEO) = 1OOOOO; M,(PMMA) = 110000
PEO/ PMMA wt . % r at i o: 100/O
90/10
80120
IO/30
60140
51.8
53.0
42.9
45.0
45.9
46.8
47.8
48.8
50.4
41.1
42.0
43.0
44.1
45.0
45.8
46.8
47.7
48.9
39.2
41.1
42.9
44.0
45.0
45.8
46.7
54
53
52
5 1
50
49
48
47
53
52
5 1
50
49
48
47
46
50
49
48
47
46
45
43
42
49
48
47
46
45
44
43
42
41
40
39
47
46
45
44
43
76.6
42
740.4
434.0
331.9
280.8
221.3
119.1
59.6
417.0
280.8
246.8
195.7
153.2
136.2
110.6
68.1
51.1
119.1
93.6
76.6
68.1
42.6
25.5
17.0
167
483
1134
1600
2550
Hot stage microscopy;
homopolymer and blends
Hot stage microscopy;
homopolymer and blends
Hot stage microscopy;
homopolymer and blends
Hot stage microscopy;
homopolymer and blends
278
278
278
278
67
117
217
275
357
547
667
Hot stage microscopy;
homopolymer and blends
278
133
900
300
333
433
734
Hot stage microscopy;
homopolymer and blends
278
63
102
102
140
1 6 3
190
250
261
305
Hot stage microscopy;
homopolymer and blends
278
37
43
57
80
98
Hot stage microscopy;
homopolymer and blends
278
References page VI - 39 1
VI / 322 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 4. contd
Polymer
Tf (Cl T, (Cl G Mm@ Remarks Refs.
Poly(oxyethylene)/poly[ I-(methoxycarbonyl)-1-methylethylene]
M,(PEO)lOOOOO; M,(PMMA)llOOOO
PEO/PMMA
100/o
90/10
80120
70130
60140
Poly(oxyethylene)/poly( I-acetoxyethylene)
PEO;M,=2.0x103
PEOKVA
100/o
90/10
42
4 1
40
39
38
54
53
52
5 1
50
49
48
41
53
52
5 1
50
49
48
41
46
50
49
48
41
46
45
43
42
49
48
41
46
45
44
43
42
4 1
40
39
47
46
45
44
43
42
4 1
40
39
38
48.6
49.5
50.9
51.7
52.1
53.6
54.6
55.5
46.0
46.9
47.8
48.6
49.7
50.6
102
125
251
1218
546
348
186
1 0 8
120
48
1998
996
144
324
258
186
120
84
2356
1986
1152
1149
744
606
192
204
4344
2292
1992
1470
1308
1008
1044
684
564
432
342
4716
3906
3222
2562
2082
1932
1542
1368
1140
1020
6167
5325
2690
1976
1116
530
164
73
4630
3879
3550
2214
2086
1537
DSC measurements; rate constants
in text, Avrami exponents
2.3 5 n 5 3.2 respectively
DSC measurements; rate constants
in text, Avrami exponents
2.3 5 n 5 3.2 respectively
DSC measurements; rate constants
in text, Avrami exponents
2.3 5 n 5 3.2 respectively
DSC measurements; rate constants
in text, Avrami exponents
2.3 5 n 5 3.2 respectively
DSC measurements; rate constants
in text, Avrami exponents
2.3 5 n 5 3.2 respectively
305
305
305
278
278
TABLE 4. contd
Polymer Tf (Cl T, P-2 G (rim/s)
Rates of Radial Spherulitic Growth VI / 323
Remarks Refs.
80120
60140
Poly(oxyethylene)/poly([ l-(methoxycarbonyl)-1-methylethylene]
PEO; M w = 990000; PMMA, M, = 525000
PEO/PMMA
100/o
9218
85115
IO/30
PEO = 990000; PPMA = 125000
100/o
51.7 1262
52.1 549.0
53.5 341.1
54.5 91.5
45.9 3824
46.8 3001
48.6 1738
49.1 1 2 8 1
50.6 878.4
51.5 622.2
52.5 237.9
53.6 183.0
54.6 0.0
45.1 1756
46.5 1354
41.6 969.9
48.5 768.6
49.5 512.4
50.5 274.5
51.5 201.3
52.6 13
1 1 67.3
1 8 7 8
22.5 56.5
2 6 56.6
30.7 31
3 6 2 4
41.7 9
4 5 5.2
5 0 1.72
5 5 0.041
5 7 0.018
15.5 4 5 0
22.5 212
2 6 217
3 1 130
3 6 7 5
4 1 2 3
4 9 1 1
5 3 1 . 3
5 5 0.43
6 0 0.014
5 0 2 2
5 1 11.5
52.5 1.2
5 4 3.2
5 6 0.82
5 8 0.18
6 0 0.014
3 5 5 5 0
4 0 381
4 5 2 0 0
4 8 9 6
5 1 3 5
5 4 9.5
5 6 2.6
5 8 0.50
1 6 2 3
2 2 16.8
2 8 11.5
3 1 1 0
3 6 8.6
2 7 8
2 7 8
3 0 7
307
307
307
307
References page VI - 391
VI / 324 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 4. cont d
Polymer
Tr ((3 T, (0 G (NW
Remarks Refs.
9218
85115
IO/30
4 1
43.5
46.5
49.5
51.5
54.5
56.5
51.5
58.5
23
30
35
42
46
49
5 1
54
56
58
60
48.5
50
54
57.6
58.2
58.3
59.3
60
35
40
45
48
50
52
54
56
51.3
58
59.5
5.2
3.0
2.4
1.4
0.83
0.42
0.17
0.10
0.06
108
58
52
70
11
1 2
5.4
2.0
0.66
0.19
0.064
1.1
3.7
9.05
3.8
0.46
0.19
0.10
0.041
611
446
229
110
52
1 7
11
2.93
1.46
0.56
0.22
Poly[oxy( 1-oxo-2,2-dimethyltrimethylene)] poly( 1 , 1-difluoroethylene); (poly(pivalolactone)/poly(vinylidene fluoride)
PPVLlPVF2; M, =250 x 103/M, =45 x 103; M, =140 x lo3
100/o, w/w 260 (3 mm) 180 6.2 x lo3 DSC isothermal rates, selected
184 3.17 x 103 values; consult reference for more
186 2.40 x lo3 details on Regime growth
189 1.22 x 103
192 0.60 x lo3
197 0.157 x 103
200 0.066 x 103
205 2.0 x 103
207 1.35 x 103
210 1.45 x 10s
215.5 2.2 x 103
70/30, w/w 169 3.52 x lo3 DSC isothermal rates, selected
174 2.08 x lo3 values; consult reference for
177 1.49 x 103 more details on Regime growth
1 8 3 6.86 x 102
190 2.65 x lo2
1 9 5 8.90 x 10
200 3.00 x 10
205 8.5
210 3.25
215 1.55
20180, w/w 260 (3 min) 165 2.21 x 102 DSC isothermal rates, selected
170 1.47 x 102 values; consult reference for
174 1.24 x lo2 more details on Regime growth
308
308
308
TABLE 4. contcf
Rates of Radial Spherulitic Growth VI / 325
Polymer Tf ((3 Tc ((2
Remarks Refs.
50/50, w/w 260 (3 min)
Poly (l,l-difluoroethylene)/poly(butylene succinate)
PVF2, M, = 140 x 103; PBSU, M = 54 x lo3
wt. % :PVF2 I PBSU 190 (5 min)
100/o
80120
60140
40160
Poly(butylene succinate)/poly (1 ,1-difluoroethylene)
PBSU, MW = 54 x 103; PVF,, M, = 140 x lo3
wt.% PBSU I PVFa 190 (5 min)
100/o
178
182
186
189
192
196
199
202
204
160
166
170.1
174
179
184
190
196
200
205
206
170
174
178
182
185
190
1 9 5
200
205
210
215
164
168
172
182
188
192
197
200
205
210
150
1 5 5
160
145
150
155
140
1 4 5
150
155
140
145
150
80
85
90
100
8.84 x 10
5.87 x 10
3.60 x 10
2.32 x 10
1.54 x 10
8.08 x 10
4.22
2.81
1.57
9.4 x 10
7.01 x 10
5.99 x 10
4.38 x 10
3.22 x 10
1.81 x 10
9.52
4.13
2.39
1.11
0.72
1.53 x 103
1.11 x 103
6.35 x 10
4.19 x 102
2.69 x 10
1.27 x lo2
4.00 x 10
1.10 x 10
4.73
2.15
0.75
6.99 x lo2
5.21 x lo2
3.93 x IO2
1.25 x lo2
5.80 x 10
2.62 x 10
1.00 x 10
6.6
3.3
1.0
1 9 7
61.1
10.8
1 8 5
116
36
222
110
44.3
13.0
1 3 3
65
17.4
1943
980
456
73.2
DSC isothermal rates, selected
values; consult reference for
more details on Regime growth
308
DSC isothermal rates, selected
values; consult reference for
more details on Regime growth
308
DSC isothermal rates, selected
values; consult reference for
more details on Regime growth
308
413
Hot-stage microscopy DSC,
T, and Ti and enthalpy
values listed in Ref. 413.
Spherulitic morphology in
all blends
Hot-stage microscopy DSC,
T, and Tg and enthalpy
values listed in Ref. 413.
Spherulitic morphology in
all blends
413
References page VI - 391
VI / 326 RATES OF CRYSTALLlZATlON OF POLYMERS
TABLE 4. contd
Polymer Tr (C) Tc (-3 G (mw
Remarks Refs.
80120 80 1842
85 969
90 434
95 169
60140 80 1470
85 710
90 248
95 130
Poly(oxyethylene); PEO/poly(octafluoropentoxytrifluoroethoxyphosphazene); PPZ/poly[oxy(l-chloromethyl)ethylene]; PECH
PEO, M, = 5 x lo6 53.8 609 Hot stage microscopy; bulk
PPZ, -unlisted 55.1 400 crystallization and morphology
PECH, M, = 7 x lo6 56 286 also recorded
PEO/PPZ: 100/O 57.1 215
58 166
58.8 142
75125 52.3 1100 Hot stage microscopy; bulk
54 563 crystallization and morphology
55.1 429 also recorded
56 286
57 239
57.9 1 9 3
50150 49.3 1402 Hot stage microscopy; bulk
50.6 1045 crystallization and morphology
57.9 770 also recorded
53.2 536
54.2 426
55.2 302
PEOKECH: 75 / 25 49.2 905 Hot stage microscopy; bulk
50.5 693 crystallization and morphology
51.5 526 also recorded
52.5 435
53.5 321
54.3 271
PEOlPPZiPECH: 66117117 49.7 633 Hot stage microscopy; bulk
50.7 528 crystallization and morphology
51.7 405 also recorded
52.7 336
53.6 279
54.5 242
PEOIPPZIPECH: 50125125 48.9 600 Hot stage microscopy; bulk
50 477 crystallization and morphology
5 1 422 also recorded
51.8 370
52.7 313
53.6 266
309
309
309
309
309
TABLE 5. POLY(CARBONATES)
Polymer Tc (Cl G (nmk.) Remarks Refs.
Poly(oxycarbonyloxy-1,4-phenylene-isopropylidene-l-4-phenylene) 190 0.0833 Hot stage optical microscopy 310
1 9 5 0.042
Poly(oxycarbonyloxy- 1,4-phenylenemethylene- 1,4-phenylene) 175 16.67 Hot stage optical microscopy 310
180 10.00
1 8 5 5.00
190 3.33
Poly(oxycarbonyloxy-1,4-phenylenethio-l,4-phenylene) 1 4 5 20.0 Hot stage optical microscopy 310
150 15.00
160 8.33
170 5.85
180 4.17
TABLE 6. POLY(ESTERS)
Rates of Radial Spherulitic Growth VI / 327
Polymer TP (Cl Tc (C) G (ds)
Remarks Refs.
6.1. HOMOPOLYMER MELTS
Poly(hydroxybutyrate)
Poly(oxydecamethyleneoxysebacoy1)
M, = 10.3 x lo3
Poly(oxyethyleneoxyadipoy1)
M, = 10.3 x lo3
Poly(oxyethyleneoxyterephthaloy1)
Poly(oxyethyleneoxyterephthaloy1)
23
30
33
38
42
45.4
55
67.4
80
100
107
1 1 5
119.5
127
129.5
100 67.1
68.1
69.1
70.1
71.1
72.0
20
40
44
47
1 2 3
140
1 4 5
1 6 1
170
190
200
210
120
130
140
150
160
170
180
190
200
210
220
140
1.50
160
170
150
160
170
180
160
170
180
190
39.6
40.9
42.3
50.3
Hot stage optical microscopy;
nucleation densities given in text
1 0 5
21.2
52.3
78.6
134
283
425
995
4117
3930
3239
1787
902
425
150
86
Measurements by Atomic Force
Microscopy in thin polymer
films; lamellar growth noted
from spherulitic-melt interfaces;
polymer characterization given in
Ref. 103(a)
1 0 3
87.35
21.67
6. 45 1
1.884
0.583
0.083
66.346
18.00
13.169
9.002
4.0
17.5
34.0
56.0
70.0
64.5
42.0
21.8
7
18
3 7
6 1
1 0 5
140
1 5 1
100
140
1 5 1
6
1 3
2 1
23
4 1
2.5
Hot stage optical microscopy;
crystallization from the glassy
state at T,
Linear growth rates by laser light
scattering; nucleation densities are
provided in the test
0.5 kbar
1.5 kbar
311
1 8 5
312
312
8
1 6
30
2
9.5
24
34
147.0
140.0
158.5
166.0
2 kbar
Hot stage optical microscopy 313
References page VI - 391
VI / 328 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 6. cont' d
Polymer Tr (Cl Tc ((3 G mm
Remarks Refs.
53. 4
57. 0
57. 6
58. 7
61. 4
67. 6
72. 0
75. 2
81. 8
58. 0
M, = 16.8 x lo3 294 220
240
M = 19. 0 x 103 120
130
140
150
160
170
180
190
200
M, =2%4x lo3 120
130
140
150
160
180
190
200
210
M,=39.1 x 103 120
130
140
150
160
170
180
190
200
Poly(oxymethyleneoxysucciny1) 16.4
M,=5.98x 103 23. 0
26. 3
28. 5
35. 6
36. 3
Poly(oxytetramethylene oxysuccinyl); PTMS M, = 1.14 x lo5 &l,/fi, = 3.1
2OO(lOmin) 89
90
91
92
93
94
Showa High Polymer Co., Japan 95
97
100
102
1 0 5
Poly(oxy-1-oxo-2-methylethylene)/poly(~-lactic acid)
M, = 150 x 103 115.2
120.2
126.0
130.3
134.4
139.0
143.8
150. 2
153. 4
120. 0
116. 0
76. 81
74. 18
51. 34
26. 17
5. 801
3. 001
41. 08
3. 100
6. 84
15. 0
47. 4
75. 2
93. 2
112.2
112.8
117.4
85. 0
3. 28
8. 50
19. 9
36. 8
56. 2
72. 1
63. 6
43. 9
20. 2
1.54
4. 40
8. 26
14. 2
18. 0
27. 8
26. 6
19. 1
13. 4
12. 00
31. 17
62. 34
44.18
91.35
91.83
162.7
146.4
119.5
102.3
82.1
71.6
54. 0
35. 7
19. 2
7. 7
3. 85
62. 2
71. 1
83. 2
82. 8
63. 8
57. 4
49. 3
Hot stage optical microscopy
Hot stage optical microscopy 315
Hot stage optical microscopy 315
Hot stage optical microscopy 316
Rate of spherulite growth; hot stage
microscopy; I, = 132C;
T, = - 38C; DSC, HNMR
IR characterization of polymer;
Density-Temp. results listed
Hot stage microscopy;
Regimes I and II crystallization
ranges cited
405
316
TABLE 6. contcl
Rates of Radial Spherulitic Growth VI / 329
Polymer Te (Cl Tc (C) G (ds)
Remarks Refs.
M, =260x lo3
M, =350x 103
M, =690 x lo3
Poly(oxyterephthalaloyloxydecamethylene) 160 (5 min)
M, = 10.0 x 103
6.2. BLENDS
Poly(oxy- 1-oxohexamethylene)/poly( 1-chloroethylene) PCL/PVC
100/o 100 (5 min)
75125
65135
60140
Poly(P-hydroxybutyrate)
isotacticlatactic
isotactic: M, = 445000
M, = 137000
atactic: M, = 21000
M, = 11000
isotacticlactactic 100/O
119.5 49.9
128.9 61.8
134.7 55.2
138.3 48.3
114.2 27.9
119.0 43.2
125.0 49.7
129.4 55.2
133.5 46.1
143.1 34.5
150.1 20.8
113.5 11.9
119.0 27.7
128.4 41.4
134.4 38.8
138.1 30.9
143.1 19.0
147.7 15.6
149.9 15.1
154.9 6.1
156.8 4.8
120.0 5.534
121.0 3.451
123.0 1.592
125.0 0.6217
126.0 0.2550
25
30
35
20
25
30
3 5
20
25
30
35
20
25
30
35
20
25
30
35
20
25
30
3 5
3 5
50
60
65
70
76
84
87.5
90
95
100
696.6
533.3
381.7
50
39.5
29.2
19.5
23.7
21.6
13.2
8.5
8.3
7.4
5.4
3.3
2.75
2.2
1.7
1.2
0.22
0.24
0.20
0.14
38.2
405
907
1103
1958
2582
3162
3435
3533
3322
2980
Hot stage microscopy;
Regimes I and II crystallization
ranges cited
316
Hot stage microscopy;
Regimes I and II crystallization
ranges cited
316
Hot stage microscopy;
Regimes I and II crystallization
ranges cited
Hot stage optical microscopy;
nucleation densities listed
Hot stage optical microscopy 318
Hot stage optical microscopy
Hot stage optical microscopy
Hot stage optical microscopy
Hot stage optical microscopy
Optical hot stage microscopy;
DSC melting characterization
also made
316
317
318
318
318
318
319
References page VI - 39 1
VI / 330 RATES OF CRYSTALLlZATlON OF POLYMERS
TABLE 6. contd
Polymer Tr (C) T, (C) G (nmh) Remarks Refs.
90/10
15125
60140
110
114
120
124
130
134.5
140
35
45
55
60
65
IO
14
71
80
83.5
87
90
94
97
100
108
105.5
107
110
112
117
126
130
142
34.4
48.3
52
58
70
74
11.5
84
81.5
90.5
100
1 0 5
110
115.5
120.5
130
35.5
49.7
55
60
65
70
II
80
84
90
94.5
91
100
104
1 0 1
110
1 1 5
120
1778
1348
763
454
199
86.9
18.9
21.0
200
469
797
1096
1508
1814
2000
2196
2382
2480
2489
2425
2365
2155
1980
1741
1592
1371
1184
153
332
111
29
16. 4
154
295
468
936
1177
1526
1612
1699
1797
1595
1439
1206
875
521
155
37. 9
131. 2
272
402
630
750
1044
1174
1250
1347
1410
1398
1216
1132
1032
910
644
642
Optical hot stage microscopy;
DSC melting characterization
also made
319
Optical hot stage microscopy;
DSC melting characterization
also made
Optical hot stage microscopy;
DSC melting characterization
also made
Rates of Radial Spherulitic Growth VI / 331
TABLE 6. contcf
Polymer Tr (Cl Tc (Cl G (ds)
Remarks Refs.
50150
130
137
40.4
50
6 1
65
70.4
75
80.5
84.5
90.0
97
100
105.0
135
1 4 3
309
2.96
12.00
291.6
433.0
617.6
769.4
921.3
985.7
1126
1126
1067
901.0
318.1
Optical hot stage microscopy;
DSC melting characterization
also made
6.3. COPOLYMERS
Poly(oxyethyleneoxyterephthalate)/poly( 1,4-cyclohexane dimethylene terephthalate) (random copolymers)
100/O, mol% 160 50 Hot stage optical microscopy
165 54 T,=280"C;Tg=76"C
l 170 76
180 85
1 8 5 79.9
190 79
1 9 5 78.1
200 63
205 57
210 40.7
215 3 5
220 22
225 1 4
230 1 0
95/5, moVmo1 160 38 Hot stage optical microscopy;
165 48 T,=269"C; T,=75.5"C
170 54.5
175 56.6
180 52
1 8 5 50
190 40.7
195 39
200 31.6
205 24.4
210 15.3
215 9.2
220 6
320
TABLE 7. POLY(AMIDES)
Polymer Tr (Cl Tc ((3 G (NW
Remarks Refs.
Poly(iminopentamethylene iminoadipoyl) Nylon 5,6
282 (30 min) 220.5
222
224.5
226
230
235
236
239
240
242
1742
1385
1210
1090
476
161.7
160.0
121.7
96.7
55.0
Hot stage optical microscopy; 3 2 1
morphology depends upon
crystallization temperature and
and is illustrated in text
References page VI - 39 1
VI / 332 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 7. contd
Polymer Tr CC) T, (Cl G (mW
Remarks Refs.
Poly(iminohexamethylene) iminoadipoyl) Nylon 66
positive spherulites 295 (30 min)
M, = 12.7 x lo3
Poly(iminohexamethyleneiminoadipoy1) Nylon 66
M, = 11.6 x lo3 295
295
295
295
285
262 (10min)
Poly(iminohexamethyleneiminoadipoy1) Nylon 66
M, = 12.9 x lo3 300 (30 min)
M, = 13.7 x lo3 300 (30 s)
M, = 14.6 x lo3 280
Poly(iminohexamethyleneiminoadipoy1) Nylon 66
300
315
Poly(iminomethyleneiminoadipoy1) Nylon 96
positive spherulites 282 (30 min) 200
203
205
207.5
213
215
218
225
230
231
234
150
175
180
190
200
210
220
230
241
247
250
252
247
251
256
257
259
261
263
265
246
248
253
1 4 1
160
180
199
215
230
234
237
239
241
244
241
243
245
248
252
241.5
243
245
248
252
241.5
243
245
248
1684
1334
1134
897
532
500
257
80.8
10.84
8.00
2.67
22000
18000
16500
13000
9500
6003
. 3,200
1,500
166.7
58.35
13.84
10.50
66.08
14.24
83.35
13.34
9.168
6.668
4.167
2.500
106.68
56.34
10.84
13503
13669
12119
8901
5167
2117
1530
920
765
471
368
283
230
180
33
204
175
1 2 8
58.34
5.50
280.0
168.4
113.4
56.6
Hot stage optical microscopy;
spherulitic morphology depends
upon crytallization temperature
and is illustrated in text
Hot stage optical microscopy;
spherulitic growth
Hot stage optical microscopy;
nucleation densities cited in text
Negative spherulites
Nucleation densities listed in text
321
322
323,325
326,327
328
329
322
322
TABLE 7. contd
Rates of Radial Spherulitic Growth VI/333
Polymer Tr (C) T, ((3
G (rim/s) Remarks Refs.
M, = 17.2 x lo3
M, =25. 5 x lo3 300 (30 s)
Poly(iminohexamethyleneiminosebacoy1) Nylon 6,lO
M, = 11.6 and 26.3 x 10
Poly(imino( 1-oxohexamethylene)) Nylon 6
M, = 27.4 x lo3 300 (30 s)
M, =24. 7x lo3
M, =49x lo3
M,=15x lo3
252
50
100
142
160
178
198
200
228
180.0
200.0
211.0
220.0
230.0
235.5
240
200.0
205.0
212.0
217.0
205.0
212.0
217.0
102.3
112.5
122.0
130.0
140.5
150.5
159.0
170.0
180.0
182.0
90
95
1 0 1
107
117
124.5
135
1 4 1
148
157
172
184
40
41
42
43
44
45
46
47
48
49
50
5 1
39
40
4 1
42
43
6.33
3650.7
4706.6
6751.3
6101.2
5201.0
3700.7
12900.6
466.7
1435.6
7951.5
5284.4
2733.8
1615.3
680.13
483.4
253.4
120.0
36.67
13.34
186
130
7
900
1478
2033
2767
3133
2933
2450
1 4 3 1
710
610
375
610
640
1108
1 5 7 1
1933
2438
2438
2105
1790
983
305
80
60
50
38
27
20
15
1 0
5.8
4.2
2.8
1.8
162
1 3 8
102
100
8 1
Positive spherulites 331
Positive spherulites
Hot stage optical microscopy
Negative spherulites
Positive spherulites
Positive spherulites
Hot stage optical microscopy;
positive spherulites
Hot stage optical microscopy;
positive spherulites
329
3 3 1
329
322
312
312
References page VI - 39 1
VI / 334 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 7. contd
Polymer Tr (C) Tc ((3 G (NW
Remarks Refs.
M, =l x lo3
44 62
4.5 35
46 27
41 2 1
48 1 5
49 8
50 6
5 1 1.7
40 197
4 1 1 5
42 100
43 15
44 58
45 42
46 28
41 1 8
48 1 3
49 6.1
50 4.2
Hot stage optical microscopy;
positive spherulites
312
8.1. HOMOPOLYMER MELTS
Poly(oxydimethylsilylene- 1,4-phenylenedimethylsilylene)
TMPS 200 (5 min)
M, = 8.7 x lo3
M, =312x lo3 200 (5 Inin)
M, = 1400 x 103 200 (5 min)
TABLE 8. POLY(SILOXANES)
Polymer Tf ((2 Tc (C) G (Mm
Remarks Refs.
23 316
30 530
40 900
50 1450
60 1640
70 1740
80 1460
90 959
100 417
110 1 6 1
120 14.5
130 0.593
24 80.0
30 113.0
40 166
60 328
70 342.0
80 246
90 146
100 65.0
110 20.0
130 0.124
134 0.0365
24 41.5
40 1 6 5
5 1 280
60 328
70 302
80 240
90 146
100 70.6
110 23.4
Hot stage optical microscopy;
selected molecular weights;
see text
Hot stage optical microscopy;
selected molecular weights;
see text
Hot stage optical microscopy;
selected molecular weights;
see text
333
333
333,388
8.2. COPOLYMERS
Poly(oxydimethylsilylene-l,4-phenylenedimethylsilylene-block-poly(oxy~me~ylsilylene)
TMPS/DMS 21.5 5.25
100/o 200 (5 min) 22.5 5.92
Hot stage optical microscopy;
crystallinites and densities
182
TABLE 8. contd
Rates of Radial Spherulitic Growth
Polymer
Tr ((2
Remarks Refs.
M, = 141 x 103 23.0
24.0
40.0
60.0
70.0
79.0
82.0
90.0
105.0
110.0
116.0
119.0
120.0
121.0
125.0
130.0
90110 - 20.0
- 10.0
0.0
10.0
20.0
30.0
40.0
45.0
50.0
55.0
60.0
70.0
80.0
90.0
100.0
110.0
115.0
SO/20 - 20.0
- 10.0
0.0
10.0
20.0
30.0
35.0
40.0
42.0
45.0
50.0
55.0
60.0
65.0
70.0
75.0
80.0
90.0
95.0
100.0
105.0
110.0
115.0
120.0
50150 - 20.0
- 10.0
0.0
10.0
20.0
25.0
30.0
38.0
7.87
7.63
24.75
41.00
40.00
30.28
30.33
21.53
6.03
3.17
14.17
5.75
5.28
4.30
0.21
0.44
2.58
17.67
75.33
240.00
531.6
851.6
1420.0
1645.0
1850.0
1883.4
1700.0
1515.0
970.0
418.3
120.2
13.52
2.70
33.5
142.2
360.0
643.3
1041.7
1346.7
1498.4
1613.4
1630.0
1636.7
1625.0
1541.7
1396.7
1225.0
1018.4
798.3
585.0
241.7
129.7
58.8
21.3
5.62
0.925
0.177
501.6
558.3
550.0
351.6
260.0
215.0
173.3
111.6
also listed
Hot stage optical microscopy;
crystallinites and densities
also listed
Hot stage optical microscopy;
crystallinites and densities
also listed
Hot stage optical microscopy;
crystallinites and densities
also listed
182
182
1 8 2
References page VI - 391
40160
30/10
VI / 336 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 8. contd
Polymer Tr (Cl T, (0 G (rim/s) Remarks Refs.
42.0 86.8
45.0 69.3
50.0 45.2
55.0 26.8
62.5 9.58
70.0 2.18
- 20.0 278.3
- 15.0 283.3
10.0 280.0
0.0 235.0
10.0 165.0
20.0 109.83
23.5 94.83
30.0 75.00
35.0 51.33
40.0 35.33
45.0 22.83
50.0 12.17
55.0 8.17
58.5 3.25
67.5 0.32
- 20.0 261.7
-10.0 188.3
0.0 119.84
10.0 66.50
20.0 35.67
25.0 24.00
30.0 15.83
35.0 9.250
40.0 5.133
45.0 3.067
50.0 0.558
Hot stage optical microscopy;
crystallinites and desnsities
also listed
Hot stage optical microcopy;
crystallinites and densities
also listed
182
182
TABLE 9. OTHERS
Polymer Tf ("Cl T, (C) G (rim/s)
Remarks Refs.
9.1. HOMOPOLYMER MELTS
Poly(ary1 ether ketone ether ketone ketone)
PEKEKK; 100/O, w/w
176
179
193
210
[pJ+QJ+~c,] g
(repeat unit)
II
296
313
327
338
335
183
188
204
224
242
272.5
Poly(oxy-l,4-phenyleneoxy-l,4-phenylenecarbonyl-l,4-phenylene) PEEK
T,=340"C 240
T, = 144C 260
277
287
1350
1627
1840
1900
1850
1693
1540
1607
1515
1055
773
718
189
1862
2042
2217
Stage I spherulite growth conventional
microbeam SALS; synchrotron time
resolved SAKS
Stage II spherulite aggregates
(higher rate)
2017
1833
980
540
264
1 6 1
Hot stage microscopy; crystallinity,
lamellar dimensions, t t/s values
also given in text
335
402
TABLE 9. contd
Rates of Radial Spherulitic Growth VI / 337
Polymer
Tr (C) T, (C) G (rim/s)
Poly(oxy-l,4-phenyleneoxy-l,4-phenylenecarbonyl-1,4-phenylene) PEEK ICI grade 150P
Remarks Refs.
Poly(thio- 1 ,Cphenylene) Ryton
Poly(thio- 1,4-phenylene) Fortron
Poly(thio-1,4-phenylene)
M, = 24000
M, / M, = 1.4
M, = 49000
M, =63000
M, / M, = 1.5
Poly(thio- 1,4-phenylene)
M, =56000
400(15 min) - 270
275
280
285
290
295
298
300
305
310
315
320
325
210
275
280
285
290
295
298
300
305
310
315
320
325
220
225
230
235
240
250
255
260
265
84
19
74
69
64
59
54
48.7
88
8 3
78
13
68
63
58
52.5
92
81
81.8
16.7
71.8
67
62
56.6
255.3
14.60 x lo*
12.88 x 102
9.91 x 102
6.95 x lo*
5.26 x lo*
3.60 x lo*
2.90 x lo*
2.42 x lo*
1.91 x 102
1.05 x 102
0.627 x lo*
0.364 x 102
0.171 x 102
12.0 x 102
10.4 x 102
7.94 x 102
5.37 x 102
3.97 x 102
2.97 x lo2
2.50 x lo*
1.97 x 102
1.54 x 102
0.845 x 102
0.384 x lo*
0.215 x lo*
0.119 x 102
14.5
54.4
31.6
23.2
13.59
7.81
4.92
2.48
0.95
1387
1243
995
783
551
429
216
1 4 8
490
410
300
232
244
100
61
20.5
414
356
244
159
130
19
4 1
20
Hot stage microscopy with video
accessories; Tf N 395C
261
Note decrease for higher fusion
condition
267
Hot stage and video micrometer
assembly with optical microscope;
DSC measurements; computer
modeling
221
Bulk nucleation density; density
measured Avrami exponent N 3
221
Hot stage microscopy; DSC rates
listed in text Avrami 2<n< 3 values
221
227
221
225
230
235
Growth rates measured as function of
polymer end group
337
References page VI - 39 1
VI / 338 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 9. contd
Polymer Tr (Cl T, (3 G bmW
Remarks Refs.
Na+ washed
Mn *+ washed
Acid washed
Poly(thio- I ,4-phenylene) Phillips Pet.
M,=15x103
M, = 51 x 103
Phillips Pet. Co.
Poly(thio- 1,4-phenylene)
240
245
250
255
225
235
240
245
250
225
230
235
245
250
255
260
225
230
240
250
255
260
100
110
120
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
1 1 5
120
125
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
102
106
110
114
118
120
235
0.87
10.0
91.0
680.0
1200.0
1200.0
2300.0
2300.0
2200.0
1700.0
1200.0
710.0
390.0
160.0
53.0
12.0
1.30
0.094
1.40
5.2
10.0
25.0
73.0
160.0
250.0
300.0
280.0
260.0
240.0
180.0
98.0
48.0
21.00
7.90
1.80
0.13
8.5
3.0
1.5
0.9
0.71
0.54
0.36
Hot stage microscopy; Regimes I and
II crystallization noted
152
Hot stage microscopy; Regimes I and
II crystallization noted
1 5 2
Crystallization rates from DSC peak 338
time (mins); measurements below
Tmax
were made by upquenching
from the amorphous state; Ti N 330C
using Hoffman-Weeks plot
TABLE 9. contd
Polymer Tr (C) Tc (Cl G (ds)
Rates of Radial Spherulitic Growth
Remarks
VI / 339
Refs.
Random copolymer with 5% metamethylene linkages
Random copolymer with 8% metamethylene linkages
Random copolymer with 10% metamethylene linkages
Poly(thio- 1,4-phenylene)
M, = 63000
TCB, 0 mol%
M, = 75000
TCB, 0.13 mol%
M,=65000
240
245
250
255
260
265
270
110
1 1 5
120
125
130
1 3 5
140
145
200
210
220
230
235
240
245
1 0 5
110
120
130
140
150
190
200
205
210
215
220
225
105
110
120
130
140
150
160
170
180
190
200
205
210
215
220
219.7
225
230
235
240
245
250
220
225
230
235
245
250
255
220
0.53
0.82
1.30
2.40
5.20
8.00
17.5
6.71
3.16
1.90
1.23
0.88
0.70
0.53
0.46
0.39
0.59
1.2
2.30
2.81
5.01
9.47
14.93
5.80
1.97
1.09
0.67
0.47
1.75
2.52
4.19
5.26
7.40
9.62
23.02
13.4
7.10
2.65
1.34
0.845
0.620
0.520
0.490
0.760
1.11
1.80
2.54
3.81
6.21
10.2
120
102
75
50
3 3
22
1 4
104
76
54
38
1 6
11.4
5.7
89
T; N 290C 338
Tf, N 283C
T;-273C
338
338
Optical hot stage microscopy 338
Optical hot stage microscopy 338
Optical hot stage microscopy 338
References page VI - 39 1
VI / 340 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 9. contd
Polymer Tt (C) T, (Cl
Remarks Refs.
TCB, 0. 2 mol%
catena-Poly(selenium)
Selenium (Gallard Schlesinger
Chemical Manufacturing Co.)
Selenium (Yokozawa Co.)
99.999%
600 (2 h) and ice
water quenched
230 (1 hr) and
quenched
9.2. IONOMERS
Poly(thio- 1,4-phenylene) ionomers
PPWNa +
PPS/Ca 2+
PPS/Zn2+
PPSlZn +
PPSIH +
Poly(oxyethylene) complex with p-nitrophenol
(M, = 6000)
225
230
235
240
245
250
255
80
90
100
110
120
130
140
150
80.0
87
90
100
1 0 5
110
120
225
230
235
240
245
250
255
225
230
235
240
245
250
255
225
230
235
240
245
250
255
225
230
235
240
245
250
245
158.3
159.0
161.3
165.2
166.2
170.0
175.0
175.1
28
30.5
34
64
44
30
22
20
8.8
4.3
0.171
0.808
1.535
2.383
3.083
5.834
4.884
2.85
0.27
0.50
0.65
1.70
2.72
4.10
7.68
1 7 5
129
92
62
43
52
1 4
142
106
7 1
49
8 1
1 6
28
123
93
63
42
28
15.6
9.0
107
79
53
36
22
1 0
43
113.0
72.95
32.13
15.70
3.22
0.74
0.07
o.144
6660
8470
11310
Hot stage optical microscopy;
purity = 99.9999%
Spherulitic structures; growth rates
of chlorinated polymer listed in text
PPS with end-group counterions; growth
rates in order PPSCa+>PPSH+>
PPSZn2+> PPSNa+; Growth rates
obtained by hot stage optical
microscopy; rate constants documented
Regime II crystallization; Transition II
to III at 160C approx.
Hot stage optical microscopy
338
338
338
338
VI / 342 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 10. contd
Polymer Tr (Cl Tc (C) to.5 (s) n k ( s- ") Remarks Refs.
Poly( 1-butenylene)
cis-1,4-Poly(butadiene)
M, = 3.15 x 105
M, / M, =31t O. 4
cis content - 96.5%
Poly(l-butene)
A4,=13 X 103
M, =l 50x lo3
Poly( 1-butene); unfractionated
M, =409 x lo3
Poly(l-butene)
isotactic; unfractionated
Solution concn.
0.5 g/d1
1 .O g/d1
2.0 g/d1
Poly( 1-butene)
M, =964x lo3
M, =679x lo3
M, =349x lo3
Mu=289 x lo3
16.1
78.3
79.2
80.3
81.4
82.3
83.4
0 (30min) - 80
- 7 0
- 60
- 5 0
- 4 0
- 30
- 25
- 20
- 15
65
70
80
85
90
92
95
100
95
98
102
105
80
78
74
12
170 (30min) 95
98
102
1 0 5
58
58
58
90
88
80
78
86
84
82
78
16
72
70
84
82
80
78
76
70
66
80
78
76
70
68
66
62
605
973
2063
571
1538
539
3893
51.6
60
96
222
456
708
1572
7500
15000
60000
189600
43
32
25
22
750
15000
60000
189600
27000
12600
9600
55
37
15
1 2
80
65
44
29
22
1 8
1 4
99
73
58
45
38
24
1 7
1 0 1
86
62
43
38
3 3
26
Molecular chain extension starts here
2.8 5 n 5 5.4 4.8 x lo-l6 Measured by HFT-NMR;
3.4 x 10-14 1a.s values not listed
2.2 x 10-t*
3.25 x 1O-9
7.45 x 10-s
3.97 x 10-s
3.74 x 10-s
4.5 x 10-l
6.1 x lo-l3
342
Nucleation densities cited in text 251
3.05
3.10
3.43
3.80
1.9
2.0
1.9
2.0
3.05
3.10
3.43
3.80
- 2.4
- 2.4
- 2.4
1.9
2.0
2.0
1.9
1.9
2.0
1.9
2.2
2.1
2.2
2.0
2.0
2.0
2.1
2.1
2.3
2.1
2.1
1.9
1.9
1.9
2.0
2.0
2.2
2.0
1.59 x 10-6 Dilatometry
2.98 x lo-
2.51 x 1O-9
2.00 x 10-13
5.10 x 10-4 Calorimetry; DSC
6.89 x 1O-4
16.3 x 1O-4
14.0 x 10-4
Dilatometric rate constants
expressed in text in min-
2 5 1
121
306
Crystallized from amyl acetate
solution; k values listed in min-
3.20 x 1O-4 121
5.64 x 1O-4
18.0 x 1O-4
50.2 x 1O-4
1.55 x 10-4 121
1.98 x 1O-4
4.31 x 10-4
4.48 x 1O-4
9.84 x 1O-4
11.3 x 10-4
33.3 x 10-4
0.708 x 1O-4 121
1.62 x 1O-4
1.08 x 1O-4
2.04 x 1O-4
1.80 x 1O-4
9.15 x 10-4
20.8 x 1O-4
1.03 x 10-4 121
1.28 x 1O-4
2.19 x 1O-4
3.12 x 1O-4
4.17 x 10-4
3.64 x 10-4
11.1 x 10-4
TABLE 10. contcf
Pol ymer
Tf (Cl Tc (Cl t0.s 6)
Rates of Bulk Crystallization (Avrami Constants) VI / 343
n k ( s- ") Remarks Refs.
M, =96x lo3
Poly( 1 -butenylene); hydrogenated
Phillips Pet Co.
M, =.5.10 x lo3
M, = 13.3 x lo3
M, =340. 0 x lo3
Poly( 1-butenylene) tram
M, =49x lo3
GW
M,=59 x 103
M, =70x lo3
68
66
62
60
58
97.0
99.0
100.0
101.0
102.0
103.0
104.0
95.0
97.0
99.0
100.0
101.0
102.0
89.0
91.0
92.0
93.0
94.0
95.0
96.0
89.5
91.5
92.5
93.5
94.5
95.5
96.5
157 120
119
117
1 1 5
1 1 3
108
120
119
117
115
1 1 3
108
1 0 5
55
54
53
52
49
45
55
54
100 (15min) 30.0
35.0
40.0
45.0
30.0
35.0
40.0
45.0
30.0
35.0
40.0
45.0
136 1.9
1 0 1 2.0
52 2.0
3 3 2.0
25 1.8
40
44
66
78
98
126
186
34
40
64
13
89
1 3 5
59
92
1 2 5
1 7 3
262
427
876
68
135
180
282
498
1056
2334
1.26
1.13
0.62
0.47
0.41
0.35
0.32
0.22
0.19
0.21
0.19
0.14
0.08
1.74
1.41
1.10
0.74
0.28
0.15
0.12
0.08
420 2.6
1200 2.6
3300 2.6
1200 2.6
180 4.4
450 4.5
3360 3.2
16800 2.6
174 5.0
456 4.0
3300 2.9
14400 2.8
0.54 x 10-4
0.86 x 10-4
2.43 x 1O-4
6.85 x 1O-4
19.4 x 10-4
0.064
0.77
27.4
119
3010
8050
28.7
96.6
310
543
1090
1340
0.052
0.922
10.2
273
1490
930
68.4
360
DSC; for sample details consult
text; crystallinity, T, listed
in tables
DSC; for sample details consult
text; crystallinity, T, listed
in tables
DSC; for sample details consult
text; crystallinity, T, listed
in tables
DSC; for sample details consult
text; crystallinity, T, listed
in tables
DSC; melt to condis crystal;
transformation I: two Avrami
regions exist; nucleation time
and crystallinities are listed
Transformation region II
DSC, condis to rigid crystal
transformation; region II
Dilatometry; values of k in
original text
Dilatometry; values of k in
original text
Dilatometry; values of k in
oritinal text
344
344
344
344
1 8
1 8 5
1 8 5
1 8 5
References page VI - 39 1
VI / 344 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 10. contd
Polymer Tr (Cl Tc (Cl to.5 6) n k ( s- ") Remarks Refs.
M, =l l x lo3
M, =94x lo3
M, = 106 x lo3
Poly( 1-butenylene) tram
M, =30x lo3
Poly( I-butenylene) cis 1,4
M, = 740000
M, / M, =1. 25;
v2 = 1.0
v2 =0. 79
v2 =&I%
v2 =0. 42
v2 =0. 32
Poly(chlorotrifluoroethylene)
Poly(ethylene) fraction
n-Hexadecane
M, =3x 10
vz = 0.540
Polyethylene fractions
cl-Chloronaphthalene
M, =4000
vz=l
v2 =0. 70
v2 =0. 46
30. 0
35. 0
40. 0
45. 0
30. 0
35. 0
40. 0
45. 0
30. 0
35. 0
40. 0
45. 0
100 (15 min) 45.0
42. 0
40.0
37.5
35.0
32.5
27.5
213.0
214.3
214.8
204.7
205.7
207.3
199.2
201.7
203.0
198.3
200.5
201.7
197.8
198.5
200.0
180
186
1 9 1
94
1 9 5
196
197
1 9 7
105.75
107.5
108.5
110.5
210
246
3300
9600
216
660
3900
14400
420
1560
5160
19200
12840
5100
2280
1050
600
360
192
13 x 102
18 x lo2
22 x 102
5. 5 x 102
9. 9 x 102
14 x 102
5. 0 x 102
14 x 102
23 x lo2
11 x 102
30 x 102
44 x 102
18 x lo2
22 x 102
49 x 102
180
480
1500
2820
4200
5220
8580
11160
2. 4
5. 4
19.2
102.0
120 0.13
1 2 1 0.17
122 0.21
1 2 3 0.52
124 1.56
1 2 5 9.60
109 0.14
110 0.16
1 1 1 0.18
112 0.25
1 1 3 0.72
114 2.22
1 0 1 0.14
102 0.17
1 0 3 0.24
104 0.30
3. 6
3.1
3.1
2. 0
3. 2
2. 2
2.1
3.1
2. 6
2. 4
2. 6
2. 8
2. 7
2. 8
2. 8
2. 2
2. 2
4 324
Dilatometry; values of k in
original text
185
Dilatometry; values of k in
original text
185
Dilatometry; values of k in
original text
185
k, values listed in text 343
HFT-NMR measurements from 345
toluene solution @ 0.32 < vz 5 1.0
volume fractions; to.5 (s)is
replaced by to.1 (s) in column 4
345
345
345
346
Crystallization measurements 1 6 7
carried out in solution by
dilatometty rat e dat a from
transformation plots; 212 = polymer
volume, fraction used in solution
324
324
TABLE 10. contd
Rates of Bulk Crystallization (Avrami Constants) VI / 345
Polymer
Tr (C) T, (3 to.5 (4
n k( s- ") Remarks Refs.
212 =0.30
M, = 10000
v2 = 0. 46
M, = 100000
v2 = 0. 46
M, =250000
v2=1
Mn = 250000
212 = 0.70
M, =250000
v2 =0.46
M, =250000
v2 = 0.30
1 0 5 0.54
9 8 0.20 4 3 2 4
100 0.36
1 0 1 0.5
102 0.81
1 0 3 1.82
124 0.13 3 3 2 4
1 2 5 0.16
126 0.34
127 0.72
1 2 8 3.30
109 0.78 3 3 2 4
110 0.10s
1 1 1 0.15
1 1 3 0.30
116 0.81
106 0.20 3 3 2 4
1 0 8 0.36
109 0.54
1 1 1 1.80
102 0.35 3 3 2 4
1 0 3 0.47
104 0.84
1 0 5 1.14
122 0.09 3 3 2 4
1 2 3 0.104
124 0.13s
1 2 5 0.16
126 0.27
127 0.54
1 2 8 1.62
113 0.08 4 3 2 4
1 1 5 0.22
116 0 27 3 2 4
117 0.36
118 0.72
1 0 5 0.26 3 2 4
1 0 7 0.54
1 0 8 0.84
110 1.80
102 0.33 3 2 4
1 0 3 0.42
104 0.57
1 0 5 0.72
106 2.16
124 0.192 3 3 2 4
1 2 5 0.39
126 0.66
1 2 7 1.33
128 4.19
1 1 3 0.16 3 3 2 4
114 0.25
1 1 5 0.36
116 0.57
1 0 5 0.30 3 3 2 4
1 0 7 0.66
108 0.90
110 3.12
102 0.18 3 3 2 4
1 0 3 0.21
104 0.27
1 0 5 0.384
106 0.54
Poly(ethylene) fractions
a-Chloronaphthalene 98.0 0.26 4 Dilatometry: 3 3 6
References page VI - 39 1
VI / 346 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 10. contd
Polymer Tr V-2 Tc (Cl to.5 (4 n k ( s- ") Remarks Refs.
M, = 14000
v* =0.003
M, =20000
v2 = 0.003
M, = 41000
v2 = 0.003
M, = 190000
?J2 = 0.003
M2 = 1200000
v2 = 0.003
Poly(ethylene) fractions
Decalin
M, = 100000
z12 = 0.003
Xyl ene
M, = 100000
212 = 0.003
Tetralin
M, = 100000
v2 = 0.003
cc-Chloronaphtbalene
M, =100000
v2 =0.003
Poly(ethylene) Marl ex 50
Poly(ethylenes)
M, = 1.69 x lo3
M, = 120 x lo3
M, =90.5 x 103
M, =599x lo3
98.9
100.1
100.9
101.9
98.0
99.0
99.9
100.9
98.25
99.2
100.1
100.9
101.8
98.1
98.9
100.0
100.9
102.0
96.4
98.4
99.4
100.4
81.8
82.8
83.7
85.2
86.4
87.2
87.2
88.1
89.0
90.0
87.9
89.4
90.5
91.5
92.4
93.1
98.9
100.0
100.9
102.0
122
1 2 3
124
1 2 5
126
127
128
129
130
151.7
151.0
153.0
154.3
154.3
155.0
155.3
157.0
173.0
173.8
175.0
177.0
5.40
14.70
48.60
156.00
2.40
6.48
16.20
42.00
492
9.60
27.60
69.00
186.00
9.60
28.20
36.00
84.00
420.00
2.55
9.60
25.50
66.00
2.40
3.90
6.30
19.80
60.30
126.00
3.00
5.10
12.00
24.00
2.16
3.72
10.20
21.00
45.00
156.00
90.00
270.00
780.00
3720.0
528
750
1080
1560
3420
11400
34800
198000
1140000
328
364
571
969
930
1380
1610
7210
295
322
485
895
4
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
1.3
1.3
1.5
1.6
1.6
1.6
1.6
1.7
1.2
1.3
1.5
1.5
crystallinity = 85%
Crystallinity = 90% 336
336
Crystallinity = 95% 336
Crystallinity = 75% 336
Dilatometry;
crystallinity = 95%
Crystallinity = 90%
Crystallinity = 90%
Dilatometry
Pulsed NMR;
pressure = 1 kbar
2kbar
348
348
TABLE 10. contd
Rates of Bulk Crystallization (Avrami Constants) VI / 347
Polymer
Tr (Cl Tc (C) to.5 (9
n k (s -) Remarks Refs.
Poly(ethylene) HDPE
Dow 08064N
Dow 10062N
Phillips Marlex EHM 6006
Phillps Marlex EHM 6030
Phillips Marlex TR-855
DuPont Alathon 7480
Soltex T60- 1000
Soltex T60-2000
ARC0 Super Dylan 5503A
ARC0 Super Dylan 5503B
Sinclair 2907
177.3
179.0
195.0
197.0
197.3
199.0
199.3
201.0
217.0
219.0
221.0
221.3
223.0
227
200 (2min) 124
124
1 2 5
126
127
120
1 2 1
122
120
1 2 1
122
1 2 3
124
1 2 5
120
1 2 1
122
1 2 3
124
122
1 2 3
124
122
123
124
125
120
1 2 1
122
1 2 3
1 0 5
123
124
1 2 5
126
120
1 2 1
121.5
122
120
1 2 1
122
125
1 2 3
120
1 1 7
1 1 5
1 1 3
112
1 4 3
1 4 1
989
3580
384
521
594
785
950
1800
260
367
670
806
2880
350
165
1 6 5
338
750
1920
5 1
8 1
162
42
46
60
136
351
36
56
108
222
308
66
78
156
1 6 5
263
510
998
54
100
222
496
240
480
518
1500
45
96
150
261
48
8 1
252
714
370
250
62.5
31.3
19.2
7.14
1429
476
1.5
1.7
1.3
1.4
1.4
1.5
1.6
1.7
1.6
1.7
1.7
1.7
1.7
1.5
2.32
2.35
2.29
2.05
2.24
2.53
2.44
2.60
3 kbar
4 kbar
5 kbar
Bulk rates by DSC; crystallinity
melting points and density
data are given inthe original
references; Ii is proportional
to lYz (see original text)
348
348
348
349
349
349
2.46
2.20
2.25 349
2.72
2.76
2.56
2.48
3.18 349
2.46
2.58
1.89 349
1.93
1.96
1.85
2.36 349
2.61
2.63
2.18
2.26
2.32 349
2.50
2.25
2.47
1.96 349
2.28
2.23
2.60
2.07 349
1.98
2.62
Transmitted light intensity;
(a) atmospheric pressure
256
(b) 0.5 kbar 256
References page VI - 39 1
VI / 348 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 10. contcf
Polymer Tr ((3 T, (Cl to.5 6)
n k (s-) Remarks Refs.
M, = 166 x lo3
Poly(ethylene)
I: M =52 x 10-a
M,/M, = 2.7
II: M, =54 x 10-s
M,/M, =3.0
Poly(ethylene), unfractionated
M, =64000
M, = 14000
Poly(ethylene) fractions
M, = 15500
138
137
135
133
157
156
153
1 5 1
149
147
145
167
1 6 5
163
1 6 1
159
157
156
155
177
176
174
172.5
170
168
167
166
160 (15min) 127.6
126.6
126.1
125.6
125.1
124.1
170 (30min) 95
98
102
105
lO(I1)
12m
17(11)
600
150.6
152.1
153.6
171.6
175.6
177.5
193.4
195.8
197.3
199.2
220.3 18.7
222.7 19.4
225.2 22.3
227.6 47.2
229.1 52.4
226.6 21.6
228.6 25.4
230.5 47.5
232.4 67.8
196.6
198.8
186.6
189
137
62.6
28.8
154
769
250
1 1 5
75
42.9
19.2
2000
769
303
149
107
57.8
44.1
33.3
1250
769
500
189
88.5
50.0
34.1
25.6
6780
3000
2190
1500
1080
420
7500
15000
60000
189600
12000
3600
90
24000
357.0
1200.0
10242.0
76.3
586.0
2100.0
46.3
55.2
99.0
100.0
1.6
1.6
1.6
1.4
1.2
3.05
3.10
3.43
3.80
between
1 and 3339
with pressure
1.9
0.9
20.0
1.7
2.1
2.1
1.3
1.3
1.6
1.7
1.0
1.0
1.1
1.2
1.2
1.2
1.2
1.3
1.3
2.8
2.7 2.8
2.9
(c) 1 kbar 256
(d) 1.5 kbar
(e) 2.Okbar
DSC; rates are also given in
text after quenching; some
dilatometry results also available;
k,values are also cited
Dilatometry from amyl acetate
solution; k, values listed
in text
Dilatometxy; pressure
1000kg/cm2; AT, (C) is
cited; not t,; see text
2000 kg/cm*; pressures up
to 5000 kg/cm* reported
Pressure = 840 kg/cm2
1950 kg/cm2
3400 kg/cm 2
51OOkg/cm*
5300kg/cm2
Avrami exponent of extended
chain crystallization in
256
256
306
339
339
339
263
TABLE 10. contd
Polymer Tf (3 Tc (Cl
Rates of Bulk Crystallization (Avrami Constants) VI / 349
n k ( s- ") Remarks Refs.
M, f M, = 1.2-1.3
M, = 150000
M, / M, = 1.2-1.3
Poly(ethylene), fractionated
M, = 18.5 x lo3
M, =7. 3 x lo3
M, = 1.8 x lo3
Poly(ethylene) fractions
M, =25. 0
M, =41.0
M, / M, =1.6
Poly(ethylene), fractions
M, =5. 9 x lo3
M,=14x 103
M, =20x lo3
M, =47x lo3
M, = 122 x lo3
187.5
188.5
183.6
185.3
186.3
187.3
125.4
125.8
126.9
127.6
127.8
128.5
128.6
126.6
127.5
128.5
129.5
130.5
131.0
128.6
128.7
129.5
130.0
130.3
124.5
125.5
126.5
127.5
96
174
282
636
128.0
129.0
130.5
125.1
126.1
127.1
128.1
126.1
127.1
128.1
129.1
130.1
1 2 5
126
127
128
129
130
1 2 5
126
127
128
129
130
1 2 5
127
128
129
130
1 3 1
132
906
1212
3216
5826
8220
18180
21300
810
2100
4200
2. 9
3. 2
3. 3
3. 0
3. 2
3. 3
parentheses; calorimetry
(DTA) @ 2.44 kg/cm*
3.1
3.1
3.1
3. 0
3. 0
2. 8
2. 7
3. 5
3. 5
3. 5
3. 5
3. 5
3. 5
3. 5
3. 5
3. 5
3. 9
3. 8
2. 6
2. 3
2. 2
2. 6
2. 9
2. 4
3
Dilatometry; column 4 gives
values of to.l(min); note: n is
independent of T, for each
fraction
53 4
280
1500
5000
4. 2 3
20
130
1050
5600
2. 3
4
6. 8
1 8
76
220
2. 5
4
6. 5
1 2
35
190
4. 7
9. 5
1 7
36
130
670
10700
344
344
6000
1080
114
60
1.45 x 10-4
5.51 x 10-s
3. 27 x 1O-6
8. 68 x 1O-7
3. 30 x 10-7
1.04 x 10-7
9.01 x 10-s
4. 69 x 1O-6
5. 62 x 1O-7
3. 66 x 1O-8
1.18 x 1O-9
3. 42 x lo-*
5. 62 x lo-l4
7. 48 x 10-6
1.86 x 10-s
8. 30 x lo-
5. 65 x 10-l
9. 52 x lo-
2. 40 x 10-l
6. 00 x lo-*
2. 3 x lo-*
1.5 x 10-3
3. 6 x 1O-4
1.4 x 10-4
2. 0 x 10-s
Dilatometry; col. #5 lists primary 304
process; 4 lists time (min-) 304
304
304
Calorimetry; fractions from
Marlex 60; column 5 listed
as time (min-)
284
344
344
344
References page VI - 39 1
VI / 350 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 10. contd
Polymer TF ((3 T, (Cl to.5 6)
n k (s -) Remarks Refs.
M =200 x 103 125
126
1 2 7
128
129
130
M, = 284 x 103 125.1
126.1
127.1
128.1
129.1
130.1
131.1
132.1
M, =600 x IO3 125.1
126.1
127.1
128.1
129.1
130.1
131.1
132.1
M, = 1.2 x 106 125.1
126.1
127.1
128.1
129.1
130.1
M, = 8.0 x lo6 125.1
126.1
127.1
128.1
129.1
130.1
116
117
118
118
119
120
1 2 1
122
1 2 3
124
1 2 5
125.5
126
M = 5.0 x 106 116
117
118
119
120
1 2 1
122
123
124
1 2 5
126
M = 3.0 x 106 116
117
118
119
120
1 2 1
122
3.4
4.8
7.5
1 5
3 5
7 5
6.5
1 3
2 3
4 5
100
3 2 0
1600
17000
9
1 6
3 2
6 5
180
4 6 0
2 0 0 0
21000
1 7
3 7
120
3 9 0
1400
7 5 0 0
2 0
6 2
2 6 0
1020
4 6 0 0
36000
0.053
0.080
0.14
0.14
0.21
0.51
0.91
2.00
4.35
10.5
31.3
83.3
0.048
0.091
0.13
0.26
0.43
1.02
2.17
4.17
10.9
27.8
90.9
0.05
0.077
0.12
0.25
0.42
0.87
2.38
3 4 4
3 4 4
Calorimetry (DSC); column 4
gives to.25 (min), not the half-
time listed in column 4
332
2
332
2 332
TABLE 10. contd
Rates of Bulk Crystallization (Avrami Constants) VI / 351
Polymer
Tr (Cl T, (Cl to.5 (4
n k (s-) Remarks Refs.
123
124
125
126
M, =8.0 x lo5 116
117
118
119
120
121
122
123
124
125
126
127
127.5
M, = 4.25 x lo5 116
117
118
119
120
121
122
123
124
125
126
126.5
127
127.5
M = 1.07 x 105 116
117
118
119
120
121
122
123
124
125
126
127
127.5
128
M = 1.95 x 104 116
117
118
119
120
121
122
123
124
125
125.5
126
127
M,= 11.4 x 103 117
118
119
120
121
121.5
122
4.76
10.0
29.4
76.9
0.041 3 3 3 2
0.08
0.14
0.26
0.49
0.99
1.85
4.0
8.3
21.7
55.5
133.3
227.3
0.047 3 3 3 2
0.07
0.13
0.26
0.40
0.63
1.49
2.38
5.0
10.3
29.3
38.5
66.7
102.0
0.055 3 3 3 2
0.083
0.16
0.28
0.44
0.76
1.28
2.50
4.2
8.3
18.2
33.3
66.7
156.3
0.043 3 3 3 2
0.063
0.13
0.19
0.30
0.47
0.71
1.20
1.92
3.3
5.9
15.6
71.4
0.045 332
0.067
0.11
0.20
0.33
0.53
References page VI - 391
VI / 352 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 10. contd
Polymer Tt ((2 T, (Cl t0.s (s)
n k ( s- ' ) Remarks Refs.
M, =KOx lo3
M, =5600
M, =3. 9x lo3
M, =2. 9 x lo3
Poly(ethylenes)
M, = 51.5 x lo3
M, / M, =1.5
0 branches/l000 CH2s
122.5
123
123.5
i24
124.5
125
125.5
126
126.5
1 2 7
118
119
120
1 2 1
122
1 2 3
124
124.5
125
125.5
126
113
114
1 1 5
116
117
118
119
120
1 2 1
121.5
122
122.5
123
123.5
124
1 1 1
112
113
114
1 1 5
116
117
118
119
120
1 2 1
122
1 2 3
1 1 1
112
113
114
115
116
117
118
119
120
0.71
1.54
4 . 0
5.9
11.5
25.0
66.7
0.043
0.077
0.13
0.24
0.40
0.77
2.4
4.8
10.9
28.6
83.3
0.063
0.093
0.13
0.16
0.22
0.26
0.38
0.67
1.4
2.2
4.8
13.5
27.0
55.6
196.0
0.034
0.076
0.10
0.14
0.19
0.24
0.38
0.71
1.79
6.67
52.6
3 5 7
2 0 0 0
0.054
0.085
0.12
0.16
0.21
0.30
0.50
1.16
4.35
25.0
155 (15min) 123.4 28.5
124.5 45.0
125.5 96.5
126.5 188
127.5 323
4
332
4 332
3 3 2
3 3 2
332
Not listed Expressed as LDI techniques see Ref. 94; SAXS 3 5 0
to.5 only
dimensions and oe values
tabulated and regimes cited
TABLE 10. contd
Polymer
Tr (0 Tc (C) to.5 w
Rates of Bulk Crystallization (Avrami Constants) VI / 353
n k ( s- ") Remarks Refs.
M, = 89.9 x 103
127.8
129.0
130.0
131.2
1.55 (15min) 119.6
M, / M, =1.53
6.67 branches/1000 CHas
M,=41.8 x lo3
M, / M, =1.17
15.5 branches/1000 CHas
M, =54.7 x lo3
M, / M, =1.69
13.64 branches/1000 CHgs
M, =65. 5 x lo3
M, / M, =2.1
32 branches/l000 CH2s
120.5
121.5
122.7
123.8
125.0
155 (15min) 116.5
117.5
118.5
120.0
120.8
121.8
122.6
123.7
127.7
155 (15min) 111.5
112.5
113.5
144.5
115.5
116.7
118.5
119.7
121.0
115 (15 min) 97.5
98.3
99.3
100.3
101.2
102.5
103.3
104.4
105.3
106.3
107.3
10.2. BLENDS AND COPOLYMERS
Poly(ethylene)/poly(l-phenylethylene)
PE/pS 175 122
123
124
1 2 5
126
Rigidex SO/Carinex SR61 122
50150, w/w 123
124
125
126
Poly(ethylene-co-1-acetoxyethylene) Hostalen, GC 6400
0 wt.% VA 126.9
MI=4.5g/lOmin 125.9
125.1
124.1
123.2
5.5 wt.% VA 102.2
MI= 1.6g/lOmin 101.2
100.4
99.4
98.4
97.5
96.5
439
993
8130
4330
76.5
133
188
358
636
1453
60
137
243
389
680
1239
2778
3985
4167
76.5
98.0
1 3 3
1 7 3
263
330
873
1686
6710
58
98
182
304
573
840
1570
1908
3310
3345
3378
126 1.57
144 1.86
264
2.29
540 2.44
1140 2.26
96 1.88
125 1.94
228 2.32
444 2.59
9000 2.36
1071
704
367
138
90.5
1628
878
589.5
318
158
92
60
Not listed Expressed as LDI techniques see Ref. 94; SAXS 350
to.5 only dimensions and u, values
tabulated and regimes cited
Not listed Expressed as LDI techniques see Ref. 94; SAXS 350
to.5 only dimensions and ue values
tabulated and regimes cited
Not listed Expressed as LDI techniques see Ref. 94; SAXS 350
to.5 only dimensions and ue values
tabulated and regimes cited
350
Listed in text; DSC, mech.
properties text crystallinity
and morphology
351
351
Calorimetry: data interpolated
from original plots
356
356
References page VI - 39 1
VI / 354 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 10. contd
Polymer Tf (Cl Tc ((3 to.5 (9 n k (s -) Remarks Refs.
14.0 wt.% VA 87.6
MI = 6.5 g/l0 min 86.6
85.7
84.8
83.9
17 wt.% VA 80.1
MI= 108gllOmin 89.1
78.3
77.4
76.4
75.6
74.6
73.7
72.6
71.7
70.7
19 wt.% VA 81.0
MI = 98 g/10 min 80.2
79.3
78.3
77.3
76.5
75.5
74.5
73.5
19 wt.% VA 81.1
MI = 2.7 g/l0 min 80.3
79.3
78.4
77.4
24 wt.% VA 68.6
MI = 19 g/l0 min 67.8
66.8
65.9
Polypropylene/ethylene-propylene rubber
230 (2mi n) 126
128
130
132
PPfEPR 134
100/o, wl w 136
Melt flow index = 15; Monte11 Polyolefins G. Natta Res. Centre, Ferrara, Italy
PP/EPR 230 (2min) 120 188
122 288
124 431
126 678
128 1068
130 1693
132 2700
PPiEPR 230 (2min) 120 1 2 3
40160, w/w 122 244
124 376
126 596
128 1045
130 1780
Poly( 1-hexadecene), PHD isotactic 36
M, = 7800 38
isotacticity = 43% 40
41
42
43
M, = 2800 36
isotacticity = 62% 38
40
4 1
42
1334
770
553.0
3.53
241
2444
1735
1098
731
467.5
297
1 8 3
120
83.5
55.5
35.6
2200
1560
900
605
389.4
246.6
1 5 5
97.2
62.4
904
689
508
302
169.2
716
639
438.6
343.2
188
268
455
774
1169
1892
356
356
356
356
356
2.45
2.55
2.72
2.78
2.51
2.58
3.58 x 1O-6 Rates by DSC; spherulite 403
growth rates also reported
8.80 x lo-* (see Section 2)
7.60 x 1O-9
4.20 x 1O-9
2.48
2.36
2.24
2.30
2.34
2.40
2.38
2.68
2.79
2.59
2.52
2.57
2.56
4.3
3.7f0.6
1.95 x 10-6
8.38 x lo-
6.57 x lo-*
5.83 x 10-9
1.77 x 10-6
2.15 x lo-
1.04 x 10-7
5.37 x 10-9
7.30 x 10-4 Measurements by DSC; 352
2.45 x 1O-3 SAXS data included; units
5.70 x 10-j of k are (min-) not (s-)
1.32 x lo-* and independent of T,
7.64 x 10-2 for these comb-like
4.10 x 10-l polymers; T, = 58C
8.05 x 100 352
9.60 x 10-l
1.49 x 10-l
6.49 x lo-*
2.65 x lo-
TABLE 10. contd
Rates of Bulk Crystallization (Avrami Constants) VI / 355
Polymer Tr (C) T, (0 to.5 6)
n k (s-y Remarks Refs.
M, = 1800
isotacticity = 91%
Poly(isoprene) cis
room temperature; crosslinked
at 0.5 MR; 20% gel
Poly(isoprene) cis
Natural Rubber
trunk Gutta Percha
[q] = 2.8 in toluene at 30
Poly(isoprene) tram- 1,4
LMF Spalding Co. R-308
43
44
4.5
36
38
40
4 1
42
43
44
45
0
- 10
- 15
- 20
0
- 10
- 15
- 20
0
- 10
- 15
- 20
0
- 10
- 15
- 2 0
0
- 10
- 15
- 2 0
0
- 10
- 15
- 20
- 5
-11
- 16
- 17
- 22
- 27
- 3 3
- 3 8
35
40
45
47
49
5 1
53
55
57
59
100 (30min) 20.5
26.5
30.5
36.5
40.5
45.0
100 (30min) 20.5
26.5
30.5
36.5
40.5
188160
30480
14820
10560
9060
4668
21240
4896
3186
1896
2107
654
55200
19800
12000
10200
9000
9000
14400
23400
768
1260
6780
11700
19800
31800
64500
129000
291000
720000
475
641
919
2160
3995
11417
3.3 * 0.4
9.95 x 10-3
3.45 x 10-3
8.86 x 10-4
2.51 x 10
2.89 x 10
3.57 x 10
1.36 x 10-l
5.46 x lo-*
1.22 x 10-2
2.96 x 1O-3
2.46 x 1O-4
3.6
3.6
3.5
3.5
2.45
2.90
2.95
2.85
2.10
2.15
2.15
2.10
1.65
1.60
1.57
1.55
1.40
1.55
1.37
1.40
1.35
1.30
1.35
1.13
6.25 x 1O-9
3.20 x 1O-9
9.44 x 10-11
7.50 x lo-
1.22 x lo-
9.30 x 10-3
3.6 x lo-*
1.84 x 1O-8
3.12 x 1O-9
6.40 x 10-l
352
Dynamometer for to.l(s);
10% transformation
elongation ratio;
ci=l
a =2
166,353
a =3
a=4
CL=5
a =6
104,354,355
109,359,355
Dilatometry; other grades 109,359,355
of polymer are presented
Rate results from dilatometry
measurements
242
References page VI - 39 1
VI / 356 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 10. contd
Polymer
Tr (Cl Tc (Cl to.5 (4 n k (s-) Remarks Refs.
HMF Spalding Co.
Balta
Poly(isoprene) Irons- 1,4
M,=49x 103
M,=59x 103
M,=70x 103
M,=77 x lo3
M, =94 x lo3
M, = 106 x lo3
Vulcanized rubber
Extension ratios: 1 x 1
1.5 x 1.5
2 x 2
2.5 x 2.5
3x3
Poly (1-phenylethylene)
isotactic (90%)
M,=4 x lo5
45.0 2.21 x lo-
20.5 6.25 x 1O-8
26.5 3.20 x lo-*
30.5 9.44 x lo-0
36.5 7.50 x 10-10
40.5 1.22 x lo-to
45.0 5.56 x 10 -I2
20.5 9.26 x lo-
26.5 3.60 x 1O-8
30.5 1.84 x 1O-8
36.5 1.89 x lo-
40.5 2.12 x lo-0
45.0 2.73 x lo-l2
100 (5 min) 30.0 240 x 1O-3
32.5 108 x 10-s
35.0 462 x 1O-3
37.5 570 x 10-4
40.0 102 x 10-s
42.5 216 x lO-j
45.0 474 x 10-7
30.0 360 x 1O-3
32.5 78 x 1O-3
35.0 156 x lo-
37.5 60 x lo-
40.0 96 x 1O-6
42.5 498 x 10 -7
45.0 168 x 10-7
30.0 74.3 x 10-s
32.5 169 x 1O-3
35.0 210 x 10-4
37.5 84 x 10-4
40.0 330 x 10-6
42.5 252 x 1O-7
45.0 126 x 1O-7
100 (5 min) 30.0 198 x 10-z
35.0 102 x 10-s
37.5 360 x 1O-5
40.0 384 x 10-e
42.5 474 x 10-7
45.0 60 x 1O-7
100 (5 min) 32.5 120 x 10-s
35.0 174 x 10-4
31.5 558 x 10-s
40.0 420 x 1O-5
42.5 114 x 10-j
45.0 450 x 10-6
100 (5 min) 30.0 150 x 10-s
32.5 276 x 1O-4
35.0 120 x 10-s
37.5 414 x 10-s
40.0 78 x 10-5
42.5 234 x 1O-6
45.0 144 x 10-7
45.0 11417 5.56 x lOI3
- 21
50
55
60
65
70
3.0 10-s
2.4
1.7
1.1 2.7 x 1O-5
0.7 2.6 x 1O-3
3.97 x 10-s
3.63 x 1O-5
5.15 x 1o-5
5.74 x 10-j
6.67 x 1O-5
242
242
Transformation rates by DSC;
heat of fusion and melting
points also provided
357
357
357
357
357
Biaxial crystallization X-ray
kinetics; Avrami analysis
358
Solvent, dimethyl phthalate, (DMP); 400
DMSO &TP solvents;
Tmax = N 70C in DMP;
polymer-solvent interaction
is DMP > DMSO > TP
TABLE 10. contd
Polymer Tr (0 T, (0
Rates of Bulk Crystallization (Avrami Constants) VI / 357
n k ( s- ") Remarks Refs.
7 5
80
90
Poly( 1 -phenylethylene) isotactic 228. 0 ( 1 mi n) 180
M, =850x lo3 230.0 (1 min)
234.0 (1 min)
237. 0 ( 1 mi n)
227. 5 ( 1 mi n)
240. 0 (1 min)
243. 0 ( 1 mi n)
229.5 (1 min)
M, =850 x lo3 233. 0 (1 mi n) 170. 0
180.0
160.0
150.0
190.0
Poly( 1-phenylethylene); syndiotactic
M, = 803000 300 (1 min) 110
115
120
125
1 3 5
1 4 5
155
170
180
190
2 0 7
2 2 0
2 2 5
2 3 0
2 3 5
2 4 0
2 4 6
2 5 0
M, =562000 300 (1 min) 110
1 1 5
120.5
130
150
160
1 7 5
188
2 0 2
2 1 5
2 2 0
2 3 0
2 3 5
2 4 0
2 5 0
M, =348000 300 (1 min) 110
1 1 5
120
1 2 5
134.5
146
156
166
1 7 5
182.5
190
2 0 0
2 1 2
2 3 0
235
168.0
198.0
222.0
282.0
3 7 2
4 1 4
5 9 4
7 8 0
2 1 0
2 1 0
2 8 8
3 3 0
4 2 0 0
5.72 x 1O-5
4.67 x 1O-5
1.46 x 1O-5
DSC measurements; see text 3 5 9
DSC 3 5 9
15343
4783
1972
9 8 8
3 2 6
144
7 8
4 3
3 2
2 5
2 2
2 3
2 5
2 9
3 7
4 9
7 9
164
2 4 4 0
1005
5 0 4
187
5 6
3 6
2 6
21.3
2 1
24.5
27.5
4 0
5 6
87.8
4 8 5
9 2 0
4 3 6
2 3 7
144.5
70.7
42.0
29.6
2 2
18.8
17.9
16.6
18.2
19.5
35.7
54.5
3.00
2.88
Rate values listed in text in s-
vs. T, ; rate is MW dependent;
T, - 543K; T, - 373 K
3 9 8
3 9 8
3 9 8
References page VI - 39 1
VI / 358 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 10. cont'd
Polymer Tf (3 Tc ((2
n k (s-") Remarks Refs.
K+ ions
Rb+ ions
Cs+ ions
Cs+ ions
Hf ions
239
245.5
250
Poly( 1-phenylethylene), PS (syndiotactic)
M,=609000; 1.5mol% 330 (3 min) 149
neutralized with various 155
counterions cations Na+ ions 160
165
170
1 7 5
1 8 1
189
200
204
210
154.5
160
1 6 5
170
1 7 5
1 8 1
190
200
205
209.5
215
219.5
154.5
160
1 6 5
170
1 7 5
182
190
200
204
210
215
220
225
150
1 6 5
170
1 7 5
182
1 8 5
200
209.5
214.5
220
225
232
210
214
220
225
231.5
87.8
167.6
472
1 9
11
6.8
5.1
4.1
4.0
3.97
6.1
13.4
21.3
30.3
10.4
6.5
4.8
3.9
3.6
3.6
5.0
8.1
11.8
16.8
244.4
35.7
9.7
5.9
4.1
3.3
2.9
3.05
3.9
6.0
8.5
10.6
15.1
20.1
30.2
6.0
4.5
3.6
3.1
2.9
2.9
3.3
5.6
7.0
9.9
14.0
27.7
1.4
1.8
2.8
4.5
11.9
DSC measurements for to.5
values; T, identical for all
materials; the counterion
affects rate as Nat <K+
< Rb + < Cs + for isothermal
changes
360
360
360
360
360
360
360
Poly( 1 -phenylethylene)/poly[oxy(2,6-dimetbyl- 1 ,4-phenylene)]
syndiotactic 245
M, = 129000 244
SPSiPPO; loo/O, wlw 243
242
241
240
1360
1210
925
676
571
489
DSC measurements; hot stage
microscopy spherulitic growth
rates listed
3 6 1
TABLE 10. contd
Rates of Bulk Crystallization (Avrami Constants) VI / 359
Polymer Tr CC) T, (3 to.5 (9 n k ( s- ") Remarks Refs.
239 431
231 251
236 219
235 137
M, =32000 240 1289
M, =244000 239 1154
SPS/PPO; 90/ 10 238 905
236 695
235 560
234 462
SPSIPPO; 80120 240 1923
239 1450
238 1294
236 1042
235 824
Poly( 1-phenylethylene)/poly( 1-methoxyethylene) PVME
SPS/FVME; 90/ 10 231 1502
236 1450
235 1065
233 719
232 645
231 486
SPSKVME; 80120 231 2060
236 1850
235 1602
234 1444
232 1165
231 1113
Poly( 1-phenylethylene)(S)/poly(trans-l-butylene)(B)/poly(imino-l-oxohexamethylene)(C)-co-poly(E-caprolactam)
361
361
3 6 1
361
Poly(a-caprolactam) (100%)
Wt.% composition ratios:
35S/15B/50C
27S/15B/58C
33S/06B/61C
205/15B/65C
9S/14B/llC
Poly(propylene)
250 (3 min) 37
39
40
4 1
43
45
41
39
40
43
45
37
38
39
40
4 1
43
37
39
40
4 1
43
45
38
39
40
43
44
36
31
38
39
4 1
42
43
64
1 2 5
177
223
518
923
2374
170
359
719
1564
86
1 1 5
1 5 1
200
269
549
76
1 5 1
169
213
420
858
96
132
1 7 5
512
691
16
94
1 1 3
1 6 5
317
398
581
2.63 zt 0.10 DSC measurement under nitrogen; 362
rate constants given in min-;
also spherulitic growth rates listed;
nucleation dependent upon block
size and type
2.31f0.11 362
2.54 f 0.08 362
2.341t0.15 362
2.03 * 0.03 ~ 362
1.92 3~ 0.06 362
References page VI - 391
VI / 360 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 10. contd
Polymer Tf (Cl Tc CC) to.5 Cd
n k ( s- ") Remarks Refs.
139
140
1 4 1
M, =307 x 103 1 3 5
140
1 4 5
150
1 5 5
M, =447x103 190 (10min) 137.1
134.1
133.0
130.2
M, =447 x lo3 190 (10min) 140.0
137.5
135.0
132.5
130.0
127.5
125.0
122.5
120.0
117.0
M, =447 x lo3 190 (10min) 145.0
(nucleated with 1 wt.% 143.5
indigo) 142.5
141.5
140.5
Poly(propylene) Shell Carlona White
M,=196x103 270 (30min) 75
100
110
1 2 5
Poly(propylene)
M, =300x lo3 47
50
5 1
52
53
54
65
67
69
70
7 1
72
Poly(propylene) isotactic 200 (5 min) 120
M, =947000; M, f M, =8. 7 123
Tacticity = 96.5%; [n] = 3.48 dllg 1 2 5
1 2 8
130
132
M, = 129000; M, / M, =11 120
M, = 50.5 x 103 1 3 5
140
145
150
1 5 5
M, = 96.8 x lo3 1 3 3
134
1 3 5
136
137
1 3 8
474
1524
6870
26400
117000
636
894
1356
2124
3564
5256
8094
11154
16320
642
2280
11400
32400
152400
6600
2820
2220
780
8280
5340
2400
1344
756
486
378
288
222
168
990
720
612
498
438
3.0
6.7
11.1
100.0
2045
3296
3952
4528
5494
6740
2068
2892
3863
4685
5717
7339
9 1
1 6 1
267
427
825
1508
56
2.9
2.9
2.9
3.1
2
2
2
2
2
2
2
2
4
4
4
4
4
4
4
4
4
4
4
Dilatometry 363
363
363
Hot stage optical microscopy
DSC; rates are also given in
test after quenching; results
also available; k, values
are also cited
DSC; Rates are also given in 343
text after quenching, some
dilatometry results also available;
k, , n values are also cited
DLI (depolarized light intensity)
94(b)
rate measurements
0.3 g/100 ml decalin 364
0.3 g/100 ml tetralin
DSC measurements to give
rate data; interfacial energy
o e = 92 erg/cm 2 ; average rate
constant listed; Ti = 184.3C;
ge = 77 erg/cm; average rate
constant listed; T, = 178.7C
365
TABLE 10. contd
Rates of Bulk Crystallization (Avrami Constants) VI / 361
Polymer
Tr (Cl Tc ((3
n k (s -) Remarks Refs.
Tacticity = 97%; [q] = 0.66 dl/g
Poly(propylene) isotactic
Tacticity[m] = 99.8;
[mm] = 99.7; [mmm] = 99.4
M, =44350; [q] =53 dl/g
Tacticity[m] = 99.77;
[mm] = 99.7; [mmm] = 99.4
M, = 16940; [q] = 26 dl/g
Poly(propylene), unfractionated
M, = 4.47 x 105
Poly(propylene), unfractionated
Poly(propylene), unfractionated
Profax, P =2300
P= 1200
P =7300
1 2 3
125
128
130
132
135
200 (5 min) 124
1 2 5
126
1 2 7
128
129
130
132
134
1 3 5
136
1 2 5
126
127
1 2 8
130
132
133
135
138
140
137.5
135.0
132.5
130.0
127.5
1 2 5
122.5
120
1 1 7
95
100
1 0 5
110
1 1 5
117
120
122
1 2 5
127
130
132
1 3 5
1 3 3
134
1 3 5
136
137
1 3 8
139
140
1 4 1
1 3 5
140
1 4 5
150
1 5 5
1 3 5
140
100
1 6 5
256
599
1 2 7 1
1789
24
30
52
64
99
1 3 7
192
512
749
1 6 2 1
2041
29
42
50
67
154
276
610
638
1729
8280
5340
2400
1344
756
486
378
288
222
168
38
48
66
78
115
130
1 8 1
242
407
561
917
1529
2073
636
894
1356
2,124
3564
5256
8094
11148
16320
474
1524
6870
26400
117000
642
2280
2
2.96
3.05
3.05
3.05
3.03
2.96
3.08
3.12
3.03
2.97
3.05
3.03
2.98
Hot stage microscopy;
Tf, = 186.4C;
ue = 125 erg/cm*
T; = 177.oc;
ue = 69 erg/cm
365
365
365
3.50 x 10-5 Calorimetry (DSC): values in 179
9.52 x lo- column 5 in min-
4.02 x 1O-4
1.35 x 10-3
5.39 x 10-3
1.05 x 10-Z
1.80 x lo-
3.16 x lo-*
Values for log k are reported;
isotactic index 95-97%;
[q] = 1.64 in decalin at 135C
200
Dilatometry: k for n = 3 (min)
in column 6 364
5.82 x 1O-4
2.10 x 10-4
6.01 x 1O-5
1.56 x lo-
3.31 x 10-6
1.03 x 10-6
2.82 x lo-
1.08 x lo-
3.45 x 10-s
1.43 x 10-3 394
4.23 x 10m5
4.62 x lo-
8.14 x 1O-9
9.35 x lo-
5.66 x 1O-4 394
1.26 x 1O-5
References page VI - 391
VI / 362 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 10. contd
Polymer Tf (Cl Tc (2 to.5 (s)
n k ( s- ") Remarks Refs.
Poly(propylenes) isotactic
metallocene type
M, =678- 288 K
Poly(propylene)/poly(ethylene)
PE: M, =307~10- ~; M, = 10.2~10~
M, =307x 103; M, = 15.6x lo3
i-PPIHDPE: 100/O
90110
70130
60140
50150
40160
30170
10190
1 4 5
150
1 5 5
114
116.5
118
120.5
123
126
128.8
130.7
132.5
122
1 2 3
124
125
127
130
1 3 1
132
1 2 3
124
125
126
127
128
130
132
123
124
1 2 5
126
127
128
130
1 3 1
125
126
126
127
122
1 2 3
124
1 2 5
1 2 5
125.5
126
122
1 2 3
124
1 2 5
1 2 5
126
126
122
123
124
124.5
1 2 5
125.5
126
11400
32400
152400
6 7 0
8 7 0
1090
1500
2445
4315
8430
14520
27130
152
187
2 3 7
3 0 5
4 5 6
981
1320
1763
1 3 8
2 1 0
3 0 9
3 5 4
6 7 5
6 6 8
1140
1863
124
2 1 5
3 5 5
4 5 0
6 7 5
8 5 0
1210
2 0 4 0
4 2 0
5 6 6
6 4 7
7 6 3
119
163
2 4 2
3 3 0
5 5 8
847
1285
9 1
110
2 3 0
5 2 3
6 1 4
9 4 0
1777
110
190
441
7 3 0
1260
1650
2 8 8 0
3
3
3
3
3
3
3
3
5
4
4
3
3
3
3
3
4
5
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1.01 x 10-7
4.40 x 10-9
4.23 x 10-l
Isothermal crystallizations
measured by DSC; times @
20% not 50% conversion are
listed; average curve, digitized
values
DSC
DSC
DSC
DSC
DSC
DSC
DSC
DSC
3 6 6
6
6
6
6
TABLE 10. contd
Rates of Bulk Crystallization (Avrami Constants) VI / 363
Polymer
Tr (Cl Tc ((2
n k (s -) Remarks Refs.
o/100 122 9 1 2
1 2 3 120 2
124 223 2
12.5 354 2
122.5 548 2
126 900 2
126.5 1415 2
121 3750 2
PP/LDPE: 100/O 127.8 573.1
125.8 349.0
122.8 189.6
90110 127.8 704.8
125.8 401.6
122.8 207
80120 127.8 848.2
125.8 439
122.8 231.6
60140 125.8 788.1
122.8 219.8
127.8 1130.0
122.8 355.1
40160 127.8 1440.6
125.8 805.6
122.8 340.2
Poly(propylene)/poly(ethylene) low density; melt flow indices 2.9/6.7 g/min wt.% l-PPILDPE
DSC 6
DSC measurements 277
DSC measurements 271
DSC measurements 277
DSC measurements 271
DSC measurements 211
100/o
9515
90110
85115
80120
Poly(propylene-co-ethylethylene)
isotactic; 0 wt.% 1-butene
13.5 wt.% 1-butene
200 (10min) 125
130
132
1 3 5
1 2 5
130
132
135
125
130
132
135
125
130
132
1 3 5
1 2 5
130
138
1 3 5
120
1 2 1
122
123
124
1 2 5
126
127
128
129
1 1 3
114
1 1 5
116
117
118
119
120
1 2 1
137
419
856
2001
133
415
594
1 4 4 1
217
709
1123
2257
1 9 3
559
1254
1849
241
747
1212
2684
130
1 7 5
230
295
380
460
550
750
1010
1300
1 7 5
190
250
295
430
503
642
750
1070
3.4
3.5
3.3
3.0
2.9
3.0
3.0
2.9
2.7
2.7
2.6
2.4
2.4
2.5
2.4
2.3
2.4
2.4
2.4
2.16
2.29
2.41
2.52
2.63
2.12
2.19
2.93
3.06
3.17
1.93
1.95
2.05
2.11
2.25
2.30
2.39
2.45
2.58
Two roll mill-blended; DSC 361
measurements radial spherulitic
growth rates also measured; Avrami
exponent 1.09 <n 53.86; log k,
tabulated for various ns 367
367
367
367
Calorimetry; values in column 6
tabulated here as - 113 log k
298
298
References page VI - 39 1
VI/364 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 10. contd
Polymer Tr (Cl Tc ((3 n k (s-) Remarks Refs.
Poly(propylene-star-ethylene)
ethylene content; 2.7 mol% 100
1 0 5
110
115
125
5.7 mol% 100
105
110
1 1 5
120
6.9 mol% 100
105
110
1 1 5
120
8.7 mol% 100
1 0 5
110
120
11 .O mol% 100
105
110
115
120
120
1 2 1
122
123
124
125
126
127
128
129
Poly(propylene)
29.8 wt.% I-butene
34.5 wt.% 1-butene
53.3 wt.% 1-butene
122
100
1 0 1
102
103
104
105
103
104
1 0 5
106
107
108
76
77
78
79
80
8 1
1190
355
535
640
720
960
1050
270
330
360
420
500
660
390
420
560
670
810
1100
78
252
654
2460
7865
64
1 3 3
369
1203
2453
49
87
245
816
2453
44
72
153
958
23
35
69
216
750
1 6 1
199
242
299
366
443
554
688
845
992
Poly(propylene) in poly(propylene) poly[imino(l-oxohexamethylene)] Nylon 6
124 60
1 2 5 72
126 92
127 1 1 7
128 156
129 182
Poly(propylene) crystallinity
72.6%, polyamide 6, 23.1%
Poly(propylene) in poly(propylene)/poly(imino( 1-oxohexamethylene)]/nylon 6 poly(propylene) modified with 10% maleic acid
122 100 4 Poly(propylene) crystallinity
123 125 4 82.2%
124 155 4
2.6 2.62
2.2 2.02
2.3 2.05
2.2 2.11
2.3 2.15
2.4 2.24
2.3 2.27
2.1 2.24
2.7 2.32
2.7 2.35
2.7 2.41
2.7 2.48
2.7 2.59
2.3 2.04
2.3 2.06
2.3 2.16
2.3 2.22
2.3 2.28
2.4 2.49
298
298
298
Crystallization rates measured by
DSC; linear growth rate
measurements also listed
368
368
368
368
368
Poly(propylene) crystallinity 61%; 368
this polymer is basic to the
blend study immediately below it
368
TABLE 10. contd
Rates of Bulk Crystallization (Avrami Constants) VI / 365
Polymer
Ti (Cl T, (Cl to.5 (s)
n k ( s- ") Remarks Refs.
DSC studies
Compatabilizing agent: maleic 250
anhydride used at l-10 wt.%
levels. Only DSC rates listed;
PP, 0%, used as reference
250
Maleic acid compatabilizer 250
in PP: O-10 wt.%; reference
PA rates in text DSC rate studies,
thermal and mechanical
properties in text
250
1 2 5 196 4
126 245 4
127 304 4
128 357 4
129 466 4
190 0.016
Poly (propylene)/poly[imino( 1-oxo-hexamethylene)]; PP in PP/PA
70130 wt.%; 0% anhydride 124 60 3
125 72 3
126 92 3
127 117 3
128 156 3
129 182 3
70/30 wt.%; 10% PP modified 122 100 4
with anhydride 123 1 2 5 4
124 1 5 5 4
125 196 4
126 245 4
127 304 4
128 357 4
129 446 4
Poly [imino (l-oxo-hexamethylene)]/poly (propylene) PA in PP/PA wt.%: 0% compatabilizer
203 170 3
204 203 3
205 276 3
206 329 3
207 419 3
208 636 3
10% compatabilizer 203 213 3
204 252 3
205 324 3
206 499 3
TABLE 11. POLYOXIDES
Polymer Tr (3 T, (C) to.5 (s) n k( P) Remarks Refs.
11.1. HOMOPOLYMER MELTS
Poly(oxyetbylene)
M, =23x lo3
M, / M, = 1.2(GPC)
100 (10min)
M, =42x lo3 100 (10min)
M, / M, = 1.3
M,=84x lo3
M, f M, = 1.21 100 (10min)
M, = 130 x lo3 100 (10min)
M, / M, = 1.35
M, =240 x lo3
M, f M, = 1.22
54.7
55.6
57.0
58.1
59.4
54.7
55.6
57.0
58.1
59.4
54.7
55.6
57.0
58.1
59.4
54.7
55.6
57.0
58.1
59.4
54.7
55.6
432
780
2640
7200
Dilatometry/crystallinity values
cited for to.1 transformation
369
369
960
2940
16200
960 369
1440
3600
369
462
1200
4620
Dilatometqkrystallinity values
cited for to.1 transformation
369
369
369
References page VI - 39 1
VI / 366 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 11. cont' d
Polymer Tf (3 Tc U-3 to.5 w
n k ( s- ") Remarks Refs.
M, =540x lo3
M, f M, = 1.53
M, = 1.570 x lo3
M, / M, = 1.85
M, =0. 3 x lo3
M, =0. 4x lo3
M, =0. 6 x 103
M, = 1.0 x lo3
57. 0
58. 1
59. 4
100 (10min) 54.7
55. 6
57. 0
58. 1
59. 4
100 (10min) 54.7
55. 6
57. 0
58. 1
59. 4
88 ( 15 min) - 13.0
- 14.0
- 15.0
- 20. 0
+0. 3
- 1.0
- 1.9
- 3. 9
- 5. 4
- 6. 4
- 7. 1
16. 9
14. 9
14. 1
12. 9
30. 4
30. 1
26. 8
25. 0
45. 1
44. 5
43. 5
42. 4
39. 8
30. 4
M, =2. 0x lo3 49. 3
48. 2
48. 0
46. 5
45. 5
43. 1
M, =3. 0x lo3 49. 4
48. 5
46. 9
45. 5
44. 5
M, =4. 0 x lo3 51. 0
49. 9
48. 5
46. 9
44. 5
M, =6. 0 x lo3 55. 7
52. 2
49. 9
48. 5
46. 9
M,=15x103 58.1
57. 4
55. 7
53. 2
52. 2
M, =20x lo3 59. 3
M, = 1.5 x lo3
780
1380
522
660
558
960
558
1146
888
600
354
360
270
1140
720
660
600
240
3870
600
564
378
2460
1170
600
444
14400
7380
3210
2280
1020
240
12120
6000
3540
2340
1506
1380
12540
3360
1560
990
660
24480
3060
1440
1044
456
19860
1344
642
480
426
15120
6720
2520
900
672
13140
2. 3
2. 5
1. 7
2. 3
2. 2
2. 2
2. 2
2. 3
2. 1
1. 2
1. 2
1. 9
1. 7
1. 8
2. 1
2. 1
2. 2
2. 0
1. 7
2. 0
1. 8
2. 3
2. 3
1. 7
2. 7
1. 9
1. 7
1. 7
1. 7
1. 5
1. 8
1. 7
1. 5
1. 4
1. 8
1. 7
1. 5
1. 4
2. 1
2. 2
1. 9
1. 4
1. 4
2. 2
Dilatometrykrystallinity 369
Dilatometryhystallinity values
cited for to.1 transformation
369
369
See text DSC and dilatometry; polymer
sources listed in text
TABLE 11. contd
Rates of Bulk Crystallization (Avrami Constants) VI / 367
Polymer
Tr (0 T, (Cl n k (s -) Remarks Refs.
M, = 12.6 x lo3
Carbowax 6000
M, =72.2 x lo3
WSR-N 10 Union Carbide
59.0
58.1
57.1
56.0
55.0
T,+25
(60 min)
55.6
56.7
56.7
56.7
56.8
56.5
56.3
56.9
56.6
58.1
58.0
58.1
58.1
58.2
58.2
58.1
58.1
58.5
59.0
59.8
59.5
59.4
59.0
59.0
59.4
59.6
59.0
50.0
59.1
59.6
60.0
T,+25
(60 min) 58.5
58.0
57.8
58.6
58.8
59.1
59.2
57.8
59.2
59.6
59.8
59.5
59.6
59.6
59.5
59.2
59.6
59.6
59.6
59.9
59.6
59.8
61.1
61.0
61.0
60.9
6 9 0 0 2.5
4 8 8 4 2.1
1476 2.0
1200 1.9
6 1 2 1.8
2.9
3.2
3.7
5.0
5.1
4.8
6.1
6.2
6.4
2.6
3.7
4.0
5.0
4.7
5.0
6.7
6.6
6.2
2.2
2.9
4.4
4.3
5.2
5.2
5.6
5.8
6.0
6.3
6.1
6.7
6.6
3.2
3.0
3.3
3.9
5.2
5.3
6.7
5.5
5.8
3.2
2.9
3.0
3.9
3.3
3.5
4.5
4.4
3.5
5.9
5.0
4.1
3.9
2.9
3.1
4.1
4.8
Shear dilatometer; couette,
geometry; shear rate (SK)
0
0
1.4
5.4
10.9
28.0
45.7
56.1
93.4
0
1 . 3
5.3
10.8
11.0
19.4
32.5
54.8
84.1
0
0
3.0
5.3
8.6
9.3
10.8
11.0
20.2
35.7
40.0
44.6
68.9
Shear rate (s-l)
0
0
0
5.4
7.6
17.0
25.2
37.6
36.5
0
0
0
1.4
3.0
5.4
8.4
9.6
10.8
17.1
19.8
27.1
38.9
0
0
1.4
3.1
1 6 7
167
References page VI - 391
VI/368 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 11. contd
Polymer
Tr (3 T, (0 n k( s- ") Remarks Refs.
M, = 3.5 x 103
M, / M, < 1.2
61.0
61.0
61.8
61.3
69 (15min)
M, =4. 5 x 1O-3
M, / M, < 1.04
M, =7. 0x lo3
M, / M, < 1.2
M, =9. 0x lo3
M, / M, = 1.07
M, =20. 0 x lo3
M, I M, = 1.3
M, = 100.0 x lo3
M, / M, is unknown
M, =23 x lo3 100 (10 min) 54.7
M, / M, =1.2(GPC) 5.6
57.0
58.1
59.4
MY=42 x lo3 100 (10min) 54.7
M, I M, = 1.3 55.6
39.3
40.4
41.7
43.5
44.4
45.3
46.4
35.0
37.0
39.0
40.4
42.7
43.4
45.0
39.8
41.2
43.4
44.9
47.0
49.4
40.1
43.4
48.4
49.6
44.4
46.3
48.4
51.7
53.2
39.8
43.4
47.3
49.4
51.5
53.9
39.5
40.0
45.6
46.8
47.9
48.9
50.0
51.3
51.9
54.4
55.2
45.6
46.8
47.9
48.9
50.0
51.3
51.9
54.4
55.2
432
780
2640
7200
4.9
5.0
5.1
5.1
2.7
2.9
2.6
2.5
2.6
2.6
2.9
3.0
3.1
3.1
3.1
3.0
2.8
2.9
2.4
2.4
2.1
2.1
2.4
2.4
1.9
2.0
2.3
2.1
2.5
2.7
2.4
2.4
2.1
2.2
2.2
2.3
2.3
2.1
2.1
2.47
2.50
3.00
2.68
2.87
3.08
3.04
2.85
3.46
3.33
3.22
0.95
1.12
1.06
1.02
0.95
0.98
1.02
0.86
0.79
10-l 5.4
10-10 9.1
10-l 9.2
10-s 28.5
0.11 Slightly degraded after the
4.5 x 10-t determinations; DSC
1.6 x IO-* measurements
3.3 x 10-s
3.0 x 10-4
8.0 x 1O-5
2.3 x 1O-6
1.99
0.93
0.34
0.19
2.6 x lo*
4.2 x lo3
2.5 x lo4
2.1
1.2
0.23
7.7 x 10-2
8.2 x 1O-3
3.8 x 1O-4
1.85 DSC
0.68
2.6 x lo-
8.3 x 1O-4
0.49
0.13
2.2 x 10-2
7.4 x 10-4
3.1 x 10-s
6.7
2.7
0.58
0.15
1.6 x lo-*
1.0 x 103
8.23
2.96
0.90
0.50
0.20
3.65 x lo-*
3.71 x 10-s
1.95 x 10-4
1.14 x 10-s
4.38 x 1O-9
2.40 x 10-l
1.16
0.82
0.56
0.30
0.14
4.21 x lo-*
1.04 x 10-2
3.88 x 1O-3
1.06 x 1O-3
DSC used for bulk rate constants;
two stage Avrami rates cited;
Stage I
Stage II
160(a)
160(a)
160(a)
1Wa)
160(a)
1Wa)
Dilatometry; crystallinity values 160(a)
cited as ta.t(s), not 20.5
Dilatometry; crystallinity values 160(a)
cited as ta.t(s), not to.5
TABLE 11. contd
Polymer
Tt ((3 T, (Cl to.5 6)
Rates of Bulk Crystallization (Avrami Constants) VI / 369
n k ( s- ") Remarks Refs.
M,=84x lo3
M, / M, =1.21
M, = 130 x lo3
M, / M, = 1.35
M, =240x lo3
Mw/ Mn=1.22
M, =540x lo3
M, I M, , = 1.53
M, = 1570 x lo3
M, / M, =1.85
M, =20x lo3
M, = 1.6 x lo3
M, / M, , = 1.05
M, =4.1 x lo3
M, / Mn= 1.05
M, =20x lo3
M, / Mn= 1.2
[?)I = 0.374
M, =2OOx lo3
M, / Mn= 1.2
[q] = 1.92
M, =6OOx 10s
M, / M, = 1.2
[q] = 3.65
Poly(oxyethylene)
0% silica
57.0 960
58.1 2940
59.4 16200
100 (10min) 54.7 960
55.6
57.0
58.1
59.4
100 (10min) 54.7
55.6
57.0
58.1
59.4
54.7
1440
3600
462
1200
4620
55.6
57.0
58.1
59.4
100 (10min) 54.7
55.6
57.0
58.1
59.4
100 (10min) 54.7
55.6
57.0
58.1
59.4
88 (15 min) 59.3
59.0
58.1
57.1
56.0
55.0
54.0
52.0
48.2
100 (15 min) 43.3
44.8
45.9
49.2
50.9
53.4
54.8
56.3
57.0
57.5
58.2
55.9
57.8
58.2
58.9
59.7
55.0
57.2
58.2
58.9
59.4
60.2
780
1380
522
660
558
960
558
12960
6900
4884
1476
1206
612
540
492
300
600
3120
73200
2760
9600
277200
1140
2640
8100
17940
33360
840
3360
3492
12180
27840
1140
5760
6540
18900
25680
91200
120 (45 min) 53.7
54.7
55.8
2334
3873
7381
Dilatometry; crystallinity values 160(a)
cited as to.l(s), not to.5
Dilatometry; crystallinity 160(a)
values cited as to.i(s), not 10.5
Dilatometry; crystallinity values 160(a)
cited as to.r(s), not to.5
Dilatometry; crystallinity values
cited as to.i(s), not 10.5
Dilatometry; crystallinity values
cited as to.i(s), not to.5
160(a)
160(a)
Dilatometry; crystallinity values 160(a)
cited as to.i(s), not to.5
Dilatometry; crystallinity values
cited as TO.J(S), not 10.5
160(a)
2.21
2.5
2.1
2.0
1.
1.8
DSC; rates are also given in text 343
after quenching; some dilatometty
results also available; k, values
are also cited
Dilatometry; selected values
only listed
295
295
295
295
295
Dilatometry; Me3SiCl-
treated silica
11
References page VI - 39 1
VI / 3 7 0 RATES OF CRYSTALLI ZATI ON OF POLYMERS
T A B L E 1 1 . contd
Polymer Tr ((2 Tc (Cl to.5 6)
n k (s -) Remarks Refs.
2% silica
5% silica
10% silica
Poly(oxymethylene)
M, =66x 10s
M,=41 x 103
M, =35 x lo3
Poly(oxymethylene-oxyethylene)
M, = 9. 4 x 103 80 (4h)
Unfractioned
M, =6. l x lo3
M,=lOx 10s
M, =30x 10s
Poly(oxypropylene)
h4, =3OOx 103
M, =3OOx 103
56. 8
57. 8
53. 7
54. 1
55. 8
56. 8
57. 8
53. 7
54. 7
55. 8
56. 8
53. 6
54. 7
55. 7
56. 8
57. 8
140.0
142.5
145.0
147.5
150.0
152.5
155. 0
157.5
160.0
19.5
2 2
2 5
2 8
3 5
19.5
2 2
2 5
2 8
3 5
0
2
4
6
8
1 0
1 2
1 4
1 5
0
2
4
8
1 0
1 4
1 6
1 9
2 1
125 (1Omin) 49.7
48. 5
47. 5
46. 7
45. 5
42. 8
40. 3
38. 7
125 (10min) 50.0
47. 5
45. 0
15071
32221
1941
3533
6888
14065
31488
1770
3291
6578
13432
1282
2128
3873
8093
17707
3 6
4 8
7 2
90
185
420
1800
6000
24900
4. 0
5. 7
10.5
2 2
1400
240
342
630
13200
84000
2 6
2 8
2 5
2 8
2 6
3 4
7 5
126
135
1 6
1 6
1 4
3 1
2 5
3 9
3 4
1 0 1
290
12600
10680
8580
6600
3540
2520
1650
1200
15660
8640
4500
DSC measurements of rate, average
to.5 values interpolated from
mean line of data of 3 samples;
lamellar thickness and
spherulitic growth rates listed
in text
2. 8
2. 8
4.1
4.1
3. 0
2. 8
2. 8
4.1
4.1
3. 0
2. 07
2. 93
2.19
2. 65
2. 34
2. 40
2. 00
2. 00
1.90
2. 03
2. 05
1.90
2. 26
1.90
1.90
2.12
1.95
2. 00
3.1
3. 0
3. 0
3. 6
3. 3
3.1
3. 0
2. 7
2.1
2.1
2. 2
1 0
8. 8
11
8. 8
1 0
6. 0
1.2
0. 43
0. 38
2 7
2 7
3 5
7. 2
11
4. 5
6. 0
0. 67
0. 085
Rate constants also listed in text
Dilatometry; two crystal
modifications
DSC
DSC
Hot stage optical microscopy
DSC; rates are also given in text
after quenching; some diletometry
results also available
297
372
372
372
TABLE 11. contd
Polymer
Tf (C) Tc (Cl
Rates of Bulk Crystallization (Avrami Constants) VI / 371
n k (s -) Remarks Refs.
After quenching
Poly(oxytetramethylene)
M = 13.4 x 103
Poly(oxytrimethylene)
M,=79x lo3
42.5
40.0
38.5
35.0
- 53.5
- 52.0
- 50.0
2 6 0 208.8
209.8
211.1
212.0
212.7
212.9
213.5
80 (15 min) - 50.2
- 44.4
- 39.3
- 36.7
- 33.8
- 28.7
- 26.5
- 23.6
- 18.9
- 14.5
- 10.2
- 6.9
- 4.0
- 0.4
11.2. BLENDS
2 5 8 0
1620
1200
2.0
1920
9 9 0
4 8 0
579.7
333.5
242.4
224.6
200.6
189.4
201.8
208.0
276.1
369.9
658.6
1195.2
2371.5
8000.0
2.2
2.3
2.1
Poly(oxyethylene)/Poly([1-(methoxycarbonyl)-l-methylethylene] PEOlO/PMMA (isotactic)
100/o 46.6
49.3
50.1
51.0
52.0
53.0
53.9
90/10 46.4
47.3
48.1
49.2
50.1
51.0
52.0
53.0
80120 43.2
44.2
45.2
46.2
47.1
48.1
49.1
50.1
60140 39.2
40.1
41.1
42.1
43.1
44.2
45.2
46.1
47.2
2 1 9
2 1 9
49.1
114.1
213.7
417.8
766.3
2631
3076
85.9
125.9
206.5
317.0
382.9
1 6 7 1
3681
4615
202.0
251.8
798.9
967.7
2047
3681
4615
6185
346.8 2 1 9
417.8
540.5
656.5
1312
1312
2298
3076
9 2 3 0
2 1 9
2.6 8.8 x 10-s DSC; polymerization met hod; 373
2.8 x lo- catalyst and T&optical)
7.4 x 10-9 given in text
3.1 x 10-g
1 . 5 x 10-9
9.2 x lo-lo
5.6 x lo-O
2 9 0
References page VI - 391
VI / 372 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 11. contd
Polymer
Tf (3 T, (Cl to.5 6) n k (s -)
48.1 3681
49.0 6185
Poly(oxyethylene)/poly(octafluoropentoxy~fluoroe~oxyphosphazene)/poly[oxy(l-(chloromethyl)ethylene]
Remarks Refs.
PEO, M, =5 x 106; PPZ, Unlisted M,; PECH, M, =7 x lo5
PEOIPPZ: 100/O
PEOAPZ: 75125
PEOIPPZ: 50150
PEOIPECH: 75125
PEO/PECH: 50/50
PEOIPPUPECH: 66117117
PEOKPZPECH: 50125125
100 (5min) 52 2.1 2.51 x lo-* Measurement s made by DSC and
53 2.0 5.25 x lo-* optical hot stage microscopy;
54 2.1 2.34 x lo-* T, values and morphology
52 1.6 2.09 x lo-* documented units of k are
53 1.7 0.93 x 10-z unspecified in text-assumed to
54 1.7 0.30 x 10-z be in seconds
52 1.5 1.07 x 10-z
53
54
52
53
54
50
5 1
52
52
53
54
50
5 1
52
1.6
1.7
2.0
2.3
2.1
1.8
1.9
2.1
2.0
2.1
1.9
1.9
2.0
2.1
0.58 x lo-*
0.27 x lo-*
0.30 x 10-s
0.15 x 10-s
0.85 x 1O-3
0.15 x 10-s
0.85 x 1O-3
0.43 x 10-s
1.66 x 10-z
0.50 x 10-2
0.28 x lo-*
2.29 x lo-*
0.72 x lo-*
0.17 x 10-z
TABLE 12. POLY(CARBONATES)
Polymer Tf (0 Tc (C) to.5 (s)
Poly(oxycarbonyloxy- 1,4-phenyleneisopropylidene- 1 ,Cphenvlene)
Bistan AF 35
M, =62.5 x lo3 40
25
40
Poly(oxydecamethyleneoxysebacoy1) 135 (15 min) 73.7
M = 14. 4 x 103 73.2
M, = 28.6 x lo3 72.8
72.0
71.8
70.8
69.2
68.2
67.2
66.6
65.8
Poly(oxyethyleneoxyadipoy1) 125 (15min) 39.0
M,=20x 103 37.5
36.8
36.1
35.6
34.2
33.2
32.1
29.9
27.8
25.7
23.5
21.6
18.5
598.5
268.9
2308.5
2964.1
35400
16560
13140
6780
6120
2100
900
678
444
396
324
28800
10800
8580
7800
6000
2880
1020
2052
1090
756
438
336
252
120
n k (s-) Remarks Refs.
3
3
3
3
2.7
2.6
2.6
2.6
2.9
2.2
1.6
1.6
1.5
DSC; solvent induced crystallization 374
in CC1 4 and acetone; crystallinity
cited; film thickness; 20000
& 1OOOOnm
k,values listed in text
2.4
2.5
2.4
2.4
2.4
2.7
2.4
2.7
2.4
2.4
1.9
k, values listed in text DSC; rates
are also given in text after
quenching some dilatometry;
results also available
Table 12. contd
Rates of Bulk Crystallization (Avrami Constants) w / 3 7 3
Polymer Tf (C) T, (C) to.5 (s) n k ( s- ") Remarks Refs.
Poly(oxyethyleneoxysebacoy1)
M, = 14.4 x 103
0.5% soln. in tricresol
of 0.74 dllg
135 (15min) 71.4
70.9
70.1
69.6
68.6
67.6
65.7
64.7
63.5
62.5
3960
3540
2220
1440
648
510
408
294
2.8
2.5
2.6
2.6
2.5
2.5
2.2
2.0
2.0
1.9
DSC rates are also given in text 343
after quenching; some dilatometry
resultsavailable; k, values are
also cited
TABLE 13. POLY(ESTERS)
Polymer Tr (Cl Tc (2 to.5 Cd
n k ( s- ") Remarks Refs.
13.1. HOMOPOLYMER MELTS
Poly (ethylene-2,6-naphthalate)
PEN (5); intrinsic viscosity
N 0.6 dl/g
PEN (6); intrinsic viscosity
N 0.7 dllg
Poly(oxyethyleneoxyterephtbaloy1)
M = 6. 65 x lo3
M = 11.75 x lo3
M = 8.10 x IO3
M = 7.10 x lo3
M=5. 35 x lo3
M,=81.7 x lo3
M, =69. 7x lo3
280 (10 min) 230
235
240
250
320 230
235
240
250
280 230
235
240
250
320 230
235
240
250
221
230
235
227
230
232
235
227
230
232
235
227
230
232
235
225
227
232
235
270 (30min) 225
230
235
240
270 (30min) 225
230
235
240
110
170
358
1104
107
254
395
1042
147
223
374
799
165
338
527
1232
72
111.6
349.2
73.2
133.2
177.0
297.0
46.2
88.2
126.0
244.8
58.2
112.2
163.8
328.2
81.0
138.6
441.0
906
1812
4536
9816
486
1392
3348
8418
2.6
3.1
3.4
2.6
3.4
3.4
3.9
2.4
3.4
3.9
4.0
2.6
3.1
3.8
4.0
2.0
3.3
3.5
DSC measurements. Column 4 412
contains T, (time to attain
max.heat flow and crystallinity,
Xc); proportional to tcs
Range of crystalline order
0.4 < Xc < 0.45. Non-isothermal
data are listed in text ; spherulitic
morphology is discussed
DSC; k (mm+) listed in text;
crystallinities also cited
375
375
375
0.0288 mol% Sb203 376
0.0288 mol% Sb203 376
References page VI - 39 1
VI / 374 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 13. contd
Polymer Tr (Cl Tc (C) to.5 (4
n k ( s- ") Remarks Refs.
M, =49. 0x lo3
M, =30. 6x lo3
oriented fibers
DuPont, Qpe A Mylar
M, =35. 5x lo3
[q] = 0.580
Intrinsic viscosity
[q] = 0.573
M, = 12.2 x lo3
Poly(oxyetbylene oxyterephthaloyl)
(Various data compiled by author)
270 (30min) 235
240
242
270 (30min) 235
240
242
RT quench 95
100
1 0 5
110
1 1 5
95
100
1 0 5
110
115
95
100
105
110
277 95
100
105
110
230
235
240
95
100
105
110
230
235
240
95
100
1 0 5
110
230
235
240
295.0 228.3
230.2
232.6
233.7
234.6
236.8
237.2
239.8
107
108
110
112
116
1 2 5
205
216
227
232
236
237
1 1 3
114
117
124
1398
3498
4158
978
2340
3408
17190
7020
4800
900
600
14400
3540
840
660
300
1920
480
360
180
1380
720
240
150
360
780
210
2400
1200
480
240
600
1260
5400
1080
450
234
132
240
600
1620
120
100
80
564
371
139
59
1 7 3
393
549
734
937
1110
862
655
342
0.0288 mol% Ca(OOCCHs)2
Fibers, fa = 0.032a; crystallinity
and density listed
fa = 0.044; crystallinity and
density listed
fa = 0.123; crystallinity and
density listed
DSC; crosslinked with
1 mrad y-radiation
2 mrad y-radiation
3 mrad y-radiation
2.0 3.3 x 10-s DSC; polymerization method,
1.6 x 1O-6 catalyst and T, (optical) given
5.1 x 10-7 in text
5.4 x 10-7
3.3 x 10-7
1.2 x 10-7
1.5 x 10-7
4.8 x lo-*
Crystallized from glassy state;
average to.5 values, interpolated
Nucleated with low mol. wt.
poly~propylene)
Nonnucleated polymer
376
376
378
373
379
TABLE 13. contd
Rates of Bulk Crystallization (Avrami Constants)
Polymer Tf (Cl Tc (3
n k (6') Remarks Refs.
Poly(oxyhexamethylene-
terephthaloyl) PET
1 3 3
202
215
226
231
233
235
112
1 8 8
203
215
220
224
227
229
231
232
215
219
223
224
226
227
228
285 26.6
26.9
27.6
25.5
25.1
Poly(oxyhexamethyleneoxyterephthaloy1)
M, = 11.8 x lo3 186 131.5
132.7
134.0
135.2
136.6
138.0
Poly(oxy-1-oxo-2,2-dimethylethylene)
M,=71 x 103 250 (5 min) 186.0
M, = 163 x lo3 188.5
191.0
194.0
197.0
Poly(oxy-1-oxyethylene)
M, =20-145 x lo3 201
203
205
207
Poly(oxy-1-oxohexamethylene)
M,=9.4x lo3 T, + 24 (60 min) 48.1
48.0
48.0
48.3
48.1
48.1
48.6
48.4
49.8
49.8
49.8
49.8
49.8
49.8
1 7 5
72
213
444
607
810
1044
77
8 3
144
258
390
566
706
868
994
1134
362
538
700
809
953
1080
1259
222
243
439
444
720
2.9
84 2.7
162 2.5
192 2.4
492 2.3
582 2.3
27.8
38.4
52.2
66.2
3.0
3.7
3.9
3.7
3.7
4.0
5.0
5.5
2.9
2.9
3.1
4.5
4.2
4.3
1 0
50
100
1 2 5
150
1.2 x 10-s
6. 1 x 1O-9
1.4 x 10-s
5. 3 x 10-10
1.6 x 10-t
3. 1 x lo-
4 (approx.)
;; 1::
10 -9
10 -9
10 -
10 m8
;; 1::
10 m9
10 -8
10 -8
10 -
10 -to
10 -9
Nucleated with poly(propylene)
Nucleated with LLDPE
Nonnucleated polymer; these
constitute te.s(s) averages
compiled from the literature
Avrami equation does not fit data;
Malkin equation was used (see Ref.);
crystallization temp. expressed as
T, - T, (C); Pressure MPa;
T, =264.2-0.5058P;
dT,jdP = 0.506/MPa;
T, = 234.6- 0.533OP; @ 1OMPa;
dTldt = 2.5
373
Dilatometry, DSC thermograms 380
and to.1 values also given; higher
fractions up to M, = 241 x lo3
are measured
DSC 371
Shear dilatometer, shear rate(s-)
0
1.4
2.9
5.2
10.9
14.6
16.0
26.9
0
1.3
2.8
5.1
8.9
10.8
167
References page VI - 39 1
VI / 376 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 13. contd
Polymer
Tr P-2 T, (3 to.5 (9
n k (s -) Remarks Refs.
49.5 4.7 10 -
49.8 4.9 10 -1
49.8 5.1 10 -
49.9 5.0 10 -1
50.9 2.9 10 -s
50.9 3.2 10 -9
50.9 4.0 10 -10
50.8 4.1 10 O
50.8 4.8 10 -*
50.8 4.8 10 -1
50.9 5.0 10 -1
50.9 4.1 10 -O
Poly(oxypentamethyleneoxyterephthaloy1)
M = 13.4 x 103 260* 210.1
211.7
212.1
213.6
214.3
214.7
214.9
Poly(decamethylene-4,4-diphenoxyterephthaloyl) PDDPT
265 * 234
235
236
238
239
240 246
241
280* 237
238
239
240
241
300* 237
238
239
240
Poly(hexamethylene-4,4-diphenoxyterephthaloyl) PHDPT
190* 171.5
172
172.5
173
173.5
200* 1 7 1
171.5
172.5
173
173.5
174
174.5
240* 170
1 7 1
171.5
173
173.5
174
174.5
175
30
48
60
108
144
2
324
72
90
156
264
486
84
132
258
522
57
78
102
144
54
54
78
102
144
192
264,
42
42
48
78
90
114
174
288
2.8
3
3
3
3
3
2
3
3
3
2
2
3
2
2
2
3
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
7.1 x 10-9
2.1 x 10-9
1.5 x 10-9
3.7 x 10-10
2.6 x 10-l
1.5 x 10-10
8.9 x 10-l
11.2
14.9
26.6
48.0
3.0
5.5
11.0
14.3
16.0
24.9
47.2
15.3
Crystallinity with time of
transformation cited
Dilatometry 343
DSC studies; transformation
after conditioning @265C
from the nematic state
247
Transformation from the nematic
state after conditioning
@28oC
Transformation from the isotropic
state after conditioning
@3OoC
DSC rate; transformation from
nematic state after conditioning
@ 190C
248
Transformation from nematic
state after conditioning @2OOC
Transformation from the isotopic
state after conditioning @24oC
* Denotes mesophase conditioning temperature; not Tr.
TABLE 13. contd
Polymer
Tf (C) Tc (Cl
Rates of Bulk Crystallization (Avrami Constants) VI / 377
n k (s-) Remarks Refs.
Poly(hexamethylene-4,4-diphenoxyterephthaloyl PHXDPT
280* 262
262.5
263
263.5
264
264.5
285 + 262
262.5
263
263.5
264.5
265
265.5
13.2. BLENDS AND COPOLYMERS
Poly(oxy-l-oxohexamethylene)/poly(l-chloroethylene)
PCLIPVC: 70130 100 (5min) 5
1 5
25
65135 5
1 5
25
60140 5
1 5
25
50150 5
1 5
25
60 2
60 2
18 2
90 2
102 2
120 2
30 2
36 2
48 2
66 2
90 2
96 2
138 2
216 3
372
1200
600 3
900
2220
2760 3
2100
3480
37800 3
28800
35700
Poly(oxyethyleneoxyterephthaloyl)/poly(ethylene- 1,2-diphenoxyethane- 1,2-dicarboxylate)
PET/PC: O/100, w/w 80 0.164
90 0.159
100 0.154
120 0.123
130 0.109
140 0.089
150 0.078
170 0.064
33 167, wlw 80 0.105
90 0.109
100 0.108
110 0.095
120 0.083
130 0.064
150 0.045
170 0.004
50150, w/w 80 0.078
90 0.081
95 0.083
100 0.083
110 0.077
120 0.074
130 0.062
140 0.06
150 0.055
170 0.051
67133, wl w 80 0.07
90 0.072
100 0.071
1 0 5 0.076
110 0.072
120 0.061
* Denotes mesophase conditioning temperature, not Tr.
4.36 x lo-*
1.41 x 10-2
1.95 x 10-s
1.99 x 10-s
7.60 x 1O-4
7.57 x 10-s
4.57 x 10-6
8.50 x 1O-6
2.62 x 1O-6
2.45 x 1O-9
3.98 x 1O-3
3.16 x 1O-9
DSC studies transformation
from the nematic state after
conditioning @28oC
248
Transformation from nematic
state after conditioning
@285C
318
DSC used; rates expressed in s- ;
T, =288C; T, =72C
T, = 284C; T, = 71C
T,=274C; T,=71C
T, = 276C; T, =70C
References page VI - 39 1
VI / 378 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 13. contd
Polymer Tr (Cl Tc (Cl to.5 6)
n k (s-) Remarks Refs.
130 0.049
140 0.045
150 0.04
o/100, w/w 100 0.018
110 0.02
120 0.027
130 0.031
140 0.03
160 0.02
170 0.018
Poly(oxyethyleneoxyterephthaloyl)/poly(oxybutyleneoxytereph~aloyl)
PET/PBT: 100/O, w/w 280 (5 min) 119 2920
129 940
139 423
150 234
159 183
169 169
1 9 5 247
205 334
216 693
224 1256
229 2098
100 2017
1 0 5 615
110 500
1 9 5 1 3 3
221 1 1 5
120 157
125 1 3 1
130 107
1 3 5 8 3
210 282
216 369
223 1016
225 1290
230 3105
75 2000
80 494
85 485
90 327
94 176
100 1 6 1
1 0 5 110
110 107
1 1 5 8 8
120 54
1 2 5 5 1
1 8 5 119
206 232
210 337
215 515
217 587
218 602
222 805
227 1888
T, = 280C
DSC measurement; t, values are
90110, w/w
75125, w/w
listed in text; relation to k (se)
is not specified
Poly(oxyethyleneoxyterephthaloyl)lPoly(oxyc~bonyloxy-1,4-phenylene-isopropylidene-1,4-phenylene)
PET/PC 285 (5mi n) 210 13.10 x 10s DSC measurements; Avrami n
M, = 16000 215 9.76 x lo3 variable; optical micrographs
M, = 57000 220 5.74 x 10s included on text
M, = 24000 225 3.42 x lo3
100/o, wl w 230 2.14 x lo3
Additive modified 220 22.26 x lo3 With antioxidant Itganox, 2 ppm
225 11.82 x lo3
230 6.68 x 103
235 3.42 x lo3
3 8 2
382
382
TABLE 13. contd
Polymer
Tr (Cl Tc (0
Rates of Bulk Crystallization (Avrami Constants) VI / 379
n k (s-) Remarks Refs.
220
225
230
235
220
225
230
235
215
220
225
230
280 (1 min) 230
(5 min)
(1Omin)
(15 min)
(20 min)
(30 min)
300 (1 min) 230
(5 min)
(1Omin)
(20 min)
(30 min)
Poly(butylene naphthalate terephthalate)-co-poly(hydroxybutylnaphthalate)
BHBTAHBN: 100/O, w/w T, + 40 (6 min) 1 6 1 65
62.9137.1, w/w 164 9 1
1 6 7 1 3 3
170 204
100/o, wl w 1 6 1 8 5
55.5 144.5, w/w 164 27
1 6 7 201
170 336
100/o, wl w 1 6 1 97
45.6154.5, w/w 164 1 5 1
167 250
170 471
Poly(butylene naphthalate terephthalate)-co-poly(hydroxybutylnaphthalate)
BHBTiPHBN: 100/O, w/w T, + 40 (6 min) 1 6 1 65
62.9137.1, w/w 164 9 1
1 6 7 1 3 3
170 204
100/o, w/w 1 6 1 85
55.5144.5, w/w 164 27
167 201
170 336
100/o, w/w 1 6 1 97
45.6154.5, w/w 164 1 5 1
167 250
170 471
2.5
2.7
2.9
3.0
2.5
2.8
2.8
2.9
2.7
2.9
2.9
3.0
2.5
2.7
2.9
3.0
2.5
2.8
2.8
2.9
2.1
2.9
2.9
3.0
20.62 x lo3
10.92 x lo3
6.25 x lo3
2.90 x lo3
24.46 x lo3
13.77 x 103
8.13 x lo3
3.50 x 103
23.96 x lo3
14.90 x 103
8.83 x lo3
4.88 x 103
18.90 x 103
17.05 x 103
13.94 x 103
12.22 x 103
8.77 x 103
6.65 x lo3
7.26 x lo3
5.50 x 103
2.46 x lo3
1.23 x lo3
0.08 x 103
2.91 x 1O-5
7.52 x 1O-6
1.49 x 10-s
3.12 x lo-
9.30 x 10-4
1.41 x 10-4
6.23 x lo-
1.08 x lo-
6.19 x 1O-6
9.61 x lo-
2.33 x lo-
2.10 x 10-s
2.91 x 10m5
7.52 x 1O-6
1.49 x 10-s
3.12 x lo-*
9.30 x 10-4
1.41 x 10-4
6.23 x lo-
1.08 x 10-7
6.19 x 1O-6
9.61 x lo-
2.33 x lo-
2.10 x 10-s
Effect of fusion on rate
Effect of fusion on rate
DSC measurements
DSC measurements
DSC measurements
DSC measurements
DSC measurements
DSC measurements
395
395
395
395
DSC measurements 404
DSC measurements 404
DSC measurements 404
DSC measurements 404
DSC measurements 404
DSC measurements 404
TABLE 14. POLY(AMIDES)
Polymer Tr (Cl Tc(C) n k (s) Remarks Refs.
Poly(imino( 1-oxo-hexamethylene)) Nylon 6
M, = 14.6 x lo3
Poly[imino(l-oxohexamethylene)] Nylon 6
205
207
209
210
212
215
48
49
49.5
1080
2040
3600
4980
6000
12600
1848
1608
1230
Dilatometry
DSC rate measurements from
the glassy state; rate constants
listed for non-integer rt values
289
401
References page VI - 391
VI / 380 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 14. contd
Polymer Tf (C) TAT) to.5 6) II k 6)
Remarks Refs.
Poly[imino(l-oxohexamethylene)]
M, = 11.6 x lo3
M,=17x103
Poly[imino( 1-oxohexamethylene)] Nylon 6
Poly[imino(l-oxohexamethylene)] Nylon 6
51.5
52.5
57.6
60.2
62.9
241
2 4 7
2 5 0
2 5 2
2 4 3
2 4 7
2 5 0
2 5 2
2 5 3
2 4 7
2 5 0
2 5 2
253
2 5 4
2 4 7
2 5 0
2 5 2
2 5 5
2 5 7
178.0
182.1
186.1
189.2
193.2
195.3
199.3
203.3
210.4
176.0
178.0
182.1
184.1
186.1
189.2
191.2
193.2
195.3
197.3
199.3
203.3
184.1
186.1
191.2
195.3
199.3
201.3
203.3
205.3
207.3
2 0 4
205
2 0 7
2 0 8
2 0 9
203
2 0 4
2 0 5
2 0 6
2 0 7
2 0 8
7 5 0
4 9 3
9 3
4 5
21.6
9 8
122
160
2 6 2
4 0 0
5 6 0
9 6 0
3 0 0 0
13100
2 4
3 0
4 2
5 3
6 0
120
186
3 0 4
325
6 0 0
9 2 0
2 1 0 0
3 2
3 6
7 6
120
192
3 4 0
4 7 5
7 6 0
1230
1 0 7
166
255
271
3 9 8
170
203
2 7 6
3 2 9
4 1 9
6 3 6
3
3
3
4
3
3
3
3
4
3
3
3
3
4
3
3
3
3
4
2.3
2.1
2.0
2.0
1 9
1.8
2.05
1.9
2.35
4.5
4.7
4.7
4.6
4.8
4.4
3.6
3.3
3.4
3.0
3.1
2.7
3.2
3.25
4.15
4.4
4.6
5.4
5.4
5.6
6.1
3
3
3
3
3
3
3
3
3
3
3
1.48 x 10-9 Rate constants in (min-) 323
1. 71 x 10-10
1.39 x 10-l
6.71 x lo-l6
3.06 x 1O-9
7.40 x 10 -O
7.40 x 10-l
3.52 x 10-l
5.71 x 10-16
1.53 x 10-9
6.50 x 10 -lo
6.00 x lo-
5.48 x 10-16
1.90 x 10-9
5.10 x 10-10
3.75 x 10-10
2.70 x 10 -I4
Values cited in DSC; induction times cited in text 383
text in (min-)
With 0.1% kaolin
With O.Ol-0.5% talc
This polyamide is used in the
blend below; see text
250
2 5 0
TABLE 14. contd
Rates of Bulk Crystallization (Avrami Constants)
Polymer Te (Cl TAT)
t l
k W)
Remarks Refs.
Poly[imino(l-oxohexamethylene)] Nylon 6
linear 240 (10min)
M, = 16000
M, = 29000
DP = 270
3-arm branched dendrimers 240 (10 min)
M, = 19000
M, =36000
DP = 300
6-arm branched dendrimers
M,=21000
M, =42000
29.5
33.4
35.6
38.5
41.2
45.0
26.5
30.6
32.3
35
4 1
23
28.3
30.8
33.1
37
Poly[imino(l-oxo-dodecamethylene)] Nylon 10
M, = 15.7 x lo3
[q] = 1.34 dllg
(m-cresol at 20C)
M, =29. 6 x lo3
M, =41.2 x lo3
[q] = 1.70 dl/g
M, =9. 5 x lo3
[q] = 0.92 dllg
(m-cresol at 20C)
M, =23. 9x lo3
[ill = 1.80dl/g
M, =23. 9x lo3
[r/l = 1.80dllg
220 (15 min) 163
164
1 6 5
166
167
168
169
164
1 6 5
166
167
168
169
1 6 1
162
1 6 3
164
1 6 5
220 (2 h) 162
1 6 5
167
169
162
1 6 5
1 6 7
169
162
165
167
169
Poly(iminoadipoy1 iminohexamethylene) Nylon 66
M, = 12.7 x lo3 162
1 7 5
187
200
212
224
238
20
29
34
40
44
60
70
80
4.3
4.9
4.9
5.2
5.3
4.9
4.7
5.2
5.3
5.0
5.3
5.5
5.6
4.9
4.9
5.6
5.9
5.0
4.4
4.9
4.2
5.7
5.0
5.6
4.7
4.5
4.7
4.4
4.7
4.6
DSC; k values listed in text
Dilatometry; k values also cited
in (min-)
Contains 0.1% kaolin
384
384
384
77.2
665
560
432
605
280
384
605
493
385
278
868
646
510
416
309
DSC measurements of 10.5 and k;
morphological study reported
168
240
330
498
600
996
1200
192
240
348
546
750
996
348
426
666
858
996
360
696
1128
3000
522
1110
2070
3750
396
720
1332
2400
385
385
385
385
385
385
1.4
1.85
3.03
4.0
9.1
16.7
40.0
10000
6600
1000
500
380
33
6.3
4.3
Light depolarization technique; 94
spherulite growth from the melt
Growth from glassy state; spin line 94
quenched and subsequently
crystallized; fiber birefringence
development using LDT on hot
stage assembly between
crossedpolars.Amorphous
condition verified X-ray diffraction
References page VI - 391
VI / 382 RATES OF CRYSTALLlZATlON OF POLYMERS
TABLE 14. contd
Polymer Tr (Cl Tc(C) to.5 6)
n k (~1
Remarks Refs.
14.1. BLENDS OF POLY(AMIDES)
Poly(iminohexamethyleneaminoadipoyl)/poly[2-2-bis(3,4-dicarbox~-uhenoxy)phenylpropane-2-phenylene bisimide]
300 (5min) 237
(Nylon 66/PEI)
wt %
100/o 238.5
240
242
244
9515 237
238.5
240
242
244
90/10 237
238.5
240
242
244
246
-29 - 2.4 <-n-<-3.0 k vaiues
34
44
79
1 0 5
38
50
55
94
158
39
58
69
100
1 6 5
300
32
40
40
7 1
1 1 1
198
294
29
40
52
69
100
34
42
65
94
120
listed in text
as min-
DSC studies under nitrogen;
textures are spherulitic
T; = 295C
85/15 236
237
238.5
240
242
244
246
75125 237
238.5
240
242
244
50150 237
238.5
240
242
244
Poly[imino( 1-oxo-hexamethylene)]/poly(iminohexamethyleneimioadipoyl)/[imino(1-oxohexamethylene)]
Nylon 6/Nylon 66kaprolactam (mol/mol/mol)
616.614.4 Ti + 30(10-20min) 207 12.3
209 22.7
210.5 42.1
6 16.618.2
212 76.3
Ti + 30 (lo-20min) 205 14.8
206.5 26.4
208
210
616.6117.5 Ti + 30 (lo-20min) 205
206.5
208
194
6/66-4,4 Ti + 30 (lo-20min) 1 9 5
198
201
204
52.7
84.7
19.6
34.6
52.3
93.4
12.3
22.7
40.8
74.4
6/PXD.6-4.1 Tz + 30 (lo-20min) 182 12.4
186 23.9
6/MXD.6-3.4
189 46.5
192 71.0
Ti + 30 (lo-20min) 189.5 13.2
1 9 3 27.0
199 53.8
202.5 128
Tz unlisted
T;=287C
Ti unlisted
T;=281 C
T;=273C
DSC rate measurements; 386
Polymers characterized by pyrolysis,
NMR; Tz using Glory copolymer
theory (see Ref. 215)
386
386
386
386
386
TABLE 14. contd
Rates of Bulk Crystallization (Avrami Constants) VI / 383
Polymer
Tr (Cl TO3 to.5 (9
n
k (0
Remarks Refs.
6/I-3.8 Tz + 30 (lo-20min) 182 27.0 386
185 53.8
188 75.9
1 9 1 194
194 190.4
6/MXD.I-3.9 Ti + 3 0 (lo-20min) 175 30.8 386
187 110.6
6/6.T-4.5 Ti + 30 (lo-20min) 168 53.5 386
1 7 1 69.5
174 96.0
177 142.6
180 198.2
TABLE 15. POLY(URETHANES)
Polymer
Tr (Cl Tc(C) to.5 6)
n
k (s)
Remarks Refs.
Poly(oxycarbonyliminotetramethylene iminocarbonyl oxyhexamethylene)
M,=lOx 103 195 (10min) 169 3540
167 1650
1 6 5 1110
1 6 3 630
162 360
Poly(oxycarbonyliminohexamethylene iminocarbonyl-bis(oxyethylene)
150 (10min) 109 17280
107 8880
[q] = 0.81 in 1 0 5 4860
0.5% m-cresol 103.5 3060
100 960
95 630
After quenching 14.2 5580
16.2 3960
17.8 3000
20.3 1950
22.3 1320
25.6 600
27.2 432
28.2 330
Poly(oxycarbonyliminohexamethylene iminocarbonyl-tris(oxyethylene))
140 (10min) 8 5 4260
8 1 2160
78 1350
75 930
72 630
69 420
After quenching 14.7 3960
16.1 2940
19.0 1320
22.0 960
24.5 630
26.0 390
2.1
2.1
2.0
1.9
2.0
3
3
3
3
3
3
k, values listed in text
k, values listed in text
k, values listed in text
343
343
343
15. 1. BLENDS OF POLY(URETHANES)
Poly[imino(l-oxohexamethylene)] Nylon 6; 70/30 blend with 10% polypropylene with maleic anhydride
203 213 3
204 252 3
205 324 3
206 497 3
28.0 300
References page VI - 39 1
VI / 384 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 16. POLY(SILOXANES)
Polymer Tf (Cl TX3 to.5 6) n k (s)
Remarks Refs.
Poly(oxydimethylsilylene) DMS 20 - 55.6
- 6.7
M,=4OOx 103 - 58.0
- 59.6
- 60.5
- 63.0
- 65.0
- 67.0
- 115
After quenching - 109
Poly(oxydimethylsilylene-1,4-phenylenedimethylsilylene)
TMPS
M, = 15.8 x lo3 200 (5 min) 100
110
1 1 5
120
126.5
M, =37. 5 x lo3 100
110
115
120
126.5
M, = 109 x lo3 100
110
1 1 5
120
126.5
M, =245x lo3 100
110
1 1 5
120
126.5
M, =380x lo3 100
110
115
120
126.5
Poly(oxydimethylsilylene) 20 - 55.6
- 56.7
M, =4OOx lo3 - 58.0
- 59.6
- 60.5
- 63.0
- 65.0
- 67.0
-115
After quenching - 109
900
660
480
420
318
228
174
138
1080
108
82
2553
6383
24000
111540
54
1580
4110
10000
55050
105
2857
5405
15000
56075
316
8571
13636
30000
120000
3191
20000
35294
99174
272727
900
660
480
420
318
228
174
138
1080
108
2.2
2.1
2.0
2.1
2.1
2.0
2.0
2.0
2.2
2.1
2.0
2.1
2.1
2.0
2.0
2.0
Other bulk transformation 387,388
methods DSC and SAXS
have been used on these same
fractions
387.388
387.388
387.388
387.388
343
TABLE 17. POLY(PHOSPHAZENES)
Polymer Tf (C) It
k 6)
Remarks Refs.
Poly[bis(4-fluorophenoxy) phenylphosphazene]
M, =0.16 x lo6 215 (5mi n) 120
M, = 1.18 x lo6 122.5
125
127.5
129.5
Poly[bis(trifluoroetboxy) phosphazene)]
229.8
230.2
230.5
4
6.5
1 5
63
2200
N 2.0 DLI technique cross-polars with 389
Chino controller and accessories;
textures recorded
-2.OfO.l 1 8 1 0
913
644
DSC isotropic thermotropic (2D) 406
transformation rates: 10 ks -*
: .
8
8
18
18
$ 8
4 3
-
!fS.
-
189
106
231.0 471
231.5 186
228.6 -2.OfO.l 8 7 6 0 DLI isotropic + 2D transformation
229.6 3410 rates: lOks-
230.6 1030
231.1 701
231.6 289
232.6 60.8
233.6 17.0
234.6 2.97
73.0 N 2.0 zk 0.1 40600 DSC thermotropic (2D) + 3D
73.3 18000 crystalline transformation rates:
73.6 6270 10 ks-2
73.9 2210 Small birefringence changes
74.2 927 negated the DLI measurement
Poly[bis(phenylphenoxy) phosphazene]
290 (10min) 237.5 - 2.0 * 0.1 49300 DLI method for isotropic + 2D 401
237.9 16600 thermotropic transition rate:
238.3 4080 lOks-*
238.1 1630
239.1 -2.0*0.1 716
239.5 199
239.9 53.0
240.3 27.6
240.1 10.7
198.5 -2.OfO.l 48000 DLI method for 2D thermotropic
198.9 29200 + 3D crystalline transformation
199.6 10700 rate: lOks-*
200.0 5210
200.4 1750
200.9 450
201.4 71.1
Poly[di(p-methylphenoxy) phosphazene]
1 0 1 7.2 i n si tu SAXS synchrotson radiation 1 7
107 54 rate measurements; induction
112 89 times by WAXS and SAXS are
112.5 104 listed in text
117.5 150
118.5 154
129 263
132.5 984
TABLE 17. contd
Rates of Bulk Crystallization (Avrami Constants) VI / 385
Polymer
Tf (Cl Tc(C) to.5 6)
n
k (~7
Remarks Refs.
TABLE 18. OTHERS
Polymer
Tr (2 TO-2 to.5 6) II k (0
Remarks Refs.
Poly(oxy- 1 ,Cphenyleneoxy-1,4-phenylenecarbonyl- 1,4-phenylene)
PEEK Poly(etberetherketone) 188.8 5.1
182.3 5.1
175.2 4.7
171.3 6.9
167.1 7.5
164.4 7.8
Poly(oxy- l,Cphenyleneoxy- 1,4-phenylenecarbonyl- 1,4-phenylene)
PEEK Poly(etheretherketone) 160 126
original polymer 164 54
M, = 14000 168 24
172 1 8
Melt crystallized 290 21.6
300 40.2
310 136.2
1.8 x lo- 50b
4.7 x lo-IO 20
1.6 x lo- 10
6.6 x 10-16 5
7.7 x 10-19 2
2.9 x 10m4 1
2.5-2.6
2.3-2.4
DSC; Nonisothermal rates from
glassy state; crystallinity,
density listed
DSC; k values in text in min-
380
408
408
Re f e r e n c e s VI - page 39 1
VI / 386 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 18. contd
Polymer Tf (C) TX3
n k 6)
Remarks Refs.
Solvent treated and desorbed 1 6 8
172
176
180
184
190
194
Poly[oxy-1-methyl-2-oxyethylene]; poly(L-lactic acid)
200 (20min) 80
90
100
110
120
Poly[oxy- 1-methyl-2-oxyethylene]; poly(L-lactic acid)
M, =700000 220 (10min) 70
75
80
8 5
90
95
100
109.5
1 1 5
120
1 2 5
130
134.5
140
1 4 5
149.5
1 5 5
159
1 6 5
Poly(L-lactide-co-meso-lactide) 8 5
M,, = 10.1 x 103; wt. (0% meso) 90
95
100
105
110
1 1 5
120
1 2 5
130
1 3 5
M, = 15.7 x 103; wt. (0% meso) 90
100
110
120
130
M, = 8.8 x 103; wt. (3% meso) 8 5
90
95
100
105
110
1 1 5
120
25
,
Poly(L-lactide)
M, = 11.4 x 10; wt. (3% meso) 100
1 0 5
110
1 1 5
M, = 5.8 x 103; wt. (6% meso) 100
110
570
522
450
330
276
222
180
88
420
270
228
174
114
210
240
306
522
374
684
288
240
342
804
1434
660
486
564
516
360
414
492
690
1668
1176
1182
1332
684
648
408
2.62
2.73
2.82
2.66
3.24
2.5
2.5
2.7
2.4
1.25 x 10m3 DSC measurement s; various 1 4 5
1.19 x 10-s analysis of kinetic data
2.97 x 1O-3 are presented
2.81 x 1O-3
1.88 x 1o-3
5.79 x 10-6 Light depolarization technique; 390
3.96 x lO-5 morphology and X-ray diffraction
1.33 x 10-4 reported; k expressed t-s by the
4.44 x 10-4 authors; values are not listed
1.49 x 10-s
3.35 x 10-s
6.79 x lo-
4.48 x lo-
4.10 x 10-s
2.81 x 1O-3
1.73 x 10-s
6.61 x 10-4
4.29 x 10m4
2.31 x lO-4
1.01 x 1o-4
5.30 x 10-s
2.14 x 1O-5
1.85 x 10-s
1.41 x 10-s
Kinetics made using DSC 391
2.7
3.4
3.2
2.4
TABLE 18. contd
Rates of Bulk Crystallization (Avrami Constants) VI / 387
Polymer TP (Cl Tc(C) to.5 (4
n k WY
Remarks Refs.
120
M, = 11.4 x 10; wt. (6% meso) 110
Poly(L-lactide-co-meso-lactide)
M, = 12.3 x 103; 90
(wt . 0% meso); 100
wt. 6% talc additive 110
120
M, = 10.5 x 103;
(wt . 3% meso); 90
wt. 6% talc additive 100
110
120
M, = 12.2 x 103; 90
(wt . 6% meso); 100
wt. 6% talc additive 110
120
M, = 8.1 x lo3 90
(wt . 9% meso) 100
wt. 6% talc additive 110
120
Poly(L-lactide-co-meso-lactide)
(wt . 9% meso)
M, = 3.9 x 103;
wt. 2% talc additive 90C
M, =4. 6 x 103;
wt. 6% talc additive
M, =5. 5 x 103;
wt. 11% talc additive
M, =5. 3 x 193;
wt. 2% talc additive
wt. 2% talc additive
wt. 6% talc
wt. 11% talc
wt. 21% talc
Poly(thio-1,4-phenylene) 208.8
218.3
217.3
227
235.8
245.1
254.1
263.3
272.7
Poly(thio-1,4-phenylene) 250
Phillips Pet. Co. research grade R-4 245
M, =51 x lo3 240
235
230
220
215
Phillips Pet. Co. Resin grade V-l 250
M,=15x103 245
240
235
M, = 15 x IO3 220
215
Poly(thio-1,4-phenylene) Ryton V-I (Phillips Pet. Co.)
320 240
243
245
249
255
&irradiated polymer 320 240
243
245
696
2640
<60
<60
<60
<60
120
84
<60
126
342
180
234
882
528
360
600
2 900
1134
762
600
444
1176
876
732
732
215.5
163.6
144.8
92.9
43.4
19.5
7.41
1.68
0.125
170
100
48
34
26
1 7
1 4
240
140
60
40
22
1 7
97.3
1 0 1
142
207
601
76.6
120
137
2.3
2.7
2.3
2.3
2.2
2.6
2.9
2.3
2.3
2.6
2.5
2.6
2.0
2.4
2.2
2.1
2.5
2.2
391
Kinetics measured by DSC 391
391
391
391
Kinetics measured by DSC 391
391
391
391
391
391
391
391
391
DSC 392
392
64.8 x 1O-6 DSC measurement 392
59.1 x 10-6
29.8 x 1O-6
12.6 x 1O-6
1.1 x 10-s
170 x 10-s DSC measurement 392
98 x lop6
70 x 10-6
392
References page VI - 39 1
VI / 388 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 18. contd
Polymer Tf (Cl Tc(C) to.5 (s)
n
k (~7
Remarks Refs.
Poly (thio- 1,4-phenylene) (PPS
homopol ymer) 0 %
metamethylene linkages
251
255
102
106
110
114
Random copolymer with 5%
metamethylene linkages
Random copolymer with 8%
metamethylene linkages
Random copolymer with 10%
metamethylene linkages
118
120
235
240
250
245
255
260
265
270
110
1 1 5
120
1 2 5
130
1 3 5
140
145
200
210
220
230
235
240
245
250
105
110
120
130
140
150
190
200
205
210
215
220
225
1 0 5
110
120
130
140
150
160
170
180
190
200
205
210
215
220
329
507
8.5
3.0
1.5
0.9
0.71
0.55
0.36
0.53
1.30
0.82
2.40
5.20
8.00
17.5
6.71
3.16
1.90
1.23
0.88
0.77
0.53
0.46
0.39
0.59
1.20
2.30
2.81
5.01
9.47
23.5
14.93
5.80
1.97
1.09
0.670
0.470
1.75
2.52
4.19
5.26
7.40
9.62
23.02
13.4
7.10
2.65
1.34
0.845
0.620
0.520
0.490
0.760
1.11
1.80
2.54
3.81
6.21
10.20
5.7 x 10-6
1.7 x 10-6
Crystallization rates listed as DSC 411
peak times (mins); measurements
below
T
nmx
were made by upquenching
from the amorphous state
CT: N
330C using Hoffman-
Weeks plot)
T; N 290 C
T,f - 283 C
T; c-u 273 C
TABLE 19. COMPOSITES
Rates of Bulk Crystallization (Avrami Constants)
Polymer
Te ((3 to.5 6)
II k 6) Remarks Refs.
Poly(thio- 1,4-phenylene) unreinforced
With commercial glass (70% wt.)
Unsized glass (35% wt.)
Sized glass
Commerci al carbon (66% wt . )
Unsized AS4 (36% wt.)
Sized AS4 (39% wt.)
Graphitized Thomel (35% wt.)
Poly(thio- 1 ,4-phenylene)
Unreinforced
Unsized AS4, 54 wt.%
Sized AS4, 64%
Graphitized Thomel, 65%
Phillips prepreg 66 wt.%
220
225
230
235
240
220
225
230
235
240
220
225
230
235
240
220
225
230
235
240
220
225
230
235
240
220
225
230
235
240
220
225
230
235
240
220
225
230
235
240
220
225
230
235
240
220
225
230
235
240
220
225
230
235
240
220
225
230
235
240
220
225
230
235
240
6.89 x 10
4.19
4.11
1.35
1.10
11.23 x 10
7.24
5.78
5.72
3.14
163 x 10
7.14
5.46
3.17
0.81
17.0 x 10
12.1
9.11
4.9
1.84
38.4 x 10
14.1
7.83
5.61
6.87
2.54 x 10
1.55
6.67
0.93
0.37
204.8 x 10
165.3
75.3
28.3
15.8
158.3 x lo5
79.3
28.90
13.95
6.08
176
258
438
800
1409
209
317
395
516
718
294
311
540
457
700
232
195
183
198
222
294
413
540
457
700
2.2 2 n 5 2.7 Modeled from rate data; tr,z 393
values are graphical; Avrami
n variable
2.1 2 ns2.5 393
2.3 < n 5 2.5
2.2 5 n 5 2.5
2.3 5 n 5 2.5
2.1 In12.4
2.0 5 n 5 2.4
1.6<n< 1.7
393
393
393
393
393
393
394
394
394
394
394
References page VI - 39 1
VI / 390 RATES OF CRYSTALLIZATION OF POLYMERS
TABLE 19. contd
Polymer Tf (Cl Tc(C) tos 6)
n k 6)
Remarks Refs.
Poly(oxyethyleneoxyterephthaloy1) modified
Modified/unsized Kevlar
Modified/unsized glass
220
22.0 x 103 DSC measurements; fibers 395
225
12.0 x 103 enhanced rate of crystallization
230 6.5 x lo3
235 3.37 x 103
225
17.60 x lo3 395
230 9.14 x 103
235 4.23 x lo3
220
17.25 x 10 395
225 10.45 x 102
230 5.53 x 102
235 2.34 x lo*
19.1. COMPOSITES OF BLENDS
Poly(oxyethyleneoxyterephthoyl)lPoly(oxycarbonyloxy- 1,4-phenylene-isopropylidene- 1,4-phenylene) PET/PC
Poly(carbonate) 80/20, w/w 220 20.4 x lo3 DSC measurements 396
Unreinforced 220 20.4 x lo3
36% wt. Kevlar 220 13.1 x 103
49% wt. Kevlar 220 11.4 x 103
68% wt. Kevlar 220 5.96 x lo3
Unreinforced 230 6.09 x lo3
36% wt. Kevlar 230 3.82 x lo3
68% wt. Kevlar 230 0.77
Poly(oxyethyleneoxyterephtholy)/Poly(oxycarbonyloxy-1,4-phenylene-isopropylidene-1,4-phenylene) PET/ PC
220 24.4 x lo3
13.9 x 103
8. 3 x 10
3. 4 x 103
11.4 x 10 397
6. 8 x 103
4.5 x 10
2. 3 x lo3
10.9 x 103 397
6.35 x lo3
3.9 x 10
2.02 x 10
225
60140, wl w 230
235
Unsized Kevlar 215
220
225
230
Unsized glass 215
220
225
230
Poly(oxyethyleneoxyterephthoyl)/Poly(oxycarbonyloxy-1,4-phenylene-isopropylidene-1,4-phenylene) terephthalate)
220 20.7 x IO3
Poly(carbonate) 80/20, w/w
80/20 unsized Kevlar
SO/20 unsized glass
Poly(thio- 1,4-phenylene) unreinforced
Unsized AS4 36 and 38 wt.%
Sized AS4 39 wt.%
225 11.3 x 103
230 6.03
235 3.1
215 17.7 x 103
220 11.5 x 103
225 6.8 x 10
230 4.0 x 103
215 15.6 x lo3
220 9.5 x 10
225 5.5 x 10
230 3.12 x lo3
205 124
210 215
215 356
220 513
225 914
230 1022
235 2350
240 2760
220 1 7 1
225 246
230 435
235 788
240 1400
220 122
225 1 9 7
230 289
235 511
396
396
396
DSC measurements; optical
microscopy of composites
394
TABLE 19. contd
Re f e r e n c e s
Polymer
Tr ((3 Tc(C)
n k 6)
Remarks Refs.
Poly(thio- 1,4-phenylene) unreinforced 220
22. 5
230
235
240
Unsized Kevlar 58 wt . % 220
225
230
235
240
Phillips prepreg 55 wt . % 220
225
230
235
240
Sized Kevlar 53% wt.% 220
225
230
235
240
Poly(thio-1,4-phenylene) poly(phenylene sulfide) (PPS)
100/o, wl w 250
251
263
268
269
PPSlFortron glass 251
257
263
268
Poly(thio- 1,4-phenylene) (unreinforced) 220
100/o, w/w 225
230
235
240
With sized glass 220
35/ 65, wi w 230
240
58. 6
106. 3
215. 3
497. 1
558. 4
58. 5
110.7
242. 0
558. 4
167
261
440
796
1391
167
440
988
176
258
438
DSC measurements Avrami
variable; optical microscopy
of composites
799
1409
116
172
232
335
570
43
60
86
163
327
26
52
69
126
253
DSC measurements
394
394
394
227
227
397
391
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Isomorphous Polymer Pairs
G. Allegra, S. V. Meille
Dipartimento di Chimica del Politecnico, Milano, Italy
W. Porzio
lstituto di Chimica delle Macromolecole del C.N.R., Milano, Italy
A. Introduction VI-399
B. Techniques VI-400
C. Tables of lsomorphous Pairs of Monomer
Units VI-401
Table 1. lsomorphous Units Within the Same
Macromolecules (Copolymers) VI-401
1 .I. lsomorphous Units with
Different Chemical Constitution VI-401
1.2. lsomorphous Units with
Different Configurations and/or
with Head-to-Head,
Head-to-Tail Constitutional
Disorder
Table 2. lsomorphism of Macromolecules
D. References
VI-405
VI-405
VI-406
A. I NTRODUCTI ON
This chapter is intended to provide a list of known pairs of
isomorphous monomeric units in synthetic crystalline
polymer systems; we shall regard as isomorphism the
statistical copresence of different units within the crystal-
lites. Additional information will be also given, namely:
(a) the approximate range of relative concentrations
where isomorphism is observed;
(b) the chain conformation in the crystalline state, the
type of isomorphism (see below);
(c) the physicochemical techniques used in the investi-
gation (see Section B); and
(d) the references to the scientific contributions wherein
the isomorphism is demonstrated, implied, or
claimed.
Systems in which the molar fraction of either type of
monomeric units does not exceed about 5% have been
disregarded. Cocrystallization of hydrogenated and deuter-
ated units has not been considered as relevant in this context
either.
Although we are aware of the growing expansion and
importance of copolymer systems producing mesophases
(92), we have chosen to limit our list to isomorphism in
the classical crystallographic sense. In particular, polymer
systems were regarded as crystalline either (i) when off-
meridional X-ray reflections appear on the nonequatorial
layers, or (ii) if the sample is shown to undergo a transition
to a mesophase system before melting, as may be revealed
by DSC methods. Sometimes distinctions between real
crystalline systems and mesophases may be difficult, such
as in the case of several polyesters. In all instances in which
some degree of uncertainty is implied, an asterisk has been
inserted.
The isomorphous polymer pairs are subdivided accord-
ing to the scheme already proposed in a review article on
the subject (2). Two basic classes of macromolecular
isomorphism were distinguished, namely isomorphism of
whole homopolymer chains (Class 1) and isomorphism of
monomeric units within copolymer chains (Class 2)
(2,62,63). Class 1 may be further subdivided into three
different subclasses: subclass 1.1, where the monomeric
units differ in chemical constitution (copolymers in the
usual sense) (Table 1.1); subclass 1.2, where the monomeric
units have randomly opposite, nonsuperimposable config-
urations (Table 1.2); and subclass 1.3, where the mono-
meric units, although stereochemically identical, assume
different conformations at random. In spite of the scientific
relevance of the last subclass in the context of polymer
structure, we have preferred to omit the corresponding
table, in view of both, the relatively low relevance of the
issue for many people interested in polymer isomorphism,
and of the wide ensemble of polymers that are presumably
affected by this crystallographic disorder under appropriate
circumstances. Also, for the sake of greater generality, we
have included in subclass 1.2 (Table 1.2) all the cases where
the isomorphous units are related either by geometrical
stereoisomerism or by random head-to-head, head-to-tail
enchainment. Concerning Class 2, the subclass consisting
of stereochemically identical chains with randomly oppo-
site orientations of their axes within the crystal is not
VI / 399
VI / 400 ISOMORPHOUS POLYMER PAIRS
reported for the same reasons given above for subclass 1.3.
Consequently, only isomorphous systems consisting of
stereochemically different homopolymer chains are
reported. In each case, the two units of the isomorphous
pair are separated by a slash.
From a crystallographic viewpoint the following two
types of polymer isomorphism may be distinguished (the
different monomeric units will be designated as A and B).
Type 1: Homopolymers AN and BM have a similar
crystal structure, with sufficiently small differences in unit
cell dimensions. Binary systems, whether copolymers or
homopolymer mixtures, display the same structure at any
intermediate composition, except for a continuous change
in cell dimensions (isomorphism in a true sense). The
homopolymer chains may possess helical conformations
with slightly different ratios of monomeric units per helix
pitch, in which case intermediate helix conformations
should appear at intermediate compositions.
Type 2: The two homopolymers have different crystal
structures and in each of them some amount of monomeric
units of the other may be accommodated. Accordingly, the
structure of the homopolymer corresponding to the mono-
meric units with prevailing amount is observed, and an
abrupt change in the structure of the second homopolymer
may take place at a suitable composition. The simultaneous
presence of both structures may also be observed within
some intermediate composition range, in analogy with low-
molecular weight systems (isodimorphism).
These types correspond to the first two types of polymer
isomorphism suggested by Natta (62,63), who also
proposed a third type whenever one of the two homo-
polymers is unable to crystallize by itself. We have thought
it expedient to include these caseswithin Type 2, parti-
cularly in view of the difficulty in ascertaining the complete
inability of either homopolymer to crystallize. It should
be added in this context that no assumption concerning
thermodynamic stability of the following isomorphous
systems is implicit here; on the other hand, the crystal
packing and friction forces may well be strong enough in
most cases as to prevent any appreciable solid-solid trans-
formation.
Concerning the partition of the data within each separate
heading (1.1, 1.2, etc.), we tried to conform to the standard
criteria adopted in this book. Each monomeric unit is
assigned to the class corresponding to the higher ranking
monomer.
Whenever a crystallizable copolymer is constituted by a
regularly repeating sequence of monomeric units, iso-
morphism is usually ruled out in view of the very presence
of constitutionally repeating units, i.e., of an effective
homopol ymer.
Several vinyl copolymers show macromolecular iso-
morphism when the side groups are sterically ordered. If, as
it always happens in the examples known hitherto, the order
is of the isotactic type, we have called them isotactic
(copolymers).
Several cases are known of polymers having long,
regular side groups (comb-like copolymers or the like) that
may promote crystallization in spite of lack of configura-
tional order in the main chain. These systems are not
considered as belonging to the present list if crystalliza-
tion is basically due to regular packing of the side chains
only.
Whenever the conformation of the chain skeleton may be
described as a regular helix, we have used the symbolism
recommended by the document Terminology Relating to
Crystalline Polymers of IUPAC (1984) and adopted, e.g.,
by R. L. Miller in the chapter Crystallographic Data for
Various Polymers of this book. As an example, the helical
conformation of the crystalline isotactic copolymers of 3-
methyl- 1-butene and 4-methyl- 1 -pentene (see Ref. 14),
corresponding to four monomeric units in one turn, each
unit having two skeletal atoms, is designated as 2 * 4/l.
However, referring to the general notation p/q, we have not
considered as helical those conformations where both p and
q are equal to unity (i.e., one repetitive unit in one turn). In
these instances, qualifications such as extended, planar
zig-zag, etc. are used to characterize the conformation.
Also, whenever the helix structure is not explicitly reported
by the author, the general term helical is adopted.
It may happen that, for a given concentration of the two
monomeric units, more than one crystalline phase is ob-
served. Under these circumstances, the corresponding chain
conformations are reported.
For a discussion of macromolecular isomorphism, see
Refs
6. T
XR
XRl
MP
TA
D M
MA
D
I R
ED
CA
2,90,91, and some of the papers quoted therein.
ECHNIQUES
Qualitative evaluation of crystallinity by diffraction
methods
Structural analysis by diffraction methods (including
observation of continuous changes of lattice spa-
cings)
Optically determined melting point
Thermal analysis (DSC, DTA, etc.)
Dynamical-mechanical measurements (e.g.,
mechanical and dielectric relaxation experiments)
Morphological analysis (electron microscopy, SAXS
etc.)
Density determination by flotation techniques
Infrared spectroscopy
Electron diffraction
Conformational analysis
lsomorphous Units Within the Same Macromolecules (Copolymers) VI / 401
C . TABLES OF ISOMORPHOUS PAIRS OF MONOMER UNITS
TABLE 1. ISOMORPHOUS UNITS WITHIN THE SAME MACROMOLECULES (COPOLYMERS)
Monomer giving isomorphous copolymers
Mel% of first
Type of
component i somorphi sm Chai n conf ormat i on Techniques Refs.
1.1. ISOMORFHOUS UNITS WITH DIFFERENT CHEMICAL CONSTITUTION
1. 1. 1. MAIN-CHAIN CARBON COPOLYMERS
Copoly(alkenamers)
truns- 1 -Pentenamer/truns- 1-octenamer
truns- 1 -Pentenamer/truns- 1 -heptenamer
truns- 1 -Octenamer/truns- 1 -dodecenamer
Copoly(alkenes)
Ethylene/propylene
Propylene/n- 1 -hexene
Propylene/n- 1 -butene
n-1-Butene/3-methyl-I-butene
n- 1 -Butene/n- 1 -pentene
n- 1 -Butene/n- 1-hexene
n- 1 -Butene/4-methyl- 1 -pentene
n-1-Buteneln-1-octene
n-I-Butene
n-1-Buteneln-I-decene
n- 1 -Butene/n- 1-dodecene
3-Methyl- 1 -butene/4-methyl- 1 -pentene
4-Methyl-pentene/l-pentene
4-Methyl- 1 -pentene/n- 1 -hexene
4-Methyl- 1 -pentene/4-methyl- 1 -hexene
4-Methyl- 1 -penteneln- 1 -octene
4-Methyl-1-penteneln-1-decene
Copoly(vinyls) (nonhalogenated)
Ethylene/vinyl alcohol
O- 50
100-20
100-O
100-70
100-85
100-O
Ethylene/(ethylene + CO) 100- 50
Isopropyl vinyl etherlsec-butyl vinyl ether 100-O
Copoly(vinyls) (halogenated)
Ethyleneltetrafluoroethylene 100-O
Vinyl fluoridelvinylidene fluoride
Vinyl fluoride/tetrafluoroethylene
Vinylidene fluorideltrifluoroethylene
Vinylidene fluoride/tetrafluoroethylene
Vinylidene fluoridelchlorotrifluoroethylene
Vinylidene fluoride/bromotrifluoroethylene
Trifluoroethylene/tetrafluoroethylene
Tetrafluoroethylene/chlorotrifluoroethylene
Tetrafluoroethylene/bromotrifluoroethylene
Tetrafluoroethylene/bexafluoropropylene
Vinyl chloridelvinylidene chloride
100-o
100-O
100-O
100- 70
100- 50
89-3
100-O
100-O
94-16
100-30
100- 75
75-50
50- O
100-50
100- 90
100- 90
100- 50
50- O
50- 100
100-o
100-20
100- 90
88-15
15-o
52
55
100-O
100-O
100- O
100-10
100-o
100-o
100- 55
100- 93
1
1
1
2
2
2
2
1
1
2
2
2
2
2
2
2
2
2
2
2
2
1
2
2
2
1
1
2
1
2
2
2
2
2
2
1
2
2
100-85, 44-O 2
Extended, planar zig-zag XRl
Extended, planar zig-zag XRl
Extended, planar zig-zag XRl
Planar zig-zag
Isotactic (2*3/l)*
Isotactic (2*3/l)
Isotactic (2*3/l)
Isotactic (2*4/l) and (2*29/8)
Isotactic (2*3/l)
Isotactic (2*3/l) and (2*29/8)
Isotactic (2*3/l) and (2*29/8)
Isotactic (2*3/l) and (2*7/2)
Isotactic (2*7/2)
Isotactic
(2*3/l) and (2*29/8)
Isotactic (2*3/l) and (2*29/8)
Isotactic (2*3/l) and (2*29/8)
Isotactic (2*4/l)
Isotactic (2*4/l) and (2*7/2)
Isotactic (2*4/l)
(2*4/ 1)
Isotactic (2*7/2)
Isotactic (2*7/2)
Isotactic (2*7/2)
Isotactic (2*7/2)
Isotactic (2*7/2)
MP,
XRl,
XR, TA
XR, TA, DM
XRl, MP
XRl, MP, MA
XRl
XRl, MP
XRl, MP
XRl, MP
XRl, MP
XRI, MP
XRl, MP
XRl, MP
XRl, MP,
XRl
TA, DM
TA, DM
XRl, MP
XRl, MP
XRl, MP
Planar zig-zag
Planar zig-zag
Isotactic (2* 17/5)
XRl
XRl, D M
XRl
ED, MA
XR, MP
Planar zig-zag
Planar zig-zag
Planar zig-zag
Planar zig-zag
(TGTG) n
Helical
Planar zig-zag, (2*3/l)
Planar zig-zag, (TGTG) n
Planar zig-zag, (TGTG),
Planar zig-zag
XRl, TA, MA
XRl
CA
XRl, MP
XRl, MP
XR, TA, DM
Planar zig-zag, (2* 17/ 1)
Planar zig-zag
Helical, planar zig-zag
Helical
Helical
Helical
Planar zig-zag, (TGTG),
XRl
XRl, IR
XRl
XRl, TA, MA
XRI
XRl
XRl
XRl, TA, MA
XRl, T A
XRl, TA
XRl, TA
XRl, TA, MA
20,57,60
20,57,60
20,57,60
5,6,71,77,
8,9X
77
67
84
4 1
83
84
84
84
84
84
84
70
85
1 5
4 1
41
3
85
8 5
1 2
58
11,17,18
1
3
34
88,55
29
6 1
6 1
94
53
80
52
34
55
55
55
34
56
56
87
65
References page VI - 406
VI / 402 ISOMORPHOUS POLYMER PAIRS
TABLE 1. contd
Monomer giving isomorphous copolymers
Mel% of first
Ppe of
component i somorphi sm Chai n conf ormat i on Techniques Refs.
Copoly(styrenes)
Styrenelp-methylstyrene
Styrenelo-methylstyrene
Styrenelo-fluorostyrene
Styrenelp-fluorostyrene
Styrenelp-ethylstyrene
Styrenelp-chlorostyrene
Styrenelp-bromostyrene
100-50
100- 80
100-O
100- 50
50- O
100- 85
100- 85
100- 85
1. 1. 2. MAIN-CHAIN HETEROATOM COPOLYMERS
Copoly(ethers)
Trioxane/l$dioxolane 100- 84
Copoly(aldehydes)
Acetaldehyde/propionaldehyde 100-O
Acetaldehydeln-butyraldehyde 100-O
Acetaldehyde/isobutyraldehyde 100-O
Propionaldehydeln-butyraldehyde 100-O
n-Butyraldehydelisobutyraldehyde 100-O
n-Butyraldehydeln-heptanal 100-O
Copoly(carbonates)
HydroquinonelchlorohydroquinoneKOC12 100-O
ToluenehydroquinonekhlorohydroquinoneKOCl2 100-O
Copoly(esters)
Ethylene glycol, sebacic acid/undecanedioic Equimolar
acid/dodecanedioic acid proportion of
the three acids
Ethylene glycol, terephthalic acidlp-hydroxy- loo-90,40-o
benzoic acid
Ethylene glycol, terephthalic acid/isophthalic 100-70, 30-O
acid
Ethylene glycol, terephthalic acidlp-hydroxyoxy- 100-O
propoxybenzoic acid
Ethylene glycol, terephthalic acid/l,Cbis-@- only 50
carboxyphenoxy)butane
Ethylene glycol, 1,4-bis-(p-carboxyphenoxy) only 50
butane/p-y-hydroxypropoxybenzoic acid
Tetramethylene glycolldecamethylene glycol, 30- O
adipic acid
Pentamethylene glycol/decamethylene glycol, 40- O
adipic acid
Hexamethylene glycol, adipic acid/decamethyl- 100-O
ene glycol, sebacic acid
Hexamethylene glycol, sebacic acid/decamethyl- 100-O
ene glycol, adipic acid
Decamethylene glycol, adipic acidlsebacic acid 100- 70
Decamethylene glycol/hydroquinone, adipic acid 100- 70
Decamethylene glycol/diethylene glycol, adipic 100-70
acid
4,4-Dihydroxybiphenyl, pimelic acid/azelaic acid 100-O
4,4-Dihydroxybiphenyl, azelaic acid/ 100-60, 25-O
decanedioic acid
4,4-Dihydroxybiphenyl, decanedioic acid/ 100-O
tetradecanedioic acid
4,4-Dihydroxybiphenyl, dodecanedioic acid/ 100-O
tetradecanedioic acid
Lactic acid R/S 100- 85
Copoly(amides)
Hexamethylenediamine, adipic acidkebacic acid 100-60, 50-O
Hexamethylenediamine, adipic acidkyclohexane- 100- 70
dicarboxylic acid
2
2
1
2
2
2
2
2
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2*
2*
2
Isotactic (2*3/l)
Isotactic (2*3/l)
Isotactic (2*3/l)
Isotactic (2*3/l)
Isotactic (2*4/l)
Isotactic (2*3/ 1)
Isotactic (2*3/l)
Isotactic
(2*9/5)*
Isotactic copolymer (2*4/l)
Isotactic copolymer (2*4/l)
Isotactic copolymer (2*4/l)
Isotactic copolymer (2*4/l)
Isotactic copolymer (2*4/l)
Isotactic copolymer (2*4/l)
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, distorted planar
Extended, distorted planar
Extended, distorted planar
Extended, distorted planar
Extended, distorted planar
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag *
Extended, planar zig-zag
Extended, planar zig-zag
XRl, M P
XRl, M P
XRl, M P
XRl, M P
XRl, MP
XRl, M P
XRl, M P
XRl, TA, D
XRl
XRl
XRl
XRl
XRl
XRl
XR, MP
XR, MP
XR
XR, TA, D
XR, TA, ED, MA
D
XR
XR, MP
XR
XR
MP
MP
XRl, TA
XRl, TA
MP
MP
MP
XRI, TA
XRl, T A
XRl, TA
XRl, TA
XR, MA, TA
XR
MP
62,63
62,63
62,63
62,63
62,63
62,63
62,63
78
78
78
78
7 8
78
50
48
39
48
43
44
45
46
28
28
42
42
2 8
28
28
86
8 6
30
7
72
TABLE 1. contd
lsomorphous Units Within the Same Macromolecules (Copolymers) VI / 403
Monomer giving isomorphous copolymers
MO]% of first
Type of
component i somorphi sm Chai n conf ormat i on Techniques Refs.
Hexamethylenediamine, adipic acidlterephthalic
acid
Hexamethylenediamine, adipic acid/
nonamethylene diamine, azelaic acid
Hexamethylenediamine/decamethylene-
diamine, adipic acid
Hexamethylenediamine, adipic acid/deca-
methylene diamine, sebacic acid
Hexamethylenediamineltmns- 1 $cyclohexanebis-
methylamine, adipic acid
Hexamethylenediamine, suberic acid/4-benzene-
diacetic acid
Hexamethylenediamine/decamethylene-
diamine, adipic acid
Hexamethylenediamine/decamethylenediamine,
sebacic acid
Hexamethylenediamine, sebacic acidlp-phenylene-
dipropionic acid
Hexamethylenediamine, sebacic acid/
3+carboxy-methyleneoxy)
phenylpropionic acid
Hexamethylenediamine, sebacic acid/
4-(p-carboxy-methylene)phenylbutyric acid
Hexamethylenediamine/N,N-diisobutyl-
hexamethylene diamine, sebacic acid
Hexamethylenediamine, sebacic acid/l ,4-
(dicarboxy-methyleneoxy)phenylene
Hexamethylenediamine, undecanedioic acid/
6-oxa-hendecanedioic acid
Hexamethylenediamine, undecanedioic acid/
6-thio-hendecanedioic acid
Hexamethylenediaminela,%-p-xylenediamine,
sebacic acid
Hexamethylenediamine, p-phenylenedipropionic
acid/4+-carboxymethylene)phenylbutyric acid
Hexamethylenediamine, p-phenylene-
dipropionic acid&@-carboxymethyleneoxy)-
phenylpropionic acid
Hexamethylenediamine, p-phenylene-
dipropionic acid/p-bis-(carboxymethyleneoxy)-
phenylene
100-O
100-60, 50-O
100-70, 60-O
100-65, 50-O
loo-70*
40-o*
100-O
100-O
100-O
100-O
100-O
100-O
100-O
100-O
100-O
50-o*
100-O
100-O
100-O
Hexamethylenediamine, 3-CJ-carboxymethyleneoxy) 100-O
phenylpropionic acid/p-bis-(carboxymethyleneoxy)
phenylene
Heptamethylenediamine, adipic acidkerephthalic 100-O
acid
Heptamethylenediamine/4-oxa-heptamethylene- 75, 50, 25
diamine, adipic acid
Heptamethylenediamine, adipic acidkoxa-hepta- 75, 50, 25
methylenediamine, terephthalic acid
Heptamethylenediamine, terephthalic acid/4-oxa- 75, 50, 25
heptamethylenediamine, adipic acid
Heptamethylenediamine/4-oxa-heptamethylene- 75, 50, 25
diamine terephthalic acid
Octamethylenediamine, adipic acidkerephthalic 100-O
acid
Octamethylenediamine/2,2-p-phenylene-bis- lOO-O*(lOO-60)
ethylamine, adipic acid
Octamethylenediamine/2,2-p-phenylene- loo-o*(loo-10)
bis-ethylamine, azelaic acid
Octamethylenediamine, sebacic acid/ 100-O
4-benzenedipropionic acid
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
MP
XR
T A
XR
XR
XR
MP
MP
XR
XR
MP
XR, MP
XR, MP,
MP
XR, MP
XR, MP
MP
MP
MP
XR, MP
XR, MP
XR, MP
MP
MP
XR, MP, DM
XR, MP, DM
XR, MP, DM
XR, MP, DM
XR, MP, DM
MP
MP
MP
MP
96,66,72
23
40
7
7
7
72
9.5
7
7
28
8 1
8 1
8 1
89
8 1
74
74
95
8 1
8 1
8 1
8 1
96
1 9
1 9
1 9
1 9
1 9
96
95
9 5
95
References page VI - 406
VI / 404 ISOMORPHOUS POLYMER PAIRS
TABLE 1. cont d
Monomer giving isomorphous copolymers
Mel% of first
Type of
component i somorphi sm Chai n conf ormat i on Techniques Refs.
Octamethylenediamine/2,2-p-phenylene- loo-o*(loo-10)
bis-ethylamine, sebacic acid
Octamethylenediamine/2,2-p-phenylene- loo-o*(loo-30)
bis-ethylamine, suberic acid
Octamethylenediamine/bis(4-aminocyclohexyl) loo-0*(90, 50)
methane, dodecanedioic acid
Nonamethylenediamine, adipic acidlterephthalic 100-O
acid
Nonamethylenediamine/bis(4-aminocyclohexyl) 100-O
methane, octanedioic acid
Nonamethylenediamine/bis(4-aminocyclohexyl) 100-O
methane, dodecanedioic acid
5-Methyl-nonamethylenediamine/bis-(4-amino- loo-0*(90, 50)
cyclohexyl)methane, dodecanedioic acid
Decamethylenediamine, adipic acidlsebacic acid 100-O
Decamethylenediamine, adipic acidkerephthalic 100-O
acid
DecamethylenediaminekGs(4.aminocyclohexyl) loo-0*(90, 50)
methane, dodecanedioic acid
Undecamethylenediamine, adipic acidkerephthalic 100-O
acid
Dodecamethylenediamine, adipic acidkerephthalic 100-O
acid
Dodecamethylenediamine/bis(4-aminocyclohexyl) lOO-0*(90, 50)
methane, dodecanedioic acid
1,4-Bis(aminomethyl)cyclohexane (cisltrans), 100-O
adipic acid
1,4-Bis(aminomethyl)cyclohexane (cisltruns), 100-O
sebacic acid
1,4-Bis(aminomethyl)cyclohexane (cisltrans),
dodecanedioic acid 100-O
~,a-p-Xylenediamine, nonanedioic acid&oxa- 100-O
nonanedioic acid
cc,~-p-Xylenediamine, nonanedioic acid/5- 100-O
thio-nonanedioic acid
cc,cc-p-Xylenediamine, undecanedioic acid/ All proportions of
6-oxa-undecanedioic acid/6-thio-undecanedioic the three acids
acid
cc,a-p-Xylenediamine, triadecanedioic
acid/7-oxa-triadecanedioic acidl6-oxa-
triadecanedioic acid
r&cc-p-Xylenediamine, triadecanedioic
acid/7-thio-triadecanedioic acid
ct,ct-p-Xylenediamine, pentadecanedioic
acid/6-oxa-pentadecanedioic acid
cc,cl-p-Xylenediamine, pentadecanedioic
acid/&tia-pentadecanedioic acid
~,a-p-Xylenediamine, 7-oxa-triadecanedioic
acid/7-thio-triadecanedioic
4-Oxa-heptamethylenediamine, adipic
acidkerephthalic acid
Caprolactam/4(-aminomethylcyclohexyl)
carboxylic acid
Caprolactam!4(-aminomethyl)benzoic acid
Caprolactamly-4(-aminomethyl)propionic acid
Caprol act am-o-l aurol act am
Copoly(peptides)
cc-Methyl-S-glutamate/y-benzyl-S-glutamate
cL-Methyl-S-glutamate/y-methyl-R-glutamate
cc-Benzyl-S-glutamate/S-phenylalanine
Butyl-S-aspartatelbenzyl-S-aspartate
All proportions of
the three acids
100-O
100-O
100-O
100-O
75, 580, 25
100-70, 50-O
100- 70
100-80, 15-o
100-70, 30-O
100-O
100-O
80
87- O
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Twist boat, planar zig-zag
Twist boat, planar zig-zag
Twist boat, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
Extended, planar zig-zag
cc-helix, (3* 18/5)
cc-helix, (3* 18/5)
a-helix, (3*18/5)
cc-helix, (3*4/l)
MP
MP
T A
MP
T A
XR, TA
XR, TA
XR
MP
T A
MP
MP
XR, TA
XRl
XRl
XRl
MP
MP
XR, MP, D
MP
MP
MP
MP
MP
XR, MP, DM
MP
XR, MP
MP
XR, TA, IR
XRl, TA, D, IR
T A
D M
XRl
XRl, IR
MA, ED
XRl, TA, IR, DM
9 5
9 5
1 6
96
1 6
1 6
1 6
7
96
1 6
96
96
1 6
69
69
69
74
51
68
5 1
75
74
36
38
TABLE 1. contd
lsomorphism of Macromolecules VI / 405
Monomer giving isomorphous copolymers
Mel% of first
bpe of
component i somorphi sm Chai n conf ormat i on Techniques Refs.
Copoly(diacetylenes)
(General formula [(=A-C=C- y=),, (=&-C=C-y=),_,)1,
R R
p-Tolylsulfonyloxymethyl/p-fluorosulfonyl-
oxymet hyl
p-Tolylsulfonyloxymethyl/p-chlorosulfonyl-
oxymet hyl
p-Tolylsulfonyloxymethyl/p-bromosulfonyl-
oxymethyl
p-Tolylsulfonyloxymethyl/p-naphthylsulfonyl-
oxymet hyl
p-Tolylsulfonyloxymethyl/p-methoxysulfonyl-
oxymet hyl
Methylcarbazolyl/methylcarbazolyl,
methylanthryl
Copoly(phosphazenes)
(General formula [(RO) ,(RO) 2-,PN] .)
R R
Phenyllp-ethylphenylene
4-Chlorophenylene/4-methylphenylene
4-Chlorophenylene/4-ethylphenylene
4-Chlorophenylenelphenyl
4-Chlorophenylene/3-methylphenylene
4-Chlorophenylene/3-chlorophenylene
4-Methylphenylene/3-methylphenylene
3-Chlorophenylene/4-methylphenylene
3-Chlorophenylene/3-methylphenylene
100-O
100-80
100- 93
100- 90
100-90
100-94
100-85/15-O
50 only
50 only
50 only
50 only
50 only
50 only
50 only
50 only
Ii
1
1
1
1
1
1
2
1*
1*
2
2
2
2
2
1*
Ii
truns-Planar
truns-Planar
truns-Planar
truns-Planar
trans-Planar
truns-Planar
(cis-trans)z
(cis-truns)~
(cis-lruns)~
(cis-lrans)2
(cis-truns)~
(cis-tram)2
(cis- tram) 2
(cis-tram)2
(cis- tram) 2
XRl
XRl
XRl
XRl
XRl
XRl
XRl, TA
XRl, TA
T A
XRl, TA
T A
T A
T A
T A
T A
1.2. ISOMORIHOUS UNITS WITH DIFFERENT CONFIGURATIONS AND/OR WITH HEAD-TO-HEAD, OR HEAD-TO-TAIL
CONSTITUTIONAL DISORDER
Poly(viny1 alcohol)
Poly(viny1 fluoride)
Poly(vinylidene fluoride)
Poly(chlorotrifluoroethylene)
Poly(ethylene-aZt-
chlorotrifluoroethylene)
Poly(pcarboxypheny1 methacrylate)
Poly(butadiene-alt-acrylonitrile)
Atactic pol ymer
Atactic polymer with
constitutional disorder
Constitutional disorder
Atactic pol ymer
Atactic polymer with
constitutional disorder
Atactic pol ymer
Atactic pol ymer
26
24,25
2 5
4
4
21
33
9
9
9
9
9
9
9
9
Planar zig-zag
Planar zig-zag
Planar zig-zag
(2*14/l)
(2*16/l)
Extended, distorted planar
Extended, distorted planar
Extended, distorted planar
XRl 12,13,14
XRl 64
XRl, CA 29
XRl 1 3
XRl 54
XRl 16
XRl, ED, MA, TA 1 0
XR, IR 32
TABLE 2. ISOMORPHISM OF MACROMOLECULES
Monomer giving isomorphous copolymers
Poly(propylene)/poly(l-butene)
Poly(4-methylpentene)/poly(4-methylhexene)
Poly( 1-propylvinyl ether)/poly(sec-butyl
vinyl ether)
Poly(styrene)lpoly(styrene-co-p-methyl styrene)
(70/30, mollmol)
Poly(oxy-4,4-biphenylene oxy dodecanoyl)l
Mel% of first
component
100-80 and 20-O
100-75 and 20-O
100-O
50
100-O
Me of
isomorphism Chain conformation Techniques Refs.
2 Isotactic polymers (2*3/l) DM, MA, TA, ED 37
1 Isotactic polymers (2*7/2) XRl, M P 3
1 Isotactic polymers (2*17/5) XRl, M P 3
1 Isotactic polymers (2*3/l) XRl, IR 63
2 Planar zig-zag XRl, TA, MA 86
poly(oxy-4,4-biphenylene oxy-tetradecanedioyl)
References page VI - 406
VI / 406 ISOMORPHOUS POLYMER PAIRS
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Miscible Polymers
Sonja Krause
Department of Chemistry, Rensselaer Polytechnic Institute, Troy, New York, USA
S. H. Goh
Department of Chemistry, National University of Singapore 119260, Singapore
A. Definition of Miscibility
B. Data Collection VI-4
C. Arrangement of the Tables VI-4
D. Tables VI-4
Table 1. Chemically Dissimilar Polymer Pairs
Miscible in the Amorphous State at
Room Temperature VI-4 1
Table 2. Polymer Pairs Containing One
Monomer in Common, Miscible in
the Amorphous State at Room
Temperature VI-444
Table 3. Chemically Dissimilar Polymer Triads
(and Tetrads) Miscible in the
Amorphous State at Room
Temperature VI-448
Table 4. Polymer Pairs Miscible in the
Amorphous State at Room
Temperature; Molecular Weight
Dependence Investigated VI-450
Table 5. Polymer Pairs that Appear to Have
High Temperature Miscibility Although
Immiscible at or Below Room
Temperature VI-452
Table 6. Polymer Pairs Miscible at Room
Temperature that Appear to Have a
Lower Critical Solution Temperature
(LCST) Above Room Temperature VI-454
Table 7. Polymer Pairs that Appear to Have
Both a Lower Critical Solution
Temperature and a Upper Critical
Solution Temperature VI-458
Table 8. Polymer Pairs that Cocrystallize VI-459
E. References VI-461
A. DEFINITION OF MISCIBILITY
A rigorous definition of miscibility is used in the following
tables. In order to be classified as miscible polymers, there
must be some evidence in the literature that the polymers
are miscible on a submolecular (segmental) scale. If the
polymer mixture contains several phases, the polymers will
be listed as miscible even if segmental miscibility data
exists in only one of these phases, but this is noted under
Comments in the Tables. Tables l-7 list miscibility in the
amorphous state. A polymer pair will be listed as miscible
even if one or both of the polymers forms a single-
component crystalline phase in the mixture; a note about
the existence of crystallinity, however, is made under
Comments. Evidence for miscibility of a polymer with only
one microphase in a microphase separated block copolymer
is also noted. In other cases, literature data indicated
miscibility with a known block copolymer, but no data were
shown which indicate whether the mixture still contained
the second microphase. In those cases, no comments are
made in these Tables, and readers will have to make
judgements of their own. Since miscibility on a submole-
cular or segmental scale includes cocrystallization, some
mixtures that have proven cocrystallization behavior are
shown in Table 8.
There is some controversy in the literature about the
dimensions of the submolecular scale of segment mixing
that indicates true miscibility in the amorphous state of
polymers. Followers of one school of thought feel that
every segment of polymer A must be surrounded by the
numbers of segments of polymers A and B whose fraction
is governed by the volume fraction of the two polymers
present in that phase. This is the random mixing assumption
implicit in the Flory-Huggins theory of polymer solutions
and mixtures. These ideas are much too rigorous for real
solutions, even solutions of small molecules. It is well
known that clustering occurs in real solutions, so that
volume elements containing an unexpectedly large number
of one of the solution components (in solutions of small
molecules) or segments of one of the polymers (in polymer
mixtures) can and do occur. Thus, data generated by some
solid state NMR techniques and some fluorescence
techniques that can show the proximity of two polymers
over a distance of l-2 nm have often been misinterpreted to
show immiscibility in a miscible polymer system. In fact,
data showing that a large proportion of the nearest neighbor
segments of a particular polymer belong to the same
polymer could simply indicate clustering in a homogeneous
phase.
VI / 409
VI / 410 MISCIBLE POLYMERS
B. DATA COLLECTION
The following tables include information from the third
edition of Polymer Handbook, additional information
from an incomplete polymer-polymer miscibility database
compiled by one of us (SK), and the data from papers (but
not patents) published in the English language and listed in
CA Selects-Polymer Blends and Science Citation Index
through December 1995 as compiled by one of us (SHG).
Note that Table 8 contains less complete information for the
earlier years than the other tables because most of the
information in this table comes from the incomplete
database. The inclusion of patents and papers in languages
other than English by SHG would have necessitated a great
deal more time and additional data compilers.
C. ARRANGEMENT OF THE TABLES
The following eight tables have essentially the same format
as those compiled for the third edition of Polymer
Handbook. Each table contains a particular mixture only
once. The column labeled Polymer I of is an alphabetical
listing. The column labeled Polymer II of is an
alphabetical listing of the polymers miscible with the
appropriate polymer from the first column. The common
names of polymers were used whenever possible; some-
times the Chemical Abstracts or IUPAC names of polymers
also appear. Unfortunately, we could not cross-list the many
possible names of the polymers. Thus, it may be necessary
to look for a particular polymer under several names in
these tables.
The column labeled Methods very briefly indicates the
method(s) used by the experimenters to determine mis-
cibility in amorphous phases. A large number of such
methods exist, but two of these are most commonly used.
One of these involves the determination of glass transition
temperatures (Tgs) by methods such as DSC, DTA,
dynamic mechanical measurements, dilatometry, or other
methods. The observation of a single T, for the amorphous
portion of a polymer mixture, especially if it is intermediate
between those of the constituent polymers and varies
monotonically between these values as the mixture
composition changes, has generally been considered a
reliable indication of a miscible polymer pair. This method
is difficult to use when the T,s of the constituent polymers
are close together, perhaps within 10C of each other.
Furthermore, the glass transition region of a miscible
polymer pair is often broader than that of the unmixed
polymers. Some experimenters have interpreted this as an
indication of two overlapping glass transition regions, but
we have taken the existence of such a broad glass transition
region as an indication of miscibility. We feel that a broad
glass transition region probably indicates the existence of
composition fluctuations rather than two overlapping T,s.
The criterion of sample clarity has often been used as an
indication of miscibility. This criterion will not work if the
constituent polymers have the same refractive index or if
they are so immiscible that they form phases so large that
they do not scatter light appreciably. Furthermore, semi-
crystalline mixtures are always turbid, even if their
amorphous phases are completely miscible. In addition,
on at least one occasion, a set of polymers was turbid at low
temperatures, clear at intermediate temperatures, and turbid
again at high temperatures only because their refractive
indices became almost identical at the intermediate
temperatures.
All single methods, not all of them described here, of
determining polymer-polymer miscibility sometimes give
ambiguous results. Unless many experimenters have used a
variety of methods to determine miscibility, the inferences
drawn from the data may be wrong. This is one of the
reasons for listing the methods used and the references that
describe the experiments, results, and interpretation. Some
of the mixtures listed in these tables, especially when only a
single mixture has been reported in a single reference, may
turn out to be less miscible than stated. This is especially
possible because some of the methods that were used in the
original investigations do not necessarily probe miscibility
as such. For example, a negative volume change on mixing,
that is, a shrinkage on mixing, could possibly be observed if
each of the coexisting phases contains both polymers,
though in different proportions, and if each of the
coexisting phases has a negative volume change on mixing.
Also, FTR methods generally involve the observation of
absorption band shifts due to hydrogen bonding between
polymers; however, this hydrogen bonding could conceiv-
ably occur on phase boundaries or within coexisting phases
each of which contains both polymers, but in different
proportions.
The Comments column in the Tables indicates composi-
tions of copolymers, whether the samples were semicrystal-
line, and other relevant data.
The eight tables are:
1. Chemically dissimilar polymer pairs miscible in the
amorphous state at room temperature. Some of these
polymers may be copolymers, but the polymer pairs may
not have any monomer units in common. One or both of
the polymers may be semicrystalline.
2. Polymer pairs containing one monomer in common (at
least one of these must be a copolymer), miscible in the
amorphous state at room temperature. One or both of the
polymers may be semicrystalline.
3 Chemically, dissimilar polymer triads and tetrads mis-
cible in the amorphous state at room temperature. It
seemed reasonable to place mixtures of three or four
polymers that were miscible in a separate table.
4. Polymer pairs miscible in the amorphous state at room
temperature. Molecular weight dependence investigated.
These are usually polymer pairs that are miscible when
the molecular weights are low and immiscible as when
the molecular weights are increased.
5. Polymer pairs that appear to have high temperature
miscibility although immiscible at or below room
temperature (Upper Critical Solution Temperature
[UCST] behavior).
6. Polymer pairs miscible at room temperature that appear
to have a lower critical solution temperature (LCST)
above room temperature. These polymer pairs are also
listed in one of the earlier tables, usually Table 1 or 2.
7. Polymer pairs that appear to have both lower and upper
critical solution temperatures.
8. Polymer pairs that cocrystallize and form mixed crystals.
These blends are generally composed of polymers with
similar subunits that can substitute for each other in the
same unit cells; this is generally called isomorphous
replacement. This Table is probably incomplete even
though cocrystallization is expected to be rare.
Abbreviations
DSC Differential scanning calorimetry
FTI R Fourier-transform infrared spectroscopy
D. TABLES
IGC
LS
MW
M
MW
NMR
NRET
PALS
SAXS
SALS
SANS
SEM
T,
T,
WAXD
Chemically Dissimilar Polymer Pairs VI / 411
Inverse gas chromatography
Light scattering
Molecular weight (unspecified)
Number-average molecular weight
Weight-average molecular weight
Nuclear magnetic resonance spectroscopy
Nonradiative energy transfer fluoro-
spectroscopy
Positron annihilation lifetime spectroscopy
Small-angle X-ray scattering
Small-angle light scattering
Small-angle neutron scattering
Scanning electron microscopy
Glass transition temperature
Melting temperature
Wide-angle X-ray diffraction
TABLE 1. CHEMICALLY DISSIMILAR POLYMER PAIRS MISCIBLE IN THE AMORPHOUS STATE AT ROOM TEMPERATURE
Polymer I of Polymer II of Method Comments Refs.
2-Acrylamido-2-methyl-
propanesulfonic acid
Acrylic acid
Vinylpyridine
Acrylamide
Acrylamide-co-NjV-dimethyl-
acrylamide
Caprolactam (nylon 6)
NJ-dimethylacrylamide
Ethylene glycol
Acrylic acid-co-ethylene
Acrylic acid-co-styrene
Vinyl alcohol
Vinyl methyl ether
N-vinylpyrrolidone
Caprolactam (nylon 6)
Caprolactone
Ester
Acrylonitrile-co-butadiene
Ethyl methacrylate
Ethyl methacrylate-co-
4-vinylpyridine
Ethylene glycol
Isobutyl methacrylate-co-
4-vinylpyridine
Methyl methacrylate
n-Propyl methacrylate
Vinyl methyl ether
Cellulose acetate-butyrate
Chloroprene
Epichlorohydrin
Nitrocellulose
Vinyl acetate-co-vinyl chloride
Single T,
NMR
Fluorescence study
Single Ts; WAXD
Fluorescence study
Single Tp; FTIR; NMR
FTIR; T,-depression; NMR
Single T,
NMR
Single Tg
Single Tg
Single T,
Single Ts; IGC
Single T,,; IGC
Single Tg
Single Tz; ICC
Single T,
Single Tg
Single T,
Some compositions
appeared homogeneous
Single Tg when 1 had 18%
acrylonitrile; sorption of
solvent vapors
Single Tg
Transparent films when I had
28.6-44.4% acrylonitrile
Single loss peak when 5 40%
II was 2- or 4-vinylpyridine 354
(2 blend systems); formed complexes
Formed complexes 1 0 1 2
Formed complexes; II had 6.0-55 859
mol% acrylamide
Semicrystalline 1 1 4 0
Formed complexes 859
Semicrystalline when > 50% II 374,712,953,
1115,1128
Semicrystalline 197,1211,1255,1256,1257
Formed 1: 1 complexes 1 6 0
Formed complexes 1 1 2 8
I had 19 wt.% acrylic acid 564
I had 11.4-20.8 wt.% acrylic acid 383
I had 20% acrylic acid; II was nylon 6, 471,884
nylon I1 or nylon 12 (3 miscible
blend systems)
I had 2.65-20 wt.% acrylic acid 72,lOOl
1 had 20 mol% acrylic acid 1001
I had 21 wt.% acrylic acid 384
I had 20 mol% acrylic acid 1001
I had 8-20 wt.% acrylic acid 72,382,384
I had 2.65-8.84 wt.% acrylic acid 70
I had 8-20 wt.% acrylic acid 576
-
30,249,452,65 1
Two phases in electron micrograph 93,797
when I had 18% acrylonitrile may
indicate a crystalline phase; two
torsional transitions when I had 2
28% acrylonitrile
II had 26-54 wt.% acrylonitrile 966
Immiscible when I had 18.4% 93,296,398,399
acrylonitrile 452
Two loss peaks when > 50% vinyl 296,452
vinyl acetate in II; clear films acetate in II 539,65 I
for some mixtures of
commercial polymers
References page VI - 46 1
VI / 412 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Refs.
Acrylonitrile-co-butadiene-co-
methyl acrylate
Acrylonitrile-co-butadiene-co-
styrene
Acrylonitrile-co-methyl
methacrylate
Acrylonitrile-co-methyl
methacrylate-co-cl-
methylstyrene
Acrylonitrile-co-cc-methylstyrene
Acrylonitrile-co-p-
methylstyrene
Vinyl chloride Single Tg; IGC
Vinyl chloride Single Tr; microscopy
Vinyl chloride, head-to-head
Ethylene-air-maleic anhydride
Single T,
Single Ts; microscopy
Propylene-co-vinyl chloride Single T,
NJ-dimethylacrylamide Single Tg; transparency I had 70 wt.% acrylonitrile (AN) 6 4 8
Maleic anhydride
Vinyl chloride
N-vinylpyrrolidone
Vinyl chloride
Single Ts; transparency
Single Ts; transparency
Single Ts; transparency
Single Tg
I had 70 wt.% AN
II had 2-17 wt.% AN
I had 70 wt.%-AN
I had 8158134 or 32.3/8.1/59.6/
acrylonitrile/methyl methacrylate/
a-methylstyrene
6 4 8
1091
6 4 8
93,1078
Alkyl methacrylate Single Ta; transparency I had 30 wt.% acrylonitrile (AN); II 266,268,279
n-Butyl methacrylate
n-Butyl methacrylate-co-methyl
methacrylate
Ethyl methacrylate
Ethyl methacrylate-co-methyl
methacrylate
Ethylene, chlorinated
Maleic anhydride-co-styrene
Methyl methacrylate
Methyl methacrylate-co-2,2,6,6-
tetramethyl-piperidinyl
methacrylate
n-Propyl methacrylate
Vinyl chloride
Acetonyl methacrylate Single Ts; transparency I had 43-61 wt.% AN 118
2-Bromoethyl methacrylate
n-Butyl methacrylate
2Chloroethyl methacrylate
Chloromethyl methacrylate
Cyclohexyl methacrylate
2,6-Dimethyl- 1,4-phenylene ether
Ethyl methactylate
Methyl methacrylate
Methylthiomethyl methacrylate
n-Propyl methacrylate
Tetrahydrofurfuryl methacrylate
Tetrahydropyranyl-2-methyl
methacrylate
Single Tp; transparency
Single T.; transparency
Single Tr; transparency
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,; transparency
I had 14-61 wt.% AN
I had 13.6 wt.% AN
I had 18.3-46 wt.% AN
I had 13-42 wt.% AN
I had 5 22 wt.% AN
I had 5 5.0 wt.% AN
I had 12-33 wt.% AN
I had 12-34 wt.% AN
I had 19-34 wt.% AN
I had 6-28 wt.% AN
I had 12-48 wt.% AN
I had 5-29 wt.% AN
6 0 8
2 8 5
6 1 3
2 6 3
1 2 0
2 7 5
2 8 5
2 8 5
269
2 8 5
286
119
Single Ta
Single Tp; transparency
Single Ts
Single Tr; transparency
Single T,
Single Tg
Single T,
Single Tp; transparency
Single Ta
Single Ta
I had 29-45 wt.% acrylonitrile 9,79,85,161,196,
452,484,520,561,
614,615,632,682,755
799,860,867,885,1186
I was hydrogenated; I had 38 wt.%
acrylonitrile
I had 23.5-56.6 wt.% acrylonitrile
I was made from a copolymer of
AN/MA (75/25) grafted onto
BD/AN (70/30) copolymer
I was Blendex 701; II had 3.2 or 3.8%
propylene; electron micrographs
may indicate two phases
158
1 1 5 6
107
had an alkyl group of acetonyl,
chloromethyl, 2-chloroethyl, 2-
hydroxyethyl, 2-hydroxypropyl,
methoxymethyl, methylthiomethyl
or tetrahydrofurfuryl (8 miscible
blend systems)
I had 12 wt.% AN
I had 30 wt.% AN; II had 70 wt.%
methyl methacrylate
I had lo-28 wt.% AN
I had 30 wt.% AN; II had 30 or 60
wt.% methyl methacrylate
Depended on AN and Cl contents
Region of miscibility was sensitive
to MW
1 5 2
289
1 5 2 , 2 7 7
287
I had lo-37 wt.% AN; I had 30 wt.%
AN and II was atactic or isotactic
(Ref. 277); I had 6.5-30 wt.% AN
(Ref. 1010)
1 5 2 , 2 7 7 ,
1 0 1 0
I had 30 wt.% AN; II had 2 76.2 wt.% 272,274
methyl methacrylate
I had 17-20 wt.% AN
I had 30 wt.% AN; miscible when melt
blended or cast from methyl ethyl
ketone; immiscible when cast from
tetrahydrofuran; I had 11.9-30
wt.% AN (Ref. 1010)
1 5 2
4 3 5 , 6 8 4 ,
1 0 1 0
Chemically Dissimilar Polymer Pairs VI / 413
TABLE 1. contd
Polymer I of Polymer II of Method Comments Refs.
Acrylonitrile-co-styrene Acetonyl methacrylate
Arylate
Arylate of tetramethylbisphenol-A
Benzyl methacrylate
2-Bromoethyl methacrylate
Butylene adipate
Butylene sebacate
n-Butyl methacrylate-co-methyl
methacrylate
ferr-Butyl methacrylate-co-methyl
methacrylate
Caprolactone
2-Chloroethyl methacrylate
Chloromethyl methacrylate
Copolyarylate of Tetramethylbis-
phenol-A and tetrabromobis-
phenol-A
Copolycarbonate of bisphenol-A
and tetramethylbisphenol-A
Cyclohexyl methacrylate
Cyclohexyl methacrylate-co-methyl
methacrylate
2,6-Dimethyl- 1,4-phenylene ether
2,6-Dimethyl- 1 &phenylene ether,
benzoylated
Ethylene adipate
Ethyl methacrylate
Ethyl methacrylate-co-methyl
methacrylate
E t h y l methactylate-co-2,2,6,6-
tetramethyl-piperidinyl
methacrylate
Ethyloxazoline
Hexamethylene sebacate
2-Hydroxyethyl methacrylate
2-Hydroxypropyl methacrylate
Itaconic anhydride-co-methyl
methacrylate
Methoxymethyl methacrylate
Methyl methacrylate
Methyl methacrylate-co-
N-phenylitaconimide
Methyl methacrylate-co-phenyl
methacrylate
Methyl methacrylate-co-2,2,6,6-
tetramethyl-piperidinyl methacrylate
Single T,; transparency
Single T,
Single T,
Single T,
Single T,; transparency
Single T,
Single T,
Single TB; transparency
Single T,
Single T,; FTIR; microscopy;
LS
Single T,; transparency
Single T,; transparency
Single T,
Single T,
Single T,; transparency
Single T,
Single T,
Single T,
Single T,
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,
Transparency
Single T,; transparency
Single T,
Single T,; transparency
Transparency
Single T,
Single T,
Single T,; transparency
Methylthiomethyl methacrylate
Novolac
Single T,; transparency
Single T,
Oxy-1,4-phenylene-sulfonyl- Modulus-temperature
1,4-phenylene oxy-2,6-diisopropyl-
1,4-phenylene isopropylidene
3,5-diisopropyl- 1,4-phenylene
Phenyl acrylate Single T,
I had 33-58 wt.% AN 121
Miscibility the greatest when 7
AN=25%
I had 4-13 wt.% AN 1048
I had 7.8-24.3 wt.% AN 1180
I had lo-58 wt.% AN 608
I had 13-32.3 wt.% AN 228
I had 13-20 wt.% AN 228
I had 22 wt.% AN; II had 70 wt.% 289, 405
methyl methacrylate
Miscibility depended on compositions 6 2 1
of I and II
I h a d 1 3 - 3 0 wt . % AN 228, 295, 458, 565, 729,
1021,1047,1097,1145,1185
I had 12.5-43 wt.% AN 613
I had 12-37 wt.% AN 262
Miscibility depended on compositions
of I and II
I had 5 18 wt.% acrylonitrile; II had 5 22 431
wt.% bisphenol-A
I had 5 20 wt.% AN 119
Miscibility depended on compositions 621
of I and II
I had 5 10.5 wt.% AN 457,1022
I had 18 mol% AN; II had 35 or 776
86% benzoylated units
I had 25-28 wt.% AN 228
I had 5.5-28.0 wt.% AN (Ref. 229); 112,229,489
I had 9-34 wt.% AN (Ref. 112)
I had 22 wt.% AN; II had 30 or 50 288
wt.% methyl methacrylate
I had 30 wt.% AN; II had 5 13.3 wt.% 274
2,2,6,6-tetramethyl-piperidinyl
methacrylate
I had 25-40 wt.% AN; two T,s when 426, 652
I had 8, 23.5 or 70% AN
I had 16.2 wt.% AN 228
I had 22 wt.% AN 277
I had 22 wt.% AN 279
Miscibility depended on compositions 920
of I and II
I had 30 wt.% AN 269
I had 9.4-34.4 wt.% AN (Ref. 789); 56, 164, 229,
I had 9.5-28 wt.% AN (Ref. 229); 392, 566,
I h a d 9 - 3 9 w t . % A N 598,651,670,741,
(Ref. 164) 782, 789
Miscibility depended on compositions 169
of I and II
Miscibility depended on compositions 6 2 1
of I and II
I had 22 or 30 wt.% AN; II had 531.4 272, 274
wt.% 2,2,6,6-tetramethyl-piperidinyl
methacrylate
I had 9-36 wt.% AN 267
I had 25 wt.% AN; II was formaldehyde 2 2 1
+ 13/17/70 mol% p-rert-butylphenoll
m-cresollo-cresol
I had 13-16% AN 685
I had 14.6-34.1 wt.% AN (Ref. 717) 717,1171,
or 11.5-32 wt.% AN (Ref. 1171) 1180
References VI - 46 1 page
VI / 414 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Refs.
n-Propyl methacrylate Single T,
Acrylonitrile-co-vinylidene
chloride
Tetrahydrofurfuryl methacrylate
Tetrahydropyranyl-2.methyl
methacrylate
Vinyl chloride
Caprolactone
Single T,; transparency
Single Tg; transparency
Single T,
Single T,
Ally1 alcohol-co-styrene
Hexamethylene terephthalate Single T,
Ester Single T,
Amic acid
Amideimide
n-Amy1 methacrylate
Aramide
Aramide
Aramide
3,3-Diamino-4,4-benzidine
isophthalamide
Phenol-formaldehyde
Imide Single T,
Novolac Single T,
Resol Single T,
Shellac Single T,
Vinyl chloride
Vinyl chloride, chlorinated
Vinyl chloride-co-vinylidene
chloride
Amide
Butylene terephthalate
Caprolactam-co-laurolactam
Caprolactam-co-2-pyrrolidinone
Copolyester
Cycloaliphatic amide Single T,
Ethylene terephthalate
Amide
Cycloaliphatic amide Single T,
Amide Single T,; T,-depression
Transparency; FTIR
Clear before and after curing
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
I had 5.7-19.5 wt.% AN (Ref. 229) or 9-24 2 2 9 ,
wt.% AN (Ref. 1090) 1 0 9 0
I had 9-48 wt.% AN 281,286
I had 5 31 wt.% AN 116
I had 11.5-26 wt.% AN 437
I was usually Saran F (80% vinylidene 31,825,887
chloride); semicrystalline when 5 70
wt.% I
Probably semicrystalline; 1 was Saran 3 6
F(SO% vinylidene chloride)
I had Mw = 1.4-2.1 kg/mol and had 46,869
1.3-7.7 wt.% OH groups; II was butylene
adipate, butylene sebacate, caprolactone,
1,4-cyclohexane dimethylene succinate,
decamethylene sebacate, 2,2-dimethyl-
1,3-propylene adipate or hexamethylene
sebacate (7 blend systems); high OH
content of I favored miscibility
I was PARC-TPI 1071
I was made from 4.4.methylene-
dianiline and pyromellitic dianhydride
II was Polyimide P84; miscible over
certain composition range
I was made from rosin
1 was made from rosin maleic anhydride
Diels-Alder adduct with 4.4.diamino-
diphenylmethane
1
538
466
468
I was made from rosin-imidoamino
acid with 4,4-diaminodiphenylmethane
469
-
319,649,812,850
II had 65 or 68 wt.% Cl 319,810
II was Saran, 2 80% vinylidene chloride 407,812
I was made from 2,2,4-trimethyl- 211,212,
1,6-hexanediamine and terephthalic acid
(Trigamid T); semicrystalline; II was
nylon 6, nylon 6,6, nylon 6,12, nylon
6,9 or nylon 6,10 (5 miscible blend
systems)
I was Trogamid T, semicrystalline
I was Trogamid T; II had 43.8-55.6
mol% caprolactam; semicrystalline
I was Trogamid T, II had 93.5 mol%
caprolactam; semicrystalline
I was Trogamid T, II was made from
1,4-cyclohexanedimethanol/ethylene
glycol/terephthalic acid (PETG 6763)
I was Trogamid T, II was made from
1,4- and 1,3-benzenedicarboxylic acids
and a mixture of 1 &hexanediamine
and bis(4aminocyclohexyl)methane
(Bexloy AP C-803)
I was Trogamid T; semicrystalline
I was made from 1,6-hexanediamine and
a mixture of isophthalic and tereph-
thalic acids (Zytel 330); semicrystal-
line; II was nylon 6, nylon 6,6, nylon
6,9 or nylon 4,6 (4 miscible blend
systems)
I was Zytel 330; II was Bexloy AP C-803
I was poly[2,2-bis(trifluoromethyl)-4,4-
biphenylene dicarboxamide]; II was
nylon 6, nylon 4,6, nylon 6,6, nylon
595
596
213,214
213,214
596
212
596
2 1 2 , 2 1 3
2 1 2
1013
Chemically Dissimilar Polymer Pairs VI / 415
TABLE 1. contd
Polymer I of Polymer II of Method Comments Refs.
Aramide
6,9, nylon 6,lO or nylon 11 (6 blend
systems)
I was made from bisphenol-A and a
mixture of terephthalic acid/isophthalic
acid/Wet+butyl-isophthalic acid = 44,
44/12 (Polyarylate C); II was
Trogamid T
I was Polyarylate C; II was made from
5-ret-t-butylisophthalic acid/isophthalic
acid 90, 10 and 1,12-diaminododecane
(Aramide-S)
I was made from bisphenol-A and a
mixture of terephthalic acid/isophthalic
acid/5-tert-butyl-isophthalic acid = 42.5/
42.5/ 15 (Polyarylate D); II was made
from adipic acid and m-xylene-diamine/
hexamethylene diamine 80/20
(Aramide-M)
I was Polyarylate D; II was Trogamid T
I was Polyarylate D; II was Aramide-S
I was made from bisphenol-A and a
mixture of terephthalic acid/isophthalic
a&l/5-tert-butyl-isophthalic acid = 37.5/
37.5/25 (Polyarylate E); II was
Aramide-M
I was Polyarylate E; II was Trogamid T
I was Polyarylate E; II was Aramide-S
I was made from bisphenol-A and a
mixture of terephthalic acid/5-tert-butyliso-
phthalic acid 50/50 (Polyarylate F); II
was Trogamid T
I was Polyarylate F; II was Aramide-S
I was made from bisphenol-A and a
mixture of terephthalic acid/isophthalic
acid 50/50 (Ardel D-100); miscibility
arised from transesterification
I was Ardel D-100; II was made
from cyclohexane dimethanol and tereph-
thalic acid/isophthalic acid (80-87%
tere) (Kodar A-150) and another
copolymer with tere/iso ratio of 70/30
Arylate Single T, 188
1 8 9
1 8 9
1 8 9
1 8 9
1 8 9
1 8 9
1 8 9
1 8 9
1 8 9
687
687
Aramide-S Single T,
Aramide-M Single T,
Aramide
Aramide-S
Aramide-M
Single T,
Single T,
Single T,
Aramide
Aramide-S
Aramide
Single T,
Single T,
Single T,
Aramide
Carbonate of bisphenol-A
Single T,
Single T,
Copolyester Single T,
Copolyester Single T, I was Ardel D-100; II was made from
cyclohexane dimethanol, ethylene
glycol and terephthalic acid (molar
ratio 1:2:3, PETG-6763)
I was Ardel D-100; miscibility arised
from transesterification
I was Ardel D-100; miscibility arised
from transesterification
Semicrystalline
291,687
Ethylene terephthalate Single T,
Single T,
Single T,
Single T,
Single T,
687
687
907
906
334
Hydroxyether of bisphenol-A
(Phenoxy)
But yl ene sebacate Arylate of tetramethyl-
bisphenol-A
Aryl ether ketone
Aryl sulfone
y-Benzyl glutamate
Bis(methyoxyethoxyethoxy)
phosphazene
Hexamethylene sebacate
Etherimide
Semicrystalline
I was made from 4,4-difluoro-benzo-
phenone and hydroquinone; II was
Ultem 1000
I was made from p-phenoxybenzoyl
chloride; II was Ultem 1000
I was Radel A; II was XU-218
Miscible as random coils but not as
a-helics
II had 10, 20 or 30 mol% acrylic acid
334
3 7 5
8 1 3
1 0 8 7
1 0 8 7
1 0 8 7
Etherimide Single T,
Single T,
Dynamic mechanical methods;
DSC
Single T,; transparency
Single T,; transparency
Single T,; transparency
Imide
y-Butyl glutamate
Acrylic acid-co-methyl methacrylate
Methacrylic acid-co-methyl
methacrylate
Styrene-co-styrene-4-carboxylic acid
II had 20 mol% methacrylic acid
II had 75 mol% styrene
References page VI-461
VI / 416 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Ref s.
Bis(methoxyethoxyethoxy-
ethoxy)phosphazene
3-Bromo-2,6-dimethyl-
1,4-phenylene ether
3-Bromo-2,6-dimethyl-
1,4-phenylene oxide-co-
2,6-dimethyl-1,4-phenylene
ether
Styrene-co-p-vinylphenol Single T,; transparency
p-Vinylphenol Single T,; transparency
p-Vinylphenol Single T,; transparency
p-Bromostyrene Single T,; microscopy
p-Bromostyrene-co-styrene
p-Bromostyrene
Single T,; microscopy
Single T,; microscopy
2-Bromoethyl methacrylate
p-Bromostyrene-co-styrene
Butadiene
Butadiene-co-styrene rert-Butylstyrene
1 -Butene
Butyl acrylate
Butyl acrylate-co-methyl
methacrylate
Butyl methacrylate
n-Butyl methacrylate-co-
methacrylic acid
n-Butyl methacrylate-co-
4-vinylpyridine
N-Butyl-3-hydroxymethyl
carbazoyl methacrylate
rert-Butylstyrene
Styrene
Tetrahydrofurfuryl methacrylate
2,6-Dimethyl- 1,4-phenylene ether
Butadiene
Diene-co-ethylene-co-propylene
Isoprene
Glycerol ester of hydrogenated rosin
1 -Pentene
Propylene
Ethylene, chlorinated
4-Hydroxystyrene-co-styrene
Vinyl chloride
Vinyl chloride-co-vinylidene
chloride
Vinyl chloride
p-(2-Hydroxy-hexafluoroisopropyl)
styrene-co-styrene
p-(2-Hydroxy-hexafluoroisopropyl)-
cc-methylstyrene-co-styrene
Vinyl chloride
Vinyl chloride-co-vinylidene
chloride
Styrene-co-4-vinylpyridine
Styrene-co-methacrylic acid
w-Hydroxybutyl-3,5-dinitrobenzoyl
methacrylate
Cyclohexyl acrylate
Cyclohexyl methacrylate
Single T,; microscopy
Single T,
Single T,; transparency
Single T,; microscopy
Single T,
Single T,
Single T,; microscopy; light
scattering; NMR
Single dynamic mechanical
loss peak
Single dynamic mechanical
loss peak
Single T,
Single T,
Single T,; transparency
Single T,
Single T,; transparency
Single T,; transparency
Single T,; electron microscopy
Single T,; transparency
NMR II had 1.5 mol% OH-containing 8 9
Single T,; transparency;
miscible in solution
Single T,; transparency
Single T,; FTIR
Single T,; FTIR
Single T, - 6 9 3
Single T,; transparency
-
7 6 5
Single T,; transparency 7 6 5
II had 78 mol% styrene 1 0 8 7
1 0 8 7
1 0 8 7
-
4 0 2
II had 5 85 mol% styrene 402
I had 5 22 mol% 2,6-dimethyl-1,4-phenyl- 402
ene ether
Miscible up to full bromination of I
when I had MW 5 40 kg/mol and II
had MW 5 30 kg/mol
402,530
Semicrystalline; II was butylene adipate, 1 1 3 7
caprolactone, 2,2-dimethyl-1,3-propylene
adipate, 2,2-dimethyl-1,3-propylene
succinate, ethylene adipate, or hexame-
thylene sebacate (6 miscible blend
systems)
-
606
I had 2 53 mol% styrene 402
I was 1,4-polybutadiene; II had 63% 1,2- 7 0 1
Commercial samples; many mixtures 92,440,45 1
had two T,s
Depended on microstructure; 47,80,149,237,249,
immiscible when I and II 335,520,542,548,549,
were both highly cis; 757,770,771,787,854,
I was deuterated (Ref. 335) 901,1032,1063
I had 25% styrene; II had 1 3 8
M, = 0.835 kg/mol
I had 25% styrene; II had
M, = 0.5 kg/mol
1 3 9
-
1 9 0
Semicrystalline 190,502,657
II had 49.8 or 62.1% Cl; immiscible 1 0 0
when II had 48.0% Cl
I was rerr-butyl; II had 28-66 mol%
4-hydroxystyrene
8 9 7
Some papers showed two T,s 425,655,812,845,
(Refs. 812, 866) or phase separation 846,850,851
in solution (Ref. 425) 866
II was Saran ( 2 80% vinylidene 812
chloride)
I was Degalan V26(90% methyl 654,886
methacrylate) (Ref. 886); I had 75%
butyl acrylate) (Ref. 654)
II had 83.3-98.25 mol% styrene; 103,572,646,
immiscible when II had 99.0 mol% 807
styrene
I was n-butyl, isobutyl or set-butyl 319,425,649,
653,846,810,850
II was Saran, 2 80% vinylidene; I was 409,812
n-butyl, isobutyl or set-butyl
I had 8 or 18 mol% methacrylic acid; II 985
had 15, 22 or 28 mol% 4-vinylpyridine
I had 10.6, 18.9 or 26 mol% 4-vinyl- 198,985
pyridine; II had 12, 24 or
29 mol% methacrylic acid
TABLE 1. contd
Chemically Dissimilar Polymer Pairs VI / 417
Polymer I of Polymer II of Method Comments Refs.
Butylene adipate
Butylene dodecamethylene
dicarboxylate
Butylene 2,6-naphthalene
dicarboxylate
Butylene sebacate
Butylene terephthalate
Caprolactam
Caprolactone
lsoprene
3,3,5-Trimethyl-cyclohexyl
methacrylate
Epichlorohydrin
Hydroxyether of bisphenol-A
(Phenoxy)
Vinyl acetate-co-vinylidene chloride
Vinyl bromide Single T,
Vinyl chloride Single T,
Vinyl chloride Single T,
Ethylene 2,6-naphthalene
dicarboxylate
Epichlorohydrin
Vinyl chloride
Arylate
Butylene oxide-y-butylene
terephthalate
Copolyester
Copolyester
Decamethylene-4,4-terephthaloyl-
dioxydibenzoate
Ethylene terephthalate
Hydroxyether of bisphenol-A
(Phenoxy)
Vinyl acetate-co-vinylidene chloride
Vinyl chloride
Vinyl chloride, chlorinated
Acrylic acid
Hexamethylene adipamide
Methacrylic acid
Styrene, sulfonated and
Li-neutralized
Styrene, sulfonated and
Mn-neutralized
Styrene, sulfonated and
&-neutralized
Acrylonitrile-co-ferf-butylstyrene
3,3-Bis(chloromethyl)oxetane
Chlorostyrene
Epichlorohydrin
Ester
Ethylene, chlorinated
Hydroxyether of bisphenol-A
(Phenoxy)
Nitrocellulose
Vinyl acetate-co-vinylidene chloride
Vinyl bromide
Single dynamic mechanical
loss peak
Single T,; transparency
1 had M, = 0.835 kJ/mol 11 was
natural rubber
1 3 8
765
Single T,
Single T,; melt
transparent; IGC
Single T,
Semicrystalline
Semicrystalline when 5 60 wt.% II
2 2 3
332,1205
II was Saran C ( 2 80% vinylidene
chloride); semicrystalline
31
Semicrystalline when 5 70 wt.% II
Semicrystalline
1 5 0
900
872
Single T, Blend had 2 80 wt.% I 1 2 3 8
Single T,
Single T,
Single T,; X-ray scattering
Single T,; dielectric loss
measurements; microscopy
Single T,
Semicrystalline
Semicrystalline
Semicrystalline
11 had 84 wt.% butylene terephthalate
223
872
1040
554,703
768
Single T,
Semicrystalline when 2 25 wt.% I; II
was CP-350(bisphenol-A-neopentyl
glycol terephthalate)
Semicrystalline; II was made from
bisphenol-A and l/l or l/3 tereph-
thaloyl chloride/isophthaloyl chloride
O-50% II in blend
438,439
Single T,; microscopy;
T,-depression
Single T,
Single T,; melt transparent
660,661,662
Semicrystalline 219,220,916
Semicrystalline 688,689,735
Single T,
Single T,
Single T,
Single T,
Single T,; enthalpy recovery
kinetics
S A X S
Single T,
II had 2 80% vinylidene chloride 3 6
Semicrystalline 36,686
Semicrystalline 3 6
Semicrystalline 378
Semicrystalline 215,830
Semicrystalline
II had 9.8 mol% sulfonated groups;
semicrystalline
3 7 1
583,584
Single T,; T,-depression
Single Ts; T,-depression
Single T,; SALS; microscopy
Single T,
Single T,
II had 10.2 mol% sulfonated groups;
Semicrystalline
523
II had 10.1 mol% sulfonated groups;
semicrystalline
524
1 1 7 5
301,445
18,32
Single T,
II had 19.8-39.6 wt.% acrylonitrile
Semicrystalline; 11 was Penton
II was o-chlorostyrene or mixed o-
and p-isomers; semicrystalline
when 221% 1
Semicrystalline 82,223
DSC; SALS; X-ray diffraction; II was made from terephthaloyl chloride 8 2 1
microscopy and 4,4-bis(6-hydroxy-hexyloxy)
biphenyl
Single T, Semicrystalline when 5 90% II; II had 32,55,191
2 30% Cl; two Tss when 11 had 295
25% Cl
Single T,; melt Semicrystalline when > 50 wt.% 1 82,193,332,982
transparent; IGC
Single T, 2 50% I; semicrystalline when 82,352,353
250% I
Single T, 1 had 66 wt.% Cl; semicrystalline when 18,32
250 wt.% I
Single T, 11 was Saran C ( 2 80 mol% vinylidene 31,887
chloride); semicrystalline
Single T, Semicrystalline when > 30% I 1 4 7
References page VI - 46 1
VI / 418 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Refs.
Caprolactone-co-ethylene
terephthalate
Vinyl chloride, chlorinated
Vinyl chloride-co-vinylidene
chloride
Vinylidene fluoride
Vinyl methyl ether
Ethylene, chlorinated
Hydroxyether of bisphenol-A
(Phenoxy)
Vinyl chloride
Carbon monoxide-co-ethyl
acrylate-co-ethylene
Vinyl chloride, chlorinated
Vinyl chloride
Vinyl chloride Single T,; NMR
Single T,
Single 7s
I,-depression
Single T,
Single T,
Single T,; FTIR
Single T,
Single T,
Single T,
Carbon monoxide-co-
2-ethylhexyl acrylate-co-
ethylene
Carbon monoxide-co-ethylene-
co-vinyl acetate
Vinyl chloride
Chlorostyrene
Propylene, chlorinated
Vinyl chloride
Carbonate of bisphenol-A Alkylene terephthalate Single T,
BiphenyL4,4ylene sebacate
Butylene adipate
Butylene terephthalate
p-rerr-Butylphenol formaldehyde
Caprolactone
Caprolactone-co-ethylene
terephthalate
Carbonate
Copolyestet
Copolyester
Copolyester
Copolyester
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,; FTIR
Single T,
Single T,; SANS; SAXS;
FTIR; NMR
Single T,; STIR
Single T,; transparency II was carbonate of bisphenol-E,
bisphenol-F, bisphenol-Z, bisphenol
chloral, dimethylbisphenol-A,
dimethylbisphenol-Z, norborane, or
tetramethylbisphenol-F (8 miscible
blend systems)
Single T,; melt transparent Semicrystalline when cast from solvent 5 8 5
Single T,
Single T,; melt transparent
Single T,
Semicrystalline when 2 3 0 % I 82,352,353,446
628,635,872,900,
1082
II had 67.2 wt.% Cl; semicrystalline 54
when 2 50 wt.% I
Semicrystalline; II had 79% or 88% 31,825.868,
vinylidene chloride; some samples
of II were Saran B
Semicrystalline
I had 33-89 wt.% ethylene tereph-
thalate; II had 67.2 wt.% Cl
II had 48-82 wt.% ethylene tereph-
thalate
I had 33 or 44 wt.% ethylene tereph-
thalate
1 had 33 wt.% ethylene terephthalate
Semicrystalline when I had > 60%
ethylene; I had 4.0-19.6% carbon
monoxide, 5.5-35.4% ethyl acrylate,
and 34.2-79.6% ethylene
I had 17.8/34.2/47.9 or 18.6/39.6/41.8 = 6 9 2
8 7 3 , 8 8 7
3 8 6
1145
5 2 5 , 8 9 2
1243
525
5 2 5
6 9 2
carbon monoxide/2-ethylhexyl
acrylatelethylene
I was Elvaloy 741; II was a mixture of
o- and p- isomers
I was Elvaloy 741
Semicrystalline when I had > 60%
ethylene; I was Elvaloy 741 or
10.5/66.1/22.8 or 10.2/58.2/31.5 =
carbon monoxide/ethylene/vinyl
18
18
21,40,92
acetate
II had an alkylene group of 2-ethyl-
2-methylpropylene, 1,7-heptylene,
1,9-nonylene or 1,5-pentylene
(4 blend systems); miscibility arised
1074
from trans-esterification
Up to 40 wt.% II in blend
Semicrystalline
Semicrystalline, especially when 2
25 wt.% II
II had 48 or 58 wt.% ethylene
terephthalate
3 8 7
1 7 4 , 1 7 6
1132
1057
174,176,645
948,949,950
1 1 2 0 . 1 2 4 2
4 2 7
up to 80 wt.% II; II was prepared from
bisphenol-A and 1 / 1 = terephthalic/
isophthalic acid
II was made from terephthalic acid 23,1093
and 1,4-cyclohexane-dimethanol and
up to 60 mol% ethylene glycol
Semicrystalline; II was KODAR A150, 1 7 4 , 5 5 6
made from 1,4cyclohexanedime- 581,1251
than01 and l/4 = isophthalic/tereph-
thalic acid
II was Hytrel 5556, a multiblock
copolymer with poly(tetramethylene
ether)glycol terephthalate soft segment
2 4 8
TABLE t. contd
Chemically Dissimilar Polymer Pairs
Polymer I of Polymer II of Method Comments Refs.
1,4-Cyclohexane-dimethylene
succinate
1,4-Cyclohexane-dimethylene
terephthalate
Cyclohexyl methacrylate-co-methyl
methacrylate
Ethylene adipate
Ethylene succinate
Ethylene terephthalate
p-@Hydroxy-hexafluoroisopropyl)
styrene-co-styrene
Maleic anhydride-co-styrene
Methacrylic acid-co-styrene
Methyl methacrylate
Methyl methacrylate-co-
p-methylstyrene
Methyl methacrylate-co-
N-phenylmaleimide
Methyl methacrylate-co-
phenyl methacrylate
Methyl methacrylate-co-styrene
Novolac
Phenyl methacrylate
Pyrrole
Vinylidene chloride-co-vinyl chloride
Carbonate of
hexafluorobisphenol-A
Carbonate of tetramethyl-
bisphenol-A
Alkyl methacrylate
Isopropyl methacrylate
Methyl methacrylate-co-
a-methylstyrene
Acrylonitrile-co-a-methylstyrene
Acrylonitrile-co-styrene
Ally1 alcohol-co-styrene
Butylene sebacate
Caprolactone
Carbonate of bisphenol-A
Carbonate
Ester
Maleic anhydride-co-styrene
Methyl methacrylate-co-styrene
cl-Methylstyrene
p-Methylstyrene-co-tetrahydro-
furfuryl methacrylate
Single T,
Single T,; melt transparent
Single T,
Single T,
Single T,
Single T,
Single T,; transparency
Light scattering
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,; transparency
Single Tg; transparency
Single T,
Single T,
Single Tg; FTIR
Single T,
Single T,
Single T,
Single T,; transparency;
dielectric spectroscopy
Single T,; transparency
Single T,
Single T,
Single T,
Single T,
Single T,
and tetramethylene terephthalate
hard segment
Semicrystalline 1 7 4 , 1 7 5
Semicrystalline 174,486,581
II had 6.1-43.8 wt.% cyclohexyl 574,622,1039
methacrylate
Semicrystalline 1 7 4 , 1 7 6
Semicrystalline 1 7 4 , 1 7 6
Semicrystalline; > 50 or 75% II; two T,s 337,593
when 5 60% II 603,1151
II had 29-78 mol% styrene; immiscible 571,646,
when II had 83 mol% styrene 807
II had 8% maleic anhydride 712
II had 2-23 wt.% methacrylic acid 10,ll
Blends prepared by precipitation of THF 29,109,
solutions in n-heptane or cast from 481,486,715
hot THF solutions
II had 2 70 wt.% methyl methacrylate 357
II had 2 70 wt.% methyl methacrylate 357
II had 16-63 wt.% phenyl methacrylate 622
II had 5 14 wt.% styrene
II had MW = 1 kg/mol and was made
from formaldehyde and 13/17/70
mol% =p-tert-butylphenyllm-cresoll
o-cresol
577,930
2 2 1
-
480,622
Blend had 7% II 856
II had 13.5 wt.% vinyl chloride; semi- 8 7 1
crystalline when 5 25 wt.% I
II had an alkyl group of methyl, ethyl or 225,430
n-propyl (3 miscible blend systems)
5 70 wt.% I in blend 430
II had 81 or 95 wt.% methyl 930
methacrylate
II had 4-16.5 wt.% acrylonitrile
II had < 13% acrylonitrile
II had < 19.1 wt.% ally1 alcohol
Semicrystalline
Semicrystalline
-
1 0 1 0
8,225,1069
225
227
227
51,427,1124
11 was carbonate of bisphenol-AP, 427
bisphenol-E, bisphenol-F, bisphenol-S,
bisphenolz, bisphenol chloral, di-
methylbisphenol-A, dimethylbisphenol-Z,
norbonane, tetramethylbisphenol-F
or tetramethylbisphenol-P
(11 miscible blend systems)
II was decamethylene decamethylene 227
dicarboxylate, decamethylene sebacate,
ethylene adipate, hexamethylene
decamethylene dicarboxylate, or
hexamethylene sebacate (5 miscible
blend systems)
II had 8% maleic anhydride 2 2 5
II had ~50 wt.% methyl 575,884,1194
methacrylate
-
II had 5 50 mol% tetrahydrofurfuryl
methacrylate
227
270
References page VI - 461
VI / 420 MISCIBLE POLYMERS
TABLE 1. cont d
Polvmer I of Polvmer II of Method Comments Ref s.
Cellulose
Cellulose acetate
Cellulose acetate-butyrate Ethylene-co-vinyl acetate
Cellulose acetate propionate Alkylene glutarate Single T,
Cellulose triacetate
Chitin
Chitin-g-2-methyl-2-oxazoline
Chitosan
Chitosan acetate
p-Chloro-(3-ethenoxypropyl)
cinnamate
Khloroethyl methacrylate
Styrene-co-tetrahydrofurfuryl
methacrylate
Acrylonitrile
Caprolactone
Ethylene glycol
Vinyl acetate
Vinyl alcohol
4-Vinylpyridine
2,6-Dimethyl- 1,4-phenylene ether,
phosphonate derivative
2,6-Dimethyl-3-bromo-1,4-phenylene
ether, phosphonate derivative
Styrene, phosphonate derivative
Styrene, phosphorylated
Styrenephosphonate ester
styrene-co-vinylidene chloride
phosphonylated, chloromethylated
styrene-co-inylidene chloride
phosphonylated
4-Vinylpyridine
Hydroxybutyrate-co-valerate Single T,; WAXD; NMR
Highly subsitituted cyanoethyl
cellulose
N-Vinylpyrrolidone
Vinyl alcohol
Vinyl chloride
Ethylene oxide
Ethylene oxide
p-Methoxy-(6-ethenoxyhexyl)
cinnamate
p-Methoxy-(6-ethenoxypropyl)
cinnamate
p-Methyl-(3-ethenoxypropyl)
cinnamate
Alkyl methacrylate
2-Chloroethyl methacrylate Alkyl methacrylate Single T,; transparency
N-vinylpyrrolidone Single T,
Single T,
NMR; single T,; microscopy;
WAXD
NMR
Single T,; FTIR
Single T,
NMR; FTIR; T,-depression
Single T,, NMR
Single T,
II had 5 5 3 mol% tetrahydrofurfuryl 270
methacrylate
560,627,1208
5 5 6
-
-
2 70% I i n blend
-
II had 9.5% P
625,1075
6 2 6
560,623,744,1075
559,1208
87
Single T, II had 10.5% P 87
Single T, II had 8.0% P 87
Single T, II had more than 1 phosphoryl group per 5 5 0
4 styrene units
Single T, Blend initially prepared was hetero- 7 9 2
geneous, became miscible when
annealed above T,
Single T,; electron microscopy I was Eastman 394-45; II had 7% P, 88
Single T,
Single T,; cast films
transparent
Single T,; transparent films
Single T,; PTIR; microscopy
Single T,; PTIR
Single Tg; PTIR
Sinlge I,; PTIR
T,,, depression
FTIR; microscopy
Single T,
Single T,
Single T,
Single T,; transparency
Single s; transparent melt
Single T,; transparent melt
14.5% Cl
II had 8.6% P 87
Semicrystalline; I had 39.4% acetyl content 27,86
or had lOH/2 glucose
I had 18.5/45 = acetic acid/butyric acid 93,452
and II had 80% vinyl acetate; two T,s
when II had 70% vinyl acetate
II had 10 mol% valerate; miscible when 8 4
blend had 20-50% II, and partially
miscible when blend had 60-80% II
The alkylene group was ethylene, 9 2 7
diethylene, hexamethylene, penta-
methylene, tetramethylene or trimethylene
(6 miscible blend systems)
-
1 0 2 6
-
1 1 3 3
-
9 1 3
Blend had 5 10 wt.% II 914
-
1 2 4 5
-
1 2 2 7
-
5 1 5
-
5 1 5
-
5 1 5
The alkyl group of II was methyl, ethyl, 1 1 5 2
n-propyl, isopropyl, n-butyl or tetra-
hydrofurfuryl (6 miscible blend systems)
II was butylene adipate, caprolactone,
2,2-dimethyl-1,3-propylene adipate,
2,2-dimethyl-1,3-propylene sebacate,
2,2-dimethyl-l$propylene succinate
or hexamethylene sebacate (6 miscible
blend systems)
1 1 5 4
The alkyl group of II was methyl,
ethyl or tetrahydrofurfuryl
(3 miscible blend systems)
II was butylene adipate, caprolactone,
2,2-dimethyl-1,3-propylene adipate,
2,2-dimethyl- 1,3-propylene sebacate,
ethylene adipate or hexamethylene
sebacate (6 miscible blend systems)
6 1 2
6 0 9 , 6 1 1
-
607
TABLE 1. contd
Chemically Dissimilar Polymer Pairs VI 1421
Polymer I of Polymer II of Method Comments Refs.
Chloromethyl methacrylate
Chloroprene
3Xhloropropyl methacrylate
o-Chlorostyrene
o-Chlorostyrene-co-
p-chlorostyrene
o-Chlorostyrene-co-o-
fluorostyrene
p-Chlorostyrene-co-o-
fluorostyrene
p-Chlorostyrene-co-styrene
Collagen hydrolyzate
Copolyester
Copolyester-carbonate
Alkyl methacrylate
Carbonate of bisphenol-A
Ester
N-vinylpyrrolidone
Ethylene-co-methyl acrylate
Isoprene, epoxidized
Acrylonitrile-co-p-methylstyrene
Acrylonitrile-co-styrene
Ester
Tetrahydrofurfuryl methacrylate
Styrene
2,6-Dimethyl-1,4-phenylene ether
Styrene
2,6-Dimethyl-1,4-phenylene ether
2,6-Dimethyl-1,4-phenylene ether
2,6-Dimethyl-1,4-phenylene ether
Ethyl acrylate
Hydroxyether of bisphenol-A
(Phenoxy)
p-(2-Hydroxy-hexafluoroisopropyl)
styrene-co-styrene
Viny1 chloride
Viny1 chloride
Ethylene terephthalate
Single T,
Single T,
Single T,; transparent melt
Single T,
Single T,; phase contrast
microscopy
Single T,; FTIR
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,; transparency
Single T,
Single T,; transparency; NMR
Single T,; transparency; NMR
Single T,
Single T,
Single T,
Single T,; clear films
Single T,; clear films
Single T,
Single T, for II with soft
segments of I
Single T,
Single T,
II had an alkyl group of methyl, ethyl, 1 2 3 , 2 7 3
n-propyl, isopropyl, acetonyl or tetra-
hydrofurfuryl (6 miscible blend systems)
Miscibility depended on method of 2 7 1
preparation
II was butylene adipate, caprolactone, 609,611
2,2-dimethyl-1,3-propylene adipate,
2,2-dimethyl-1,3-propylene sebacate,
2,2-dimethyl-1,3-propylene succinate,
ethylene adipate, ethylene succinate or
hexamethylene sebacate (8 miscible
blend systems)
607
Semicrystalline 396
597
II had 15-33 wt.% AN
II had 12-35 wt.% AN
II was butylene adipate, caprolactone,
2,2-dimethyl-l$propylene adipate or
hexamethylene sebacate (4 miscible
blend systems)
1 1 0 5
1 1 0 5
1111
1104
-
I had 23-64% p-chlorostyrene
396
1 6
After quenching from 145C; I had 1 3 1 , 8 0 3
71-92 mol% o-chlorostyrene; two T,s
when I had 5 62 mol% o-chlorostyrene
I had 14-40 mol% o-chlorostyrene; two 22,840,
T,s when I had >36 mol% 843
o-chlorostyrene
I had 13-74 mol% p-chlorostyrene; two
Tss when I had > 74 mol%
p-chlorostyrene
22,840,
843
I had 2 34.7 mol% styrene; two 243,413,
T,s when I had < 34.7 mol% styrene 749
-
578
I was cyclohexylene dimethylene 689
tere/isophthalate
I was KODAR PETG (made from 571,646
terephthalic and isophthalic acid and
ethylene glycol and 1,4-dihydroxymethyl
cyclohexane; II had 60 mol% styrene;
immiscible when II had 2 83 mol%
styrene
I was VITEL PE-307; II had 83-90.3
mol% styrene
646
I was VITEL VPE-5545; II had 83 mol%
styrene; immiscible when II had 90.3
mol% styrene
646
I was Hytrel, a multiblock copolymer 343,344,
with poly(tetramethylene ether) glycol 617
terephthalate soft segments and
tetramethylene terephthalate hard
segments; hard segments crystalline;
two T,s after 130C annealing; Refs.
343, 344 showed single T, to 50
or 60 wt.% I
I was made from adipic acid, hexane-
1,6-diol and neopentanediol and had
.W, = 2 kg/mol
3 3 1
I was from l/2 = terephthalate/ 3
bisphenol-A with ester and carbonate
linkages
References page VI - 46 1
VI / 422 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Ref s.
Copolyether-amide
Copolymer of bromohydro-
quinone and 4,4-(decame-
thylenedioxy) bibenzoic acid
2Cyanoethyl methactylate
Cyanomethyl methacrylate
1,4Cyclohexanedimethylene
succinate
1,4-Cyclohexanedimethylene
1,4Cyclohexanedicarboxylate
Cyclohexyl methacrylate
Decamethylene decamethylene
dicarboxylate
Decamethylene sebacate
Dianhydrosorbityl dicarboxylate
2,3-Dichloro-1-propyl acrylate
2,2-Dichloroethyl methacrylate
2,6-Diethyl- 1,4-phenylene ether
NJ-dimethylacrylamide
Vinyl chloride Single T,
N-vinylpyrrolidone Single T,; transparency
Copolymer of p-hydroxybenzoic Single T,; microscopy
acid and 3.methyl- 1,6-hexanediol-
terephthalic acid
Copolymer of 4,4-(decamethylene- Single T,; microscopy
dioxy)-bibenzoic acid and 4,4-
(ethylenedioxy)diphenol
Alkyl methacrylate
2-Ethyl-2-oxazoline
2-Hydroxyethyl methacrylate
2-Hydroxypropyl methacrylate
Tertiary amide
Single T,
Single T,
Single T,; FTIR
Single T,; FTIR
Single T,
Alkyl methacrylate
2-Ethyl-2-oxazoline
Tertiary amide
Single T,; FTIR
Single T,
Single T,
Epichlorohydrin Single T,
Hydroxyether of bisphenol-A Single T,; transparent melt
(Phenoxy)
Vinyl chloride-co-vinylidene chloride Transparent melt;
large T,-depression
Vinyl chloride Single T,
Arylate Single T,; PALS
Carbonate of bisphenol-A Single TL PALS
Vinyl chloride Single T,; NMR
Vinyl chloride-co-vinylidene chloride Single T,
2-Vinylnaphthalene
Vinyl chloride
Epichlorohydrin
Dianhydrosorbityl dicarboxylate
Single T,; excimer
fluorescence
Single T,
Single T,
Single T,; microscopy
Ethyl acrylate-co-glycidyl
methacrylate
Alkyl methacrylate
Single T,
Single T,; transparency
Styrene
Ally1 alcohol-co-styrene
Alkyl methacrylate
Single T,
Single Tg; FTIR
Single Tg; FTIR
I was made from adipic acid and
hexane- 1 ,6-diol and neopentane-diol
and diphenyl carbonate
Studied up to 30% II; I was made from
isophthaloyl chloride and c&4,4-
diamino-dibenzo- 18-crown-6
Transition temperature from a mesophase
to an isotopic phase changed
continously and smoothly depending
on the composition
Transition temperature from a mesophase
to an isotopic phase changed
continously and smoothly depending
on the composition
II had an alkyl group of methyl, acetonyl
or tetrahydrofurfuryl (3 miscible
blend system)
Blend had 2 80 wt.% I
-
Blend had 2 50 wt.% I
II was NJ-dimethylacrylamide, N-methyl-
N-vinylacetamide or N-vinyl-
2.pyrrolidone (3 blend systems); formed
complexes
II had an alkyl group of acetonyl,
2-hydroxyethyl or 2-hydroxypropyl
(3 miscible blend systems)
Blend had 2 60 wt.% I
Complexation formation; II was
N-vinylpyrrolidone, N,N-dimethyl-
acrylamide or N-methyl-N-vinylacet-
amide (3 miscible blend system)
Semicrystalline
Semicrystalline 2 50 wt.% I
II was Saran (86.5% vinylidene chloride)
Semicrystalline 5 30 wt.% II
II was Ardel DlOO
II was Ardel DIOO
-
Semicrystalline > 75% II; II had 86.5
wt.% vinylidene chloride
I had low MW, II had MW = 70 kg/m01
Semicrystalline
Semicrystalline
6 Miscible blend systems based on
different polyesters; the dicarboxylate
was adipate, oxalate, sebacate, suberate
or succinate
II had 65% ethyl acrylate
The alkyl group of II was methyl, ethyl,
n-propyl, isopropyl, n-butyl, isoamyl,
cyclohexyl or tetrahydrofurfuryl
(8 miscible blend systems)
Formed complexes; II had 4.5 or
6.5 wt.% OH groups
II had an alkyl of chloromethyl,
2-chloroethyl, 3.chloropropyl,
3 3 3
7 2 0
3 8 0
3 8 0
1 2 3 4
1 2 3 6
1235
1235
1236
1233,
1235
1 2 3 6
1 2 3 6
2 2 3
332
8 6 8
8 9 8
1251
1251
6 4 1
409,870
2 3 1
8 7 2
2 2 3
9 2 5
181
1 1 1 0
1 3 4
974
1 1 0 8
TABLE 1. contd
Chemically Dissimilar Polymer Pairs VI / 423
Polymer I of Polymer II of Method Comments Refs.
Vinylidene fluoride
N,N-Dimethylacrylamide- Vinyl chloride
co-ethylene
Z,h-Dimethyl- I ,4-phenylene ether Acrylic acid-co-styrene
p-Bromostyrene-co-fluorostyrene
Cyclohexylmaleimide-co-styrene
o-Fluorostyrene-co-p-fluorostyrene
2,6-Dimethyl- 1,4-phenylene
ether, carboxylated
2,6-Dimethyl- 1,4-phenylene
ether, brominated
phosphonylated
2,6-Dimethyl-1,4-phenylene
ether, modified
2,6-Dimethyl- 1,4-phenylene
ether, sulfonylated
o-Fluorostyrene-co-styrene
p-Fluorostyrene-co-styrene
p-(2-Hydroxy-hexafluoroisopropyl)
styrene-co-styrene
Luoloylmeleimide-co-styrene
Maleic anhydride-co-styrene
Methacrylic acid-co-styrene
2-Methyl-6-benzyl- 1,4-phenylene
ether
Methyl methacrylate-co-styrene
2-Methyl-6-phenyl-1,4-phenylene
ether
a-Methylstyrene
a-Methylstyrene-co-styrene
o-Methylstyrene
p-Methylstyrene
p-Nitrostyrene-co-styrene
N-phenylmaleimide-co-styrene
Styrene
Styrene, head-to-head
Styrene, iodinated
Styrene, sulfonated and
metal-neutralized
Styrene, syndiotactic
Styrene-b-isoprene-h-styrene
Styrene-co-2,2,6,6-tetramethyl-
piperidinyl methacrylate
Urethane acrylate
Styrene
Cellulose acetate
Epichlorohydrin, modified
Acrylonitrile-co-styrene
p-Bromostyrene
o-Bromostyrene-co-p-bromostyrene
p-Chlorostyrene
o-Chlorostyrene-co-p-chlorostyrene
o-Chlorostyrene-co-o-fluorostyrene
Single T,
Single T,
Single T,
Single T,; FTIR
Light scattering
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,
Light scattering
Single Ts; transparency;
microscopy
Single T,
Single T,; transparency
Single T,
Single T,
Single T,
Single T,
NMR
Single T,
Single T,
Single T,; light scattering
Single T,; transparency: NMR
Single T,
Single T,
Single T,
Single T,
Single T, for mixed with
styrene blocks of II
Single T,
Single T,; FTIR
Single T,
2.bromoethyl or 2-iodoethyl
(5 miscible blend systems)
Semicrystalline 2 60 wt.% II 2 4 1
I had 71.4 or 73.1 wt.% ethylene; two 563
T,s when I had 2 75.1 wt.% ethylene
II had 4.7-8.5 wt.% acrylic acid 921,1022
II had 1 l-73 mol% p-bromostyrene 547,834
I had 83 wt.% styrene 712
II had IO-38% para isomer; two Tss 412,835
when II had 5 or > 43% para isomer
II had 2 9 mol% styrene 836,839,842
II had 244 mol% styrene 531,532,836,839,842
II had 77.9-90.3 mol% styrene 571,572,646,807
II had 81 wt.% styrene 712
II had 5.9-12.5 wt.% maleic anbydride 232,233,
1022,1026
11 had 5.9 or 7.8 mol% methacrylic acid 917,921
7 5 1
II had 2-20 wt.% methyl
methacrylate
258,461,1022
152,753
All compositions of II
NMR showed heterogeneity on a
3-nm scale
134,459,691
459,754
1 9 5
-
195,235,788
II had < 22 mol% nitrostyrene 155,158
II had 84 or 90 wt.% styrene 712,1102
-
39,201,526,589,663,
750,753,784,1207
463
II had < 47% iodination 2 6 1
II had up to 7.8 mol% sulfonation (Ref. 677); 6 7 7 ,
II had 2.8 mol% sulfonation and was 1200
neutralized by Na, Zn, Ni or Mn, and
miscible when blend had 5 40 wt.% I
(Ref. 1200)
-
954
II had block MW 15-51-17 and 568
78-52-80 kg/m01
II had 5 24 wt.% 2,2,6,6-tetramethylpiperi-
dinyl methacrylate
257
I and II formed interpenetrating network
Il.8 mol% of repeat units in I carboxy-
lated; two T,s when 35.0 mol% repeat
units in I carboxylated
567
874
Single T,; electron microscopy II was Eastman 394-45 8 8
Single T,
Single T,
Both I and II had at least 25% carbazolyl
or 3,5-dinitrobenzoyl groups
I had 20-26 wt.% sulfonylation
664
410
Single T,
Single T,
Single T,
Single T,
Single T,
I had > 12 mol% sulfonylation 1216,122O
High p-bromostyrene content and high 1 2 1 6
degree of sulfonylation favored
miscibility
I1 had > 9 mol% sulfonylation 1217,122O
Miscibility depended on compositions 1 2 1 7
of I and II
Miscibility depended on compositions 1 2 1 8
of I and II
References page VI - 46 1
VI f 424 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Refs.
cc,cc-Dimethyl-B-propiolactone
(pivalolactone)
Dimethylsiloxane
Dimethylsiloxane, modified
2,6-Dipropyl-1,4-phenylene ether
Dodecamethylene adipamide,
NJ-dimethyl substituted
Dodecamethylene adipate
Dodecamethylene decamethylene
dicarboxylate
Dodecamethylene dodeca-
methylene dicarboxylate
Enaminonitrile
Epichlorohydrin
Epichlorohydrin-co-ethylene
glycol
Ester
p-Chlorostyrene-co-o-fluorostyrene
o-Fluorostyrene
p-Fluorostyrene
o-Fluorostyrene-co-p-fluorostyrene
p-Fluorostyrene-co-styrene
Phenylvinyl set-butyl ether-alt-
N-phenylmaleimide
Phenylvinyl ethyl ether-alt-
N-phenylmaleimide
Styrene
Vinyl chloride
Ethylene-co-methyl acrylate
Butyl methacrylate
Ethylene glycol
Styrene
p-@Hydroxy-hexafluoroisopropyl)
styrene-co-styrene
Epichlorohydrin
Vinyl chloride
Vinyl chloride
Vinyl chloride
Ethylene glycol
Tertiary amide
4-Vinylpyridine
Acrylonitrile-co-styrene
Alkyl acrylate
Alkyl methacrylate
Butyl acrylate rubber
Ethyl acrylate rubber
Ester
Glycidyl methacrylate
Glycidyl methacrylate-co-methyl
methacrylate
Hexamethylene sebacate
Methacrylonitrile-cc-methyl
methacrylate
Methyl methacrylate
Vinyl acetate
Neopentyl glycol adipate
Ester
Ester
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
T,-depression
Single T,; FTIR
Single T,; FTIR
Single T,; FTIR
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Transparency
Single T,; microscopy
Melting behavior
Miscibility depended on compositions
of I and II
I had 4- 17 mol% sulfonylation
I had 17-66 mol% sulfonylation
Miscibility depended on compositions
of I and II
I had 20-26 wt.% sulfonylation
I had 68-87 mol% sulfonylation
I had 61-91 mol% sulfonylation
I had c 31 wt.% sulfonylation
Semicrystalline
I had a small amount of vinyl groups;
II had 21 wt.% methyl acrylate
One of the methyl groups in the repeating
unit of I was changed to 4-hydroxy-
4,4-bis (trifluoromethyl) butyl group
One of the methyl groups in the repeating
unit of I was changed to 4-hydroxy-
4,4-bis(trifluoromethy1) butyl group
-
Semicrystalline when 5 50% substitution
on I
Semicrystalline
Semicrystalline
Semicrystalline
Semicrystalline
-
II was NJ-dimethylacrylamide, 2-ethyl-
2-oxazoline or N-vinyl-2-pyrrolidone
(3 miscible blend systems)
-
II had 18 or 25 wt.% acrylonitrile
II had an alkyl group of ethyl or n-propyl
(2 miscible blend systems)
II had an alkyl group of ethyl, n-propyl,
n-butyl or cyclohexyl (4 miscible
blend systems)
II was Hycar 4043
II was Hycar 4051EP
II was ethylene adipate, ethylene sebacate
or 2,2-dimethyl-1,3-propylene adipate
(3 miscible blend systems)
-
II had 76% glycidyl methacrylate
II had 30-40 mol% methacrylonitrile
Broad T, might due to separate phases
with differing T,s within the mixture
-
I was Hydrin 200; refractive indices not
equal in the temperature range
investigated
13 Miscible blend systems based on
different linear aliphatic polyesters
Both polymers I and II were liquid
crystalline; II had one more
ethylene unit in the main chain
1218
1 2 2 0
1 2 2 0
1 2 1 5
410
1 2 1 9
1 2 1 9
410
32,33
1 1 8 2
127
1 2 7
1 3 4
454
2 2 3
8 7 2
8 7 2
8 7 2
5 8 7
5 8 7
5 8 7
3 0 5
224,226
2 2 4
2 2 6
2 2 6
2 2 3 , 2 7 8
8 6 4
8 6 4
8 6 4
8 6 4
1 3 5 , 2 2 4
3 0 3
2 8 8
9 2 5
9 7 9
TABLE 1. contd
Chemically Dissimilar Polymer Pairs VI 1425
Polymer I of Polymer II of Method Comments Refs.
Ester, hyperbranched and Aramide
3,5dihydroxyphenylterminated
Amide
Butylene adipate
Copolyester
Ester, hyperbranched and Butylene terephthalate
3,5-diacetoxyphenyl-terminated
Copolyester
Ether ether ketone Arylketone
Etherketone
Etherimide
Ether sulfone
Ether ether ketone, sulfamidated Amideimide
Ether ether ketone, sulfonated Amideimide
Etherimide
Ether ether sulfone,
Epoxy
phenolphthalein
Etherimide Amideimide
Ethylene terephthalate
Imide
Etherimide ether Thioetherimide ether
Ether ketone ketone
Ether sulfone
Etherimide
Aramid
Ether urethane
Imide
Imide
NJ-(oxydi-p-phenylene)
isophthalamide
Phenylene ether ether ketone
Phenylene ether sulfone ketone
Phenylene sulfone ether sulfone
ketone
Phenylene thioether ether ether
ketone
m-Phenylene isophthalamide
Vinyl chloride
3-Ethenoxypropyl cinnamate
Ethyl acrylate
p-Methyl-(3-ethenoxypropyl)
cinnamate
Novolac
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,; microscopy;
WAXD; T,-depression
Single T,
Single T,: FTIR
Single T,; FHR
Single T,; FTIR
Single T,; microscopy
Single T,
Single T,; microscopy;
T,-depression
Single T,
T,,-depression
Single T,
Single T,; NMR
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
II was Trogamid T or MXD-6 1 1 2 5
II was nylon-6
-
II was made from terephthalic acid and
a mixture of ethylene glycol and
1,4-cyclohexane dimethanol
-
1 1 2 5
1 1 2 5
9 6 5
1 1 2 5
II was made from terephthalic acid and 1 1 2 5
a mixture of ethylene glycol and
1,4cyclohexane dimethanol
II had 25, 50 or 57% ketone content 333
I was oxy- 1,4-phenyleneoxy- 1,4- 739
phenylenecarbonyl-1 ,Cphenylene;
II was oxy- 1,4-phenylenecarbonyl-
1,4-phenylene; semicrystalline
I was Victrex 450G; II was Ultem 172,946,1037
1000; semicrystalline 1 1 7 8
- 883
I had degree of sulfamidation of 1.33; 1 0 6 1
II was Torlon 4000T
I had degree of sulfonation of 0.42, 0.53 414,1061
or 1.00; II was Torlon 4OOOT
II was Ultem 1000 414,1061
Miscible when II was cured by amine; 1 0 2 3
immiscible when II was cured by
anhydride
I was Ultem 10000; II was Torlon 1 1 4 7
4203L
I was Ultem 1000 942,1054.1127
I was Ultem 1000; II was based on
diphenylpyromellitic dianhydride
(DPPMDA) (3 different imides)
I was made from 4,4-oxydianiline
(ODA) and 4,4-( 1,4-phenylene-
dioxy)diphthalic acid; II was made
from ODA and 4,4-thio-diphthalic
anhydride
II was Ultem 1000
II was made from isophthaloyl
chloride and bis(4-aminophenyl) ether
II was Polyimide XU218
II was Matrimide 5218
-
-
-
-
-
Prepared by in sifu blending
20 or 40 wt.% II; I was Adiprene
L-100 and 4,4-methylene-bis-
2-chloroaniline
-
II had MW about 1 kg/mol: II was
formaldehyde and 13/17/70, mol% =
p-rerr-butylphenollm-cresollo-cresol or
formaldehyde and 15/17/68 mol% =
2-terr-butylphenollm-cresollo-cresol
240
1000
946
562,600
372
510,940
1031
1 1 8 4
1 1 8 4
1 1 8 4
1 1 8 4
1 0 3 0
344
515
2 2 1
References page VI - 461
VI / 426 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Ref s.
Ethyl acrylate-co-methacrylo-
nitrile-co-a-methylstyrene
Ethyl acrylate-co-methyl
methacrylate
Ethyl acrylate-co-4-vinylpyridine
(N-ethylcarbozol-3-yl)methyl
acrylate
(N-ethylcarbozol-3-yl)methyl
methacrylate
Ethyl methacrylate
Ethylene, chlorinated
Ethylene, chlorosulfonated
Ethylene adipate
Ethylene-co-methacrylic acid
Hexafluoroacetone-co-
vinylidene fluoride
Styrene, sulfonated
Styrene-co-p-vinylphenol
Vinyl chloride
Single T,
Single T,; FTIR
Single T,; FTIR
Single T,
II had 8 mol% vinylidene fluoride
II had 7.2 mol% sulfonated units
II had > 4.46 mol% vinylphenol
In siru polymerized II; other mixtures
formed two phases (Refs. 296, 426
for example)
411,1059
1198
1198
8 4 6
Vinyl chloride-co-vinylidene chloride Single T,; transparency II was Saran ( > 80% vinylidene chloride); 8 1 2 , 8 7 0
Vinylidene fluoride
Vinyl chloride
Vinyl chloride
Styrene-co-styrene sulfonic acid
Vinyl chloride
Vinyl chloride, sulfonated
2-(3,5-Dinitrobenzoyl) oxyethyl
methacrylate
2.(3,5-Dinitrobenzoyl) oxyethyl
methacrylate
Novolac
Ethyl acrylate
p-(2.Hydroxy-hexafluoro-
isopropyl)styrene-co-styrene
Vinyl acetate
Vinyl chloride
Single T,; transparency
Single T,; transparency
I had MW = 50 kg/mol; two Tss
when I had MW = 140 kg/mol and
II was Saran (86.5 wt.% vinylidene
chloride)
Semicrystalline 2 25 wt.% II 56,80,844
I had 2/40/58 = ethyl acrylate/meth- 422,424
acrylonitrile/a-methylstyrene or
unknown composition
Single T,; electron microscopy I was Polaroid K120N (95% methyl 8 8 6
Single T,; transparency
Single T,
Single T,
Single T,; NMR
Single T,; NMR
Single T,; FTIR
Single T,
Single T,; transparency
Transparency
Single Ts; transparency
Vinyl chloride-co-vinylidene chloride Single T,; transparency
Vinylidene fluoride Single T,
Acrylonitrile-co-butadiene Single T,
Hexamethylene terephthalate Single T,
Methyl methacrylate Single T,; transparency;
electron microscopy
Neopentyl glycol adipate Single T,
Vinyl chloride, chlorinated Single T,
Vinyl chloride Single T,
Hydroxyether of bisphenol-A Single T,; transparent melt
(Phenoxy)
Ethylene glycol FTIR
Ethylene glycol-co-propylene glycol Single T,; FTIR
2-Ethyl-2-oxazoline FTIR
Styrene-co-2-vinylpyridine FTIR
methacrylate)
I and II both 2 5% of second
monomer (data obtained < 10%
substitution)
210,773
I had 2- 14 mol% 4-vinylpyridine
I had 6.2 mol% 4-vinylpyridine; II
had 3.7 mol% sulfonic acid
1 3 7
1 3 7
760
-
7 6 1
II had MW about 1 kg/m01 and was 221,434
formaldehyde and 13/17/70 mol% =
p-rert-butylphenolZm-cresol/o-cresol
-
1 5 6
II had 90.3-98.9 mol% styrene 103,57 1,646
Transparent film when I ~25 wt.% or
when content of I toward 100 wt.%
634
-
234,3 19,649,
8 12,846
II was Saran ( > 80% vinylidene chloride) 409,812,
or 86.5 wt.% vinylidene chloride; 870
semicrystalline 5 30% I
Semicrystalline when 2 40% II; two 244,361,476
T,s when >60% II 630,695
Depended on Cl content and acrylo- 9 6 , 1 6 1
nitrile content
I had 48% Cl; immiscible with I had
36% Cl
3 6
I had 2 50 wt.% Cl; II was atactic, 99,296,8 12
isotactic or syndiotactic (Ref. 1204) 848,1204
I had 42 or 48 wt.% Cl; immiscible 288
when I had 5 36 wt.% Cl
I and II with identical chlorine 8 1 8
content were immiscible
I had 1% S as SO2CI and 42 wt.%
Cl; stated immiscible when I had 30
wt.% Cl in Ref. 296
200
Semicrystalline when >_ 50 wt.% I 332
I had 55 wt.% methacrylic acid
I had 18, 32, 44 or 55 wt.% methacrylic
acid; II had 70 wt.% ethylene oxide
I had 44 wt.% methacrylic acid
1 had 32 wt.% methacrylic acid; II had
70 wt.% 2-vinylpyridine
287
494
512
495
TABLE 1. contd
Chemically Dissimilar Polymer Pairs
Polymer I of Polymer II of Method Comments Refs.
Ethylene-co-methacrylic
acid, zinc neutralized
Ethylene-co-methyl acrylate-
co-unspecified acid
Ethylene orthophthalate
Ethylene glycol
Ethylene-co-sulfur dioxide-
co-vinyl acetate
Tetramethylene glycol
Vinyl ethyl ether
Vinyl methyl ether
2-Vinylpyridine
Vinyl methyl ether
4-Vinylpyridine
Vinyl chloride
Vinyl acetate
Copolyester-polyurethane
Epoxy resin
Ethersulfone
Ethyl methacrylate
Ethylene-co-vinyl acetate
Hydroxyether of bisphenol-A
(Phenoxy)
p-(2-Hydroxy-hexafluoroisopropyl)
styrene-co-styrene
Methacrylic acid
Methacrylic acid-cd-styrene,
Na-neutralized
Methyl methacrylate
Resorcinol
Styrene, sulfonated and
Na-neutralized
Styrene-co-p-vinylphenol
Styrene-co-vinylphenol trifluoro
methyl carbinol
Sulfone
Vinyl acetate
Vinyl chloride
Vinylnapthalene
p-Vinylphenol
Vinyl chloride
F T I R
FTIR
Single T,; FTIR
NMR
Single T,
Single T,
Single T,
Single T,
Single T,; light scattering
Single T,
Single T,
Single T,; NMR
Single T,
Single T,; NMR
FTIR
Single Ts; FTIR; NMR
NMR
Single T,
Single T,
Single T,
Transparency; light scattering
Single T,
Single T,; T,-depression;
NMR; IGC
Single T,
FTIR; NMR; X-ray diffraction
Single T,; transparency
I had 55 wt.% methacrylic acid
I had 55 wt.% methacrylic acid
I had 18, 32, 44 or 55 wt.% methactylic
acid
496
496
494
Miscible when I had 18 wt.% methacrylic
acid and formed complexes when I
had 44 or 55 wt.% methacrylic acid;
formed complexes when I had 32 wt.%
methacrylic acid and was 5 35%
I in blend
494
I had 44 wt.% methacrylic acid 732
I had 15 wt.% methacrylic acid and
60% zinc-neutralized
I was Vamac N-123
52
3 9 5
-
829
-
3 6 3
Miscible when II was uncured; immiscible 3 1 3 ,
when II was cured (Ref. 313) 1118,1119
317,534,743
-
II had 87.1 wt.% vinyl acetate (Ref. 132);
II had 73.4 wt.% vinyl acetate, miscible
with I of M, = 20 and 100 kg/mol
(Ref. 328)
1 3 0
132,
328
Semicrystalline when >40% I 363,364,690
II had 77.9 mol% styrene and I/II was
l/8-1/2; semicrystalline and no
amorphous phase
806
Formed complexes in water and
dimethylsulfoxide
374,1128
I had 5.6-17.9 mol% acid 1 0 9 8
I was miscible with atactic or syndio- 124,389,511
tactic II and immiscible with isotatic 552,759,
II; semicrystalline when >20 wt.% I 1 1 9 2
-
51
II had 2.9-8.8 mol% sulfonation; miscible 498
when blend had low I content
II had 13.1 mol% styrene and I/II was 806
l/8- 1 / 1; semicrystalline at higher I
content and no amorphous phase
miscibility
II had 84.4 mol% styrene and I/II was 806
l/8-1/4 or II had 54.5 mol% styrene
and I/II was l/8-1/2; semicrystalline
at higher I content and no
amorphous phase miscibility
I had M, = 3.5- 4.0 kglmol; immiscible 796
when I had M, = 200 kg/m01
Ref. 397 stated miscible when 2 40 wt.% 311,397,
II in blend; Ref. 311 stated completely 5 5 3
miscible if I had M, = 20 kg/mol,
and miscible up to 50 wt.% II if I had
M, = 100 kg/mol
Semicrystalline 418,1126,994
Semicrystalline when >50% I; two 178,580,679
amorphous phases when 25-50% I
Semicrystalline 668,888,1150,
1 1 4 9
I had 72.7/8.8/18.5 = ethylene/sulfur
dioxide/vinyl acetate; immiscible when
339
References page VI - 46 1
VI / 428 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Refs.
Ethylene terephthalate Hydroxyether of bisphenol-A
(Phenoxy)
Liquid crystalline copolyester
Single T,
Single T,
Ethylene-co-vinyl acetate
Ethylene-2,6naphthalene
dicarboxylate
Acrylic acid-co-alkyl acrylate
Single T,
Single T,
3-Alkyl thiophene
Aniline, N-octadecylated
Chloroprene
Hexafluoroacetone-co-vinylidene
fluoride
Novolac
Propylene, chlorinated
Vinyl chloride
Vinyl chloride, chlorinated
Ethylene-co-vinyl Vinyl chloride
acetate-co-unnamed monomer
Ethylene-co-vinyl alcohol Alkyl methacrylate
Amide
Copolyamide
2-Ethylhexyl methacrylate
4-Vinylpyridine
Styrene-co-hexyl methactylate
N-ethyl-3-hydroxymethyl-
carbazoyl methacrylate
2-Ethyl-2-oxazoline
w-Hydroxyalkyl-3,5-dinitrobenzoyl
methacrylate
Acrylic acid
Acrylic acid-co-styrene
Ally1 alcohol-co-styrene
Aramid
Ether sulfone
Hydroxyether of bisphenol-A
(Phenoxy)
Maleimide-co-styrene
Novolac
Sulfone, carboxylated
Microscopy
Microscopy
Single T,; microscopy
Single T,
Single T,; FAIR
Single T,
Single T,
Single T,
Single T,
Single T,; FTIR
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,; FTIR
Optical microscopy;
light scattering
Light scattering, transparency
Single T,; transparency
Single T,
Single T,
Single T,
I had 89.0/3.2/7.8 = ethylene/sulfur
dioxide/vinyl acetate
T,s of I and II were close; semi-
crystalline
6 8 9
II was copolymer of ethylene terephthalate
(40%) and hydroxybenzoic acid (60%)
(Ref. 898) or a segmental block
copolyester (Ref. 1099)
898,
1099
Miscibility arised from trans-
esterification
9 1 2
II had an alkyl group of n-butyl, ethyl,
ethylhexyl or methyl (4 blend systems);
miscibility depended on compositions
of I and II
924
I had 20 wt.% of vinyl acetate; II had
an alkyl group of dodecyl or octyl;
blend had < 30 wt.% II
1033,1095
I had 20 wt.% vinyl acetate; II was
60.2 mol% alkylated
1 2 4 6
I had 28 wt.% vinyl acetate
I had 2 70% vinyl acetate; II had
8.9 mol% hexafluoroacetone
1081
3 3 6
I had 14-50 wt.% vinyl acetate 1 1 3 0
I had 40, 44.3 or 45 wt.% vinyl acetate; 499,500
II had 40 or 50 wt.% Cl
I had 65-75 wt.% vinyl acetate; two 216,222,
Tss when I had 40-45 wt.% vinyl 3 2 5 , 3 3 0 ,
acetate; ambiguous when I had 45-65 452,541,
wt.% vinyl acetate 672,756
Stated that there was a miscible region
when I had 0.4-0.75 mol% ethylene
and II had 0.4-0.8 mol% vinyl
chloride
Semicrystalline; I was du Pont de
Nemours PB3041 (> 60% ethylene)
II had an alkyl group of methyl, n-octyl
or n-decyl (3 miscible blend
systems); I had 21 mol% vinyl alcohol
I had 33 mol% vinyl alcohol; II was
nylon 12 or nylon 6,12 (2 miscible
blend systems)
II had 60 mol% nylon 6 units and 40 mol%
nylon 12 units; I had 59 mol%
vinyl alcohol
I had 68 mol% vinyl alcohol
I had 3-5% acrylic acid; II had 30%
styrene and 5-15% 3-(dimethyl-
amino)-2,2-dimethylpropyl
methacrylate
II had an alkyl group of butyl, hexyl,
pentyl or propyl (4 blend systems)
Formed complexes in water, methanol
or dioxane
II had 74 mol% acrylic acid
II had 4.5 or 6.5 wt.% of hydroxyl group
-
II had 9.5-48.2 mol% maleimide
Formed complexes in methanol or
acetone
II had 2 0.93 degree of carboxylation
7 4 7
41
1 0 5 4
4
909
1 0 4 5
766
694
5 1 7
5 1 7
974
5 3 3
5 9 9
426
188
5 1 7
2 5 4
TABLE 1. contd
Chemically Dissimilar Polymer Pairs VI / 429
Polymer I of Polymer II of Method Comments Refs.
2-Ethyl-6-propyl-
1,Cphenylene ether
2Fluoroethyl methacrylate
p-Vinylphenol
Vinylidene fluoride
Styrene
Alkyl methacrylate
Single T,
Single T,
Single T,
Single T,
3-Fluoropropyl methacrylate Alkyl methacrylate Single T,
Ester Single T,
Glycidyl methacrylate Acrylonitrile-co-styrene
Methyl methacrylate
a-Methylstyrene
Glycidyl methacrylate- Acrylonitrile-co-styrene
co-methyl methacrylate
Glycidyl methacrylate-co-styrene Carbonate of tetramethylbisphenol-A
2,6-Dimethyl- 1,Cphenylene ether
Vinylidene fluoride
Hexadecamethylene dodeca- Vinyl chloride
methylene dicarboxylate
Hexafluoroisopropyl methacrylate Alkyl methacrylate
Hexamethylene adipamide
(nylon 6,6)
Hexamethylene adipate
Hexamethylene isophthalate
Hexamethylene sebacate
Hexamethylene terephthalate
I-Hexene
Hexyl methacrylate
3-Hydroxybutyrate
3-Hydroxybutyrate-co-
3-hydroxyvalerate
Hydroxyether of bisphenol-A
(Phenoxy)
Ethylene terephthalate
Ester
Amide
Vinyl acetate-co-vinylidene chloride
Vinyl bromide
Vinyl chloride
Hydroxyether of bisphenol-A
(Phenoxy)
Vinyl chloride
1-Pentene
Vinyl chloride
Vinyl chloride-co-vinylidene chloride
Cellulose acetate-butyrate
Cellulose acetate-proprionate
Cellulose tributyrate
Epichlorohydrin
Ethylene glycol
Ethylene glycol-co-lactide
Lactide
Methyl methacrylate
Vinyl acetate
Vinyl alcohol
p-Vinylphenol
Vinylidene fluoride
Single T,; transparency
Single T,
Single T,; microscopy
Single T,; microscopy
Single T,; microscopy;
T,,, depression
Single T,
Single T,
Single T,; microscopy
Single T,
Single T,
NMR
Single T,; FTIR
Single T,;
T,-depression
Single T, Acrylonitrile-co-butadiene-co-styrene
Vinyl chloride
2,2-Dichloroethyl methacrylate
2,2-Dichloroethyl methacrylate-co-
methyl methacrylate
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
ITIR; NMR
Single T,; microscopy
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,; transparency
Single T,
Single T,; FTIR
Single Ta; FTIR
Formed complexes in dioxane
>50 wt.% II
II had an alkyl group of methyl or ethyl
(2 miscible blend systems)
II had an alkyl group of methyl or
tetrahydrofurfuryl (2 miscible
blend systems)
II was butylene adipate or 2,2-dimethyl-
1,3-propylene adipate (2 miscible
blend systems)
II had 32.3-58.8 wt.% AN
II had M, 5 4.25 kg/mol
II had M, = 3.5 kg/mol
Miscibility depended on compositions
of I and II
I had 1.6-37.1 wt.% GMA
I had 1.6-18.6 wt.% GMA
I had 5 35.7 wt.% GMA
Semicrystalline
II had an alkyl group of methyl or
ethyl (2 miscible blend systems)
Blends prepared by coprecipitation;
blends prepared by melt blending
showed no sign of hydrogen-bonding
II was butylene sebacate or butylene
succinate (2 miscible blend systems)
Polymer II was nylon 6,5, nylon 6,7,
nylon 6,8 or nylon 6,9 (4 miscible
blend systems)
Semicrystalline; II was Saran C ( 2 80%
vinylidene chloride)
Semicrystalline when 2 50% I
Semicrystalline when > 75% I
Semicrystalline; deposited from some
solvents as two phases
-
Especially when II was polymerized
in situ (Ref. 846); stated as immiscible
in Ref. 812
517,857
2 4 3
1 3 4
1 1 5 3
1 1 5 5
1 1 5 5
1 0 0 7
1 0 0 7
1 0 0 9
1 0 0 7
1 0 0 7
1 0 0 7
1 0 0 9
8 7 2
1 1 5 3
656
925
962
31
1 5 0
872,900
7 3 5
36
1 9 0
812,846,
850
II was Saran ( 2 80% vinylidene chloride) 409,8 12
Semicrystalline 719,933,1183
Semicrystalline 719,1183
Semicrystalline 1 1 8 3
Semicrystalline 987,1183,1201
Semicrystalline 37.4641237
II had 15 wt.% ethylene glycol 1241
923,1079
Blend had 5 20 wt.% I 1103,1183,1189
Semicrystalline 292,465
Blend had a large amount of I 1 2 3 9
- 1 0 4 3
Semicrystalline 407,414
I had 16% hydroxyvalerate 1 8 0
I had 16 or 18% hydroxyvalerate 1 8 0 , 9 5 2
-
1017
II had 5 62 wt.% methyl methacrylate 1 0 1 7
References page VI - 46 1
VI / 430 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Ref s.
Ether sulfone
Ethylene oxide-co-propylene oxide
Methyl methacrylate
Vinyl methyl ether
Vinylpyridine
N-vinylpyrrolidone
Urethane
Hydroxyether of bisphenol-A, N-vinylpyrrolidone
benzoylated
Hydroxyether of bisphenol-A, 2-Vinylpyridine
modified
Hydroxyether of phenolphthalein Butylene terephthalate
Carbonate of bisphenol-A
Ether sulfone
Ethylene glycol
l3-Hydroxyethyl-3,5-dinitro- N-alkyl-3.hydroxymethylcarbazoyl
benzoyl methacrylate methacrylate
N-(2-hydroxyethyl)carbazoyl
methacrylate
2-Hydroxyethyl methacrylate Acrylamide-co-styrene
p-(2.Hydroxy-hexafluoroisopropyl) Butyl acrylate
-a-methylstyrene-co-styrene
Butyl methacrylate
Methyl methacrylate
p-(2.Hydroxy-hexafluoro-
isopropyl)styrene-co-styrene
Methyl methacrylate-co-
2-vinylpyridine
Aramide
Butyl methacrylate
cc,w-Decanedicarboxylic-co-
hexanediamine acid (nylon 6,12)
Hydroxypropyl L-glutamate
Methyl methacrylate
2-Hydroxypropyl methacrylate
Vinyl acetate
Vinyl methyl ether
Vinyl methyl ketone
Tertiary amide
Imide Ether ketone ketone
Ether ketone
Imide
Light scattering
Single T,
Single Tg; NMR
Single T,; IGC
Single T,; FIIR
Single T,; transparency: FIIR
Single T,
Single T,; FTIR
Single T,; FTIR
Single T,
Single T,
Single T,; FAIR
Single T,
Single T,
Single T,
Single T,; NRET
Single T,
Single T,
Single T,
Single T,
Single T,; transparency
Single T,; NRET
Single T,
Single T,; light scattering;
microscopy
Single Tg; transparency;
NMR; FTIR; WAXD;
NRET
Single T,; transparency
Single T,; transparency
Transparency
Single T,; FTIR
Single T,
Single T,
X-ray diffraction
-
II had 2 22 mol%
ethylene oxide
714
1025
II was atactic, isotactic or syndiotactic 112,218,
775,910
-
II was 2- or 4-vinylpyridine
(2 miscible blend systems)
690,819,820,996
9 8 1
1253
II was made from l/1/2 = polycapro- 7 3 0
lactone diol (M, = 2.1 kg/mol)/
1,4-butanedioV4,4-diphenylmethane
diisocyanate
- 1002
OH groups in I was converted to benzoate, 9 8 9
acetate or methoxy group
- 3 1 0
- 3 1 0
- 3 0 6
- 3 0 9
II had an alkyl group of butyl, decyl, 6 9 3
dodecyl, ethyl, hexadecyl, hexyl,
methyl, octyl or tetradecyl (9 miscible
blend systems)
- 6 9 3
II had 40, 47 or 52 mol% acrylamide 955.1248
I had > 1.2 mol% OH-containing 9 0
monomer
I had > 2.8 mol% OH-containing
monomer
1 1 6 6
I had 2 1.9 mol% OH-containing
monomer
9 0
I, had 2 6 mol% OH-containing monomer 3 7 7
I had 60 mol% styrene; two T,s when
I had 83 mol% styrene; II was
iminotrimethylhexamethylene-
iminoterephthaloyl
571,646
I had >l mol% OH-containing
monomer; formed complexes when I
had 18 mol% OH
Semicrystalline
1 1 6 6
454
Blend had ~50 ~01% II 971
I had > 8 mol% OH; formed complexes 57 1,646,
when I had 24 mol% OH; II was 1021,l 116,
isotactic or syndiotactic 1117,1241
(Ref. 1116,1117)
I had 90.3 mol% styrene 5 7 1 , 6 4 6
I had 83.3-99.9 mol% styrene 571,572,646
I had 90.3 mol% styrene 561
Formed complexes; II was dimethyl- 9 7 5
acrylamide, N-methyl-N-vinylacetamide
or ethyloxazoline (3 blend systems)
I was made from pyromellitic dianhydride 1179
(PMDA) and 4,4-bis(3-aminophenoxy)
biphenyl
I was the same as the previous system; II
was Victrex 220P; blend had
5 50 wt.% I
1179
I was made from PMDA and
oxydianiline; II was made from
391
TABLE 1. contd
Chemically Dissimilar Polymer Pairs
Polymer I of Polymer II of Method Comments Refs.
Imide
Imide
Imide
Imide
Imide
Imide
Imide
Imide
Imide
Imide
Imide
2-Iodoetbyl methacrylate Acrylonitrile-co-p-methylstyrene
Acrylonitrile-co-styrene
Ester
cis-Isoprene
lsoprene, chlorinated
lsoprene, modified by
hexafluoroisopropanol group
Tetrahydrofurfuryl methacrylate
Butadiene-co- 1,2-vinylbutadiene
cis-Pentenamer
Vinylethylene
Ethylene-co-vinyl acetate
Alkyl methacrylate
Ethylene-co-methyl acrylate
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,; WADX; SAXS
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,; NMR
Single Tg; transparency
Single T,; FTIR
Single T,; FTIR
PMDA and p-phenylenediamine;
~90% II in blend
I was made from 2,2-bis(3,4-dicarboxy-
phenyl)hexatluoro-propane dianhydride
(6FDA) and 2,2-bis(3-aminophenyl)
hexafluoropropane (3,3-6F-diamine);
II was made from 6FDA and 2,2-bis
(4.aminophenyl)hexafluoropropane
(4,4-6F-diamine)
I was made from 4,4-biphthalic anhydride
(BPDA) and 3,3-6F-diamine; II was
made from BPDA and 4,4-6F-diamine
I was made from 3,34,4-benzophenone-
tetracarboxylic dianhydride (BTDA)
and 3,3-6F-diamine; Il was made
from BTDA and 4.4.6F-
diamine
I was made from 3,3,4,4-diphenyl-
ethercarboxylic dianhydride (OPDA)
and 3,3-6F-diamine; Il was made from
OPDA and 4,4-6F-diamine
I was made from PMDA/BPDA/
3,3-6F-diamine = 25 125150; II was
made from PMDA/BPDA/4,4-6F-
diamine = 25/25/50
I was made from PMDA/BTDA/3,3-
6F-diamine = 25125150; II was made
from PMDA/E3TDA/4,4-6F-
diamine = 25 / 25150
I was made from PMDA/OPDA/
3,3-6F-diamine = 25/25/50; II was made
from PMDA/BTDA/4,4-6F-
diamine = 25 f 25150
I was made from 3,3,4,4-diphenyltetra-
carboxylic dianhydride (DBTA) and
oxydianiline (DOA); II was made
from 4,4-thiodiphthalic anhydride
and ODA
I was made from DBTA and 3,3-hexa-
fluoroisopropylidene dianiline
(3,3-HIPD); II was made from DPTA
and 4,4-hexafluoroisopropylidene
dianiline (4,4-HlPD)
I was made from 5,5-[2,2,2trifluoro-
I-(trifluoromethyl)ethylidene]
bis- 1,3-isobenzofuranedione (A) and
HIPD; II was made from A and
4,4-HIPD
I was made from BTDA and 3,3-HIPD;
II was made from BTDA and
4,4-HIPD
II had 21-42 wt.% AN
II had 13-51 wt.% AN
II was butylene adipate, caprolactone,
2,2-dimethyl-1,3-propylene adipate
or hexamethylene sebacate (4 miscible
blend systems)
II had > 32.3% vinylbutadiene
-
1 3 0
1 3 0
1 3 0
1 3 0
1 3 0
130
1 3 0
1244
957
951
951
1 1 0 6
1 1 0 6
1111
1 1 0 7
420
17
II had 86% 1,2-butadiene 570,697,700,810,811
Semicrystalline; commercial samples 503,665
II had an alkyl group of methyl or 959
n-butyl (2 miscible blend systems)
II had 40 or 75 wt.% methyl acrylate 959
References page VI - 461
VI / 432 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Ref s.
Ethylene-co-methyl methacrylate
Ethylene-co-vinyl acetate
Methyl acrylate
Methyl acrylate-co-styrene
Isoprene-srut-N-(2-hydroxyethyl) Styrene-stut-N-itaconimidyl-
carbazole methacrylate 3.5dinitrobenzoate
Isoprene-b-methyl methacrylate
lsopropenyl methyl ketone
Isopropyl acrylate
Maleic acid-co-styrene
Maleic anhydride-alt-
cc-methylstyrene
Maleic anhydride-co-styrene
Acrylonitrile-co-styrene
p-(2-Hydroxy-hexafluoroisopropyl)-
a-methylstyrene-co-styrene
p-Vinylphenol
Isopropyl methacrylate
Vinyl butyral
2,6-Dimethyl- 1,4-phenylene ether,
sulfonylated
Caprolactone
Carbonate of tetramethylbisphenol-A Single T,
2,6-Dimethyl-1,4-phenylene ether Single T,
Maleimide-air-a-methylstyrene
Methacrylate, liquid crystalline
2,6-Dimethyl- 1,4-phenylene ether,
sulfonylated
Ethyl methacrylate
Methyl methacrylate
n-Propyl methacrylate
Vinyl methyl ether
2,6-Dimethyl-1,4-phenylene ether,
sulfonylated
Methacrylate, liquid crystalline
Methacrylic acid-co-cc- Butyl methacrylate-co-
methylstyrene 4-vinylpyridine
Methacrylic acid-co-styrene
Methacryloyl glycine-co-styrene Ethyl methacrylate Fluorescence study
Methacrylonitrile-co-
cc-methylstyrene
Methacrylonitrile-co-
p-methylstyrene
Vinyl chloride Single T,
n-Butyl methacrylate Single T,
Ethyl methactylate Single T,
Methyl methacrylate Single T,
Isopropyl methacrylate Single T,
Methacrylonitrile-co-styrene
Ethyl methacrylate-co-
4-vinylpyridine
Methyl methacrylate-co-
4-vinylpyridine
Ethyl methacrylate
n-Propyl methacrylate
t-Butyl methacrylate-co-
methyl methacrylate
Cyclohexyl methacrylate-co-
methyl methacrylate
Ethyl methacrylate
Methyl methacrylate
Single T,: FTIR
Single T,; FTIR
Single T,; FTIR
Single Ts; FTIR
Single T,
Single T,
microscopy
Single T,; NMR; FTIR
Single T,; transparency
Transparency
Single T,
Single T,
Single T,
Single T,
Single T,; NMR; FAIR
Single T,
Single T,
Single T,
Single Ts; microscopy
Single T,; FTIR
Single T,; FTIR
Single T,; FTIR
Single T,; fluorescence study
Single T,
Single T,
Single T,
Single T,
Single T,; transparency;
II had 50 wt.% methyl methacrylate
II had 35 or 70 wt.% vinyl acetate
-
II had 28 wt.% methylacrylate
Polymer had at least 20 mol% of
electron-donor or electron-acceptor
grow
9 5 9
9 5 9
9 5 9
959
9 6 3
II had 22 wt.% acrylonitrile 1 0 4 9
II had 2 1.6 mol% OH groups 1 2 5 4
I was Daidou Kogyo Styrite HS-2
II had < 55 mol% sulfonylation
1035
4 5 3
452
8 3 8
I had 14 or 25 wt.% maleic anhydride;
semicrystalline
192
I had < 12% maleic anhydride
I had < 10% maleic
anhydride
1008
1008
I was alternating copolymer and had
< 55 mol% sulfonylation
I had O-33 wt.% maleic anhydride
I had 8-33 wt.% maleic anhydride
I had 0- 18.1 wt.% maleic anhydride
I had 4.7 wt.% maleic anhydride
Depended on degree of sulfonylation
of II
8 3 8
73
7 3 , 9 9 9
73
8 6 2
8 3 7
I had electron-donating (carbazolyl
methylene)aniline groups; II had
electron-accepting groups
I had 50.6 mol% methacrylic acid (MA);
II had 18 or 26 mol% vinylpyridine
(VP)
1 0 7 7
1131
I had 50.6 mol% MA; II had 23
mol% VP
1131
I had 50.6 mol% MA; II had 8
mol% VP
1131
Miscible when cast from toluene or
dioxane; immiscible when cast from
chloroform; I had 93.4-96.7
mol% styrene
103
Miscible when cast from toluene;
immiscible when cast from chloroform:
I had 93.8-97.2 mol% styrene
I was azeotropic
103
4 2 3
II had 12-28 wt.% of methactylonitrile
(MAN)
944
II had 12-55 wt.% MAN
II had 19-70 wt.% MAN
I had 19-34 wt.% MAN when II had
M, = 161 kg/mol; I had 16-34 wt.%
MAN when II had M, = 41.6 kg/mol
I had 12-43 wt.% MAN
Miscibility depended on composition
of I and II
944
944
944
9 4 4
1 1 3 9
Miscibility depended on composition
of I and II
1 1 3 9
I had 4.5-44 wt.% methacrylonitrile
(MAN)
9 4 3
Miscibility range varied in various 970,986,
fluorescence spectroscopy studies 1018,
especially at the low MAN end 1 1 3 9
TABLE 1. contd
Chemi cal l y Di ssi mi l ar Pol ymer Pai rs VI 1433
Polymer I of Polymer II of Method Comments Refs.
Isopropyl methacrylate Single T,; transparency
n-Propyl methacrylate
4-[[6-(Methacryloyloxy)hexyl]- 4-[[6-(Methacryloyloxy)hexyl]
oxyl-N-[(9-methyl-2-carbazolyl) oxy]-N-(4-nitrobenzylidene)
methylenelaniline aniline
4-[ [ l -[4(-Methoxyphenyl)azo] 4-[[l-[(4-cyanobiphenyl)-4)oxy]-
phenyll-4-oxy]-3-propyl] 3-propylloxylstyrene
oxylstyrene
p-Methoxystyrene-co-p-vinyl- Alkyl acrylate
phenol
Methyl acrylate
Vinyl acetate Single T,; FTIR
Epichlorohydrin Single T,
Epichlorohydrin-co-ethylene glycol Single T,
Ethylene glycol
Nitrocellulose
Vinyl acetate
Single T,
Single T,
Single T,; transparency;
NMR
Vinyl chloride-co-vinylidene chloride Single T,; transparency
Vinylidene fluoride
Methyl acryl,ate-co-vinylcarbazole Methyl methacrylate-co-2(3,5-
dinitrobenzoyl)oxyethyl
methacrylate
Styrene-co-2(3,5dinitrobenzoyl)
oxyethyl methacrylate
Methyl l-bicyclobutane- Acrylonitrile-co-styrene
carboxylate
Ethylene glycol
2-Methyl-6-ethyl- 1,4-phenylene Styrene
ether
a-Methyl-a-ethyl-P-propiolactone Vinyl chloride
Methyl methacrylate Acrylonitrile-co-methyl
methacrylate-co-styrene
4.[[2-(Acryloyloxy)ethyl]-
ethylamino]-4-nitroazobenzene
4.[[2-(Acryloyloxy)ethyl]-
ethylamino]-4-chloro+nitro-
azobenzene
p-rerr-Butylphenol-co-formaldehyde
Carbon monoxide-&-propylene
Carbonate
Carbonate of bisphenol chloral
Copolycarbonate of bisphenol-A
and hexafluorobisphenol-A
p-Chlorophenol-co-formaldehyde
Epichlorohydrin-co-ethylene glycol
Ethyl acrylate
Ethyl methacrylate
Formaldehyde-co-p-nitrophenol
Formaldehyde-co-phenol
Hexafluoroacetone-co-vinylidene
fluoride
Single T,; transparency
Single T,
Single T,
Single T,; FTIR
Single T,; transparent melt
Single T,
Single T,
Single T,; transparency
Single T,; transparency
Single T,
Single T,
Single T,
Single T,; NMR
Single T,; NMR
Single T,; FTIR; WAXD
Single T,; FTIR; NMR
Single T,; transparency
Single T,; NMR
Single T,; transparency
Single T,; FTIR
Single T,
Single T,
Single T,
Single T,; FTIR
Single T,; FTIR
Single T,
I had 12-38 wt.% MAN when II had
M, = 161 kg/mol; I had 8-43 wt.%
MAN when II had M, = 41.6 kg/mol
I had 2-32 wt.% MAN
Polymer I and polymer II were liquid
crystalline
9 4 3
9 4 3
1 0 7 6
Blend showed liquid crystallinity 1 0 4 2
II had an alkyl group of methyl or ethyl
(2 miscible blend systems); I had
33-63 mol% vinylphenol
I had 33-63 mol% vinylphenol
1 1 7 7
1 1 7 7
226
I had 50 mol% epichlorohydrin 226
(Hydrin 200)
-
226
-
416
Probably formed two phases when 453,601,615
deposited from some solvents 1 1 9 6
(Refs. 601)
II was Saran ( 2 80% vinylidene chloride); 812,870
I had MW = 1.0 kg/mol; two T,s
when I had MW = 576 kg/mol in
Ref. 870
Semicrystalline 844,1122
Both I and II had > 27 mol% monomer 705
with interactive groups
Both I and II had > 12 mol%
monomer with interactive groups
II had 24-38 wt.% acrylonitrile
5 20 wt.% II
-
Semicrystalline when blend had 75% I
II had 40/39.1/20.9 or 61.1/19.6/19.3 =
styrene/methyl methacrylatel
acrylonitrile
-
-
1 7 3
202
202
1 3 4
3 3
620
1 2 2 8
1 2 2 8
-
647.1056
-
1 2 2 9
II was carbonate of bisphenol-F or 426
bisphenol-AF (2 miscible blend
systems)
-
110.426,673,983
II had 4.5-14.0 wt.% hexafluoro- 430
bisphenol-A
647
-
224
-
1 5 6
Made from slurries of polyethyl 763
methacrylate and methyl methacrylate;
inherently unstable, phase separation
upon heating
-
647
-
647
-
443
References page VI - 46 1
VI / 434 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Ref s.
N-Maleimide-co-styrene
Methoxymethyl methacrylate
Methyl acrylate
cc-Methylstyrene
Nitrocellulose
Novolac
Propylene glycol
Tetrafluoroethylene-co-vinylidene
fluoride
Trifluoroethylene-co-vinylidene
fluoride
Vinyl acetate
Vinyl acetate-co-vinyl chloride
Vinyl chloride
Vinyl chloride, chlorinated
Vinyl chloride-co-vinylidene chloride
Vinyl chloroacetate
Vinylidene fluoride
Methyl methacrylate, imidized Acrylonitrile-co-styrene
Methyl methacrylate-co-styrene
Methyl methacrylate-co-
vinylpyridine
2.Methyl-2-oxazoline
2-Methyl- I-pentene sulfone
Vinyl chloridg
Copolycarbonate of bisphenol-A
and tetramethylbisphenol-A
Copolycarbonate of hexafluoro-
bisphenol-A and tetramethyl-
bisphenol-A
Acrylic acid-co-butyl acrylate
Ally1 alcohol-co-styrene
Hydroxyether of bisphenol-A
2-Hydroxypropyl methacrylate
Vinyl alcohol
Vinyl chloride
Vinyl fluoride
p-Vinylphenol
Novolac
Single T,; FTIR
Single Ts
Single T,
Single T,
No phase separation in
solution or films
Single T,; FTIR
Single T,; SAXS
Single Ts; T,-depression
Light scattering: FTIR;
T,-depression
Single Ts; FTIR; LS;
microscopy
Single T,; transparency
Single T,; transparency
Single T,; FTIR
Single T,; transparency
Single T,
Single T,; NMR
Single Ts
1
Single Ts
Single T,; transparency
Single Ts
Single T,; FTIR
Single T,; FTIR
Single T,; FTIR
Single T,; FTIR
Single T,; FTIR
Single T,
Single T,
Single T,; FTIR
Single T,
II had 8, 14 or 21 wt.% N-maleimide 1213
264
-
156
-
167, 765
199, 296, 452, 651
II had MW about 1.0 kg/m01 and was 221,434,473
formaldehyde and 13/17/70 mol% =
p-rert-butylphenollm-cresol/o-cresol or
formaldehyde and 15/17/68 mol% =
2-r-butylphenoUm-cresol/o-cresol; I
was isotactic, atactic or syndiotactic
I had MW = 550 kg/mol; II had MW = 521
1 .O-3.9 kg/mol
II had 80 mol% vinylidene fluoride 113,324
II had 58 or 75 mol% vinylidene
fluoride
713,1066
Miscible when cast from chloroform or 302, 602,
cyclohexanone; immiscible when cast 726, 777,
from tetrahydrofuran or melt blended 778, 928,
1092
II had 5.9- 15.1 ~01% vinyl acetate 236, 296, 452,
497, 651
Especially when II was polymerized 66, 338, 368,
in siru (Ref. 846); I of all tacticities 641,642,653,
miscible with II (Ref. 338); increase 812,846,850,
in isotactic content and mol. wt. of I 892,893,895
reduced miscibility with II (Ref. 893)
II had 63-68 wt.% Cl; I was atactic, 506,833,1204
isotactic of syndiotactic (1204)
II was Saran (> 80% vinylidene chloride) 4 0 9 , 5 0 6 ,
or 86.5 wt.% vinylidene chloride; 8 1 2 , 8 7 0
semicrystalline when 2 20% II and I
was isotactic, and when 2 75% II and
I was atactic for the second II
-
179
Semicrystalline when > 35-65% II; I 124,293,
was isotactic, atactic or syndiotactic 320,342,361,
569,618,630,
643, 644, 696
I had 53-91 wt.% imidized units; II had 230,1123
5.7-33 wt.% acrylonitrile; miscibility
depended on extent of imidization
of I and acrylonitrile content of II
I had 53-85 wt.% imidized units 230
I had 5 33 wt.% methyl methacrylate; 431
II had < 15 wt.% bisphenol-A
I had 9, 20 or 33 wt.% methyl methacrylate; 1194
II had 20 wt.% hexafluorobisphenol-A
I had 13-20 mol% vinylpyridine; II had
13- 20 mol% acrylic acid
II had 6.5 wt.% OH group
385
978
978
-
-
I ~50 wt.% in blend
I ~50 wt.% in blend
978
913
442
442
978
II had MW = 1.0 kg/mol and was form- 221
aldehyde and 13/17/70 mol% =p-rert-butyl-
phenolltn-cresoho-cresol or formaldehyde
and 15/17/68 mol% = 2-terr-butylphenoll
m-cresollo-cresol
TABLE 1. contd
Chemically Dissimilar Polymer Pairs
Polymer I of Polymer II of Method Comments Refs.
2-Methyl-h-propyl- 1,
4-phenylene ether
a-Methyl-cc-n-propyl-
P-propiolactone
a-Methylstyrene
Styrene
Vinyl chloride
Alkyl methacrylate
p-Methylstyrene
cc-Methylstyrene-co-
4-(2.hydroxyethyl)
a-methylstyrene
cc-Methylstyrene-co-[4-( 1 , 1 , 1
trifluoro-2-hydroxyethyl)-
wmethylstyrene
N-Methyl-N-vinylacetamide
Monomethyl itaconate
Natural rubber, epoxidized
Cyclohexyl acrylate
Cyclohexyl acrylate
Cyclohexyl methacrylate
2,6-Dimethyl-1,4-phenylene ether,
bromobenzylated
Alkyl acrylate
Alkyl methacrylate
Dialkyl itaconate
Vinyl acetate
4-Vinylpyridine
N-Vinyl pyrrolidone
Alkyl acrylate
Alkyl methacrylate
Dialkyl itaconate
Vinyl acetate
4-Vinylpyridine
N-Vinyl pyrrplidone
Ally1 alcohol-co-styrene
Thiocarboate
Acrylic acid-co-ethylene
Alkyl acrylate-co-vinylidene chloride
Chloroprene
Ethylene, chlorinated
Ethylene, chlorosulfonated
Novolac
Propylene, chlorinated
Single T,
Single T,; transparency
Single T,; transparency
Single TB; transparency
Single T,; transparency
Single T,; transparency
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,; FTIR
Single T,
Single T,
^
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Vinyl chloride
Vinyl chloride, plasticized
Single T,
Single T,
1 3 4
Semicrystalline when > 50% I 32,33
II had an alkyl group of cyclohexyl, ethyl 1 1 6 , 7 6 5
or n-propyl (3 miscible blend
systems)
-
7 6 5
-
765
-
1 1 6 , 7 6 5
II had 9, 16 or 37% bromination 2 6 1
I had 6, 41, 72 or 89 mol% u-methyl- 968
styrene; II had an alkyl group of
ethyl, ret--butyl or methyl (3 blend systems)
I had 6, 41, 72 or 89 mol% 968
c1- methylstyrene; II had an alkyl group
of ethyl, terr-butyl or methyl (3 blend systems)
I had 6, 41, 72, or 89 mol%
cc-methylstyrene; II had a dialkyl group
of dimethyl, diethyl, di-tert-butyl or
di-n-propyl (4 blend systems)
I had 6, 41, 72 or 89 mol%
a-methylstyrene
I had 6, 41, 72 or 89 mol%
cc-methylstyrene
I had 6, 41, 72 or 89 mol%
a-methylstyrene
I had 23, 47, 60, 84 or 93 mol% cr-methyl-
styrene; II had an alkyl group of methyl,
ethyl or terr-butyl (3 blend systems)
I had 23, 47, 60, 84 or 93 mol%
cc-methylstyrene; II had an alkyl group
of methyl, ethyl or cerr-butyl
(3 blend systems)
I had 23, 47, 60, 84 or 93 mol%
a-methylstyrene; II had a dialkyl
group of dimethyl, diethyl, di-n-propyl
or di-tert-butyl (4 blend systems)
I had 23, 47, 60, 84 or 93 mol%
cc-methylstyrene
I had 23, 47, 60, 84 or 93 mol%
a-tqethylstyrene
I had 23, 47, 60, 84 or 93 mol%
a-methylstyrene
II had 4.5 or 6.5 wt.% OH group; formed
complexes in 2-butanone
II had methyl, ethyl or propyl side
groups
I had 50 mol% epoxidation; II had
6 mol% acrylic acid; blend had >50
wt.% II
I had 50 mol% epoxidation; II had 10%
alkyl acrylate
I had 50 mol% epoxidation
I had 50 mol% epoxidation; II had 25
or 48% Cl
I had 25 mol% epoxidation; II was
Hypalon 40
I had 50 mol% epoxidation
968
969
969
969
968
968
968
969
969
969
973
669
1 1 3 4
400
1 0 6 5
543
590
4 0 1
I had 50 mol% epoxidation
I had 5 0 mol% epoxidation
I had 50 mol% epoxidation; II had
40 phr dioctyl phthalate
400
507,827,828
826
References page VI - 46 1
VI 1436 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Refs.
Neopentyl glycol adipate
(2.2.dimethyl-l&propylene
adipate)
Neopentyl glycol succinate
(2,2-dimethyl-1,3-propylene
succinate)
Nitrocellulose
Novolac
Phenolphthalein
polyether ether ketone
Phenolphthalein
polyether ether sulfone
Phenol-formaldehyde
Phenyl acrylate
Phenylene, sulfonated
p-Phenylene benzobisoxazole
2.2~(m-Phenylene)-
5,5 -bibenzimidazole
Hydroxyether of bisphenoi-A
(Phenoxy)
Single T,; transparency
Vinyl acetate-co-vinyl chloride Single T,; transparency
Vinyl chloride Single T,; transparency
Vinyl chloride-co-vinylidene chloride Single T,
Vinylidene fluoride
Epichlorohydrin
Clear melt although refractive
indices very different;
T,-depression
Single T,; transparency
Hydroxyether of bisphenol-A Single T,; transparency
(phenoxy)
Vi nyl chl or i de . Single T,; transparency
Vinyl chloride-co-vinylidene chloride Single T,
Single T,; FTIR
Vinyl acetate Single T,; clear films
n-Butyl methacrylate Single T,; FTIR
Vinyl acetate Single T,
Vinyl methyl ether Single T,
Epoxy
Single T,
Hydroxyether of bisphenol-A
WenoW
Sulfone
N-Vinylpyrrolidone
N-Vinylpyrrolidone
Single T,
Single T,
Single T,
Single T,
N,N-Dimethylacrylamide Single T,
Methyl methacrylate-co-styrene
Vinyl benzoate
Ethyl acrylate-co-4-vinylpyridine
Amide
5.
Amide
. 1
Arylate
Single T,
Single T,; transparency
Single T,
Single T,; dielectric
measurements; WAXS;
LS
4
Single T,; microscopy;
dielectric measurements
Single T,
Carbonate of bisphenol-A
Imide
FTIR
Single T,; FTIR
Imide
Imide
Imide Single T,; FTIR
Single T,; FTIR
Single T,; FTIR
- 3 3 2
II had 2 or 17 wt.% vinyl acetate 276
277
Semicrystalline; II was Saran (86.5 wt.%
vinylidene chloride)
Semicrystalline
8 6 8
2 8 7
- 2 2 3
Semicrystalline 5 20 wt.% II 3 3 2
9 0 0
5 60 wt.% I; possible second T, when 8 6 8
>60 wt.% I; semicrystalline
I had 12.62 or 13.42% N; II was 3 9 3
butylene adipate, caprolactone,
ethylene adipate or valerolactone
(4 miscible blend systems)
236,42 1,452
-
I had MW about 1.0 kg/mol and was
formaldehyde and 15/17/68 mol% =
2-tert-butylphenollm-cresoho-cresol
I had MW about 1.0 kglmol and was
formaldehyde and 13, 17/70 mol% =
p-terr-butylphenobm-cresol/o-cresol
Formed complexes from acetone, dioxane
and ethyl acetate
II had > 20 wt.% methyl methacrylate
-
II was Zjtel 330 (Du Pont)
II was nylon-6,6; semicrystalline 1084
-
II was made from 3,3,4,4-benzo-
phenonetetracarboxylic dianhydride
and 3,3-diaminobenzophenone
(LARC TPI)
4 3 4
221
221
3 1 2
3 0 8 , 3 1 2
3 0 8 , 3 1 1
307
307
881
4 3 3
535
5 9 2
945
125
594
299
II was 2,2-bis(3,4-dicarboxy- 507,509,748,
phenoxy)phenylpropane-2-phenylene 823
bisimide(Ultem 1000)
II was made from 3,3,4,4-benzophenone- 115,507,
tetracarboxylic dianhydride and 748
5,6-amino-1-(4-aminophenyl)-1,3,3-
trimethylindam (XU 218)
11 was made from benzophenone- 507,781
tetracarboxylic dianhydride and 4/ 1
mixture of 2,4-toluenediisocyanate
TABLE 1. cont ' d
Chemi cal l y Di ssi mi l ar Pol ymer Pai rs
Polymer I of Polymer II of Method Comments Refs.
m-Phenylene isophthalamide
Phenylene sulfide
p-Phenylene terephthalamide
n-Propyl acrylate
n-Propyl methacrylate
Propyloxazoline
Propylene
Propylene, chlorinated
Rubber, chlorinated
St yr e ne
Styrene, sulfonated
Imide sulfone Single T,; FTIR
Imide sulfone, fluorinated Single T,; FTIR
Siloxaneimide, segmental copolymer Single loss tangent peak
Aramide Single T,
HexamethyleneGophthalamide
Heptamethylene isophthalamide
m-Xylene adipamide
Phenylene sulfide ether
Amide
p-Phenylene 1,3,4-oxadizole
Vinyl chloride
Vinyl chloride
Vinyl chloride-co-vinylidene chloride
Single T,
Single T,
Single T,
Single T,
Single T,; FTIR
Miscroscopy; FTIR
Single T,; transparency
Single T,; transparency
Single T,; transparency
Styrene Single T,
Hydrogenated oligocyclopentadiene Melting point depression;
WAXS; SANS
2,2-Dimethyl- 1,3-propylene adipate Single T,; transparency
Vinyl methyl ether Phase diagram
Carbonate of tetramethylbisphenol-A Single T,; light scattering;
NMR; PALS
2-Chlorostyrene Negative volume change
of mixing
Copolycarbonate of bisphenol-A Single T,; transparency
and tetramethylbisphenol-A
Cyclohexyl acrylate Single T,
Cyclohexyl methacrylate Single T,; transparency
Cyclohexyl methacrylate-co-methyl Single T,
methacrylate
2,6-Dimethyl-1,4-phenylene ether, Single T,
bromobenzqlated
2,6-Dimethyl-1,4-pbenylene Single T,
-.
ether, sulf8nated
2,6-Dimethyl-1,4-phenylene ether-co- Single T,
2,3,6-trimethyl-1,4-phenylene oxide
Ethyl methacrylate Single T,
o-Fluorostyrene-co-p-fluorostyrene Single T,
cc-Methylstyrene Single T,
n-Propyl methacrylate Single T,
Vinyl methyl ether Single T,; transparency;
NMR; attenuated total
reflectance IR
Vinyl methyl ether Single T,
Vinyl methyl ether SANS; NMR
Alkylene glycol FTIR
amine-terminated
NjV-Dimethylacrylamide Transparency; NMR
2,6-Dimethyl- 1,4-phenylene ether Single T,
10,12-Docosadiynylene diisonicotinate Single T,; FTIR
Ethylene oxide Single T,
and 4,4-diphenylmethanediiso-
cyanate(P1 2080)
II was made from 3,3,4,4-benzophenone- 105,369,
tetracarboxylic dianhydtide and 492
3,3-diaminodiphenyl sulfone
>_80%1 369
II was 3,3,4,4-benzophenone-tetra- 1 0 5
carboxylic dianhydride and 3,3 -diamino-
diphenylsulfone based polyimide and
dimethylsiloxane segmental
copolymer
II was a copolyamide of 1,6-hexane- 993
diamine, caprolactam and terephthalic
acid (BASF Ultramid T) or Selar 3426
(Du Pont) (2 blend systems)
Semicrystalline 81,993
Semicrystalline 81
Semicrystalline 993
Semicrystalline 926
Semicrystalline; II was nylon 6 or 477
nylon 6,6 (2 miscible blend systems)
-
1080
-
8.50
-
319,649,812,850
Semicrystalline when 2 65% II; II was 409,812,
Saran ( 2 80% vinylidene chloride) 870
or 86.6 wt.% vinylidene chloride
~25 wt.% I in blend 442
-
550
I had 67 wt.% Cl 287
250
Semicrystalline after long annealing 3 16,359,428,
741,1100,1230,1231
-
814
II had 2 85 wt.% tetramethylbis- 4 3 1
phenol-A
-
765
-
116,621,765
II had 2 21.6% cyclohexyl meth- 6 2 1
acrylate
II had :I 76% bromination 259
II had < 1.9% sulfonation 3 4 5
I was atactic or isotactic; II had < 20 638
mol% 2,3,6-trimethyl-1,4-phenylene oxide
Miscible when melt blended 7 2
II had 10 or 23 mol% p-fluorostyrene 1 1 4 4
710,722,822,865,875
Miscible when melt blended 7 2
Two phases when deposited from 43,44,62,126,475,
some solven+s 565,616,964
I was syndiotactic; blend had ~20 954
wt.% I
I was atactic or isotactic 915,918,1199
I had 4.5 mol% sulfonation; II 246
had M, = 0.9 kg/m01 (Jeffamine ED-900)
I had 12 mol% sulfonation 487,1064
I had < 2.6% sulfonation 3 4 5
I had 9 mol% sulfonation 990,991
I had 1.35 or 4.51 mol% SOsH; II 8 6 1
end-capped with propylamine groups
References page VI - 461
VI / 438 MISCIBLE POLYMERS
TABLE 1. cont d
Polymer I of Polymer II of Method Comments Refs.
Styrene, sulfonated and
metal-neutralized
Styrene-co-styrene-
4.carboxylic acid
Styrene-co-4-vinylbenzene
phosphonic acid
Styrene-co-4-vinylbenzoic acid,
K-neutralized
Styrene-co-4-vinylbenzoic acid,
triethylammonium ionomer
Styrene-co-4-vinylphenyl-
dimethylsilanol
Bis[2-[2-(2-methoxyethoxy)ethoxy]
ethyl itaconate
Methyl methacrylate
Methyl methacrylate-co-
4-vinylpyridine
Urethane
Amide
Amide
Amide
Amide
Amide
Ethyl acrylate-co-4-vinylpyridine
N,N-Dimethylacrylamide
Methyl methacrylate
Styrene-co&vinylbenzene
phosphonic acid diethyl ester
5,7-Dodecadiyne-1,12-dicarboxylic
acid, K-neutralized
5JDodecadiyne- 1,12-dicarboxylic
acid, triethylammonium ionomer
n-Butyl methacrylate
N-Vinyl-2-pyrrolidone
Styrene-co-p-vinylphenol Bis[2-[2+methoxyethoxy)
ethoxylethyl] itaconate
n-Butyl methacrylate
Caprolactone
NJ-Dimethylacrylamide
Ethyl methacrylate
n-Hexyl methwrylate
Methyl methacrylate
. <
Styrene-co-4-vinylpyridine
Vinyl butyl ether
4-Vinylpyridine
Isoprene, sulfonated
N,N-Sulfa-p-phenylene Vinyl alcohol
terephthalamide
4-Vinylpyridine
N-Vinylpyrrolidone
Sulfone of hexafluorobisphenol-A Methyl methacrylate
Sulfone of tetramethylbisphenol-A Acrylonitrile-co-a-methylstyrene
Acrylonitrile-co-styrene
Single T,; FTIR I had 14 mol% sulfonation 1086
Single T,; transparency I had 12 mol% sulfonation 4 8 7
NMR I had 9.9% sulfonation; II had 11.1% 6 0 4
vinylpyridine
FTIR I had 7.9 mol% sulfonation 801
Single T,; FTIR; SAXS I was lightly sulfonated and Mg- or 1038
Mn-neutralized; II was nylon 6
Single T,; FITR; SAXS I had 9.7 mol% sulfonation and Li- 1138
neutralized; II was nylon 4
Single T, I had 9.8 mol% sulfonation and Li- 1135
neutralized; II was nylon 6,6 or nylon
6,lO (2 blend systems)
Single T,; FTIR; SAXS I had 5.4 or 9.8 mol% sulfonation and 1168,1223
Li-neutralized; II was nylon 6
Single T,; NMR; FTIR; SAXS I had 6.5-9.0 mol% sulfonation and 1083,1223
FTIR
Zn-neutralized; II was nylon 6
I had 2.1-7.3 mol% sulfonation and
Zn-neutralized; II had 2.4- 10.6 mol%
1 1 7 6
Single T,; transparency
Single T,; transparency
Single T,
Single T,
Single T,; FTIR
Single T,; FTIR
Single T,; FTIR
Single T,; FTIR
Transparency; FTIR;
fluorescence study
Single T,
Transparency; FTIR;
single T,; NMR
Transparency; fluorescence
s t u d y
FTIR; LS
Single T,; transparency;
fluorescence study; ^
FTIR; NMR
F T I R
Single T,
Single T,; transparency
Single T,
Single T,
NMR
Single T,
Single T,
Single T,
vinylpyridine
I had 25 or 54 mol% acid groups 4 8 7
I had 25 mol% acid units
Both I and II had 7.5 or 13.3 mol%
4 8 7
1250
phosphorus moiety
I had 26 mol% acid group 9 9 0
I had 26 mol% acid group
I had 9-34 mol% silanol group
990,991
1112,1114
I had 2 4 mol% silanol group; formed
complex when II had > 34 mol%
silanol group
II had 22 mol% vinylphenol
I had 8, 25, 43 or 75 wt.% vinylphenol
I had 10-20.4 wt.% vinylphenol
1 had 22, 42 or 82 mol% vinylphenol
I had >0.93 mol% vinylphenol
I had 8, 25 or 43 wt.% vinylphenol
1086
103,876
905,1206
487,1064
103
876,922
1 had >0.93 mol% vinylphenol; II 103,487,1055
was atactic, isotactic or syndiotactic
I had 48 wt.% vinylphenol
I had 50 mol% vinylphenol
II had &IO% substituted and partly
cyclized; immiscible when II had
2% substituted
734
832
210,896
-
972
-
-
I had M, = 27 kg/mol and 11 had
M, = 1.21 kg/mol; blends of
polymers of higher MW
showed LCST
972
972
931
II had 9-19 wt.% AN when I had M, = 908,931
4.8kg/mol; II had 16-19 wt.% AN when
I had M, = 12.4 kg/m01
II had 11-25 wt.% AN when I had
M, = 4.8 kg/mol; II had 13-20 wt.%
Chemi cal l y Di ssi mi l ar Pol ymer Pai rs VI 1439
TABLE 1. contd
Polymer I of Polymer II of Method Comments Refs.
Tetratluoroethylene, sulfonated
Tetrafluoroethylene-aIt-vinyl
alcohol
Tetrahydrofurfuryl methacrylate
Tetrahydropyranyl-2-methyl
methacrylate
2,2,2-Trichloroethyl methacrylate
3,3,5Trimethyl cyclohexyl
methacrylate
Trifluoroethylene
Trimethylene adipate
Urethane
Maleic anhydride-co-styrene
Ethyl acrylate-co-
4-vinylpyridine
Alkyl methacrylate
Methyl acrylate
Viny1 acetate
Ally1 alcohol-co-styrene
Epichlorohydrin
Hydroxyether of bisphenol-A
Wnw)
Vinyl chloride
Viny1 chloride-co-vinylidene chloride
Ally1 alcohol-co-styrene
Epichlorohydrin
Hydroxyether of bisphenol-A
(phenoxy)
Vi n y 1 c h l o r i d e
Vinyl chloride-co-vinylidene chloride
p-Vinylphenol
Alkyl methacrylate
Single T,
Single T,
Single T,; FTIR
Single T,; FTIR
Single T,; FTIR
Transparency
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,
Transparency
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,
Single T,; transparency
Single T,; transparency
3,3,5-Trimethyl-cyclohexyl acrylate Single T,; transparency
Vinylidene fluoride Single T,
Viny1 chloride Single T,; transparency
Carbonate of bisphenol-A Single T,
Ethylene glycol F T I R
Ethylene-co-methyl acrylate Single T,; FlIR
Ethylene glycol-co-propylene glycol Single T,; FTIR
Methacrylic q-id-co-styrene
-f
Urethane
Vinyl chloride
N-vinylpyrrolidone
Urethane, functionalized Acrylic acid-co-styrene
2-Methyl-5-vinylpyridine
-co-styrene
Single T,
Single T,
Single T,
Single T, for II with hard
segments of I; soft segment
Tss also observed; clear
films
Single loss peak; microscopy
Single T,
AN when I had M, = 12.4 kg/mol
II had 17 or 18 wt.% maleic anhydride
when I had M, = 4.8 kg/mol
I had equivalent weight of 1.155 kg/mol
II had an alkyl group of methyl or
ethyl (2 miscible blend systems)
-
-
II had 5.4-6.0% OH
-
-
-
II had 88% vinylidene chloride
II had 5.4-6.0 wt.% OH
-
-
-
II had 88% vinylidene chloride
-
II had an alkyl group of methyl,
ethyl, n-propyl, isopropyl,
cyclohexyl or tetrahydrofutfuryl
(6 miscible blend systems)
-
Semicrystalline
When 2 75% II
I was based on polycarbonate dials
and/or polypropylene glycol; miscible
when blend had lo-20 wt.% I
1 was made from a mixture of 2,4-
and 2,6-tolyldiisocyanate and
1,4-butanediol
I was Estane 58311; II had 21 wt.%
methyl acrylate
I was made from a mixture of 2,4-
and 2,6-tolyldiisocyanate and
1,4-butanediol; II had 70 wt.%
ethylene glycol
I had polyether segment with MW =
1.0 or 2.0 kg/mol; II had 10.5%
methacrylic acid, Li-neutralized
I and II were separate polymers; I was
4,4-diisocyanate diphenyl methane
(MDI)/dipropylene glycol = 9/ 10 mol
ratio; II was poly G55-56 polyoxy-
ethylene-co-oxypropylene, 45%
ethylene oxide, MW = 2.0 kg/mol/
MDI/l/l
Blend had 5 39 wt.% I
I was segmented, made from methylene
bis(4-phenyl isocyanate) and poly-
(ethylene glycol) and cis-2-butene-
1,4-diol and butane- 1,4-dial
l had tertiary amine group; II had 15
or 30 mol% acrylic acid; linear blend
of I and II or interpenetrating polymer
network of I and II
I carried pendant carboxylated groups
neutralized by ammonium ion
9 3 1
5 9 1
9 6 1
9 6 1
9 6 1
2 5 3
1 1 7
253
2 8 1
1 1 7
1 1 8
1 1 7
1 1 8
1 1 7
1 1 7
1 1 8
1110
765
252
872
997
141,347
1181
1 4 5
707
5 2 1
1 0 2 9
206
346
706
References page VI - 46 1
VI f 440 MISCIBLE POLYMERS
TABLE 1. cont d
Polymer I of Polymer II of Method Comments Ref s.
Valerolactone
Vinyl acetate
Vinyl acetate-co-vinylidene chloride
Vinyl bromide
Vinyl chloride
2-Bromoethyl methacrylate
Chloroalkyl methacrylate
Hexafluoroacetone-co-vinylidene
fluoride
Maleic anhydride-co-styrene
hydrolyzed
Vinyl nitrate
Vinyl acetate-co-vinyl chloride
Vinylidene fluoride
n-Butyl methacrylate-co-isobutyl
methacrylate
Hexyl acrylate-co-methyl acrylate
Vinyl alcohol
Vinyl alcohol
Vinyl alkanoate
Vinyl butyral
Vinyl chloride
n-Butyl methacrylate
Ethylene imine
Methacrylic acid
Vinyl alkanoate
N-Vinylpyrrolidone
Urethane elastomer
Acetonyl methacrylate
Acrylic acid-co-carbitylacrylate-
co-cc-methylstyrene-co-styrene
Acrylonitrile-co-n-butyl acrylate
Alkyl acrylate
Alkyl methacrylate
Butadiene, epoxidized
Butadiene-co-styrene, epoxidized
*
Butyl acrylam;co-ethyl acrylate
Butyl acrylate-co-hexyl acrylate
Butyl acrylate-co-methyl acrylate
Butyl methacrylate-co-methyl
methacrylate
Caprolactone-co-L-lactide
Caprolactone-co-lignin
Caprolactone-co-methylcaprolactone
2,2-Dimethyl- 1,3-propylene sebacate
Ethyl acrylate-co-hexyl acrylate
Single T,
Single T,
Single T,
Single T,; transparency
Single T,; transparency
Single T,
Single T,
Single T,; phase contrast
microscopy
Single T,
Single T,
Single T,
Single T,
Single T,
NMR
Single Ts; microscopy
Single T,; transparency
Single T,
Single T,; transparency
Single T,
Optical microscopy
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,; microscopy
Single T,
Single T,; transparency
Single T,
Ethyl acrylate-co-methyl methacrylate Single T,
Ethylene-co-vinyl acetate Permittivity measurements
Methyl acrylate-co-hexyl acrylate Single T,
Methyl methacrylate-b-styrene
-
Semicrystalline; II was Saran C ( 2
80% vinylidene chloride)
-
Semicrystalline when _> 50% I
Miscible when cast from methyl ethyl
ketone; immiscible when cast from
tetrahydrofuran
31
150
32,34,35
610
II had chloromethyl or 2-chloroethyl
group (2 blend systems)
6 1 0
II had 8.9 mol% hexafluoroacetone 748,1073
l&43% hydrolyzed 61
-
12
Semicrystalline 5357
Miscibility range depended on composi- 748
tions of I and II; I had 2 81 wt.%
vinyl chloride
I had 5-23.7 ~01% vinyl acetate; II had
15-88 ~01% hexyl acrylate; miscibility
depended on compositions of
I and II
3 7 9
I had 5.9-15.1 wt.% vinyl acetate 497
Semicrystalline 1 0 2 4
-
1255,1256,1257
The alkanoate was butyrate, caprate,
caproate, caprylate or laurate
(5 miscible blend systems)
_< 50% II
9 2 5
II from methylene bisdiphenyl diurethane
and polytetramethylene ether glycol;
miscible with hard segment
II was an oligomer with M, = 1.07 and
M, = 3.32 kg/mol
II had 53, 67 or 84 mol% butyl acrylate
II had pentyl or propyl group
(2 blend systems)
II had cyclohexyl or isopropyl group
(2 blend systems)
II had 50 mol% epoxidation
II had 45 wt.% styrene; epoxidation >
40 mol%
II had 22.9, 43.5 or 52.8% butyl
acrylate
II had 47.8% butyl acrylate
II had 44.6% butyl acrylate
II had 30 or 70% methyl methacrylate
II had 5 40 wt.% lactide
II was a 7-armed starlike polymer
containing 20 wt.% lignin derivative
Whatever composition of II
II had 41.7 or 43.2% ethyl acrylate
II had 10% ethyl acrylate
II had 70% vinyl acetate; composition
dependent; miscible when blend
contained 2 25% II
II had 9.7% methyl acrylate
No gross phase separation when I
had M, = 43 kg/mol; PMMA and PS
block had the same M, = 40
kg/mol in II
2 0 9
762
123
6 8 3
6 5 5
851
3 1 9
5 4 6
5 4 4
851
851
851
8 8 0
831
9 8 4
831
611
851
875
6 7 8
851
376
Chemically Dissimilar Polymer Pairs VI / 441
TABLE 1. contd
Polymer I of Polymer II of Method Comments Refs.
Nitrile rubber, carboxylated
Pentyl acrylate-co-propyl acrylate
Vinyl acetate
Vinyl chloride, chlorinated Alkyl methacrylate
Butadiene, epoxidized
Butadiene-co-acrylonitrile
Ethylene terephthalate
Hexamethylene sebacate
Hexamethylene terephthalate
Maleic anhydride-ran-styrene
a-Methyl-a-n-propyl-/3-propiolactone
Urethane
Viny1 chloride-co-vinylidene
chloride
Valerolactone
Alkyl methacrylate
Butylene adipate
Butylene sebacate
Dodecamethylene adipate
Dodecamethylene decamethylene
dicarboxylate
Dodecamethylene dodecamethylene
dicarboxylate
Hexadecamethylene dodecamethylene
dicarboxylate
Hexamethylene sebacate
Vinyl fluoride Vinylidene fluoride
Vinyl p-methoxycinnamate
Vinyl p-methylcinnamate
Vinyl methyl ether
p-Chloro-(3-ethenoxypropyl)
cinnamate,.
Vinyl p-chlorocinnamate
Vinyl cinnamate
p-Chloro-(3-ethenoxypropyl)
cinnamate
p-Cyano-(3.ethenoxypropyl)
cinnamate
3-Ethyoxypropyl cinnamate
Vinyl p-chlorocinnamate
Viny1 cinnamate
Acrylonitrile-co-styrene
Alkyl acrylate
2-Chlorostyrene
Epichlorohydrin
Maleic anhydride-co-styrene
Methyl methacrylate-co-styrene
cc-Methylstyrene
a-Methylstyrene-co-4-
(2-hydroxyethyl)-cc-methylstyrene
Single T,
Single T,
Single T,
Single T,; transparency
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,; FTIR; SAXS
NMR, dielectric spectroscopy
Single T,
Single T,
Light scattering
Single T,
II was Krynac-221 1 1 7 0
II had 48.1% propyl acrylate 8 5 1
Ref. 59 stated miscible when cast from 59,183
methyl ethyl ketone and immiscible
when cast from tetrahydrofuran;
Ref. 183 stated blends cast from both
THF and MEK were immiscible
I had 65 or 68 wt.% Cl; II had n-butyl, 319,812
cyclohexyl, ethyl, n-hexyl, n-propyl
or isopropyl group (6 blend systems)
II had 20 or 43 mol% epoxidation 779
Depended on Cl-content and acrylo- 96,152,355,356
nitrile content
Probably semicrystalline
I had 67.2 wt.% Cl; semicrystalline
when 2 50 wt.% II
Semicrystalline
I was Goodrich CPVC 3010; II had
86% styrene
I had 67.2 wt.% Cl
I had 67 wt.% Cl; II had a soft poly
(tetramethylene adipate) segment
capped with 2-hydroxyethyl acrylate
I had 67.2 wt.% Cl
I had 12% vinyl chloride; II had phenyl
or isopropyl group (2 blend systems)
I had 13.5 wt.% vinyl chloride;
semicrystalline
I had 13.5 wt.% vinyl chloride;
semicrystalline
I had 13.5 wt.% vinyl chloride;
semicrystalline
I had 13.5 wt.% vinyl
chloride; semicrystalline
I had 13.5 wt.% vinyl chloride;
semicrystalline
I had 13.5 wt.% vinyl chloride;
semicrystalline
I had 13.5 wt.% vinyl chloride;
semicrystalline
Semicrystalline; later work found the
blends immiscible (Ref. 298)
-
-
-
-
-
-
II had < 10-l 1% acrylonitrile
II had an alkyl group of ethyl, n-propyl
or n-butyl (3 miscible blend
systems)
-
II had -15% maleic anhydride
II had < 60 mol% methyl methacrylate
-
II had 6-89 mol% a-methylstyrene
3 6
54
36
68,69
54
246
54
409
873
873
8 7 3
8 7 3
8 7 3
8 7 3
8 7 3
252,298
515
515
515
515
5 1 5
5 1 5
5 1 5
5 1 5
576
9 4 1
1 2 0 3
911,1129
576
1 0 8 , 3 2 1
318
1 7 0
References page VI - 46 1
VI / 442 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Ref s.
Vinyl methyl ketone
p-Vinylphenol
a-Methylstyrene-co-4-( 1 , l,l-
trifluoro-2-hydroxyethyl)-
cc-methylstyrene
a-Methylstyrene-co-styrene
m-Methylstyrene-co-styrene
o-Methylstyrene-co-styrene
p-Methylstyrene-co-styrene
Nitrostyrene-co-styrene
Styrene-co-l-vinylnaphthalene
Single T,
Light scattering
FTIR; light scattering
FTIR; light scattering
Light scattering
Single T,
Light scattering
Styrene-co-2-vinylnapthalene
Vinyl alkanoate
Single T,; FTIR;
light scattering
Single T,; IGC
l-Vinylnaphthalene Single T,; FTIR
Vinylidene fluoride
Vinylidene fluoride
Acetonyl methacrylate
4-Acetoxystyrene
Amide
Single T,; transparent melt
Single T,; transparent melt
Single T,; transparency
Single T,; FTIR
Single T,
Butyl acrylate-co-t-butyl acrylate
Butylene adipate
Butylene terephthalate
Caprolactone
Cellulose tripropionate
Copolyester
Dialkyl itaconate
Single T,
Single T,; FTIR; NMR
Single T,; FTIR
Single T,; FTIR; IGC
Single T,
Single T,; FTIR
Single T,; FTIR
NJ-dimethylacrylamide Single T,
2&Dimethylpropylene terephthalate
Ethyl acrylate
y-Ethyl L-glutamate
Ethyl methacrylate
Ethyl methacrylate-co-methyl
methacrylate
Ethylene adipate
Ethylene 2,6-naphthalene
dicarboxyla@
Ethylene succinate
Ethylene terefihthalate
Ethylene-co-vinyl acetate
Hexamethylene sebacate
n-Hexyl methacrylate-co-methyl
methacrylate
Hexylene-m-xylene dicarboxamide
2-(2.Methoxyethoxy)ethyl
methacrylate
y-Methyl L-glutamate
Methyl acrylate
Methyl methacrylate
n-Propyl acrylate
n-Propyl methacrylate
Isopropyl methacrylate
Styrene-co-4-vinylbenzenephos-
phonic acid diethyl ester
Styrene-co-4-vinylpyridine
Styrene-co-2.vinylpyridine
Single T,; FTIR
F T I R
FTIR; microscopy
Single T,; FTIR
Single T,; FTIR
Single T,: NMR
Single T,; FTIR
Single T,
Single T,; FTIR
Single T,; FTIR
Single T,
Single T,; FTIR
Single T,
Single T,; FTIR
FTIR; microscopy
FTIR; NMR
Single T,; FTIR; NMR
F T I R
FTIR; single T,
Single T,
Single T,; FTIR; NMR
Single T,
Single T,; FIIR
Tetrahydrofuran FTIR; transparency
II had O-96 mol% a-methylstyrene 170
II had 77.5 or 88 wt.% styrene 3 1 8
II had 76.5 or 87.5 wt.% styrene 1 0 2 8
II had 76.2 or 86.8 wt.% styrene 1028
11 had 2 61 mol% styrene 318,1016
II had 5 25.6 mol% nitrostyrene 158,166,192
II had 17.4, 23, 50 or 80 wt.% styrene; 381,406
depended on composition of blend
II had 19.2, 51 or 84 wt.% styrene 318,1175
The alkanoate was butyrate or propionate 988
(2 miscible blend systems)
II had M, = 5.4 kg/mol; blend contained 407
65-85 wt.% II
Semicrystalline 5 8
Semicrystalline 5 8
118
340
Polymer II was nylon 6, nylon 6,6 or 1 0 8 8
nylon 11 (3 miscible systems);
semicrystalline
II had 64 mol% butyl acrylate 8 9 7
Semicrystalline 667,919,1088,1089
Semicrystalline 1088,1089
Semicrystalline 143,667,1088,1096
1 0 8 8
II was five different copolyesters 1 0 8 9
II had a dialkyl group or methyl, ethyl, 1034.1086
bis[2-[2-(2.methoxyethoxy)ethoxy]
ethyl or bis[2-(2-methoxyethoxy)ethyl
(4 miscible blend systems)
Formed complexes in dioxane or 487,795,857,
acetone 1088,1089
-
1088,1089
143
-
639,902
146,282,733,1164
II had 30, 60 or 70 wt.% MMA 1162,1164
Semicrystalline 667,919,1089
1088,1089
Semicrystalline
Semicrystalline
II had 70% vinyl acetate
Semicrystalline
II had 20, 38 or 48 wt.% n-hexyl
methacrylate
-
9 1 9
1 0 8 9
143,144,588
6 6 7
9 5 8
1 0 8 8
1 0 8 6
-
639,902
143.889,894,1195,1224
-
146,282,487,733,1164,1224
143,641
146,282,733
-
2 8 0
II had > 7.5 mol% phosphorus groups 1 2 4 9
II had 50 mol% 4-vinylpyridine 8 3 2
Formed complexes in ethanol; II had 70 9 7 6
mot% 2.vinylpyridine
-
734
TABLE 1. contd
Chemically Dissimilar Polymer Pairs VI / 443
Polymer I of Polymer II of Method Comments Refs.
Tetrahydrofurfuryl methacrylate
2,2,5-Trimethylene terephthalamide
Vinyl acetate
Vinyl methyl ether
Vinylpyridine
Vinyl propionate
N-vinylpyrrolidone
N-vinylpyrrolidone
Ethyl acrylate
Alkyl methacrylate
Ally1 alcohol-co-styrene
Aramide
Benzimidazole
n-Butyl methacrylate-co-2.
hydroxyethyl methacrylate
Haloalkyl methacrylate
Copolyamide
Dialkyl itaconate
Epoxy resin
Ethersulfone
Ethylene glycol
Epichlorohydrin
Ethyl methacrylate-co-2-
hydroxyethyl methacrylate
2-Hydroxyethyl methacrylate
2-Hydroxyethyl methacrylate-co-
methyl methacrylate
2-Hydroxypropyl methacrylate
Methacrylic acid
Monoalkyl itaconate
S u l f o n e
Sulfone, carioxylated
.,
Vinylidene fluoride
Vinylpyridine
Vinyl alcohol
Vinyl alcohol-co-vinyl acetate
Vinyl chloride
Vinyl formal
Acetonyl methacrylate
N,N-Dimethylacrylamide
Ethyl methacrylate-co-methyl
methacrylate
Methacrylic acid-co-methyl
methacrylate
Methyl methacrylate-co-styrene
N-Methyl-N-vinylacetamide
Methoxymethyl methacrylate
Pivalolactone
N-Vinylpyrrolidone
Hydroxyalkyl methacrylate
Single T,
Single T,
Single T,; FTIR
Single T,; FTIR
Single T,; FTIR
Single T,
Single T,; transparency; IGC
Single T,
Single Tp; transparency
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,; FTIR
Single T,
Single T,
Single T,; FTIR
Single T,
Single T,
Single T,
Single T,; transparency
Single Tg; transparency
Single T,; transparency
Single T,; transparency
NMR
F T I R
Single T,; transparency
Single T,; transparency
Single T,; NMR
Single T,
Single T,
Single T,: FTIR
Single T,
Single T,
T,-depression
Single T,; T,-depression
Single T,
Single T,
Single T,
T,-depression
Single T,
Single T,; FTIR
-
282
-
1 0 8 8
-
143,144,588
-
1 1 5 0
Formed complexes; II was 2- or 832,976
4-vinylpyridine (2 miscible systems)
Formed complexes from methanol 8 5 7
-
60,6 I
II had an alkyl group or methyl or 607,1141
ethyl; miscible when cast from
chloroform (Ref. 1141); immiscible
when cast from DMF (Ref. 607)
II had 5.4-6.0 or 7.3-8.0 wt.% OH 284,977
Polymer II was five different types of 947
aramides
-
II had > 20.9 mol% 2-hydroxyethyl
methacrylate
947
5 0 1
II had a haloalkyl group of 607,1109,1141
chloromethyl, 2-chloroethyl,
3-chloropropyl, 2-bromoethyl or
2.iodoethyl (5 miscible blend systems)
II had 1 / 1 / 1 = caprolactam/hexa- 315
methylene adipamide/hexamethylene
sebacamide structural unit
II had an dialkyl group of dimethyl, 1 1 4 1
di-2-chloroethyl or di-3-chloropropyl
(3 miscible blend systems)
-
370
-
3 0 7
I had MW = 360 kg/mol; II had MW = 780
0.3 kg/mol
-
300
II had _> 7.5 mol% 2-hydroxyethyl 265
methacrylate
-
284
II had 2 1.9 mol% 2-hydroxyethyl 5 0 1
methacrylate
284,977
Formed complexes 1 1 2 8
II had an alkyl group of benzyl or 95,938
ethyl (2 blend systems); formed
complexes
-
2 5 5
II had degree of carboxylation 255
0.43-1.93
Semicrystalline 624,659,805,856,890,998
II had 2 70% vinyl alcohol 2 0 7
-
300
-
349,1044
Semicrystalline 1 2 2
Semicrystalline 242
II had 16-80 wt.% methyl 283
methacrylate
Semicrystalline; II had 2.2-9.5 mol% 1 0 9 4
methacrylic acid
II had < 13 ~01% styrene 388
Semicrystalline 242
Semicrystalline 267
Semicrystalline 1 0 3 8
Semicrystalline 17,94,241,408
I was 2- or 4-vinylpyridine; II had an 937
alkyl group of 2-hydroxyethyl or
3-hydroxypropyl (4 miscible systems)
References page VI - 461
2-Vinylpyridine
4-Vinylpyridine
2,3-Xylenyl methacrylate
VI / 444 MISCIBLE POLYMERS
TABLE 1. contd
Polymer I of Polymer II of Method Comments Refs.
Monoalkyl itaconate
Vinyl acetate-co-vinyl alcohol
Vinyl butyral
Aramide
Methylocellulose
Sulfone, carboxylated
p-Phenylene terephthalamide
2,6-Xylenyl methacrylate
Single T,; FTIR I was 2- or 4.vinylpyridine; II had an 939,1014,
alkyl group or methyl or ethyl 1 2 1 2
(4 miscible systems); formed
complexes
Single T,; FUR I was 2- or 4-vinylpyridine (2 miscible 934,935,991
systems); II had 29-88 mol%
vinyl alcohol
S A L S I was 2- or 4-vinylpyridine (2 miscible 1 0 0 3
systems)
Single T,; PTIR II was made from hexamethylene- 161
diamine and a mixture of tereph-
thaloyl and isophthaloyl dichlorides
Single T,; NMR
-
559
Single T,; transparency II had degree of carboxylation 256
0.43-1.93
Transparency; mi croscopy - 329
Single T, 1 1 5 8
TABLE 2. POLYMER PAIRS CONTAINING ONE MONOMER IN COMMON, MISCIBLE IN THE AMORPHOUS STATE AT ROOM
TEMPERATURE
Polymer I of Polymer II of Method Comment s Refs.
Acrylic acid-co-styrene
Acrylonitrile-co-butadiene
Styrene-co-maleic anhydride-
-co-acrylonitrile
Acrylonitrile-co-methyl
methacrylate
Acrylonitrile-co-methyl
methacrylate-co-
cc-methylstyrene
Acrylonitrile-co-methyl
methacrylate-co-styrene
Acrylonitrile-co-a-methylstyrene
Acrylonitrile-co-cc-methylstyrene-
co-styrene
Acrylonitrile-co-styrene
Methyl methacrylate-co-styrene Single T,
Acrylonitrile-co-butadiene Single T,; clear films;
electron microscopy
Acrylonitrile-co-styrene Single T,
Acrylonitrile-co-vinylidene chloride Single T,
Acrylonitrile-co-styrene Single T,
Maleic anhydride-co-styrene Single T,
Acrylonitrile-co-N-phenylitaconimide Single T,
Itaconic anhydride-co-methyl
methacrylate
Methyl methacrylate-co-
N-phenylitaconimide
Methyl methacrylate
Single T,
Single T,
Single T,
Acrylonitrile-co-styrene Light scattering
Methyl methacrylate Light scattering
Acrylonitrile-co-methyl methacrylate Single T,
Acrylonitrile-co-styrene Single T,
Acrylonitrile-co-cc-methyl
styrene-co-styrene
Acrylic acid-co-styrene
Acrylonitrile-co-benzyl methacrylate
Acrylonitrile-co-fumaromtrile-
co-styrene
Acrylonitrile-co-methyl methacrylate
Acrylonitrile-co-N-phenylitaconimide
Acrylonitrile-co-styrene
p-(2-Hydroxy-hexafluoroisopropyl)-
styrene-co-styrene
Maleic anhydride-co-styrene
Clear films
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,; no visible phase
separation
Single T,; clear film
Single T,
Miscibility depended on compositions 7 2
of I and II
Difference in composition between 19,47,101,106,
I and II 5 22% acrylonitrile
I had 23.6-49.6 ~01% AN; II had 19
wt.% AN
149,390,452
1 6 2
966
Miscibility depended on compositions
of I and II
965
Miscibility depended on compositions
of I and II
9 6 5
168
Miscibility depended on compositions
of I and II
-
920
168
I had 20/20/60 = acrylonitrile/methyl
methacrylatela-methylstyrene
6 3 3
-
3 5 8
-
-
I had 32.3 wt.% acrylonitrile; II had
27 wt.% acrylonitrile
Difference in composition between I
and II < 12% acrylonitrile
3 5 8
1 . 5 2
1 5 5 , 6 8 4
7 6 9
-
I had 32-40 wt.% AN; II had
1 1 - 17 wt.% fumaronitrile
3 8 0
1 1 8 0
1 2 2 2
-
Difference in composition between I
and II < 3.5% acrylonitrile
I had 70% styrene; II had 90.3%
styrene
1 6 4 , 6 2 0
168
485,582
571,646
I had 44.4-94.6 wt.% styrene; II had 25,462,554,
50-91.5 wt.% styrene 745.1008
Polymer Pairs Containing One Monomer in Common VI / 445
TABLE 2. contd
Polymer I of Polymer II of Method Comments Refs.
3-Bromo-2,6-dimethyl-
1,4-phenylene ether
3-Bromo-2,6-dimethyl-
1,4-phenylene ether-co-
2,6-dimethyl- 1,4-phenylene
ether
p-Bromostyrene-co-styrene
Butadiene
Butadiene-co-styrene Butadiene-co-styrene Single T,; microscopy
Butyl acrylate-co-butyl
methacrylate
Butyl acrylate-co-
N-hydroxyethylcarbozolyl
acrylate
Butyl acrylate-co-ethyl acrylate Butyl acrylate-co-ethyl acrylate Clear films
Butyl acrylate-co-methyl Butyl acrylate-co-methyl Single T,; clear films
methacrylate methacrybte
n-Butyl methacrylate n-Butyl methacrylate-co-styrene Single T,; clear films
n-Butyl methacrylate-co-p- n-Butyl methacrylate-co- Single T,; microscopy
chlorostyrene p-chlorostyrene
n-Butyl methacrylate-co-N- n-Butyl methacrylate-co- Single T,
hydroxyethylcarbazoyl P-hydroxyethyl-3,5-dinitrobenzoyl
acrylate acrylate
Butyl methacrylate-co-methyl Butyl methacrylate-co-methyl Clear films
methacrylate methacrylate
n-Butyl methacrylate-co-styrene
Caprolactam-co-caprolactone
Caprolactam-co-caprolactone-co-
laurolactam
2,6-Dimethyl-1,4-phenylene
ether, sulfonylated
Dimethylsiloxane, functionalized Dimethylsiloxane, functionalized Single T,
N-phenylitaconimide-co-styrene Single T,
N-phenylmaleimide-co-styrene Single T,
3-Bromo-2,6-dimethyl-1,4-phenylene Single T,; microscopy
ether-co-2,6-dimethyl-
1,4-phenylene ether
2,6-dimethyl-1,4-phenylene ether Single T,; microscopy
Styrene Single T,
Butadiene Single T,
Butadiene-co-styrene Single T,
Styrene Single dynamic mechanical
loss peak
Butyl acrylate-co-butyl methacrylate Clear films
Butyl acrylate-co-p-hydroxyethyl-
3,5-dinitrobenzoyl acrylate
Single T,
Ethyl acrylate Clear films
n-Butyl methacrylate-co-styrene Single T,; microscopy
Styrene Single T,; clear films
Caprolactone-co-laurolactam Single T,
Caprolactam-co-laurolactam Single T,
2,6-Dimethyl-1,4-phenylene ether,
sulfonylated
Single T,
-
-
II had 2 48 mol% 3-bromo-
2,6-dimethyl- I ,4-phenylene oxide
1 6 4
25,26
402
I had 2 62 mol% 2,6-dimethyl-
1,4-phenylene ether
402
I had 2 90 mol% styrene 402,785
Semicrystalline; I was SKD (87% cis-1,4) 25 1,736
and II was SKBM (Ref. 251); I had 50%
vinyl-1,2, 35% cis-1,4 and 15% trans-
1,4, and II had 98% cis-1,4 (Ref. 736);
I had 50% vinyl-1,2, 35% cis-1,4 and
15% trans-1,4, and II had 55% tmns-
1,4, 35% cis-1,4 and 10% vinyl-l,2
(Ref. 736)
II had > 70% butadiene; immiscible 92,149,182,
when II had ~60% butadiene 237,238,520,548,
549,737,770,171,
787,882
Difference in composition between I 182,519,520,
and II ~20% styrene; two T,s 455,757,771
when composition difference > 20%
I had 25% styrene; II had M, 5 917;
5 50% II; two loss peaks
when 75% II
Difference in composition between I
and II 25% butyl acrylate;
immiscible when composition
difference 50% butyl acrylate
I had 6 or 48 mol% electron donating
carbozoyl groups; II had 10 or 63
mol% electron withdrawing
dinitrobenzoyl groups
Difference in composition between I
and II 25% ethyl acrylate; immiscible
when composition difference 50%
ethyl acrylate
I had 75% ethyl acrylate; immiscible
when I had 5 50% ethyl acrylate
Difference in composition between I
and II < 10% methyl methacrylate
II had 2 90 wt.% n-butyl methacrylate
-
I had 9 mol% carbazoyl groups; II had
9 mol% dinitrobenzoyl groups
Difference in composition between I and
II 5 20-30% butyl methacrylate,
depending on compositions of I
and II
I had 2 90 wt.% styrene
I and II had various compositions
I and II had various compositions
Difference in degree of sulfonylation
between I and II in the range of
20-26 wt.%
I had 4- 15 mol% electron-donating
carbazoyl or N-methylaniline groups;
II had 4- 15 mol% electron-accepting
1 3 8 , 1 3 9
453
7 2 3
453
453
447,448
238
7 6
723
76,447
7 6
239
1 1 2 6
992
410
723
References page VI - 46 1
VI / 446 MISCIBLE POLYMERS
TABLE 2. cont d
Polymer I of Polymer II of Method Comments Ref s.
Epichlorohydrin
Ethyl acrylate-co-ethyl
methacrylate
Ethyl acrylate-co-methyl
methacrylate
Ethylene, chlorinated
Ethylene-co-vinyl acetate
Ethylene-co-vinyl chloride
Ethylene naphthalene-
2,6-dicarboxylate
Ethyl methacrylate-co-methyl
methacrylate
Epichlorohydrin-co-ethylene glycol Single T,
Ethyl acrylate-co-ethyl methacrylate Clear films
Ethyl methacrylate Clear films
Ethyl acrylate-co-methyl methacrylate Clear films
Ethylene, chlorinated
Ethylene-co-methyl acrylate
Ethylene-co-vinyl acetate
Ethylene, low density
Ethylene-co-vinyl acetate
Ethylene-co-vinyl alcohol
Vinyl acetate-co-vinyl chloride
Ethylene-co-vinyl chloride
Vinyl chloride
Ethylene naphthalene-
2,6-dicarboxylate-co-
4-hydroxybenzoate
Ethyl methacrylate-co-methyl
methacrylate
o-Fluorostyrene-co-p-fluorostyrene o-Fluorostyrene-co-p-fluorostyrene
o-Fluorostyrene-co-styrene
p-Fluorostyrene-co-styrene
Hydrocarbon polymer,
chlorinated
p-Hydroxybenzoic acid-co-
6-hydroxy-2-naphthoic acid-
co-terephthalic acid-co-
hydroquinone
Hydroxybutyrate
Isoprene
Maleic anhydride-co-styrene
Maleimide-co-styrene
o-Fluorostyrene-co-styrene
Styrene
Styrene
Hydrocarbon polymer, chlorinated
p-Hydroxybentoic acid-co-
6-hydroxy-2.naphthoic acid
Hydroxybutyrate
Hydroxybutyrate-co-hydroxyvalerate
Isoprene-styrene block copolymer
Acrylonitrile-co-styrene
Maleic anhydride-co-styrene
Methyl methacrylate-co-styrene
Styrene-co-2-vinylpyridine
Single T,; clear films
Single T,; phase contrast
microscopy
Single T,; microscopy
Single T,
Single T,; microscopy
Single T,; FTIR
Single T,
Single T,
Single T,
NMR
Single T,
Single T,
Single T,
Single T,
Single T,
Clear films
Single T,; X-ray diffraction
Microscopy; SAXS
Microscopy; melting behavior
Electron microscopy
Single T,, transparency,
microscopy
Single T,
Single T,
Single T,; FTIR
dinitrobenzoyl groups; donor/
acceptor = 1 /I
I was Hydrin 100; 11 was Hydrin 200
I and II had 25, 50 or 75% ethyl
acrylate
I had 75 wt.% ethyl methacrylate;
immiscible when I had 5 50 wt.%
ethyl methacrylate
Difference in composition between I and
II < 20-27% ethyl acrylate depending
on compositions of I and II
Difference in composition between I
and II 5 1.2-13.3 wt.% Cl depending
on compositions of I and II
Semicrystalline when I had 25 wt.% Cl;
I had 25 or 48 wt.% Cl
I had 35.4-52.6 wt.% Cl; II had
50-60 wt.% ethylene
I:11 = 50 : 50
I and II had 7-100 wt.% vinyl acetate
I had 21 mol% vinyl acetate; II had 21
mol% vinyl alcohol
Difference in vinyl chloride or ethylene
content of 1 and II < 15 mol%
I had > 80 mol% vinyl chloride
II had 20 mol% 4-hydroxybenzoate
I and II had 10 and 23 mol%
p-fluorostyrene, respectively
I had 18 or 49% o-fluorostyrene; II had
40 or 77% o-fluorostyrene
I had 18, 40 or 49% o-fluorostyrene
and II had M, = 15 kg/mol I had 18%
o-fluorostyrene and II had
M, = 1 lOkg/mol
I had 8 or 16 mol% p-fuorostyrene; II
had M, = 40 or 326 kg/mol
One series derived from reduction of
polyvinyl chloride and one series
derived from chlorination of
polyethylene
X-ray diffraction showed no significant
transesterification occurred in the
mixture
3 7 3
4 5 3
4 5 3
447
97,98,
636,817
3 9 6
849
1 1 7 2
9 2 5
960
145,746
70,71
7 0
1 0 2 7
716.
7 1 6 .
9 8
1 4 4
1 4 4
1 4 4
1 1 4 4
7 5
9 2
I was isotactic; II was atactic 9 0 3
II had 3.8-22.3 mol% hydroxyvalerate 1142,1143
I had M, = 6.5-53.9 kg/mol; II was diblock, 3 7 8
triblock or four-arm star copolymer
having total M, = 26-622 kg/mol
I had 15.3 wt.% maleic anhydride; II 436,555
had 15.0, 19.5 or 25.0 wt.%
acrylonitrile
Miscibility occurred when difference in
MA contents between I and II
was c2.5 ~01%
1159
Miscibility depended on compositions
of I and II
I had 86 wt.% styrene; IH had 30 wt.%
styrene
1008
1214
Polymer Pairs Containing One Monomer in Common VI 1447
TABLE 2. contd
Polymer I of Polymer II of Method Comments Refs.
Methacrylic acid-co-methyl
methacrylate
Methacrylic acid-co-styrene
Methacrylonitrile-co-styrene
[4-(Methacryloyloxy)-butyl]-
pentamethyldisiloxane
[4-(Methacryloyloxy)-butyl]-
pentamethyldisiloxane-co-
methyl methacrylate
Methyl acrylate
Methyl acrylate-co-methyl
methacrylate
Methyl acrylate-co-vinyl acetate
Methyl methacrylate
Methyl methacrylate-co-
(N-ethylcarbazol-3-yl)methyl
methacrylate
Methyl methacrylate-co-styrene
p-Nitrostyrene-co-styrene
Novolac resin
N-Phenylmaleimide-co-styrene
Styrene
Styrene-co-styrenesulfonic acid
Styrene-co-vinylphenol
Sulfone
Viny1 acetate-co-vinyl chloride
Methyl methacrylate-co-
4-vinylpyridine
Butyl methacrylate-co-
methacrylic acid
Styrene-co-4-vinylpyridine
Methacrylonitrile-co-methyl
methacrylate
Methacrylonitrile-co-styrene
[4-(Methacryloyloxy)-butyl]-
pentamethyldisiloxane-co-
methyl methacrylate
Methyl methaclylate
Methyl acrylate-co-vinyl acetate
Methyl acrylate-co-methyl
me t h a c r y l a t e
Vinyl acetate
Ethyl methacrylate-co-methyl
methacrylate
Methyl methacrylate
Methyl methacrylate-alt-styrene
Methyl methacrylate-co-2-[(3,5-
dinitrobenzoyl)oxy]ethyl
methacrylate
Acrylonitrile-co-styrene
Maleic anhydride-co-styrene
Methyl methacrylate-co-N-
phenylitaconimide
Methyl methacrylate-co-styrene
N-Phenylitaconimide-co-styrene
p-Nitrostyrene-co-styrene
Novolac resip
4-Cyanostyrene-co-styrene
2-Cyanostyrene-co-4-cyanostyrene-
co-styrene
Styrene
Styrene, iodinated
Styrene-co-p-vinylphenol
Styrene-co+vinylphenol
Styrene-co-vinylphenol
Vinylphenol
Sulfone, carboxylated
Vinyl chloride
Viny1 chloride, chlorinated
Phase diagram
Single T,
Phase diagram
Single T,
Single T,
Single T,; clear films
Single T,; clear films
Clear films
Clear films
Clear films
Single T,
Single T,
Single T,; microscopy
Single T,
Single T,
Single T,
Single T,
Single Ts; microscopy
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Transparency
Single T,; FTIR
FUR
FTIR
Single T,; FTIR
Single T,
I had 91.48 or 77.7 mol% methyl
methacrylate; II had 80.2 mol%
methyl methacrylate
I and II had 13.7 and 20.2 mol%
methacrylic acid, respectively; both
were Na-neutralized
I had 89.5 mol% styrene; II had 83.9
mol% styrene
Miscibility depended on compositions
of I and II
Miscibility depended on compositions
of I and II
II had 67% methyl methacrylate
I had 67 or 75% methyl methacrylate
II had 25-75% methyl acrylate
Difference in composition between I
and II 28-48% methyl acrylate when
I and II had degree of polymerization
= 400 and 20-35% methyl acrylate
when I and II had degree of
polymerization = 3000, depending
on compositions of I and II
I had 25-75% vinyl acetate
I was isotactic; II had 5 45% ethyl
methacrylate
I was isotactic; II was sydiotactic
Deuterated blends were miscible;
miscibility affected by
deuteration of I
I and II had similar acceptor or donor
content
-
-
-
-
-
I was formaldehyde and l3/17/70
mol% =p-tert-butyl phenol/m-cresol/
1051
1 9 8
970
970
64
64
453
447
453
727
727
1 0 0 6
1 1 6 0
1 6 4 , 4 0 4
404
1 6 8
76,444
1 6 8
1 5 8
2 2 1
o-cresol; II was formaldehyde and 15/85
mol% = 2-rerr-butyl phenol/o-cresol; I
and II had MW 0.8- 1.6 kg/m01
I had 39 wt.% styrene; II had 58.5-83.1
mol% styrene
1 8 7
II had 23.5 or 22.7 mol% styrene; ratios
of 2.cyanostyrene/4-cyano-styrene
were 25175 or 78:22
1 8 7
I had MW = 0.8 kg/mol; II had
MW = 8420 kg/mol; I/II = 31.7/68.5
II had degree of iodination of 6 or 15%
I had 86 mol% styrene; II had 22 mol%
vinylphenol
1 0 2
2 6 1
1 0 8 6
I had 1.8-9.9 mol% acid; II had
1.9-9.9 mol% pyridine
1 1 9 0
349
I had > 11 mol% OH groups
Degree of carboxylation of II < 1.3
1247,108s
1 2 5 8
Single T,; microscopy of fibers I had 78 or 86 wt.% vinyl chloride 449
Single T,
-
7 4 5
References page VI - 46 1
VI / 448 MISCIBLE POLYMERS
TABLE 2. contd
Polymer I of Polymer II of Method Comments Refs.
Vinyl acetate-co-vinyl sterate
Vinyl chloride
Vinyl chloride, chlorinated
Vinyl acetate-co-vinyl sterate
Propylene-co-vinyl chloride
Vinyl chloride
Vinyl chloride, chlorinated
Single T,; microscopy I and II had 21-98 wt.% vinyl acetate 9 2 5
Single T,; microscopy of fibers II had 89 or 91 wt.% vinyl chloride 449
Single T, Up to 61.3 or 65.2% Cl in I with 91,504,505
dependence on mol% CC12 groups
Single T, Difference in composition between I 98,504
and II 5 3-4% Cl depending on
composition of I and II with
dependence on number of CC1 2
groups
TABLE 3. CHEMICALLY DISSIMILAR POLYMER TRIADS (AND TETRADS) MISCIBLE IN THE AMORPHOUS STATE AT ROOM
TEMPERATURE
Polymer I of Polymer II of Polymer III of (and Polymer IV of) Method Comment s Refs.
Acrylic acid-co-styrene
Acrylonitrile-co-butadiene
Acrylonitrile-co-butadiene-
co-styrene
Acrylonitrile-co-methyl
methacrylate
Acrylonitrile-co-
a-methylstyrene
Acrylonitrile-co-
N-phenylitaconimide
Acrylonitrile-co-styrene
Ethylene glycol Methyl methacrylate Single T,
Vinyl chloride Vinyl chloride-co-vinylidene chloride Single T,
Carbonate of bisphenol-A Propylene-co-vinyl chloride Single T,
Acrylonitrile-co-styrene Maleic anhydride-co-styrene Single T,
Acrylonitrile-co-styrene Methyl methacrylate-co-N-phenyl-
itaconimide
Acrylonitrile-co-styrene Methyl methacrylate-co-styrene Single T,
Acrylonitrile-co-styrme Vinyl chloride
.:
Ethyl methacrylate Methyl methacrylate
Acrylonitrile-co-styrene N-phenylitaconimide-co-styrene
Butylene adipate Carbonate of bisphenol-A
Caprolactone Carbonate of bisphenol-A
Caprolactone Hydroxyether of bisphenol-A
(phenoxy resin)
Caprolactone Maleic anhydride-co-styrene
Caprolactone Vinyl chloride
Carbonate of bisphenol-A Cyclohexane dimethylene succinate
Ethyl methacrylate Maleic anhydride-co-styrene
Ethyl methacrylate Methyl methacrylate
Methyl methacrylate Vinyl chloride
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
Single T,
-
I had 12.2, 20.8 or 33.1 mol%
acrylic acid
384
Semicrystalline; I had 30 or 40
wt.% acrylonitrile; III had
65 wt.% vinylidene
chloride
860
I was Blendex 701; II was
Merlon M39, M-60; III had
3.2 or 3.8% propylene;
I/II/III = l/1/2; two T,s
when I/II/III = 317110
I had 12% acrylonitrile; II
had 25% acrylonitrile;
III had 25% maleic
anhydride
1 0 7
74
I had 68 or 95 ~01% MMA; II
had 63 or 70 ~01% styrene;
III had 12 or 45 ~01% MMA;
three miscible binary pairs;
there was an immiscibility
loop
967
I had 2.7-7.4 ~01% acrylo- 1 6 3 , 1 6 5
nitrile; II had 14.5-49.5 ~01%
acrylonitrile; III had
11.2- 16.0 ~01% styrene
I had 32.3 wt.% acrylonitrile; 684
II had 27 wt.% acrylonitrile;
>25% I
I had 30 wt.% acrylonitrile
I had 6 or 9 ~01% acrylonitrile;
II had 22, 44 or 65 ~01%
acrylonitrile; III had 12 or
42 ~01% styrene
2 9 0
157
I had 12 or 25% acrylonitrile 7 3 8
-
7 3 8
I had 5.7-30 wt.% AN 1209,1052
I had 15 wt.% AN; III had 1 2 1 0
14 wt.% maleic anhydride
Miscible when I/II/III = 68/ 351
16116
7 3 8
I had 25% acrylonitrile;
III had 14-25% acrylonitrile
I had 30 wt.% acrylonitrile;
some blends showed LCST
I had 23 wt.% acrylonitrile
7 4
2 8 0
3 4 9
Chemically Dissimilar Polymer Triads (and Tetrads) VI / 449
TABLE 3. contd
Polymer I of Polymer II of Polymer III of (and Polymer IV of) Method Comments Refs.
n-Amy1 methacrylate
Arylate
3-Bromo-2,6-dimethyl-
1,4-phenylene ether-co-
2,6-dimethyl-
1,4-phenylene ether
p-Bromostyrene-co-styrene
Butylene terephthalate
Caprolactone
n-Butyl methacrylate
n-Propyl methacrylate
Butylene therphthalate
p-Bromostyrene-co-
styrene
Vinyl chloride Single T,
Vinyl chloride Single T,
Hydroxyether of bisphenol-A (phenoxy) Single T,
2,6-dimethyl- 1,4-phenylene ether Single T,;
microscopy
p-Bromostyrene-co- Styrene
styrene
2,6-Dimethyl-1,4- Styrene
phenylene ether
p-Bromostyrene-co- 26Dimethyl-1,4-phenylene ether
styrene (polymer IV of styrene)
2,6-dimethyl- 1,4- Styrene
phenylene ether I
Carbonate of bisphenol-A Hydroxyether of bisphenol-A (phenoxy)
Hydroxyether of Methyl methacrylate
bisphenol-A (Phenoxy)
Carbonate of bisphenol-A Carbonate of tetramethylbisphenol-A
Carbonate of bisphenol-A. Hydroxyether of bisphenol-A (phenoxy)
Single T,;
microscopy
Single Ts;
microscopy
Single T,;
microscopy
Single T,;
microscopy
Single T,
Single T,,
microscopy
Single T,
Single T,
Hydroxyether of Vinyl methyl ether Single T,
bisphenol-A (Phenoxy)
Vinyl chloride Vinyl chloride, chlorinated Single T,
Carbonate of bisphenol-A
Carbonate of tetra-
methylbisphenol-A
2-Chlorostyrene
Carbonate of bisphenol
chloral
Carbonate of tetra-
methylbisphenol-A
Carbonate of tetra-
methylbisphenol-A
Carbonate of tetra-
methylbisphenol-A
Methyl methacrylate
Cyclohexyl acrylate
Copolyester
Epoxy
i
.,
Epichlorohydrin
Etherimide
Ether urethane
Methyl methacrylate
Acrylonitrile-co-styrene
Single T,
Single T,
Methyl methacrylate-co-styrene
Styrene
Single T,
Single T,
Methyl methacrylate-co-styrene
Styrene
Single T,
Single T,; light
scattering
Hydroxyether of bisphenol-A (phenoxy) Single T,,
microscopy
Ethylene glycol
Methyl methacrylate
Methyl methacrylate
Vinyl acetate
Amideimide Ether ether ketone, sulfonated
Ether ether ketone Liquid crystalline polymer
Oxytetramethylene-co-
oxyditetramethylene-
co-terephthalic acid
Vinyl chloride
Single T,
Single T,
Blend had > 70 wt.% III
Blend had > 70 wt.% III
I was Arilef U-100;
III > 30 wt.%
1 1 5 7
1 1 5 7
7,208,366
5 37 mol% brominated monomer 402
in I and in II
5 16 moI% brominated monomer 402
in I and in II
5 45 mol% brominated
monomer in I
402
5 26 mol% brominated
monomer in I and in II
5 29 mol% p-bromostyrene in I
402
402
-
Blend had >.50 wt.% II
6 0 8 , 6 8 1
1 0 5 3
Miscible at all compositions
Generally miscible when > 60
wt.% I in blend
1 0 7 0
125
Miscible at al1 compositions;
all blends showed LCST
II had 67.2 wt.% Cl; generally
miscible when I > 40%
at high II/III ratio and
miscible when I > 26%
at low II/III ratio
3 0 3
2 0
427
III had 2.7-19.7 wt.% AN 1 0 6 8
III had 4.5-58.5 wt.% MMA 1 0 6 8
-
488,1068
-
884
Three miscible binary pairs;
there was an immiscibility
loop in the phase diagram
II/III = l/l; I was made from
6513015 = terephthalatel
isophthalate/sebacate and
70/20/ 10 = ethylene glycol/
resorcinal di@-hydroxy
ethyl)ether/poly(tetra-
methylene ether)glycol; II
was 4/l by wt. = Araldite
6099/Araldite 60 10
Miscible at all compositions
Miscible at all compositions;
all blends showed LCST
I was Ultem 1000; II was
Torlon 4OOOT; III had
degree of sulfonation of
0.53 or 1.00
1 1 6 7
2
5 7 3
304
415
I was Ultem 1000; II was 7 8
Victrex 450G; III was HX4000
I was Adiprene L-100 and 344
4,4-methylene-bis-2-chloro-
aniline: I/II/III = I/ l/2;
two 7s~ when I/II/III =
1/2/l and l/l/l
References page VI - 461
VI / 450 MISCIBLE POLYMERS
TABLE 3. contd
Polymer I of Polymer II of Polymer III of (and Polymer IV of) Method Comments Refs.
Ethyl methacrylate Methyl methacrylate p-Vinylphenol Single T,; FTIR: Blend had 2 60 wt.% III 1 1 6 1 . 1 1 6 3
microscopy
Methyl methacrylate Vinylidene fluoride Single T, Blend had 30-80 wt.% III 414
Ethylene, chlorinated Natural rubber, epoxidized Vinyl chloride Single T, II was 50 mol% epoxidized 3 9 4
Ethylene, chlorosulfonated Natural rubber, Nitrile rubber, carboxylated Single T, I had 35% Cl and 1% S 7 0 2
epoxidized (Hypalon-40); II was 50
mol% epoxidized; III was
Krynac-211
Ethylene glycol Vinyl acetate p-Vinyl phenol Single T,; FTIR Three miscible binary pairs; 491,124O
there was an immiscibility
loop in the phase diagram
Hexafluoroacetone- Methyl methacrylate Vinyl acetate Single T, I had 9 mol% hexafluoro- 1073
co-vinylidene fluoride acetone
Methyl acrylate Vinyl acetate p-Vinylphenol Single T, Miscible at all compositions 1240
Methyl acrylate-co-styrene Vinyl acetate p-Vinylphenol Single T, I had 28 wt.% styrene 1 2 4 0
Methyl methacrylate Vinyl acetate Vinylidene fluoride Single T, - 9 5 6
Natural rubber, epoxidized Nitrile rubber, Chloroprene Single T, I was 50 mol% epoxidized; 14
carboxylated II was Krynac-211; I/II/III =
l/l/l
Neopentyl glycol adipate Vinyl chloride Vinylidene fluoride Single T, III c50 wt.% 490
Styrene-co-4-vinylpyridine Vinyl acetate @Vinylphenol Single T, I had 30 wt.% styrene 1 2 4 0
TABLE 4. POLYMER PAIRS MISCIBLE IN THE AMORPHOUS STATE AT ROOM TEMPERATURE, MOLECULAR WEIGHT DEPENDENCE
INVESTIGATED
Polymer I of Polymer II of Method Comments Ref s.
Acrylonitrile-co-a-methylstyrene Carbonate of bisphenol-A Single T,; transparency I had 9-12 wt.% AN; miscible when
II had M, = 3.8 kg/mol; immiscible when
II had M, = 9.9 kg/m01
Acrylonitrile-co-styrene Carbonate of bisphenol-A Single T,; transparency I had 24.6 wt.% AN and II had M, =
3.8 kg/mol; miscible when I had M, =
3.137 kg/mol and immiscible with I had
M, = 6.085 kg/mol
3-Bromo-2,6-dimethyl- Styrene Single T,; transparency 1 had MW 5 40 kg/mol; II had MW
1.4.phenylene ether 5 30 kg/mol
n-Butyl methacrylate Styrene Single T,; transparency I had M, = 320 kg/mob II had MW =
171 kg/mol; two T,s when II had
MW = I 100 kg/mol
Carbonate of bisphenol-A Ester Single T, II was made from 4,4-(2.norbornyl-
idene)di-phenol and a mixture of
terephthalic acid and azelaic acid;
miscible with I had M, = 28.1 kglmol;
immiscible when I had M, = 73.2 kg/mol
2,6-Dimethyl- 1 ,Cphenylene ether Alkylstyrene Transparency I had M, = 5-500 kg/mol and II was
a ring-alkyl (with various carbon
atoms) styrene. Raising MW of
II eventually produced a transition
from clear to hazy or cloudy films in
each system except that containing
poly-a-methylstyrene. With this resin,
clear single-T, films were obtained
even with M, of I = 500 kg/mol and
M, of II = 800 kg/m01
p-Bromostyrene Transparency II had M, = 29.1 kg/mol and M, = 32 kg/mob
M, limit for miscibility in 50/50 blend
of I with II was 6.2 f 2.4 kg/mol. When
p-rerr-Butylstyrene Transparency
II had M, = 6.4 kg/mol and M, = 7.04 kg/mol,
M, limit for miscibility of I was
14 * 4 kg/mol
930
9 3 2
5 2 9
193
1232
4 0 3
4 0 3
II had M, = 113 kg/mol and M, = 289 kg/mol; 4 0 3
M, limit for miscibility in 50/50 blend
of I with II was 4.5 kg/mol Z+ 0.7 kg/mol
Molecular Weight Dependence of Miscible Polymers VI / 451
TABLE 4. contd
Polymer I of Polymer II of Method Comments Refs.
4-Ethylstyrene
4-Methoxystyrene
4-Methylstyrene
4-n-Propylstyrene
Vinylbenzylchloride
4-Vinylbiphenyl
Vinylnaphthalene
Vinyltoluene
Ethylene Dimethylsiloxane
Ethylene glycol Propylene glycol
Vinyl acetate
Sulfone
Hydroxybutyrate
cis-Isoprene
Lactide
Styrene
Methyl methacrylate
Vinyl cyclohexane
Carbonate ogbisphenol-A
./
Carbonate of hexafluorobisphenol
A-co-carbonate of tetramethyl-
bisphenol-A
Styrene
a-Styrene
Sulfone
Transparency
Transparency
Transparency
Transparency
Transparency
Transparency
Transparency
Transparency
Cloud point curve
Miscibility stated
Single T,
Scattering turbidimetry
Microscopy
Single dynamic mechanical
loss peak
Single dynamic mechanical
loss peak
Single T,; transparency
Single T,; transparency
Single T,, transparency
Single T,; transparency
Single T,; transparency
II had M, = 139 kg/mol and M, = 158 kg/mol; 403
M, limit for miscibility in 50/50 blend
of I with II was 22.4 kg/mol
II had M, = 282 kg/mol and M, = 457 kg/mol; 403
A4, limit for miscibility in 50/50 blend
of I with II was 3.6 kglmol
II had M, = 118 kg/mol and M, = 265 kg/mol; 403
M, limit for miscibility in SO/50 blend
of I with II was 35.5 kg/mol
II had M, = 128 kg/mol and M, = 267 kg/mol; 403
M, limit for miscibility in 50/50 blend
of I with II was 14 f 4 kg/mol
II had M, = 16.8 kg/mol and M, = 29.3 kg/mol; 403
M, limit for miscibility in 50/50 blend
of I with II was 14 * 4 kg/mol
II had M, = 79 kg/mol and M, = 153 kg/mol; 403
M, limit for miscibility in 50/50 blend
of I with 11 was 7 ?c I .6 kg/mol
II had M, = 13 kg/mol and M, = 32.6 kg/mol; 403
M, limit for miscibility in 50/50
blend of I with 11 was 10.2 kg/mol
II had M, = 20.7 kg/mol and M, = 40.4 kg/mol; 403
M, limit for miscibility in 50/50
blend of I with II was 69 & 25 kg/mol
I was oligomeric polyethylene with 584
M, = 0.254 to 2.234 kg/mol and II was
oligomeric polydimethylsiloxane with
M, = 0.505 to 4.5 kg/mol
I and II both had MW < 1 kg/mol 6 5
I had M, = 20 kg/mol miscible with II; 328
I had M, = 100 kg/mol miscible with
II when blend had 5 50% II
Blends with II >40 wt.% were homo- 796
geneous when I had MW = 3.5-4.5 kg/mol
and II had MW = 35.6 kg/mol. Blends
were heterogeneous at all compositions
when I had MW = 200 kg/mol
Miscible when II had M, = 1.759 kg/mol; 923
immiscible when II had M, = 159.4 kg/mol
I was natural rubber; II had M, 5 0.375 kg/mol; 1 4 0
two peaks when 11 had M, 10.6 kg/mol
I was natural rubber; II had M, 5 0.375 kg/mol; 1 4 0
two peaks when II had M, 2 0.65 kg/mol
Miscible when M, of I/II were 2.4 kg/mol/ 930
38 kg/mol, 10.55 kg/mol, 38 kg/mol,
60 kg/mo1/9.9 kg/mol, 105 kg/mo1;/9.9 kg/mol;
immiscible when M, of I/II were
20.3 kg/mo1;/38 kg/mol, 33.5 kg/mo1;/25.9 kg/mol,
33.5 kg/mo1;/38 kg/mol and 60 kg/mo1;/38 kg/mol
II had 60 wt.% HFPC and M, = 33 kg/mol, 1 1 9 4
and miscible when I had M, =
4-9.9 kg/mol; when II had M, =
103 kg/mol, it was miscible with I having
M, = 4 kg/mol and 11 kg/mol only
Miscible when I had M, = 2.4 kg/mol and 640,804,
II had M, = 2.95 kg/mol; blends showed 929
UCST when I and II had higher M,
(Ref. 929)
Immiscible when I had M, = 6.7 kg/mol
and II had M, = 105.5 kg/mol; miscible
when I and II had lower M,
Miscible when I had M, = 1.2 1 kg/mol or and
2.4 kg/mol and II had M, = 12 kg/mol;
immiscible when I had M, = 4.25 kg/mol
and II had M, = 34 or 44 kg/mol
929
9 3 1
References page VI - 461
VI / 452 MISCIBLE POLYMERS
TABLE 4. contd
Polymer I of Polymer II of Method Comments Ref s.
Methyl methacrylate-co-styrene styrene
n-Methylstyrene Styrene
cc-Methylstyrene-co-styrene
Propylene
Styrene, deuterated
Styrene
Ethylene-co-propylene
Styrene Carbonate of bisphenol-A
Carbonate of dimethylbisphenol-A
Carbonate of tetramethylbisphenol
p-Vinylphenol
o-Chlorostyrene-co-p-chlorostyrene
Vinyl methyl ether
2-Viny1 naphthalene
Diethyl itaconate
Single T,; transparency
Single T,; transparency;
neutron scattering
Single T,
Single T,
Single T,
Single T,; transparency
Single T,; transparency
Single T,; transparency
Single T,
Single T,
Single T,
Single T,
I had 26% styrene and II had
MW = 0.6 kg/mol or I 5 5 7 , 8 0 4
had 62.6% styrene and II had MW
5 2.1 kg/mol or I had 80% styrene and
II had MW 5 4 kg/mol
Miscible when I had M, = 55 kg/m01 and 38,42,63,
II had M, = 22 or 52 kg/mol; immiscible 159,203,
when II had M, = 341 kg/m01 (Ref.929) 6 9 1 , 7 1 0 ,
721,822,
8 6 5 , 9 2 9
I had M, = 25.8-78.3 kg/mol; II had M, =
36.1-84.1 kg/mol
I had M, = 59-818 kg/mob II had
3-79 mol% a-methylstyrene
Miscible when I had M, = 33 kg/m01 and
II had M, = 44.5 kg/mol; immiscible when
I and II had higher M,
I had M, = 0.58, 0.68, 0.95 or
II had M, =3. 8, 9, 25. 9
or 38 kg/mol; miscibility depended
on M, and composition of blend
II had M, = 30 kg/mol; miscible when I had
M, = 0.58, 0.68 or 0.95 kglmol; immiscible
when I had M, = 2. 95 kg/m01
II had M, = 31 kg/mol; miscible when I had
M, = 2.95 kg/mol; partially miscible when
I had M, = 9.2 or 17.5 kg/mol; immiscible
when I had M, = 341 kg/m01
I had M, = 2.2-93 kg/mol; II had 7-100
mol% o-chlorostyrene
671
159
1101
9 3 0
930
930
131
I had mol. wt. 0.8-233 kg/mol; II had 878,724
mol. wt. 1.0-97.5 kg/m01
I had MW = 2. 2 kg/mol; II had MW 5 70 kg/mol 7 3 1
II had M, = 9.4 kg/mol and was miscible 1 0 3 4
with I having M, = 1.5-7 kg/mol,
9- 11 kg/mol;, 22 or 30 kg/mol; II had
M, = 61 kg/mol and was miscible with I
having M, = 1.5-7 kg/mol and
9- 11 kg/moI
S
TABLE 5. POLYMER PAIRS THAT APPEAR TO HAVE HIGH TEMPERATURE MISCIBILITY, ALTHOUGH IMMISCIBLE AT OR BELOW ROOM
TEMPERATURE (UCST BEHAVIOR)
Polymer I of Polymer II of Comments References
Acrylonitrile-co-styrene Sulfone of tetramethylbisphenol-A
Aramide
Butadiene
Imide
Butadiene
Butadiene, perdeuterated
Butadiene-co-styrene
Styrene
Butadiene-co-styrene
Terpene resin, hydrogenated
Styrene
I had 9 wt.% AN and II had M, = 4.8 kg/mol; I had 11 wt.% 9 3 1
AN and II had M, = 12.4 kg/mol
I was Aramid 341; II was Polyimide UR 1 1 3 6
I had 98% c&1,4; II had 71% vinyl-l,2 and 19% 7 3 6
tram- 1,4
Both I and II were c&1,4 4 9
I was &s-1,4; II had 23-30 wt.% styrene 362,650,737,
797,1121
II was hydrogenated or partly deuterated, I and II had
MW = 2.0 kglmol (Ref. 516); I had M, = 0.96 kg/mol and
II had M, = 9.0 kg/mol (Ref. 808)
I had lo-70.4% l&content
II was hydrogenated or partly deuterated; II was 68.4 wt.%
styrene and had MW of IO kg/m01 and II had MW
of 100 kg/m01
516,808
1062
5 1 6
TABLE 5. contd
Polymer Pairs that Show UCST Behavior VI 1453
Polymer I of Polymer II of Comments References
Caprolactone
Carbonate of bisphenol-A
Chlorostyrene-co-styrene
Cyclohexyl methacrylate
2,2-Dimethyl- 1,3-propylene sebacate
Dimethylsiloxane
Epoxy
Ether ether sulfone
Etherimide
Ethyl methacrylate
Ethylene
Ethylene, chlorinated
Hemicellulose
Isophthalamide-61 (iminoiso-
phthaloyl-iminohexamethylene)
Isoprene
Maleic anhydride-co-styrene
Methyl methacrylate
1,3-Phenylene adipamide
Styrene
Vinyl chloride
Vinylidene fluoride
Vinylidene fluoride-co-
tetrafluoroethylene
Ester
Methacrylic acid-co-styrene
Liquid crystalline polymer of
biphenyl-4,4-ylene sebacate
Segmented copolyetherester
2,6-dimethyl-1,4-phenylene oxide
Cyclohexyl acrylate
Haloalkyl methacrylate
Methyl ethyl siloxane
Phenyl methyl siloxane
Acrylonitrile-co-butadiene, carboxyl
terminated
2,6-Dimethyl-1,4-phenylene oxide
Ether ether ketone-co-ether ether sulfone
Ethylene terephthalate-co-ethylene
naphthalate
Ethyl acrylate ..
Propylene
Ethylene, chlorinated
Lignin
Hexamethylene adipamide (nylon 6,6)
Vinylethylene
Sulfone of tetramethylbisphenol-A
Carbonate of dimethylbisphenol-A
Carbonate of tetrachlorobisphenol-A
Carbonate of tetramethylbisphenol-P
Hydroxybutyrate
Styrene
Sulfone of tetramethylbisphenol-A
Sulfone of tetramethylhexafluoro-bisphenol-A
Sulfone of tetramethylbisphenol-P
Vinyl chloride
Hexamethylene adipamide (nylon 6,6)
Caprolactone
Carbonatg of bisphenol chloral
cc-Methylstyrene
o-Methflstyrene
p-Methylstyrene
m-Methylstyrene
Styrene, brominated
Styrene, deuterated
Sulfone of tetramethylbisphenol-A
Sulfone of tetramethylbisphenol-P
Sulfone of tetramethylhexafluorobisphenol-A
Vinyl methyl ether
Acrylonitrile-co-methyl methactylate-co-
cc-methylstyrene
Methyl methacrylate
Vinylidene fluoride-co-hexafluoroacetone
II was made from adipoyl chloride and 4,4-bis(6-hydro-
8 2 1
hexyloxy)biphenyl
II had 4-23 wt.% methacrylic acid 1 0
Blend had 50-80 wt.% II 387
I had a hard tetramethylene terephthalate segment 1 0 1 5
and a soft polytetramethylene-ether-glycol
terephthalate segment
I had 32.9 mol% styrene 234,863
- 765
II had a haloalkyl group of 2-bromoethyl, 2-chloroethyl, 611,1137,1111
3-chloropropyl or 2-iodoethyl (4 blend systems)
- 341
- 469
I was Epon 828, M, =0.38 kg/mol; II had 17 wt.% acrylonitrile, 492
M, = 3.5 kg/mol
II was diglycidyl ether of bisphenol-A
II had 50% ether ether sulfone
The higher the ethylene naphthalate content in II, the
lower the UCST
-
II was atactic; no UCST when II was isotactic; from
high temperature phase diagrams
Cl contents = 40-50 wt.%
Blend had 10, 80 or 90 ~01% of II
Interchange reaction slow
II was syndiotactic and had 92% vinyl-1,2-
I had 14 wt.% maleic anhydride; II had M, = 4.8 kg/m01
I had M, = 1.21 or 2,4kg/mol; II had M, = 33 kg/mol
I had M, = 1.21 kg/mol; II had M, =41 kg/mol
I had M, = 1.21 or 2.4 kg/mol; II had M, = 31 kg/mol
I had M, = 2.03-6.0 kg/mol; II had M, =
1.95-9.2 kg/mol
I had M, = 1.21 or 2.4kg/mol; II had M, =4.8
or 12.4 kg/mol
I had M, = 1.21 kg/mol; II had M, = 40 kg/mol
I had M, = 1.21 kg/mol; II had M, = 40 kg/mol
-
I was made from m-phenylenediamine and adipic
acid; interchange reaction slow
I had M, = 0.95 kg/mol
I had M, =0.58 or 0.68 kg/mol; II had M, = 30 kg/mol
UCST increased with molecular weight
-
-
II had 27 or 29 mol% brominated units
1 1 4 8
740
1072
766
452
816
1188
899
363
931
930
930
930
1189
558,929,1146
931
931
931
674
899
629
930
514
24
24,786
24
784
48,879
I had M, = 1.21 or 2.4 kg/mol; II had M, = 4.8 or 12.4 kg/mol
I had M, = 1.21 kg/mol; II had M, = 40 kg/m01
I had M, = 1.21 kg/mol; II had M W = 40 kg/m01
By extrapolation of solution data
II had 32.3 wt.% AN, 8.1 wt.% MMA and 59.6 wt.% =-MS;
blend had 50-80 wt.% II
9 3 1
9 3 1
9 3 1
1 6 8
1 0 7 8
-
I had 80 mol% vinylidene fluoride; II had 92 mol%
vinylidene fluoride
References page VI - 46 1
VI / 454 MISCIBLE POLYMERS
TABLE 6. POLYMER PAIRS MISCIBLE AT ROOM TEMPERATURE THAT APPEAR TO HAVE A LOWER CRITICAL SOLUTION TEMPERATURE
(LCST) ABOVE ROOM TEMPERATURE
Polymer I of Polymer II of Comments Refs.
Acrylic acid, Li-neutralized Ethylene oxide
Acrylic acid-co-styrene Ethyl methacrylate
Methyl methacrylate
n-Propyl methacrylate
Acrylonitrile-co-butadiene-co-methyl Ethylene-alt-maleic anhydride
acrylate
Acrylonitrile-co-c-methyl styrene Acetonyl methacrylate
n-Butyl methacrylate
n-Butyl methacrylate-co-methyl methacrylate
Carbonate of tetramethylbisphenol-A
Ethyl methacrylate
Ethyl methactylate-co-methyl methacrylate
Methoxymethyl methacrylate
Methyl methacrylate
Methyl methacrylate-co-2,2,66tetramethyl-
piperidinyl methacrylate
Methylthiomethyl methacrylate
n-Propyl methacrylate
Acrylonitrile-co-p-methylstyrene
Tetrahydrofurfuryl methacrylate
Vinyl chloride
Acetonyl methactylate
n-Butyl methacrylate
Cyclohexyl methacrylate
Acrylonitrile-co-styrene
Ethyl methacrylate
n-Propyl methacrylate
Tetrahydrofurfuryl methacrylate
Tetrahydropyranyl-2-methyl methacrylate
Acetonyl methacrylate
Acrylonitrile-co-methyl methacrylate
Butyl methacrylate-co-methyl methacrylate
Caprolactone
Copolycarbonate of bisphenol-A and
tetramethylbisphenol-A
Cyclohexyl methacrylate
2,6-Dimethyl-1,4-phenylene ether, benzoylated
Ethyl methacrylate
Maleic anhydride-co-styrene
Methoxymethyl methacrylate
Methyl methacrylate
Methyl metiacrylate-co-2,2,6,6-tetramethyl-
Aniline, N-octadecylated
Aramide
Arylsulfone
2-Bromoethyl methacrylate
Butadiene
piperiditiyl methacrylate
Methyl methacrylate-co-N-phenylmaleimide
Methylthiomethyl methacrylate
Phenyl acrylate
n-Propyl methacrylate
Tetrahydrofurfuryl methacrylate
Tetrahydropyranyl-2-methyl methacrylate
Vinyl chloride
Ethylene-co-vinyl acetate
Caprolactan-co-laurolactam
Imide
Vinyl acetate
Butadiene
Isoprene
Butyl acrylate Ethylene, chlorinated
Vinyl chloride
0.1-0.4 mole fraction of I was neutralized
I had 8.84 wt.% acrylic acid
I had 2.65-20.0 wt.% acrylic acid
I had 2.65-8.84 wt.% acrylic acid
I was Barex 210
I had 30 wt.% acrylonitrile (AN)
I had 12 wt.% AN
I had 30 wt.% AN; II had 70 wt.% methyl methacrylate
I had 4-16.5 wt.% AN
I had 30 wt.% AN (Ref. 277); II had lo-28 wt.% AN
(Ref. 152)
I had 30 wt.% AN: II had 60 wt.% methyl methactylate
I had 30 wt.% AN
I had 30 wt.% AN and II was atactic or isotactic
(Ref. 277); I had 31.3, 33.1, 34.8 or 41.3 wt.% AN
(Ref. 790); I had IO-37 wt.% AN (Ref. 152)
I had 30 wt.% AN; II had 2 76.2 wt.% methyl
methacrylate)
I had 30 wt.% AN
I had 17-20 wt.% AN
I had 30 wt.% AN
I had 11.9-30 wt.% AN
I had 43.0-61.0 wt.% AN
I had 13.6 wt.% AN
I had 15.8-21.3 wt.% AN
I had 26.5-32.3 wt.% AN
I had 21.3-26.5 wt.% AN
I had 32.3-46.5 wt.% AN
I had 23.8-26.5 wt.% AN
I had 33-58 wt.% AN
Some blends showed LCST
Some blends showed LCST
I had 24-28 wt.% AN
Some blends showed LCST, depending on compositions
of I and II
I had 13.4-19.8 wt.% AN
I and 18 mol% AN; II had 35% benzoylated unit
I had 5.5-28 wt.% AN
1115
7 2
384,856
8 5 6
1 1 5 6
2 6 6
152
289
1 0 1 0
1 5 2 , 2 7 7
2 8 9
266
152,277,790,
1 0 1 0
272,274
2 6 8
1 5 2
281
1 0 1 0
121
2 8 5
1 2 0
2 8 5
2 8 5
2 8 5
1 1 9
121
620
4 0 5
565,1145
4 3 1
120
776
229,489
Some blends showed LCST 436,462,555
I had 30 wt.% AN 258
I had 9.4, 9.8, 27.0, 28.2, 30.5 or 34.4 wt.% AN 56,164,
(Ref. 506); I had 29.4-39.3 wt.% AN (Ref. 164) 460,506,566
I had 22 or 30 wt.% AN; II had 69, 74 or 85.5 wt.% 272,274
methyl methacrylate
I had 24.6 wt.% AN; II had 23.5 wt.% N-phenylmaleimide 185
I had 34.5 wt.% AN 269
I had 14.6, 29.9 or 34.1 wt.% AN 717
I had 5.7-19.5 wt.% AN 229,109O
I had 34.5-46.6 wt.% AN 286
I had 2.2 or 22-30.5 wt.% AN 119
I had 11.5-26 wt.% AN 437
I was 60.2% alkylated; II had 20 wt.% vinyl acetate 1 2 4 6
I was Trogmid T, II had 43.8 mol% caprolactam 2 1 3
I was Radel A; II was XU 218 3 7 5
Blends cast from methyl ethyl ketone 610
I had 50% vinyl-1.2, 35% cis-1,4 and 15% trans-1,4; 7 3 6
II had 55% ?rans-1,4, 35% cis-1,4 and 10% vinyl-l,2
I had 5 59% 1,4 content and II was c&1,4 isomer 335,810
(Ref. 810); I was deuterated and II was protonated
(Ref. 335)
- 1 0 0
- 655,845,850,851
Polymer Pairs that Show LCST Behavior
TABLE 6. contd
Polymer I of Polymer II of Comments
Refs.
Butyl methacrylate
N-butyl-3-hydroxymethyl-
carbazoyl methacrylate
p-rert-Butylstyrene
Caprolactone
Carbon monoxide-co-ethyl
acrylate-co-ethylene
Carbonate of bisphenol-A
Carbonate of hexafluorobisphenol-A
Carbonate of tetramethylbisphenol-A
Carbonate of tetramethylbisphenol-P
Caprolactone
Cellulose acetate
1-Chloroethyl methacrylate
2-Chloroethyl methacrylate
Chloromethyl methacrylate
o-Chlorostyrene
o-Chlorostyrene-co-p-chlorostyrene
2,2-Dichloroethyl methacrylate
2,6-Dimethyl-1,4-phenylene ether
2,6-dimethyl-1,Cphenylene
ether, sulfonylated
Dodecamethylene decamethylene
dicarboxylate
Dodecamethylene dodecamethylene
dicarboxylate
p-(2-Hydroxy-hexafluoroisopropyl)styrene-
co-styrene
II had 90.3-90.8 mol% styrene
w-Hydroxybutyl-3,5-dinitrobenzoyl methacrylate -
Cyclohexyl acrylate
Cyclohexyl methacrylate
Ethylene, chlorinated
Vinylidene fluoride
Vinyl chloride
-
II had 30 or 42.1 wt.% Cl
Blends rich in I showed LCST
I had 13.8/7.41/78.8 = carbon monoxide/ethyl
acrylatelethylene
Caprolactone
-
Cyclohexyl methaqlate-co-methyl methacrylate II had 5 3.3 wt.% cyclohexyl methacrylate (Ref. 574);
II had 14.7-34.3 wt.% cyclohexyl methacrylate
(Ref. 81)
Methyl methacrylate
Methyl methacrylate-co-p-methylstyrene
Methyl methacrylate-co-N-phenylmaleimide
Methyl methaclylate-co-phenyl methacrylate
Methyl methacrylate-co-styrene
Alkyl methacrylate
Acrylonitrile-co-styrene
Methyl methacrylate-co-styrene
Styrene
Styrene
Styrene-co-p-vinylphenol
Vinyl methyl ether
4-Vinylpyridine
Alkyl methacrylate
Ethyl methacrylate
Alkyl methacrylate
Styrene
Styrene
Alkyl methacrylate
Acrylic acid-co-styrene
Acrylonitrile-co-styrene
o-Chloros,tyrene-co-p-chlorostyrene
o-Chlorostyrene-co-o-fluorostyrene
p-Chlorostyrene-co-o-fluorostyrene
o-Fluorostyrene-co-p-fluorostyrene
o-Fluorostyrene-co-p-bromostyrene
a-Fluorostyrene-co-styrene
p-Fluorostyrene-co-styrene
Maleic anhydride-co-styrene
Methyl methacrylate-co-styrene
o-Fluorostyrene
p-Fluorostyrene
Phenylvinyl set-butyl ether-alt-N-phenyl-
maleimide
Phenylvinyl ethyl ether-alt-N-phenylmaleimide
Vinyl chloride
Vinyl chloride
Vinyl chloride-co-vinylidene chloride
Blends prepared by precipitation of tetrahydrofuran
solutions by n-heptane; or by solution casting from
tetrahydrofuran at high temperature
II had 2 70 wt.% methyl methacrylate
II had 2 70 wt.% methyl methacrylate
II had 16-63 wt.% phenyl methacrylate
II had 5 14 wt.% styrene
II had an alkyl group of ethyl, n-propyl or isopropyl
(3 blend systems)
II had 2 or 11.5% acrylonitrile
II had 4.5, 32.5, 33.5 or 35 wt.% methyl methacrylate
646
298
765
765
5 3 , 1 9 1
386
692
56,177,645
81,574
109,481,486
357
357
81
577
427,430
225
429,575,884
(Ref. 575); II had 4.5-33.5 wt.% methyl methacrylate
(Ref. 429)
I had M, = 341 kg/mol; II had M, = 33 kg/mol
359,428,741,930
I had M, = 9.2 kg/mol; II had M, = 31 kg/mol
II had 10 wt.% vinylphenol
I was lOH/2 glucose
II had an alkyl group of ethyl, n-propyl, isopropyl or
n-butyl (4 blend systems)
-
II had an alkyl group of ethyl, isopropyl or n-propyl
(3 blend systems)
I had 7 l-92 mol% o-chlorostyrene
II had an alkyl group of n-propyl, isopropyl, n-butyl or
isoamyl (4 blend systems)
II had 6.3 or 8.5 wt.% acrylic acid
II had 6.3 wt.% acrylonitrile
-
II had about 14-40 mol% o-chlorostyrene
II had 66-74 mol% p-chlorostyrene
II had lo-38% p-fluorostyrene
II had 68 or 73 mol% bromostyrene
II had 9-20 mol% styrene
II had about 22-54 mol% styrene
II had 4.6-9.9 wt.% MA (Ref. 1226); II had 7.3-12.5
wt.% MA (Ref. 1022)
II had 12.5-20 wt.% methyl methacrylate
I had 4- 17 mol% sulfonylated units
I had 17-66 mol% sulfonylated units
I had 87 mol% sulfonylated units
I had 87 or 91 mol% sulfonylated units
-
-
II had 13.5 wt.% vinyl chloride
930
905
1 1 4 5
86
1152
612
273
15
803
1110
1 0 2 2
1 0 2 2
1 6
8 4 0 , 8 4 1
8 4 0 , 8 4 1
8 3 5
834
839,842
531,839,842
1022.1226
1 0 2 2
1 2 2 0
1 2 2 0
1 2 1 9
1 2 1 9
872
872
8 7 3
References page VI - 461
VI / 456 MISCIBLE POLYMERS
TABLE 6. contd
Polymer I of Polymer II of Comments Ref s.
Epichlorohydrin
Ether sulfone
Ethyl acrylate
2-Ethylhexyl methacrylate, modified
N-ethyl-3-hydroxymethylcarbazoyl
methacrylate
Ethyl methacrylate
Ethyloxazoline
Ethylene, chlorinated
Ethylene orthophthalate
Ethylene ether
Ethylene-co-vinyl acetate
2-Fluoroetbyl methacrylate
3-Fluoropropyl methacrylate
Hexadecamethylene dodecamethylene
dicarboxylate
n-Hexyl methacrylate
Hydroxyether of bisphenol-A
Wenoxy)
I- Hydroxyether of phenolphthalein
B-Hydroxyethyl-3,5-dinitrobenzoyl
methacrylate
2-(Hydroxyhexafluoroisopropyl)
styrene-co-styrene
Hydroxypropyl Glutamine
2-Iodoethyl methacrylate
Isoprene
Maleic anhydride-co-styrene
Methacrylonitrile-co-p-methylstyrene
Methacrylonitrile-co-styrene
Alkyl acrylate
Alkyl methacrylate
Ethyl acrylate rubber
Vinyl acetate
N-vinylpyrrolidone
Imide
Hexafluoroacetone-co-vinylidene fluoride
Vinylidene fluoride
Hexyl methacrylate-co-styrene, modified
o-Hydroxyalkyl-3,5-dinitrobenzoyl methacrylate
p-(2-hydroxy-hexafluoroisopropyl)styrene-
co-styrene
Vinyl chloride-co-vinylidene chloride
Vinylidene fluoride
Aramid
:
Ether sulfone
Ethylene-co-vinyl acetate
Methyl methacrylate
Vinyl acetate
Enaminonitrile
Ether sulfone
Ethylene-co-vinyl acetate
Sulfone
Hexafluoroacetone-co-vinylidene fluoride
Vinyl chloride
Alkyl methacrylate
Methyl methacrylate
Vinyl chloride
Styrene-co-p-vinylphenol
Alkyl methacrylate
Ether sulfone
Ethylene oxide-co-propylene oxide
Vinyl methyl ether
Butylene tetephthalate
Ether sulfone
Ethylene gfycol
N-alkyl-3-hydroxymethylcarbazoyl methacrylate
Methyl methacrylate
Vinyl methyl ether
Styrene-co-p-(hexafluoro-2-hydroxy-2-propyl)-
cc-methylstyrene
Tetrahydrofurfuryl methacrylate
cis-Butadiene-co- 1,2-vinylbutadiene
Ethyl methacrylate
Methyl methacrylate
n-Propyl methacrylate
n-Butyl methacrylate
Ethyl methacrylate
Methyl methacrylate
Isopropyl methacrylate
n-Propyl methacrylate
Ethyl methacrylate
II had an alkyl group of ethyl or n-propyl
(2 blend systems)
II had an alkyl group of methyl, ethyl, n-propyl, n-butyl
or cyclohexyl (5 blend systems)
-
-
II was Matrimide 5218
II had 8 mol% hexafluoroacetone
I had 3-5% acrylic acid; II had 30% styrene and
5-15% 3-(dimethylamino) 2,2-dimethylpropyl
methacrylate
II had an alkyl group of butyl, hexyl, pentyl or propyl
(4 blend systems)
II had 90.3-98.8 mol% styrene
II had 86.5 wt.% vinylidene fluoride
I was syndiotactic or atactic; LCST below T, of II if
I had high MW isotactic
-
I had 35.4-52.6 wt.% Cl; II had 40-45 wt.%
vinyl acetate
I had 50-52 wt.% Cl
2 2 4
2 2 4
2 2 6
3 0 5
300
510
411,1059
56,844
7 6 6
694
646
8 7 0
56,695,802
532
599
8 4 9
99,848
I had M, = 9.5 kg/mol; no LCST when I had M, = 5.1 kg/mol
8 2 9
- 5 8 5
- 317,534,743,853
- 1 2 9
M, of I = 3.5-4.5 kg/mol; II was Udel P1700 796
I had 70% vinyl acetate; II had 8.9 mol%
3 3 6
hexafluoroacetone
I had 3 0 or 3 7 wt.% ethylene 631,678
II had an alkyl group of methyl or ethyl (2 blend systems) 1 1 5 3
1 1 5 5
8 7 2
II had 7 or 9 wt.% vinylphenol
II had an alkyl group of methyl, tetrahydrofurfuryl or
tetrahydropyranyl-2-methyl (3 blend systems)
922
111,118,253
714,764
II had 22, 50 or 66 mol% ethylene oxide
-
-
1 0 2 5
8 1 8
310
306
309
II had an alkyl group of butyl, decyl, dodecyl, ethyl,
hexadecyl, hexyl, octyl or tetradecyl
I had 90.3-96.1 mol% styrene
6 9 3
646
I had 90.3-99.9 mol% styrene
II had 98.5 mol% styrene; blend had ~50 ~01% I
646
9 7 1
I had 8, 10, 13 or 33 wt.% maleic anhydride
I had 0- 18.1 wt.% maleic anhydride
I had 15-25 wt.% MAN
I had 40, 46 or 53 wt.% MAN
I had 34, 53, 56 or 68 wt.% MAN
I had 22-31 wt.% MAN and I had M, = 161 kg/mol; II had
17-31 wt.% MAN and I had M, =41.6kg/mol
-
II had 5 24.3% vinylbutadiene
I had O-33 wt.% maleic anhydride
1 1 0 7
420
7 3
7 3
7 3
944
944
944
944
I had 37 or 40 wt.% MAN 944
I had 5.6, 35.4 or 40.1 wt.% MAN 9 4 3
Polymer Pairs that Show LCST Behavior VI/457
TABLE 6. contd
Polymer I of Polymer II of Comments Refs.
Methyl acrylate
Methyl methacrylate
Methyl methacrylate, imidized
c+Methylstyrene
cL-Methylstyrene-run-4-
(2-hydroxyethyl)-a-methylstyrene
a-Methylstyrene-srat--[4-( l,l,l-
trifluoro-2-hydroxyethyl)-
a-methylstyrene
Neopentyl glycol adipate
(2,2-dimethyl-1,3-propylene
adipate)
Neopentyl glycol succinate
(2,2-dimethyl- 1,3-propylene
succinate)
Oxymethylene
Phenol-formaldehyde
p-Phenylene benzobisoxazole
2,2-(m-Phenylene)-5,5-
bibenzimidazole
Methyl methacrylate
n-Propyl methacrylate
Vinylidene fluoride
Acrylonitrile-co-methyl methacrylate-co-styrene
Carbonate of bisphenol chloral
Copolycarbonate of bisphenol-A and
hexafluorobisphenol-A
Epichlorohydrin-co-ethylene glycol
Ethylene, chlorinated
Ethylene glycol
Hexafluoroacetone-co-vinylidene fluoride
N-maleimide-co-styrene
Styrene-co-p-vinylphenol
Sulfone of hexafluorobisphenol-A
Tetrafluoroethylene-co-vinylidene fluoride
Vinyl acetate
Vinyl chloride
Vinyl chloride, chlorinated
Vinyl chloride-cd-vinylidene chloride
Vinylidene fluoride
Acrylonitrile-co-styrene
Carbonate of tetramethylbisphenol-A
Carbonate of tetramethylbisphenol-P
Ethyl methacrylate
Methyl methacrylate
n-Propyl methacrylate
Styrene
Tetrahydropyranyl-2-methyl methacrylate
Alkyl acrylate
Alkyl methacrylate
Dialkyl itaconate
Vinyl acetate
Vinyl pyrrolidone
4-Vinylpyridine
Alkyl acrylate
i
Alkyl methacrylate
.I
Dialkyl itaconate
Vinyl acetate
Vinyl pyrrolidone
4-Vinylpyridine
Hydroxyether of bisphenol-A (phenoxy)
Hydroxyether of bisphenol-A (phenoxy)
Vinyl chloride-co-vinylidene chloride
Novolac
Methyl methacrylate-co-styrene
Nylon
Imide
I had 46.6-62.8 wt.% MAN 1 0 1 8
I had 2-32 wt.% MAN 943
- 56,844
II had 40.0/39.1/20.9 or 61.1/19.6/19.3 of S/MMA!AN 620
- 110,930
II had 5.3- 14 wt.% hexafluorobisphenol-A 430
II had 50 mol% ethylene glycol 224
II had 56-68 wt.% Cl; I was atactic, isotactic or 1204
syndiotactic
- 224
- 443
II had 8, 14 or 21 wt.% N-maleimide 1 2 1 3
I was syndiotactic; II had 5 mol% vinylphenol 1 0 5 5
I had M, = 2.4 kg/mol;, 1.21 or 4.25 kg/mol; II had 9 3 1
M, = 27 kg/mol or 56 kg/mol
II had 80 mol% vinylidene fluoride 324
Blends cast from chloroform or cyclohexanone 302,777,778,1092
368,506,653,742
II had 63, 65 or 68 wt.% Cl 506,833
I was atactic or isotactic; II had 86.5 wt.% vinylidene 506,870
chloride
LCST above decomposition temperature of I 5 5
I had 53-91 wt.% imidized unit; II had 5.7-33 wt.% 230
acrylonitrile; some blends showed LCST
I had M, = 3.5 or 6.7 kg/mol; II had M, = 33 kg/m01 930
I had M, = 3.5 or 6.7 kg/mol; II had M, = 31 kg/mol 930
- 765
- 1 6 7 , 7 6 5
- 765
710,722,865,929
1 1 6
II had an alkyl group of methyl, ethyl or rert-butyl
(3 blend systems)
968
II had an alkyl group of methyl, ethyl or rert-butyl
(3 blend systems)
968
II had an alkyl group of methyl, ethyl, n-propyl,
n-butyl or rerr-butyl (5 blend systems)
-
-
II had an alkyl group of methyl, ethyl or f-butyl
(3 blend systems)
968
969
969
969
968
II had an alkyl group of methyl, ethyl or r-butyl
(3 blend systems)
968
II had an alkyl group of methyl, ethyl, n-propyl,
n-butyl or r-butyl (4 systems)
968
969
969
969
- 332
332
II was Saran, 86.5 wt.% vinylidene chloride; LCST
above T, when 5 50 wt.% I
-
II had 30.4-83.5% MMA
II was Zytel 330 (Du Pont) or nylon 6.6
(2 blend systems)
8 6 8
8 5 8
433
945
II was Ultem 1000 or XU218 (2 blend systems)
1 1 4
References page VI - 461
VI 1458 MISCIBLE POLYMERS
TABLE 6. contd
Polymer I of Polymer II of Comments Ref s.
n-Propyl methacrylate
Styrene
Styrene, sulfonated and
Zn-neutralized
Styrene, sulfonated and neutralized
Vinyl acetate
Vinyl acetate-co-vinyl chloride
Vinyl butyral
Vinyl chloride
Vinyl methyl ether
Vinyl methyl ketone
p-Vinylphenol
2-Vinylpyridine
4-Vinylpyridine
Vinylidene fluoride
Vinyl chloride-co-vinylidene chloride
Copolycarbonate of bisphenol-A and
tetramethylbisphenol-A
o-Fluorostyrene-co-p-fluorostyrene
Caprolactam (nylon 6)
Caprolactam (nylon 6)
Hexafluoroacetone-co-vinylidene fluoride
Maleic anhydride-air-styrene, hydrolyzed
n-Butyl methacrylate
Hexyl acrylate-co-methyl acrylate
Methyl methacrylate
Vinylpyridine
Acrylonitrile-co-n-butyl acrylate
Alkyl acrylate
Alkyl methacrylate
Butyl acrylate-co-ethyl acrylate
Butyl acrylate-co-hexyl acrylate
Butyl acrylate-co-methyl acrylate
Butyl acrylate-co-methyl methacrylate
Butyl methacrylate-co-methyl methacrylate
Ethyl acrylate-co-hexyl acrylate
Methyl acrylate-co-hexyl acrylate
Pentyl acrylate-co-propyl acrylate
Acrylonitrile-co-styrene
Alkyl acrylate
2-Chlorostyrene
Hydrogeneous styrene-b-deuterated styrene
Maleic anhydride-co-styrene
cc-Methylstyrene
a-Methylstyrene-co-4-(2-hydroxyethyl)-
cc-methylstyrene
a-Methylstyrene-co-4-( 1.1, l-trifluoro-
2-hydroxyethyl)-a-methylstyrene
a-Methylstyrene-co-styrene
m-Methylstyrene-co-styrene
o-Methylstyrene-co-styrene
p-Methylstyrene-co-styrene
Methyl me@acrylate-co-styrene
Nitrostyrene-co-styrene
Styrene-c&l-vinyl naphthalene
Styrene-co-2-vinyl naphthalene
Styrene-co-4-vinylstilbene
4-Acetoxystyrene
Aramide
2-Hydroxyethyl methacrylate
Vinyl acetate-co-vinyl alcohol
Methoxymethyl methacrylate
II had 86.5 wt.% vinylidene chloride
II had 2 85 wt.% tetramethylbisphenol-A
I had M, = 7 kg/mol; II had 10 or 33 mol% p-fluorostyrene
I had 6.5, 8.1 or 9.0 mol% sulfonated units
I was neutralized by Li, Mg or Zn
II was 1.8-43% hydrolyzed; LCST increased with
increasing degree of hydrolysis
I had 5.9-15.1 ~01% vinyl acetate
I had 5-23.7 ~01% vinyl acetate; II had 15-88 ~01%
hexyl acrylate; some blends showed LCST
I had 5.9-15.1 ~01% vinyl acetate
II was 2- or 4-vinylpyridine (2 blend systems)
II had 53, 67 or 84 mol% butyl acrylate
II had an alkyl group of n-propyl or n-amyl
(2 blend systems)
II had an alkyl group of n-butyl or n-amyl
(2 blend systems)
II had 22.9, 43.5 or 52.8% butyl acrylate
II had 47.8% butyl acrylate
II had 44.6% butyl acrylate
II had 75% butyl acrylate
II had 30 or 70% methyl methacrylate
II had 41.7 or 43.2% ethyl acrylate
II had 9.7% methyl acrylate
II had 48.1% propyl acrylate
II had 5 lo- 11% acrylonitrile
II had an alkyl group of ethyl or n-butyl
(2 blend systems)
-
-
II had < 15% maleic anhydride
-
II had 6-89 mol% cc-methylstyrene
II had O-93 mol% a-methylstyrene
II had 77.5 or 88 wt.% styrene
II had 76.5 or 87.5 wt.% styrene
II had 76.2 or 86.8 wt.% styrene
II had 61-95 wt.% styrene
II had < 60 mol% methyl methacrylate
II had 5 25.6 mol% Nitrostyrene
II had 17.4 wt.% styrene
II had 19.2 wt.% styrene
Cloud point was sensitive to the cis- fraction of
4-stilbenzyl groups
II made from hexamethylenediamine and a mixture
of isomers of phthalic acid
-
II had 32-55 mol% vinyl alcohol
1083
1223
1073
6 7
4 9 7
3 7 9
497
1003
6 5 5
8 5 1
649,653
851
8 5 1
8 5 1
654
6 5 3
8 5 1
8 5 1
8 5 1
5 7 5
9 4 1
1 2 0 3
1 0 1 9
5 7 5
318
1 7 0
1 7 0
3 1 8
1 0 2 8
1 0 2 8
318,1016,1028
108
1 6 5 , 1 9 2
3 1 8
3 1 8
3 6 5
340
767
9 3 7
1 0 4 6
2 6 7
TABLE 7. POLYMER PAIRS THAT APPEAR TO HAVE BOTH A LOWER CRITICAL SOLUTION TEMPERATURE AND A UPPER CRITICAL
SOLUTION TEMPERATURE
Polymer I of
Acrylonitrile-co-styrene
Butadiene
Caprolactone
Polymer II of
Acrylonitrile-co-butadiene
Butadiene-co-styrene
Acrylonitrile-co-styrene
Comments
I had 25 wt.% acrylonitrile; II had 40 wt.% acrylonitrile
II had 45 wt.% styrene
II had 12.4-26.4 wt.% acrylonitrile
Refs.
6 3 6
7 9 7
1193
Table 7. contcf
Polymer Pairs with Both LCST and UCST
Polymer I of Polymer II of Comment s Refs.
Carbonate of bisphenol-A
Dimethylsiloxane
2-Hydroxyethyl Acrylate-co-liquid
crystalline acrylate
o-Methylated phenol formaldehyde
Styrene
Methyl methacrylate Blends showed a LCST-UCST loop 72,479,1085
Methylphenylsiloxane 467
2-Hydroxyethyl acrylate-co-liquid crystalline Both I and II had 6% 2-hydroxyethyl acrylate; the 1 2 5 2
acrylate liquid crystalline polyacrylates had different
spacer groups
Methyl methacrylate I had 20 or 50% of OH group methylated 432
Methyl methacrylate-co-styrene I had 20 or 50% of OH group methylated; II had 50 432
or 60% methyl methacrylate
2,6-Dimethyl-1,4-phenylene ether, carboxylated II had 8.0- 10.3 mol% carboxyl group 1 4 8
TABLE 8. POLYMER PAIRS THAT CO-CRYSTALLIZE
Polymer I of Polymer II of Method Comment s Refs.
Butylene terephthalate Butylene glycol-b-butylene
terephthalate
T, and T, by DSC, dielectric
loss measurements
Butylene glycol-b-butylene
terephthalate
T, and T, by DSC, dielectric
loss measurements,
microscopy
Ester-ether segmented polymer Dielectric loss peak and T,
by DSC
Ether ether ketone Ether ether ether ketone T, and T, by DSC
Ether ether ketone ketone T, and T, by DSC
Ether ketone
Ether ketone
Ether-co-ketone
T, and T, by DSC
T, and T, by DSC; WAXD
T, and T, by DSC
Two T,s when I was Valox 310 (General
Electric) having M, = 20 kg/mol and II
contained 44-67 wt.% butylene terephthalate;
single T, and single T, when II contained
85 wt.% butylene terephthalate; single T,
indicated that only one type of crystal
was present
Single T, and single T, when I was Valox
310 (General Electric) with M, = 33 kg/
mol, II contained 84 wt.% butylene
terephthalate and I/II = l/3 to 3/l; thermal
analysis and morphological evidence pointed
to extensive co-crystallization in this mixture;
two T,s when II contained 50 wt.%
butylene terephthalate
I was Valox 310 (General Electric) with M, = 20
kg/mol; II was comprised of a poly(butylene
oxide) soft segment and a hard segment
4GT-butylene terephthalate, and had total
MW = 25 to 30 kg/mol; single beta dielectric
loss peak and single T, were found when II
was 44 or 67 wt.% 4GT, single T, between
the T,s of the pure components indicated
co-crystallization; two dielectric loss peaks
and two T, when II was 84 wt.% 4GT
Single T, and single T, when I contained
33% ketone linkages and had melt flow = 3.0
dglmin at 400C and II had melt flow = 10
dglmin; I/II = 1 / 1
Single T, and single T, when I contained
33% ketone linkages and had melt flow = 3.0
dg/min at 400C and II contained 50%
ketone linkages and had melt flow =
4.0 dglmin; I/II = l/l
Single T, and single T, when I contained
33% ketone linkages and had melt flow = 3.0
dg/min and II contained 50% ketone
linkages and had melt flow = 1.5 dg/min;
I / I I = l / l
Single composition-dependent melting
endotherms obtained upon quenching when
I had intrinsic viscosity = 1.124 dl/g in
sulfuric acid at 30C and II had intrinsic
viscosity = 1.107 dl/g in sulfuric acid at 30C
but it did not happen when other thermal
histories were imposed
Single T, and single T, when I contained
33% ketone linkages and had melt flow = 3.0
554
703
704
333
3 3 3
333
739
333
References page VI - 46 1
VI / 460 MISCIBLE POLYMERS
TABLE 8. contcf
Pol ymer I of Polymer II of Method Comment s Refs.
Ethylene
Ethylene
Ether ketone (polymer II),
etherimide (polymer III)
Butadiene, hydrogenated
Ethylene
Ethylene, deuterated
Ethylene-co-vinyl acetate
Ethylene-co-vinyl acetate Ethylene-co-vinyl acetate
T, and T, by DSC
DSC, SALS and SEM
DSC and SALS
DSC, SAXS and X-ray
diffraction
T, by DSC
DSC, SALS and SEM
DSC, SALS and SEM
dg/min and II contained 57% ketone
linkages and had melt flow = 1.5 dg/min;
I/II =1/l
I had reduced viscosity = 1.05 dl/g in 1 wt.%
cont. sulfuric acid at 23C; II had reduced
viscosity = 1.9 dl/g in the same condition
as for I; III was Ultem 1000 from GE
with reduced viscosity = 0.5 dl/g in 0.2 wt.%
chloroform at 25C; single T, and single
T, for I/II/III = 25 / 25150
I was narrow MW fraction with M, = 113
kg/mol and M, = 105 kg/mol; II contained
2.2-5.5 mol% ethyl branches and had
M, = 103-420 kg/mol and M, = 83- 156
kg/mol; stated that I and II co-crystallized
upon rapid crystallization from the melt when
II contained up to 2 mol% of ethyl branches
I was polyethylene and II was UHMWPE with
MW = 5,000 kg/mol; I was LLDPE
(GRSN-7047 from Union Carbide with
M, = 134 kg/mol and M, / M, =4) , or I was
HDPE (Chemplex 6186 with M, =
134.8 kg/mol and MJ M, = 7. 4) ; only a
single composition dependent T, was
observed; SALS showed the co-crystallization
took place; but when I was LDPE (M, =
114 kg/mol and MJM, = 5.2), separate
crystals were formed
I was linear LLDPE and II was HDPE;
co-crystallization was evidenced by a single
T, by DSC; stated that X-ray diffraction
peak width, SAXS and Raman spectra
were all consistent with a single crystallizing
species; but for HDPE/LDPE and LLDPB/
LDPE, separate crystals were seen with two
T, ' s being found by DSC
I was HDPE with M, = 100 kg/mol and
M, = 11 kg/m01 and II was LLDPE with
M, = 350 kg/m01 and M, = 16 kg/mol;
after the blend with I/II = 25/75 by weight
was crosslinked either by irradiation or by
peroxides in the liquid state above a critical
degree of cross-linkage, the DSC curve
of the blend showed only one single melting
point on heating and only one single
crystallization peak on cooling; Refs.
45, 348,478, 579 and 676 also discussed
the miscibility of PE/PE blends
Single T, varying smoothly with composition
and no gross segregation occurred
I was narrow MW fraction with M, = 113
kg/mol and M, = 105 kg/mol; II contained
1.12-6.6 mol% of acetate branches and
had M, = 60.3- 105 kg/mol and M, =
23.5-43.6 kg/mol; stated that I and II
co-crystallized upon rapid crystallization
from the melt contained up to 2 mol% of
acetate branches
I and II had M, = 60.3- 105 kg/mol, M, =
23.5-43.6 kg/mol, and they were different
in the content of acetate branches; stated
that these copolymers containing about
l-2 mol% of acetate branches were found to
co-crystallize with one another
3 3 4
13
483
7 8 3
360
2 1 7
13
13
Re f e r e n c e s VI / 461
T ABL E 8. contd
Polymer I of Polymer II of Method Comment s Refs.
Glutamate Glutamate Dynamic mechanical I or II was poly(L-glutamate) or 717
measurements, X-ray pOl y(D-ght aI I X3t e) having m number of
diffraction methylene group in the ester group of a
general formula as -CHsCHsCOO-(CHz),-
CsHs-, m might be 1, 2 or 3 so the
component polymer would be represented
as Lm or Dm; the MW of both components
were 135 to 380 kg/mol and M, / M, = 1.1
to 1.2; stated that binary blends of L2, D2,
L3 and D3 were miscible and formed iso-
morphous mixed crystals at all
compositions, whereas other pairs, with the
exception of LliDl, were immiscible
Isopropyl vinyl ether, isotactic secButy1 vinyl ether, isotactic Unit cell dimension from Co-crystallization at all compositions 605
X-ray diffraction
4-Methyl-1-hexene, isotactic 4-Methyl-1-pentene, isotactic Unit cell dimensions from Co-crystallization only below 25 wt.% I and 605
X-ray diffraction above 75 wt.% I
Tetrafluoroethylene Tetrafluoroethylene-co- Dynamic mechanical II had 98-99 mol% tetrafluoroethylene; 1 1 7 3
pertluoroalkyl vinyl ether measurements single a-transition from DMA
Trifluoroethylene-co- Trifluoroethylene-co-vinylidene DSC, X-ray and phase-contrast No phase separation by phase-contrast 800
vinylidene fluoride fluoride
:
microscopy microscopy, a sharp single X-ray peak,
intermediate in spacing between those of the
individual copolymers, and clearly different
from their superposition, and only one
ferroelectric transition and only one melting
point by DSC, indicated co-crystallization
within the same lattice when I was 52/48 mol%
vinylidene fluoride (VDF)/trifluoroethylene
(TFE), II was 65/35 mol% VDF/TFE, or
I was 65 135 mol% VDFJTFE, and II was 73127
mol% VDF/TFE; but two X-ray peaks and
two ferroelectric transitions and two melting
points when I was 52/48 and II was
73127 mol% VDF/TFE
Vinyl alcohol Vinyl alcohol D S C I and II had a diad syndiotacticity of 54 1 1 9 7
and 58 mol%, respectively
Vinylidene fluoride-co- Vinylidene fluoride I had 9.1, 14.3 or 17.6 mol% tetrafluoroethylene 980
tetrafluoroethylene
Hexafluoroacetone-co- DSC I had 80 mol% vinylidene fluoride; II had 951
vinylidene fluoride 92 mol% vinylidene fluoride; single
melting peak
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Heat Capacities of High Polymers*)**
M. Pyda and B. Wunderlich
Department of Chemistry, The University of Tennessee, Knoxville, TN 37996-l 600, USA
Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6197, USA
A. Introduction VI-483
B. Experimental Curves VI-485
C. Data Tables for Solids and Liquids VI-486
Table 1. cis-1,4-Poly(butadiene) (PBDc)+ VI-486
Tabl e 2. trans-1,4-Poly(butadiene) (PBDt) VI-487
Table 3. &-I ,4-Poly(2-methylbutadiene)
(PMBD) VI-488
Table 4. Poly(ethylene) (PE) VI-488
. Tabl e 5. Poly(propylene) (PP) VI-489
Table 6. Poly(1 -butene) (PB) VI-490
Table 7. Poly(1 -pentene) (PPE) VI-490
Table 8. Poly(1 -hexene) (PHE) VI-491
Table 9. Poly(isobutene) (PIB) VI-492
Table 10. Poly(4-methyl-l -pentene) (P4MPE) VI-492
Table 11. Poly(tetrafluoroethylene) (PTFE) VI-493
Table 12. Poly(vinyl fluoride) (PVF) VI-494
Table 13. Poly(vinylidene fluoride) (PVF2) VI-494
Table 14. Poly(trifluoroethylene1 (P3FE) VI-495
Table 15. Poly(vinyl chloride) (PVC) VI-496
Table 16. Poly(vinylidene chloride) (PVC21 VI-496
Table 17. Poly(chlorotrifluoroethylene)
(PC3FE) VI-497
Table 18. Poly(vinyl alcohol) (PVA) VI-498
Table 19. Poly(vinyl acetate) (PVAc) VI-498
Table 20. Poly(styrene) (PSI VI-499
Table 21. Poly(a-methylstyrene) (PMS) VI-500
Table 22. Poly(vinyl benzoate) (FVBZ) VI-500
Table 23. Poly(methyl acrylate) CPMA) VI-501
* The submitted manuscript has been authored by a contractor of the US
Government under the contract No. DE-AC05960R22464. Accordingly,
t he US Gover nment r et ai ns a non- excl usi ve, r oyal t y- f r ee l i cense t o
publish, or reproduce the published form of this contribution, or allow
others to do so, for US Government purposes.
** The work on the data bank mentioned in this chapter involved (in prior
years) in particular Dr. U. Gaur, Dr. A. Mehta, Dr. S. F. Lau, and Dr. M.
Varma-Nair. Financial support from the National Science Foundation,
presently under Grant # DMR-9703692 (Polymers Program) was essential
for the completion of the work. The present work is also supported by the
Di vi si on of Mat eri al s Sci ences, Offi ce of Basi c Energy Sci ences, US
Department of Energy at Oak Ridge National Laboratory, managed by
Lockheed Mart i n Energy Research Corp. for t he US Depart ment of
Energy, under contract number DE-AC05960R22464.
t General Note: The letters in parenthesis (after polymer names)
correspond to the authors file number in Ref. 40, and are not necessarily
the accepted abbreviation.
Table 24. Poly(ethyl acrylate) (PEA)
VI-502
Table 25. Poly(n-butyl acrylate) (PnBA) VI-502
Table 26. Poly(iso-butyl acrylate) (PIBA) VI-503
Table 27. Poly(methacrylic acid) (PMAA) VI-504
Table 28. Poly(methyl methacrylate) (PMMA) VI-504
Table 29. Poly(ethyl methacrylate) (PEMA)
VI-505
Table 30. Poly(n-butyl methacrylate) (PnBMA) VI-506
Table 31. Poly(isobutyl methacrylate) (PIBMA) VI-506
Table 32. Poly(hexyl methacrylate) (PHMA) VI-507
Table 33. Poly(acrylonitrile1 (PAN) VI-508
Table 34. Poly(methacrylamide1 (PMAM)
VI-508
Table 35. Poly(oxy-1 -oxoethylene) (PGL) VI-509
Table 36. Poly(oxy-I -oxohexamethylene) (PCL)VI-510
Table 37. Poly(oxyethyleneoxyterephthaloyl)
(PET)
Table 38. Poly(imino-1 -oxohexamethylene)
(Nylon 6)
Table 39. Poly(iminoadipoyliminohexa-
methylene) (Nylon 66)
Table 40. Poly(iminoadipoyliminododeca-
methylene) (Nylon 612)
Table 41. Poly(oxymethylene1 (POM)
Table 42. Poly(oxyethylene)
Table 43. Poly(oxytrimethylene) (P03M)
Table 44. Poly(oxytetramethylene) (P04M)
Table 45. Poly(oxypropylene1 (POPr)
Table 46. Poly(oxy-1,4-phenylene) (POPhI
Table 47. Poly(oxy-2,6-dimethyl-
1,4-phenylene) (PPO)
Table 48. Poly(oxy-2,6-diphenyl-
1,4-phenylene) (POPPO)
Table 49. Poly(oxycarbonyloxy-
1,4-phenylene-isopropylidene-
1,4-phenylene) (PC)
Table 50. Trigonal Selenium (SeTI
D. References
A. INTRODUCTION
VI-51 0
VI-5
VI-51
VI-5
VI-51 3
VI-514
VI-514
VI-51 5
VI-51 5
VI-51 6
VI-51 7
VI-51 7
VI-51 8
VI-51 9
VI-51 9
The molar heat capacity at constant pressure, C,, is
defined as the amount of heat, Q, needed to raise the
temperature, T, of one mole of substance at constant
(atmospheric) pressure by one kelvin in the absence of
latent heat effects, such as heats of fusion, crystallization,
VI / 483
VI / 484 HEAT CAPACITIES OF HIGH POLYMERS
reaction, etc. In differential form, one writes: C, =
dQ/dT = @HIaT) p n,
[ = heat capacity at constant pres-
sure p, and number of moles, IZ (for polymers
usually expressed per mole of repeating unit, i.e. for
poly(propylene) per 0.04208 kg); H = enthalpy = U +pV
( U = total energy, V = molar volume)]. Frequently, one
makes use of the specific heat capacity, cp, which refers
commonly to the heat capacity of one gram of material
(cp = C,/M, where M represents the molar mass of the
repeating unit in Da).
The heat capacity is not only of theoretical interest, but
has also considerable importance for practical applications,
e.g., for calculation of enthalpy differences between two
temperatures or as the basis for interpretation of differential
scanning calorimetry (DSC) curves. Furthermore, C, is a
basic quantity of thermodynamics. All integral functions
can be derived from the data on C,: the enthalpy,
H = s C, dT, equal to the total heat content when
integrated from 0 K to the temperature of interest and
adding all intervening heats of transition, AH, at their
equilibrium transition temperatures (energy and enthalpy
are conserved as expressed by the first law of thermo-
dynamics); the entropy, S = s (C,/T) dT, a measure of the
degree of disorder of the sample, also to be integrated from
0 K to the temperature of interest and to be corrected by the
intervening entropies of transition, As (S = 0 J/K/m01 for
equilibrium crystals at OK and positive for all other
temperatures and states-third law of thermodynamics; and
the free enthalpy, G = H - TS, a measure of the stability of
the sample (the state with the lowest free enthalpy is most
stable - second law of thermodynamics). Figure 1 displays
these integral functions for the example of polyethylene
(PE, see Table 4) (34).
A representative experimental heat capacity measured by
differential scanning calorimetry (DSC) is given in Fig. 2
for semicrystalline poly(oxyethyleneoxyterephthaloy1)
(PET, see Table 37) (35). It can be seen that the heat
capacity, C,, given in J/Wmol, is not a single-valued
function of temperature. It depends on the state of the
polymer [crystalline, amorphous (solid or liquid), or
semicrystalline]. The common semi&ystalline samples,
characterized by their weight fraction (or percentage)
crystallinity w,, are not in equilibrium, and their heat
capacity depends on the thermal history since different
cooling or annealing conditions may lead to different values
of w,. In addition, particularly in the melting region, the
method of measurement, such as DSC or temperature-
modulated DSC (TMDSC), may also yield different
experimental answers (35). The TMDSC (heavy curve) is
a measure of the limited reversibility of the melting
of polymers, while the DSC curve is a measure of the
breadth of the melting which arises from crystallite size-
distributions and reorganization during melting (36).
I
In case of amorphous polymers (or the amorphous
portion of a semicrystalline polymer) the heat capacity
changes at the glass transition temperature, T,, by AC,,
proportional to the weight fraction of amorphous material
present, as shown in Fig. 3. In addition, the value of AC, is
often proportional to the number of flexible parts (beads)
into which the repeating unit can be divided [Z 11 J/K (mol
of beads)- (34)]. The detailed apparent heat-capacity
response of the sample in the glass-transition region is
dependent on the thermal history of the substance under
investigation and also on the heating rate of measurement.
A maximum of heat capacity may be caused by enthalpy
relaxation and may easily be confused with a melting
process, as illustrated in Fig. 3, for atactic poly(styrene)
(PS, see Table 20.). A number of other non-equilibrium
processes that change the appearance of the heat capacity
are (34): minima (exotherms) caused by stress relaxation
that may be confused with a crystallization process, crystal
perfection, annealing or fusion that add to or subtract from
the heat capacity. Positive (endothermic) effects are usually
indicative of disordering, negative (exothermic) effects are
usually indicative of ordering (36).
Plotting AC, versus AH allows extrapolation of data of
semicrystalline samples to the completely amorphous and
crystalline states, as shown in Fig. 4 (37). Negative
deviations from the straight line exist for many stiffer
polymers and indicate the presence of a rigid-amorphous
fraction, i.e. a third phase in a semicrystalline sample that
does not become mobile at the glass transition, but is not
crystalline (three-phase model with the third phase most
likely placed at the surfaces of the crystals where molecules
continue into the amorphous phase). The effect of a rigid-
amorphous phase on the heat capacity of poly(oxymethy-
lene) is shown in Fig. 5 (38).
The heat capacity tables of this chapter contain mean
values of the best data available in the literature. To make
the tables universal, effects of broad glass transitions,
thermal history, rigid-amorphous fractions, and effects of
fusion, annealing, or crystallization were eliminated by
appropriate extrapolation. Data for the solid refer to
crystals as well as glasses. Only in the temperature range
from 0 to perhaps 70K are the heat capacities of glasses
slightly higher than that for crystals. For semicrystalline
samples between glass transition and melting, the crystal-
linity must be known. The heat capacity is then the sum of
the heat capacities of the crystalline weight fraction and the
melt weight fraction, as shown in Fig. 6. Fusion, annealing
and crystallization, as well as glass transition broadening,
must be added from additional experimental information, as
illustrated above.
The tables given in this chapter are based on the ATHAS
Data Bank of experimental heat capacities and its update
for 1990 [U. Gaur, H. C. Shu, A. Mehta, S. F. Lau, B. B.
Wunderlich, M. Varma-Nair, and B. Wunderlich, J. Phys.
Chem. Ref. Data, 10, 89, 119, 1001, 1051, (1981), 11, 313,
1065, (1982), 12, 29, 65, 91 (1983), and 20, 349, (1991)].
The term NA in the value-column indicates that no
recommendation of experimental data can be made at
present; NA in the index-column is a reminder that the
data point is gained by extrapolation of the experimental
data due to transition effect.
The experimental data bank, as presented in this chapter,
has been interpreted in terms of the molecular motion of the
Experimental Curves VI / 485
polymers (39). The results of this extended data bank can be
accessed over the World Wide Web (40). It contains data
tables for over 200 polymer and polymer-related materials,
including all poly(amino acids) and some proteins. In
addition to the experimental data as shown in Tables l-50,
the ATHAS Data Bank contains a link of the solid heat
capacity to approximate vibrational spectra as illustrated in
Fig. 7 for poly(ethylene). Also, empirical addition schemes
for the heat capacity of liquid and solid polymers have been
developed, based on the molecular structure (41). An
example is given in Fig. 8, for a series of aliphatic nylons
(see also Tables 38-40).
B. EXPERIMENTAL CURVES

g 10
0
3 Hc
F-10
(@j- -20
f -30
40
30
2 0
-40
I I I I ! I I I I
idi 4.6 K
-50;
I I I II -. --7 -- I I I I
I
200 400 600 800 1000
Temperature (K)
Figure 1. The integral thermodynamic functions 14, G, and
JS = H - G for PE. The subscripts a refer to the amorphous,
c to the crystalline samples; the equilibrium melting occurs at
J,; Hz is set arbitrarily to zero, it can also be adjusted to the heat
of formation AHf( J) by adding the integral of C, from 298.15 to
0 K to AHf (298.15) (Ref. 34).
z 800
melt crystallized
2
quasi-isothermal (60 s/l .O K) -
5 600
standard DSC ( 1 0 Wmin) -
computed trace (wc = 44%) - - - -
0
melt heat capacity
crystal heat capaci ty
400 450 500
Temperature (K)
Figure 2. Experimental heat capacities of PET. The glass-
transition region is marked by Jg, the melting region by J,.
The solid, thin lines indicate the data of Table 37, the dashed line
indicates the crystallinity-corrected heat capacity for the semi-
crystalline sample, 44% crystalline, 56% amorphous. The quasi-
isothermal data were measured by TMDSC at 2 K intervals with a
sinusoidal temperature modulation of L ! I 1 .O K and a modulation
period of 60s (Ref. 35).
I
CP
Figure 3. Schematic of the change of the heat capacity at the
gl ass t r ansi t i on ( t op) and exper i ment al dat a by DSC f or
polystyrene after cooling at different rates (bottom). The five
characteristic temperatures of the glass transition (Jb, J l, T,, J2,
J,) are marked and apply to a given time scale only. The
experimental data display an enthalpy relaxation (endothermic
peak if the cooling rate that sets the thermal history is less than the
heating rate). The samples l-7 were cooled at 0.084, 0.20, 0.52,
1 .lO, 2.50, 5.00, and 30.0 K/min, respectively.
14.4
Heat of Fusion (kJ/mol)
Figure 4. Change of the heat capacity of poly(oxymethylene-
carbonyloxyethylene) (poly-pdioxanone) at the glass transition
with heat of fusion. (Ref. 37).
References page VI - 5 19
VI / 486 HEAT CAPACITIES OF HIGH POLYMERS
Temperature (K)
Figure 5. Effect of a rigid-amorphous fraction on the heat
capacity of semicrystalline polyfoxymethylene). The measured
C, of a 67% crystalline sample (as determined from its heat of
fusion) shows the heat capacity expected for an 80% crystalline
sample. The 13% difference from w, is attributed to the rigid-
amorphous phase (Ref. 38).
2 6
2 2
\
l r:
r
l *
c
4
18
0 0. 2 0. 4 0. 6 0. 8 1 I
Crystallinity wc
Figure 6. Heat capacity of polyfethylene) as a function of
/crystallinity above the glass transition temperature (T, = 237 K).
The extrapolated data for zero crystallinity are entered into
Table 4 for the amorphous (melt) state, for crystallinity one, for
the solid.
heat c apac i t y) A
I
IA
- I I I I
2 0 0 4 0 0 6 0 0
Temperature (K)
Fi gure 7. The contributions of skeletal and group vibrations to
the heat capacity of polyethylene at constant volume, C,. Note
that, once established, the vibrational heat capacity can be
extended safely beyond the range of measurement and deviations
from the calculated heat capacity can be interpreted in terms of
large-amplitude motion and ordering or disordering.
500 600
Temperature (K)
Fi gure 8. Heat capacity of various aliphatic nylons as measured
(heavy lines) and computed from the equation (thin lines)
(Nc = number of carbon atoms, NN number of nitrogen atoms
per repeating unit).
C. DATA TABLES FOR SOLIDS AND LIQUIDS
TABLE 1. cis-1,4-POLY(BUTADIENE) (PBDc)
-@-y=y-c~&
H H
T (K)
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
NA 1 . 1 8
NA 6.52
11.79
16.15
19.98
23.18
26.16
29.07
31.87
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 1. contd
tram-1,4-Poly(butadiene)
TABLE 2. tram-1,4-POLY(BUTADIENE) (PBDt)
T WI
Solid Mel t
Index Value Index Value
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
34. 63
37. 34
40. 05
42. 82
45. 62
48. 50
53. 93
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
I NA
NA
- NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
104.20
106.00
107.70
109.50
111.30
113.10
114.90
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Notes
References: 1. U. Gaur, S. E Lao, B. B. Wunderlich, B. Wunderlich, J. Phys.
Chem. Ref. Data, 12 (l), 41 (1983).
2. J. Grehowicz, W. Aycock, B. Wunderlich, Polymer, 27,575 (1986).
T,: 171.OK (AC, = 29.10)
T , :
Solid:
Mel t :
284.0K
lo-20 K
30-160K
170-600 K
lo-280 K
290-350 K
360-600K
(C, = 86.7%i03.1)
Calculated C, value by fitting experimental data
above 22 K to the Debye function (Data Bank, 1980)
Experimental C, data (Data Bank, 1980)
C, data are not available
Melt unstable
Experimental C, data (Data Bank, 1985)
C, data are not available
+~-~=~-c~zf
H H
Solid Mel t
Index Value Index Val ue
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0. 80
4. 82
9. 70
14. 39
18. 74
22. 56
25. 89
29. 00
32. 02
34. 98
37. 86
40. 70
43. 53
46. 26
48. 99
51. 71
54. 52
57. 88
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
116.60
118.40
120.20
122.00
123.70
125.50
127.30
129.10
130.90
132.60
134.40
136.20
138.00
139. 00
141. 50
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
References page VI - 5 19
VI / 488 HEAT CAPACITIES OF HIGH POLYMERS
TABLE 2. contd TABLE 3. contd
Not e s
References: 1. U. Gaur, S. F. Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Data,
12 (l), 41 (1983).
T,:
T, :
Sol i d:
Mel t :
2. J. Grebowicz, W. Ayock, B. Wunderlich, Polymer, 27, 575 (1986).
180.0 K (AC, = 28.20)
356.0 K (C, = 107.5- 115.9) (Crystal + Condis Crystal)
437.0 K (Condis Crystal + Melt)
10 -2OK Calculated C, value by fitting C, data above
22 K into the Debye function (Data Bank,
1980)
30-180K Experimental C, data (Data Bank, 1980)
190-600 K C, data are not available
lo-350 K Melt unstable
360-430 K Extrapolated data from C, in the region of
440-500 K (Condis Cry%. Region; Ref. 2)
MO-500 K Experimental C, data (Data Bank, 1985)
510-600 K C, data are not available
TABLE 3. cis-1,4-POLY(2-METHYLBUTADIENE) (PMBD)
+x-cc=c-cH~~-
AH l!I
3
T W
Solid Mel t
Index Value I n d e x Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
2.50
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
2.41
8.32
14.24
19.54
24.34
28.83
33.06
37.07
40.90
44.58
48.12
51.57
54.93
58.23
61.48
64.70
67.89
71.06
74.85
78.03
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
*NA
., NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
108.90
111.00
112.80
114.70
116.70
118.70
120.90
123.20
125.40
127.80
130.20
132.60
135.00
137.50
139.90
142.40
144.80
NA
NA
NA
NA
T W)
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
Solid Mel t
Index Value Index Value
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
Not e s
References: U. Gaur, S. E Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
Ref. Data, 12 (l), 41 (1983).
T,: 200.0 K (AC, = 78.03-108.9)
Solid: lo-190K Experimental C, data (Data Bank, 1980)
200 K Extrapolated value from C, in the region of
170-190K (Data Bank, 1980)
210-600 K C, data are not available
Mel t : lo-190K Melt unstable
200 K Extrapolated data from C, in the region of
210-360K (Data Bank, 1980)
210-360K Experimental C, data (Data Bank, 1980)
370-600 K C, data are not available
TABLE 4. POLY(ETHYLENE) (PE)
T 0-Q
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
0.10
0.73
1.84
3.19
4.52
5.74
6.83
7.79
8.66
9.45
10.20
10.92
11.60
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 4. contd
T (K)
Solid Mel t
Index Value Index Value
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
12. 25
12. 87
13. 45
14. 00
14. 53
15.05
15.57
16.10
16.66
17.25
17.88
18.55
19.23
1 9 . 9 1
20. 58
21. 21
21. 81
22. 38
22. 95
23. 56
24. 30
25. 25
26. 51
28. 13
30. 12
32. 36
34. 19
36. 19
38. 27
40. 44
42. 68
44. 98
47. 35
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
. .
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
28. 30
28. 73
29. 16
29. 60
30. 03
30. 46
30. 89
31. 33
31. 76
32. 19
32. 62
33. 06
33. 49
33. 92
34. 35
34. 79
35. 22
35. 65
36. 08
36. 52
36! 95
37. 38
37. 81
38. 25
38. 68
39. 11
39. 54
39. 98
40. 41
40. 84
41. 27
41. 71
42. 14
42. 57
43. 00
43. 44
43. 87
Notes
References: U. Gaur, B. Wunderlich, J. Phys. Chem. Ref. Data, 10 (l), 119 (1981).
T , : 252.0 K (C, = 18.69-28.79)
T,: 414.6 K (C, = 37.13-35.85)
Gl ass: lo-70 K Experimental glass C, data shows a slightly
Mel t : lo-230 K
higher value than cry& C, data from 10 K-to
70 K, respectively: 0.371, 1.40, 2.60, 3.90,
5.14, 6.26, 7.25 (Data Bank, 1980)
Melt unstable
240-260 K C, obtained from crystallinity extrapolation
and molten PE, match at 252 K (Data Bank,
1980)
270-380K Extrapolated value from C, in the region of
390-600 K
390-600 K Exoerimental C, data (Data Bank. 1980)
Crystal: lo-460 K
470-600 K
Experimental CE data (Data Bank; 198Oj
C, data are not available
Pol y( propyl ene) VI / 489
TABLE 5. POLY( PROPYLENE) ( PP)
tcz- f S
CH3
Solid Mel t
Index Value Index Val ue
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
0 . 5 5
3. 57
7. 07
10. 20
13. 02
15. 67
18. 27
20. 90
23. 65
26. 25
28. 69
31. 03
33. 28
35. 45
37. 57
39. 64
41. 68
43. 68
45. 66
47. 63
49. 59
51. 54
53. 50
55. 16
56. 83
58. 75
60. 87
63. 18
65. 64
68. 24
70. 95
73. 77
76. 68
79. 67
82. 73
85. 86
89. 04
92. 27
95. 55
98. 97
102. 20
105. 60
109. 00
112. 50
116.00
119.50
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
82. 29
83. 80
85. 32
86. 83
88. 34
89. 86
91. 37
92. 88
94. 39
95. 91
97. 42
98. 93
100. 45
101. 96
103. 47
104. 99
106. 50
108. 01
109. 52
111.04
112.55
114.06
115.58
117.09
118.60
120.11
121.63
123.14
124.65
126.17
127.68
129.19
130.70
132.22
133.73
References page VI - 5 19
VI / 490 HEAT CAPACITIES OF HIGH POLYMERS
TABLE 5. contd
Notes
References: U. Gaur, B. Wunderlich, J. Phys. Chem. Ref. Data, 10 (4), 1051
( 1981) .
T, : 260.0 K (C, = 64.92-82.29)
T , : 460.7 K (C, = 119.7-112.7)
Gl ass: lo-250K Experimental glass C, data shows a slightly
higher value than tryst. C, data from 10 K to
250K, respectively: 1.876, 5.077, 8.721,
11.89, 15.01, 18.36, 20.91, 23.54, 26.07,
28.51, 30.85, 33.11, 35.30, 37.42, 39.48,
41.48, 43.43, 45.35, 47.44, 49.63, 51.92,
54.31, 56.80, 59.40, 62.10. (Data Bank, 1980)
Mel t : lo-250 K Melt unstable
260-270 K Extrapolated value from C, in the region of
280-300 K and region of 420-600 K
(Data Bank, 1980)
280-300 K C, of amorphous PP obtained from crystal-
linity extrapolation of experimental C, data of
semicrystalline samples (Data Bank, 1980)
310-410K Extrapolated value from C, in the region of
420-600 K (Data Bank, 1980)
420-600 K Experimental C, data (Data Bank, 1980)
Cr ys t al : lo-460 K Experimental C, data (Data Bank, 1980)
470-600 K C, data are not available
TABLE 6. POLY(l-BUTENE) (PB)
$CHz--Ht
CHz- CH3
Solid Melt
T (K) Index Value Index Value
10 0.96 NA NA
2 0 5.42 NA NA
3 0 10.20 NA NA
4 0 14.86 NA NA
5 0 19.26 NA NA
6 0 23.27 NA NA
70 27.01 NA NA
8 0 30.69 NA NA
9 0 34.30 NA NA
100 37.78 NA NA
110 41.16 NA NA
120 44.35 rNA NA
130 47.47 NA NA
* 140 50.48 NA NA
150 53.38 NA NA
160 56.22 NA NA
170 59.08 NA NA
180 62.06 NA NA
190 65.14 NA NA
2 0 0 68.40 NA NA
2 1 0 71.88 NA NA
2 2 0 NA 75.05 NA NA
2 3 0 NA 78.32 NA NA
2 4 0 NA 81.59 NA NA
2 5 0 NA NA NA 107.81
2 6 0 NA NA NA 109.65
2 7 0 NA NA NA 111.49
2 8 0 NA NA NA 113.33
2 9 0 NA NA NA 115.18
3 0 0 NA NA NA 117.02
310 NA NA NA 118.86
3 2 0 NA NA NA 120.71
3 3 0 NA NA NA 122.55
TABLE 6. contd
T (K)
Solid Melt
Index Value Index Value
3 4 0
3 5 0
3 6 0
3 7 0
3 8 0
3 9 0
4 0 0
4 1 0
4 2 0
4 3 0
4 4 0
4 5 0
4 6 0
4 7 0
4 8 0
4 9 0
5 0 0
5 1 0
5 2 0
5 3 0
5 4 0
5 5 0
5 6 0
5 7 0
5 8 0
5 9 0
6 0 0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA 124.39
NA 126.24
NA 128.08
NA 129.02
NA 131.76
133.61
135.45
137.29
139.14
140.98
142.82
144.67
146.5 1
148.35
150.19
152.04
153.88
155.72
157.57
159.41
161.25
163.10
164.94
166.78
168.62
170.47
172.31
Notes
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem. Ref. Data,
12 (l), 34 (1983).
T, :
T , :
Solid:
249.0 K
411.2K
lo-210K
220-240 K
250-600K
Mel t : lo-230K
240-380K
390-600K
(C, = 84.54-107.6)
Experimental C, data of semicrystalline
sample (Data Bank, 1980)
Extrapolated value from C, in the region of
180-210K (Data Bank, 1980)
C, data are not available
Melt unstable
Extrapolated value from C, in the region of
390-630 K
Experimental C, data (Data Bank, 1980)
TABLE 7. POLY(l-PENTENE) (PPE)
t W-$;t
CH2- CH2- CH3
T (W
Solid Melt
Index Value Index Value
1 0
2 0
3 0
4 0
5 0
6 0
7 0
8 0
9 0
100
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
T A B L E 7 . contd
T W)
Solid Mel t
Index Value Index Value
1 1 0
120
1 3 0
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
4.50
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
87.90
90.86
93.82
96.78
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
s NA
NA
* NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
126.70
129.64
132.58
135.52
138.46
141.40
144.34
147.28
150.22
153.16
156.10
159.04
161.98
164.92
167.86
170.80
173.74
176168
179.62
182.56
185.50
188.44
191.38
194.32
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Notes
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem. Ref. Data,
12 (I), 36 (1983).
T,: 233.0 K (C, = 97.67-124.7)
T,: 403.2 K
Solid: IO-190K C, data are not available
200-230 K Experimental C, data of semicrystalline
isotactic sample~agree with amorphous atactic
sample (Data Bank, 1980)
Mel t :
240-600 K
lo-230K
240-470 K
480-600 K
C, data are not available
Melt unstable
Experimental C, data from atactic sample
above T, and isotatic sample above T, (Data
Ba n k , 1 9 8 0 )
C, data are not available
Poly(1 -hexene) VI / 491
T A B L E 8. POLY(l-HEXENE) (PHE)
$ CHz- YHt
CH2- CH2- CH2- CH3
Solid Mel t
T WI
Index Val ue Index Val ue
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
9.09
16.42
24.00
30.16
36.71
42.67
48.33
53.74
59.08
64.30
69.61
74.68
79.88
84.96
89.69
95.11
100.90
106.45
112.09
117.74
123.38
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
152.77
156.47
160.18
163.88
167.58
171.28
174.98
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
References page VI - 5 19
VI / 492 HEAT CAPACITIES OF HIGH POLYMERS
TABLE 8. contd TABLE 9. contd
Not e s
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, .I. Phys. Chem. Ref. Data,
T,:
Solid:
Mel t :
12~w&1983).
(C, = 125.1-150.2)
20-190K Experimental C, data of total amorphous
sample (Data Bank, 1980)
200-220 K Extrapolated value from C, in the region of
170- 190 K (Data Bank, 1980)
230-600 K C, data are not available
lo-220 K Mel t uns t abl e
230-290 K Experimental C, data from amorphous sample
above T, (Data Bank, 1980)
300-600 K C, data are not available outside the region of
223-290 K
TABLE 9. POLY(ISOBUTENE) (PIB)
CH3
+CHZ-+t
CH3
T (K)
Solid Mel t
Index Value Index Value
1 0
2 0
3 0
4 0
5 0
6 0
70
8 0
9 0
100
110
120
130
140
150
160
170
180
190
2 0 0
2 1 0
2 2 0
2 3 0
2 4 0
2 5 0
2 6 0
2 7 0
2 8 0
2 9 0
3 0 0
3 1 0
3 2 0
3 3 0
3 4 0
3 5 0
3 6 0
3 7 0
3 8 0
3 9 0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
4.66
7.84
10.76
13.69
16.78
20.10
23.65
27.34
30.97
34.58
38.15
41.72
45.20
48.59
51.82
55.01
58.07
61.22
63.34
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
INA
., NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
85.63
88.08
90.52
92.97
95.41
97.86
100.31
102.75
105.20
107.64
110.09
112.54
114.98
117.43
119.87
122.32
124.77
127.21
129.66
NA
T (W
Solid Mel t
Index Val ue Index Value
4 0 0
4 1 0
4 2 0
4 3 0
4 4 0
4 5 0
4 6 0
4 7 0
4 8 0
4 9 0
5 0 0
5 1 0
5 2 0
5 3 0
5 4 0
5 5 0
5 6 0
5 7 0
5 8 0
5 9 0
6 0 0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem. Ref. Data,
12 (I), 38 (1983).
T,: 200.0 K (C, = 63.34-85.63)
T , :
Solid:
317.0K
20-180 K
190-200 K
Mel t :
210-600 K
lo-190K
200 K
210-380K
390-600 K
Experimental
sample (Data
C, data of glassy amorphous
Ba n k , 1 9 8 0 )
Extrapolated value from C, in the region of
160-180K (Data Bank, 1980)
C, data are not available
Melt unstable
Extrapolated value from C, in the region of
210-380 K
Experimental C, data from amorphous sample
above T, (Data Bank, 1980)
C, data are not available
TABLE 10. POLY(4-METHYL-1 -PENTENE) (P4MPE)
f CH2- 7f ,CH3
CH2- CH,
CH3
T (K)
Solid Mel t
Index Value Index Val ue
1 0
2 0
3 0
4 0
5 0
6 0
7 0
8 0
9 0
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
47.21
52.54
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 10. contd
Solid
Mel t
T 6) Index Value Index Value
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
57.52
62.22
66.72
71.06
75.29
79.45
83.57
87.66
91.75
95.87
100.00
104.20
108.40
112.80
117.10
121.60
126.20
130.80
135.60
140.40
145.40
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
I NA
N A
- NA
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N4
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
Notes
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem. Ref. Data,
12 (l), 39 (1983).
T,: 303.0 K (Cp = 147.0-180.7)
T,: 523.2 K
Solid: lo-70 K C, data are not available
80-300 K Experimental C, data (Data Bank, 1980)
310-600K C, data are not available
Mel t : lo-600 K C, data are not available
Poly(tetrafluoroethylene1 VI / 493
TABLE 11. POLY(TETRAFLUOROETHYlENE) (PTFE)
F
+++
F
T (K)
Solid Mel t
Index Value Index Val ue
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
570
580
1.23
3.92
6.30
8.44
10.31
12.27
14.17
16.02
17.75
19.37
21.20
22.90
24.53
26.13
27.65
29.13
30.62
31.98
33.24
34.47
35.67
36.82
37.94
39.03
40.10
41.13
42.15
43.15
44.13
45.09
46.02
46.95
47.86
48.76
49.63
50.49
51.35
52.17
52.99
53.81
54.60
55.39
56.15
56.91
57.65
58.39
59.10
59.82
60.51
61.20
61.88
62.55
63.20
63.86
64.48
65.12
65.75
66.36
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
46.85
47.61
48.36
49.12
49.89
50.65
51.42
52.19
52.96
53.74
54.52
55.30
56.08
56.87
57.66
58.45
59.24
60.04
60.84
61.64
62.44
63.25
64.06
64.87
65.39
65.72
66.05
66.38
66.72
67.05
67.38
67.71
68.04
68.38
68.71
References page VI - 5 19
VI / 494 HEAT CAPACITIES OF HIGH POLYMERS
TABLE 11. c ontd
Solid Mel t
T (K) Index Value Index Value
590 66.96 69.04
600 67.58 69.37
Notes
Reference: S. F. Lau, H. Suzuki, B. Wunderlich, J. Polym. Sci., Polym. Phys. Ed.,
22, 379 (1984).
T,: 240.0 K (C, = 39.03-46.85)
T,: 605.0 K (C, = 67.88-69.54)
Solid: 10-600 K All data are taken from the experimental C,
data of tryst. PTFE (Recommended Data, 1984)
Mel t : lo-230 K Melt unstable
240-470 K Extrapolated value from C, in the region of
480-700 K
480-600 K Experimental C, data, preliminary recommended
data, 1984, based on experiments from 560 to 700 K
and crystallinity extrapolation at low temperature
(Eqs. 4 and 4 of reference)
TABLE 12. POLY(VINYL FLUORIDE) (PVF)
T (W
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
NA
NA
NA
NA
NA
NA
NA
NA
NA
0. 47
2. 80
5. 70
8. 50
11. 80
14. 50
17. 10
20. 27
22. 18
23. 96
25. 64
27. 25
I
28. 83
30. 39 -
31. 95
33. 51
35. 09
36. 70
38. 34
40. 02
41. 75
43. 52
45. 34
47. 23
49. 17
51. 18
53. 25
55. 40
57. 62
59. 91
62. 29
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 12. contd
T (K)
Solid Mel t
Index Value Index Val ue
340
350
360
370
380
390
400
410
420
430
440
450
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Notes
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem. Ref. Data,
12 (l), 43 (1983).
T,: 314.0 K CC. = 63.27-81.07)
T:,:
Solid:
503.2K r
lo-70 K C, data are calculated from the Tarasov eq.
(Data Bank, 1980)
SO-310K Experimental C, data (Data Bank, 1980)
Mel t :
320-600 K
lo-600K
Cd data are not available
C, data are not available
TABLE 13. POLY(VINYLIDENE FLUORIDE) (PVFZ)
H F
-t&-L+
lb A
T (K)
Solid Mel t
Index Value Index Value
1 0 1 . 2 8 NA NA
20 5. 25 NA NA
30 9. 10 NA NA
40 12. 20 NA NA
50 15. 00 NA NA
60 17. 90 NA NA
TABLE 13. contd
T (W
Solid Mel t
Index Value Index Value
7 0
8 0
9 0
100
110
120
1 3 0
1 4 0
150
160
170
1 8 0
190
200
210
220
230
240
250
260
270
280
2 9 0
300
310
3 2 0
330
340
350
3 6 0
3 7 0
3 8 0
390
4 0 0
4 1 0
4 2 0
4 3 0
4 4 0
4 5 0
4 6 0
4 7 0
4 8 0
4 9 0
5 0 0
5 1 0
5 2 0
5 3 0
5 4 0
5 5 0
5 6 0
5 7 0
5 8 0
5 9 0
6 0 0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
20.90
23.80
26.10
28.40
30.90
33.00
35.20
37.50
39.60
41.80
44.00
46.10
48.30
50.30
52.80
54.90
57.10
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA.
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
-. NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Notes
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, .I. Phys. Chem. Ref. Data,
12 (l), 45 (1983).
T,: 233.0 K (C. = 57. 80-80. 60)
T,:
Solid:
Mel t :
483.2 K
lo-230 K
240-600 K
10-600 K
r
Experimental C, data (Data Bank, 1980)
C, data are not available
C, data are not available
Poly(trifluoroethylene) VI / 495
TABLE 14. POLY(TRlFLUOROETHYLENE) (P3FE)
F F
+Ut
AA
T (K)
Solid Mel t
Index Value Index Val ue
10
2 0
3 0
4 0
5 0
6 0
7 0
8 0
9 0
100
110
120
130
140
150
160
170
180
190
2 0 0
2 1 0
2 2 0
2 3 0
2 4 0
2 5 0
2 6 0
2 7 0
2 8 0
2 9 0
3 0 0
3 1 0
3 2 0
3 3 0
3 4 0
3 5 0
3 6 0
3 7 0
3 8 0
3 9 0
4 0 0
4 1 0
4 2 0
4 3 0
4 4 0
4 5 0
4 6 0
4 7 0
4 8 0
4 9 0
5 0 0
5 1 0
5 2 0
5 3 0
5 4 0
5 5 0
5 6 0
5 7 0
5 8 0
NA NA
NA NA
12.29
15.24
17.61
20.28
23.65
26.43
29.99
33.21
36.15
38.89
41.48
43.97
46.39
48.78
51.16
53.56
55.99
58.46
61.00
63.61
66.3 1
69.11
72.01
75.02
78.16
81.43
84.84
88.40
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
References page VI - 5 19
VI / 496 HEAT CAPACI TI ES OF HI GH POLYMERS
TABLE 14. contd
Solid Mel t
T WI Index Value Index Value
590 NA NA NA NA
600 N A NA NA NA
Notes
Reference: U. C&r, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem. Ref. Data,
12 (l), 46 (1983).
T,: 304.0K (C, = 89.87-110.87)
T , : 495.2 K
Solid: 30-300 K Experimental C, data (Data Bank, 1980)
310-600K C, data are not available
Mel t : 10-600 K C, data are not available
TABLE 15. POLY(VINY1 CHLORIDE) (PVC)
T (K)
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
NA
NA
NA
NA
NA
NA
NA
NA
1.81
5.91
9.95
13.38
16.28
18.77
20.99
23.05
24.98
26.82
28.59
30.29
31.94
33.56
35.15
36.73
38.31
39.88
41.45
43.03
44.61
46.21
47.79
49.37
50.99
52.63
54.29
55.95
57.64
59.35
61.11
62.94
64.88
66.96
68.85
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
r-NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A :
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
91.08
94.56
98.05
TABLE 15. contd
Solid Mel t
Index Val ue Index Val ue
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Not e s
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem. Ref. Data,
12 (l), 49 (1983).
T,: 354.0 K (C, = 69.62-88.99)
Tm: 546.0 K
.
Solid:
Mel t :
IO-350 K
360-600 K
lo-350 K
360-380 K
390-600 K
All data are taken from the experimental C,
of glass (Data Bank, 1980)
C, data are not available
Melt unstable
Experimental C, data (Data Bank, 1980)
C, data are not available
TABLE 16. POLY(VINYLIDENE CHLORIDE) (PVCZ)
T (W
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
NA NA
NA NA
NA 7.32
NA 12.53
NA 17.38
21.49
26.08
30.01
33.38
36.31
38.91
41.26
43.45
45.53
47.53
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 16. contd
Solid Mel t
T W Index Value Index Value
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
49.50
51.46
53.44
55.45
57.51
59.64
61.84
64.12
66.50
69.98
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
NA
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
NA
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
3 NA
N A
- NA
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
Notes
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem. Ref. Data,
12 (1). 52 (1983).
T,: 255.0 K (C, = 70.26)
T,:
Solid:
Mel t :
463.0 K
30-50 K
60-250 K
260-600 K
30-600 K
C, data are calculated from the Tarasov eq.
(Data Bank, 1980)
Experimental C, data (Data Bank, 1980)
C, data are not available
C, data are not available
Poly(chlorotrifluoroethylene) VI / 497
TABLE 17. POLY(CHLOROTRIFLUOROETHYLENE) (PC3FE)
T (K)
Solid Mel t
Index Value Index Val ue
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
32.46
36.77
40.81
44.63
48.24
51.69
55.00
58.18
61.26
64.26
67.18
70.05
72.87
75.66
78.41
81.15
83.87
86.57
89.27
91.98
94.68
97.39
100.10
NA 102.90
NA 105.60
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
References page VI - 5 19
VI / 498 HEAT CAPACITIES OF HIGH POLYMERS
TABLE 17. contd TABLE 18. contd
T (K)
Solid Mel t
Index Value Index Value T (K)
Solid Mel t
Index Value Index Value
590 N A NA NA NA
600 NA NA NA NA
Not e s
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem. Ref. Data,
12 (l), 54 (1983).
T,: 325.OK (C, = 107.0)
T, : 493.OK
Sol i d: lo-70 K C,data are not available
80-300 K Experimental C, data (Data Bank, 1980)
310-320K Extrapolated value from C, in the region of
80-300 K (Data Bank, 1980)
330-600 K C, data are not available
Melt: 30-600 K C,data are not available
TABLE 18. POLY(VINY1 ALCOHOL) (PVA)
fC%-~Hf
OH
T W
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
NA
NA
NA
NA
NA
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
11.78
15.05
17.94
20.46
22.69
24.69
26.54
28.29
29.98
31.66
3
33.34 *c
35.06
36.84
38.69
40.64
42.69
44.85
47.16
49.60
52.21
54.99
57.95
61.12
64.50
68.11
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
N A
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
N A
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
Not e s
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, I. Phys. Chem. Ref. Data,
12 (l), 56 (1983).
Sol i d: lo-50 K C,data are not available
60-300 K Experimental C, data (Data Bank, 1980)
310-600K C,data are not available
Mel t: 30-600 K C,data are not available
TABLE 19. POLY(VINYL ACETATE) (PVAc)
f CH2- yt
O-C--H3
a
T (W
Solid Mel t
Index Val ue Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA N A
27.81
31.17
34.54
37.91
41.27
44.64
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
T A B L E 1 9 . contd
T 6)
Solid Mel t
Index Value Index Value
140
1 5 0
1 6 0
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
48.00
51.37
54.74
58.10
61.47
64.83
68.20
71.57
74.93
78.30
81.66
85.03
88.40
91.76
95.13
98.49
101.86
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
I- N A
-i NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
157.50
158.48
159.45
160.43
161.41
162.39
163.37
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Not e s
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem. Ref. Data,
12 (I), 56 (1983).
T,: 304.0 K (C, = 103.2-156.9)
Solid: lo-70K C, data are not available
80-300K Experimental C, data (Data Bank, 1980)
310-600K C, data are not available
Mel t : lo-300 K Melt unstable
310-370K Experimental C, data (Data Bank, 1980)
380-600K C, data are not available
T A B L E 2 0 . POLY(STYRENE) (PS)
Poly(styrene) VI / 499
f CH2- $f
C&s
T WI
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
3.33
10.77
17.47
23.13
28.01
32.37
36.38
40.17
43.81
47.37
50.88
57.38
57.89
61.43
65.01
68.65
72.36
76.14
80.01
83.97
88.03
92.19
96.01
100.16
104.45
108.85
113.36
117.96
122.64
127.38
132.18
137.02
141.92
146.85
151.82
156.81
161.84
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
195.93
198.59
201.24
203.89
206.55
209.20
211.85
214.51
217.16
219.81
222.46
225.12
227.77
230.42
233.08
235.73
238.38
241.04
243.69
246.34
248.99
251.65
254.30
References page VI - 5 19
VI/500 HEAT CAPACI TI ES OF HI GH POLYMERS
TABLE 20. conrd TABLE 21. contd
Notes
Reference: U. Gaur, B. Wunderlich, J. Phys. Chem. Ref. Data, 11 (2), 313 (1982).
T,: 373.OK (C, = 163.4-194.1)
T, : 516.2K
Solid: lo-70K Experimental C, data of glassy samples (Data
Ba n k , 1 9 8 0 )
80-370 K C, data of glassy samples agree with C, data
of semi-crystalline samples. (Data Bank, 1980)
380-600 K C, data am not available
Mel t : lo-370K Melt unstable
380-600 K Experimental C, data (Data Bank, 1980)
TABLE 21. POLY(a-METHYLSTYRENE) (PMS)
T (K)
Solid Mel t
Index Val ue Index Val ue
1 0
2 0
30
4 0
5 0
6 0
7 0
8 0
9 0
100
110
120
130
140
150
160
170
180
190
2 0 0
2 1 0
2 2 0
2 3 0
2 4 0
2 5 0
2 6 0
2 7 0
2 8 0
2 9 0
3 0 0
3 1 0
3 2 0
3 3 0
3 4 0
3 5 0
3 6 0
3 7 0
3 8 0
3 9 0
4 0 0
4 1 0
4 2 0
NA 0.18
NA 1 . 4 7
NA 4.61
NA 11.10
NA 19.50
28.91
38.52
45.22
51.84
55.69
61.13
66.16
70.89
75.09
79.38
83.77
88.23
92.76
97.36
102.01
106.71
111.46
116.26
121.09
125.95
130.85
135.78
140.73
145.70
150.70
155.71
160.74
165.79
170.84
175.91
180.98
186.06
191.15
196.24
201.33
206.42
211.52
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
I NA
NA
* N A
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
T (IQ
Solid Mel t
Index Val ue Index Value
4 3 0
4 4 0
4 5 0
4 6 0
4 7 0
4 8 0
4 9 0
5 0 0
5 1 0
5 2 0
5 3 0
5 4 0
5 5 0
5 6 0
5 7 0
5 8 0
5 9 0
6 0 0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
216.61
221.69
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
252.68
258.44
264.20
269.96
275.12
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Not e s
Reference: U. Gaur, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem. Ref. Data,
12 (l), 58 (1983).
T,: 441.OK (C, = 222.2-247.5)
Solid: lo-50 K C, data are calculated from the Tarasov
equation (Data Bank, 1980)
60-440 K Experimental C, data of glassy samples (Data
Ba n k , 1 9 8 0 )
450-600 K C, data are not available
Mel t : lo-440 K Melt unstable
450-490 K Experimental C, data (Data Bank, 1980)
500-600 K C, dat a are not avai l abl e
TABLE 22. POLY(VINY1 BENZOATE) (PVBZ)
-@Hz--$ j
0-C-C6Hs
I II
c 0
T (K)
Solid Mel t
Index Value Index Val ue
1 0
2 0
3 0
4 0
5 0
6 0
7 0
8 0
9 0
100
110
120
130
140
150
160
170
180
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 22. contd
Solid Mel t
T (K) Index Value Index Value
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
106.39
111.57
116.75
121.93
127.10
132.28
137.46
142.64
147.82
152.99
158.17
163.35
168.53
173.71
178.88
184.06
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
258.08
260.96
263.84
266.7 1
269.59
272.47
275.35
278.23
281.10
283.98
286.86
289.74
292.62
295.49
298.37
301.25
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
Not es
Reference: LT. Gaur, B. B. Wunderlich, B. WunderEch, J. Phys. Chem. Ref. Data,
12 (l), 59 (1983).
T,:
Solid:
347.0 K
lo-180K
190-300 K
3IO-340K
C, data are not available
Experimental C, data (Data Bank, 1980)
Extrapolated value from C, in the region of
19O-XKIK
Mel t :
350-600K
lo-340K
_ _ _ _ _ _
C, data are not available
Melt unstable
350-360 K Extrapolated value from C, in the region of
370-500 K
370-500 K
510-600 K
Experimental C, data (Data Bank, 1980)
C, data are not available
Poly(methyl acrylate)
TABLE 23. POLY(METHYL ACRYLATE) (PMA)
VI / 501
+-b-sf
F=
OCH3
T (K)
Solid Mel t
Index Value Index Val ue
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
0.46
4.64
11.70
19.35
26.57
33.09
38.90
44.08
48.75
52.98
56.88
60.50
63.91
67.14
70.23
73.21
76.12
78.95
81.75
84.51
87.25
89.99
92.72
95.46
98.21
100.98
103.77
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
148.74
150.37
151.99
153.62
155.24
156.87
158.49
160.12
161.74
163.37
164.99
166.62
168.24
169.87
171.49
173.12
174.14
176.37
177.99
179.62
181.24
182.87
184.49
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
Re f e r e nc e s page VI - 5 19
VI / 502 HEAT CAkACITIES OF HIGH POLYMERS
TABLE 23. contd
T W)
Solid Mel t
Index Value Index Value
580 NA NA NA NA
590 NA NA NA NA
600 NA NA NA NA
Notes
Reference: U. Gaur, S. F. Lao, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
Ref. Data, 11 (4), 1074 (1982).
T,:
Solid:
Mel t :
279.0 K
lo-40K
50-270 K
280-600 K
lo-270 K
280-500 K
510-600K
(AC, = 42.30)
Extrapolated value from C, in the region of
50-270K (Data Bank, 1982)
Experimental C, data (Data Bank, 1982)
C, data are not available
Melt unstable
Experimental C, data (Data Bank, 1982)
C, data are not available
TABLE 24. POLY(ETHYL ACRYLATE) (PEA)
$ CHz- Ff
7
OCHz- CH3
T (K)
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
57.99
62.50
66.83
71.06
75.20
79.28
83.31
87.32
91.30
95.26
99.20
103.13
107.05
110.96
114.87
118.76
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA N A
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
,NA
NA
NA NA
- NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
168.06
170.22
172.39
174.55
176.72
178.88
181.04
183.21
185.37
TABLE 24. contd
Solid Mel t
T 6)
Index Val ue Index Value
340 NA NA 187.54
350 NA NA 189.70
360 NA NA 191.86
370 NA NA 194.03
380 NA NA 196.19
390 NA NA 198.36
400 NA NA 200.52
410 NA NA 202.68
420 NA NA 204.85
430 NA NA 207.01
440 NA NA 209.18
450 NA NA 211.34
460 NA NA 213.50
470 NA NA 215.67
480 NA NA 217.83
490 NA NA 220.00
500 NA NA 222.16
510 NA NA NA NA
520 NA NA NA NA
530 NA NA NA NA
540 NA NA NA NA
550 NA NA NA NA
560 NA NA NA NA
570 NA NA NA NA
580 NA NA NA NA
590 NA NA NA NA
600 NA NA NA NA
Not e s
Reference: U. Gaur, S. F. Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
Ref. Data, 11 (4), 1074 (1982).
T,: 249.0 K (AC, = 45.60)
Solid: lo-80K C, data are not available
90-240 K Experimental C, data (Data Bank, 1982)
250-600 K C, data are not available
Mel t : IO-240K Melt unstable
250-500 K Experimental C, data (Data Bank, 1982)
510-600K C, data are not available
TABLE 25. P~~Y(II-BUTYL ACRYLATE) (P~IBA)
$ CH2- yt
F=
OCH2- CH2- CH2- CH3
T WI
1 0
20
30
40
50
60
70
80
90
100
110
Solid Mel t
Index Val ue Index Value
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
71.75 NA NA
78.20 NA NA
84.65 NA NA
91.10 NA NA
TABLE 25. contd
T (K)
Solid Mel t
Index Value Index Value
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
NA
N A
N A
N A
N A
N A
N A
NA
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
97.55
104.01
110.46
116.91
123.36
129.81
136.27
142.72
149.17
155.62
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
i NA
N A
. .
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
206.90
210.19
213.49
216.79
220.09
223.39
226.68
229.98
233.28
236.58
239.88
243.17
246.47
249.77
253.07
256.37
259.66
262.96
266.26
269.56
272.86
276.15
279.45
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
Notes
Reference: LJ. Gaur, S. E Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
Ref. Data, 11 (4), 1074 (1982).
T,: 218.OK
Solid:
(AC, = 45.40)
lo-70K C, data are not available
Mel t :
SO-210K
220-600 K
lo-210K
220-440 K
450-600 K
Experimental C, data (Data Bank, 1982)
C, data are not available
Melt unstable
Experimental C, data (Data Bank, 1982)
C, data are not available
Poly(iso-butyl acrylate)
TABLE 26. POLY(ISO-BUTYL ACRYLATE) (PIBA)
t W-yj
F=O cH3
OCHy- tH- CH3
T 6)
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
155.80
163.50
171.30
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
215.17
218.55
221.94
225.32
228.7 1
232.09
235.47
238.86
242.24
245.63
248.01
252.39
255.78
259.16
262.55
265.93
269.3 1
272.70
276.08
279.47
282.85
286.23
289.62
293.00
296.39
299.77
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
Re f e r e nc e s page VI - 5 19
VI / 504 HEAT CAPACITIES OF HIGH POLYMERS
TABLE 26. contd
T (K)
Solid Mel t
Index Value Index Value
580 NA NA NA NA
590 NA NA NA NA
600 NA NA NA NA
Not e s
Reference: U. Gaur, S. F. Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
Ref. Data. 11 (4). 1074 (1982).
T, :
Sol i d:
249. 0I i . " (AC, = 36:60)
IO-210K C, data are not available
220- 240 K Experimental C, data (Data Bank, 1982)
Mel t :
250- 600 K
lo-240 K
250- 500 K
510-600K
Ct,- data are notavailable
Melt unstable
Experimental C, data (Data Bank, 1982)
C, data are not available
TABLE 27. POLY(METHACRYLIC ACID) (PMAA)
:
T (W
Solid Mel t
Index Value Index Value
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
1.23
5.50
10.85
16.38
21.76
26.90
31.80
36.46
40.91
45.18
49.27
53.23
57.06
60.77 .
64.39
67.93
71.39
74.78
78.12
81.41
84.65
87.85
91.02
94.16
97.27
100.40
103.40
106.50
109.50
112.50
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
*NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 27. contd
Solid Mel t
T (K) Index Value Index Value
350 NA NA NA NA
360 NA NA NA NA
370 NA NA NA NA
380 NA NA NA NA
390 NA NA NA NA
400 NA NA NA NA
410 NA NA NA NA
420 NA NA NA NA
430 NA NA NA NA
440 NA NA NA NA
450 NA NA NA NA
460 NA NA * NA NA
470 NA NA NA NA
480 NA NA NA NA
490 NA NA NA NA
500 NA NA NA NA
510 NA NA NA NA
520 NA NA NA NA
530 NA NA NA NA
540 NA NA NA NA
550 NA NA NA NA
560 NA NA NA NA
570 NA NA NA NA
580 NA NA NA NA
590 NA NA NA NA
600 NA NA NA NA
Not e s
Reference: U. Gaur, S. F. Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
Ref. Data, 11 (4), 1074 (1982).
Solid: lo-300K Experimental C, data (Data Bank, 1982)
310-600K C, data are not available
Mel t : 10-600 K C, data are not available
TABLE 28. POLY(METHY1 METHACRYLATE) (PMMA)
CH3
+cH, - ++
T="
OCH3
T (W
Solid Mel t
Index Value Index Value
1 0 1.67 NA NA
20 7.97 NA NA
30 14.67 NA NA
40 21.38 NA NA
50 27.67 NA NA
60 34.53 NA NA
70 41.30 NA NA
80 47.29 NA NA
90 52.64 NA NA
100 57.49 NA NA
110 61.97 NA NA
120 66.18 NA NA
130 70.20 NA NA
140 74.10 NA NA
TABLE 29. contd
T (W
Solid Mel t
Index Value Index Value
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
77.94
81.74
85.55
89.40
93.52
97.52
101.52
105.53
109.54
113.56
117.58
121.60
125.63
129.66
133.69
137.72
141.75
145.78
149.82
153.85
157.89
161.93
165.97
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NP;
NA
NA
NA
NA
I NA
NA
- NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
203.16
205.54
207.91
210.28
212.66
215.03
217.41
219.78
222.15
224.53
226.90
229.28
231.65
234.02
236.40
238.77
241.15
243.52
NA
NA
NA
NA
NA
Not e s
Reference: U. Gaur, S. F. Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. (
Ref. Data, 11 (4), 1068 (1982).
T,: 378.0 K (C, = 169.2-202.7)
Solid: lo-370 K Experimental C, data (Data Bank, 1982)
380-600 K C, data are not available
Mel t : lo-370 K Melt unstable
380-550 K Experimental C, data (Data Bank, 1982)
560-600 K C, data are not available
Poly(ethyl methacryl ate)
TABLE 29. POLY(ETHY1 METHACRYLATE) (PEMA)
CH3
+C+
F=
OCHz- CH3
T (W
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
279
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
58.84
63.60
68.42
73.28
78.17
83.08
88.01
92.94
97.88
102.83
107.79
112.75
117.71
122.67
127.64
132.61
137.58
142.55
147.52
152.49
157.47
162.44
167.42
172.39
177.37
182.34
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
218.77
222.47
226.17
229.87
233.57
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
References page VI - 5 19
VI / 506 HEAT CAPACITIES OF HIGH POLYMERS
TABLE 29. contd
T WI
5 7 0
5 8 0
5 9 0
6 0 0
Solid Mel t
Index Value Index Value
NA NA NA NA
NA NA NA NA
NA NA NA NA
NA NA NA NA
Notes
Reference: U. Gaur, S. E Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
Ref. Data, 11 (4), 1074 (1982).
T,:
Sol i d:
Mel t:
338.0 K
lo-70K
80-3303
340-600 K
lo-330 K
340-380 K
390-600K
(AC, = 31.70)
C,data are not available
Experimental C, data (Data Bank, 1982)
C,data are not available
Melt unstable
Experimental C, data (Data Bank, 1982)
C, data are not avai l abl e
TABLE 30. POLY(II-BUTYL METHAC RYLATE) (P~BMA)
CH3
+CH,-+i
y=o
T WI
Solid Mel t
Index Value Index Value,
1 0
2 0
3 0
4 0
5 0
6 0
7 0
8 0
9 0
100
110
120
130
140
150
160
170
180
190
2 0 0
2 1 0
2 2 0
2 3 0
2 4 0
2 5 0
2 6 0
2 7 0
2 8 0
2 9 0
3 0 0
3 1 0
3 2 0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
77.81
84.85
91.96
99.13
106.32
113.54
120.77
128.01
135.27
142.53
149.80
157.07
164.34
171.62
178.90
186.18
193.47
200.75
208.04
215.33
222.62
229.91
NA
NA
NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
., NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
263.41
268.29
273.17
TABLE 30. contd
T (K)
Solid Mel t
Index Value Index Value
3 3 0
3 4 0
3 5 0
3 6 0
3 7 0
3 8 0
3 9 0
4 0 0
4 1 0
4 2 0
4 3 0
4 4 0
4 5 0
4 6 0
4 7 0
4 8 0
4 9 0
5 0 0
5 1 0
5 2 0
5 3 0
5 4 0
5 5 0
5 6 0
5 7 0
5 8 0
5 9 0
6 0 0
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
NA
278.05
282.93
287.82
292.70
297.58
302.46
307.34
312.22
317.10
321.98
326.86
331.74
336.63
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
Notes
Reference: U. Gaur, S. F. Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
Ref. Data, 11 (4), 1074 (1982).
T,: 293.0 K (AC, = 29.70)
Sol i d: lo-70 K C,data are not available
80-290K Experimental C, data (Data Bank, 1982)
300-600K C,data are not available
Mel t: lo-290K Melt unstable
300-450 K Experimental C, data (Data Bank, 1982)
460-600K C, data are not avai l abl e
TABLE 31. POLY(ISO-BUTYL-METHACRYLATE) (PIBMA)
(73
fCHz-y+
7= CH3
OCH2- AH- CH3
T 00
Solid Mel t
Index Value Index Value
1 0
2 0
3 0
4 0
5 0
6 0
7 0
8 0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
90
1 0 0
1 1 0
120
1 3 0
1 4 0
150
1 6 0
1 7 0
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
173.90
181.00
188.00
195.10
202.20
209.20
216.30
223.40
230.40
237.50
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
3 NA
NA
. .
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
281.77
284.43
287.10
289.77
292.43
295.10
297:76
300.43
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 32. contd
Solid Mel t
T 6) Index Value Index Value
Notes
Reference: U. Gaur, S. E Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
Ref. Data, 11 (4), 1074 (1982).
T,: 326.0 K (AC, = 39.00)
Sol i d: lo-220 K C, data are not available
230-320 K Experimental C, data (Data Bank, 1982)
330-600 K C, data are not available
Mel t : lo-320K Melt unstable
330-400 K Experimental C, data (Data Bank, 1982)
410-600K C, data are not available
Poly(hexyl methacrylate)
TABLE 32. POLY(HEXY1 METHACRYLATE) (PHMA)
7H3
+C&-y+
T=
OCH2CH2CH2CH2CH2CH3
T (K)
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
3 10.77
315.46
320.14
324.83
329.52
334.20
338.89
343.57
348.26
352.95
357.63
362.32
367.00
371.69
376.38
381.06
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
References page VI - 5 19
VI / 508 HEAT CAPACITIES OF HIGH POLYMERS
TABLE 32. contd
T W)
Solid Mel t
Index Value Index Value
570 NA NA NA NA
580 NA NA NA NA
590 NA NA NA NA
600 NA NA NA NA
Not e s
Reference: U. Gaur, S. F. Lau, B. B. Wundedich, B. Wunderlich, J. Phys. Chem.
Ref. Data, 11 (4). 1074 (1982).
Solid: 10-600 K C, data are not available
Mel t : lo-260 K
270-420 K
430-600 K
Melt unstable
Experimental C, data (Data Bank, 1982)
C, data are not available
TABLE 33. POLY(ACRYLONlTRlLE) (PAN)
-@H~--FH+ .
C N
T 6)
Solid Mel t
Index Value Index Val ue
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
NA 1.17
NA 1. 93
NA 4. 94
NA 9. 55
NA 13.77
18.09
21.69
24. 87
27. 69
30. 22
32. 54
34. 67
36. 68
38. 59
40. 44
42. 23
44. 00
45. 75
47. 51
49. 27
51. 04
52. 85
54. 68
56. 56
58. 47
60. 43
62. 45
64. 51
66. 64
68. 83
71. 08
73. 41
75. 80
78. 27
80. 82
83. 45
86. 16
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
.t NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 33. contd
Solid Mel t
T (K) Index Value Index Val ue
390 NA NA NA NA
400 NA NA NA NA
410 NA NA NA NA
420 NA NA NA NA
430 NA NA NA NA
440 NA NA NA NA
450 NA NA NA NA
460 NA NA NA NA
470 NA NA NA NA
480 NA NA NA NA
490 NA NA NA NA
500 NA NA NA NA
510 NA NA NA NA
520 NA NA NA NA
530 NA NA NA NA
540 NA NA NA NA
550 NA NA NA NA
560 NA NA NA NA
570 NA NA NA NA
580 NA NA NA NA
590 NA NA NA NA
600 NA NA NA NA
Not e s
Reference: U. Gaur, S. F. Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
Ref. Data, 11 (4), 1074 (1982).
T, : 378.0 K
T, : 593.2 K
Solid: lo-50K C, value are calculated from the Tarasov
equation (Data Bank, 1982)
60-370 K Experimental C, data (Data Bank, 1982)
380-600K C, data are not available
Mel t : 10-600 K C, data are not available
TABLE 34. POLY(METHACRYLAMIDE) (PMAM)
T (K)
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
Solid Mel t
Index Val ue Index Val ue
NA 0. 21 NA NA
NA 2. 81 NA NA
NA 8.14 NA NA
NA 14.70 NA NA
NA 21.50 NA NA
28. 07 NA NA
34. 25 NA NA
39. 99 NA NA
45. 31 NA NA
50. 25 NA NA
54. 86 NA NA
59. 20 NA NA
63. 29 NA NA
67.18 NA NA
70. 90 NA NA
TABLE 34. contd
T (W
Solid Mel t
Index Value Index Value
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
74.48
77.94
81.30
84.59
87.81
90.98
94.11
97.21
100.30
103.30
106.40
109.50
112.50
115.60
118.70
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Nd
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
$. . NA
NA
. .
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Not e s
Reference: U. Gaur, S. F. Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
Ref. Data, 11 (4), 1074 (1982).
Solid: lo-50K C, value are calculated from the Tarasov
equation (Data Bank, 1982)
60-300 K Experimental C, data (Data Bank, 1982)
310-600K C, data are not available
Mel t : 10-600 K C, data are not available
Poly(oxy-1 -oxoethylene) VI / 509
TABLE 35. POLY(OXY-l-OXOETHYLENE) (PCL)
+W-t-O+
0
Solid Mel t
Index Value Index Val ue
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.78
3.98
8.02
12.12
16.04
19.57
22.72
25.55
28.11
30.47
32.67
34.74
36.69
38.53
40.28
41.96
43.58
45.15
46.69
48.22
49.99
51.71
53.42
55.14
56.85
58.57
60.28
62.00
63.71
65.42
67.14
68.85
70.57
72.28
74.00
75.71
77.43
79.14
80.86
82.57
84.29
86.00
87.72
89.43
91.15
92.86
94.58
96.29
98.01
99.72
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
114.13
114.51
114.90
115.28
115.66
116.04
116.42
116.80
117.18
117.56
117.94
118.32
118.70
119.09
119.47
119.85
120.23
120.61
120.99
121.37
121.75
NA
NA
NA
NA
NA
References page VI - 5 19
VI / 510 HEAT CAPACITIES OF HIGH POLYMERS
TABLE 35. contd TABLE 36. contd
Not e s
References: 1. B. Lebedev, A. Yevstropov, Makromol. Chem., 185 (6), 1235 (1984).
2. R. Pan, Master Thesis, Dept. of Chemistry, Rensselaer Polytechnic
T,:
T, :
Solid:
Institute, Dee
318.0K
501.OK
IO-290 K
300-500 K
Mel t :
510-600K
lo-310K
350-500 K
510-550 K
560-600 K
. 1986. -
(AC, = 44.7)
(AC, = 20.0)
Experimental C, data interpolated by Spline
function (Data Bank, 1985)
Linear extrapolated data from the region of
200-290K (Data Bank, 1985)
C, data are not available
Melt unstable
Linear extrapolated data from the region of
500-550K (Data Bank, 1985)
Experimental C, data (Data Bank, 1985)
C, data are not available
TABLE 36. POLY(OXY-l-OXOHEXAMETHYLENE) (PCL)
f(CHds-t-O+
0
T WI
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
2. 42
10. 72
20. 66
30. 17
37. 95
45. 74
53. 02
59. 61
65. 62
71. 14
76. 25
81. 02
85. 55
89. 91
94. 19
98. 73
103. 28
107. 83
112.38
116.92
121.47
126.02
130.57
135.12
139.67
144.22
148.77
153.32
157.87
162.42
166.97
171.51
176.06
180.61
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
. NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
180.81
183.72
186.64
189.55
192.47
195.38
198.30
201.21
204.13
207. 04
209. 96
212. 87
215. 79
218. 70
221. 62
NA
NA
NA
NA
NA
T (K)
Solid Mel t
Index Val ue Index Val ue
410
420
430
440
450
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Not e s
References: 1. B. Lebedev, A. Yevstropov, Makromol. Chem., 185 (6), 1235 (1984).
2. R. Pan, Master Thesis, Dept. of Chemistry, Rensselaer Polytechnic
Institute, Dec. 1986.
T,: 209.0 K (AC, = 60.0)
T, : 342.0 K (AC, = 38.0)
Solid: lo-200 K Experimental C, data interpolated by Spline
function (Data Bank, 1985)
210-340K Linear extrapolated data from the region of
150-200K (Data Bank, 1985)
350-600 K C, data are not available
Mel t : lo-200K Melt unstable
210-300K Linear extrapolated data from the region of
342-350 K (Data Bank, 1985)
340-350 K Experimental C, data (Data Bank, 1985)
360-600 K C, data are not available
TABLE 37. P~LY(~XYETHYLENE~XYTEREPHTHAL~YL) (PET)
+~-CH~CH~-O--
0
/ \
-
yj
T WI
0 0
Solid Mel t
Index Val ue Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
12. 43
NA NA
22.91
36.18
48. 24
56. 68
63. 92
69. 95
77. 18
84. 42
91. 70
100.10
105.90
112.60
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 37. contd
T (K)
Solid Mel t
Index Value Index Value
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
119.40
126.20
133.10
140.10
147.10
154.10
161.20
168.20
175.30
182.40
189.50
196.70
203.80
210.90
218.10
225.20
232.40
239.60
246.70
253.90
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Nd
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
335.70
338.50
341.30
344.10
346.90
349.80
352.60
355.40
358.20
361.00
363.90
366.70
369.50
372.30
375.10
378.00
380.80
383.60
386.40
389.20
392.10
394.90
397.70
400.50
403.30
406.15
Notes
Reference: U. Gaur, S. F. Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
Ref. Data, 12, (1). 70 (1983).
T,: 342.0 K (C, = 255.6-333.4)
T , : 553.0 K
Solid: lo-340 K Experimental C, (Data Bank, 1983)
350-600 K C, data are not available
Mel t : lo-340 K Melt unstable
350-590 K Experimental C, data (Data Bank, 1983)
600K Linear extrapolated data from C, in the region
of 350-590 K (Data Bank, 1985)
Poly(imino-(1 -oxohexamethylene)) VI/511
TABLE 38. POLY(IMINO-(l-OXOHEXAMETHYLENE)) (NYLON 6)
t (CWs- 7-t
0
Solid Mel t
Index Value Index Value
1 0 NA
20 NA
30 NA
40 NA
50 NA
60 NA
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320 NA
330 NA
340 NA
350 NA
360 NA
370 NA
380 NA
390 NA
400 NA
410 NA
420 NA
430 NA
NA
NA
NA
NA
NA
NA
49.78
56.40
62.45
68.06
73.34
78.38
83.26
88.01
92.70
97.35
102.00
106.70
111.40
116.20
121.00
126.00
131.00
136.20
141.40
146.90
152.40
158.10
164.00
170.00
176.20
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
272.80
274.30
275.80
277.40
278.90
280.40
281.90
283.50
285.00
286.50
288.00
289.60
440 NA
450 NA
460 NA
470 NA
480 NA
490 NA
500 NA
510 NA
520 NA
530 NA
540 NA
550 NA
560 NA
570 NA
580 NA
590 NA
600 NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
291.10
292.60
294.10
295.70
297.20
298.70
300.20
301.80
303.30
304.80
306.30
307.90
309.40
3 10.90
312.40
314.00
315.50
References page VI - 5 19
VI/512 HEAT CAPACITIES OF HIGH POLYMERS
TABLE 38. c ontd
Not e s
Reference: U. Gaur, S. F. Lao, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
T,:
T , :
Sol i d:
Mel t:
Ref. Data, 12, (1). 83 (1983).
313.OK (C, = 178.1-271.7)
553.0 K
10-60 K C,data are not available
70-310K Experimental C, data (Data Bank, 1983)
320-600K C,data are not available
lo-310K Melt unstable
320-600 K Exuerimental C, data (Data Bank, 1983)
TABLE 39. POLY(IMINOADIPOYLIMINOHEXAMETHYLENE)
(NYLON 66)
T (W
Solid Mel t
Index Value I n d e x Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
210
280
290
300
310
320
330
340
3.50
360
370
380
390
400
410
420
430
440
N A
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
NA
N A
NA
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
N A N A
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
N A N A
NA NA
NA NA
NA NA
NA NA
NA NA
252.10 ,NA
263.40 NA
274.70 . NA
286.00 NA
291.30 NA
308.60 NA
320.00 NA
331.30 NA
342.60 NA
354.00 NA
N A
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
505.70
510.40
515.00
519.70
524.40
529.70
533.80
538.50
543.10
547.80
552.50
557.20
TABLE 39. contd
Solid Mel t
T (K)
Index Value Index Value
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
561.90
566.50
571.20
575.90
580.60
585.30
590.00
594.60
599.30
604.00
608.70
613.40
618.10
622.70
627.40
632.10
Not e s
Reference: U. Gaur, S. F. Lau, B. B. Wunderlich, B. Wunderlich, J. Phys. Chem.
T.:
Ref. Data, 12, (l), 84 (1983).
323.0 K CC,= 357.4-502.4)
Tm:
Sol i d:
553.0K r
lo-220 K C,data are not available
230-320 K Experimental C, data (Data Bank, 1983)
330-6COK C,data are not available
Mel t: lo-320 K
330-600K
Mklt unstable
Exoerimental C, data (Data Bank, 1983)
TABLE 40. POLY(IMlNOADIPOYLIMlNODODECAMETHYLENE)
(NYLON 612)
~NH-(CH~)~NII-~-(CH~)~O-~~.
0 0
T W)
Solid Mel t
Index Value Index Val ue
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
N A
N A
NA
N A
NA
NA
NA
NA
N A
NA
362.40
378.70
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
N A
NA
N A
NA
NA
NA
NA
NA
N A
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
TABLE 40. contd
Solid Mel t
T (K) Index Value Index Value
2.50
260
270
280
290
300
310
320 NA
330 NA
340 NA
350 NA
360 NA
370 NA
380 NA
390 NA
400 NA
410 NA
420 NA
430 NA
440 NA
450 NA
460 NA
470 NA
480 NA
490 NA
500 NA
510 NA
520 NA
530 NA
540 NA
550 NA
560 NA
570 NA
580 NA
590 NA
600 NA
395.00
411.20
427.50
443.80
460.10
476.30
492.60
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
723.00
729.10
735.10
741.10
747.20
753.20
759.30
765.30
771.30
777.40
783.40
: 789.50
795.50
801.50
807.60
831.60
819.60
825.70
831.70
837.80
843.80
849.80
855.90
861.90
867.90
874.00
880.00
886.10
892.10
Not e s
Reference: U. Gaur, S. F.
Ref. Data, 12,
T,: 319.OK
Solid: lo-220 K
230-310K
330-600 K
Mel t : lo-320 K
320-600 K
Lau, B. B. Wundedich, B. Wunderlich, J. Phys. C
(1). 87 (1983).
(C, = 507.3-722.1)
C, data are not available
Experimental C, data (Data Bank, 1983)
C, data are not availaye
Melt unstable
Experimental C, data;(Data Bank, 1983)
:hem.
TABLE 41. POLY(OXYMETHYLENE) (POM)
-CO--CHzt
T (K)
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
1 0 0
0.42
2.46
5.41
7.97
10.10
11.85
13.30
14.54
15.65
16.68
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 41. contd
Poly(oxymethylene)
T WI
Solid Mel t
Index Val ue Index Value
110
120
130
140
1.50
160
170
180
190
2qo
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
17.68
18.68
19.71
20.75
21.82
22.89
23.97
25.05
26.11
27.15
28.18
29.20
30.21
31.24
32.29
33.39
34.55
35.79
37.11
38.52
40.02
41.61
43.27
45.00
46.77
48.57
50.38
52.20
54.00
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
53.58
53.95
54.32
54.69
55.07
55.44
55.81
56.18
56.55
56.93
57.30
57.67
58.04
58.41
58.79
59.16
59.53
59.90
60.27
60.65
61.02
61.39
61.76
62.13
62.51
62.88
63.25
63.62
63.99
64.37
64.74
65.11
65.48
65.85
66.23
66.60
66.97
67.34
67.71
68.09
68.46
68.83
Notes
References: 1. U. Gaur, B. Wunderlich, J. Phys. Chem. Ref. Data, 10 (4), 1005
(1981).
Tc.:
2. H. Suzuki, B. Wunderlich, J. Polym. Sci., Polym. Phys. Ed., 23,
1671 (1985).
190.0 K fC, = 26.11-53.58)
T;:
Solid:
457.2K V
lo-390 K Experimental C, data (Data Bank, 1981)
400-600 K C. data are not available
Mel t : lo-180K
190-420 K
430-540 K
550-600 K
Ci data are not available
Extrapolated value from C, in the region of
430-540 K (Data Bank, 1985)
Experimental C, data (Data Bank, 1985)
Extrapolated value from C, in the region of
430-540 K (Data Bank, 1985)
References page VI - 5 19
VI / 514 HEAT CAPACI TI ES OF HI GH POLYMERS
TABLE 42. POLY(OXYETHYLENE)
fO-CH2CH2f
T (K)
Solid Mel t
Index Value Index Value
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.51
3.18
7.24
11.16
14.62
17.60
20.13
22.33
24.90
26.93
28.78
30.44
32.10
33.57
35.05
36.53
37.80
39.11
40.40
41.88
43.17
44.64
45.91
47.26
48.61
49.96
51.31
52.66
54.01
55.36
56.71
58.06
59.41
60.76
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
I
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
81.88
82.55
83.21
83.88
84.55
85.22
85.89
86.55
87.22,
87.89
88.56
89.23
89.89
90.56
91.23
91.90
92.57
93.23
93.90
94.57
95.24
95.91
96.57
97.24
97.91
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 42. contd
Notes
References: 1. U. Gaur, B. Wunderlich, .I. Phys. Chem. Ref. Data, 10 (4), 1010
(1981).
T,:
T,:
Solid:
Mel t :
2. H. Suzuki, B. Wunderlich, .I. Polym. Sci., Polym. Phys. Ed., 23,
1671 (1985).
260.0 K (C, = 42.65-81.61)
342.0 K
10-80 K
(C, = 61.03-90.70)
Value estimated by additivity (Data Bank,
1981)
90-220 K Experimental C, data (Data Bank, 1981)
230-340 K Extrapolated value from C, in the region of
160-220K (Data Bank, 1981)
350-600 K C, data are not available
IO-200 K C, data are not available
210-320K Extrapolated value from C, in the region of
430-540K (Data Bank, 1985)
330-450 K
460-600 K
Experimental C, data (Data Bank, 1985)
C, data are not available
TABLE 43. POLY(OXYTRlMETHYLENE) (P03M)
T W)
-EC)--(CH2)34-
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.86
4.68
9.31
13.65
17.64
21.37
25.82
29.59
32.90
35.87
38.58
41.11
43.51
45.83
48.11
50.37
52.65
54.97
57.33
59.01
61.08
63.15
65.23
67.30
69.37
71.44
73.51
75.59
77.66
79.73
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
109.24
110.25
111.26
112.27
113.28
114.29
115.30
116.31
117.32
118.33
119.34
120.35
121.36
122.37
NA
NA
NA
NA
NA
NA
NA
NA
TABLE 43. contd
Poly(oxytetramethylene) and Poly(oxypropylene) VI/515
TABLE 44. contd
T (K)
Solid Mel t
Index Value Index Value T (W
Solid Mel t
Index Val ue Index Val ue
420
430
440
450
460
410
480
490
500
510
520
530
540
550
560
570
580
590
600
N A
N A
N A
NA
N A
NA
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
NA-
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
Notes
Reference: U. Gaur, B. Wunderlich, J. Phys. Chem. Ref. Data, 10 (4), 1015 (1981).
T,: 195.OK (C, = 57.97-108.7)
T,: 308.0 K (C, = 81.39-120.1)
Solid: lo-180K Experimental C, data (Data Bank, 1981)
190-300K Extrapolated value from C, in the region of
150- 180 K (Data Bank, 1981)
310-600K C, data are not available
Mel t : lo-190K Melt unstable
200-330 K Experimental C, data (Data Bank, 1981)
340-600 K C, data are not available
TABLE 44. POLY(OXYTETRAMETHYLENE) (P04M)
--EC)--Wd4f
T (W
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
N A
N A
N A
N A
N A
N A
N A
N A
N A
1.47
6.59
12.42
18.32
24.63
29.14
34.61
39.41
43.67
47.21
50.72
54.70
57.99
61.12
64.46
67.96
71.20
74.52
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
* NA
_. NA
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
124.20
125.92
127.64
129.36
131.09
132.81
134.53
260 N A
270 N A
280 N A
290 N A
300 N A
310 N A
320 N A
330 N A
340 N A
350 N A
360 N A
370 N A
380 N A
390 N A
400 N A
410 N A
420 N A
430 N A
440 N A
450 N A
460 N A
470 N A
480 N A
490 N A
500 N A
510 N A
520 N A
530 N A
540 N A
550 N A
560 N A
570 N A
580 N A
590 N A
600 N A
N A N A
N A N A
N A
N A
N A
N A
N A
N A
N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
136.26
137.98
139.70
141.42
143.15
144.87
146.59
148.32
150.04
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
Notes
Reference: U. Gaur, B. Wunderlich, J. Phys. Chem. Ref. Data, 10 (4), 1023 (1981).
T,: 189.0 K (C, =77X-124.0)
T,: 330.0 K
Solid: lo-160K Experimental C, data (Data Bank, 1981)
170-180K Extrapolated value from C, in the region of
130-160K (Data Bank, 1981)
190-600 K C, data are not available
Mel t : lo-180K Melt unstable
190-270K Extrapolated value from C, in the region of
280-340K (Data Bank, 1981)
280-340 K Experimental C, data (Data Bank, 1981)
350-600 K C, data are not available
TABLE 45. POLY(OXYPROPYLENE) (POPr)
T (W
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
References page VI - 5 19
VI / 516 HEAT CAPACITIES OF HIGH POLYMERS
TABLE 45. contd
T WI
Solid Mel t
Index Value Index Value
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
31.21
34.33
37.37
40.34
43.22
46.03
48.76
51.41
53.98
56.48
58.89
61.23
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
,NA
NA
. NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
95.46
97.04
98.61
100.19
101.77
103.35
104.92
106.50
108.08
109.65
111.23
112.81
114.38
115.96
117.54
119.12
120.69
122.27
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Not e s
Reference: U. Gaur, B. Wunderlich, J. Phys. Chem. Ref. Data, 10 (4), 1033 (1981).
T,: 198.OK (Co = 63.05-95.20)
T, :
Solid:
Mel t :
348.OK =
lo-70K C, data are not available
80-190K Experimental C, data (Data Bank, 1981)
200-600 K C, data are not available
lo-190K Melt unstable
200-370 K
380-600 K
Experimental C, data (Data Bank, 1981)
C, data are not available
TABLE 46. POLY(OXY-1,4-PHENYLENE) (POPh)
T 6)
Solid Mel t
Index Val ue Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
109.10
112.40
115.80
119.20
122.50
125.90
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
150.30
151.70
153.10
154.60
156.00
157.40
158.80
160.30
161.70
163.10
164.50
166.00
167.40
168.80
170.20
171.70
173.10
174.50
175.90
177.40
178.80
180.20
181.60
183.10
184.50
Poly(oxy-2,6-dimethyl-1,4-phenylene) and Poly(oxy-2,6-diphenyl-1,4-phenylene) VI/517
TABLE 46. contcf
Notes
Reference: U. Gaur, B. Wunderlich, J. Phys. Chem. Ref. Data, 10 (4), 1033 (1981).
T,: 358.0K (C, = 128.6-150.0)
T,:
Solid:
Mel t :
535.03
lo-290 K
300-350 K
360-600 K
lo-350K
360-380 K
390-580 K
590-600 K
C, data are not available
Experimental C, data (Data Bank, 1981)
C, data are not available
Melt unstable
Experimental C, data (Data Bank, 1981)
Extrapolated value from C, in the region of
360-380 K & 590-620 K (Data Bank, 1981)
Experimental C, data (Data Bank, 1981)
TABLE 47. POLY(OXY-2,6-DIMETHYL-1,4-PHENYLENE) (PPO)
CH3
CH3
T W
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
4.05
11.52
19.12
26.45
33.44
40.12
46.49
52.50
57.80
63.01
68.07
72.91
77.45
82.04
86.42
89.74
94.14
98.48
102.80
107.00
111.20
115.33
119.57
123.81
128.04
132.33
136.60
140.91
145.27
149.66
154.08
158.58
162.10
166.20
170.20
174.50
178.60
182.70
186.80
190.50
194.50
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
NA
., N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
NA
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
TABLE 47. contd
T W)
Solid Mel t
Index Val ue Index Value
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
198.20
201.30
204.70
208.10
211.60
215.00
218.40
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
252.80
255.10
257.30
259.60
261.90
264.20
266.50
268.70
271.00
N A
N A
N A
Notes
References: 1. U. Gaor, B. Wunderlich, J. Phys. Chem. Ref. Data, 10.1036 (1981).
2. B. V. Lebedev, V. G. Vasilev, T. A. Bykova, E. G. Kiparisova, and
B. Wunderlich, Vysokomol. Soedin. A, 38, 216; Engl. Translat.,
Polym. Sci. Ser. A, 38 (2), 104 (1996)
T,: 482.0 K (C, = 219.1-251.0)
T,: 545.0 K
Solid: lo-70 K Experimental C, data from Ref. 2
80-320 K Average experimental C, data from Ref. 1 and 2
320-480 K Experimental C, data from Ref. 1
490-600 K C, data are not available
Mel t : lo-480 K Melt metastable
490-570 K Experimental C, data from Ref. 1
580-600 K C, data are not available
TABLE 48. POLY(OXY-2,6-DIPHENYL-1,CPHENYLENE) (POPPO)
C6HS
$ 0
Ws
T W
Solid Mel t
Index Value Index Value
1 0
20
30
40
50
60
70
80
90
100
110
120
130
140
150
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
N A N A
References page VI - 5 19
VI / 518 HEAT CAPACITIES OF HIGH POLYMERS
TABLE 48. contd
T (K)
Solid Mel t
Index Value Index Value
160
170
180
190
2 0 0
2 1 0
2 2 0
2 3 0
2 4 0
2 5 0
2 6 0
2 7 0
2 8 0
2 9 0
3 0 0
3 1 0
3 2 0
3 3 0
3 4 0
3 5 0
3 6 0
3 7 0
3 8 0
3 9 0
4 0 0
4 1 0
4 2 0
4 3 0
4 4 0
4 5 0
4 6 0
4 7 0
4 8 0
4 9 0
5 0 0
5 1 0
5 2 0
5 3 0
5 4 0
5 5 0
5 6 0
5 7 0
5 8 0
5 9 0
6 0 0
NA NA
NA NA
180.60
189.20
198.20
207.30
215.90
223.10
229.40
235.90
243.30
25 1.20
259.30
267.00
274.10
280.50
287.00
294.50
302.50
309.50
315.00
320.20
326.30
333.00
339.40
344.80
350.10
356.30
363.00
369.50
375.20
380.30
NA 387.20
NA 393.30
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
INA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N A
NA
NA
NA
476.50
483.40
490.30
497.30
504.10
510.90
517.80
524.70
531.60
538.50
545.40
Not e s
Reference: U. Gaur, B. Wunderlich, J. Phys. Chem. Ref. Data, 10, (4) 1036 (1981).
T,: 493.0 K (C, = 395. 1-471. 7)
T , : 735.0 K
Solid: lo-170K C, data are not available
180-470 K Experimental C, data (Data Bank, 1981)
480-490 K Extrapolated value from C, in the region of
420-470 K (Data Bank, 1981)
500- 600 K C, data are not available
Mel t : lo-490 K Melt unstable
500-530 K Experimental C, data (Data Bank, 1981)
540-600 K Extrapolated value from C, in the region of
500-530 K & 780-820 K
TABLE 49. POLY(OXYCARBONYLOXY-l,CPHENYLENE-
ISOPROPYLIDENE-1,4-PHENYLENE) (PC)
C3
0
T (K)
Solid Mel t
Index Value Index Value
1 0
2 0
3 0
4 0
5 0
6 0
7 0
8 0
9 0
100
110
120
130
140
150
160
170
180
190
2 0 0
2 1 0
2 2 0
2 3 0
2 4 0
2 5 0
2 6 0
2 7 0
2 8 0
2 9 0
3 0 0
3 1 0
3 2 0
3 3 0
3 4 0
3 5 0
3 6 0
3 7 0
3 8 0
3 9 0
4 0 0
4 1 0
4 2 0
4 3 0
4 4 0
4 5 0
4 6 0
4 7 0
4 8 0
4 9 0
5 0 0
5 1 0
5 2 0
5 3 0
5 4 0
5 5 0
5 6 0
5.95
25.38
39.85
52.46
63.75
73.72
82.62
91.39
100.40
109.70
118.80
128.90
139.00
148.90
158.80
168.70
178.50
188.30
198.00
207.80
217.60
227.30
237.10
247.00
256.80
266.70
276.70
286.70
296.70
306.80
316.90
327.10
337.40
347.70
358.10
368.50
379.10
389.70
400.30
411.10
421.90
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
480.30
486.00
491.80
497.60
503.40
509.20
515.00
520.80
526.60
532.40
538.20
543.90
549.70
555.50
561.30
TABLE 49. contd TABLE 50. contd
References
f (K)
Solid Mel t
Index Value Index Value
T WI
Solid Mel t
Index Value Index Value
570 NA NA NA
580 NA NA NA
590 NA NA NA
6 0 0 NA NA NA
Notes
Reference: U. Gaur, S. F. Lau, B. Wunderlich, J. Phys. Chem. Ref. Data, 12, (1) 93
(1983).
T,:
T,:
Solid:
~~~ --,
418.OK
608.2 K
lo-410K
(C, = 430.6-479.1)
Experimental C, data of glassy sample (Data
Bank, 1983)
Mel t :
420-600 K
lo-410K
420-560 K
570-600 K
C, data a& not available
Melt unstable
Experimental C, data (Data Bank, 1983)
C, data are not available
T A B L E 5 0 . TRICONAL S E L E N I U M (SeT)
+W-
T 6)
Solid Mel t
Index Value Index Value
1 0
2 0
3 0
4 0
5 0
6 0
7 0
8 0
9 0
100
1 1 0
1 2 0
130
1 4 0
1 5 0
1 6 0
1 7 0
1 8 0
1 9 0
200
210
0.64
3.45
6.34
8.85
10.98
12.80
14.39
15.80
17.10
18.19
19.10
19.84
20.49
21.07
21.58
22.03
22.41
22.75
23.05
23.32
23.56
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
5 NA
. NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
D. REFERENCES
1 . F. S. Dainton, D. M. Evans, F. E. Hoare, T. P. Melia, Polymer,
12, 297 (1962).
2. Idem, 12, 277 (1962).
3 . M. Dole, W. P. Hettinger, N. R. Larson, J. A. Wethington, J.
Chem. Phys., 20, 718 (1952).
4. B. Wunderlich, M. Dole, J. Polym. Sci., 24, 201 (1957).
5. G. T. Furukawa, M. L. Reilly, J. Res. Nat. Bur. Std., 56, 285
(1956).
6. N. Bekkedahl, H. Matheson, J. Res. Nat. Bur. Std., 15, 503
(1935).
2 2 0
2 3 0
2 4 0
2 5 0
2 6 0
2 7 0
2 8 0
2 9 0
3 0 0
3 1 0
3 2 0
3 3 0
3 4 0
3 5 0
3 6 0
3 7 0
3 8 0
3 9 0
4 0 0
4 1 0
4 2 0
4 3 0
4 4 0
4 5 0
4 6 0
4 7 0
4 8 0
4 9 0
5 0 0
5 1 0
5 2 0
5 3 0
5 4 0
5 5 0
5 6 0
5 7 0
5 8 0
5 9 0
6 0 0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
23.78
23.99
24.18
24.36
24.52
24.68
24.83
24.97
25.11
25.25
25.38
25.51
25.63
25.75
25.88
26.00
26.12
26.24
26.36
26.48
26.60
26.72
26.84
26.96
27.08
27.20
27.33
27.45
27.58
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
NA NA
40.11
39.82
39.54
39.26
38.98
38.72
38.46
38.21
37.96
37.72
37.49
37.26
37.04
36.82
36.62
36.42
36.22
36.03
35.85
35.68
35.51
35.35
35.19
35.04
34.90
34.76
34.64
34.51
34.40
34.29
Notes
Reference: U. Gaur, H. C. Shu, A. Mehta, B. Wunderlich, J. Phys. Chem. Ref.
Data, 10, (1) 89 (1981).
T,: 303.4 K (C, = 27.02-40.31)
T , : 492.2 K (C, = 27.51-35.78)
Solid: lo-500 K Experimental C, data (Data Bank, 1981)
510-600K C, data are not available
Mel t : lo-300K Melt unstable
310-600K Experimental C, data (Data Bank, 1981)
7. S. S. Chang, A. B. Bestul, .I. Res. Nat. Bur. Std., 75A, 113
(1971).
8. L. A. Wood, N. Bekkedahl, Polym. Lett., 5, 169 (1967).
9. E. Y. Roinishvili, N. N. Tavkhelidze, V. B. Akopyan, Vyso-
komol. Soedin. B, 9, 254 (1967).
10. C. W. Smith, M. Dole, J. Polym. Sci., 20, 37 (1956).
11. K. H. Hellwege, W. Knappe, W. Wetzel, Kolloid-Z., 180,
126 (1962).
12. F. S. Dainton, D. M. Evans, F. E. Hoare, T. P. Melia, Polymer,
3, 263, (1962).
VI / 520 HEAT CAPACITIES OF HIGH POLYMERS
13. H. Wilski, Kolloid-Z. -Z. Polym., 248, 867 (1971).
14. F. S. Dainton, D. M. Evans, F. E. Hoare, T. P. Melia, Polymer,
12, 286 (1962).
15. E. Passaglia, H. K. Kevorkian, J. Appl. Phys., 34, 90
( 1963) .
16. F. E. Karash, H. E. Bair, J. M. OReilly, J. Phys. Chem., 69,
2657 (1965).
17. S. Ichihara, A. Komatsu, T. Hata, Polym. J., 2, 644 (1971).
18. G. T. Furukawa, R. E. MC Coskey, G. J. King, J. Res. Nat.
Bur. Std., 50, 357 (1953).
19. G. T. Furukawa, R. E. MC Coskey, M. L. Reilly, J. Res. Nat.
Bur. Std., 55, 127 (1955).
20. B. V. Lebedev, I. B. Rabinowich, V. A. Budarina, Vysoko-
mol. Soedin. A, 9, 488 (1967).
21. Th. Grewer, H. Wilski, Kolloid-Z. -Z. Polym., 226, 46
( 1968) .
22. P. Marx, M. Dole, J. Am. Chem. Sot., 77, 4771 (1955).
23. G. T. Furukawa, R. E. MC Coskey, G. J. King, J. Res. Nat.
Bur. Std., 43, 273 (1952).
24. T. B. Douglas, A. W. Harman, J. Res. Nat,., Bur. Std., 69A,
149 (1965).
25. P. Marx, M. Dole, J. Am. Chem. Sot., 77, 4771 (1955).
26. S. Yoshida, M. Sakiyama, S. Seki, Polym. J., 1, 573 (1970).
27. J. M. OReilly, F. E. Karasz, H. E. Bair, J. Polym. Sci. C, 6,
109 (1963).
28. F. E. Karasz, H. E. Bair, J. M. OReilly, J. Polym. Sci. Part A:
2, 1141 (1968).
29. T. Hatakeyama, K. Nakamura, H. Hatakeyama, Polymer, 23,
1801 (1982).
30. V. P. Kolesov, I. E. Paylov, S. M. Skutarov, Zh. Fiz. Khim.,
36, 770 (1962).
31. D. R. Gee, T. P. Melia, Polymer, 11, 192 (1970).
32. P. Marx, C. W. Smith, A. E. Worthington, M. Dole, J. Phys.
Chem., 59, 1015 (1955).
33. R. C. Wilhoit, M. Dole, J. Phys. Chem., 57, 14 (1953).
34. B. Wunderlich, in: Academic Press, New York, 1990; E. Turi
(Ed.), Thermal Characterization of Polymeric Materials.
Academic Press, New York, 1997.
35. Okazaki, B. Wunderlich, Macromolecules, 30, 1758
( 1997) .
36. B. Wunderlich, Macromolecular Physics, vol. 3, Crystal
Melting. Academic Press, Boston, MA, 1980.
37. K. Ishikiriyama, M. Pyda, G. Zhang, T. Forschner, J. Gre-
bowicz, B. Wunderlich, J. Macromol. Sci. B: Phys., 37, 27
( 1998) .
38. H. Suzuki, J. Grebowicz, B. Wunderlich, Brit. Polymer J.,
17, 1 (1985).
39. B. Wunderlich, Pure and Applied Chem., 67, 1919
(1995).
40. World Wide Web, URL: http://funnelweb.utcc.utk.edu/
-athas.
41. R. Pan, M-Y. Cao, B. Wunderlich, J. Thermal Anal., 31,
1319 (1986); U. Gaur, M.-Y. Cao, R. Pan, B. Wunderlich, 31,
421 (1986).
Surface and Interfacial Tensions of Polymers,
Oligomers, Plasticizers, and Organic Pigments
Souheng Wu
E. I. du Point de Nemours & Company, Central Research and Development Department,
Experimental Station, Wilmington, Delware, USA
A. Introduction
1. Definition
2. Temperature Dependence
:
3. Macleods Relation
4. Molecular Weight Dependence
5. Effects of Glass and Crystal-Melt
Transi ti ons
6. Effect of Surface Chemical Constitution
7. Dispersion (Nonpolar) and Polar
Co mp o n e n t s
B. Tables
Table 1. Surface Chemical Constitution
and Surface Tension
1.1. Hydrocarbon Surfaces
1.2. Fluorocarbon Surfaces
1.3. Chlorocarbon Surfaces
1.4. Silicane Surfaces
Table 2. Surface Tension, Polarity, and
Macleods Exponent for Amorphous
Surf aces
2.1. Hydrocarbon Polymers
2.2. Styrene Polymers
5
VI-521
VI-52 1
VI-522
VI-522
VI-522
VI-522
VI-523
VI-523
VI-523
VI-524
VI-524
VI-524
VI-524
VI-524
VI-524
VI-524
VI-525
2.3. Halogenated Hydrocarbon Polymers VI-525
2.4. Vinyl Polymers - Esters VI-526
2.5. Vinyl Polymers - Others VI-526
2.6. Acrylic Polymers - Nonfluorinated VI-526
2.7. Acrylic Polymers - Fluorinated VI-527
2.8. Methacrylic Polymers -
Nonfluorinated VI-527
2.9. Methacrylic Polymers - Fluorinated VI-527
2.10. Methacrylic Hydrogels VI-527
2. 11. Polyfethers) VI-528
2.12. Polyfether) Copolymers VI-529
2. 13. Polyfesters) VI-529
2. 14. Polytcarbonates) VI-530
2. 15. Polyfsulfones) VI-530
2.16. Phenoxy Resins VI-530
2.17. Epoxy Resins VI-530
2. 18. Poly(amides)
2. 19. Polyfimides)
2. 20. Poly(imines)
2. 21. Polyfurethanes)
2. 22. Poly(siloxanes)
2.23. Organosilanes - Hydrolyzed a n d
Condensed Fi l ms
2.24. Cellulosics
2. 25. Poly(peptides)
2.26. Miscellaneous
Table 3. Interfacial Tension for Amorphous
I nt er f aces
3.1. Hydrocarbon Polymers vs. Others
3.2. Styrene Polymers vs. Others
3.3. Vinyl Polymers vs. Others
3.4. Acrylic Polymers vs. Others
3.5. Methacrylic Polymers vs. Others
3.6. Polyfethers) vs. Others
3.7. Polyfesters) vs. Others
3.8. Polyfamides) vs. Others
3.9. Epoxy Resins vs. Others
3.10. Poly(siloxanes) vs. Others
3.11. Miscellaneous
C. References
A. I NTRODUCTI ON
1. Definition
VI-530
VI-531
VI-531
VI-53 1
VI-531
VI-532
VI-533
VI-533
VI-533
VI-535
VI-535
VI-537
VI-537
VI-538
VI-538
VI-539
VI-539
VI-539
VI-539
VI-539
VI-540
VI-540
The surface (interfacial) tension is the reversible work
required to create a unit surface (interfacial) area at
constant temperature (T), pressure (P), and composition
(n) Cl), i.e.,
Y = WPhJ.
>3
(Al)
where y is the surface (interfacial) tension, G the Gibbs free
energy of the system, and A the surface (interfacial) area.
VI / 521
VI 1522 SURFACE AND INTERFACIAL TENSIONS OF POLYMERS, OLICOMERS, PLASTICIZERS, AND ORGANIC PIGMENTS
The specific surface free energyf, is the free energy per unit
surface area (I), i.e.,
fs = Y + (ClPl + C2P2) (A21
where Cj is the surface concentration (the number of moles
per unit area) of component j, and pj is the chemical
potential of component j. Thus y = fs - (Ct h t + C2~2),
which means that the surface tension is the excess specific
surface free energy. The excess means in excess of the bulk
phase. This distinguishes the surface tension and the
specific surface free energy (1).
2. Temperature Dependence
The surface tension of polymers, just as with small-
molecule liquids, varies with temperature (1) by
y = yo( 1 - T/T,) ls
(9
where ye is the surface tension at T=OK; and T, is the
critical temperature. The temperature coefficient of surface
tension is thus given (1) by
-dy/dT = (11/9)(yo/T,)(1 - T/T,)29
(A41
Since T, _N lOOOK for most polymers (l), -dy/dT is
therefore practically constant at ordinary temperatures, i.e.,
T << T,.
For polymer pairs that have an upper consolute curve
and an UCST (upper critical solution temperature), the
interfacial tension decreases with increasing temperature
and vanishes at the upper consolute temperature. This is the
case for most pairs of immiscible polymers. On the other
hand, for polymers that have a lower consolute curve and an
LCST (lower critical solution temperature), the interfacial
tension vanishes at the lower consolute point and increases
with increasing temperature in the immiscible region. A
few polymer pairs appear to behave this way (24).
3. Macleods Relation
The surface tension varies with density p according to
Macleods relation (1)
Y = YOPB W)
where y and P are constants, independent of temperature.
,B is known as the Macleods exponent, and usually has a
value of 3.0-4.5 for polymers (1). Thus the surface tension
is solely determined by the density for a given chemical
composition.
y is, to a close approximation, dependent only on the
chemical constitution, and is related to Sugdens parachor
(1) by
To = (-pr)/M, (A61
where C P, is the parachor of the repeat unit and M, its
formula weight. Equation (A6) neglects the end group
effect (1). The parachor is a group additive quantity,
independent of temperature, and its values have been
tabulated elsewhere (104,105).
Macleods relation provides a number of important
relationships for analyzing the effects of molecular weight,
glass transition, phase transition (crystallization), and
chemical constitution on surface tension, as discussed
below.
4. Molecular Weight Dependence
The surface tension varies with the number-average
molecular weight M, (1) by
Y
II4 = y114 - kl/M,
co Ml
where ycx, is the surface tension at infinite molecular weight
and kl is a constant. Equation (A7) follows directly from
Macleods relation (1). Alternatively, an empirical relation
is given (1,81) as
Y=Yoo
- k2/M,2j3
w
where k2 is a constant. Equations (A7) and (A8) fit the
experimental data equally well.
Usually, the surface tension increases with increasing
molecular weight. When the molecular weight is greater
than about 2000-3000, the surface tension reaches within
about 1 mN/m (dyne/cm) of the value at infinite molecular
weight. Therefore, the effect of molecular weight may
usually be neglected for polymers, except for oligomers.
Several exceptions have however been observed and
explained in terms of end-group effects (1,4,103).
Relationships similar to Eqs. (A7) and (Ag) may be
written for the interfacial tension (l,Sl), i.e.,
and
y = k. - k3/Mnl - kd/M,z
(A9)
y12 =kb - k;/M,2( - k;lM,$
(AlO)
where ko, k3, k4, kb, ki, and k> are constants, as discussed
elsewhere (1).
5. Effects of Glass and Crystal-Melt Transitions
Macleods relation also provides relationships for the
effects of glass and crystal-melt transitions. At the glass
transition, the surface tension is continuous, but its
temperature coefficient is discontinuous. (dy/dT) g below
the glass temperature, T,, is related to (dy/dT), above
T, (1) by
GWW, = (d~r)@~ldT), (All)
where og is the isobaric volumetric thermal expansion
coefficient in the glassy region and a, is that in the rubbery
region. Since og is usually smaller than cr,, the surface
tension varies less with temperature in the glassy region
than in the rubbery region. Since -dy/dT is usually small,
this effect is often neglected when the temperature range of
interest is small.
On the other hand, both the surface tension and its
temperature coefficient are discontinuous at the crystal-melt
transition. The surface tension of crystalline surface, yc, is
related to that of amorphous surface 7a (1) by
Yc = WPJ%a (A12)
where pc is the crystalline density, and pa the amorphous
density. Since ,B= 3.0-4.5, and usually pc > pa, the
crystalline surface can have a much higher surface
tension than the amorphous surface. For example, poly-
ethylene has ,B = 3.2, pa = 0.855 g/cc, pc = 1.0 g/cc, and
7a =35.7mN/m at 20C. Thus its crystalline surface
tension is given by
.
yc = (35.7)( l/0.855) 3.2 = 58.9 mN/m
Note that the value given above refers to a truly crystalline
surface. Most melt-crystallized semicrystalline poly-
mers, however, have amorphous surface. Only when they
are nucleated in the melt against certain nucleating
surfaces, or their single crystals are grown from solutions,
are crystalline surfaces obtained.
6 . Effect of Surface Chemical Constitution
The Macleod-Sugden equation shows that the surface
tension depends on surface chemical constitution and
density. Since the density is roughly a function of chemical
constitution (105), it is expected that a given surface
constitution will have a certain characteristic surface
tension. Some of these values are listed in Table 1. These
values should, however, be used only qualitatively.
I
7. Dispersion (Nonpolar) and Pola; Components
The surface tension can be separated into dispersion
(nonpolar) and polar components (1) i.e.,
y = yd + yp
(w
where y d is the dispersion component (arising from
dispersion-force interactions) and yp the polar component
(arising from various dipolar and specific interactions). The
polarity xp is defined as
xp = y/y
which is independent of temperature (l), i.e.,
d.xP/dT = 0
(fw
Gw
Tables VI / 523
The interfacial tension is related to the surface tension
and the polarity of the two contiguous phases by the
harmonic-mean equation (l),
or the geometric-mean equation (1,54,108,109),
712 = 71 +72 - 2(ydyd) 12
1 2 - WYM) 1/Z (A17)
where the subscripts 1 and 2 refer to the two individual
phases. The harmonic-mean equation has been shown to
predict the interfacial tension between polymers adequately,
whereas the geometric-mean equation is often less
satisfactory (1,4).
The yd and yp components can be determined either
from the inter-facial tension or the contact angles by using
Eq. (A16), the harmonic-mean equation, or less satisfacto-
rily by Eq. (A17), the geometric-mean equation, as
discussed elsewhere (1).
The polarity may also be defined in terms of the cohesive
energy density (l), i.e.,
xp = (AEP/AE) = (Sp/S)2
(A181
where AE is the cohesive energy density, AEP its polar
component, S the solubility parameter, and 6P its polar
component. The polarity values determined from interfacial
properties have been found to agree with those determined
from cohesive energy densities for a number of polymers
(1). It should be cautioned, however, that Eq. (A14) defines
the surface polarity, while Eq. (A18) defines the bulk
polarity. These two values may not be the same, if the
polymer has sufficiently long surface-active segments,
which tend to preferentially adsorb on the surfaces.
B. TABLES
Table 1 lists typical values of surface tension for some
surface chemical constitutions.
Table 2 lists the surface tension, its temperature
coefficient, polarity, and Macleods exponent for amor-
phous surfaces. The surface tension for crystalline surface
may be calculated from the amorphous value by using the
Macleods exponent. All data were obtained by direct
reversible measurements in the melt. The values for the
solid were obtained by extrapolation from the melts. These
are the most reliable and preferred. On the other hand, some
values were obtained by the contact angle method. These
are denoted with the symbol (c). The two values usually
agree well.
Table 3 lists the interfacial tension and its temperature
coefficient for amorphous interfaces. All data were obtained
by direct reversible measurements in the melt. The values
for the solid were obtained by extrapolation from the melt
and have been shown to be reliable. The interfacial tension
References page VI - 540
VI/524 SURFACE AND INTERFACIAL TENSJONS OF POLYMERS, OLICOMERS, PLASTICIZERS, AND ORGANIC PIGMENTS
may also be estimated from the surface tension and the
polarity of the two phases by using the harmonic-mean
equation (Eq. (A16)).
TABLE 1. SURFACE CHEMICAL CONSTITUTION AND SURFACE
TENSION
Surface chemical
constitution
1. 1. HYDROCARBON SURFACES
-CHs
-CH2
-CHz- and XH,
XH, (phenyl ring edge)
Surface tension at 20C
(mN/m = dynkm)
30
36
43
45
TABLE 1. contd
Surface chemical
constitution
1. 2. FLUOROCARBON SURFACES
-CFs
-CF*H
-CFs and -CFz-
-CF2-
-CH#.ZFs
-CFs-CFH-
-CF*-CH2-
-CFH-CH2-
1. 3. CHLOROCARBON SURFACES
-CHCl-CH2-
-CC12-CH2-
=CCls
Surface tension at 20C
@N/m z dynkm)
1 5
26
1 7
23
23
30
33
37
42
45
50
1. 4. SILICONE SURFACES
-0-Si(CHs) 2-O- 20
-D-Si(CHs)(CsH+D- 26
TABLE 2. SURFACE TENSION, POLARITY, AND MACLEODS EXPONENT FOR AMORPHOUS SURFACES
Polymer
Surface tension y (mN/m = dynkm) Macl eods
- dr/dT Polarity exponent
20 C 150C 200 C (mN/m/K) (xP) m
Refs.
2.1. HYDROCARBON POLYMERS
Poly(acetylene)
cis-isomer
51 Cc)
trans-isomer
52 (c)
Poly(butadiene), M, = 5400
carboxyl acid end group 48.6
methyl ester end group 43.1
Poly(butadiene-stat-acrylonitrile), carboxyl end group
18% by weight AN 51.3
M, = 5300
27% by weight AN 52.6
M, = 5900
Poly(ethylene), branched
M, =7000 * 35.3
M, =2000 33.7
Poly(ethylene), linear
.,
M,=CQ 36.8
M, =67000 35.7
Poly(ethylene-stat-acrylic acid)
mol% acrylic acid 20
59 (cl
1 4
55 Cc)
8
44 (cl
3
41 (cl
Poly(ethylene-slat-propylene)
mol% PP M,
34 37000 33.8
36 33000 33.1
44 15000 32.0
50 63000 31.0
60 58000 30.7
Poly(ethylene-stat-propylene-stat-hexadiene), EPDM,
E/PP/HD/ = 69.5/26.5/4.0 weight ratio comonomers
M, = 17000, M, =70000 34.5
-
-
29.9
28.8
40.0
40.2
26.6
25.9
29.4
28.2
-
-
-
-
25.7
25.4
24.1
23.5
23.2
26.2
-
-
22.7
23.3
35.7
35.4
23.3
22.9
26.6
25.4
-
-
-
-
22.6
22.4
21.0
20.6
20.3
23.0
-
-
0.1440
0.1098
0.0866
0.0955
0.067
0.060
0.056
0.057
-
-
-
-
0.062
0.059
0.061
0.058
0.058
0.064
0.08
0.05
0
0
0
0
0
0
0
0
0
0
3.2
3.2
3.0
3.0
3.3
3.2
2.8
5
5
70
70
70
70
l-3,7-14
1 5
9
l-3,7,11
14,15
1 9
1 9
1 9
1 9
13
13
13
13
13
20
TABLE 2. contd
Surface Tension, Polarity, and Macleods Exponent for Amorphous Surfaces VI / 525
Polymer
Surface tension y (mN/m = dynkm) Macl eods
- dyldT Polarity exponent
20 C 150C 200 C (mN/m/K) (xP) V)
Refs.
Poly(ethylene-star-vinyl acetate)
EIVA weight ratio 15125
82.3jll.l
13.4126.6
69.1130.9
61.3j38.7
Poly(isobutene)
M, =2700
Poly(isoprene)
c&isomer
cyclized
lrans isomer
Poly(4-methyl- I-pentene)
Poly(propylene)
atactic
isotactic
isotactic and atactic mixture
Poly(styrene) and copolymers, see Styrene Polymers
Poly(xylylenes), see Styrene Polymers
35.5
34.1
31.3
30.6
33.0
33.6
32 (4
34 (cl
31 (cl
25 Cc)
29.4
29.4
30.1
2.2. STYRENE POLYMERS
Poly(2-methylstyrene)
M, =3000 38.7
Poly(styrene)
M, =44000 40.7
M, =9300 39. 4
M, =1700 39.3
Poly(styrene-stat-acrylonitrile)
mol% acrylonitrile 32.7
43 (cl
27.6
42 (4
16.8
40 (cl
6.9
37 Cc)
Poly(styrene-star-2,2,3,3-tetrafluoropropyl methacrylate
mol% styrene 98
31 (cl
95
30 (cl
90
29 Cc)
80
28 (cl
70
27 Cc)
60 26 (c)
50
25 (4
40 I
25 (4
30
_.
21 (cl
20
20 (cl
1 0
19 (cl
2
19 (c)
1 18 Cc)
Poly(xylylene), see also Halogenated Hydrocarbons 46.3 (c)
2.3. HALOGENATED HYDROCARBON POLYMERS
Poly(2-chloro-1.4-xylylene), poly((3-chloro- 47.1 (c)
1,4-phenylene)ethylene)
Poly(chloroprene) 43.6
M, =30000
Poly(chlorotrifluoroethylene) 30.9
Poly(chlorotrifluoroethylene-star-tetrafluethylene)
Wt.% TFE
60 25.2 (c)
80 21.3 (c)
Poly(dichloro-1.4-xylylene), poly((dichloro- 46.3 (c)
1,4-phenylene)ethylene)
26.8
27.1
26.5
26.4
26.9
25.3
-
-
-
22.1
22.1
22.5
31.1
31.4
31.0
29.2
-
-
-
-
-
-
-
-
-
-
-
-
-
-
32.3
22.2
-
-
23.5
24.4
24.7
24.7
24.6
22.1
-
-
-
19.3
19.3
19.6
28.2
27.8
27.1
25.4
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
28.0
18.9
-
-
0.067
0.054
0.037
0.033
0.047
0.064
-
-
-
0.056
0.056
0.058
0.058
0.072
0.065
0.077
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
0.086
0.067
-
-
-
0.050
0.025
0.064
0.083
0.108
-
-
-
-
-
0
0
0.020
0.168
-
-
-
-
-
-
-
-
0.013
0.019
0.108
0.282
0.348
0.354
0.009
4.1
3.2
3.2
3.2
4.2
1 2
21-24
21-24
21-24
21-24
7,11,17,26
4,11,13,16
4,13
17,18
4,17,21
8,28-30
3 1
3 1
32
32
32
32
21
2,s
l-3,37
References page VI - 540
VI / 526 SURFACE AND INTERFACIAL TENSIONS OF POLYMERS, OLICOMERS, PLASTICIZERS, AND ORGANIC PIGMENTS
TABLE 2. contd
Polymer
Surface tension y (mN/m = dynkm) Macl eods
- dyldT Polarity exponent
20C 150C 200 C (mN/m/K) (xP) (B)
Refs.
Poly(hexachlorobutadiene)
Poly(hexafluoropropylene)
Poly(tetrafluoroethylene)
M=CC
C2,FU (M = 1088)
Poly(tetrafluoroethylene-stat-ethylene)
50/50 weight ratio TFE/E
Poly(trifluoroethylene)
Poly(viny1 chloride)
Poly(viny1 fluoride)
Poly(vinylidene chloride)
Poly(vinylidene fluoride)
41.5 (c)
17.0 (c)
12.8 (c)
23.9
21.5
27.6 (c)
27.3 (c)
41.9 (c)
38.4 (c)
45.4 (c)
33.2 (c)
2.4, VINYL POLYMERS - ESTERS
Poly(ethylene-star-vinyl acetate), see Hydrocarbon Polymers
Poly(viny1 acetate) M, = 11000-120000 36.5
Poly(viny1 butyrate) 31.1
Poly(viny1 decanoate) 28.9
Poly(viny1 dodecanoate) 29.1
Poly(viny1 hexadecanoate) 30.9
Poly(viny1 hexanoate) 29.4
Poly(viny1 propionate) 34.0
Poly(viny1 octanoate) 28.7
2.5. VINYL POLYMERS - OTHERS
Poly(acrylamide) 52.3 (c)
Poly(acrylonitrile)
50 (cl
Poly(heptafluoroisopropoxy)ethylene)
15 Cc)
Poly(l-(heptafluoroisopropoxy)methyl)
19 (cl
propylene-stat-maleic acid)
Poly( 1 -heptafluoroisopropoxy)propylene)
21 (cl
Poly(methacrylonitrile)
39 (c)
Poly(styrene-stat-acrylonitrile), see Styrene Polymers
Poly(viny1 alcohol)
37 (cl
Poly(vinyl butyral)
38 (cl
Poly(viny1 ethyl ether), poly(ethoxyethylene)
36 (cl
Poly(viny1 methyl ether), poly(methoxyethylene)
M, =46500, M, =99000
I
Poly(viny1 formal)
. .
31.8
39 (cl
2.6. ACRYLIC POLYMERS - NONFLUORINATED
Poly(acrylamide) see Vinyl Polymers (nonesters)
Poly(acrylonitrile), see Vinyl Polymers (nonesters)
Poly(n-butyl acrylate)
M, =32000
Poly(ethy1 acrylate)
M, =28000
Poly(ethylene-stat-acrylic acid), see Hydrocarbon
Polymers
Poly(2-ethylhexyl acrylate)
M = 34000
Poly(methy1 acrylate)
M, = 25000
33.7
30.7
37.0
33.7
30.2
29.2
41 .o
42.7
-
-
-
16.3
13.1
27.9
22.0
20.9
20.9
22.5
21.2
24.7
20.7
-
-
-
-
-
-
-
-
-
22.1
-
24.6
22.8
27.0
26.4
21.1
21.1
31:o
31.0
13.4
9.8
24.6
18.5
17.8
17.8
19.0
18.1
21.1
17.7
-
-
-
-
-
-
-
-
-
18.3
-
21.1
19.7
23.2
23.6
17.6
18.0
27.2
26.5
0.058
0.065
0.066
0.070
0.062
0.063
0.066
0.063
0.072
0.061
-
-
-
-
-
-
-
-
-
0.075
-
0.070
0.061
0.070
0.056
0.070
0.062
0.070
0.090
0.019
0.120
0.065
0.089
-
0.286
0.118
0.146
0.292
0.196
0.376
0.329
0.172
0.061
0.044
0.035
0.128
0.221
0.078
-
-
-
-
-
0.098
0.127
0.174
0.205
0.028
0.076
0.248
0.210
3.4
3.5
3.3
3.2
3.2
3.4
3.6
3.3
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
9
9,38,39
l-3
l-3
l-3
l-3
l-3
l-3
7.12
4,40
4,40
4,40
4,40
4,40
4,40
4,40
4 1
1
42
43
42
1
44
1
45
70
35
1
46,107
1
46,107
1
46,107
1
46,107
TABLE 2. cont'd
Surface Tension, Polarity, and Macleods Exponent for Amorphous Surfaces VI / 527
Polymer
Surface tension y (mN/m = dynkm) Macl eods
- dyldT Polarity exponent
20 C 150C 200C (mN/m/K)
(xP) m
Refs.
2.7. ACRYLIC POLYMERS - FLUORINATED
Poly((l-chlorodifluoromethyl)tetrafluoroethyl
19 (cl
acrylate)
Poly(di(chlorodifluoromethy1) fluoromethyl acrylate) 20 (c)
Poly(l,l-dihydroheptafluorobutyl acrylate)
15 (cl
Poly( 1 , 1-dihydropentafluoroisopropyl acrylate)
1.5 (cl
Poly( 1, I-dihydropentadecafluorooctyl acrylate)
10 Cc)
Poly(heptafluoroisopropy1 acrylate)
14 (cl
Poly(S-(heptafluoroisopropoxy)pentyl acrylate)
18 Cc)
Poly( 1 1-(heptafluoroisopropoxy)undecyl acrylate)
20 Cc)
Poly(2-heptafluoropropoxy)ethyl acrylate)
16 (cl
Poly(nonafluoroisobuty1 acrylate)
14 (cl
2.8. METHACRYLIC POLYMERS - NONFLUORINATED
Poly(benzy1 methacrylate)
36 (cl
Poly(n-butyl methacrylate)
M,=37000 31.2
Poly(isobuty1 met hacryl at e)
M,=35000 30.9
Poly(t-butyl methacrylate)
M,=6000 30.4
Poly(t-butylaminoethyl methacrylate)
34 (cl
Poly(dodecy1 met hacryl at e), poly(laury1 32.8 (c)
methacrylate)
Poly(ethy1 methacrylate)
M,=5200 35.9
Poly(2-ethylhexyl methacrylate)
M,=64000 28.8
Poly(n-hexyl methacrylate)
M,=52000 30.0
Poly(dimethylaminoethy1 met hacryl at e)
36 (cl
Poly(hydroxyethy1 methacrylate), see also
37 (cl
Methacrylic Hydrogels
Poly(laury1 methacrylate), see Poly(dodecy1 methacrylate)
Poly(methy1 methacrylate), see also Methacrylic Hydrogels
M=3000 41.1
Poly(pheny1 met hacryl at e)
35 (cl
Poly(n-propyl methacrylate)
M=8500 33.3
Poly(steary1 met hacryl at e), poly(octadecy1 36.3 (c)
methacrylate)
I
2.9. METHACRYLIC POLYMERS - FLUORINATED
Poly( 1 , 1-dihydropentadecafluorooctyl methacrylate) 10.5 (c)
Poly(heptafluoroisopropy1 met hacryl at e)
15 Cc)
Poly(heptadecafluoroocty1 methacrylate) 15.3 (c)
Poly(l-hydrotetrafluoroethyl methacrylate)
15 (cl
Poly( 1 , 1-dihydrotetrafluoropropyl methacrylate)
19 (cl
Poly( 1-hydrohexafluoroisopropyl methacrylate)
15 Cc)
Poly(r-nonafluorobutyl methacrylate)
15 (cl
-
-
23.5
23.1
22.7
-
-
26.8
20.8
,22.0
-
-
31.2
-
24.7
-
-
-
20.6
20.1
19.8
-
-
23.3
17.7
18.9
-
-
27.4
-
21.5
-
-
-
0.059
0.060
0.059
-
-
0.070
0.062
0.062
-
-
0.076
-
0.065
-
-
-
-
-
-.
-
-
-
-
-
-
-
-
-
-
0.158
0.139
0.120
-
-
-
-
-
-
0.281
-
-
-
0.048
-
0.094
-
-
-
-
47
47
47
47
47
47
47
47
47
49
4.2 8
2
2
1,35
1,35
1,35
1,35
1,35
1,35
5
-
-1,
4.2
-
8
49
1,35
47
50,53,54
47
51,52
47
33
47,55
48
-
-
Poly(styrene-star-2,2,3,3-tetrafluoropropyl methacrylate), see Styrene Polymers
2.10. METHACRYLIC HYDROGELS
Poly(hydroxyethy1 met hacryl at e)
dry
40 wt.% water
Poly(hydroxyethy1 methacrylate-srat-dimethyl-
aminoethyl methacrylate)
weight ratio wt.% water
99.910.1 40
9713 59
37 (c) -
69.0 (c) -
68.2 (c) -
65.3 (c) -
-
1,35
-
56
- - -
0.701
0.657
-
56
-
56
References page VI - 540
VI / 528 SURFACE AND INTERFACIAL TENSIONS OF POLYMERS, OLIGOMERS, PLASTICIZERS, AND ORGANIC PIGMENTS
TABLE 2. contd
Polymer
Surface tension y (mN/m = dynkm) Macl eods
- dyldT Polarity exponent
20 C 150C 200 C (mN/m/K) (xP) (B)
Refs.
Poly(hydroxyethy1 methacrylate-stat-methoxyethyl
methacrylate)
weight ratio wt.% water
15125 3 3 69.1 (c) -
50150 2 3 67.8 (c) -
25/70 1 9 68.0 (c) -
Poly(hydroxyethy1 methacrylate-stat-methacrylic acid)
weight ratio wt.% water
99.1/0.1 40 68.7 (c) -
9713 39 67.6 (c) -
Poly(hydroxyethy1 methacrylate-stat-methyl
methaqlate)
weight ratio wt . % wat er
95/5 43 68.6 (c) -
75125 43 67.0 (c) -
50150 2 1 65.7 (c) -
25175 7 65.6 (c) -
5195 3 54.4 (c) -
Poly(methy1 methacrylate), see also Methacrylic Polymers for Dry Surfaces
3 wt.% water 60.9 (c) -
Poly(methyoxyethy1 methacrylate)
2 wt.% water 71.1 (c) -
- -
0.670
- -
0.608
- -
0.496
- -
0.700
- -
0.704
-
0.697
- -
0.640
- -
0.543
- -
0.410
- -
0.393
- -
0.282
- -
0.301
-
56
-
56
-
56
-
56
-
56
-
56
-
56
-
56
-
56
-
56
-
56
-
56
2.11. POLY(ETHERS) (see also POLY(ETHER) COPOLYMERS, POLY(SULFONE), POLY(CARBONATE), PHENOXY RESIN, EPOXY RESIN,
VINYL POLYMERS)
Poly(chlora1)
Poly(epichlorohydrin)
M= 1500
Poly(oxybutene)-diol
Poly(oxyisobutene)-diol
M=300Oi l
Poly(oxydecamethylene)
Poly(oxyethylene)-diol
M= -17000
Poly(oxyethylene)-diol
M=6000
M=6000
Poly(oxyethylene)-dimethylether
M= 114
M= 148
M= 182
M=600
M=5000
M= 1OOOOO
Poly(oxyhexamethylene)-diol
Poly(oxymethylene)
Poly(oxypropylene)-diol
M=2025
M=?
M=3000
M=400-4100
Poly(oxypropylene)-dimethylether
M=3000
Poly(oxytetramethylene)
M=43000
M=2500
.
37.9 (c) -
-
43.2 (25C) -
-
38.2
21.5
36.1
42.9
42.9
42.5
28.6
31.1
32.9
37.5
44.1
44.2
31.4
44.6 (c)
31.5
31.7
31.2
31.1
30.7
31.9
38.2
28.0 24.0
19.0 15.7
27.2 23.8
30.1 25.2
33.0 29.2
30.1 25.4
16.0 11.1
18.6 13.8
20.5 15.8
26.1 21.7
32.7 28.3
32.8 28.4
27.5 23.7
- -
21.1 17.1
20.6 16.4
20.9 17.0
21.6 17.9
18.3 13.6
24.0 20.9
21.9 24.0
-
-
0.079
0.066
0.068
0.098
0.076
0.095
0.097
0.096
0.095
0.088
0.088
0.088
0.076
-
0.080
0.085
0.079
0.073
0.095
0.061
0.079
0.037
-
0.003 3.7
3.8
2.8
0.284 3.0
0.284 3.0
0.165 2.9
4.4
4.4
4.0
3.5
3.5
3.5
3.2
0.316 -
3.4
0.014 3.4
3.4
3.4
-
3.6
0142
-
3.7
34
57
5 8
6 1
58
959-61
9,11,12,
9,62
9,59-61
9,59-61
9,59-61
9,59-61
9,59-61
956-61
5 8
1,35
13
6 2
13,57,60,61
57,60,61
57,60,61
2,12
13
TABLE 2. contd
Surface Tension, Polarity, and Macleods Exponent for Amorphous Surfaces VI f 529
Polymer
Surface tension y (mN/m = dynkm) Macleods
- dyldT Polarity exponent
20 C 150C 200 C (mN/m/K) (xP) (P)
Refs.
2.12. POLY(ETHER) COPOLYMERS
Poly(oxyethylene)-bZock-poly(oxypropylene)-bZ~c~-poly(oxyethylene)
wt.% OP DP of blocks
OE OP OE
19.0 46 16 46
48.9 11 16 11
56.9 8 1 6 8
84.1 2 1 6 2
19.0 15 30 75
55.1 13 30 13
59.6 10 30 10
85.5 3 30 3
18.9 110 39 110
20.2 122 47 122
20.2 139 56 139
38.3 56 56 56
51.7 28 56 28
66.7 19 56 19
86.7 6 56 6
36.8
34.2
33.7
32.9
34.7
33.4
32.7
31.8
33.8
33.2
.32.3
32.4
32.1
31.9
31.7
27.8
25.0
24.3
22.8
26.6
24.7
23.7
22.1
26.3
26.0
25.5
25.0
24.4
23.8
23.2
24.3
21.5
20.7
18.9
23.5
21.3
20.2
18.4
23.4
23.2
22.9
22.1
21.4
20.7
20.0.0
0.069 0.129
0.071 0.105
0.072 0.094
0.078 0.047
0.062 0.096
0.067 -
0.069 -
0.074 -
0.058 0.095
0.056 0.074
0.052 0.069
0.057 -
0.059 -
0.062 -
0.065 -
2.8 57,60,62
3.0 57,60,62
3.1 57,60,62
3.4 57,60,62
2.5 57,60,62
2.7 57,60,62
2.8 57,60,62
3.3 57,60,62
2.6 57,60,62
2.4 57,60,62
2.5 57,60,62
2.6 57,60,62
2.7 57,60,62
2.8 57,60,62
2.9 57,60,62
Poly(oxyethylene-stat-oxypropylene)
mol% oxypropylene
1 7
30
4 1
56
16
8 5
40.5 28.1
39.3 26.9
31.5 25.5
34.9 23.2
33.4 72.3
32.4 21.3
23.4
22.2
20.9
18.7
18.0
17.0
0.095 0.139
0.095 0.127
0.092 0.112
0.090 0.061
0.086 0.040
0.086 0.03 1
3.6 57,62
3.6 57,62
3.6 51,62
3.6 57,62
3.3 57,62
3.4 57,62
Poly(oxyethylene-s~ut-oxypropylene)-bZ~c~-poly(oxydimethylsilylene)-b~oc~-poly(oxyethylene-~~u~-oxypropylene)]; i.e., Poly(oxyethylene-stut-oxypro-
pylene) has a comonomer weight ratio of 50/50, M, = 2200
wt.% of polysiloxane DP of polysiloxane
0 0
4.6 4.9
7.5 1.9
9.9 10.4
19.8 20.8
32.6 34.3
Poly(oxytetramethylene-stat-oxypropylene)
34.8 (25C) - - - - - 63
28.0 (25C) - - - - - 63
25.4 (25C) - - - - 63
21.4 (25C) - - - - - 63
20.6 (25C) - - - - - 63
I 20.5 (25C) - - - - - 63
. .
mol%
oxypropylene
MW
25 2100
35 1200
46 1900
52 2250
61 2200
8 5 1700
36.4 26.0 22.0 0.080 -
36.0 25.7 21.8 0.079 -
34.9 24.3 20.2 0.082 -
34.3 23.8 19.7 0.081 -
33.1 22.8 18.9 0.079 -
31.9 21.6 17.7 0.079 -
3.3
3.2
3.5
3.5
3.4
3.5
2.13. POLY(ESTERS)
Poly(oxydecamethyleneoxyisophthaloyl),
poly(decamethylene isophthalate)
Poly(oxydodecamethyleneoxyisophthaloyl),
poly(dodecamethylene isophthalate)
42.1 33.3 29.7 0.072 0.192 3.0 98
40.0 30.9 27.4 0.070 0.149 3.0 98
References page VI - 540
VI / 530 SURFACE AND INTERFACIAL TENSIONS OF POLYMERS, OLICOMERS, PLASTICIZERS, AND ORGANIC PIGMENTS
TABLE 2. contd
Polymer
Surface tension y (mN/m = dynkm) Macleods
- dyldT Polarity exponent
20 C 150C 200 C (mN/m/K) (xP) m
Refs.
Poly(oxyethyleneoxyterephthaloyl),
poly(ethylene terephthalate)
M, = 16000 M, = 37000
Poly(oxyhexamethyleneoxyisophthaloyl), pol y
hexamethylene isophthalate)
Poly(oxytetramethyleneoxyisophthaloyl),
poly(butylene isophthalate)
Poly(oxytrimethyleneoxyisophthaloyl),
poly(propylene isophthalate)
2. 14. POLY(CARBONATES)
Poly(oxycarbonyloxy-1, 4-phenyleneisopropylidene-
1,4-phenylene), polycarbonate of bisphenol-A
2.15. POLY(SULFONES)
Poly(oxy- 1,4-phenylenesulfonyl- 1 ,Cphenyleneoxy-
1,4-phenyleneisoproypylidene-1,4-phenylene),
polysulfone
2.16. PHENOXY RESINS
Poly(oxy- 1,4-phenyleneisopropylidene-
1,4-phenyleneoxy-2-hydroxytrimethylene),
phenoxy resin M = 30000
2.17. EPOXY RESINS
Diglycidyl ether of bisphenol-A, 2,3-di(glycidoxy-
1,4-phenylene) propane pure, M = 340
Diglycidyl ether of bisphenol-A, 2,3-(diglycidoxy-
1,4-phenylene)propane chain extended
with bisphenol-A
Diglycidyl ether of bisphenol-A with 6 wt.% of
N-N-diethylaminopropylamine
fresh, mixture, not cured
cured
Diglycidyl ether of bisphenol-A with stoichiometric
amount of triethylenetetramine cured
Diglycidyl ether of bisphenol-A with 0.5 wt.% of
N-methylaminopropyltrimethoxysilane fresh,r
mixture, not cured
Diglycidyl ether of bisphenol-A with 0.5 wt.% of
y-glycidoxypropyltrimethoxysilane
fresh, mixture, not cured
Curing agent: y-aminopropyltrimethoxysilane
M= 179
Curing agent: N,N-dibutylaminopropylamine
M= 186
Curing agent: NJ-diethylaminopropylamine
M= 130
Curing agent: N,N-dimethylaminopropylamine
M= 102
Curing agent: N-methylaminopropyltrimethoxysilane
M= 193
Curing agent: y-glycidoxypropyltrimethoxysilane
M=236
2. 18. POLY(AMIDES)
Poly(glycine), (nylon 2), see Poly(peptides)
Poly(imino( I-oxodecamethylene))(nylon 11)
44.6
45.6
47.8
49.3
42.9
45 (cl
46.6 (c)
43.0
47.2
45.6
51.2(23 C)
33.7
46.8 (c)
39.1 (c)
39.1
32.9
25.5
25.3
24.6
23.9
27.0
23.9
36.2 32.9 0.065 0.221
27.7 (280C) 24.8 (325C)
35.6 31.7 0.077 0.242
37.4 33.4 0.080 0.270
38.5 34.3 0.083 0.288
- 1,14,20&I
3.3 98
3.2 98
3.0 98
35.1 32.1 0.060
- -
0.246 -
- -
-
- -
- - - -
-
0.166
- - -
- -
- - -
- -
- -
- -
- -
- - - -
0.347
-
- -
-
0.432
- -
22.6 (225C) - -
-
3 5
65
-
35
- 67
- 3568
- 8 5
- 67,68
- 3 5
- 3 5
- 68
- 68
- 68
- 6 8
- 6 8
- 6 8
- 6 8
- 68
-
72
TABLE 2. contd
Surface Tension, Polarity, and Macleods Exponent for Amorphous Surfaces
Polymer
Surface tension y (mN/m = dynkm) Macleods
- dyldT Polarity exponent
20 C 150C 200 C (mN/m/K)
(xP) (8)
Refs.
Poly(imino( I-oxododecamethylene) (nylon 12) 35.8 (c) -
- -
Poly(imino( 1-oxohexamethylene)) (nylon 6) 38.4 (c) -
- -
- -
36.1 (265Cj
Poly(imino(l-oxotetramethylene)) (nylon 4) 48.5 (c) -
- -
Poly(imino-l,4-phenyleneiminoterephthaloyl), poly(l,4-phenylene terephthalamide)
fiber (unsized) 48.5 (c) -
- -
cast sheet (H-bonding parallel to surface) 33.7 (c) -
- -
cast sheet (H-bonding vertical to surface) 31.3 (c) -
- -
Poly(iminoadipoylirninohexamethylene) (nylon 66) 46.5 38.1 34.8 0.065
M, = 17000, M, = 35000 29.6 (280C) 26.7 (325C)
Poly(iminoazelaoyliminononamethylene) (nylon 99) 36(c) -
- -
Poly(iminopimeloy1iminoheptamethy1ene) (nylon 77) 43 (c) - - -
Poly(iminosebacoyliminodecamethylene) (nylon 1010) 32 (c)
-
Poly(iminosebacoyliminohexamethylene) (nylon 610) -
-
37.0 (265C;
Poly(iminosuberoyliminooctamethylene) (nylon 88) 34 (c) -
- -
2.19. POLY(IMIDES)
Poly(iminocarbonyl-(4,6-dicarboxy-l,3-phenylene)-
carbonylimino- 1,4-phenyleneoxy- 1,4-phenylene),
KAPTON H f i l m
HOOC
0.154
0.188
-
0.427
0.216
0.206
0.202
0.344
-
-
73
-
3 5
-
72
-
52.73
- 74
- 75
- 75
- 1,14,20,
- 7 1
- 7 1
- 7 1
- 72
- 71
0.358 -
P0ly[(l,3,5,7-tetraoxo-2,3,6,7-tetrahydro-lH,SH-benzo[l,2-~:4,5-c] dipyrrol-2,6-diyl-l,Cphenyleneoxy-l,4-phenylene), cured KAPTGN H film
35,76
-:)Q$oo*
0 0
2.20. POLY(IMINES)
Poly((benzoylimino)ethylene)
Poly((butyrylimino)ethylene)
Poly((dodecanoylimino)ethylene)
Poly((dodecanoylimino)ethylene-stat-(acetylimino)
trimethylene)
Poly((heptanoylimino)ethylene)
Poly((hexanoylimino)ethylene)
Poly(((3-methyl)butyrylimino)ethylene)
Poly((pentadecafluorooctadecanoylimino)ethykne)
Poly((pentanoylimino)ethylene)
2.21. POLY(URETHANES)
Poly(methylenediphenyldiisocyanate-alt-(butanediol
poly(oxytetramethylene)diol) (ESTANE 5714)
Poly(hexamethylene diisocyanate-alt-triethylene
glYcou
Poly(4-methyl- 1,3-phenylene diisocyanate-alt-
tripropylene glycol)
37.7 (c)
26 (cl
25 (4
22 (cl
22 (cl
22 (cl
23 (4
24 (4
11 (cl
23 (cl
39 (cl
38.6 (c)
36.3 (c)
2. 22. POLY(SILOXANES) (see al so ORGANOSI LANES)
Poly(oxydiethylsilylene)
158 CS
Poly(oxydimethylsilylene)
M=75000
25.7
20.39
21.17
21.01
- - -
0.223 - 35,76
-
-
-
-
-
-
-
-
-
-
-
-
77
77
78
78
77
77
77
77
77
79
73
73
16.2 12.5 0.073
- -
80
14.15 11.75 0.048 0.042 3.5 2.9
-
- - - -
26
13.47 10.57 0.058 - - 83
References page VI - 540
VI / 532 SURFACE AND INTERFACIAL TENSIONS OF POLYMERS, OLIGOMERS, PLASTICIZERS, AND ORGANIC PIGMENTS
TABLE 2. contd
Polymer
Surface tension y (mN/m = dynkm) Macl eods
- dyldT Polarity exponent
20 C 150C 200 C (mN/m/K) (xP) (in
Refs.
M=3900 20.17 13.93
20.59 -
20.47 12.93
60000 cS 19.8 13.5
0.048
-
0.058
0.048
- -
0.042 3.5
23
26
83
2,11,14,
80,82
SO- 82
80-82
80-82
80-82
70
70
80
-
3.5
-
3.7
-
3.7
-
4.0
M= 1274 19.9 -
M=607 18.8 -
M=310 17.6 -
M= 162 15.7 -
Poly(oxydimethylsilylene), a,w-difunctional
[R-(Si(CH3)2-O-)n-Si(CH3)2-R]
R=(CH2)3NH2
M, =2086 20.88 14.12
M, =7916 19.86 12.97
Poly(oxydimethylsilylene), a,w-difunctional
R-(Si(CH3) 2-0-),,-Si(CH3)2-R
R=(CH2)sNH2; M,=1132 21.00 14.37
R=(CH2)3COOH; M,=2194 20.54 13.52
Poly(oxydimethylsilylene) block copolymers, see Poly(&ter) Copolymers
Poly(oxymethylphenylsilylene)
102 cs 26.1 11.8
-
- -
11.52
10.32
0.052
0.053
11.82
10.82
0.051
0.054
6.3 0.11
- -
2.23. ORGANOSILANES - HYDROLYZED AND CONDENSED FILMS (see al so POLYSI LOXANES and EPOXY RESI NS)
2. 23. 1. ALKYL AND ALKYLENE SI LANES
Ethyltriethoxysilane, CH 3CH2Si(OC 2H5) 3
on silica (no catalyst)
on silica (acetic acid catalyst)
on silica (propionic acid catalyst)
on silica (piperidine catalyst)
y-Methacryloxypropyltrimethoxysilane,
CHz=C(CH3)-C(=O)O(CH2)3Si(OCH3)3
on soda-lime glass
Methyltrimethoxysilane, CH$i(OCH3)3
on soda-lime glass
Phenyltrimethoxysilane, CeHsSi(OCH3)3
on soda-lime glass
Vinyltriethoxysilane, CH 2 = CHSi(OC ZH 5) 3
on silica
Vinytrimethoxysilane, CH2 = CHSi(OCH 3)3
on soda-lime glass
I
2.23.2. AMINO SILANES
IV-P-(aminoethyl)-y-aminopropyltrimethoxysilane,
NHz(CH2)zNH(CH2)3Si(OCH3)3
on soda-lime glass
y-Aminopropyltriethoxysilane,
NH2CH$ZH2CH2Si(OC2H5)3
on soda-lime glass
2.23.3. EPOXY SILANE
Glycidoxypropyltrimethoxysilane,
H$,-,CHCH2O(CH&Si(OCH3) 3
on soOda-lime glass (no catalyst)
on soda-lime glass (acetic acid catalyst, pH = 4)
2.23.4. HALOGENATED ALKYL SILANES
36.7 (c)
34.5 (c)
27.8 (c)
33.4 (c)
44.8 (c)
28.0 (c)
43.0 (c)
33.4 (c)
28.6 (c)
33.7 (c)
35.7 (c)
49.4 (c)
66.9 (c)
- -
-
-
-
-
-
-
-
-
-
- -
- - -
- - -
- - -
- - -
- - -
- - -
- -
-
- -
p-Bromophenyltrimethoxysilane, BrC gH sSi(OCH 3) 3
on soda-lime glass 49.3 (c)
p-Chlorophenylethyltrimethoxysilane,
ClCgH4CH2CH#i(OCHj)3
on Pyrex glass 51.0 (c)
TABLE 2. contd
Surface Tension, Polarity, and Macleods Exponent for Amorphous Surfaces
Polymer
Surface tension y (mN/m = dynkm) Macl eods
- dyldT Polarity exponent
20 C 150C 200C (mN/m/K) (xP) m
Refs.
on silica 49. 9 ( c)
on stainless steel 53. 3 ( c)
on u-alumina 49. 9 ( c)
y-Chloropropyltrimethoxysilane, Cl(CH2)$i(OCH3)3
on soda-lime glass 40. 1 ( c)
on Pyrex glass 48. 8 ( c)
on stainless steel 49. 9 ( c)
3- ( 1,l -Dihydroperfluorooctoxy)propyltriethoxysilane,
CF3(CF2)6CHzO(CH2)3Si(OC2H5)3
on gold 21.5 (c)
on Pyrex glass 18. 8 ( c)
on stainless steel 18.8 (c)
y-Perfluoroisopropoxypropyltrimethoxysilane,
(CF3)2CFO(CH2)3Si(OCH3)3
on Pyrex glass 24. 2 ( c)
on silica 22. 8 ( c)
on stainless steel 18.8 (c)
2. 23. 5. MERCAPTO SILANE
y-Mercaptopropyltrimethoxysilane, HS(CH2)3Si(OCH3)3
on soda-lime glass
2.24. CELLULOSICS
Amylose
Amylopectin
Cellophane
Cellulose
regenerated from cotton
regenerated from wood pulp
Cellulose acetate
Cellulose acetate butyrate
Ethyl cellulose
Hemicellulose
arabinogalactan
galactoglucomannan
hardwood xylan
softwood xylan
Nitrocellulose
Starch
2. 25. POLY(PEPTIDES)
Casein
Poly(L-alanine)
Poly(y-benyzl L-glutamate)
Poly(glycine), (nylon2)
Poly(y-methyl L-glutamate)
a-helix random tangle
cc-sheet
cc-helix on water
P-extended chain
P-sheet
P-random chain
Mixed tl and p sheet
Wool
2.26. MISCELLANEOUS
2. 26. 1. HYDROCARBONS
Eicosane, C20Hu
M=282
Hexatriacontane, C 36H 74
M=SOl
41.9 (c)
37 ( cl
35 ( cl
45. 4 ( c)
42 ( 4
36- 42 ( c)
45. 9 ( c)
34 ( c)
32 ( 4
33 Cc)
37 ( c)
33- 37 ( c)
35 ( cl
38 Cc)
39 ( cl
43 ( cl
45. 2 ( c)
39. 2 ( c)
50.1 (c)
44. 0 ( c)
48. 0 ( c)
44. 4 ( c)
35. 5 ( c)
31. 8 ( c)
45. 4 ( c)
42.1 (c)
45 Cc)
28. 9
31.4
24 ( 4
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
25. 6 ( 60C)
26.1 (100C)
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
0. 0833
0. 066
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
0. 344
-
-
0. 296
-
-
-
0. 203
0. 224
0. 443
0. 375
0.192
0. 435
0.191
0.119
0.440
0. 359
-
0
0
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
1,35
1,35
1,35
1,35
1,35
1,35
1,35
1,35
1,35
1,35
1,35
I , 35
84
84
51,52
86
86
51,52,87,88
1
1
86
86
86
86
1
89
90
52,91
52, 92
52, 92
52, 92
41
52, 92
52, 92
41
52, 92
52, 92
90
1,9,62,102
1,9,94,102
94
References page VI - 540
VI / 534 SURFACE AND INTERFACIAL TENSIONS OF POLYMERS, OLIGOMERS, PLASTICIZERS, AND ORGANIC PIGMENTS
TABLE 2. contd
Polymer
Surface tension y (mN/m = dynkm) Macleods
- dyldT Polarity exponent
20 C 150C 200 C (mN/m/K) (xP) w
Refs.
Paraffin wax (mp 65C) 34.7 32.0 (65C) 26.9 (1500$.06
31.0 (c) - - -
25.5 (c) - - -
2.26.2. ALKANE-DIOLS
1,4-Butanediol, M = 90 44.2 37.6 (90C) - 0.094
1 , lo-Decanediol, M =174 39.3 34.2 (90C) - 0.073
1,6-Hexanediol, M = 118 42.2 36.5 (90C) - 0.081
1,5-Pentanediol, M= 104 41.6 36.7 (90C) - 0.070
1,3Propanediol, M = 76 45.9 38.9 (9OC) - 0.100
2.26.3. ADHESIVES
Natural rubber + ester rosin pressure sensitive adhesive 36 (c) -
- -
Poly(isobutene)-based pressure sensitive adhesive 30 (c) - - -
Phenol-resorcinol adhesive 52 (4 - -
Resorcinol adhesive 51 (cl - -
Urea-formaldehyde adhesive 61 (cl - -
2.26.4. SULFUR
Monomeric sulfur, below the floor temperature of 160C
y=72.95-O.l019T, for T= 120-160C
Polymeric sulfur, above the floor temperature of 160C
y = 65.31-0.05532 for T= 160-440 C
Solid sulfur
2. 26. 5. PLASTICIZERS
Di(n-butyl)-o-phthalate
M=278
Di(n-dodecyl)-o-phthalate
M=502
Di(ethyl)-o-phthalate
M=222
Di(n-heptyl)-o-phthalate
M=362
Di(methyl)-o-phthalate
M= 194
Di(n-nonyl)-o-phthalate
M=418
Di(n-propyl)-o-phthalate
M=250
Tricresyl phosphate
2. 26. 6 ORGANIC PIGMENTS
Phthalocyanine (metal-free) (pure untreated surface)
/ \
R
I
-
NC, ,C=v
Copper phthalocyanine (pure untreated surface)
128 (c)
33.1
30.8
36.6
30.0
39.5
28.9
34.4
40.9
- - -
23.1 19.2 0.077
22.6 19.5 0.063
24.6 20.0 0.092
20.6 17.0 0.072
26.9 22.0 0.097
19.9 16.5 0.069
23.3 19.1 0.085
- -
0
-
-
0.330
0.137
0.238
0.281
0.375
-
3.6
2.9
3.3
2.8
3.6
-
-
-
-
-
-
0.05 1
0.029
0.115
0.047
0.028
0.067
0.027
3.4
2.9
3.8
3.5
3.7
3.4
3.3
-
1,94,95
1
108
58
58
58
58
58
97
96
52.8 (c) -
- -
0.240 -
46.9 (c) -
- -
0.147
-
TABLE 2. contd
Interfacial Tension for Amorphous Interfaces
Polymer
Surface tension y (mN/m = dynkm) Macleods
- dy/dT Polarity exponent
20 C 150C 200 C (mN/m/K) (xP) (8)
Refs.
Chlorinated copper phthalocyanine
(pure untreated surface)
Idanthrone (pure untreated surface)
42.0 (c) -
- -
0.148
-
1,99
Isoindolinone (pure untreated surface)
Manganese 8-oxynaphthoic acid derivative
(pure untreated surface)
Mn++
y-Quinacridone (pure untreated surface)
n
Thioindigoid red (pure untreated surface)
? 7
63.2 (c) -
47.2 (c) -
51.9 (c) -
49.1 (c) -
51.4 (c) -
- -
- -
0.318
-
0.464
-
0.273 -
0.317 -
1,99
1,99
1,99
1.99
1,99
Toluidine red (pure untreated surface)
H3C
53.0 (c) - 0. 25 1
- - - 1,99
TABLE 3. INTERFACIAL TENSION FOR AMORPHOUS INTERFACES
Interfacial tension ylz (mN/m = dynkm)
Polymer 20 C 150C 200 C
3.1. HYDROCARBON POLYMERS vs. OTHERS
3.1.1. POLY(BUTADIENE) vs. OTHERS
- dy IzldT
(mN/m/k) Refs.
Poly(butadiene) vs. poly(oxydimethylsilylene)
PBD M, = 960, PDMS M, = 3900
2.48 2.07 1.91 0.00322 1 0 3
References page VI - 540
VI / 536 SURFACE AND INTERFACIAL TENSIONS OF POLYMERS, OLIGOMERS, PLASTICIZERS, AND ORGANIC PIGMENTS
TABLE 3. contd
Polymer
Interfacial tension ylz (mN/m = dynkm)
20 C 150C 200 C
- dy t2idT
(mN/mk) Refs.
Poly(butadiene) vs. poly(oxydimethylsilylene) 3.86
PBD M, = 2350, PDMS M, = 3900
Poly(butadiene) vs. poly(oxydimethylsilylene) 3.98
PBD M, = 2350 PDMS M, = 5200
Poly(butadiene) vs. poly(oxydiethylsilylene)
PBD M, = 960, PDMS M, = 5200
2.58
Poly(butadiene) vs. epoxy resin (diglycidyl ether of bisphenol-A,
chain extended with bisphenol-A)
1.77 (23 C)
3.1.2. POLY(BUTADIENE-stat-ACRYLONITRILE) vs. OTHERS
Poly(butadiene-stat-acrylonitrile) 1.23
18 wt.% AN vs. epoxy resin (same as above)
Poly(butadiene-stat-acrylonitrile) -
26 wt.% AN vs. epoxy resin (same as above)
3.1.3. POLY(ETHYLENE) vs. OTHERS
Poly(ethylene) (branched) vs. poly(propylene) (atactic)
Poly(ethylene) (linear) vs. poly(styrene)
-
8.3
-
Poly(ethylene) (branched) vs. poly(styrene)
Poly(ethylene) (branched) vs. poly(chloroprene)
Poly(ethylene) (linear) vs. poly(methy1 acrylate)
Poly(ethylene) (branched) vs. poly(methy1 acrylate)
Poly(ethylene) (linear) vs. poly(ethy1 acrylate)
Poly(ethylene) (branched) vs. poly(ethy1 acrylate)
Poly(ethylene) (linear) vs. poly(n-butyl acrylate)
Poly(ethylene) (branched) vs. poly(n-butyl acrylate)
Poly(ethylene) (linear) vs. poly(2-ethylhexyl acrylate)
Poly(ethylene) (branched) vs. poly(2-ethylhexyl acrylate)
Poly(ethylene) (linear) vs. poly(methy1 methacrylate)
Poly(ethylene) (linear) vs. poly(n-butyl methacrylate)
Poly(ethylene) (branched) vs. poly(iso-butyl methacrylate)
Poly(ethylene) (branched) vs. poly(terr-butyl methacrylate)
Poly(ethylene) (linear) vs. poly(poly(viny1 acetate)
Poly(ethylene) (branched) vs. poly(viny1 acetate)
Poly(ethylene) (branched) vs. poly(ethylene-stat-vinyl acetate),
25 wt . % VAc
5.6
4.6
10.6
-
7.5
-
5.0
5.5
3.1
3.5
11.8
7.1
5.5
5.9
14.6
-
2.0
Poly(ethylene) vs. poly(ethylene-stat-vinyl acetate), 12 wt.% VAc -
Poly(ethylene) vs. poly(ethylene-stat-vinyl acetate), 17.7 wt.% VAc -
Poly(ethylene) vs. poly(ethylene-stat-vinyl acetate), 25 wt.% VAc -
Poly(ethylene) vs. poly(ethylene-stat-vinyl acetate), 26.6 wt.% VAc -
Poly(ethylene) vs. poly(ethylene-stat-vinyl acetafe), 30.9 wt.% VAc -
Poly(ethylene) vs. poly(ethylene-stat-vinyl acetate), 38.7 wt.% VAc -
Poly(ethylene) vs. poly(ethylene-stat-vinyl acetate), 50 wt.% VAc -
Poly(ethylene) vs. poly(ethylene-stat-vinyl acetate), 75 wt.% VAc -
Poly(ethylene) (linear) vs. poly(oxyethyleneoxyterephthaloy1) 9.4
Poly(ethylene) (branched) vs. poly(oxyethyleneoxyterephthaloy1) 13.7
Poly(ethylene) (branched) vs. poly(oxytrimethyleneoxy- 15.4
isophthaloyl)
Poly(ethylene) (branched) vs. poly(oxytetramethyleneoxy- 13.5
isophthaloyl)
Poly(ethylene) (branched vs. poly(oxyhexamethyleneoxy- 11.1
isophthaloyl)
Poly(ethylene) (branched) vs. poly(oxyisophthaloyloxydeca- 8.3
methylene)
Poly(ethylene) (branched) vs. poly(oxyisophthaloyloxydodeca- 5.9
methylene)
Poly(ethylene) (linear) vs. poly(iminohexamethylene- 14.9
iminoadipoyl) (nylon 66)
Poly(ethylene) (branched) vs. poly(iminohexamethylene-
-
iminoadipoyl) (nylon 66)
Poly(ethylene) vs. poly(imino( 1-oxohexamethylene)) (nylon 6)
-
Poly(ethylene) (branched) vs. poly(oxyethylene) 11.6
2.70
2.85
2.25
1.40 (55C)
0.57 (55C)
0.58 (55C)
1.1
5.7
-
5.0
3.6
8.2
6.5
5.4
5.5
3.3
3.8
1.8
2.5
9.5
5.1
4.2
4.7
11.0
10.5
1.3
0.3
0.8
1.5
1.7
2.2
2.9
4.1
7.3
6.5 (280C)
9.8 (280C)
11.5
10.1
8.4
6.4
4.5
10.2 (280C)
17.0 (280C)
-
9.5
2.25
2.42
2.13
-
-
-
-
4.7
4.4
4.8
3.2
7.3
-
4.6
-
2.7
3.2
1.3
2.1
8.6
4.4
3.7
4.3
9.7
-
1.1
-
-
-
-
-
-
-
6.0 (325C)
9.2 (325C)
10.0
8.8
7.3
5.6
3.9
9.4 (325C)
15.2 (325C)
10.7 (250C)
8.7
0.00895
0.00865
0.00250
0.0105
0.0198
-
-
0.020
-
0.0046
0.0075
0.018
-
0.016
-
0.014
0.013
0.010
0.0078
0.018
0.015
0.010
0.009
0.027
-
0.005
-
-
-
-
-
-
-
-
-
-
0.030
0.026
0.021
0.015
0.011
-
0.041
-
0.016
103
103
1 0 3
70
70
70
1 7
8
106
46
2
1,35
46
1,35
46
1,35
46,107
1,35
46,107
8
8
2
2
7,12
1 8
12.18
2 3
23
23
23
2 3
2 3
3 5
3 5
3 5
1 4
9 8
98
98
98
9 8
3 5
14
1 0 6
12
TABLE 3. contd
Interfacial Tension for Amorphous interfaces
Polymer
Interfacial tension ylz (mN/m zz dynkm)
20 C 150C 200 C
- dy Iz/dT
(mN/m/k) Refs.
Poly(ethylene) (branched) vs. poly(oxytetramethylene) 5.1 4.1
Poly(ethylene) (branched) vs. poly(oxydimethylsilylene) 5.3 5.1
3.1.4. POLY(ETHYLENE-srut-PROPYLENE-srat-HEXADIENE), (EPDM) vs. OTHERS
EPDM (E/P/HD 69.5/26.5/4.0 weight ratio) vs. poly- 8.6 6.2 (280C)
(oxyethyleneoxyterephthaloyl), poly(ethylene terephthalate)
EPDM (E/P/HD 69.5/6.5/4.0 weight ratio) vs. poly(imino- 14.7 9.7 (280C)
hexamethyleneiminoadipoyl) (nylon 66)
Poly(ethylene-srat-vinyl acetate) vs. poly(ethylene), see reverse
Poly(ethylene-stat-vinyl acetate) vs. poly(viny1 acetate), see reverse
Poly(ethylene-stat-vinyl acetate) vs. poly(ethylene srut-vinyl acetate)
ENAc (25 wt.% VAc) vs. ENAc (12 wt.% VAc)
ENAc (25 wt.% VAc) vs. ENAc (17.7 wt.% VAc)
ENAc (25 wt.% VAc) vs. ENAc (38.7 wt.% VAc)
ENAc (25 wt.% VAc) vs. ENAc (50 wt.% VAc)
ENAc (25 wt.% VAc) vs. ENAc (75 wt.% VAc)
3.1.5. POLY(ISOBUTENE) vs. OTHERS
Poly(isobutene) vs. poly(viny1 acetate)
Poly(isobutene) vs. poly(oxydimethylsilylene)
3.1.6. POLY(PROPYLENE) vs. OTHERS
-
0.45
-
0.13
-
0.17
1.0
-
3.6
9.9 7.3
4.9 4.1
Poly(propylene) vs. poly(ethylene), see reverse
Poly(propylene) vs. poly(styrene)
Poly(propylene) vs. poly(oxydimethylsilylene) 3.2
3.1.7. HALOGENATED HYDROCARBON POLYMERS vs. OTHERS
Poly(chloroprene) vs. poly(ethylene), see reverse
Poly(chloroprene) vs. poly(n-butyl methacrylate) 2.2
Poly(chloroprene) vs. poly(styrene), see reverse
Poly(chloroprene) vs. poly(oxydimethylsilylene) 7 . 1
2.9
1.5
6.4
3.2. STYRENE POLYMERS vs. OTHERS
Poly(styrene) vs. poly(ethylene), see reverse
Poly(styrene) vs. poly(chloroprene) 0.7 0.5
Poly(styrene) vs. poly(methy1 acrylate)
-
3.2
Poly(styrene) vs. poly(ethy1 acrylate)
-
1.4
Poly(styrene) vs. poly(n-butyl acrylate)
-
1.4
Poly(styrene) vs. poly(2-ethylhexyl acrylate)
-
2.5
Poly(styrene) vs. poly(viny1 acetate) 4.2 3.7
Poly(styrene) vs. poly(methy1 methacrylate) + 3.2 1.5
- -
Poly(styrene) vs. poly(oxydimethylsilylene) - 6.1 6.1
Poly(styrene) vs. poly(ethylene-stat-vinyl acetate), 17.7 wt.% VAc 1.8 2.8
Poly(styrene) vs. poly(ethylene-stat-vinyl acetate), 30.9 wt.% VAc 0.3 2.1
Poly(styrene) vs. poly(ethylene-stat-vinyl acetate), 38.7 wt.% VAc 2.3 2.0
Poly(styrene) vs. poly(ethylene-star-vinyl acetate), 26.6 wt.% VAc 3.3 2.6
3.3. VINYL POLYMERS vs. OTHERS
Poly(ethylene-stat-vinyl acetate) vs. poly(ethylene), see reverse
Poly(ethylene-star-vinyl acetate) vs. polystyrene, see reverse
Poly(ethylene-snzt-vinyl acetate) vs. self, see Hydrocarbon Polymers vs. Others
3.3.1. POLY VINYL ACETATE vs. OTHERS
Poly(viny1 acetate) vs. poly(isobutene), see reverse
Poly(viny1 acetate) vs. poly(etbylene-star-vinyl acetate),
12 wt.% VAc
-
8.3
Poly(viny1 acetate) vs. poly(ethylene-stat-vinyl acetate),
17.7 wt.% VAc
-
7.5
Poly(viny1 acetate) vs. poly(etbylene-stat-vinyl acetate),
25 wt . % VAc
6.3 5.8
-
6.5
3.8
5.0
5.7 (325C)
8.8 (325C)
6.3
3.8
2.8
1.3
6.2
0.4
-
-
-
3.4
0.8
1.3
6.1
3.2
2.8
1.9
2.3
5.5
-
0.007 2,12
0.002 2,12,82
0.0093 20,35
0.0193 20,35
-
23
-
23
-
23
-
35
-
35
0.020 7
0.006 82
0.002 1 7
0.0047 2
0.0050 2
-
0.0044
0.013
-
- 0
- 0.0074
- 0.0136
0.0020
0.0050
2
46
46
46
46
2.24
8
106
82
24
24
24
24
-
23
23.
0.0043 1 2
-
23
References page VI - 540
VI / 538 SURFACE AND INTERFACIAL TENSIONS OF POLYMERS, OLIGOMERS, PLASTICIZERS, AND ORGANIC PIGMENTS
TABLE 3. contd
Polymer
Interfacial tension ylz (mN/m = dynkm)
20 C 150C 200 C
- dy &dT
(mN/m/k) Refs.
Poly(viny1 acetate) vs. poly(ethylene-stat-vinyl acetate),
26. 6 wt . % VAc
Poly(viny1 acetate) vs. poly(ethylene-stat-vinyl acetate),
30. 9 wt . % VAc
Poly(viny1 acetate) vs. poly(ethylene-stat-vinyl acetate),
38. 7 wt . % VAc
Poly(viny1 acetate) vs. poly(ethylene-star-vinyl acetate),
50 wt . % VAc
Poly(vinyl acetate) vs. poly(ethylene-stat-vinyl acetate),
75 wt . % VAc
Poly(viny1 acetate) vs. poly(n-butyl methacrylate)
Poly(viny1 acetate) vs. poly(oxytetramethylene)
Poly(viny1 acetate) vs. poly(oxydimethylsilylene)
Poly(viny1 acetate) vs. eicosane, C 2aH44
3. 3. 2. POLY(VlNYL BUTYRATE) vs. OTHERS
Poly(viny1 butyrate) vs. eicosane, C 20H4J
3.3.3. POLY(VINYL PROPIONATE) vs. OTHERS
Poly(viny1 propionate) vs. eicosane, C 2aH44
3.4. ACRYLIC POLYMERS vs. OTHERS
3.4.1. POLY(METHYL ACRYLATE) vs. OTHERS
Poly(methy1 acrylate) vs. poly(ethylene), see reverse
Poly(methy1 acrylate) vs. poly(styrene), see reverse
Poly(methy1 acrylate) vs. poly(ethy1 acrylate)
Poly(methy1 acrylate) vs. poly(n-butyl acrylate)
Poly(methy1 acrylate) vs. poly(2-ethylhexyl acrylate)
3.4.2. POLY(ETHYL ACRYLATE) vs. OTHERS
Poly(ethy1 acrylate) vs. poly(ethylene), see reverse
Poly(ethy1 acrylate) vs. poly(styrene), see reverse
Poly(ethy1 acrylate) vs. poly(methy1 acrylate), see reverse
Poly(ethy1 acrylate) vs. poly(n-butyl acrylate)
Poly(ethy1 acrylate) vs. poly(2-ethylhexyl acrylate)
3.4.3. POLY(n-BUTYL ACRYLATE) vs. OTHERS
Poly(n-butyl acrylate) vs. poly(ethylene), see reverse
Poly(n-butyl acrylate) vs. poly(styrene), see reverse
Poly(n-butyl acrylate) vs. poly(methy1 acrylateh see reverse
Poly(n-butyl acrylate) vs. poly(ethy1 acrylate), see reverse
Poly(n-butyl acrylate) vs. poly(2-ethylhexyl aciylate),
3.4.4. POLY(2-ETHYLHEXYL ACRYLATE) vs. OTHERS
Poly(2-ethylhexyl acrylate) vs. poly(ethylene), see reverse
Poly(2-ethylhexyl acrylate) vs. poly(styrene), see reverse
Poly(2-ethylhexyl acrylate) vs. poly(methy1 acrylate), see reverse
Poly(2-ethylhexyl acrylate) vs. poly(ethy1 acrylate), see reverse
Poly(2-ethylhexyl acrylate) vs. poly(n-butyl acrylate), see reverse
3.5. METHACRYLIC POLYMERS vs. OTHERS
3.5.1. POLY(METHYL METHACRYLATE) vs. OTHERS
Poly(methy1 methacrylate) vs. poly(ethylene), see reverse
Poly(methy1 methacrylate) vs. poly(styrene), see reverse
Poly(methy1 methacrylate) vs. poly(n-butyl methacrylate)
Poly(methy1 methacrylate) vs. poly(terr-butyl methacrylate)
3. 5. 2. POLY(n-BUTYL METHACRYLATE) vs. OTHERS
Poly(n-butyl methacrylate) vs. poly(ethylene), see reverse
Poly(n-butyl methacrylate) vs. poly(viny1 acetate), see reverse
-
-
4.2
5.5
8.4
7.1
1.9
3.5
2.4
4.0
6.6
2.1
3.9
1.8
3.4
3.0
6.1
5.6
4.7
3.5 -
1.2
2.8
4.5
7.3
4.6
0.9
2.5
13
3.0
5.7
1.3
3.2
1.2
1.9
2.2
- -
2.3 0.010
4.1 0.0081
6.9 0.0081
3.6 0.0195
0.5 0.0078
2.1 0.0080
0.9
2.6
5.4
1.0
3.0
1.0
1.3
1.9
0.008
0.008
0.007
0.006
0.005
0.005
0.012
0.006
23
23
23
35
8
1 2
2,12,82
40
1,35,46
1,35,46
1,35,46
1,35,46
1,35,46
1,35,46
8
2
Interfacial Tension for Amorphous Interfaces VI / 539
TABLE 3. contd
Interfacial tension ylz (mN/m G dynkm)
- dy lzldT
Polymer 20 C 150C 200 C (mN/m/k) Refs.
Poly(n-butyl methacrylate) vs. poly(chloroprene), see reverse
Poly(n-butyl methacrylate) vs. poly(oxydimethylsilylene), see reverse
3.5.3. POLY(iso-BUTYL METHACRYLATE) vs. OTHERS
Poly(iso-butyl methacylate) vs. poly(ethylene), see reverse
3.5.4. POLY(terf-BUTYL METHACRYLATE) vs. OTHERS
Poly(t-butyl methacrylate) vs. poly(ethylene), see reverse
Poly(t-butyl methacrylate) vs. poly(oxydimethylsilylene), see reverse
3.6. POLY(ETHERS) vs. OTHERS
3.6.1. POLY(OXYETHYLENE) vs. OTHERS
Poly(oxyethylene) vs. poly(ethylene), see reverse
Poly(oxyethylene) vs. poly(ethylene-stat-vinyl acetate),
25 wt . % VAc
6.4 5.8 5.5 0.0045 1 2
Poly(oxyethylene) vs. poly(2-ethylhexyl, acrylate)
Poly(oxyethylene) vs. poly(n-butyl acrylate)
Poly(oxyethylene) vs. poly(oxytetramethylene)
Poly(oxyethylene) vs. poly(oxydimethylsilylene), see reverse
Poly(oxyethylene) vs. eicosane, C 2oHu
6.6 4.8 4.1 0.014
2.8 2.0 1.7 0.0065
4.5 3.8 3.6 0.005 1
- 9.3 (90C) - 0.040
107
107
1 2
58
3. 6. 2. POLY(OXYTETRAMETHYLENE) vs. OTHERS
Poly(oxytetramethylene) vs. poly(oxyethylene), see reverse
Poly(oxytetramethylene) vs. poly(ethylene), see reverse
Poly(oxytetramethylene) vs. poly(viny1 acetate), see reverse
Poly(oxytetramethylene) vs. poly(ethylene-star-vinyl acetate),
25 wt . % VAc
1.5 1.2 1.1 0.0023 1 2
Poly(oxytetramethylene) vs. poly(oxydimethylsiloxane), see reverse
Poly(oxytetramethylene) vs. eicosane, C 20Hu
-
1.1 (90C) - 0.013 58
3.7. POLY(ESTERS) vs. OTHERS
Poly(oxyethyleneoxyterephthaloy1) vs. polyethylene, see reverse
Poly(oxyethyleneoxyterephthaloy1) vs. poly(ethylene-stat-propylene-stat-hexadiene), see reverse
Poly(oxytrimethyleneoxyisophthaloy1) vs. poly(ethylene), see reverse
Poly(oxytetramethyleneoxyisophthaloy1) vs. poly(ethylene), see reverse
Poly(oxyhexamethyleneoxyisophthaloy1) vs. poly(ethylene), see reverse
Poly(oxyisophthaloyloxydecamethylene) vs. poly(ethylene), see reverse
Poly(oxyisophthaloyloxydodecamethylene) vs. poly(ethylene), see reverse
3.8. POLY(AMIDES) vs. OTHERS
Poly(iminohexamethyleneiminoadipoy1) vs. pblyethylene, see reverse
Poly(iminohexamethyleneiminoadipoy1) vs. poly(ethylene-star-propylene-stat-hexadiene), see reverse
Poly(imino(l-oxohexamethylene)) vs. poly(ethylene), see reverse
3.9. EPOXY RESIN vs. OTHERS
Epoxy resin vs. poly(butadiene), see reverse
Epoxy resin vs. poly(butadiene-stat-acrylonitrile), see reverse
3.10. POLY(SILOXANES) vs. OTHERS
Poly(oxydimethylsilylene) vs. poly(ethylene), see reverse
Poly(oxydimethylsilylene) vs. poly(styrene), see reverse
Poly(oxydimethylsilylene) vs. poly(propylene), see reverse
Poly(oxydimethylsilylene) vs. poly(isobutene), see reverse
Poly(oxydimethylsilylene) vs. poly(chloroprene), see reverse
Poly(oxydimethylsilylene) vs. poly(vinyl acetate), see reverse
Poly(oxydimethylsilylene) vs. poly(butadiene), see reverse
Poly(oxydimethylsilylene) vs. poly(n-butyl methacrylate)
Poly(oxydimethylsilylene) vs. poly(t-butyl methacrylate)
Poly(oxydimethylsilylene) vs. poly(oxyethylene)
Poly(oxydimethylsilylene) vs. poly(oxytetramethylene)
4.2 3.8 3.6
3.6 3.3 3.2
10.8 9.8 9.4
6.4 6.3 6.2
0.0037 2
0.0025 2
0.0078 1 2
0.0012 2.12
References page VI - 540
VI / 540 SURFACE AND INTERFACIAL TENSIONS OF POLYMERS, OLICOMERS, PLASTICIZERS, AND ORGANIC PIGMENTS
TABLE 3. contd
Interfaciai tension ylz (mN/m = dynkm)
- dy 12/dT
Polymer
20 C 150C 200 C (mN/m/k) Refs.
3.11. MISCELLANEOUS
Eicosane (CzoH4) vs. poly(oxyethylene), see reverse
Eicosane (CzoHa) vs. poly(oxytetramethylene), see reverse
Eicosane (CzoH44) vs. poly(viny1 acetate), see reverse
Eicosane (C20B44) vs. poly(vinyI propionate), see reverse
Eicosane (C 20Ha) vs. poly(viny1 butyrate), see reverse
Eicosane (CzoH& vs. 1,3-propanediol 25 wt.% VAc
Eicosane (C 20H44) vs. 1 ,Cbutanediol
Eicosane (C20H& vs. 1,5-pentanediol
Eicosane (C20H44) vs. 1,6-hexanediol
Eicosane (C 20H44) vs. 1, lo-decanediol
45.9 38.9 (9OT) - 0.100 58
44.2 37.6 (9OT) - 0.094 58
41.6 36.7 (9OT) - 0.070 58
42.2 36.5 (90C) - 0.08 1 58
39.3 34.2 (90C) - 0.073 58
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February 1970.
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(1969).
Permeability and Diffusion Data
S. Pauly
Fachlaboratorium fur Permeationspriifung, Alte Schmelze 6, D-65201 Wiesbaden, FR Germany
A. introduction VI-543
B. Conversion Factors for Various Units of the
Permeability Coefficient VI-545
C. Tables
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Table 6.
VI-545
Permeability Coefficients, Diffusion
Coefficients, and Solubility
Coefficients of Polymers VI-545
1.1. Polyfalkanes) VI-545
1 . 2 . Polyfstyrenes) VI-547
1 . 3 . Poly(methacrylates) VI-548
1.4. Polytnitriles) VI-549
1.5. Poly(vinyls) VI-549
1.6. Fluorine Containing Polymers VI-552
1 . 7 . Poly(dienes) VI-553
1 . 8 . Polyfxylylenes) VI-555
1 . 9 . Poly(oxides) VI-,555
1 .I 0. Poly(esters), Poly(carbonates1 VI-555
1 .I 1. Poly(siloxanes) VI-558
1 .12. Poly(amides), Poly(imides) VI-559
1 .I 3. Polyturethanes) VI-560
1 .14. Poly(sulfones) VI-560
1 .15. Polyfaryl ether ether ketone) VI-561
1 .I 6. Cellulose and Derivatives VI-561
Permeability Coefficients of Six
Different Fluorinated +
Hydrocarbons Through Polymers VI-562
Permeability Coefficients of
Various Organic Compounds
Through Low-Density
Polytethylene) VI-562
Permeability Coefficients and
Diffusion Coefficients of an
Equimolar Mixture of Various
Compounds (1.25 M Each)
Through High-Density
Poly(ethylene) VI-564
Permeability Coefficients of
Various Organic Compounds
Through High-Density
Poly(ethylene) and
Poly(propylene) VI-564
Permeability Coefficients of
Various Organic Compounds
Table 7.
Table 8.
T
T
T
able 9.
able 10.
able 11.
Table 12.
Through Irradiation Crosslinked
Low-Density Poly(ethylene) VI-564
Permeability Coefficients of Gases
Through Irradiation Crosslinked
Low-Density Poly(ethylene)
VI-565
Permeability Coefficients of
Chemically Crosslinked
Polytoxypropylene) VI-565
Permeability Coefficients of Gases
Through Various Elastomers VI-566
Permeability Coefficients of Gases
Through Various Commercial
El ast omers at 35C.
VI-566
Permeability, Diffusion and
Solubility Coefficients of Alkanes
Through SantopreneTM (Blend of
Ethylene-Propylene Copolymer
and lsotactic Polytpropylene)) VI - 566
Permeability, Diffusion and
Solubility Coefficients of Esters
Through Polytepichlorohydrin)
(EC01
VI-567
D. References
VI-568
A. INTRODUCTION
The transmission of molecules through polymer films is
named permeability. There are many dimensions and
units found in the literature for the general expression
permeability. In this paper the permeability coefficient is
used. It has the dimension
(quantity of permeant) x (film thickness)
= (area) x (time) x (pressure drop across the film)
and is the best definition for permeability.
The permeability coefficient, in a strict sense, is not
only a function of the chemical structure of the polymer. It
also varies with the morphology of the polymer and
depends on many physical factors such as density, crystal-
linity, and orientation. However, the chemical structure of
a polymer can be considered to be the predominant
factor which controls the magnitude of the permeability
coefficient.
VI / 544 PERMEABILITY AND DIFFUSION DATA
The following general trends in permeability, as related
to some influencing factors, may be useful for the proper
interpretation of the tables:
Density can be regarded as a measure of the free volume
between the molecules of the polymer structure. In general,
the higher the density, the lower is the permeability.
Crystullinity of a semicrystalline polymer reduces the
permeability significantly compared to the value of the
corresponding amorphous polymer; i.e., the higher the
degree of crystallinity, the lower the permeability. The
crystallinity and the density of a polymer are strongly
related. The higher the crystallinity the higher is the density
of a given polymer.
Molecular mass of a polymer has been found to have
little effect on the permeability of polymers, except at a
very low range of molecular masses.
Orientation of polymer molecules reduces the perme-
ability.
Crosslinking decreases the permeability, especially for
higher degrees of crosslinking and for largemolecular size
permeants.
The method and degree of vulcanization has a significant
effect on the permeability of elastomers.
Plasticizers increase the permeability.
Humidity increases the permeability of some hydrophilic
polymers.
Liquid permeants have the same permeabilities as their
corresponding saturated vapors, though higher permeabil-
ities may occur especially if parts of the polymer are being
dissolved.
Solution cast films have variable permeabilities
depending upon the kind of solvent used and the drying
technique. Poor solvents tend to yield films of higher
permeability.
Fillers, usually inorganic fillers, decrease the perme-
ability; however, the effect is complicated by the type,
shape, and amount of filler and its interaction with the
polymer.
Thickness of film does not, in principle, affect the
permeability coefficient, the diffusion coefficient, and the
solubility coefficient. In practice, different values may be
obtained from films of variable thickness, which in turn
may be due to differences in drawing, orientation, and
crystallinity.
If a permeant does not interact with the polymer under
investigation, the permeability coefficient is characteristic
for the permeant-polymer system. This is the case with the
permeation of many gases, such as Hz, He, N2, 02, and
CO*, through many polymers. On the other hand, if a
permeant interacts with the polymer, the permeation
coefficient is no longer a constant, and may depend on
the special conditions of the measurement and the history of
the polymer film. In such cases, a single value of the
permeability coefficient does not represent the character-
istic permeability of the polymer, and it is necessary to
know the dependency of the permeability coefficient on all
possible variables in order to obtain the complete profile of
the permeability of the polymer.
In these cases, the transmission rate, which has the
dimension
Q=(
uantity of permeant)
(area) x (time)
is often used for practical purposes. Since the transmission
rate, Q, includes neither the pressure of the permeant nor
the thickness of the polymer in its dimension, it is necessary
to know either the pressure or the concentration of the
permeant and the thickness of the polymer under the
conditions of measurement.
For both P and Q, the quantity of permeant can be
expressed by mass, moles, or gaseous volume at standard
temperature and pressure. These can readily be converted
from one unit into another.
The preferred SI unit of the permeability coefficient used
in this book is
unit of P :
cm3(273.15K; 1.013 x 105Pa) x cm
cm3xsxPa
where (273.15 K; 1.013 x lo5 Pa) means standard tempera-
ture and pressure (STP). Therefore permeability coefficients
given in this paper are in the range of 10-l -
10-16cm3 x cm/cm2 x s x Pa for many polymers and
permeants.
The mostly used units and their conversion factors are
listed in Table B.
The permeation of molecules through flawless
polymers occurs by the steps of dissolution of a
permeant in the polymer and diffusion of the dissolved
permeant. The product of the diffusion coefficient D and
the solubility coefficient S is referred to as the permeability
coefficient.
P=DxS
Units of D and S used in these tables are
cm2
unit of D : -
S
unit of S :
cm(273.15K; 1.013 x 105Pa)
cm3 x Pa
The solubility coefficients cited in the following tables are
often calculated by
P
s=u
The temperature dependence of the permeability coefficient
P, the diffusion coefficient D, and the solubility coefficient
S can be represented by
P = PO x exp (-Ep/RT)
D = Do x exp (-E~/RT)
and
S = So x exp (-E~/RT)
Consequently
EP=ED+Es
where Ep is the activation energy of permeation, ED the
activation energy of diffusion, and Es the heat of solution.
PO, Do, and SO are the pre-exponential factors. Values of
Ep, ED, and Es are given in kJ/mol in the following tables.
R is the gas constant (8.3144 x lop3 kJ/Kmol); T is the
temperature in K. In the following tables the temperature
range is given in which Pa, Ep, ED, and ES are relevant, as
Poly(alkanes) VI / 545
far as the authors have reported it. The permeability
coefficient can be determined for a given temperature by
means of the pre-exponential factor Pa and the activation
energy of permeation E p. In the following tables, perme-
ability, diffusion, and solubility coefficients are listed for
many polymers. The pre-exponential factor PO, the
activation energy of permeation Ep, the activation energy
of diffusion ED, and the heat of solution Es are also given.
The pre-exponential factors DO and SO can be determined
by the following equations:
Do = D x exp (E,,/RT)
SO = S x exp (Es/RT)
B. CONVERSION FACTORS FOR VARIOUS UNITS OF THE PERMEABILITY COEFFICIENT
Multiplication factors to obtain P in:
From
km Y bl
[cm 7 kl [cm Ql
[cm31 bl
[cm 1 bl Pal
[cm 1 bl
WI PayI Wml
[cm31 b-C
I~m211~lb W
b31bml
WI bl [cm Hi
[cm31 bl
km Y I4 btml
[cm31 [mill
[cm I [WI b-4
[in3][mil]
[lOOin][day][atm]
b31bl
b I [WI btml
[cm31 bl
lm I PayI I%
b31kml
1
10-t
1.32 x lo-
3. 87 x10-14
9. 82 xlo-l2
1.52 x 10-l
7. 5 x 10-4
7. 5 x 10-s
9. 87 x 1O- 6
2. 90 x lo-l7
7. 37 x 10-15
1.14 x 10-14
1.16 x IO-l4
1
6. 57 x10
6. 57 xlo9
8.64 x 10s
2. 54 x1O-3
6. 45 x10-l
C. TABLES
.
TABLE 1. PERMEABILITY COEFFICIENTS, DIFFUSION COEFFICIENTS, AND SOLUBILITY COEFFICIENTS
OF POLYMERS
Units used in the tables are as follows: P, PO in cm3(273.15 K; 1.013 x lo5 Pa) x cm/(cm*x s x Pa); D in cm/s; S in cm3(273.15 K; 1.013 x lOsPa)/
(cm3x Pa); E,, ED, Es in kJ/mol; Tin C; (273.15 K; 1.013 x lo5 Pa) means standard temperature and pressure (STP).
Pol ymer Permeant T D (~10~)
Temp.
s (x106) Elge Pa (x10) EP ELI Es
Refs.
1. 1. POLY(ALKANES)
Poly(ethylene) LLDPE CzH40 30
Poly(ethylene)
density 0.914g/cm3, LDPE
H2
D2
He
02
AC
Ne
Kr
Xe
co2
25
25
25
25
25
25
25
25
25
68.9
1.4
6.6
3.7
2.2
2.1
0.48
2.15
4.01
9.5
0.03 1 225
0.474
0.476
6.8
0.46
0.36
2.42
0.169
0.069
0.372
1.58
1.38
0.0544 5-60 4.62
0.472 5-60 66.5
0.571 5-60 174
0.020
1.28
5.82
2.54 5-60 62.0
80
49
49
34.8 24.7 10.1 16
42.7 40.2 2.5 16
45.2 42.3 2.9 16
49
49
49
38.9 38.5 0.4 16
References page VI - 568
VI / 546 PERMEABILITY AND DIFFUSION DATA
Polymer Permeant T P (x10) D (x106)
Temp.
s ( x 106) r a nge Pa (x10) EP ED Es Re f s .
density 0.964&m, HDPE
Poly(ethylene) HDPE
C2H40 30 21.4 0.021 97.5
Poly(ethylene) (Hizex 7OMlF)
Isotropic density 0.943 g/cm3
draw ratio 8 0.958
9 0.957
10 0.958
I2 0.960
14.5 0.962
20.5 0.966
He 25 1.33 3.50 0.0379
He 25 1.46 3.20 0.0457
He 25 1.44 3.55 0.0406
He 25 0.885 2.38 0.0372
He 25 0.407 1.69 0.0241
He 25 0.278 1.14 0.0244
He 25 0.129 0.632 0.0204
Poly(ethylene) (Hizex 7OOOF)
draw ratio 1.0 density 0.945 g/cm N2 25 0.2 0.094 0.217
02
25 0.76 0.196 0.395
co2
25 3.2 0.148 2.16
He 25 1.1 3.3 0.0346
N2
25 0.11 0.075 0.138
02
25 0.34 0.099 0.346
co2 25 1.4 0.080 1.82
He 25 0.37 1.5 0.0247
02 25 0.074 0.032 0.237
co2 25 0.28 0.02 1.41
He 25 0.3 1.7 0.0188
02 25 0.10 0.0459 0.197
He 25 0.12 0.54 0.0217
02 25 0.012 0.0055 0.217
co2 25 0.045 0.0035 1.29
He 25 0.11 0.48 0.0237
02 25 0.15 0.0065 0.168
6.6 0.954
6.4
11.8 0.959
12.0 0.959
17.6
Poly(ethylene-hexene-1) c o po l y me r
( Ri gi dex 002-55)
Isotropic density 0.943 g/cm
draw ratio 7 0.955
8.5 0.958
9.5 0.959
10 0.960
I1 0.961
13 0.963
16.5 0.964
Poly(ethylene-hexene-1) c o po l y me r
( Ri gi dex 002-55)
draw ratio 1.0 density 0.945 g/cm
6.5
co 25
N2 25
CHI 25
Cd%
25
C,HI 25
C,Hs
25
C,Hs
25
SF6 25
HIS
20
NH3
20
CH3Br 20
CzfW 30
Hz0 25
He 25
02 25
Ar 25
co2 25
c o 25
N2
25
CH4 25
C2Hs
25
Cab
25
C,Hs 25
C3Hs
25
n-C4H IO
40
n-CsH 12 25
n-cd M
0
SF6
25
HIS 20
NH,
20
Hz0
25
1.1
0.73
2.2
5.1
32
II,
7.1
0.13
27.0
21.0
110
75
68
0.86
0.30
1.30
0.27
0.15
0.11
0.29
0.44
3.0
0.87
0.404
0.332 0.336 5-60 154 46.5 39.8 6.7
0.320 0.228 5-60 329 49.4 41.5 7.9
0.193 1.13 5-60 425 47.3 45.6 1.7
0.068 7.55 5-60 985 47.3 53.6 - 6.3
0.105 30.2 5-60 209 38.9 49.8 - 10.9
0.058 18.8 5-60 459 43.5 52.3 - 8.8
0.0322 21.3 5-60 1170 46.9 55.7 - 8.8
0.0135 0.95 1 5-60 4050 59.9 62.0 - 2. 1
0.0063
6.5
8.0
9.0
3.07
0.17
0.12
0.12
0.096
0.093
0.057
0.015
0.025
0.011
0.0049
0.02
0.0033
o.OQOo75
0.0016
0.028
0.18
1.1
0.22
0.15
0.15
0.51
3.0
12
8.2
8.3
0.39 5-60 29.5 55.2 62.8 - 7.6
He 25 1.11
He 25 0.23
He 25 0.878
He 25 0.773
He 25 0.695
He 25 0.515
He 25 0.257
He 25 0.206
3.27 0.0340
3.32 0.0278
f-J2
25 0.179 0.0945 0.188
02
25 0.662 0.185 0.357
co2 25 3 0.132 2.27
N2
25 0.059 0.0411 0.148
02
25 0.0522 0.0696 0.289
co2 25 1.0 0.056 1.78
O-60
10-90
5-60
5-60
5-60
5-60
5-60
5-60
5-60
5-60
5-60
5-60
5-60
48.8 33.5
0.137 29.7
0.423 35.1
5.23 37.7
0.0506 30.1
1.15 39.3
0.991 39.7
3.76 40.6
13.3 42.7
I.89 33.1
5.68 38.9
28.5 44.8
23.4 6.3
36.8 - 1.7
38.9 - 1.2
35.6 - 5.5
36.8 2.5
37.7 2.0
43.5 - 2.9
52.3 - 9.6
47.3 - 14.2
52.3 - 13.4
56.9 - 12.1
62.3
76.6
16
16
16
16
16
16
16
16
5
5
37
37
21
16
16
16
16
16
16
16
16
16
16
16
64
64
64
16
5
5
21
80
74
74
74
74
74
74
74
99
99
99
99
99
99
99
99
99
99
99
99
99
99
99
99
99
74
74
74
74
74
74
74
74
99
99
99
99
99
99
Poly(styrenes)
Permeant T P (x10) D (x106)
Temp.
s (x 106) range Po(xl 0) EP ED Es Refs.
11.7
14.7
17.6
Poly(ethylene-co-propylene) 4W60
amorphous
31.0 CH,-groups per 100 carbons
26.5 CHz-groups per 100 carbons
21.5 CHj-groups per 100 carbons
Poly(propylene)
density 0.907 g/cm3
crystallinity 50%
(Trespaphan GND)
density 0.8871 g/cm
crystallinity 43%
density 0.8931 g/cm3
crystallinity 50%
density 0.8998 g/cm-
crystallinity 58%
density 0.9016 g/cm )
crystallinity 60%
Poly(propylene)
1.2. POLYCSTYRENES)
Poly(styrale)
biaxially oriented
ultradrawn
draw ratio 1.0
1.8
3.1
4.4
5.0
He
02
CO2
He
02
He
02
co2
He
Ne
Ar
N2
He
Ne
Ar
N2
He
Ne
Ar
N2
He
HI
N2
02
co2
Hz0
CHjBr
H2S
NH3
H20
He
02
N2
CO2
He
02
N2
co2
He
02
N2
co2
He
02
N2
C~HAO
02
Hz0
He
H2
02
N2
co2
Hz0
Hz0
co2
co2
co2
CO2
co2
Poly(styrene-co-styrenesulfonic acid) Na+-polysalt
sulfonated with 0 mol% SO;
H2
(Polystyrene)
N2
02
co2
CH4
sulfonated with 15,2mol% SO,
H2
N2
02
co2
CHd
25
25
25
25
25
25
25
25
24.4
24.4
24.4
24.4
24.1
24.1
24.1
24.1
26.6
26.6
26.6
26.6
20
20
30
30
30
30
30
20
20
23
33
33
33
33
33
33
33
33
33
33
33
33
33
33
33
30
25
5 25
25
- 25
25
25
25
25
23
25
25
25
25
25
23
23
23
23
23
23
23
23
23
23
0.242
0.044
0.18
0.14
0.025
0.097
0.0098
0.034
24.0
9.0
9.8
3.7
21.8
8.5
11.0
4.1
16.0
6.9
9.2
3.7
0.28
31.0
0.33
1.7
6.9
51.0
15.0
2.4
6.9
15.8
10.6
1.68
0.424
5.43
8.98
1.48
0.355
4.64
7.7
1.28
0.306
4.05
8.69
1.78
0.494
0.9
1.9
1350
14.0
17.0
2.0
0.59
7.9
840
717
6.0
4.35
2.18
1.13
0.75
18.5
0.368
2.18
10.58
0.585
10.13
0.0975
0.743
3.53
0.150
1.2 0.0197
0.0203 0.218
0.0113 1.58
0.713 0.0197
0.0148 0.167
0.57 0.0168
0.0048 0.207
0.0025 1.32
16.5 0.146
4.5 0.20
1.06 0.93
0.67 0.545
17.9 0.121
5.3 0.16
1.3 0.83
0.94 0.44
9.4 0.17
3.5 0.20
1.06 0.87
0.79 0.46
19.5
2.1
o-so
O-50
O-50
O-50
o- s o
O-50
O-50
O-50
O-50
o-so
O-50
O-50
20-70
20-70
20-70
20-70
20-70
10-90
O-50
10-50
30-55
30-55
30-55
30-55
30-55
30-55
30-55
30-55
30-5s
30-55
30-55
30-55
30-5s
30-55
30-55
1.56
2.48
46.6
167
1.93
4.89
46.7
97.5
2.37
5.67
27.2
54.2
0.153
224
1280
278
24.0
900
1.56 x lo6
0.249
0.631
117
1010
173
0.534
103
11500
148
0.458
89.4
732
129
0.236
11.8
34.5
27.6
31.8
39.6
43.8
28.1
32.7
37.8
42.1
29.7
34.1
37.2
41.2
32.2
38.5
55.7
47.7
38.1
42.3
64.2
23.8
28
46
55
44
28
46
55
44
28
46
55
44
26
40
46
0.0022 45
0.14
10-50 0.000028 - 7.79
0.0024 248
0.0019 233
0.00075 293
0.00046 158
0.055 0.67
0.12 2.0
0.054 19.5
0.011 5.3
0.0042 2.3
0.021 3.6
0.0091 39.8
0.0026 5.8
15.0 12.6
28.5 3.3
37.1 2.5
45.8 - 2.0
24.8 3.3
31.9 0.8
42.0 - 4.2
42.9 - 0.8
27.0 2.7
31.9 2.2
39.6 - 2.4
44.0 - 2. 8
99
99
99
99
99
99
99
99
25
25
25
25
25
25
25
25
25
25
25
25
13
13
19
19
19
19,21
19
5
5
73
47
47
47
47
47
47
47
47
47
47
47
47
47
47
47
80
42
42
41
41
41
41
41
27
73
72
72
72
72
72
83
83
83
83
83
83
83
83
83
83
References page VI - 568
VI / 548 PERMEABILITY AND DIFFUSION DATA
Polymer Permeant T
Temp.
s(x106) range &(x10) EP ED Es
Refs.
Poly(styrene-co-styrenesulfonic acid)
Mg 2+-polysalt
sulfonated with 152molB SO;
sulfonated with 27.5 mol% SO;
1.3. POLY(METHACRYLATE.5)
Poly(methy1 methacrylate)
Poly(methy1 methacrylate) +
(cellulose acetate butyrate) +
(silicone) - Blend 50/40/10
Poly(methy1 methacrylate) +
(Styrene/acrylonitrile) - Blend
80/20
50/50
20/80
Poly(methy1 acrylate) +
Poly(epichlorohydrin) - Blend
100/o
75125 He
Ar
N2
Cb
50/50 He
Al
N2
CH4
25175 He
AI
N2
CHI
o/100
Poly(ethy1 methacrylate)
Poly(2-hydroxyethyl-methacrylate)
highly crosslinked
sulfonated with 27.5 mol% SO;
H2
N2
02
co2
CH4
H2
N2
02
CO2
CHI
H2
N2
02
co2
CH4
H2
He
Ar
N2
02
02
co2
Cb
Hz0
02
He
Ar
N2
CHI
He
AI
N2
CH4
He
Ne
02
AI
N2
CO2
Kr
HzS
SF6
Hz0
02O
02*
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
35
35
35
35
34
35
35
35
23
34
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
25
25
25
25
25
25
25
25
25
25
65
34
34
5.85
0.0465
0.443
2.18
0.0443
7.20
0.0563
0.510
2.25
0.0525
5.18
0.0270
0.315
1.65
0.0255
2.78
5.70
0.0158
6.15
0.116
0 . 0 6 5 3
2.33
0.00263
480
4.52
0.435
0.938
1.58
7.95
0.383
0.140
0.176
6.78
0.410
0.144
0.221
5.59
0.443
0.159
0.302
4.61
0.495
0.178
0.411
3.62
0.533
0.180
0.493
5.18
2.28
0.889
0.433
0.170
3.79
0.287
2.88
0.0127
2380
2880
2.72
5.43
0.0012
0.0080
0.0027
0.00096
0.0069
0.028
0.0078
0.0025
0.005 1
0.017
o.ca37
0.0026
7.88
0.0513
0.0385
0.0121
7.15
0.0595
0.0442
0.0167
6.54
0.0677
0.0508
0.0242
0.0792
0.0595
0.0333
4.88
0.0918
0.0655
0.0422
42.5
1.5
0.106
0.0208
0.0301
0.0336
o.cm65
0.0046
0.0@323
0.102
0.729
4.1
5.5
80.6
4.7
0.83
1.8
28.6
2.1
0.53
1.9
44.6
0.98
0.101
0.747
0.365
1.46
0.0945
0.689
0.326
1.32
0.0855
0.655
0.313
1.25
0.625
0.299
1.23
0.0743
0.580
0.275
1.17
0.0122
0.152
0.839
2.08
0.565
11.3
4.40
62.6
5.62
2333
395
25-80
25-80
2.5-80
25-80
25-80
2.5-80
25-80
25-80
2S- 80
25-65
65-80
0.255
0.242
2.1
2.03
2.18
0.435
10.1
22.8
0.885
0.00555
1.58
26.8 15.5
28.7 23.9
36.4 31.8
38.1 43.1
40.6 42.7
28.9 33.1
43.1 46. I
39.4 47.7
44.8 64.5
2.1 36.4
18.0 63.2
11.3
4.8
4.6
- 5.0
- 2. 1
- 4.2
- 3. 0
- 8.3
- 19.7
- 34.3
- 45.2
83
83
83
83
83
83
83
83
83
83
83
83
83
83
83
88
88
88
77
77
77
77
77
77
77
77
77
77
77
77
77
77
77
77
77
77
77
77
29
29
29
29
29
29
29
29
29
29
29
51
51
Poly(vinyls) VI / 549
Pol ymer Permeant T P (x103) D (~10~)
Temp.
s (x 106) range Pa (x10) EP ED Es Rers.
1.4. POLY(NITRILES)
Poly(acrylonihile)
Poly(acrylonitrile-co-styrene) 86/14
66134
57143
Poly(acrylonitrile-co-methyl
acrylate-
co-butadiene) 7911516
Poly(methacrylonitrile)
(Lopac)
Poly(methacrylonitrile-co-styrene) 97/3
82/18
61139
53147
38162
IS/82
Poly(methacryloniuile-co-styrene-
co-butadiene) 88i7/5
83/7/10
78/7/15
1.5. PoLY(VINYLS)
Poly(viny1 acetate)
02
co2
HZ0
02
co2
Hz0
02
CO2
Hz0
02
CO2
H20
02
co2
Hz0
02
co2
HZ0
02
co2
H20
02
co2
Hz0
02
co2
Hz0
02
co2
Hz0
02
co2
Hz0
02
co2
Hz0
02
co2
HZ0
02
co2
Hz0
02
co2
HZ0
02
co2
H20
02
co2
H20
02
co2
HZ0
He
HZ
Ne
02
AI
Kr
25
25
25
25
38
25
38
25
38
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
38
25
38
25
38
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
f 25
25
.
25
25
25
25
25
25
25
25
25
10
30
10
30
10
30
10
30
10
30
10
30
o.Oca15
o.ooo6o
230
o.cQ41
0.014
0.012
0.022
490
520
0.0032
0.011
640
0.036
0.16
1500
0.14
0.27
1800
0.35
1.0
19Qo
0.0041
0.012
970
o.ooo9o
0.0024
310
0.0026
0.0053
0.0081
0.016
260
270
0.0018
0.0059
370
0.0098
0.038
700
0.068
0.21
1300
0.12
0.38
1400
0.29
0.88
IMX)
0.81
2.4
1500
0.0036
0.011
450
0.0052
0.015
500
0.0072
0.024
580
4.95
9.44
2.99
6.84
0.838
1.97
0.136
0.367
0.0569
0.143
0.0172
0.0582
o.OGa3
o.OOQ2
0.0026
0.0018
6.46
9.55
1.32
2.63
0.794
1.66
0.0178
0.0562
0.00479
0.0162
0.000602
0.00295
0.3
1.2
0.38
2.1
0.0784
0.101
0.237
0.254
0.106
0.118
0.766
0.637
1.11
0.943
2.78
1.96
O-20
25-40
O-20
25-40
O-20
25-40
O-20
25-40
O-20
25-40
O-20
25-40
0.00134
2.23
0.0023
10.4
0.000111
14.1
o.ooo74
1680
0.0471
4950
0.00826
7.71 x 105
13.2 17.4
31.2 22.4
15.7 21.6
41.7 31.4
11.5 30.8
39.8 35.4
20.2 46.4
56.1 60.7
32.1 47.6
61.2 69.1
30.8 60.7
76.2 81.2
- 4.2
8.8
- 5. 9
10.3
- 19.3
4.4
- 26.2
- 4.6
- 15.5
- 7.9
- 29.9
- 5.0
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
14
14
14
14
14
14
14
14
14
14
15
15
References page VI - 568
VI / 550 PERMEABILITY AND DIFFUSION DATA
Pol ymer Permeant T P (x1013) D (x106)
Temp.
s (x 106) range PO (x10) EP ED Es Refs.
Poly(vinyl benzoate)
Poly(viny1 butyral)
Poly(vinyl-p-isopropylbenroate)
Poly(vinyl-m-methylbenzoate)
Poly(viny1 chloride)
unplasticized
unplasticized
(Pentafoml Type TH 170/01)
CH4
CO2
Poly(viny1 alcohol) He
H2C
D2<
N2C
N**
OZC
02
CO><
co/
HlSC
C&OC
H20
H2
He
Ne
Ar
Kr
N2
02
co2
H20
He
Ne
Al
Kr
Xe
02
co2
CH4
A l
co2
He
H2
Ne
N2
Ar
Kr
02
co2
CH.4
Hz0
H2S
NH3
CzH40
He
N2
Al
CO2
CH4
25
35
20
25
100
14
14
25
23
25
25
2s
0
25
25
70
25
70
25
70
2s
3s
70
25
70
25
70
25
70
2s
70
25
3s
70
25
25
80
25
80
2s
80
2s
80
2s
80
25
80
2s
80
25
80
25
80
- 35
35
25
25
25
25
2s
25
80
25
25
25
25
20
20
30
35
35
35
35
35
0.0237
1.52
0.00075
0.00672
0.0134
0.0001
0.248
0.00665
0.00005
0.00924
65.0
0.0052
0.001s
5.25
6.55
18.3
6.67
17.1
1.51
4.28
0.358
0.459
1.24
0.192
0.712
0.071
0.43
0.124
0.463
0.715
2.11
4.17
4.74
8.06
608
8.93
49.9
3.88
13.9
1.90
7.67
0.940
6.25
0.00942
4.62
2.44
12.4
0.647
2.99
15.7
32.9
1.32
5.65
0.642
5.05
1.5
1.3
0.29
0.0089
0.0086
0.0060
0.14
0.034
0.12
0.021
206
0.14
3.7
4.4
2.52
0.00709
0.0277
0.182
0.00810
0.0017
0.00747
1.39
20.4
0.045 0.53
1.93
6.39
6.17
16.1
1.08
3.83
0.033
0.0491
0.181
0.0059
0.049
O.OC064
0.026
0.158
0.079
0.309
0.020
0.030
0.117
15.5
51.9
2.72
8.71
0.165
1.11
0.0388
0.393
0.00579
0.0898
0.279
1.948
0.117
0.874
0.0760
0.638
0.0462
0.478
0.0738
0.0361
2.8
0.5
0.25
0.0038
0.0012
0.00041
0.012
0.002s
0.0013
0.024
0.000046
0.0013
0.00188
0.00339
0.00145
0.34
0.29
0.11
0.11
0.14
0.11
1.08
0.93
0.69
3.25
1.45
11.1
0.48
0.29
0.91
0.68
20.9
16.2
6.9
0.0578
0.096
0.0585
0.160
1.15
0.691
3.91
1.61
16.5
5.14
0.0546
0.637
0.550
0.348
20.6
5.17
2.84
1.163
0.870
14.0
0.055
0.26
0.12
0.23
0.75
0.54
0.29
4.7
1.7
25-40
20-60
60-85
20-60
60-85
20-60
60-85
20-60
60-85
20-60
60-85
20-60
20-60
60-85
20-60
60-85
20-60
60-85
20-67
67-95
20-67
67-95
20-67
67-95
20-67
67-95
20-67
67-95
20-67
67-95
20-67
67-95
20-67
67-95
20-67
67-95
25-80
25-80
25-80
25-80
25-80
25-70
75-90
25-80
25-90
25-85
25-80
0.72 x 10
0.0055
0.251
0.00345
0.458
0.00137
0.758
0.0020
0.863
0.00188
2.565
0.00723
0.00104
1.26
0.00060
2.76
0.00020
0.734
0.590
0.537
0.00251
1.09
0.00131
11.6
0.000248
40.6
O.OOCOO289
534.8
0.00180
6.92
0.000878
19.4
0.000110
3.57
0.000512
58.7
0.212
1.46
0.274
9380
6.28
24.2
8.85 x lo5
179
930
7950
2.04
82.7
16.7
27.2
15.5
29.1
16.9
34.5
21.4
38.4
22.8
43.1
28.6
22.4
42.3
16.7
40.2
9.6
32.6
27.5
27.3
16.0
33.1
16.2
41.8
13.8
46.1
14.2
54.5
16.4
38.9
17.9
46.1
4.8
34.0
14.8
47.4
29.9
34.5
34.1
69.0
57.8
55.3
86.6
55.8
56.8
66.2
22.9
80.8 1.9
21.9 5 . 2
24.5 2.7
16.9 - 1.3
22.4 6.7
23.2 - 6.3
28.6 5.9
31.6 - 10.1
38.1 0.29
38.4 - 15.5
50.7 - 7.7
46.0 - 17.5
33.0 - 10.6
45.2 - 2.9
25.1 - 8.5
30.5 9.8
32.9 2 3 . 4
45.2 1 2 . 5
18.4 9.1
23.5 3.7
17.1 ~ 1.1
23.4 9.6
27.5 - 11.3
39.7 2.1
32.2 - 18.3
47.3 - 1.3
36.1 - 22.0
61.5 ~ 7.0
26.8 - 10.4
37.4 1.4
29.3 - 11.4
42.4 3.6
30.4 25.5
43.9 9 . 9
33.1 - 18.3
48.1 - 0.6
20.7 9.2
34.5 0
31.5 2.6
61.9 7.1
51.5 6.3
62.8 - 7.5
128.5 -41. 9
54.6 1.2
64.6 7 . 8
70.3 - 4. 1
41.8 - 18.9
15
86
10
28
57
11
11
28
59
28
28
28
37
98
65
65
65
65
65
65
65
86
65
65
65
65
65
65
65
65
65
65
86
65
98
86
86
86
86
86
86
86
86
86
86
86
86
86
86
86
86
86
86
86
86
32
32
32
32
32
32
32
32
32
32
32
5
5
80
7s
75
75
7s
75
Pol ymer Permeant T P (X10S) D (x106)
Poly(vinyls) VI 1551
Temp.
s (x10) RX@ Pa (x10)
EP ED Es Refs.
unplasticized
(CS 5760)
plasticized with tricresyl
triphospate %
0
5
1 0 . 2
15
2 0 . 1
30.8
40.0
0
5
1 0 . 2
15
2 0 . 1
30.8
H e 3 5
N2 3s
Al 3 5
CO2
3 5
CHa 3 5
H2
Hz
H2
Hz
Hz
H2
H2
CO
co
CO
CO
co
co
CO
2 7
2 7
2 7
2 7
27
27
27
27
27
27
27
27
27
27
Poly(vinyl chloride)/Oligo(dimethylsiloxane)
100/o
9000
75125
60/40
40/60
30170
Poly(viny1 chloride)-g-
oligo(dimethylsiloxane)lOligo(dimet-
hylsiloxane)
100/o
80/20
60140
so/50
Poly(viny1 flouride)
Poly(vinylidene chloride)
Poly(vinylidene chloride) (Saran)
Poly(vinylidene chloride-co-vinyl
chloride)
8802 plasticized with
acetyltributyl citrate (%)
0.5
2. 7
N2
02
N2
02
N2
02
N2
02
N2
02
N2
02
N2
02
N2
02
N2
02
N2
02
N2
02
N2
02
N2
02
N2
02
N1
02
H2
He
N2
02
co2
CH4
02
He
N2
02
co2
CH,Br
HZS
Hz0
2s
25
25
2s
2 5
2 5
2 5
25
2 5
2 5
2 5
25
2 5
2 5
2s
25
2s
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
) 25
2 5
.
2 5
35
3 5
3 5
35
3 5
3 5
3 5
34
30
30
30
30
30
2 5
2.24
0.00501
0.0208
0.138
0.00638
1. 8
1. 4
1.3
1. 3
1. 6
2. 1
2. 7
0.019
0.012
0.013
0.014
0 . 0 2 1
0.079
0.281
0.0226
0.103
0.0281
0.120
0.0316
0.151
0.0359
0.164
0.0656
0.295
0.153
0.678
0.320
1 .I4
1.51
3.83
0.0269
0.164
0.027 1
0.165
0 . 0 4 3 I
0.254
0.0609
0.413
0.120
0.795
0.417
2.43
1.01
4.99
0.41
0.98
0.0068
0.030
0.20
0.0075
0.00038
0.233
0.000706
0.00383
0.0218
0.00218
0.027
7.0
HsO 30 1 . 3 8
HK
30 3.07
0.00137
0.00242
0.00145
0.00033 1
0.48
0.456
0.422
0.444
0.473
1 . 5 6
2.25
0.0023
0.0021
0.0016
0.002s
0.0029
0.0054
0.029
O-90 900 70.3
O-90 8 2 5 66.6
O-90 24.8 51.5
9.6 x lo- 27.6 30- 7s 1 . 5 8 x lo5 74.5
IO-60 863 46.1
75
75
7 5
75
75
45
45
4s
45
45
45
45
45
45
45
45
45
45
45
8 5
8 5
8 5
85
85
85
8 5
8 5
85
8 5
8 5
85
85
85
85
8 5
8 5
8 5
8 5
8 5
8 5
8 5
85
85
8 5
8 5
85
85
8 5
8 5
96
96
96
96
96
96
96
10
3 7
3 7
3 7
3 7
8
2 1
so
50
References page VI - 568
VI 1552 PERMEABILITY AND DIFFUSION DATA
Pol ymer Permeant T P (x10)
Temp.
s (x106) range PO (x10) EP ED Es Refs.
4.9
H20
7.2 H20
Poly(viny1 cyclohexanecarboxylate) He
He
02
02
AI
Al
Ar
N2
N2
co2
co2
1.6. FLUORINE CONTAINING POLYMERS
Poly(tetrafluoroethylene)
HZ
H2
N2
02
co2
NO>
NzO4
D>
T2
CH4
He
Ne
4r
Kf
Xe
H,O
CH4
C2H6
(Hostaflon PFA)
Poly(tetrafluorethylene-co.
hexafluoropropene)
(Teflon FEP)
C,Hs
n-c 4H 10
i-CdH 10
He
02
N2
co2
CH4
SO2
Cl1
HCl
H20
N2
02
co2
CHa
C2H6
Cd38
n-cd 10
i-C qH ,o
CH,Cl
Cd6
Hz0
Poly(teuafluorethylene-co-ethylene)
(Host&m ET)
He
02
N2
co2
HK
He
02
N2
co2
CHa
Cl2
HCl
SO2
H>O
Polv(trifluorochloroethvlene)
unplasticized
K&F 300 film of about
30% crystallinity
He
H2
N2
02
co2
Hz0
30
30
25
70
25
70
25
35
70
25
70
25
70
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
38
90
90
90
90
90
23
22
23
24
25
24
23
22
23
25
25
25
90
90
90
90
90
i 25
25
- 25
70
23
23
23
23
23
25
22
23
23
23
23
23
23
25
80
20
20
25
40
40
25
4.77
7.38
9.69
33.5
1.30
6.50
0.851
1.17
4.75
0.256
1.82
5.05
21.4
7.4
7.25
1.0
3.2
7.5
12.0
28.0
7.48
6.19
0.56
9.0
2.69
1.50
0.73
0.30
6
3.85
2.15
0.96
0.878
0.345
33.0
3.17
0.92
10.0
0.79
2.11
1.35
2.04
13.4
1.19
3.68
9.53
9.98
6.23
3.11
2.18
0.855
0.763
0.263
12.8
37.3
4.23
0.40
0.137
1.49
2.8
5.67
0.78
0.25
4.39
0.23
0.807
2.2
1.96
74
115
5.1
0.705
0.0037s
0.030
0.158
0.218
7.33
20.3
0.122
0.772
0.0670
0.106
0.570
0.0421
0.368
0.0254
0.270
0.147
0.088
0.0152
0.095
0.0037
0.025
0.116
0.052
0.023
0.811
0.251
0.056
0.015
0.004
0.221
0.0763
0.0251
0.0187
0.0086
0.0948
0.184
0.105
0.491
0.140
0.0489
0.0278
0.0146
0.148
0.166
1.08
0.835
1.27
1.10
0.934
0.609
0.492
20.0
8.36
4.94
1.2
2.1
9.2
320
110
6.42
11.9
2.46
1.09
1.09
2.66
4.83
7.40
1.74
2.81
3.87
4.69
4.03
1.25
2.02
9.08
2.15
4.37
6.38
7.8
5.86
0.00667 11.5
2.45 x 10 -4 107
15-52
52-85
15-52
52-85
15-52
52-85
15-52
52-85
15-52
52-85
20-130
20-130
20-130
20-130
20-130
20-130
40-195
40-195
40-19s
40-195
40-195
20-100
20-90
20-100
20-100
20- 100
5-100
20-100
20-80
lo-80
20-80
20-80
20-80
40-195
40- 195
40- 195
40- 195
40- 195
40-120
40-120
25-60
60-85
20- 100
20- 100
S-100
20-100
20-100
20-100
20-100
5-100
20-55
55-9s
25-75
O-80
40-80
0.0158
0.547
0.00302
7.26
0.0115
20.2
0.00690
60.4
0.00233
6.68
0.0415
0.0202
0.00698
0.00248
0.00087
9.7 x lo-
-6
0.273
0.251
0.923
1.22
4.64
0.0119
0.0386
0.105
0.0236
0.292
0.0425
0.0259
0.122
0.0797
0.273
0.109
0.0443
1.09
1.22
6.30
134
4200
0.945
122
0.494
1.58 x 10
-7 -
0.0557
0.371
0.0790
0.0562
0.326
0.0349
0.394
0.0137
0.000121
0.0387
150
4.35
24.8
18.3
27.7
19.2
39.7
23.6
43.5
25.3
49.4
15.2
36.1
21.4
24.4
19.1
14.0
10.7
- 2. 1
33.7
35.2
41.6
42.7
49.6
14.5
23.1
28.7
19.2
31.8
24.5
24.3
27.0
21.4
30.6
25.5
20.9
35.0
36.8
43.9
54.2
67.4
34.8
49.5
26.2
15.6
22.8
32.1
31.2
23.3
34.9
26.3
29.8
21.8
1.2
17.1
23.4
30.2
59.9
46.9
49.4
16.3 0.25
23.7 4.4
30.9 - 11.7
41.1 - 0.34
34.6 - 11.1
43.5 - 0.011
35.6 -11.1
46.9 1.8
37.5 - 22.3
47.7 - 11.7
29.9 - 5. 5
26.3 - 7.2
28.6 - 14.6
58.6 - 47.9
34.7 - 1.0
36.2 - 1.0
44.8 - 3.2
51.5 - 8.8
58.1 - 8.5
38.5 - 7.9
34.7 - 9.2
36.6 - 15.7
41.3 - 6.3
53.8 - 17.0
59.5 - 15.6
65.0 ~ 10.8
77.8 - 10.4
so.1 - 15.3
69.1 - 19.6
56.4 ~ 30.2
16.5 - 32.1
5 0
50
81
81
81
81
81
86
81
81
81
81
81
23
49
23
23
23
23
23
49
49
49
49
49
49
49
49
98
53
53
53
53
53
73
73
73
73
73
73
73
73
73
24
24,67
24
53,55
53.55
53,ss
53,55
53,55
55
55
56,66
56,66
54
54
54
54
54
73
73
73
73
73
73
73
73
73
73
10
10
20
20
20
37
Polytdienes)
Permeant T D (~10~)
Temp.
s (x 106) r a ng e PO ( x10 ) EP ED Es Refs.
ctystallinity 80%
crystallm1ty 30%
plasticized
Poly(tifluorochloroethylene-co-
ethylene) (H&r)
Poly(viny1 fluoride) (Tedlar)
Poly(viny1 fluoride) (Kynar)
1.7. POLYCDIENES)
Poly(butadiene)
cis-1.4
Poly(butadiene-co-acrylonitrile)
80/20 (Perbunan 18)
13121 (Perbunan, German)
68132 (Hycx OR 25)
61/39 (Hycar OR 15)
Poly(butadiene-co-styrene)
92/8 (Ameripol 1502)
80/20 (Hycar 2001)
Poly(butadiene) hydrogenated
ctystallinity 29%, Hydropol
density 0.894 g/cm
CzH20
CH 1Br
N2
02
co2
N2
02
co2
He
02
N2
CO2
Hz0
He
N2
02
co2
H20
He
Hz
Al
N2
02
CHI
co2
n2
N2
02
co2
He
Ne
Ar
N2
He
Hz
N2
02
co2
He
H2
N2
02
CO2
Cd+2
C3H8
He
H1
N2
02
co2
He
H2
N2
02
co2
He
Ne
Al
N2
He
Ne
AT
N2
He
02
AI
co2
C O
N2
CH4
C2Hb
CA
C3Hb
c3ns
SF6
60
60
25
40
40
50
30
50
23
23
23
23
23
23
23
23
23
23
35
35
35
35
35
35
35
25
25
25
25
24
24
24
24
25
25
25
25
25
25
25
25
25
25
25
so
25
25
25
25
25
25
. . 25
2s
25
25
24
24
24
24
24
24
24
24
25
25
25
25
25
25
25
25
25
25
25
25
3.3
3.45
0.0022s
0.0188
0.036
0.413
0.42
5.63
4.0
0.114
0.0457
0.457
2.8
0.347
0.0012
0.0139
0.069
10.1
1.29
0.404
0.0323
0.0167
0.0620
0.0150
0.388
31.6
4.84
14.3
104
24.5
14.4
30.8
14.4
12.7
18.9
1.89
6.15
47.6
9.2
11.9
0.8
2.9
23.2
18.7
58.5
7.4
8.85
0.454
1.76
13.9
5.13
5.35
0.177
0.721
5.59
17.2
7.28
9.53
3.83
10.1
3.76
3.37
1.28
11.8
8.49
8.29
36.3
4.64
3.00
9.77
25.0
169
62.2
40.5
0.849
1.87
0.336
0.00985
0.00716
0.0172
0.00294
0.00566
9.6
1.1
1.5
1.05
15.7
6.55
4.06
2.96
15.5
6.43
0.51
0.79
0.425
11.7
4.5
0.25
0.43
0.19
0.0764
0.141
11.2
3.85
0.152
0.28
0.107
7.92
2.43
0.064
13.6
0.038
15.7
5.47
1.39
1.05
16.0
4.23
58.0
42.8
15.1
1.2
0.96
0.91
0.82
0.74
0.54
0.24
0.31
0.20
0.12
0.056
25-75
40-60
40-80
0.394
0.234
0.457
7.21
0.326 25-50
0.444 25-50
0.957 25-50
9.87 25-50
0.156 o- 45
0.220 o-45
0.758 o-45
0.488 o- 45
0.0819 25-50
0.296 25-50
0.375 25-50
0.77 25-50
11.2 25-50
0.0789 25-50
0.267 25-50
0.316 25-50
0.671 25-50
12.2 25-50
24.5 25-50
41.5
0.0661 25-50
0.227 25-50
0.296 25-50
0.632 25-50
13.0 25-50
0.0592 25-50
0.217 25-50
0.276 25-50
0.533 25-50
14.7 25-50
0.110 O-50
0.133 O-50
0.686 o- 50
0.365 O-50
0.0628 O-50
0.0885 O-50
0.581 O-50
0.30 O-50
0.0781 S-60
0.708 5-60
0.864 5-60
3.99 S-60
0.566 5-60
0.405 5-60
1.81 5-60
10.4 5-60
54.5 5-60
31.1 S-60
33.8 5-60
1.52 5-60
1.05
0.698
2.03
2.15
4.91
2.27
0.683
0.0855
0.096
0.084
0.078
1.24
3.52
34.9
230
6.43
1.24
7.43
180
37.3
20.0
282
1.9
8.97
473
85.6
55.5
2.23
14.9
2330
444
272
4.79
0.908
7.88
8.63
1.41
0.56
19.2
23.8
17.2
128
292
85.8
324
489
942
543
340
680
1680
7790
49.8
45.6
46.5
37
37
20
20
20
20
20
20
54
54
54
54
54
54
54
54
54
54
78
78
78
78
78
78
78
27.6 21.3 6.3
34.3 30.1 4.2
29.7 28.5 1.2
21.8 30.6 - 8.8
20.3 17.3 2.9
21.8 17.4 4.4
19.4 21.3 - 1.9
21.3 25.0 - 3.7
35
35
35
35
25
25
25
25
28.5 17.6 10.9
30.1 26.0 4.1
41.5 35.6 5.9
36.0 33.9 2.1
29.3 38.5 - 9.2
29.3 21.8 7.5
33.1 28.9 4.2
47.7 43.5 4.2
40.6 38.5 2.1
33.9 44.8 - 10.9
41.0 51.5 - 10.5
30.9 21.8 9.1
34.3 29.3 5.0
51.5 49.0 2.5
43.9 43.1 0.8
37.7 50.2 - 12.5
32.2 23.0 9.2
36.8 31.8 5.0
57.8 53.2 4.6
50.2 45.6 4.6
43.9 56.1 ~ 12.2
35
35
35
35
35
35
35
35
35
35
35
3s
35
35
35
35
35
35
35
35
35
35
26.8 23.7 3.1
29.2 29.4 - 0.2
33.7 33.3 0.4
36.3 36.0 0.3
29.5 18.0 11.5
29.5 25.7 3.8
42.2 41.3 0.9
41.6 42.2 - 0.6
25
25
25
25
25
2s
25
25
35.2 24.7 10.5
41.0 38.9 2.1
43.1 40.2 2.9
36.4 36.8 - 0.4
44.8 37.3 7.5
46.9 39.4 7.5
45.6 44.0 1.6
41.9 49.4 - 7.5
36.0 45.2 - 9.2
40.2 48.2 - 8.0
43.5 52.3 - 8.8
56.9 60.3 - 3.4
16
16
16
16
16
16
16
16
16
16
16
16
References page VI - 568
VI 1554 PERMEABILITY AND DIFFUSION DATA
Pol ymer Permeant T P (x1013) D (~10~)
Temp.
s (x106) range PO (x10) EP ED Es Refs.
Poly(chloroprene) (Neoprene C)
Ar
co2
(Neoprene W)
(Neoprene)
Poly(dimethylbutadiene)
(Methyl rubber)
CH4
HZ0
NH?
SO2
H20
HzOf
He
H2
D2
02
N2
He
HZ
N2
02
co2
CH4
Poly(ethylene-co-propylene-co-
diene)
H20
Poly(isobutene-co-isoprene) 9812
(Butyl rubber)
H2Of
He
HI
N2
02
co2
C2H2
CJH8
Hz0
Poly(isoprene), amorphous
(Natural rubber)
He
02
Ar
co2
c o
Poly(isoprene)
WLVW
(Vulcanized punfied gutta perch?.)
N2
CHI
CzHa
C3H4
C3Hb
C,HE
SF6
CzHz
n-Cd I O
n-CsH12
Hz0
HI
N2
co2
H20
Poly(isoprene-co-acllonitrile) 74126 He
H2
N2
02
co2
Poly(isoprene-co-methacrylonitrile)
74126
H2
N2
02
co2
Poly(isoprene) hydrochloride
(Pliofilm FM-I)
He
N2
02
co2
H2S
CzH40
CH jBr
25
25
25
25
25
25
25
25
25
23
23
35
35
35
35
35
25
25
25
25
25
25
23
23
25
25
25
25
25
25
50
37.5
25
25
25
25
25
25
25
25
25
25
25
25
25
50
50
25
25
:50
25
. 50
25
50
25
50
25
25
25
25
25
25
25
25
25
25
20
30
30
30
30
0
60
10.2
2.96
0.88
2.84
19.2
2.41
683
837
5130
15.0
20.7
20.0
6.62
2.23
10.8
12.8
0.355
1.58
5.63
0.622
157
367
6.32
5.43
0.243
0.977
3.89
1.26
10.3
82.5
17.6
17.2
115
11.8
7.11
22.1
415
154
126
2.70
74.5
526
1240
1720
10.9
106
4.64
56.3
1.62
23.7
26.7
281
379
5.85
5.58
0.136
0.642
3.26
10.2
0.449
1.77
10.7
14.3
0.113
40.5
0.91
0.075
548
25.5
3.8
0.38
0.24
0.16
0.23
60.4
9.33
10.7
1.01
0.533
3.9
0.079
0.14
0.063
5.93
1.52
0.045
0.081
0.0578
0.0203
0.0224
21.6
1.73
1.36
1.25
1.35
1.17
0.89
0.40
0.50
0.31
0.21
0.115
0.467
5.0
21
0.7
5.3
0.5
4.2
0.47
4.1
8.01
2.47
0.045
0.092
0.031
3.55
0.123
0.24
0.091
0.286
0.740
0.355
86.8
176
0.0247
0.221
0.188
0.656
0.419
0.326
0.454
1.13
8.98
0.109
0.355
0.543
1.20
6.71
6.22
46.4
1.02
1.26
9.20
0.874
0.608
2.55
83.5
49.7
60.0
2.35
16.0
0.227
0.493
0.661
1.05
0.326
0.562
5.52
6.81
0.073 I
0.227
0.306
0.701
10.6
0.286
0.365
0.740
11.8
23-60
23-60
25-50
25-50
25-50
25-50
25-50
25-50
23-60
23-60
25-50
25-50
25-50
25-50
25-50
25-50
20-50
20-50
20-50
20-50
20-50
20-50
20-50
20-50
20-50
20-50
25-50
15-40
50-70
15-40
50-70
15-40
50-70
15-40
50-70
25-50
25-50
25-50
25-50
25-50
25-50
Z-50
25-50
25-50
lo-60
30-60
8. 80
54.7
224
2499
4.04 x 10
2.4 x lo6
6.84 x lo*
745000
2.34
12.8
349
68.3
71.9
407
2.38
9.15
0.755
3.16
12.2
6.08
3.76
17.7
1.34
4.62
17.0
296
0.582
2560
0.197
1560
0.316
217
0.0671
2.17
26.2
13500
1330
4690
8.80
1090
209
273
1.43
103000
35.6
83.3
49.2
27.6
33.5
55.7
47.3
46.9
62.3
52.8
31.8
36.4
52.3
44.8
41.5
48.6
29.3
32.7
21.8
31.0
35.6
31.0
22.6
28.9
23.0
35.6
30.6
42.3
23.0
49.8
21.8
52.3
25.5
39.3
14.7
31.8
38.1
62.8
53.2
52.3
33.9
53.6
46.1
42.3
36.0
73.1
27.6 6 . 3 33236
39.4 2.1 33.36
43.1 1.3 33,36
36
45.2 - 9.6 33,36
33
31
33
33
52
52
90
90
90
90
90
35,58
31.4 2.1 35
51.9 3.8 35
46.5 0.8 35
53.6 - 6 . 7 35,33
58
52
52
24.3 7.5 35
33.9 2.5 35
50.7 1.6 35
49.8 - 5. 0 35
50.2 - 8. 7 35
53.6 - 5.0 35
35
12
19.7 16
33.5 - 4.2 16.35
33.1 - 0.4 16
34.3 - 12.5 16.35
31.0 0 16
33.5 2.1 16,35
36.4 - 5. 4 16
42.7 16
37.7 - 15.1 16
42.1 - 13.8 16
46.5 - 23.5 16,35
50.2 - 14.6 16
39.8 -9.2 35
58
58
31,98
31.8 13.0 34
26.4 -0.4 34
38.5 13.8 34
26.8 - 2. 1 34
41.0 13.8 34
28.1 0.4 34
41.0 0.8 34
28.1 1 0 . 5 34
31
20.5 11.3 35
31.0 7.1 35
60.7 2.1 35
50.7 2.5 35
60.3 - 8.0 35
28.9 5.0 35
48.6 5.0 35
40.2 5.9 35
51.1 -8.8 35
10
37
37
37.43
8
37
37
Poly(esters), Polykarbonates) VI 1555
Pol ymer Permeant T D (x106)
Temp.
s (x106) tXge PO (x10) EP ED Es Refs.
(Pliofilm NO)
Poly(methyl-l-pentenylene)
Poly(Zmethyl-l,3-pentadiene-u-4.
methyl-1,3-pentadiene 8505
1.8. POLY(XYLYLENES)
Poly@-2,6-dichloroxylylene)
Poly(chloro-p-xylylene)
(parylene C)
1. 9. POLY(OXIDES)
Poly(oxymethylene)
grafted with 2.8% butadiene
(Hostaform)
Poly(oxy-2,6-dimethyl-1.4.
phenylene)
Poly(phenylene oxide) brominated
0% Brg
36% Br
91% Br
106% Br
Hz0
He
H2
N2
02
co2
H2
N2
02
CO2
Hz0
He
H2
N2
02
CO2
co2
Hz0
co2
Hz0
02
c o2
H>O
H e
H2
N2
02
co2
Hz0
co2
CHA
co2
CHI
co2
CHI
co2
CHI
1.10. POLY(ESTERS), POLY(CARRONATES)
Poly(oxybutyleneoxyterephthaloyl),
amorphous
He
Ne
Ar
co2
Poly(oxycarbonyloxy-
1,4-phenyleneisopropylidene-
IA-phenylene) (Lexan)
He
H2
Ne
Al
02
co2
SF6
H>O
N2
Poly(oxyethyleneoxyisophthaloy1)
Poly(oxyethyleneoxyterephthaloyl),
amorphous
crystallinity 40%
02
He
Ar
N2
02
CH4
co2
He
N2
2s
25
25
2s
2 5
25
25
2 5
2 5
2 5
2 5
2 5
25
25
2 5
2 5
2 5
2 5
25
25
23
23
2 3
25
2 5
2 5
25
25
25
3 5
3 5
35
3 5
3 5
3 5
3 5
35
2 5
2 5
25
2 5
2 5
2 5
1 0 0
2 5
1 7 5
2 5
1 7 5
25
25
1 7 5
25
25
1 7 5
30
2 5
25
25
25
2 5
2 5
2 5
90
25
90
75.8
1 0 2
5.87
24.2
69.5
32.0
2.06
7.52
33.8
4.97
1 . 4 1
0.717
0.00626
0.0358
0.105
1 . 3 5
683
3.83
998
0.057
1 . 2 8
422
58.5
84.6
2.86
1 1 . 9
56.8
3045
3 8
2.2
3 8
2.0
5 1
2.6
8 1
4.7
1 . 2 8
0.237
0.078
0.217
7.5
9.0
1 0 . 9
0.6
32.3
1 . 0 5
22.5
6.0
4.88 x 10
0.075
1050
0.225
1 4 . 3
-6
0.012
2.37
0.0217
0.0108
0.0444
0.0070
0.227
1 . 0 9
6. 3
0.00513
4100
0.55
1 . 0 1
684
0.30
0.555
0.00594
0.103
0.0675
0.00178
0.00351
0.00164
0.014
0.027
0.044
0.070
0.0601
0.17
0.17
0.021
0.16
0.016
0.20
0.02
0.30
0.033
0.13
0.022
o.co4o
0.0062
0.64
0.015
0.53
0.021
1 . 0 7
2.40
0.0102
0.691
1.36
84.6
0.391
0.670
0.0863
0.567
4.62
9.64
2530
8.69
1430
94.6
1797
21.7
1 0 . 6
23.7
1 1 . 8
25.4
1 3 . 1
27.2
14.3
0.888
0.997
1 . 9 7
3.46
1 . 3 8
4.15
6.12
5.03
1 2 4
1.0 x 10-7 4.94
0.68
0.0029 0 . 4 1
3. 1 0.077
0.0024 0.79
0.0019 0.55
0.0045 0.98
0.00030 2. 3
0.00083 28.0
2.0 0.052
0.0013 0.45
25-60
25-50
25-50
25-50
25-50
30-80
lo-80
10-80
10-80
lo-80
10-80
25- 1 0 0
25-100
25-100
25-100
23-60
25-125
25-175
25-125
125-175
O-125
125-175
25-100
25-125
125-175
0- 125
125-175
20-60
20-60
20-60
20-60
20-60
20-60
20-80
X0-130
20-80
80-130
5.08
336
59.6
41.9
0.0129
0.462
0.129
0.095
0.0126
0.129
0.0248
0.0816
0.00544
70.2
0.00252
0.0919
0.00365
29.7
46.9
39.4
34.8
1 9 . 5
21.7
24.1
31.3
29.5
27.8
31.4
1 3 . 0
2 5 . 1
6.3
14.1
20.1
22.6
22.6
54.4
1 9 . 3
31.0
1 5 . 9
0.0118 53.6
3.21 x 10 125.6
0.00559 25.1
1 . 0 9 41.9
0.0199 21.3
o.OiI319 28.9
0.00025 26.4
0.227 37.7
0.00021 24.7
0.0232 27.6
0.00308 1 9 . 7
0.0266 25.5
0.00275 32.7
20.6 59.0
58.6
46.5 0.4
41.0 - 1.6
36.0 - 16.5
14.6 7. 1
1 8 . 5 5.6
30.1 1. 2
32.5 - 3. 0
51.3 - 23.4
49.0
38.5
20.9 1. 7
2 5 . 1 - 2.5
32.2 - 12.9
37.7 - 21. 8
83.7 - 30.1
26.0
1 9 . 2 - 1.1
48.2 - 15.1
47.7 - 23.9
48.6 - 14.7
51.1 - 27.2
52.3 - 28.5
2 0 . 1 0.9
27.6 0.9
44.0 - 18.4
58.6 0
39
4 1
4 1
4 1
4 1
4 1
35
3 5
3 5
3 5
48
84
84
84
84
84
38
38
38
38
73
73
73
41
41
4 1
4 1
4 1
40
1 0 0
1 0 0
1 0 0
1 0 0
100
1 0 0
loo
100
44
44
44
44
22
22
22
22
22
22
22
22
22
22
22
22
22
60
17,18
17,18
17,18
1 7 . 1 8
17,18
17,18
17,18
17,18
17.18
17,1x
References page VI - 568
VI 1556 PERMEABILITY AND DIFFUSION DATA
Polymer Pemleant T P (x10) I.3 (x106)
Temp.
s (x106) r a ng e Pg ( x10 ) EP ED Es Rds.
(Myl= A)
(Hostaphan)
Poly(ethylene terephthalate)
Poly(ethylene terephthalate-co-
isophthalate) 50150
Poly(ethylene terephthalate-w-2,6-
naphthalene dicarboxylate) 50/50
Poly(oxyterephthaloyloxymethylene-
1,4-cyclohexylenemethylene)
Poly(tetmmethylene adipate) diol
molecular weight 1050
densi t y 1.2Ogkm
mol ecul ar wei ght 1510
densi t y 1.19g/cm3
molecular weight 2100
densi t y 1.18gkm
Poly(carbonate) (Lexan)
Poly(carbonate)
Poly(carbonate-sulfone)
(diphenyl carbonate + l,lO-
decanediol)
(diphenyl carbonate + 1,4-bis(3-
hydroxypropylsulfonyl)butane
Poly(tetrabutylene carbonate)
Poly(tetrachlorine carbonate)
Poly(tetramethylene hexafluoro
car bonat e)
Poly(tetmmethylene carbonate)
Poly(tetmmethylene carbonate) diol
mol ecul ar wei ght 1150
density 1.29 g/cm
CH*
co2
HZ
D2
N2
02
CH,Br
Cd40
Hz0
HIS
NHs
N2
02
02
HZ0
Hz0
02
02
02
02
co2
c o
N2
CH4
Hz0
02
co2
c o
N2
CHI
HZ0
02
co2
c o
N2
Cl&
H20
HZ0
co2
CH4
co2
co2
co2
CH*
co2
CH4
co2
CH4
co2
CH4
02
co2
c o
N2
CH4
Hz0
25
90
25
90
25
90
25
25
25
25
25
2 5
25
20
20
20
23
30
23
25
30
30
30
3 5
3 5
3 5
35
35
23
35
35
3 5
3 5
3 5
2 3
3 5
3 5
3 5
35
35
23
25
35
35
25
25
35
35
3 5
35
3 5
3 5
35
3 5
3 5
35
3 5
35
35
23
0. 0257
0. 31
0. 00257
0. 091
0. 118
1.0
0. 448
0. 073
0. 0038
0. 030
0. 013
0. 084
98
0. 14
1 . 1
0. 0034
0. 014
0. 042
1 4
1 3
0. 019
0. 03 1
0. 19
0. 0975
0. 525
0. 0278
0. 563
4. 8
0. 195
0. 113
0. 383
5925
1. 5
1 5
0. 9
0. 6
1. 2
7425
1050
4. 5
0. 20
9. 5
0. 035
3. 17
0. 0945
5. 00
0. 168
82. 5
3. 45
13. 2
0. 60
0. 105
0. 675
0. 0525
0. 0308
0. 0375
825
0. 0035
o.cmo13
o. m57
o.OOLw71
0. 0065
0. 0035
0. 0048
0. 014
0. 076
0. 027
0. 039
0. 027
0. 041
0. 16
0. 057
0. 074
0. 053
0. 058
0. 055
0. 39
0. 13
0. 11
0. 22
0. 17
0. 078
0. 0209
0. 0046
0. 0166
0. 0013
0. 0253
0. 0022
0. 24
0. 0348
0. 061
0. 008 1
0. 029
0. 012
0. 010
0. 019
0. 008
0. 012
0. 72
2. 0
20. 0
195
0. 62
0. 49
0. 61
1. 3
0. 1275
1.95
0. 07125
0. 1275
9525
0. 3525
8. 25
0. 2625
0. 2100
0.66OQ
10875
0. 375
6. 53
0. 750
0. 270
0. 750
9525
14. 5
4. 0
19. 1
1. 24
19. 6
7. 61
32. 6
9. 58
21. 5
7. 37
0. 368
5. 40
0. 525
0. 165
0. 473
7223
20- 80
80- 130
20- 80
80- 130
20- 80
80- 130
0. 0122
0. 744
osm719
63. 2
0. 000197
22. 2
- 25- 80 0. 000945
- 25- 80 0. 000026
25- 90 0. 0163
25- 90 0. 000534
10-M 0. 00032
10-40 0. 00012
32. 2 46. 1
44. 4 50. 7
36. 8 52. 3
61. 5 67. 0
18. 4 50. 2
51. 1 64. 5
30. 8
16. 8
34. 8
21. 7
2. 9
0.1
- 13. 0 17. 18
0 17,18
- 22. 2 17,18
- 12. 9 17,18
- 31. 4 17. 18
- 19. 7 17.18
57
57
37
3 1
31
3 7
2 1
5
5
6 1
72
60
7 3
98
60
60
60
76
76
76
76
76
76
76
76
76
7 6
76
76
76
76
76
76
76
76
98
100
1 0 0
95
95
100
1 0 0
1 0 0
100
1 0 0
100
100
1 0 0
76
76
7 6
7 6
16
76
Poly(esters), Poly(carbonates)
Pol ymer Permeant T P (X10S) D (~10~)
Temp.
s (x 106) range PLJ(xlO) EP ED Es RePs.
molecular weight 1570
density 1.27 g/cm
molecular weight 3070
density 1.21 g/cm3
Poly(hexamethylene carbonate) diol
molecular weight 1040
density 1.29 g/cm 3
molecular weight 1320
density I .25 g/cm 3
molecular weight 1500
density 1.20 g/cm
molecular weight 2380
densi t y 1.18gkm
mol ecul ar wei ght 2860
densi t y 1.18gkm
Poly(pentamethylene-hexamethylene
carbonate) diol
mol ecul ar wei ght 2170
densi t y 1.18gkm
Poly(dipropylene glycol carbonate)
di ol
molecular weight 3010
densi t y 1.19g/cm3
Poly(dipropylene
glycol)poly(propylene glycol
carbonate) diol
mol ecul ar wei ght 2020
densi t y 1.16gkm
Poly(triethylene glycol carbonate)
di ol
molecular weight 2580
densi t y 1.20gkm
02
co2
co
N2
CH4
HZ0
02
CO2
co
N2
CHI
Hz0
02
co2
co
N2
CH4
Hz0
02
co2
co
N2
CH4
Hz0
02
co2
co
N2
CH4
H20
02
co2
co
N2
CH4
Hz0
02
co2
co
N2
CH4
HK
02
co2
co
N2
CH4
Hz0
02
co2
co
N2
CH4
HK
02
co2
co
N2
CH4
Hz0
co2
co
N2
CHI
Hz0
3 5
3 5
3 5
3 5
3 5
2 3
3 5
3 5
3 5
3 5
3 5
2 3
3 5
3 5
3 5
3 5
3 5
2 3
3 5
3 5
3 5
3 5
3 5
2 3
3 5
3 5
3 5
3 5
3 5
2 3
3 5
3 5
3 5
3 5
3 5
2 3
3 5
3 5
3 5
3 5
3 5
2 3
3 5
3 5
3 5
3 5
3 5
i 23
. 35
3 5
3 5
3 5
3 5
2 3
3 5
3 5
3 5
3 5
3 5
2 3
3 5
3 5
3 5
3 5
3 5
2 3
0. 143
1.35
0. 105
0. 0660
0. 105
2100
0. 308
2. 48
0. 143
0.0900
0. 0975
1875
0. 188
1.05
0. 0450
0. 0450
0. 0375
825
0. 225
2. 03
0. 150
0. 0825
0. 0675
1050
0. 623
2. 85
0. 225
0. 173
0. 165
1575
1.65
11.3
0. 750
0. 570
0. 825
3450
2. 18
9. 00
0. 975
0. 900
1. 20
4200
0. 825
7. 50
0. 443
0. 278
0. 480
2475
0. 398
2. 70
0. 135
0. 0825
0. 105
2025
0. 975
7. 28
0. 585
0. 278
0. 570
3000
0. 263
3. 15
0. 143
0. 0825
0. 150
9750
0. 054
0. 017
0. 033
0. 050
0. 019
0. 020
0. 072
0. 026
0. 043
0. 026
0. 015
0. 030
0. 022
0. 022
0. 015
0. 017
O.Oal
0. 013
0. 026
0. 029
0. 015
0. 037
0. 012
0. 015
0. 12
0. 038
0. 056
0. 076
0. 019
0. 017
0. 19
0. 21
0. 14
0. 17
0. 11
0. 070
0. 22
0. 27
0. 23
0. 24
0. 12
0. 076
0. 079
0. 089
0. 074
0. 079
0. 038
0. 034
0. 081
0. 035
0. 033
0. 040
0. 021
0. 019
0. 23
0. 061
0. 16
0. 13
0. 048
0. 020
0. 079
0. 050
0. 063
0. 074
0. 037
0. 034
0. 263
7. 50
0. 315
0. 105
0. 540
10575
0. 473
9. 75
0. 345
0. 345
0. 675
6143
0. 825
6. 98
0. 300
0. 263
0. 825
6825
0. 825
7. 05
0. 375
0. 225
0. 563
7230
0. 525
7. 50
0. 450
0. 225
0.900
923
0. 825
5. 33
0. 525
0. 338
0. 750
4973
0. 975
3. 38
0. 450
0. 360
0. 975
5595
1.05
8. 25
0. 600
0. 353
1.28
7215
0. 488
7. 50
0. 405
0. 210
0. 495
10800
0. 420
12.0
0. 375
0. 218
1. 20
15000
0. 330
6. 30
0. 225
0. 113
0. 405
25500
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
7 6
References page VI - 568
VI / 558 PERMEABILITY AND DIFFUSION DATA
Pol ymer Permeant T P (x1013) D (x106)
Temp.
s (x106) IXgCZ PO (x10) EP ED Es Refs.
Poly(hexamethy1en.e carbonate
pentametbylene ester) dial
molecular weight 2470
density 1.17g/cm3
1.11. POLY(SILOXANES)
Poly(oxydimetbylsilylene) with 10%
filler Scantocel cs,
vulcanized silicon rubber
Poly(methyl ethyl siloxane)
Poly(methy1 propyl siloxane)
Poly(methy1 octyl siloxane)
Poly(hiflouropropy1 siloxane)
Poly(triAouropropy1 methyl siloxane)
Poly(pheny1 methyl siloxane)
Poly(dimethy1 silmethylene)
Poly(silethylene siloxane)
Poly(silhexylene siloxane)
02
co2
co
N2
CH4
Hz0
He
NC?
Al
Kr
Xe
H2
N2
02
c o 2
C3H8
n-Cd 10
HsO
H2
He
N2
02
co2
CHI
CzH4
CzH6
CzHa
H2S
NH3
He
02
co2
CHa
He
02
co2
CHa
H2
He
N2
02
co2
CHa
CzH4
CzHrc
CxHs
H2S
NH3
Hz0
He
02
co2
CH4
He
02
c o2
CHa
He
02
co2
CH4
He
02
co2
CH4
He
02
co2
CHI
3 5
3 5
35
35
3 5
2 3
0
0
0
0
0
0
0
0
2 5
2 5
0
3 5
3 5
35
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
35
35
3 5
3 5
3 5
3 5
3 5
3 5
3 5
35
3 5
3 5
35
3 5
3 5
3 5
3 5
3 5
3 5
. 25
3 5
3 5
3 5
3 5
3 5
3 5
3 5
35
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
35
35
3 5
3 5
1 . 5 0
20.3
0.750
0.600
1 . 2 8
655
1 7 5
1 4 3
413
765
1910
348
1 7 0
367
2430
319
14600
32300
705
420
353
695
3489
1 0 0 2
2738
3150
6338
6413
9015
1 7 2
234
1130
356
191
287
1 7 2 7
428
233
99.8
65.3
1 4 4
695
236
608
720
1 4 9 3
1470
2213
1 6 0 5 0
185
1 6 3
1 0 4 1
151
25.5
24.0
1 7 9
27.0
73.5
75.8
412
97.5
204
296
1412
448
1 4 6
1 9 9
980
296
0.24
0.16
0.24
0.18
0.14
0.11
41
1 6 . 1
1 2 . 2
8.0
4.8
47.0
8. 5
1 2 . 0
1 2 . 0
2.4
0.630
1 2 . 8
0.315
0.330
0.900
59250
0.424
0.888
3.36
9.67
39.4
0.73
2.00
3.06
2.4
608
- 40-25
-40-o
-40-o
-40-o
-40-o
- 40-25
- 40-25
- 40-25
O-70
-40-o
35-65
0.0946
0.0543
0.0606
0.0134
0.00781
0.145
0.0197
0.0169
0.00401
0.0303
1 4 . 3 8.0
1 3 . 5 8.4
9.8 1 0 . 3
6.5 1 2 . 2
3.2 1 4 . 0
1 3 . 7 9. 3
1 0 . 8 1 1 . 3
8. 7 9.0
6. 3 1 1 . 3
1 4 . 2
6.3
5. 1
- 0.5
- 5. 7
- 10.8
4.4
- 0.5
- 0.3
- 5.0
76
7 6
76
76
76
76
2.41
2
2
2
2
2,41
2.41
2,41
4 1
46
2
3
82
82,94
82
82,94
82,94
82.94
8 2
82
8 2
8 2
8 2
94
94
94
94
94
94
94
94
82
X2,94
82
82.94
82.94
82,94
8 2
8 2
8 2
8 2
82
9 8
94
94
94
94
94
94
9 4
94
94
94
9 4
9 4
94
94
9 4
9 4
9 4
9 4
9 4
9 4
Poly(amides), Polytimides) VI / 559
Po l y me r Permeant T P (403) D (~10~)
Temp.
s (x106) tXge Pa(xlO) EP ED Es
Refs.
Poly(siloctylene siloxane)
Poly(meta-silphenylene siloxane)
Poly(pa-silphenylene siloxane)
1.12. POLY(AMIDES), POLY(IMIDES)
Poly(iminoadipoyliminohexa-
met hyl ene) ( Nyl on 66)
undrawn
drawn
Poly(imino-1-oxohexamethylene)
(Nyl on 6)
Poly(imino-1-oxoundecamethylene)
( Nyl on I I )
Poly(5,7-dihydro-1,3,5,7-tetraoxo-
benzo[1,2-c:4,5-cldipyrrole-
2,6[1H,3H]-diyl-1,4-phenylene-
oxy-1,4-phenylene) (Kapton)
Poly(2,2-his@-trimellitoxyphenyl)
propane dianhydride-co-3.3 -
dimethyl-benzidine)
Poly(2,2-his@-trimellitoxyphenyl)
propane d&hydride-co-/l,4 -
diaminodiphenyl ether)
Poly(2,2-his@-trimellitoxyphenyl)
pr opane dianhydride-w-4,4-
di ami nodi phenyl met hyl ene)
Poly(2,2-bis(p-trimellitoxyphenyl)
pr opane di anhydr i de- co- benzi di ne)
Poly(2,2-his@-himellitoxyphenyl)
propane dianhydride-w-3.3 ,4,4-
tetraaminodiphenyl ether)
Poly(3,3,4,4-benzophenone
tetracarboxylic dianhydride-co-
m,m-diaminodiphenyl met hyl ene)
Poly(3,3,4,4-benzophenone
tetracarboxylic dianhydride-co-m,p-
diaminodiphenyl methylene)
Poly(3,3,4,4-benzophenone
teaacarboxylic dianhydride-co-pp-
di ami nodi phenyl met hyl ene)
Poly(3,3,4,4-benzophenone
tetmcarboxylic dimhydride-co-pg -
diaminodiphenyl ether)
He
02
co2
CH4
He
02
co2
CH4
He
N2
02
co2
Ch
Czb
CA
C3Hs
HIS
NH,
co2
co2
co2
co2
He
N2
02
co2
Hz0
HIS
NH,
CHsBr
He
H2
Ne
AI
co2
02
Hz0
HZ
N2
02
02
co2
Hz0
02
Hz0
02
co2
Hz0
02
co2
H20
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
5
2 5
5
2 5
2 0
3 0
3 0
2 0
2 5
3 0
2 0
6 0
3 0
3 0
3 0
4 0
4 0
1 6 0
3 0
3 0
3 0
3 0
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
1 3 1
1 7 8
899
270
6 3 . 0
5 5 . 5
389
7 9 . 5
2 4 . 5
2. 40
8. 21
3 8 . 3
7. 65
15.0
11.3
19.5
1 4 1
223
0. 018
0. 052
0. 023
0. 071
0. 398
0. 00713
0. 0285
0. 066
0. 139
0. 255
0. 878
0. 63
1. 46
1.34
0. 26
0. 143
0. 754
4. 85
0. 0384
0. 304
3. 62
0. 0363
0. 233
3. 49
0. 0343
0. 220
0. 542
0. 00485
0. 0344
5. 52
0. 0439
0. 326
0. 0235
0. 0340
2 9 1
0. 0578
573
0. 140
0. 324
9 8 4
0. 0927
0. 357
719
94
94
9 4
9 4
9 4
9 4
9 4
9 4
82. 94
8 2
82. 94
82. 94
82. 94
8 2
8 2
8 2
8 2
8 2
0. 00018 9. 97
O.OQO83 6. 32
O.OQO18 12.8
O.OQO48 14.8
o.OQO47
3 . 5
0. 984
0. 437
0. 0372
0. 0191
0. 168
0. 0018
0. 396
0. 00222
0. 0106
0. 329
0. 00206
0. 00878
0. 289
0. 00187
0. 00736
0. 0536
0. 000327
0. 00167
0. 402
0. 00223
0. 0102
5 5 . 7
0. 0424
0. 136
0. 0592
0. 385
3. 94
21400
1.22
1.73
2. 87
1.10
1.76
2. 65
1.21
1.83
2. 99
1.01
1.49
2. 06
1.37
2. 32
3. 19
O - 9 0
O - 9 0
O - 9 0
O - 8 0
6 0 - 8 0
1 0 - 5 0
2 0 - 6 0
2 0 - 6 0
40-60
40-60
135-240
3 0 - 8 0
1.05
0. 975
1.2
2400
0. 0827
0. 342
0. 30
1.38
0. 338
0. 00028
O.OOL26
3 6 . 4
4 6 . 9
4 3 . 5
4 0 . 6
5 8 . 2
5 3 . 2
2 7 . 6
3 1 . 4
3 5 . 2
4 1 . 9
3 3 . 9
18.4
- I.28
1 0
3 7
3 7
3 7
2 0
8
5
3 7
2 2 . 2 5 . 4 1
2 9 . 7 1.7 1
3 2 . 7 2.5 1
4 4 . 8 - 2.9 I
5 1 . 9 - 18.0 I
3 1 . 0 - 12.6 6 7
4 2 . 0 - 43.2 6 8
104
1 0 4
1 0 4
1 0 4
1 0 4
104
104
1 0 4
104
1 0 4
1 0 4
1 0 4
1 0 4
1 0 4
1 0 4
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
References page VI - 568
VI/560
Polymer
PERMEABILITY AND DIFFUSION DATA
Temp.
Pemwant T P (x103) D (~10~) s (x106) range PcJ (x10) EP ED Es Re f s .
Poly(3,3,4,4-benzopbenone
tetracarboxylic dianhydride-co-
benzi di ne)
Poly(3,3,4,4-benzophenone
tetracarbaxylic dianhytide-co-p-
phenylenediamine)
Poly(3,3,4,4-benrophenone
tetmcarboxylic dianhydride-co-m-
*phenylenediamine)
Poly(3,3,4,4-benzophenone
tetracarboxylic dianhydride-co-
diaminodiphenyl sulfide)
Poly(3,3,4,4-benzophenone
tetracarboxylic dianhydride-co-
m,m-diaminobenzophenone)
Poly(3,3.4,4-benzophenone
tetracarboxylic dianhytide-co-m.p -
diaminobenzophenone)
Poly(3,3,4,4-benzophenone
tetracarboxylic dianhydride-co-pp-
diaminobenzophettone)
Poly(3,3,4,4-benzophenone
tetmcarboxylic dianhydtide-co-pp-
diaminostilbene)
Poly(pyromellitic dianhydride-co-
benzi di ne)
Poly(pyromellitic dianhydride -co-
m,m-diaminobenzophenone)
Poly(pyromellitic dianhydride -co-
p,p-diaminobenzophenone)
Poly(pyromellitic dianhydtide -co-
p,p-diatnincdiphenyl ether)
Poly(pyromellitic dianhydride -co-
p,p-diamincdiphenyl sulfide)
Poly(pyromellitic dianhydride -co-
pp-diaminodiphenyl methylene)
1.13. POLY(URETRANES)
Poly(Z-methyl-2-
dimethylaminomethylpropylenehexa
met hyl ene dicarbamate)
(Poly(NPM-HMDI))
Poly(Z-methyl-2-
dimethylaminomethyl-1,3-
propylene-diphenylmethane-4,4-
dicarbamate)
(Poly(NPM-MDI))
Poly(uethane-sulfone)
(tolylene diisocyanate + l,lO-
decanediol)
(tolylene diisocyanate + 1,3-bis(3-
hydroxypropylsulfonyl)propane)
(tolylene diisocyanate + 1,4-bis(3-
hydroxypropylsulfonyl)butane)
1.14. POLY(SULFONES)
Poly(sulfone)
Poly(tetramethylsulfone)
02
co2
H2O
02
H20
02
co2
Hz0
02
co2
Hz0
02
CO2
HZ0
02
co2
Hz0
02
CO2
H20
02
CO2
02
CO2
H20
02
H20
02
CO2
Hz0
02
CO2
H20
02
Hz0
02
co2
H20
N2
02
N2
02
CO2
CO2
CHa
co2
en4
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
95
2 5
2 5
2 5
2 5
2 5
3 5
3 5
3 5
3 5
0. 00668
0. 0234
9 4 . 4
0. 0103
2 3 1
0. 0308
0. 0882
804
0. 0992
0. 307
787
0. 0219
0. 0807
428
0. 0450
0. 0887
5 2 1
0. 0451
0. 132
599
0. 00214
0. 00692
0. 0260
727
0. 242
1.36
1882
0. 336
1882
0. 368
1.32
1582
0. 53975
0. 0645
0. 0105
0. 0675
0. 23
0. 0038
4. 20
0. 19
15.8
0. 71
0. 020 2 0 . 7
0. 0034 5. 60
0. 064 2 4 . 7
0. 0079 9. 14
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
1 0 5
9 1
9 1
9 1
9 1
95
95
9 5
1 0 0
100
1 0 0
1 0 0
Permeant T P (x1013)
Cellulose and Derivatives VI 1561
Temp.
s (x106) range Po(xl0) EP ED Es Refs.
Poly(dimethylsulfone) co2
CH4
Polyfteh-amethylhexafluorosulfone) co2
CHa
1.15. POLY(ARYL ETHER ETHER KETONE)
Poly(ary1 &her ether ketone) He
02
CO2
semicrystalline (30%) H20
1.16. CELLULOSE AND DERIVATIVES
Cellulose hydrate HeC
(Celloph&x)
H2
N2C
02c
co*<
SO*
HZS
H2S
NHs
H20
H2h
N2h
h
:&I~
H2
N2
02
CO*
H2d
Nzd
02d
CO/
NHzd
SO*
H2Sd
Cellulose acetate He
Hz
N2
02
c o 2
H20
H20
HIS
HzS
CHI
C*H40
CH3Br
Cellulose acetobutyrate
02
Cellulose nitrate He
H2
N2
02
Ar
co2
so2
NH,
Hz0
35
35
25
55
75
25
55
75
25
55
75
5
20
35
40
50
60
65
80
95
20
25
25
25
25
25
25
45
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
20
c 20
35
- 30
35
30
35
30
35
25
25
30
30
35
30
30
34
25
20
25
25
25
25
25
25
25
1.58
0.0525
54
2.25
0.0094 16.8 100
0.0010 5.09 100
0.14 39.5 100
0.016 14.6 100
5.24
9.90
14.0
0.41
0.82
1.21
2.03
3.40
4.54
0.000375
0.00472
0.0024
0.0016
0.00353
0.00129
0.0086
0.0045
0.0118
18900
0.012
0.00507
0.00536
0.00974
0.0244
0.00559
0.00665
0.0539
0.0598
0.0138
0.0087
0.192
133
28.4
0.425
10.2
2.63
11.2
0.21
0.173
0.585
0.788
17.3
4.47
4130
5500
2.63
4.58
0.154
30.0
4.2
3.56
5.18
1.5
0.087
1.46
0.0825
1.59
1.32
42.8
4720
25-75 17.2
25-75 18.7
25-75 13.8
0.0017
0.0053
0.0082
0.0152
0.0190
0.0356
0.0390
0.0660
0.133
41.4
1.6 x 1O-6 276 45-60 2.1 x 106 89.6
- 25-60 0.00975 27.1
- 25-60 0.00375 20.9
0.0218 18.0
lo-60 0.0053 0
lo-60 0.0053 0
0.0010 266 O-60 0.000668 20.5
0.0022 207 O-60 0.00188 21.4
0.431 1.2
0.0193 0.45
0.15 0.975
0.00753 1.05
0.0221 7.2
0.0018 7 3 . 3
0.00786 544
0.0262 18000
23.8
101
101
101
101
101
101
101
101
101
102
102
103
to2
103
102
103
103
103
10
28
28
28
28
28
28
8
28
28
28
28
28
28
28
28
28
28
28
28
28
28
28
28
10
10
87
37
87
37
87
37
a7
21
21
8
8
a7
37
37
51
9
10
9
9
9
9
9
9
9
References page VI - 568
VI / 562 PERMEABILITY AND DIFFUSION DATA
Pol ymer Permeant T P (x10) D (x106)
Temp.
s (x106) range PO (x10) EP ED Es Refs.
CZHL
CzHs
2 5
2 5
2 5
2 0
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
3 0
4 0
5 0
6 0
7 0
2 5
3 0
4 0
5 0
6 0
7 0
2 5
3 0
4 0
5 0
6 0
7 0
2 5
2 5
3 0
0. 0473 0. 00013 3 6 . 2 9
0. 0063 o.ocOo21 2 9 . 6 9
4 0 . 1
6 5 . 3
3. 32
1 1 . 0
7. 65
8 4 . 8
1 9 8
529
6700
6 . 9
10.0
10.3
12.2
14.9
20.1
2. 78
4. 73
5. 32
6. 36
9. 05
10.8
2 . 9
4. 20
6. 30
7. 43
9. 77
11.4
2. 78
5. 75
308
2.21
0. 233
0. 639
0. 403
0. 565
0. 0734
0. 146
0. 0286
0. 019
1.8
1.43
1.73
1.88
15.0
270
363
23400
3 6 . 3
9
1 0
9
9
9
9
9
9
9
9
7 9
7 9
7 9
7 9
7 9
9
7 9
7 9
7 9
7 9
7 9
9
7 9
7 9
7 9
7 9
7 9
9
9
3 7
Ethyl cellulose He
H2
N2
02
Al
co2
.
so2
NH,
(Ethocel610) CzHz,O
0. 00293 9 4 . 7
0. 00146 1 9 9
0. 00138
0. 00124
2 0 1
462
Thickness 0.29 mm.
b Thi ckness 0.84mm.
Relative humidity 0%.
d Relative humidity 100%.
Plasticizer was low-molecular-weight polytrifluorochloroethylene.
f 3.5% aqueous sodium chloride solution (simulated sea water).
8 The % bromination refers to 100 times the number of bromine atoms per repeat unit.
! Relative humidity 43%.
Relative humidity 76%.
1 Plasticized.
TABLE 2. PERMEABILTY COEFFICIENTS OF SIX DIFFERENT FLUORINATED HYDROCARBONS
THROUGH POLYMERS
Polymer
CFC13 CFzClz CF3Cl CHFCI 2 CHFzCl CFzCl-CFzCl
(24.5C) (20C) (20C) (20C) ( 20C) (ZOOC)
Poly(ethylene) low density 37.5
high density 9.75
high density, drawn 3.38
Poly(propylene) 4.88
Poly(viny1 chloride) 0.697
(Genotherm UG), unplasticized
Poly(viny1 chloride) 656 -
(Guttagena T52), plasticized
Poly(oxyethyleneoxyterephthaloy1) 0.00188
[Poly(ethylene terephthalate)]
(Hostaphan)
Poly(imino- I-oxohexamethylene) 0.0315
(Supronyl S)
Poly(imino-1-oxohexamethylene) 52.5
(Supronyl N), plasticized
152
30
4.35
137
0.00668
2.03
0.673
0.326
0.132
0.00585
1.88
0.374
0.161
0.00338
0.0016
0.795
0.106
0.0266
0.0018
0.0016
0.212
0.0683
0.0336
0.00728
0.00503
0.914
0.219
0.133
0.151
0.0247
63.8 1.88 0.359 0.185 0.054 0.0649
0.00135 0.0016 0.00135 0.00165 0.0039 0.00343
0.0111 0.00623 0.00803 0.00923 0.0075
3.6 0.254 0.00473 0.00143 0.00225 0.0133
a Ref. 61; Pincm? x cm/(cm* x s x Pa) x lo-l3
TABLE 3. PERMEABILITY COEFFICIENTS OF VARIOUS ORGANIC COMPOUNDS THROUGH
LOW-DENSITY POLY(ETHYLENE)
Permeant 0C 21.1C 54.4C 73.9c
Acetaldehyde 1.34 2.36
Acetanilide 0.008 0.16 1.34
Acetic acid 0.14 1.22 25.9 119
Permeability Coefficients of Various Organic Compounds through Low-Density Poly(ethylene) VI / 563
Permeant
Acetic anhydride
Acetone
Ally1 alcohol
Amy1 acetate
i-Amy1 alcohol
i-Amy1 propionate
n-Amy1 propionate
Aniline
.
Benzaldehyde
Benzene
Benzoic acid
Benzyl alcohol
n-Butyl acetate
n-Butyl alcohol
s-Butyl alcohol
t-Butyl alcohol
Butyraldehyde
n-Butyric acid
Camphor
Carbon tetrachloride
Chloroacetic acid
m-Chloroaniline
Chlorobenzene
Chloromaleic anhydride
p-Chlorotoluene
Cyclohexane
Decane
1,2-Dibromoethane
Dibutyl ether
Dibutyl phthalate
o-Dichlorobenzene
Diethylene glycol
Diethyl ether
Diethyl oxalate
Dipentene
Ethyl acetate
Ethyl alcohol
Ethylene glycol
Ethylene glycol monobutyl ether
Ethyl formate
Ethyl mercaptan
Ethyl propionate
Formaldehyde
Formamide
Formi c aci d
Furfuryl alcohol
Glycerin
n-Heptane
n-Heptene
n-Heptyl acetate
Heptyl alcohol
n-Hexane
Hydroquinone
Methyl acetate
Methyl alcohol
Methyl ethyl ketone
Methylcyclohexane
Nitrobenzene
Nitroethane
Nitromethane
Octadecane
Octyl alcohol
Oxalic acid
i-Pentane
n-Pentane
Phenol
0.05 1
0.55
0.063
0.22
0.32
2.67
0.57
3.42
0.078
3.9
11.8
0.67
2.61
1 7 3
0.028
0.16
5.9
0.18
0.24
0.10
3.93
1.89
0.12
240
0.12
0.63
179
0.28
119
98.7
28.0
55.0
33.6
11.6
72.3
9.04
106
83.7
295
54.2
430
0.098
0.15
17.7
23.4
81.0
1770
2.24
116
417
5400
14.2
0.04
0.05
0.02
0.35
0.075
8.02
14.8
10.6
229
39.3
8.5
3080
5.9
59
109
92.8
393
228
63.7
17700
23.6
20
22.7 1730 8300
11.8
12.4
3.7
1640
1470
480
7300
5900
1620
4.4 582
5.7
1230
10.9
60.9
0.30
11800 18.9 1 2 3
0.28
50.3
6.5
0.28
3140
5.9
0.75
798
1 4 9
3190
669
0.50
70.8 0.26
5.9
157
9.8
0.21
0.20
0.26
0.09
13.8
3931 10.2 15700
0.10 4.7 20.0
0.63
3200
0.14
1040
. .
19.1 106
106
7.1
0.39
138 3540
0.02
11800
0.14
18.9
5.5
0.48
4.95
1 0 8
1.93
1.06
0.83
0.71
0.20
0.1
1.45
10.9
128
39.3
550
0.15
0.38
39.3
25.1
1 6 5
1 1 3
0.039 10.1
0.08
1970
5900
9.4
73.9
0.09
7860
23600
47.1
18.9
38.1
0.04
106
206
0.2
References page VI - 568
VI / 564 PERMEABILITY AND DIFFUSION DATA
Permeant
n-Propyl alcohol
LPropylamine
Tetradecane
Tetradecene
Toluene
1 , 1,l -Trichloroethane
o-Xylene
p-Xyl ene
0.03 0.2 8.8 66.0
0.90 16.0 275 1260
0.67 5.7 159 393
4.7
22.7 199 2270 11300
102
P 14.2 1 0 1 1420 6530
33.7 1 9 1 1890 6410
y Ref. 62; P ing x mm/Cm* x d)
TABLE 4. PERMEABILITY COEFFICIENTS AND DIFFUSION COEFFICIENTS OF AN EQUIMOLAR MIXTURE OF
VARIOUS COMPOUNDS (1.25 M EACH) THROUGH HIGH-DENSITY POLY(ETHYLENE)
Permeant
P D (~10~)
22 C 50 C 22 C 50 C
1,1,2-Trichlorethane (0.167 g/ml)
1,2-Dichloroethane (0.124 g/ml)
Methylene chloride (0.106 g/ml)
Styrene (0.130 g/ml)
Benzene (0.098 g/ml)
Toluene (0.098 g/ml)
Naphthalene (0.160 g/ml)
2-Methyl naphthalene (0.178 g/ml)
2.4
3.3
5.3
2.7
3.1
3.3
0.73
0.49
8.8
14.6
5.9
10.0
10.0
10.2
4.4
2.7
0.0142 0.0833
0.0225 0.114
0.0889
0.0500 0.167
0.0417 0.361
0.0722 0.417
0.0333
0.0203
Ref. 92; Ping x mm/(m* x d) and Dincm2/s
TABLE 5. PERMEABILITY COEFFICIENTS OF VARIOUS ORGANIC COMPOUNDS THROUGH HIGH-DENSITY
POLY(ETHYLENE) AND POLY(PROPYLENE)
Permeant
Hi gh-densi ty poly(ethylene)
22.8C 48.9C
Poly(propylene)
22.8C 48.9 c
Acetic acid
Acetone
n-Butyl ether
Carbon tetrachloride
n-Decane
Dipentene
Ethyl acetate
Methanol
Toluene
0.39
0.67
6.6
32
7.3
7.6
1.7
0.1
39
2.36
3.9 0.28 8.84
43.6
260 1 8 1 1100
39 22 153
54 29.5 1 6 1
18.5 5.8 55
2.0 0.08 1.5
196 142 770
n Ref. 62; Ping x mm/(m*x d)
TABLE 6. PERMEABILITY COEFFICIENTS OF VARIOUS ORGANIC COMPOUNDS THROUGH IRRADIATION
CROSSLINKED LOW-DENSITY POLY(ETHYLENE)
Permeant
Poly(ethylene) unirradiated Poly(ethylene) irradiated with 260 kGy
(crystallinity 58%) (electron irradiation)
T P Temp. range PO
EP
T P Temp. range PO
EP
Acetic acid 21.1 1.27 20-75 1.108 x 103 72.9 21.1 1.55 20-75 2.783 x 10 68.8
Amy1 acetate 21.1 3.80 20-75 2.016 x lOI 83.0 21.1 5.03 20-75 3.269 x lOI 77.9
Aniline 21.1 0.70 20-75 6.088 x 104 84.0 21.1 0.81 20-75 2.315 x lOI 81.1
Benzaldehyde 21.1 2.76 20-75 6.375 x 1014 80.7 21.1 3.36 20-75 4.513 x lOI 79.6
Benzene 21.1 1 8 1 20-75 1.083 x lOI 60.8 21.1 207 20-75 1.677 x 10 55.2
Permeability Coefficients of Gases through LDPE and Poly(oxypropylene) VI / 565
Poly(ethylene) unirradiated Poly(ethylene) irradiated with 260 kGy
(crystallinity 58%) (electron irradiation)
T P Temp. range PO EP T P Temp. range PO EP
Permeant
Dibutyl ether 21.1 37.1 20-75 3.051 x 103 67.0 21.1 45.2 20-75 7.153 x lo* 63.1
Ethyl acetate 21.1 9.39 20-75 6.831 x 1014 78.2 21.1 11.4 20-75 1.797 x 104 74.4
nrtleptane 21.1 110 20-75 1.756 x 10 l2 57.5 21.1 120 20-75 5.55 x 10 54.4
Methyl alcohol 21.1 0.43 20-75 1.160 x lOI 75.7 21.1 0.49 20-75 7.843 x 102 74.0
Methyl ethyl ketone 21.1 5.03 20-75 3.195 x 104 77.7 21.1 5.86 20-75 4.310 x lOi 78.1
n-Propyl alcohol 21.1 0.20 20-75 3.195 x 10S 91.2 21.1 0.36 20-75 1.639 x lOI 82.6
o-Xylene 21.1 116 20-75 8.599 x 103 67.0 21.1 120 20-75 6.676 x 10 60.4
Ref. 63.
TABLE 7. PERMEABILITY COEFFICIENTS OF GASES THROUGH IRRADIATION CROSSLINKED
LOW-DENSITY POLY(ETHYLENE)a
Gas
Irradiation
Dose b (kGy)
D (x106)
(cm 2/s)
P (x103)
(cm3 x cm/cm2 x s x Pa)
EP
Wmol)
He 0
2 0 0
5 0 0
N2 0
100
2 0 0
5 0 0
CH4 0
2 0 0
5 0 0
C2H6 0
2 0 0
5 0 0
C3Hs 0
2 0 0
5 0 0
0.52
0.35
0.33
0.31
0.18
0.16
0.15
0.05
0.04
0.03
82.5
78.8
18.0
17.3
15.0
12.8
47.3
44.3
36.8
82.5
78.0
69.0
142
112
9 0
20.7
22.5
26.3
28.5
30.1
33.5
34.5
37.6
39.8
50.0
54.7
55.6
26.0
27.7
28.1
28.1
30.1
31.3
40.3
40.7
41.1
41.0
43.4
45.9
45.3
48.1
50.3
a Ref. 71.
* Films were irradiated in acetylene atmosphere; doze rate was 6.15 kGyih.
TABLE 8. PERMEABILITY COEFFICIENTS OF CHEMICALLY CROSSLINKED POLY(OXYPROPYLENE)
Polymer
Molecular mass of
poly(oxypropylene)
between crosslinks
Permeability coefficient for 23C ( x 1013)
Hz
c o
Poly(oxypropylene), crosslinked with
stoichiometric quantities of tris
(p-isocyanatophenylthiophosphate)
(Desmodur RF)
a Refs. 69 and 70; Pincm3 x cm/(cm2 x s x Pa).
4 2 5 2.86 0.0608
7 2 5 7.26 0.65
1025 18.80 2.93
2 0 0 0 28.73 7.65
3 0 0 0 44.10 12.60
References page VI - 568
VI 1566 PERMEABILITY AND DIFFUSION DATA
TABLE 9. PERMEABILITY COEFFICIENTS OF GASES THROUGH VARIOUS ELASTOMERS
Permeation coefficient
NZ 02 cot HZ
He
Elastomer 20C 80C 20C 80C 20C 80C 20C 80C 20C 80C
NBR shore 70 , 0.172 5.39 0.639 10.8 6.11 61.1 3.25 27.2 2.56 25.6
NBR shore 60 0.161 6.11 0.75 1 6 . 1 6.11 83.3 3.75 47.2 2.33 33.1
NBR shore 50 0.23 1 6.39 0.722 13.6 4.08 28.6 4.58 38.3 2.31 20.6
NEM shore 70 0.275 4.78
SBR shore 52 0.583 10.8 2.14 24.2 1 3 . 1 77.8 6.67 48.6 4.31 28.9
NR shore 66 1.72 33.9 5.06 55.6 35.6 2 3 9 9.17 86.1 4.53 34.7
CR shore 42 0.611 12.8 1. 31 30.6 6.94 75.0 5.00 61.1 3.42 26.4
VMQ shore 50 128 331 2 8 6 5 2 8 2 2 5 583 156 4 4 4
EC0 shore 65 0.169 3.25
FKM shore 70 0.172 4.75 0.306 7.22 3.53 61.1 2.58 41.7 4.89 48.1
ACM shore 70 0.694 13.3 2.58 18.6 27.8 52.8 10.6 80.6 6.39 43.1
EPDM shore 68 2.08 22.5 6.11 42.2 12.8 48.1 15.6 86.1 10.0 61.1
CIIR shore 68 0.119 2.22 0.242 4.08 1.42 24.4 1.92 26.1 2.28 20.0
CSM shore 70 0.144 3.92 0.494 7.78 3.47 16.7 2.94 20.8 2.97 26.4
AU shore 94 0.286 4.72
Ref.89;Pin10~3cm3xcm/(cm2xsxPa).
TABLE 10. PERMEABILITY COEFFICIENTS OF GASES THROUGH VARIOUS COMMERCIAL ELASTOMERS AT 35C
He HZ DZ 02 N2
Elastomer
tradename Pb DC Sd Pb DC Sd Pb DC Sd Pb DC Sd Pb DC Sd
Hypal on @ 40 6.6 6.31 0.10 8.25 2.65 0.31 7.65 2.32 0.33 1.78 2.04 0.87 0.473 0.10 0.48
Hypal on 8 45 8.63 10.3 0.08 11.7 4.84 0.24 11.2 5.35 0.21 3.15 4.86 0.65 0.960 0.34 0.28
Viton@ E60 22.9 8.10 0.28 7.95 1.87 0.42 750 1.79 0.42 1.71 1.39 1.23 0.638 0.06 0.99
Viton@ GF 32.9 18.3 0.18 16.4 3.45 0.47 15.7 2.78 0.56 3.15 3.86 0.82 1.60 0.13 1.24
Hydrin @ 100 w/filler 1.13 0.73 0.15 1.05 0.23 0.47 1.20 0.18 0.67 0.233 0.03 0.73 0.113 0.008 1.43
Hydrin @ 100 4.13 5.26 0.08 6.68 2.92 0.23 6.60 2.93 0.23 0.788 0.17 0.47 0.330 0.09 0.36
Kraton@ G1652 34.0 19.9 0.17 51.5 12.3 0.42 48.2 10.1 0.48 20.0 1.92 1.04 7.35 1.18 0.62
Ibaton@ FG 34.7 22.4 0.15 50.2 11.6 0.43 44.9 9.68 0.46 18.4 1.43 1.29 6.47 0.98 0.66
Ibaton@ KG VTEOS 33.8 20.5 0.16 52.3 13.3 0.39 47.7 9.93 0.48 19.1 1.81 1.06 7.43 1.14 0.65
a Ref. 90.
bPin 10~3cm3xcm/(cm2xsxPa).
c D in 10 -6 cm 2/s.
d S in 10 -6 cm /(cm 3 x Pa),
.
TABLE 11. PERMEABILITY, DIFFUSION AND SOLUBILITY COEFFICIENTS OF ALKANES THROUGH SANTOPRENETM
(BLEND OF ETHYLENE-PROPYLENE COPOLYMER AND ISOTACTIC POLY(PROPYLENE))
Alkane Tb PC Dd S Temp. range E$ ED ES
n-Pentane 2 5 1. 51 6.07 0.25
n- Hexane 2 5 1. 11 2.88 0.39 25-70 13.86 12.87 0.99
4 0 1.48 3.83 0.39
5 5 1.85 4.63 0.40
n-Heptane 2 5 1.39 3.22 0.43 25-70 8.64 8.23 0.41
4 0 1.67 3.74 0.45
5 5 2.13 4.72 0.45
7 0 2.12 4.82 0.44
n-Octane 2 5 1.03 1.83 0.56 25-70 14.10 12.89 1. 21
4 0 1.38 2.36 0.58
5 5 1.73 2.88 0.60
7 0 2.18 3.64 0.60
Permeability, Diffusion and Solubility Coefficients of Esters through Poly(epichlorohydrin) VI 1567
Alkane Tb PC Dd S Temp. range
E$ ED ES
n-Nonane
n-Decane
n- Dodec ane
n-Tetradecane
n-Hexadecane
2,2,4-Trimethylpentane
Cyclohexane
1,2,3,4-
Tetrahydronaphthalene
2 5
4 0
5 5
7 0
2 5
4 0
5 5
7 0
2 5
4 0
5 5
70
2 5
4 0
5 5
7 0
2 5
4 0
55
7 0
2 5
4 0
5 5
7 0
2 5
4 0
5 5
7 0
2 5
4 0
5 5
7 0
0.82
1.13
1.50
1.99
0.67
0.87
1.13
1.47
0.37
0.52
0.76
1.10
0.28
0.34
0.55
0.75
0.17
0.27
0.38
0.49
0.56
0.76
0.89
1.12
0.85
1.27
1.82
2.08
0.49
0.74
0.92
1.29
1.69
2.23
2.87
3.79
1.34
1.78
2.10
2.67
0.78
1.04
1.44
2.05
0.62
0.69
1.08
1.49
0.34
0.55
0.74
0.97
1.66
2.07
2.40
3.05
0.90
1.27
1.74
1.90
0.56
0.80
0.93
1.19
0.49
0.51
0.52
0.53
0.50
0.49
0.54
0.55
0.47
0.50
0.53
0.54
0.45
0.49
0.51
0.50
0.50
0.49
0.51
0.51
0.34
0.37
0.37
0.37
0.94
1.00
1.05
1.09
0.88
0.93
0.99
1.08
25-70 16.65
25-70 14.86
25-70 20.80
25-70 19.48
25-70 20.04
25-70 12.67
25-70 17.43
25-70 17.81
15.12
12.67
18.30
17.41
19.43
11119
14.70
13.69
1.53
2.19
2.51
2.07
0.61
1.48
2.74
4.12
a Ref. 93.
* Tand Temp. range in C.
P in 10m6cm3 x cm/(cm* x s).
d Di n 10~6cm2/~.
e Sin cm3/cm3.
f Ep, ED and Es in !t.J/mol.
TABLE 12. PERMEABILITY, DIFFUSION AND SOLUBILITY COEFFICIENTS OF ESTERS THROUGH
POLY(EPlCHLOROHYDRlN) (ECO)
Alkane Temp. range
Ed ED E S
Methyl acetate - 25 0.998 0.712 1.40 25-50 16.25 18.21 - 1.94
4 0 1.450 1.069 1.36
5 0 1.640 1.246 1.32
(Ethyl acetate) 2 5 0.765 0.561 1.36 25-60 12.48 14.78 - 2.30
4 4 0.985 0.779 1.26
6 0 1.304 1.052 1.24
(n-Butyl acetate) 2 5 0.346 0.295 1.17 25-60 14.34 15.02 - 0.68
4 4 0.480 0.418 1.15
6 0 0.636 0.559 1.14
(Iso-amyl acetate) 2 5 0.317 0.267 1.19 25-60 15.99 17.34 - 1.35
4 4 0.486 0.420 1.16
6 0 0.621 0.554 1.12
(Methyl salicylate) 2 5 0.146 0.071 2.06 25-60 31.15 31.15 0.10
4 4 0.327 0.155 2.11
6 0 0.546 0.263 2.08
a Ref. 97.
b T and Temp. range in C.
CPin10-6cm3xcm/(cm2xs).
d D in 10 - cm */s.
e Sin cm/cm3.
f Ep, ED and ES in kJ/mol.
References page VI - 568
VI 1568 PERMEABILITY AND DIFFUSION DATA
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(1986).
Refractive Indices of Polymers
James C. Seferis
Polymeric Composites Laboratory, Department of Chemical Engineering, University of Washington, Seattle, WA, USA
A. Introduction VI-571
B. Molar Refraction VI-571
C. Refractive Indices of Heterogeneous Polymers VI-572
D. Optical Anisotropy VI-572
E. Applications VI-573
Table 1. Intrinsic Optical Properties of
Selected Polymers VI-573
Table 2. Average Refractive Indices of
Polymers (in Order of Increasing n) VI-574
Table 3. Average Refractive Indices of
Polymers (in Alphabetical Order) VI-578
F. References VI-582
A. INTRODUCTION
The refractive indices of polymers provide fundamental
physical property information that can be used in
characterization, processing, and usage analyses. In-depth
description of refractive indices based on classic electro-
magnetic theory can be found in basic texts (1,2). The
purpose of this monograph is to provide a convenient
reference of values and some general remarks in approx-
imating and utilizing refractive indices of polymers.
The refractive index, reported as the velocity of light in a
vacuum relative to the velocity in the, polymer, depends on
the wavelength of light. All values reported in this chapter
refer to the sodium spectral line X g 5893& referred to as
no in this literature. However, for simplicity, the subscript
D is omitted here in the subsequent discussion and tables. In
general, it should be kept in mind that for any polymer, the
refractive index represents an average property of its
aggregate state (3,4). Orientation, conformation, as well
as phase changes may all contribute to variations in the
index of refraction of a polymer with a given chemical
structure. Thus, the refractive index may not be expected to
be equal along all axes of the molecule (5). Consequently,
the measured refractive index is an average value, with
contributions from the refractions of the molecules
different chemical bonds. It can be shown from classic
electromagnetic theory that the square of the refractive
index (n2) is the appropriate form to use in molecular
descriptions of refractive indices since it is related to the
dielectric tensor, having a magnitude as well as a
directional description (1,4). However, since 1.3 < n < 1.7
for most polymers, correlations proposed for n2 almost
always find a simplified version with n (3,4).
B. MOLAR REFRACTION
The molar refraction of a substance, a product of its
refractive index, molecular weight, and density, may be
assumed to be a fundamental physical property of materials
(1). Furthermore, the molar refraction may be treated (as
established by Denbigh) as the sum of the bond refractions
that make up the molecule (6). These two postulates make
possible, the calculation of the refractive indices of
polymers almost from first principles (7,8). Two useful
relations for the molar refraction, R, areprovided here (1):
The Lorentz-Lorentz equation
n2-1M
R=--
n2+2p
(Bl)
The Gladstone-Dale equation
R=(n-1);
W)
where p is the density of the polymer and M its molecular
weight. The molar refraction may be assumed to be the sum
of the refractions of all the bonds or groups that make up
the polymer system, i.e., R = xi Ri (6,7). Chemical group
refractivities that can be used in the calculation of refractive
index of polymers have been recently summarized by Van
Krevelen (8). For example, for a homopolymer whose
repeat monomer unit refractivity, RM, is known, with
R = DP RM (where DP is the degree of polymerization) and
M = DPMhl (MM = molecular weight of the monomer
unit), then the refractive index of the polymer by the
Gladstone-Dale expression (Eq. B2) becomes
DPRM = (n - l)?o r n= l+$p (B3)
In
This may be calculated only from a knowledge of the
monomer unit molar refraction and molecular weight. The
VI / 571
VI / 572 REFRACTIVE INDICES OF POLYMERS
use of bond or group refractions in the calculation of
refractive indices of polymers has been demonstrated to be
in good agreement with the measured values for homo-
geneous, unoriented polymers (8).
C. REFRACTIVE INDICES OF HETEROGENEOUS
POLYMERS
For polymeric systems whose phase dimensions are below
the wavelength of the incident light, the application of the
Maxwell relations is valid and the refractive index of the
polymer may be expressed in terms of the dielectric
constants of the constituent phases (1). The dielectric
constant, k, is equivalent to the square of the refractive
index (k = n2), and it can be demonstrated that an upper
bound of the refractive index of the polymer may be
obtained as the sum of dielectric constants of the
constituent phases (43):
n2 z.z
c
Vinf
(Cl)
i
where ni and vi(c vi = 1) are the refractive indices and
volume fractions of the constituent phases of the compo-
nents that make up the polymer. Similarly, the lower bound
of a polymers refractive index may be computed as the
sum of the inverse of the dielectric constants of the
constituent phases (4):
1
c
Vi
z= i 3
w
For most heterogeneous polymers, however, whose
constituent refractive indices differ by less than 0.2, i.e.,
(ni - nj I 0.2), the refractive index of the polymer may be
computed by the Gladstone-Dale relation, assuming
additivity of the refractive indices of the constituent phases
(394):
n =
c
Vini i
w
i
. .
The calculation methods described above may be used
for multiphase polymers such as blends, block or graft
copolymers, composites, and semicrystalline polymers.
D. OPTICAL ANISOTROPY *
Small as well as long polymer molecules exhibit different
refractive indices parallel and perpendicular to the mole-
cular chain axis. Thus, all polymers should be viewed as
intrinsically anisotropic. The degree of anisotropy exhibited
in bulk property behavior will depend on the molecular
orientation imposed by deformation during processing or
testing. Only in its unoriented state can a polymer be
*See also corresponding table in this Handbook.
characterized by a single refractive index, since its optical
properties will be identical in all directions. Consequently,
optical anisotropy is one of the simplest and often used
methods of studying orientation in polymers (5). By
polarizing light in a specific direction, the refractive index
of a polymer can be measured in that direction. Conse-
quently, all three principal refractive indices of a polymer,
n,, nY, n,, corresponding to an x, y, and z direction, can be
measured. For example, a refractometer fitted with a
polarized eye piece has been successfully used to measure
refractive indices along the major axes of polymer films (9).
The average refractive indices of a polymer may be
computed from the refractive indices along the axes of
the polymer:
n =(n, + ny +n,)/3
W)
For the unoriented (isotropic) condition (n, = ny =n,), a
single value of the refractive index provides a unique
optical description (n = n, = ny = n,). For oriented poly-
mers, the difference in refractive indices along two
orthogonal directions can be used as the measure of optical
anisotropy and, consequently, orientation of the polymer.
The difference in refractive indices is defined as the
birefringence or double refraction. According to Stein (5),
there are three birefringences, Ais that may be defined for
a Cartesian coordinate system, with two of them being
independent. They are
Anxy=n,-nY
WV
Anxz = n, - n,
P3)
An, = ny - n, = An, - An,
(W
For a polymer exhibiting transverse isotropic symmetry,
as in the case of uniaxial orientation (i.e., deformation
along one axis), a single birefringence is enough to
characterize orientation and anisotropy. For example, for
a polymer oriented uniaxially along the x direction,
An , = An, and An,, = 0. For a fully oriented polymer,
where the molecular chain axis is aligned with the
deformation axis (perfect orientation) a limiting value of
birefringence is reached, which is defined as the intrinsic
birefringence of the polymer (10,ll) and denoted as
An, = nkf
where f is the Hermans orientation function
W)
3cos28 - 1
f= 2 Qw
defined on the average angle 8 that the molecular chain axis
makes with the deformation axis. The Her-mans orientation
function (D6), - l/2 5 f 5 1 assumes the value of - l/2
when the molecular chain axis is perpendicular to the
deformation axis; 0 for random orientation (isotropy); and
- 1 for perfect alignment of the chains with the deforma-
tion axis. The use of the refractive index in the calculation
of birefringence, rather than the difference of some function
of the dielectric constant (n2 or l/n2), is an approximation
to optical anisotropy. Thus, if the birefringence is used as a
measure of orientation, as was proposed by Stein, form
effects should be considered (5,7,11)
The importance of form may be estimated from bond
polarizabilities for a given polymer (4,7). Thus, to
characterize completely the optical properties of a given
polymer, its average refractive index as well as the intrinsic
and form birefringences must be specified. To date, very
few polymers have been optically characterized in such
detail. However, as more refined and specific performance
is demanded from polymers, this information is forth-
coming. In order to demonstrate the usefulness of complete
characterization and to summarize the data available till
date, an example for semicrystalline polymers is provided,
along with a table showing reported values (for a few
polymers) of average refractive indices and intrinsic
birefringences.
E. APPLICATIONS
Using Eq. (B2), the unoriented refractive index of a
semicrystalline polymer may be calculated from a knowl-
edge of its intrinsic crystalline and noncrystalline densities
and refractive indices. First, the volume fraction crystal-
linity, ucrr is calculated from the densities:
V
P - Pm
cr =
Pa - Pnc
(El)
where p is the bulk measured density, and per and pnc are
the crystalline and noncrystalline densities. Then the
average refractive index is
Intrinsic Optical Properties of Selected Polymers VI / 573
From Steins equation of birefringence additivity (neglect-
ing form birefringence) (5,ll)
where Andy r and An:, are the crystalline and noncrystal-
line intrinsic birefringences, and fcr and fnC are the
corresponding crystalline and noncrystalline Hermans
orientation functions.
If the intrinsic properties of a semicrystalline polymer
are known, Eq. (E2) can be used to calculate the volume
fraction crystallinity by simply measuring the polymers
refractive index, while Eq. (E3) can be used to obtain the
value of the noncrystalline orientation function by measur-
ing birefringence and crystalline orientation by an inde-
pendent technique [e.g., wide angle X-ray (5)]. For a single-
phase polymer like polystyrene, the orientation function can
be directly calculated from the measured birefringence
value and the known intrinsic birefringence:
w
Once these quantities are known, it becomes possible to
completely characterize and predict the optical anisotropy
of a given polymer from its unoriented to its oriented state
(334).
Table 1 is provided to demonstrate that such basic optical
parameters may be obtained from the literature (3,4,9,12-
16). The recognition of polymers as anisotropic hetero-
geneous systems continues to expand and their refractive
indices provide useful insight into their process-structure-
property interrelations (18-20). It is hoped that continuous
investigations in existing as well as new polymers will
expand this compilation.
Finally, Table 2 provides average refractive indices of
polymers arranged in order of increasing values, while
Table 3 provides the same list in alphabetical order. Some
additional values from the recent literature (21-23) have
been added to the earlier compilation (17) to form the
material for the present edition.
TABLE 1. INTRINSIC OPTICAL PROPERTIES OF SELECTED POLYMERS
Phase average Intrinsic birefringence
Crystalline Noncrystalline refractive indices (x 103)
density densi ty
Polymer
(PC& (Pm) ncr nne Anit A4
Poly(propylene) 0.936 0.850 1.519-1.524 1.471 23-30 60-86
Poly(ethylene) 1.000 0.855 1.560-1.565 1.476-1.483 58-66
Low orientation 120
High orientation 194
Poly(oxyethylene-oxyterephthaloyl) 1.455 1.335 1.639-1.643 1.570-1.577 220-230 220-275
Poly(styrene) Amorphous 1.06 Amorphous 1.590-1.592 Amorphous 195
References page VI - 582
VI / 574 REFRACTIVE INDICES OF POLYMERS
TABLE 2. AVERAGE REFRACTIVE INDICES OF POLYMERS (IN ORDER OF INCREASING n)=
Polymer
Poly(tetrafluoroethylene-co-hexafluoropropylene)
Poly(pentadecafluorooctyl acrylate)
Poly(tetrafluoro-3-(heptafluoropropoxy)propyl acrylate)
Poly(tetrafluoro-3-(pentafluoroethoxy)propyl acrylate)
Poly(tetrafluoroethylene)
Poly(undecafluorohexy1 acrylate)
Poly(nonafluoropenty1 acrylate)
Poly(tetrafluoro-3-(trifluoromethoxy)propyl acrylate)
Poly(pentafluoroviny1 propionate)
Poly(heptafluorobuty1 acrylate)
Poly(trifluoroviny1 acetate)
Poly(octafluoropenty1 acrylate)
Poly(pentafluoropropy1 acrylate)
Poly(2-heptafluorobutoxy)ethyl acrylate)
Poly(2,2,3,4,4,4-hexafluorobutyl acrylate)
Poly(trifluoroethy1 acrylate)
Poly(2-( 1,1,2,2-tetrafluoroethoxy)ethyl acrylate)
Poly(trifluoroisopropy1 methacrylate)
Poly(2,2,2-trifluoro- 1 -methylethyl methacrylate)
Poly(2-trifluoroethoxy)ethyl acrylate
Poly(trifluorochloroethylene)
Poly(vinylidene fluoride)
Poly(oxydimethylsilylene) (poly(dimethy1 siloxane))
Poly(trifluoroethy1 methacrylate)
Poly(oxypropylene)
Poly(viny1 isobutyl ether)
Poly(vinyl ethyl ether)
Poly(oxyethylene)
Poly(viny1 butyl ether)
Poly(viny1 pentyl ether)
Poly(viny1 hexyl ether)
Poly(4-methyl-1-pentene)
Cellulose acetate butyrate
Poly(4-fluoro-2-trifluoromethylstyrene)
Poly(viny1 octyl ether)
Poly(vinyl-2-ethylhexyl ether)
Poly(viny1 decyl ether)
Poly(2-methoxyethyl acrylate)
Poly(buty1 acrylate)
Poly(terr-butyl methacrylate)
Poly(viny1 dodecyl ether)
Poly(3-ethoxypropyl acrylate)
Poly(oxy-1-oxopentamethylene)
Poly(viny1 propionate)
Poly(viny1 acetate)
Poly(viny1 methyl ether)
Poly(ethy1 acrylate)
Poly(ethylene-co-vinyl acetate) (80%-20% vinyl acetate)
Cellulose propionate
Cellulose acetate propionate
Benzyl cellulose
Phenol-formaldehyde resins
Cellulose triacetate
Poly(viny1 methyl ether) (isotactic)
Poly(3-methoxypropyl acrylate)
Poly(2-ethoxyethyl acrylate)
Poly(methy1 acrylate)
Poly(isopropy1 methacrylate)
Poly( I-decene)
Poly(propylene) (atactic, density 0.8575 g/cm3)
Poly(viny1 set-butyl ether) (isotactic)
Poly(dodecy1 met hacryl at e)
Poly(oxyethyleneoxysuccinoy1) (poly(ethylene succinate))
Poly(tetradecy1 methacrylate)
n T (C)
1.338
1.339 25
1.346 25
1.348 25
1.35- 1.38
1.356
1.360 25
1.360 25
1.364 25
1.367 25
1.375 25
1.380 25
1.385 25
1.390 25
1.392 25
1.407 2 5
1.412 25
1.4177 20
1.4185
1.419
25
1. 42- 1. 43
1.42 25
1.43
1.437
1.4495
1.4507 30
1.4540 30
1.4563 30
1.4563 30
1.4581 30
1.4591 30
1.459-1.465
1. 46- 1. 49
1.46
1.4613
1.4626
1.4628
1.463
1.4631
1.466
1.4638
1.4640
1.465
1.465
1.4665
1.4665
1.467
1.4685
1. 47- 1. 50
1. 47- 1. 49
1.47
1. 47- 1. 58
1. 47- 1. 70
1. 47- 1. 48
1.4700
1.471
1.471
1.472-1.480
1.4728
1.4730
1.4735
1.4740
1.4740
1.4744
1.4746
30
30
30
25
30
20
20
30
25
50
20
20
20
20
30
25
25
20
20
30
20
25
30
TABLE 2. contd
Average Refractive Indices of Polymers (Increasing n) VI / 575
Polymer n
T (-3
Poly(ethylene-co-propylene) (EPR-rubber)
Poly(hexadecy1 methacrylate)
Poly(viny1 formate)
Poly(2-fluoroethyl met hacryl at e)
Poly(isobuty1 methacrylate)
Ethyl cellulose
Poly(viny1 acetal)
Cellulose acetate
Cellulose acetate (39.8% acetyl content)
Cellulose tripropionate
Poly(oxymethylene)
Poly(viny1 butyral)
Poly(n-hexyl methacrylate)
Poly(n-butyl methactylate)
Poly(ethylidene dimethactylate)
Poly(2-ethoxyethyl met hacryl at e)
Poly(oxyethyleneoxymaleoy1) (poly(ethylene maleate))
Poly(n-propyl methacrylate)
Poly(3,3,5-trimethylcyclohexyl methacrylate)
Poly(ethy1 methacrylate)
Poly(2-nitro-2-methylpropyl methacrylate)
Poly(triethylcarbiny1 methacrylate)
Poly( 1, 1-diethylpropyl methacrylate)
Poly(methy1 methacrylate)
Poly(2-decyl-1,3-butadiene)
Poly(viny1 alcohol)
Poly(ethy1 glycolate methacrylate)
Poly(3-methylcyclohexyl methacrylate)
Poly(cyclohexy1 cc-ethoxyacrylate)
Methyl cellulose (low viscosity)
Poly(4-methylcyclohexyl methacrylate)
Poly(decamethylene glycol dimethacrylate)
Poly(urethanes)
Poly( 1,2-butadiene)
Poly(viny1 formal)
Poly(2-bromo-4-trifluoromethylstyrene)
Cellulose nitrate
Poly(sec-butyl a-chloroacrylate)
Poly(2-heptyl-1,3-butadiene)
Poly(ethy1 cc-chloroacrylate)
Poly(2-isopropyl-1,3-butadiene)
Poly(2-methylcyclohexyl met hacryl at e) i
Poly(propylene) (density 0.9075 g/cm3)
Poly(isobutene)
. .
Poly(borny1 met hacryl at e)
Poly(2-tert-butyl-1,3-butadiene)
Poly(ethylene glycol dimethacrylate)
Poly(cyclohexy1 met hacryl at e)
Poly(cyclohexanediol-1,4-dimethacrylate)
Butyl rubber(unvulcanized)
Poly(tetrahydrofurfury1 met hacryl at e)
Gutta percha (0)
Poly(ethylene) ionomer
Poly(oxyethylene) (high molecular weight)
Poly(ethylene) (density 0.914 g/cm3)
(density 0.94-0.945 g/cm3)
(density 0.965 g/cm3)
Poly( 1-methylcyclohexyl methacrylate)
Poly(2-hydroxyethyl met hacryl at e)
Poly(viny1 chloroacetate)
Poly(butene) (isotactic)
Poly(viny1 methacrylate)
Poly(N-butyl methacrylamide)
1.4748-1.48
1.4750
1.4757
1.4768
1.477
1.479
1. 48- 1. 50
1. 48- 1. 50
1.4700
1. 48- 1. 49
1.48
1.48-1.49
1.4813
1.483
1.4831
1.4833
1.4840
1.484
1.485
1.485
1.4868
1.4889
1.4889
1.4893
1.490
1.4899
1.49-1.53
1.5214
1.4903
1.4947
1.4969
1.497
1.4975
1.4990
1. 5-1. 6
1.5000
1.50
1.5
1. 5- 1. 514
1.500
1.5000
1.502
1.5028
1.5028
1.5030
1.505-1.51
1.5059
1.5060
1.5063
1.5066
1.5067
1.508
1.5096
1.509
1.51
1. 51- 1. 54
1.51
1. 52- 1. 53
1.545
1.5111
1.5119
1.512
1.5125
1.5129
1.5135
30
20
20
20
2 1
25
20
20
20-25
20
20
25
25
20
20-25
20
20
20
23
20
20.5
20
20
20
20
25
20
20
25
25
25
30
20
20
20
24.6
20
20
20
20
20
20
20
20
20
25
20
20
References page VI - 582
VI / 576 REFRACTIVE INDICES OF POLYMERS
TABLE 2. contd
Polymer
n T CC)
Gutta percha (u)
Terpene resin
Poly( 1,3-butadiene)
Shellac
Poly(methy1 a-chloroacrylate)
Poly(2-chloroethyl methacrylate)
Poly(2-diethylaminoethyl met hacryl at e)
Poly(2-chlorocyclohexyl methacrylate)
Poly(l,3-butadiene) (35% cis; 56% truns; 7% 1,2-content)
Natural rubber
Poly(ally1 methacrylate)
Poly(viny1 chloride) + 40% dioctyl phthalate
Poly(acrylonitrile)
Poly(methacrylonitrile)
Poly( 1,3-butadiene) (high &-type)
Poly(butadiene-co-acrylonitrile)
Poly(methy1 isopropenyl ketone)
Poly(isoprene)
Poly(ester) resin, rigid (ca. 50% styrene)
Poly((N-2-methoxyethyl)methacrylamide)
Poly(2,3-dimethylbutadiene) (methyl rubber)
Poly(viny1 chloride-co-vinyl acetate) (95/.5-90/10)
Poly(acrylic acid)
Poly(l,3-dichloropropyl methacrylate)
Poly(2-chloro-1-(chloromethyl)ethyl methacrylate)
Poly(acrolein)
Poly(l-vinyl-2-pyrrolidone)
Poly(N-methylmaleimide-alt-isobutene)
Hydrochlorinated rubber
Poly(imino( 1-oxohexamethylene)) (nylon 6)
Poly(iminoadipoyliminohexamethylene) (nylon 6,6)
Poly(iminoadipoylimino tetramethylene) (nylon moulding 6,lO)
oriented fibres
Poly(butadiene-co-styrene) (- 30% styrene) block copolymer
Poly(cyclohexy1 cc-chloroacrylate)
Poly(2-chloroethyl wchloroacrylate)
Poly(butadiene-co-styrene) ( N 75/25)
Poly(2-aminoethyl methacrylate)
Poly(furfury1 methacrylate)
Proteins
Poly(butylmercapty1 methacrylate)
Poly(l-phenyl-n-amyl methacrylate)
Poly(N-methyl-methacrylamide)
Cellulose
Poly(viny1 chloride)
Urea-formal dehyde resi n
Poly(sec-butyl a-bromoacryl at e)
Poly(cyclohexy1 a-bromoacryl at e)
Poly(2-bromoethyl met hacryl at e)
Poly(dihydroabietic acid)
Poly(abietic acid)
Poly(ethylmercapty1 methacrylate)
Poly(N-ally1 methacrylamide)
Poly(l-phenylethyl methacrylate)
Poly(vinylfuran)
Poly(2-vinyltetrahydrofuran)
Poly(viny1 chloride) + 40% tricresyl phosphate
Epoxy resins
Poly(p-methoxybenzyl methacrylate)
Poly(isopropy1 met hacryl at e)
Poly(p-isopropylstyrene)
Poly(chloroprene)
Poly(oxyethylene)-w-benzoate-w-methacrylate)
Poly(p,p-xylylenyl dimethacrylate)
1.514
1.515
1.5154
1.51
1.517
1.517
1.5174
1.5179
1.5180
1. 519- 1. 52
1.5196
1.52
1.52
1.5187
1.52
1.52
1.52
1.5200
1.521
1. 523- 1. 54
1.5246
1.525
1.525-1.535
1.527
1.5270
1.5270
1.529
1.53
1.53
1. 53- 1. 55
1.53
1.53
1.53
1.515- .l
1.53
1.532
1.533
1.535
1.537
1.5381
1. 539- 1
1.5390
1.5396
1.5398
1.54
565
.541
1. 54- 1. 55
1. 54- 1. 56
1.542
1.542
1.5426
1.544
1.546
1.547
1.5476
1.5487
1.55
1.55
1.55
1. 55- 1. 60
1.552
1.552
1.554
1.554- 1.558
1.555
1.5559
50
25
25
1.53
20
20
20
20
20
25
20
20
20
25
20
20
25
25
20
20
20
20
25
25
20
25
20
20
20
20
20
20
20
20
20
TABLE 2. contd
Average Refractive Indices of Polymers (Increasing II) VI / 577
Polymer n
T t-3
Poly(l-phenylallyl methacrylate)
Poly(p-cyclohexylphenyl methacrylate)
Poly(2-phenylethyl methacrylate)
Poly(oxycarbonyloxy- 1,4-phenylene- 1-propylbutylidene- 1,4-phenylene)
Poly(l-(o-chlorophenyl)ethyl methacrylate)
Poly(styrene-co-maleic anhydride)
Poly(l-phenylcyclohexyl methacrylate)
Poly(oxycarbonyloxy- 1,4-phenylene- 1,3-dimethylbutylidene- 1,4-phenylene)
Poly(methy1 ar-bromoacrylate)
Poly(benzy1 methacrylate)
Poly(2-(phenylsulfonyl)ethyl met hacryl at e)
Poly(m-cresyl methacrylate)
Poly(styrene-co-acrylonitrile) (- 75/25)
Poly(oxycarbonyloxy- 1,4-phenyleneisobutylidene- 1,4-phenylene)
Poly(o-methoxyphenyl methacrylate)
Poly(pheny1 methacrylate)
Poly(o-cresyl methacrylate)
Poly(dially1 phthalate)
Poly(2,3-dibromopropyl met hacryl at e)
Poly(oxycarbonyloxy- 1,4-phenylene- 1 -methyl-butylidene- 1,4-
phenylene)
Poly(oxy-2,6-dimethylphenylene)
Poly(oxyethyleneoxyterephthaloy1) (amorphous) (poly(ethylene
terephthalate))
Poly(viny1 benzoate)
Poly(oxycarbonyloxy- 1,4-phenylenebutylidene-1,4-phenylene)
Poly( 1 ,2-diphenylethyl methacrylate)
Poly(o-chlorobenzyl methacrylate)
Poly(oxycarbonyloxy-1,4-phenylene-sec-butylidene-1,4-phenylene)
Poly(oxypentaerythritoloxyphthaloy1)
Poly(m-nitrobenzyl methacrylate)
Poly(oxycarbonyloxy- 1,4-phenyleneisopropylidene- 1,4-phenylene)
Poly(N-(2-phenylethyl)methacrylamide)
Poly(4-methoxy-2-methylstyrene)
Poly(o-methylstyrene)
Poly(styrene)
Poly(oxycarbonyloxy- 1,4-phenylenecyclohexylidene- 1,4-phenylene)
Poly(o-methoxystyrene)
Poly(diphenylmethy1 methacrylate)
Poly(oxycarbonyloxy-l,4-phenyleneethylidene-1,4-phenylene)
Poly(p-bromophenyl met hacryl at e)
Poly(Nbenzy1 methacrylamide)
Poly(p-methoxystyrene)
Hard rubber (32% S)
Poly(vinylidene chloride)
Poly(sulfides) (Thiokol)
Poly(o-chlorodiphenylmethyl methacrylate)
Poly(oxycarbonyloxy-1,4-(2,6-dichloro)phenylene-isopropylidene-1,4-(2,6-dichloro)phenylene)
Poly(oxycarbonyloxybis( 1,4-(3,5dichlorophenylene)))
Poly(pentachloropheny1 methacrylate)
Poly(o-chlorostyrene)
Poly(pheny1 a-bromoacryl at e)
Poly(p-divinylbenzene)
Poly(N-vinylphthalimide)
Poly(2,6-dichlorostyrene)
Poly@-naphthyl methacrylate)
Poly(cx-naphthyl carbinyl methacrylate)
Poly(sulfone)
Poly(2-vinylthiophene)
Poly(wnaphthy1 methacrylate)
Poly(oxycarbonyloxy- 1,4-phenylenediphenyl-methylene- 1,4-phenylene)
Poly(viny1 phenyl sulfide)
Butylphenol formaldehyde resin
Urea-thiourea-formaldehyde resin
Poly(vinylnaphthalene)
1.5573
1.5575
1.5592
1.5602
1.5624
1.564
1.5645
1.5671
1.5672
1.5680
1.5682
1.5683
1.57
1.5702
1.5705
1.5706
1.5707
1.572
1.5739
1.5745
1.575
1.5750
1.5775
1.5792
1.5816
1.5823
1.5827
1.584
1.5845
1.5850
1.5857
1.5868
1.5874
1.59-1.592
1.5900
1.5932
1.5933
1.5937
1.5964
1.5965
1.5967
1.6
1.60-1.63
1. 6-1. 7
1.6040
1.6056
1.6056
1.608
1.6098
1.612
1.6150
1.6200
1.6248
1.6298
1.63
1.633
1.6376
1.6410
1.6539
1.6568
1.66
1.660
1.6818
20
20
20
20
2 1
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
25
20
20
20
20
20
20
20
25
20
References page VI - 582
VI / 578 REFRACTIVE INDICES OF POLYMERS
TABLE 2. contd
Polymer n T CC)
Poly(vinylcarbazole) 1.683 20
Naphthalene-formaldehyde resin 1.696
Phenol-formaldehyde resin 1.70
Poly(pentabromopheny1 methacrylate) 1.71
Temperature in C are listed when available. In general, n may be assumed to decrease with increasing temperature. Approximate change may be calculated as
dn/dT= - 1 x 10e4 to 2 x IO-/T for glassy polymers and dn/dT= - 3 x 10e4 to 5 x 1O-4/C for amorphous unoriented polymers above the glass transition.
TABLE 3. AVERAGE REFRACTIVE INDICES OF POLYMERS (IN ALPHABETICAL ORDER)
Polymer
Benzyl cellulose
Butylphenol formaldehyde resin
Butyl rubber(unvulcanized)
Cellulose
Cellulose acetate
Cellulose acetate (39.8% acetyl content)
Cellulose acetate butyrate
Cellulose acetate propionate
Cellulose nitrate
Cellulose propionate
Cellulose triacetate
Cellulose tripropionate
Epoxy resins
Ethyl cellulose
Gutta percha (a)
Gutta percha (8)
Hard rubber (32% S)
Hydrochlorinated rubber
Methyl cellulose (low viscosity)
Naphthalene-formaldehyde resin
Natural rubber
Phenol-formaldehyde resin
Phenol-formaldehyde resins
Poly(abietic acid)
Poly(acrolein)
Poly(acrylic acid)
Poly(acrylonitrile)
Poly(ally1 methacrylate)
Poly(2-aminoethyl methacrylate)
Poly(N-ally1 methacrylamide)
Poly(N-benzyl methacrylamide)
Poly(n-butyl methacrylate)
Poly(benzy1 methacrylate)
Poly(bomy1 methacrylate)
Poly(2-bromoethyl methacrylate)
Poly(p-bromophenyl methactylate)
Poly(2-bromo-4-trifluoromethylstyrene)
Poly(l,2-butadiene)
Poly( 1,3-butadiene)
Poly( 1,3-butadiene) (high &-type)
Poly(l,3-butadiene) (35% cis; 56% trans; 7% 1,2content)
Poly(butadiene-co-acrylonitrile)
Poly(butadiene-co-styrene) ( N 75/25)
Poly(butadiene-co-styrene) (- 30% styrene) block copolymer
Poly(butene) (isotactic)
Poly(buty1 acrylate)
Poly(sec-butyl cl-bromoacrylate)
Poly(sec-butyl a-chloroacrylate)
Poly(2-rert-butyl-1,3-butadiene)
n T (C)
1. 47- 1. 58
1.66
1 SO8
1.54
1.48-1.50
1.4700 25
1. 46- 1. 49
1. 47- 1. 48
1. 5- 1. 514
1. 47- 1. 49
1. 47- 1. 48
1. 48- 1. 49
1. 55- 1. 60
1.479 2 1
1.514 50
1.509
1.6
1. 53- 1. 55
1.497 25
1.696
1. 519- 1. 52
1.70
1. 47- 1. 70
1.546 25
1.529
1.527 25
1.52
1.5187 25
1.5196 20
1.537 20
1.5476 20
1.5965 20
1.483 20-25
1.5680 20
1.5059 20
1.5426 20
1.5964 20
1.5 25
1.5000 20
1.5154 25
1.52
1.5180
1.52
1.535
1.53
1.5125
1.4631 30
1.466 20
1.542 25
1.500 25
1.5060 24.6
TABLE 3. contd
Average Refractive Indices of Polymers (Alphabetical Order)
Polymer n
T (-3
Poly(tert-butyl methacrylate)
Poly(butylmercapty1 methacrylate)
Poly(N-butyl methacrylamide)
Poly(o-chlorobenzyl methacrylate)
Poly(2-chloro-1-(chloromethyl)ethyl methacrylate)
Poly(2-chlorocyclohexyl methacrylate)
Poly(o-chlorodiphenylmethyl methacrylate)
Poly(2-chloroethyl a-chloroacrylate)
Poly(2-chloroethyl methacrylate)
Poly( 1-(o-chlorophenyl)ethyl methacrylate)
Poly(chloroprene)
Poly(o-chlorostyrene)
Poly(m-cresyl methacrylate)
Poly(o-cresyl methacrylate)
Poly(cyclohexanediol- 1,4-dimethacrylate)
Poly(cyclohexy1 wbromoacrylate)
Poly(cyclohexy1 cl-chloroacrylate)
Poly(cyclohexy1 a-ethoxyacrylate)
Poly(cyclohexy1 methacrylate)
Poly@-cyclohexylphenyl methacrylate)
Poly(decamethylene glycol dimethacrylate)
Poly( 1 -decene)
Poly(2-decyl-1,3-butadiene)
Poly(dially1 phthalate)
Poly(2,3-dibromopropyl methacrylate)
Poly(l,3-dichloropropyl met hacryl at e)
Poly(2,6-dichlorostyrene)
Poly(2-diethylaminoethyl methacrylate)
Poly( 1,l -diethylpropyl methacrylate)
Poly(dihydroabietic acid)
Poly(2,3-dimethylbutadiene) (methyl rubber)
Poly( 1,2-diphenylethyl methacrylate)
Poly(diphenylmethy1 methacrylate)
Poly(p-divinylbenzene)
Poly(dodecy1 methacrylate)
Poly(ester) resin, rigid (ca. 50% styrene)
Poly(2-ethoxyethyl acrylate)
Poly(2-ethoxyethyl methacrylate)
Poly(3-ethoxypropyl acrylate)
Poly(ethy1 acrylate)
Poly(ethyl a-chloroacrylate)
Poly(ethy1 glycolate methacrylate)
Poly(ethy1 methacrylate)
Poly(ethylene) (density 0.914g/cm3) i
(density 0.94-0.945 g/cm3)
(density 0.965 g/cm3)
Poly(ethylene) ionomer
Poly(ethylene-co-propylene) (EPR-rubber)
Poly(ethylene-co-vinyl acetate) (80%-20% vinyl acetate)
Poly(ethylene glycol dimethacrylate)
Poly(ethylidene dimethacrylate)
Poly(ethylmercapty1 met hacryl at e)
Poly(Z-fluoroethyl methacrylate)
Poly(4-fluoro-2-trifluoromethylstyrene)
Poly(furfury1 met hacryl at e)
Poly(2-heptafluorobutoxy)ethyl acrylate)
Poly(heptafluorobuty1 acrylate)
Poly(2-heptyl-1,3-butadiene)
Poly(hexadecy1 met hacryl at e)
Poly(2,2,3,4,4,4-hexafluorobutyl acrylate)
Poly(n-hexyl methactylate)
Poly(Z-hydroxyethyl met hacryl at e)
Poly(iminoadipoyliminohexamethylene) (nylon 6,6)
Poly(iminoadipoylimino tetramethylene) (nylon moulding 6,lO)
oriented fibers
1.4638
1.5390
1.5135
1.5823
1.5270
1.5179
1.6040
1.533
1.517
1.5624
1.554-1.558
1.6098
1.5683
1.5707
1.5067
1.542
1.532
1.4969
1.5066
1.5575
1.4990
1.4730
1.4899
1.572
1.5739
1.5270
1.6248
1.5174
1.4889
1.544
1.525
1.5816
1.5933
1.6150
1.4740
1. 523- 1. 54
1.471
1.4833
1.465
1.4685
1.502
1.4903
1.485
1.51
1.52-1.53
1.545
1.51
1.4748-1.48
1. 47- 1. 50
1.5063
1.4831
1.547
1.4768
1.46
1.5381
1.390
1.367
1.5000
1.4750
1.392
1.4813
1.5119
1.53
1.53
1.515-1.565
25
20
20
20
20
20
20
25
25
20
20
20
20.5
20
20
20
20
20
20
20 -
20
20
20
25
20
25
20
25
20
20-25
20
20
20
20
20
20
20
25
25
30
25
20
20
References page VI - 582
VI / 580 REFRACTIVE INDICES OF POLYMERS
TABLE 3. cont d
Polymer
n T (Cl
-
Poly(imino(l-oxohexamethylene)) (nylon 6)
Poly(isobutene)
Poly(isobuty1 methacrylate)
Poly(isoprene)
Poly(2-isopropyl-1,3-butadiene)
Poly(isopropy1 methacrylate)
Poly(p-isopropylstyrene)
Poly(methacrylonitrile)
Poly(p-methoxybenzyl met hacryl at e)
Poly(2-methoxyethyl acrylate)
Poly((N-2-methoxyethyl)methacrylamide)
Poly(4-methoxy-2-methylstyrene)
Poly(o-methoxyphenyl methacrylate)
Poly(3-methoxypropyl acrylate)
Poly(o-methoxystyrene)
Poly@methoxystyrene)
Poly(methy1 acrylate)
Poly(methy1 cc-bromoacrylate)
Poly(methy1 a-chloroacrylate)
Poly(methy1 isopropenyl ketone)
Poly(methy1 methactylate)
Poly(N-methyl-methacrylamide)
Poly(Cmethyl-1-pentene)
Poly( 1-methylcyclohexyl methacrylate)
Poly(2-methylcyclohexyl methacrylate)
Poly(3-methylcyclohexyl methacrylate)
Poly(4-methylcyclohexyl methacrylate)
Poly(N-methylmaleimide-alt-isobutene)
Poly(o-methylstyrene)
Poly(a-naphthyl carbinyl methacrylate)
Poly(a-naphthyl methacrylate)
Poly(P-naphthyl methacrylate)
Poly(m-nitrobenzyl methacrylate)
Poly(2-nitro-2-methylpropyl methacrylate)
Poly(nonafluoropenty1 acrylate)
Poly(octafluoropenty1 acrylate)
Poly(oxycarbonyloxybis( 1,4-(3,5-dichlorophenylene))
Poly(oxycarbonyloxy-1,4-(2,6-dichloro)phenylene-isopropylidene-1,4-(2,6-dichl~
Poly(oxycarbonyloxy- 1,4-phenylene- 1,3-dimethylbutylidene- 1,4-phenylene)
Poly(oxycarbonyloxy-1,4-phenylene-l-methyl-butylidene-1,4-phenylene)
Poly(oxycarbonyloxy-1,4-phenylene-l-propylbutylidene-l,4-phenylene)
Poly(oxycarbonyloxy- 1,4-phenylene-sec-butylidene- 1 ,Cphenylene)
Poly(oxycarbonyloxy- 1,4-phenylenebutylidene- 1,4-phenylene)
Poly(oxycarbonyloxy- 1,4-phenylenecyclohexylfdene- 1,4-phenylene)
Poly(oxycarbonyloxy- 1,4-phenylenediphenyl-methylene- 1,4-phenylene)
Poly(oxycarbonyloxy- 1,4-phenyleneethylidene- 1 ,Cphenylene)
Poly(oxycarbonyloxy- 1,4-phenyleneisobutylidene- 1 ,Cphenylene)
Poly(oxycarbonyloxy- 1,4-phenyleneisopropylidene- 1 ,Cphenylene)
Poly(oxy-2,6-dimethylphenylene)
Poly(oxydimethylsilylene) (poly(dimethy1 siloxane))
Poly(oxyethylene) (high molecular weight)
Poly(oxyethylene)-a-benzoate-o-methacrylate)
Poly(oxyethyleneoxymaleoy1) (poly(ethylene maleate))
Poly(oxyethyleneoxysuccinoy1) (poly(ethylene succinate))
Poly(oxyethyleneoxyterephthaloy1) (amorphous) (poly(ethylene terephthalate))
Poly(oxymethylene)
Poly(oxy-1-oxopentamethylene)
Poly(oxypentaerythritoloxyphthaloy1)
Poly(oxypropylene)
Poly(pentabromopheny1 methacrylate)
Poly(pentachloropheny1 methacrylate)
Poly(pentadecafluoroocty1 acrylate)
1.53
1.505-1.51
1.477 2 0
1.521 2 0
1.5028 3 0
1.4728 2 0
1.552
1.554 2 0
1.52
1.552 2 0
1.463 2 5
1.5246 2 0
1.5868 2 0
1.5705 2 0
1.471 2. 5
1.5932 2 0
1.5967 2 0
1. 472- 1. 480
1.5672 2 0
1.517 2 0
1.5200 2 0
1.4893 2 3
1.490 2 0
1.5398 2 0
1.459-1.465
1.5111 2 0
1.5028 2 0
1.4947 2 0
1.4975 2 0
1.53
1.5874 2 0
1.63
1.6410 2 0
1.6298 2 0
1.5845 2 0
1.4868 2 0
1.360 2 5
1.380 2 5
1.6056
1.6056
1.5671
1.5745
1.5602
1.5827
1.5792
1.5900 2 0
1.6539
1.5937
1.5702
1.5850
1.575
1.43
1.4563 3 0
1. 51- 1. 54
1.555 2 0
1.4840 2 5
1.4744 2 5
1.5750 2 0
1.48 2 0
1.465 5 0
1.584 2 0
1.4495
1.71
1.608 2 0
1.339 2 5
oro)phenylene))
TABLE 3. contd
Polymer
Average Refractive Indices of Polymers (Alphabetical Order) VI / 581
n
T (Cl
Poly(pentafluoropropy1 acrylate)
Poly(pentafluoroviny1 propionate)
Poly(l-phenyl-n-amyl methacxylate)
Poly(pheny1 a-bromoacryl at e)
Poly(pheny1 methacrylate)
Poly( 1 -phenylallyl methacrylate)
Poly( 1-phenylcyclohexyl methacrylate)
Poly( 1-phenylethyl methacrylate)
Poly(2-phenylethyl methacrylate)
Poly(N-(2-phenylethyl)methacrylamide)
Poly(2-(phenylsulfonyl)ethyl methacrylate)
Poly(n-propyl methacrylate)
Poly(propylene) (density 0.9075 g/cm3)
Poly(propylene) (atactic, density 0.8575 g/cm3)
Poly(styrene)
Poly(styrene-co-acrylonitrile) (- 75/25)
Poly(styrene-co-maleic anhydride)
Poly(sulfides) (Thiokol)
Poly(sulfone)
Poly(tetradecy1 methacrylate)
Poly(tetrafluoro-3-(heptafluoropropoxy)propyl acrylate)
Poly(tetrafluoro-3-(pentafluoroethoxy)propyl acrylate)
Poly(tetrafluoro-3-(trifluoromethoxy)propyl acrylate)
Poly(2-( 1,1,2,2-tetrafluoroethoxy)ethyl acrylate)
Poly(tetrafluoroethylene)
Poly(tetrafluoroethylene-co-hexafluoropropylene)
Poly(tetrahydrofurfury1 met hacryl at e)
Poly(triethylcarbiny1 methacrylate)
PoIy(2,2,2-trifluoro-I-methylethyl methacrylate)
Poly(trifluorochloroethylene)
Poly(2-trifluoroethoxy)ethyl acrylate)
Poly(trifluoroethy1 acrylate)
Poly(trifluoroethy1 methacrylate)
Poly(trifluoroisopropyl methacrylate)
Poly(trifluoroviny1 acetate)
Poly(3,3,Qrimethylcyclohexyl methacrylate)
Poly(undecafluorohexy1 acrylate)
Poly(urethanes)
Poly(viny1 acetal)
Poly(viny1 acetate)
Poly(viny1 alcohol)
Poly(viny1 benzoate)
Poly(viny1 butyl ether)
Poly(viny1 see-butyl ether) (isotactic)
Poly(viny1 butyral)
. .
Poly(viny1 chloride)
Poly(viny1 chloride) + 40% dioctyl phthalate
Poly(viny1 chloride) + 40% tricresyl phosphate
Poly(viny1 chloride-co-vinyl acetate) (95/5-90/10)
Poly(viny1 chloroacetate)
Poly(viny1 decyl ether)
Poly(viny1 dodecyl ether)
Poly(viny1 ethyl ether)
Poly(vinyl-2-ethylhexyl ether)
Poly(viny1 formal)
Poly(viny1 formate)
Poly(viny1 hexyl ether)
Poly(viny1 isobutyl ether)
Poly(viny1 methacrylate)
Poly(viny1 methyl ether)
Poly(viny1 methyl ether) (isotactic)
Poly(viny1 octyl ether)
Poly(viny1 pentyl ether)
Poly(viny1 phenyl sulfide)
1.385
1.364
1.5396
1.612
1.5706
1.5573
1.5645
1.5487
1.5592
1.5857
1.5682
1.484
1.5030
1.4735
1.59-1.592
1.57
1.564
1. 6-1. 7
1.633
1.4746
1.346
1.348
1.360
1.412
1.35(- 1.38)
1.338
1.5096
1.4889
1.4185
1. 42- 1. 43
1.419
1.407
1.437
1.4177
1.375
1.485
1.356
1.5-1.6
1. 48- 1. 50
1.4665
1. 49- 1. 53
1.5214
1.5775
1.4563
1.4740
1. 48- 1. 49
1. 54- 1. 55
1.52
1.55
1.525-1.535
1.512
1.4628
1.4640
1.4540
1.4626
1.50
1.4757
1.4591
1.4507
1.5129
1.467
1.4700
1.4613
1.4581
1.6568
25
25
20
25
20
20
20
20
20
20
25
20
20
20
2 1
30
25
25
25
25
20
20
2 5
25
20
2 5
20
20
20
20
30
30
2 5
30
30
30
30
20
30
30
20
20
30
30
30
20
References page VI - 582
VI / 582 REFRACTIVE INDICES OF POLYMERS
TABLE 3. contd
Polymer
Poly(viny1 propionate)
Poly(vinylcarbazole)
Poly(vinylfuran)
Poly(vinylidene chloride)
Poly(vinylidene fluoride)
Poly(vinylnaphthalene)
Poly(l-vinyl-2-pyrrolidone)
Poly(N-vinylphthalimide)
Poly(2-vinyltetrahydrofuran)
Poly(2-vinylthiophene)
Proteins
Shellac
Terpene resin
Urea-formal dehyde resi n
Urea-t hi ourea-formal dehyde resi n
Poly@,p-xylylenyl dimethacrylate)
n T PC)
1.4665 20
1.683 20
1.55 20
1. 60- 1. 63
1.42 25
1.6818 20
1.53
1.6200 20
1.55 20
1.6376 20
1.539-1.541
1. 51- 1. 53
1.515 25
1. 54- 1. 56
1.660 25
1.5559 20
F. REFERENCES
1 . J. R. Partington, An Advanced Treatise of Physical Chem-
istry: Physico-Chemical Optics, vol. IV, Longmans, Green
and Co., London, 1960.
2. J. F. Nye, Physical Properties of Crystals, Oxford Uni-
versity Press, London, 1960.
3. J. C. Seferis, R. J. Samuels, Polym. Eng. Sci., 19, 975
(1979).
4. A. R. Wedgewood, J. C. Seferis, Polym. Eng. Sci., 24, 328
(1984).
5. R. S. Stein, G. L. Wilkes, in: I. M. Ward, (Ed.) Structure
and Properties of Oriented Polymers, Wiley, New York,
1975.
6. K. G. Denbigh, Trans. Faraday Sot., 36, 936 (1940).
7. R. L. Rowell, R. S. Stein, J. Chem. Phys., 47, 2985 (1967).
8. D. W. Krevelen, Properties of Polymers - Part III: Proper-
ties of Polymers in Fields of Force, 3rd ed., Elsevier, New
York, 1990.
9. R. J. Samuels, J. Appl. Polym. Sci., 26, 1383 (1981).
10. l? H. Hermans, Contribution to the ,Physics of Cellulose
Fibers, Elsevier, New York, 1946.
11. R. S. Stein, J. Polym. Sci. A-2, 7, ld21 (1969).
12. A. J. devries, C. Bonnebat, J. Polym. Sci., Polym. Symp.,
58, 109 (1977).
13. A. J. devries, Pure Appl. Chem., 53, 1011 (1981).
14. R. S. Stein, J. Appl. Phys., 32, 1280 (1961).
15. G. W. Shael, J. Appl. Polym. Sci., 8, 2717 (1964).
16. G. W. Shael, J. Appl. Polym. Sci., 12, 903 (1968).
17. J. C. Seferis, in: J. Brandrup, E. H. Immergut (Eds.),
Polymer Handbook, 3rd ed., Wiley, New York, 1989,
p. vv451.
18. C. Y. Cha, R. J. Samuels, J. Polym. Sci. B: Polym. Phys., 33,
259 (1995).
19. S. S. Hardaker, R. J. Samuels, J. Polym. Sci. B: Polym.
Phys., 35, 777 (1997).
20. C. Cha, R. Samuels, S. Hardaker, R. Gregory, Synthetic
metals, 84, 743 (1997).
21. S. Hayashi, K. Asada, S. Hovike, H. Furahata, T. Hirai, J.
Colloid Interface Sci., 176, 370 (1995).
22. D. F. Stamatialis, M. Wessling, M. Sanopoulou, H. Strath-
mann, J. H. Petropoulos, J. Membrane Sci., 130, 75 (1997).
23. T. Doi, S. Yukioka, H. Inoue, A. Akimoto, J. Appl. Pol. Sci.,
63, 925 (1997).
Radiation Resistance of Plastics
and Elastomers
Tadao Seguchi, Yosuke Morita
Takasaki Radiation Chemistry Research Estiblishment, Japan Atomic Energy Research Institute (JAERI),
Takasaki, Gunma 370-I 2, japan
A. Introduction VI-583
1. General Comments VI-583
2. Criterion for Radiation Resistance . VI-583
3. Factors of Influence and their Consideration
in Tables VI-583
3.1. Type of Polymer and Formulation VI-583
3.2. Type of Radiation and Dosimetry VI-584
3.3. Dose Rate and the Atmosphere VI-584
3.4. Temperature VI-584
3.5. Other Stresses VI-584
B. List of Symbols Used VI-584
C. Tables of Radiation Resistance VI-585
Table 1. Thermoplastics VI-585
Table 2. Elastomers VI-586
Table 3. Aromatic Polymers VI-587
Table 4. Organic Composite Materials VI-588
D. References VI-588
A. INTRODUCTION
1. General Comments
The data on radiation resistance -have been compiled
mainly for practical polymer materials that have been
classified into four groups: thermoplastics, elastomers, all
aromatic polymers, and composite materials. The values of
radiation resistance were determined by the change in
mechanical properties. Radiation-induced degradation of
polymer materials depends greatly on the irradiation
conditions, as indicated in the tables; hence, the reader is
advised to use these data with caution, considering all the
factors.
2. Criterion for Radiation Resistance
Radiation resistance is characterized by the half-value-dose
of significant changes in mechanical properties. For
elastomers and thermoplastics, with large ultimate elonga-
tion by tensile test, the resistance is characterized by 100%
elongation at break. The half-value-dose means the
absorbed dose that reduces a property to 50% of its initial
value under defined environments. The SI unit gray (Gy;
1 Gy = 1 J/kg = 100rad) is used, and values in tables are in
units of MGy (lo6 Gy) when there is no notation. In cases
where the absorbed dose in the experiment was terminated
before reaching the criterion, the dose is given with the sign
>.
The properties can be affected differently, therefore more
than one relevant property should be considered. In most
cases, the properties used to characterize radiation resis-
tance are the elongation at break for elastomers and flexible
plastics, and the flexural strength for rigid plastics and
composite materials. However, the elongation at break
sometimes increases with elastomers deterioration, but in
that case, the strength decreases greatly.
3. Factors of Influence and their Consideration
in Tables
Radiation resistance depends on polymer formulation as
well as on the conditions of radiation exposure, such as the
environmental atmosphere, temperature, dose rate, mechan-
ical stress, etc. The most effective factor is the oxidation
induced by radiation. Radiation resistance is indicated in
two categories, with and without oxidation, together with
the irradiation conditions employed.
3.1. Type of Polymer and Formdafion The polymer
samples reported were generally formulated by mixing with
chemical agents, such as of stabilizers and fillers.
Elastomers were normally crosslinked. The formulation
and/or crosslinking have many variations for a given type of
polymer. The formulation is determined by the suppliers
based on the application (which may need, improve the
mechanical or thermal properties), and the contents are
usually not disclosed. Radiation resistance is influenced by
formulation and crosslinking. In general, radiation resis-
tance can be increased with inorganic fillers, with good
adhesion between the polymer and reinforcing fillers, with
VI / 583
VI / 584 RADIATION RESISTANCE OF PLASTICS AND ELASTOMERS
antioxidants, and with aromatic compounds. Organic fillers
usually decrease radiation resistance. Some of the aromatic
polymers reported may contain fillers of glass or carbon
fibers.
The first column of the tables give the polymer name,
along with the formulation or cross-linking. The second
column gives the form of the test sample: either sheets
(formed by heat press) or films (formed by extrusion or
inflation), and their thickness (in mm).
3.2. Type of Radiation and Dosimetry The overall
radiation effect does not depend on the type of radiation
(such as X rays, gamma rays, electron beams, nuclear
reactor irradiation, or other accelerated particle radiation),
but only on the absorbed dose. There are some uncertainties
about the given dose, especially to different types of
radiation. In the following tables, the accuracy of the dose
is estimated to be *lo% for gamma-rays and *20% for
electron beams or accelerated particles.
3.3. Dose Rate and the Atmosphere In an inert gas
atmosphere or under vacuum, the dependence of dose rate
on polymeric degradation is negligible at ambient tempera-
ture (1). If the other stresses, such as thermal degradation or
light exposure, are eliminated during irradiation, the
degradation should depend on the accumulated dose. If
oxygen is present, the induced oxidation will decrease
radiation resistance. The overall oxidation is determined by
the rate of oxygen consumption by radiation-induced
oxidation in the polymer matrix, and by the rate of oxygen
supply into the matrix. The thickness of the polymer
oxidation layer (L,,) is a function of radiation dose rate (I),
oxygen partial pressure (P,,) at one atmosphere total
pressure, oxygen permeability coefficient (P,) into the
polymer matrix, and oxygen consumption factor (a), and is
B. LIST OF SYMBOLS USED
CT Tensile strength at break (ultimate strength)
ffl/2
Half of tensile strength at break
& Elongation at break (ultimate elongation)
El/2
Half of elongation at break
E 100%
100% of elongation at break
gF
Flexural strength
ffF1/2 Half of flexural strength
IL Inter Lamella Shear Strength (ILSS)
IL112 Half of ILSS
Y
(jCo- y-rays
given by the following equation. (Ref. 2,3).
L,, = (PC P,,/Z a) 12
(1)
When the test material is a thick sheet, the oxidation layer
occurs only at the surface, and the inside is not oxidized.
The oxidation layer increases with decreasing dose rate. For
most polymers, the degradation is more progressive with
oxidation than without it. The dose rate affects the ratio
of oxidation layer to material thickness. The degradation
with oxidation can be observed by irradiation of a thin film;
here, oxidation proceeds throughout the film. Oxidation
throughout a thick film requires irradiation with oxygen
under pressure rather than decreasing the dose rate (4). In
the following tables, radiation resistance with oxidation
implies that oxidation takes place throughout the material.
The other dose-rate dependent degradation, chain-
reaction oxidation, has been reported at low dose-rate
irradiations over long time periods. We believe that it is
difficult to distinguish these chain reactions from thermal
oxidation. In the tables, the data for very low dose rate have
been excluded.
3.4. Temperature The irradiation temperature is ambient
temperature, i.e. about 20-30C. The data for low-
temperature irradiation is listed for few materials. Several
experiments performed at higher irradiation temperatures
are also listed. As the resistance depends on irradiation
temperature, it is supposed that chemical reactions increase
greatly due to the increased molecular motions during
irradiation.
3.5. Other Stresses The tables do not consider mechan-
ical stress and deformation during irradiation. These factors
can have a large influence on degradation.
EB
nH+
RT
Vat
Air
He
N2
02
Electron beams, ( ) energy
Neutron, ( ) energy
Proton, ( ) energy
Room temperature
Vaccum (including seal after vacuum)
Air atmosphere
Helium-gas atmosphere
Nitrogen-gas atmosphere
Oxygen gas, ( ) indicates pressure
- -
C. TABLES OF RADI ATI ON RESI STANCE
-7
TABLE 1. THERMOPLASTICS
Radiation resistance
Polymer Form
Property Without oxidation (surface oxidation) With oxidation
Initial Dose Dose
value Criterions (MGY) Irradiation conditions Refs. (MGy) Irradiation condition Refs. Remarks
Poly(ethylene)
low-density (LDPE),
non formulated
low-density (LDPE),
non fornmlted
cross-linked (XLPE),
formulated,
cable insulator
UHMW-PE (ultra
high molecular
wei ght - PE)
Poly(propylene) (PP).
isotactic PP
Poly(vinyl chloride)
(PVC), formulated
Poly(vinyl chloride)
(PVC), cable jacket
Poly (12.aminolauric
acid), Nylon- 12
Poly (c-caprolactam),
N y l o n - 6
Poly(ethylene-
terephthalate) (PET)
Poly(ethylene), 2,6-
naphthalate (PEN)
Poly(methylmethacrylate)
(PMMA)
Poly(styrene) (PS),
atactic PS
Poly(styrene) (PS),
syndiotactic PS
Poly(tetrafluoroethylene)
WFE)
Cross-linked PTFE
(XL-PTFE)
Poly(vinylidene fluoride)
(PVDF)
Poly(ethylee-
tetrafluoro ethylene-
co-polymer) (ETFE),
Tefzel
Sheet, 1 mm
Film, 0.1 mm
Sheet, I mm
Tube, 5 mm 4
Fiber,
0.011 mm I$
Sheet, 0.5 mm
Film, 0. I mm
Sheet. I .O mm
Tube,
O D 18mm 4
1.8mm t
Sheet. 0.5 mm
Sheet, 0.5 mm
Film, 0. I mm
Film, 0 : 280MPa
0.075 mm E : 30%
Sheet, 3 mm 0~: 130MPa
Sheet, 0.5 mm
Sheet, 0 5 mm
Sheet. 0.5 mm
Sheet, 0.5 mm
Sheet, I mm
Film, 0.1 mm
Film. 0. I mm
0 : 18MPa
E : 500%
LJ : 45MPa
E : 800%
u: 17MPa
E : 500%
cr : 20MPa
E : 700%
0 : 3.7GPa
g: 32MPa
e : 210%
E : 1200%
(r: 28MPa
E : 370%
(T : 20MPa
c: 190%
D : 80MPa
E : 430%
0: 130MPa
E : 400%
g : 220MPa
E : 7 5 %
0 : 60MPa
o : 60 MPa
(r : 55MPa
E : 400%
c: 25MPa
E : 270%
0: IlOMPa
E : 800%
c : 65MPa
E : 650%
> 1. 5
> 1.5
>2
2.0
3
3
1 .o
0 . 8
0.5
0.04
0.02
>3
1 . 7
> 1.4
I .o
>3
2 . 3
>3
>3
2 . 5
1 . 8
2 . 5
4 2
1 2
0. 15
1 . 5
> IO
2
>30
y, RT, vat, 5 kGy/h 5
EB (2 MeV), RT, vat, 2.5 kGy/s or
H+(8 MeV), RT, vat, 0.7 kGy/s 6
y, RT, vat, 6 kGy/h 7
y, RT, air, IOkGy/h 8
y, RT, vat, IO kGy/h 10
EB (2 MeV), RT, vat, 2.5 kGy/s or
H+@MeV), RT, vat, 0.7 kGy/s
y, RT, vat, 6 kGyih
6
7
y. RT, air, lOkGy/h 8
y, RT, vat, 5 kGy/h II
y, RT, vat, 5 kGy/h 1 1
y, RT, vat, IO kGy/h 1 2
H+(8 MeV), RT, vat, 0.7 kGy/s 6
y, RT, vat, IO kGy/h 1 2
y, RT, vat, IOkGy/h
y, 77 K, N 2, 30 kGy/h
H+(30, 45 MeV), RT,
vat, 30 Gy/s
y. RT, vat, 10 kGy/h
CT, 80C. vat, 10 kGy/h
y, RT, vat, 10 kGyih
1 3
14
15
1 5
I5
15
1 6
IO-20 y. SOT, vat, 10 kGy/h
0.0035 y, RT, vat, 1OkGylh
0. 015
0 . 1 y, 77 K, N 2, 30 kGy/h
2.0 y. RT, vat, 10 Gy/h
1 . 2
I .o y, RT, air, 10 Gy/h
0.3
0.4 Hf(8 MeV), RT, vat,
0.6 0.7 kGy/s
1 3
1 6
1 7
6
> 2. 5 EB (2 MeV), RT, vat, 2.5 kGy/s or
2 . 5 H+ (8 MeV), RT, vat, 0.7 kGy/s 6
0. 25
0.4
y, RT, 02 (I.OMPa), 5 kGy/h
I . o Y, RT, 02 (0.4 MPa), 6 kGy/h
2.6
0.4 /. RT, 02 (l.OMPa), 2.8 kGy/h or
0.4 air, SOGy/h
O.l- 0.2 y, RT, 02 (0.03 MPa), 10 kGy/h
0. 15 y. RT, 02 (0.1 MPa), IOkGyih
0 . 3
0 . 5
0.6
0 . 1
Y. RT, 0 2 (0.4 MPa), 6 kGy/h
Y. RT, 02 (1 MPa), 2.8 kGy/h, or
air, 50 Gy/h
0. 15
0. 18
0. 06
0. 07
1.8
1 . 4
y, RT, 0 2 (0.7 MPa), I .2 kGyih
y. RT, 02 (0.7 MPa), 1.2 kGy/h
y, RT, air, 8.5 kGy/h, or
0 2 (2 MPa), 8.5 kGylh
7 . 8
4 . 5
y. RT, 02 (0.6MPa), 8.5 kGy/h
0.0015
0.002
y, RT, air, 10 kGy/h
0. 45
0. 25
0.6
0.2
y, RT, air, 10 kGy/h
Y, RT, 0 2 (0.5 MPa), 5 kGy/h
Low dose rate in air has the same
8 effect as high dose rate in 02
under pressure
11
1 1 Inner part is not oxidized by
oxygen under pressure
Oxidation proceeds throughout
1 2 film in air at a relatively high
dose rate
1 2 Cross-linking under vacuum
i r r a di a t i on
1 6 In air, oxidation proceeds
throughout sheet
1 6 In air, oxidation proceeds
throughout sheet
17
I
References page VI-588
TABLE 2. ELASTOMERS
s
\
Polymer Form
Radiation resistance
E
Property Without oxidation (surface oxidation) With oxidation
Initial Dose
6
value Criterion
(MGY)
Irradiation conditions Refs. Irradiation conditions Refs. Remarks
5
0
0: lIMPa
c : 270%
0: 2lMPa
E : 390%
Ethyl acrylate rubber Sheet, I mm
formulated, commercial
Chlorosulphonated Sheet, I mm
polyethylene (Hypalon )
formulated
Chlorosulphonated Tube, 20mm 4
polyethylene (Hypalon ) 2 mm t
cable jacket
Ethylene-propylene- Sheet, I mm
copolymer (EPR)
formulated, commercial
Ethylene-propylene-ter- Sheet, I mm
polymer (EPDM)
formulated, commercial Tube, 5 mm #
Cable insulator
Ethylene-vinylacetate- Sheet, 1 mm
rubber (EVM or EVA)
formulated, commercial Film, 0.1 mm
y, RT, air, IOkGy/h 1 7
y, RT, air, IO kGy/h I7
y, RT, air, IO kGy/h 8
y, RT, air, IO kCy/h 17
y. RT, air, 10 kGyih 1 7
y, RT, air, lOkGy/h 8
y, RT, air, lOkGy/h 1 7
EB (2 MeV), RT, vat, 2.5 kGy/s or
H +(8 MeV), RT, vat; 0.7 kGy/s 6
y, RT, air, lOkGy/h 1 7
y, RT, air, lOkGy/h 17
y, RT, air, 10 kGy/h 17
y, RT, air, lOkGy/h 1 7
3
>2
1 . 2
0.6
Y, RT, 02 (0.5 MPa), 5 kGy/h 1 7
y. RT, 02 (0.5 MPa), 5 kGy/h 1 7
0: 12MPa
E : 520%
>2
1 . 5
y. RT, air, 50Gy/h, or
02 (l.OMPa), 2.8 kGy/h
0 : I1 MPa
E : 270%
3
>2
y. RT, 02 (0.5 MPa), 5 kGy/h
8
17
0 : 12MPa
E : 800%
c : 8.5MPa
E : 590%
cr: IlMPa
E : 270%
cr : 30MPa
E: 110%
o:MPa
E : Yo
> 1 . 5
> 1 . 5
> IO
>4
1.5
>3
> 2 . 5
2 . 5
0.7
0.8
> 1.5
> 1.5
y, RT, 02 (0.5 MPa), 5 kGy/h 1 7
>3
>3
y. RT, 02 (0.5 MPa), 5 kGy/h 17
Oxidation proceeds throughout in
2
0 2 under pressure 2
Oxidation proceeds throughout in 0 2 z
under pressure Y
Oxidation proceeds throughout at
5
very low dose rate or in O2 under
c?
pressure B
In 02 oxidation proceeds
F
throughout sheet 3+
Y
Oxidation is only on the surface
at high dose rate, and proceeds
E
throughout sheet in 02 under
pressure
Lt
Same as above P
B
Poly(vinylidene Ruoride- Sheet, I mm
co-hexafluoropropylene)
(Viton ) commercial
Poly(tetrafluoroethylene- Sheet, I mm
co-propylene)
(Aflus ) commercial
Poly-(cis-isoprene) (Natural Sheet, 1 mm
rubber)
formulated, commercial
Poly(butadiene-co- Sheet, 1 mm
acrylonitrile) (Nitrile/
butadiene rubber),
formulated, commercial
Poly(isobutene-co- Sheet, I mm
isoprene) (Butyl rubber)
formulated, commercial
Silicone rubber (Q) Sheet, 1 mm
di-methylsilicone,
commercial
Silicone rubber Sheet, I mm
di-methyl silicone/
phenyl silicone (30phr),
commercial
Poly(butadiene-co-styrene) She e t ,
(styrene-butadiene
rubber (SBR),
commercial
Polyurethane rubber Sheet,
(AU), commercial
Polyurethane-polyester, Sheet,
commercial
n:MPa
E : %
o : 22MPa
E : 580%
c: 17MPa
E : 670%
0: MPa
E : Ya
cr: MPa
t : Yo
u:MPa
E : %
mm u: MPa
E : Yo
mm 0: 1 9 MPa
E : 420%
E IMX
-3 mm c: 3 5 - 6 0 MPao ,j2
e : 600%
E IMA>
>3
0 . 5
I .o
2 . 5
2 . 5
1 . 5
0.06
0. 25
0.8
0 . 5
2 . 5
>3
y. RT, air, IO kGy/h 1 7
y, RT, air, IOkGy/h 1 7
y, RT, air, IO kGy/h 1 7
>3
2
I .4
3.0
y. RT, air, lOkGy/h I7
y. RT, air, IO kGy/h 1 7
0.5-I .O Reactor, RT, air, 200 kGyih I8
3-5
0 . 3
0 . 3
0 . 1
1 . 5
0 . 3
0 . 7
2 . 5
3
0. 06
0.2
1 . 2
0 . 8
2 . 3
2 . 3
1 . 2
0 . 7
0.4
3
0 . 2
>0.5
y. RL 02 (0.5 MPa), 5 kGyih 17 Same as above
y. RT, 02 (0.5 MPa), 5 kGy/h 1 7 Same as above
y. RT, 02 (0.5 MPa), 5 kGyih 17 Same as above
y, RT, 02 (0.5 MPa), 5 kGy/h 1 7 Same as above
y. RT, 02 (0.5 MPa), 5 kGy/h 17 Same as above
y. RT, 02 (0.5 MPa), 5 kGy/h 1 7 Same as above
y, RT, 02 (0.5 MPa), 5 kGyih 17 Same as above
y. RT, 02 (0.5 MPa), 5 kGyih 1 7 Same as above
y. RT, 02 (0.5 MPa), 5 kGy/h 1 7 Same as above
X-rays, RT, air, 100 kGy/h 1 8 Same as above
1
T A B L E 3 . A ROMA T I C POL Y MERS
Radiation resistance
Polymer Form
Property Without oxidation (surface oxidation) With oxidation
Initial Dose Dose
value Criterion (MGy) Irradiation conditions Refs. (MGY) Irradiation conditions Refs. Remarks
Poly(phenyl-amide),
Nomex
Poly-arylene-ether-nitrile,
BEK
(Idemitsu Kosan)
Poly(ether-ether-ketone)
( P E E K)
amorphous
Poly(ether-ether-ketone)
( P E E K)
crystalline
Poly(ether-ether-imide),
ULTEM
Poly(imide),
Kapton
Poly(imide),
Up&x-R
Poly(imide),
Up&x-S
Poly(imide),
Thermo-plastics,
RegulusO
Poly(ethersulfone),
(PEW
Film, 0.05 mm 0 : 100 MPa
e : 9%
Sheet, 2 mm o : 82MPa
E : 21%
CF : 107MPa
Film, 0.125 mm n : 135 MPa
E : 210%
Film, 0.050 mm g : 120 MPa
E : 220%
Film, 0.125 mm o : 190 MPa
E : 190%
Film, 0.050 mm c : 105 MPa
E : 240%
Film, 0.05 mm g : 140 MPa
E : 160%
Film, 0.125 mm 0 : 240MPa
E : 90%
Film, 0.05 mm 0 : 240MPa
E : 90- 120%
Film, 0. I25 mm g : 260 MPa
E : 130-100%
Film, 0.05 mm (T : 320MPa
E: 100%
Film, 0. I25 mm c : 390 MPa
E : 30-50%
Film, 0.05 mm g : 380MPa
E : 36%
Film, O.lOOmm 0 : 120MPa
E: 110%
Sheet, 2 mm n: 78MPa
E : 60%
Film, 0. IO mm g : 85 MPa
E : 190%
..
1 5
1 0
3 7 0
2 0 0
> 370
> 300
1 0 0
>300
125
>3Oil
8 5
>300
4 5
1 6 5
15
>300
1 4 0
>300
160
>300
6 0
>300
1 8 0
>300
>300
>300
2 3 0
>300
7 0
> 120
9 0
>2
1
y, RT, air, IO kGy/h
Reactor, RT, air, 750 kGy/h
EB (2 MeV), RT, He, 6.4 kGy/s
y, RT, N2, 16kGy/h
EB (2 MeV), RT, He, 6.4 kGy/s
y. RT, N2, 16 kGyih
y, RT, Nz, I6kGy/h
EB (2 MeV), RT, He, 6.4 kGy/s
y. RT, N1. 16 kGyih
EB (2 MeV), RT, He, 6.4 kGy/s
y, RT, N?, I6kGy/h
EB (2 MeV), RT, He, 6.4 kGy/s
y. RT, Nz, I6 kGyih
EB (2 MeV), RT, He, 6.4 kGy/s
EB (2MeV). RT, air, 5 kGy/s
EB (2 MeV), RT, vat, 2.5 kGy/s
21
2 2
2 1
2 2
2 2
2 1
2 2
21
2 2
21
2 2
21
2 4
6
6
3
I O
>I0
2 0
8
IO
8
1 2
5
I2
5
1 2
3
7
3
>20
2 0
3 6
3 0
60
4 0
Y. RT, 02 (0.5 MPa), 5 kGy/h
Y, RT, 02 (0.5 MPa), 5 kGy/h
y. RT, air, 16kGylh
Y. RT, 0 2 (0.5 MPa), 5 kGy/b
y, RT, air, 16 kGyih
y. RT, air, 16 kGy/h
Y. RT, 02 (0.7 MPa), 5 kGy/h
Y, RT, 0 z (0.6 MPa), 5 kGyib
Y. RT, 02 (0.7 MPa), 5 kGy/h
y. RT, air, 16 kGy/h
y, RT, air, 16 kGy/h
19
2 2
1 9
2 2
2 2
2 3
2 2
Oxidation of surface in air irradiation
Dose in reactor irradiation:
95% y-rays and 5% neutron;
temperature of material is
estimated to be heated up to
100 C or more
Inner part is not oxidized in air at
high dose-rate
1 9
2 2 Inner part is not oxidized in air
i r r a di a t i on
2 2 Inner part is not oxidized in air
irradiation
References page VI-588
VI/588 RADIATION RESISTANCE OF PLASTICS AND ELASTOMERS
TABLE 4. ORGANIC COMPOSITE MATERIALS
Polvmer Form
Radi at i on resi st ance wi t hout oxi dat i on
Property ( surf ace oxi dat i on)
I ni t i al Dose
val ue Criterion
(MGY)
I rradi at i on condi t i ons Ref s. Remarks
WRP(epox~ resin),
G-1OCR
GFRP(epox8 resin),
G-l 1 CR-
GPRP(epoxy resin),
(TGDDM/DDM),
Vf : 40%
GFRP(epoxy resin),
M50J/2500E
GFRP(silicon resin)
GFRP(polyester),
Vf : 40%
GPRP(Kerimide)
CFRP(epoxy resin),
T300/3601,
IM-6lR6376
CFRP(PEEK),
T6142/PEEK
CFRP(polyimide),
T800WPMR-15-R
AFRP(epoxy resin),
Kevlar 49/DGEBA,
(RBRA) s
AFRP(epoxy resin),
Kevlar 49iTGDDM/StO,
(New FiBRA)P
Sheet, 2mm up: 600MPa
OF]/2
aFl/2
aFIj2
Sheet, 2 mm by : 630 MPa
6F1/2
UFI/Z
Sheet, 2mm crF : 0.5-.7 GPa aFliz
IL : 50 MPa
~I/2
Sheet, 2 mm CTF : 0.8 GPa
IL : 60 MPa
Sheet, 4-6mm 0~ : 1.5 GPa
OFI/2
IL I,2
OFI/
Sheet, 4-6 mm bF : 2-3 GPa
OFI/
Sheet, 4- 6mm 0~ : 5 GPa oFl/Z
Sheet, 2 mm OF : 2.0GPa 6F1/2
Sheet, 2 mm bF : 700MPa aFl/2
Sheet, 2 mm (JF : 1.2GPa
IL : 80 MPa
Fabric rod, D : 1.6GPa
3-20mm 4 0~ : 150MPa
IL: 53MPa
Fabric rod, 0 : 1.6GPa
3-20mm 4 bF : 150MPa
IL: 45 MPa
aFl/2
IL I/2
0 : 90%
cF1/2
IL1/z
fJ : 90%
oFI/2
IL I/2
2 y, R T , N2, lOkGy/b
25 y, 77K, N2, 30kGy/h
2 H+ (30, 45 MeV), RT,
vat, 5 kGy/b
40 y, RT, air, lOkGy/h
> 120 EB (2MeV). RT, air, 5 kGy/s
70-90
> 60 EB (2 MeV), RT, air, 5 kGy/s
>60
50 Reactor, RT, air, I-2MGy/h
lo-50 Reactor, RT, air, l-2MGy/b
8 0 Reactor, RT, air, l-2 MGy/h
> 120 EB (2 MeV), RT, air, 5 kGy/s
> 120 EB (2 MeV), RT, air, 5 kGy/s
> 60 EB (2 MeV), RT, air, 5 kGy/s
>60
5 EB (2 MeV), RT, air, 5 kGyih
3 0
6 0
> 1205 EB (2 MeV), RT, air, 5 kGy/h
> 120
> 120
13
14
25
2 6
2 7
2 8
2 8
28
2 9
3 0
2 7
31
31
(TF : 1.2 GPa at 77 K
H+ was irradiated by beam
scanning throughout sheet
OF : 1.2GPa at 77K
In air, oxidation is limited only to the
surface layer in air at high
dose-rate
0~ : 1.2GPa at 77K
In air, oxidation is limited only to the
surface layer in air at high
dose-rate
Same as above
In air oxidation is limited only to the
surface layer in air at high
dose-rate
Same as above
Same as above
Same as above
Same as above
Same as above
Same as above
Same as above
GFRP: Glass fiber reinforced plastic; CFRP: Carbon fiber reinforced plastic; ARFP: Aramid fiber reinforced plastic.
D. REFERENCES
1. Y. Haruyama, Y. Morita, T. Seguchi, T. Tanaka, T. Kanazawa,
K. Yotsumoto, K. Yoshida, Report of Japan Atomic Energy
Research Institute, JAERI-M 88-197 (1988).
2. T. Seguchi, S. Hashimoto, K. Arakawa, N. Hayakawa,
W. Kawakami, I. Kuriyama, Radiat. Phys. Chem., 17, 195
(1981).
3. H. Kashiwabara, T. Seguchi, Ch. 11 in: A. Singh, J.
Siverman (Eds.), Radiation Processing of Polymers, Hanser
Publishers, 1991.
4. T. Seguchi, K. Arakawa, N. Hayakawa, S. Machi, Radiat. Phys.
Chem., 18, 671 (1981).
5. T. Seguchi, K. Arakawa, M. Ito, N. Hayakawa, S. Machi,
Radiat. Phys. Chem., 21, 495 (1983).
6. T. Sasuga, S. Kawanishi, T. Seguchi, I. Kohno, Polymer, 30,
2054 (1989).
7. M. Sugiyama, M. Nitta, T. Yagi, T. Seguchi, Inst. Elect. Eng.
Japan, Papers of Technical Meeting on Electrical Insulating
Materials, DEI-94-88 (1994).
8. T. Seguchi, K. Yoshida, Inst. Elect. Eng. Japan, Papers
of Technical Meeting on Electrical Insulating Materials,
EIM-82-113 (1982).
9. Y. Izumi, M. Nishii, T. Seguchi, K. Ema, T. Yamamoto, Radiat.
Phys. Chem., 37, 213 (1991).
10. E. A. Hegazy, T. Seguchi, K. Arakawa, S. Machi, J. Appl.
Polym. Sot., 26, 1361 (1981).
11. Y. Morita, T. Seguchi, Inst. Elect. Eng. Japan, Papers
of Technical Meeting on Electrical Insulating Materials,
EIM-83-131 (1983).
12. T. Saito, T. Seguchi, S. Nagano, I. Omae, JAERI-M 89-096.
13. H. Kudoh, N. Kasai, T. Sasuga, T. Seguchi, Radiat. Phys.
Chem., 43, 329 (1994).
14. H. Kudoh, T. Sasuga, T. Seguchi, in: R. L. Clough,
S. W. Shalaby (Eds.), Irradiation of Polymers, ACS Sympo.
Series 620, 1 (1996).
15. Y. Tabata, A. Oshima, K. Takashika, T. Seguchi, Radiat. Phys.
Chem., 48, 563 (1996).
16. A. Oshima, S. Ikeda, T. Seguchi, Y. Tabata, Radiat. Phys.
Chem., 49, 279 (1997).
17. T. Seguchi, T. Sasuga, K. Yoshida, H. Yagyu, Y. Yamamoto,
Inst. Elect. Eng. Japan, Papers of Technical Meeting on
Electrical Insulating Materials, EIM-82-114 (1982).
18. H. Shonbacher, M. Tablet, CERN-89-12 (1989).
19. T. Seguchi, K. Arakawa, K. Yoshida, Y. Yamamoto, H. Yagyu,
Inst. Elect. Eng. Japan., Papers of Technical Meeting on
Electrical Insulating Materials, EIM-83-132 (1983).
20. K. Arigane, A. Otomo, H. Sasajima, H. Takahashi, T. Seguchi,
S. Murakami, JAERI-Tech 94-004 (1994).
21. T. Kawamata, M. Nagai, Y. Morita, T. Yagi, T. Seguchi, Inst.
Elect. Eng. Japan., Papers of Technical Meeting on Electrical
Insulating Materials, DEI-94-91 (1994).
22. Y. Morita, K. Watanabe, H. Yagyu, Inst. Elect. Eng. Japan.,
Papers of Technical Meeting on Electrical Insulating Materi-
als, EIM-88-129 (1988) and their additional data.
23. T. Sasuga, Polymer, 29, 1562 (1989).
24. T. Hirade, Y. Hama, T. Sasuga, T. Seguchi, Polymer, 32,2499
(1991).
25. S. Egusa, H. Nakajima, M. Oshikiri, M. Hagiwara, S. Shima-
moto, J. Nucl. Mater., 137, 173 (1985).
Re f e r e n c e s VI / 589
26. K. Sonoda, Y. Yamamoto, 0. Hashimoto, T. Ono, H. Tomita,
A. Udagawa, S. Egusa, T. Sasuga, T. Seguchi, N. Tamura,
Japan. J. Appl. Phys., 28, 1950 (1989).
27. A. Udagawa, K. Yudate, H. Kudoh, T. Sasuga, Y. Morino,
T. Seguchi, JAERI-Tech 95-007 (1995).
28. H. Schonbacher, A. Stolarz-Izycka, CERN 79-08 (1979).
29. T. Hirade, N. Takeda, A. Udagawa, T. Sasuga, T. Seguchi,
Y. Hama, Adv. Composite Mater., 1, 321 (1991).
30. T. Sasuga, T. Seguchi, H. Sakai, T. Nakamura, M. Masutani, J.
Mater. Sci., 24, 1570 (1989).
31. A. Udagawa, T. Moriya, S. Matsubara, T. Seguchi, Proc.
Atomic Energy Sot. Japan. Conf., Sendai, September (1996).
PVT Relationships and Equations
of State of Polymers
Junhan Cho
Polymer Science and Engineering Department, Dankook University, Seoul 140-714, South Korea
Isaac C. Sanchez
Chemical Engineering Department, University of Texas at Austin, Austin, TX 78712, USA
A. Introduction VI-591
B. Isothermal Compressibility Equations VI-592
C. Empirical or Semiempirical 3-Parameter
Equations of State VI-593
D. Lattice or Quasi Lattice Models VI-593
E. Continuum Models VI-594
F. Tables
Table 1. Zero Pressure Volume Vo(T) and
Bulk Modulus Ba(T) VI-595
Table 2. Abbreviations of Polymer Names
and the Experimental Temperature-
Pressure Range for Polymer Liquids VI-596
Table 3. PVT Properties of Other Polymers VI-597
Table 4. Characteristic Parameters for the
Sanchez-Cho Equation of State VI-597
Table 5. Characteristic Parameters for the
Hartmann-Haque Equation of State VI-597
Table 6. Characteristic Parameters for the
Simple Cell Model Equation
of State
Table 7. Characteristic Parameters for the
Flory, Orwoll and VrijEquation
of State
Table 8. Characteristic Parameters for the
Simha-Somcynsky Equation of
St at e
Table 9. Characteristic Parameters for the
Sanchez-Lacombe Equation
of State
Table 10. Characteristic Parameters for the
AHS + vdW Equation of State
G. References
VI-598
VI-599
VI-599
VI-600
VI-600
VI-601
A. INTRODUCTION
Pressure-volume-temperature (PVT) behavior of poly-
meric materials are important both from the practical and
scientific viewpoint. On the practical side, a general
knowledge of PVT properties are often required for pro-
cessing polymers. On the scientific side, PV T properties are
often required as input information on molecular models of
polymer solutions. Information on molecular packing is
also reflected in PVT properties. Numerous equations of
state (EOS) have been developed to describe polymers. One
can divide them into two categories: phenomenological and
molecular.
Equations of state in the first category are for the
empirical representation of volumetric data. The majority
of equations in this group are the so-called isothermal
compressibility equations (l-4). The purely empirical,
original Tait equation and its modification by Tammon have
been almost exclusively used for organics, including
polymers (2,3,5,6).
Sanchez et al. re-examined polymer bulk data in a
rigorous classical thermodynamic analysis (7,8). A new
principle of temperature-pressure (T-P) superposition of
compression response was found. Stated briefly, a dimen-
sionless pressure variable is used to superpose compression
data as a function of temperature into a universal curve. The
governing parameter of compression is the first pressure
coefficient B r (= 8B/8P),=,, of the bulk modulus B. It is
related to the asymmetry of the free energy around its
minimum, between dilation and compression. For poly-
mers, Bi is around 10, and universal. A new isothermal
equation of state was formulated through a PadC analysis of
the pressure dependence of the bulk modulus (8). Both the
Tait and the Pad& equations describe almost perfectly the
isothermal pressure dependence of volume. Both can be
used to smoothen experimental PVT data.
Equations of state in the second category arise from
molecular models and the development of a proper partition
function (9). Most earlier works on this group are based on
the lattice or quasi-lattice description of a fluid. Three types
of models have played a dominant role in the past several
decades. These are the cell, hole, and lattice fluid models.
VI / 591
VI / 592 PVT RELATIONSHIPS AND EQUATIONS OF STATE OF POLYMERS
In Prigogines cell model (lo- 12), any monomer is
considered to be enclosed by the cell of surrounding
molecules. The configurational potential is separated into
the mean potential (between the center of the cell and
surroundings), and the cell potential (generated by the
movement of the central monomer within the cell). The
cell potential was further simplified to be athermal. The
Simha-Somcynsky theory (13) incorporated the lattice
imperfection (hole) into the simple cell model by Prigogine
et al. Flory et al. (14) borrowed some ideas from the cell
model (separation of internal and external degrees of
freedom) but used a Tonks gas-type description for the
repulsive part of the intermolecular potential. Unlike the
cell model, the molecules are not localized in space, and a
van der Waals mean field energy is employed. Meanwhile,
the lattice fluid model (15,16) introduces lattice vacancies
as pseudo-solvent molecules into the incompressible
Flory-Huggins model. In this model, an incompressible
polymer solution is converted into a compressible bulk
polymer liquid.
All theoretical equations of state suggest a corresponding
states behavior of polymer PVT properties that requires
three scaling parameters such as characteristic temperature
(T), pressure (P), and volume (V*).
The derivation of the partition function can in principle
be done in continuum space. This approach yields the so
called integral equation theory (9). The self consistent
integral equations of the interparticle distribution functions
are to be determined. For the simplest hard sphere chains,
several analytical equations of state were suggested by
Chiew (17-22), Wertheim (23-27) and Chapman (28,29).
Chiews equation of state is based on Baxters solution of
the Percus-Yevick integral equation for the adhesive hard
sphere (AHS) system. The AHS has a strong, but extremely
short ranged attractive interaction at its surface. This
peculiar interaction is treated as chemical bonds. Wertheim
and Chapmann considered this adhesive attraction as a
perturbation to the hard sphere potential in the framework
of graph theory. A different and unique work on this subject
was performed by Hall and coworkers (30) without
recourse to integral equation theory. A particle insertion
method was generalized to hard chains in continuum space.
To apply these continuum models to real systems, an
energetic contribution to pressure should be added on the
basis of a perturbation theory. In the simplest approxima-
tion a mean field (van der Waals) energy is added (28,31).
The incorporation of the energy term turns these off-lattice
models into 3-parameter (V *, T *, P *) corresponding states
models.
There are empirical or semiempirical equations of state
that can be included partly in the two categories. The
Sanchez-Cho (32), and the Hartmann-Haque (33) equa-
tions are considered the most important in applications.
These two equations of state also suggest a corresponding
states behavior.
This article only deals with liquid data (above T, or T,).
The mathematical expression of the liquid PVT data with
either the PadC or the Tait equations are tabulated here for
extracting the 3 characteristic parameters (V * , T *, P *) for
given corresponding states equations of state.
The characteristic parameters are essential in the
application of a given equation of state to real systems.
We present, therefore, a compendium of such parameters
for the 3-parameter equations of state described above.
These parameters have their own physical meaning
according to theories at hand. However, these are treated
as adjustable parameters in a general nonlinear regression
routine to best represent the smoothed experimental values
regenerated from the Sanchez-Cho or the Tait equations.
We used the volume data over the whole experimental T-P
range. All model parameters are determined from the same
data sets.
B. ISOTHERMAL COMPRESSIBILITY EQUATIONS
The recently found principle of temperature-pressure
(T-P) superposition (7,8) implies that the ln(V/Va), is a
function of the scaled pressure, P/Be, as is compression,
given below:
ln(V/Vo) =f & = --k+$ k
0 .( >
2
- ; (2BF - &)B2) Q3+. . .
(Al)
where VO and Bo are volume and the bulk modulus at
zero pressure, respectively. The right hand side of Eq. (Al)
is a rigorous power series expression of ln(V/Va). The
additional contributing numbers B1 (i 2 0) are the coeffi-
cients in the series expansion of the bulk modulus B in
pressure:
(42)
A tractable approximation to the infinite series in Eq. (Al)
was suggested by Sanchez et al. They utilized the empirical
observation that the bulk modulus B in Eq. (A2) is linear
in pressure to high pressures. Expecting that the modulus
B diverges as P(w < l), a PadC analysis and the suc-
cessive integration of B yielded the PadC equation (8) given
below:
ln(V/Vd = (1 -\)B1
where the curvature parameter, o, is defined as
w = B;/(B; - BoB2)
Gw
A pair of universal values of B 1 and co (B 1 = 10.2, w = 0.9)
is observed to be excellent in correlating the bulk
volumetric data of various polymers.
The historically well known Tait equation falls into the
general statement of the T-P superposition in Eq. (Al):
ln(v/va) = ln[l - Cln(1 +;;)I
(A5)
where C is universally 0.0894 (Cutlers constant). Equation
(A5) is the modified version, by Tammon, of the original
Tait equation, which was empirically formulated for water.
One should notice that the product, CBa, comprises the so-
called Tait parameter in the literature. Equations (A3) and
(A5) yield an accurate representation (within experimental
error) of isothermal, volume-pressure relationships.
The zero pressure volume, VO, and modulus, Be, are
additionally required to complete Eqs. (A3) and (A5). The
compilation of these parameters are shown in Table 1. In
this table, the abbreviation of polymer names are used. The
explanation of the abbreviated names and experimental
T-P range are listed in Table 2. Several types of fitting
functions are used for VO. Typically used are. the polynomial
and exponential expressions. For the bulk modulus, the
exponential dependence on temperature is almost exclu-
sively used. Some other polymer PV T data that are not used
to obtain the characteristic parameters can be found in the
literature, including blends and liquid crystalline polymers
(38,50,55,59-67).
C. EMPIRICAL OR SEMIEMPIRICAL 3-PARAMETER
EQUATIONS OF STATE
Equations in this section are in between the compressibility
equations and succeeding model equations of state: (a) they
are formulated on the basis of phenomenological argu-
ments; (b) they suggest a corresponding behavior or a
universal relationship between dimensionless K T and P.
The Sanchez-Cho and the Hartmann-Haque equations of
state are considered the most important equations in this
category.
Sanchez-Cho (S-C) Equation of State The Sanchez-Cho
equation of state (32) was formulated by combining the
empirically observed temperature dependence of the zero
pressure volume VO and modulus B. with the isothermal
Pad& equation, Eq. (A3):
(A@
where the required universal numbers are B 1 = 10.2, u =
0.9, and b = 9. The dimensionless variables are defined as:
~~V/V",~~TIT*,~~P/P"
(47)
The V" and P* are related to the van der Waals volume and
cohesive energy density (32). The Sanchez-Cho equation
provides volume as an explicit function of temperature and
Empirical or Semiempirical 3-Parameter Equations of State VI / 593
pressure, as is shown in Eq. (A6). Equation (A6) is to date
the most accurate 3-parameter equation of state. The
comparison of Eq. (A6) with the empirical Tait or Pad&
equation over the whole experimental T-P range gives the
average deviation in volume less than 0.0004 cm3/g. The
Sanchez-Cho equation is useful in extrapolating data to high
pressures and investigating the negative pressure region.
The three characteristic parameters for the Sanchez-Cho
equation are given in Table 4.
Hartmann-Haque (H-H) Equation of State The Hart-
mann-Haque equation of state (33) has the following
functional form:
jjj? = ~312 - ln $7
(A81
where the dimensionless variables P, p, p are defined as in
Eq. (A7). The P* is identified as the isothermal bulk
modulus extrapolated to zero temperature and pressure. The
zero pressure isobar in Eq. (A8) originates in the Simha-
Somcynsky hole model (13) in the next section. The three
characteristic parameters for the Hartmann-Haque equation
are given in Table 5. The average deviation between
Eq. (A8) and regenerated bulk PVT data (data smoothed
using the Tait Eq.) is 0.0009 cm3/g or more than a factor of
2 worse than the S-C equation.
D. LATTICE OR QUASI LATTICE MODELS
The most frequently used model equations of state based
on the lattice or quasi lattice phase space are visited in
this section. These are various cell models of Prigogine et
al., the hole model, and the lattice fluid model. The
common feature of the models in this section is the
separation of pressure into the thermal (Pth) and internal
(Pi) pressures:
where the dimensionless variables are defined as before
Eq. (A7). The physical meaning of the characteristic
parameters P *, V*, T * vary among the models. But in
general, V" is related to the van der Waals volume, T * is
proportional to monomer-monomer interaction energy, and
P" is related to the cohesive energy density.
Simple Cell Model of Prigogine et al. The cell model by
Prigogine et al. (10-12) is an extension of the cell model
for small molecules by Lennard-Jones and Devonshire (68)
to polymers. Each monomer in the system is considered to
be trapped in the cell created by the surroundings. The
general cell potential, generated by the surroundings, is
simplified to be athermal. This turns the simple cell model
into a free volume theory. The mean potential between the
centers of different cells are described by the Lennard-
Jones 6-12 potential. The dimensionless equation of state
has the following form:
References page VI - 60 1
VI / 594 PVT RELATIONSHIPS AND EQUATIONS OF STATE OF POLYMERS
P 1
7 = v2/ 3(v1/ 3 - 2-W)
The factor 2-j6 originates in the choice of the hexagonal
close packing lattice as a cell geometry. The factors 1.2045
and 1 .Ol 1 correct the effects of higher coordination shells
on the internal energy.
Table 6 gives the three characteristic parameters P *, V *,
T * for the Prigogine cell model for the polymers in Tables
1 and 2. The average deviation between Eq. (AlO) and
regenerated PVT data is 0.0008 cm3/g.
Cell Model by Flory, Orwell, and Vrij (FOV) The cell
model by Flory et al. (14) has the simpler mathematical
form than the Prigogine cell model:
P 1 1
7 = v2/3($/3 - 1)
- -
TV2
(All)
The Lennard-Jones energy is replaced with a uniform
background (van der Waals) energy.
The characteristic parameters P*, V *, T * for the FOV
theory are shown in Table 7. The average deviation between
Eq. (Al 1) and regenerated PVT data is 0.0022 cm3/g. It has
often been pointed out that the fitting performance of the
FOV theory is less accurate, especially when covering a
large pressure range. However, we present the parameters
for the whole pressure range. This will provide a guidance
when one fits the PVT data for smaller pressure ranges of
interest.
Hole Model by Simha and Somcynsky (S-S) The simple
cell model by Prigogine et al. is modified by Simha and
Somcynsky (13) to allow for lattice imperfections (holes).
The model can be written as the following equation of state:
F (yV) l/3
y=
T v[(yv)/3 - 2-/6y]
(Al4
where the factor y is the fraction of occupied lattice sites
and satisfies
(s/3c)[l + In (1 - y)/y] = -
[(yW3/3 - 2-i6y]
KYV 13
- 2-/6y]
--@$-$) ( Al 3
)
The factor s/3c in Eq. (A13) is called the flexibility ratio,
which is usually set to 1. Other factors are the same as those
in the Prigogine cell model.
In order to calculate volume at given temperatures and
pressures, one should solve Eqs. (A12) and (A13) simul-
taneously. The calculational complexity is a drawback of
this model. Simha and Somcynsky suggested the approx-
imate representation of the S-S equation of state:
v = 0.9018 exp(23.835F312)
[l - 0.089 ln{ 1 + 1.0472p exp(49.22F)}] (A14)
The characteristic parameters P, V*, T * for the S-S
theory are shown in Table 8. The parameters are obtained
by fitting the original S-S equation of state in Eq. (A12)
with Eq. (A13), rather than fitting Eq. (A14). The average
deviation between Eq. (A12) and regenerated PVT data is
0.0007 cm3/g.
Lattice FIuid Mode/ The Lattice Fluid model developed
by Sanchez and Lacombe (1516) introduces vacancies into
the classical incompressible Flory-Huggins model. The
lattice vacancy is treated as a pseudo particle in the system.
The free energy of an incompressible binary polymer
solution is then converted to that of the bulk polymer. The
equation of state for a polymer is given below:
L= -[ln(l -$) +J-] --$b-+ (A15)
Table 9 gives the three characteristic parameters P, V*,
T * for the lattice fluid (LF) theory. As was with the FOV
model, the LF model does not correlate PVT data well over
large pressure ranges. The average deviation between
Eq. (A15) and regenerated bulk PVT data is 0.0033 cm3/g.
E. CONTINUUM MODELS
The widely used models presented in the last section are
derived by considering the partition function of a chain
system on a lattice or quasi lattice. The lattice or quasi
lattice phase space can be further generalized to be a
continuum counterpart. This approach yields, in general,
the integral equation theory, which focuses on solving the
integral equations of the particle-particle distribution
functions (9). The system of hard chains has been treated
the most, because it is the simplest and provides the
possibility of analytical equation of state in some cases.
One approach of this category is to solve the integral
equations using the Percus-Yevick closure for the system
of adhesive hard sphere (AHS) mixtures (17-22). An
adhesive hard sphere is a hard sphere that has attractive
sites at surface. The attractive interaction on these attractive
sites is infinitely strong and infinitesimally short ranged.
The Percus-Yevick closure yields an analytical solution for
such systems. The adhesive attraction, which resembles the
chemical bonding, is used to build up chains by employing
the proper connectivity constraints.
A different approach of this category is to manipulate the
graphs in the cluster expansion of the system of hard
spheres with multiple attractive sites (23-29). The
attractive interaction is the same as that of the AHS
system, and is treated as a perturbation to the reference hard
sphere potential. The steric incompatibility is taken into
account by Wertheim to approximate the graph expansion
for distribution functions. This approach is called the
thermodynamic perturbation theory (TPT) (23-27) or the
statistically associating fluid theory (SAFT) (28,29).
A unique approach to the hard chain equation of state
has been developed by Hall and coworkers (30). Florys on-
lattice particle insertion analysis is generalized to the off-
lattice calculation. This theory is called the generalized
Flory (GF) model. The enhanced evaluation of the insertion
probability is further manipulated to yield the equation of
state.
Since the developed equations of state are for athermal
chain systems, an energetic contribution to pressure is
required in order for these models to be applicable to
real systems. The simplest model adds a van der Waals
(vdW) term as a perturbation to the reference pressure
(28,3 1):
Zero Pressure Volume (V&J ) and Bulk Modulus @O(T)) VI / 595
where the term with the subscript 0 implies the athermal
reference pressure. The dimensionless variables are defined
as usual (Eq. (A7)).
The specific mathematical forms of the reference
equation of state are as follows:
I, 3
0
1+ l/V
T
T o = zv2(1 - l/v)3
ww WI
F
0
3 l/V
T =-
T o V2(1 - 1/v)3
1 _ (1 -
(2 + l/V)1
(TPT or SAFT)
P
0
= 1.31659 _
2-1/V
7
T o
V2(1 - l/V)3
( w (Al9)
The three characteristic parameters P, V *, T * for the
AHS + vdW equation of state are shown in Table 10. The
average deviation between the AHS + vdW equation and
regenerated bulk data is O.OOI2 cm3/g. The parameters for
other two equations are relatively close to those for the
AHS + vdW equation, and are not tabulated here.
F. TABLES
TABLE 1. ZERO PRESSURE VOLUME (Vo(T)) AND BULK MODULUS (B,,(T))
Polymer
PDMS
PS
PoMS
PMMA
PnBMA
PCHMA
PEA
PEMA
PMA
PVAc
LPE
BPE
LDPE-A
LDPE- B
LDPE- C
PBD
PBDS
PBD24
PBD40
PBDSO
PBD87
i-PB
PAr
PCL
PC
BCPC
HFPC
TMPC
PET
PIB
PI8
PI14
P I 4 1
Vo 67 (cm 3k) Be(T) OfPa)
1. 0079 exp(9. 121 x 10m4t)
0.9287 exp(5.131 x 10m4t)
0.9396 exp(5.306 x 10e4t)
0.8254 + 2.8383 x 10-4t+ 7.792 x lo-?
0.9341 +5.5254 x 10m4t+6.5803 x lo-t2 + 1.5691 x 10-r3
0.8793 +4.0504 x 10-4t+7.774 x lo-t2 - 7.7534 x 10-t3
0.8756 exp(7.241 x 10m4t)
0.8614 exp(7.468 x 10m4t)
0.8365 exp(6.795 x 10m4t)
0.8250+5.820x 10m4r+2.940x lo-t2
0.9172 exp(7.806 x 10m4t)
0.9399 exp(7.341 x 10m4t)
1.1484 exp(6.950 x 10M4t)
1.1524 exp(6.700 x 10e4t)
1.1516 exp(6.730 x 10m4t)
1. 0970 exp(6. 600 x 10m4t)
0.9352+4.9988 x 10m4t+ 1.268 x 10m7t2
0.9352+4.9988x 10m4t+ 1.268 x lo-t2
0.9352+4.9988 x 10-4t+ 1.268 x lo-t*
0.9352 + 4.9988 x 10 -4t + 1.268 x lo-t2
0.9352+4.9988 x 10-4t+ 1.268 x lo-t2
1. 1417 exp(6. 751 x 10m4t)
0.73381 exp(1.626 x 10m5T3j2)
0.9049 exp(6.392 x 10m4t)
0.73565 exp(1.859 x 10~5T3/2)
0.6737 + 3.634 x 10-4t + 2.370 x lo-t2
0.6111+4.898 x 10-4t+ 1.730 x lo-t2
0.8497+5.073 x 10-4t+3.832 x lo-t2
0.6883 + 5.90 x 10-4t
1.0750 exp(5.651 x 10e4t)
0.9352+4.9988 x 10m4t+ 1.268 x 10-t*
0.9352+4.9988 x 10-4t+ 1.268 x lo-t2
0.9352+4.9988 x 10-4t21.268 x lo-t2
1000.00 exp(- 5.701 x 10m3t)
2426.17 exp(- 3.319 x 10m3t)
2929.53 exp(-4.114 x 10p3f)
3215.88 exp(-4.146 x 10e3t)
2535.79 exp(- 5.344 x 10e3t)
3302.01 exp(- 5.220 x 10e3t)
2161.07 exp(- 4.839 x 10d3t)
2918.34 exp(- 5.356 x 10m3t)
2637.58 exp(- 4.493 x 10m3t)
2 291.95 exp(- 4.346 x 10m3t)
1976.51 exp(-4.661 x 10d3t)
1980.98 exp(- 4.699 x 10m3t)
2157.72 exp(- 4.701 x 10m3t)
2199.11 exp(-4.601 x 10m3t)
2088.37 exp(- 4.391 x 10d3t)
1987.70 exp(- 3.593 x 10m3t)
10915.90 exp(- 5.344 x 10e3t)
10915.90 exp(- 5.344 x 10m3t)
10915.90 exp(- 5.344 x 10m3t)
10915.90 exp(- 5.344 x 10m3t)
10915.90 exp(- 5.344 x 10-3t)
1873.60 exp(- 4.533 x 10m3t)
3321.03 exp(- 3.375 x 10m3t)
2114.09 exp(- 3.931 x 10m3t)
3467.56 exp(- 4.078 x 10m3t)
4064.88 exp(-4.921 x 10m3t)
2646.53 exp(- 5.156 x 10e3t)
2588.37 exp(- 4.242 x 10-3t)
4135.35 exp(-4.150 x 10m3t)
2240.49 exp(- 4.329 x 10e3t)
10915.90 exp(- 5.344 x 10m3t)
10915.90 exp(- 5.344 x 10m3t)
10915.90 exp(- 5.344 x 10-3t)
References VI page - 60 1
VI / 596 /VT RELATIONSHIPS AND EQUATIONS OF STATE OF POLYMERS
TABLE 1. cc&d
Polymer
VO (T) (cm343 Be(T) (MW
PI56 0.9352+4.9988 x 10m4t+ 1.268 x lo-t2
i-W 1.1606 exp(6.700 x 10m4t)
a-PP 1.1841- 1.091 x 10-4t+5.286 x 10-6t2
Phenoxy 0.76644 exp(1.921 x 10-5T3/2)
PSO 0.7644+3.419x 10-4t+3.126 x lo-t*
PEO 0.8766 exp(7.087 x 10W4t)
PVME 0.9585 exp(6.653 x 10m4t)
PEEK 0.7158 exp(6.690 x 10m4t)
PTFE 0.3200- 9.5862 x 10-4t
PTHF 1.0043 exp(6.691 x 10e4t)
PMP 1.4075-9.905 x lo-4t+3.497 x 10-v
PA6 0.7597 exp(4.701 x 10m4t)
PA66 0.7657 exp(6.600 x 10m4t)
PECH 0.7216 exp(5.825 x 10m4t)
PVC 0.7196t5.581 x lo-%+ 1.468 x 10-6t2
PPO 0.78075 exp(2.151 x 10msT3/*)
E/P50 1.2291+5.799x 10m5t+ 1.964 x lo-t2
EVA18 1.02391 exp(2.173 x 10m5T3/*)
EVA25 1.00416 exp(2.244 x 10-T3/2)
EVA28 1.00832 exp(2.241 x 10e5T312)
EVA40 1.06332 exp(2.288 x 1B-5T3/2)
SAN3 0.9233 +3.936x 10-4t+5.685 x lo-t2
SAN6 0.9211+4.370 x 10-4t+5.846 x lo-t*
SAN15 0.9044+4.207 x 10-4t+4.077 x lo-t*
SAN18 0.9016+4.036x 10m4t+4.206 x lo-t*
SAN4 0.8871+3.406 x 10-4t+4.938 x lo-t2
SAN70 0.8528f3.616 x 10m4t+2.634 x lo-t2
SMMA20 0.9063 13.570 x 10-4t+6.532 x lo-t*
SMMA60 0.8610+3.350x 10-4t+6.98010-7t2
a In the mathematical expression of volume, t and Tare in C and K, respectively. See Table 2 for references.
10915.90 exp(- 5.344 x 10M3t)
1667.79 exp(- 4.177 x 10b3t)
1813.20 exp(- 6.604 x 10p3t)
4025.73 exp(- 4.378 x 10-3r)
4092.84 exp(- 3.757 x 10e3t)
2323.27 exp(- 3.947 x 10e3t)
2413.87 exp(-4.588 x 10m3t)
4340.04 exp(-4.124 x 10m3t)
4756.15 exp(- 9.380 x 10m3t)
1997.76 exp(- 4.233 x 10e3r)
376.7 + 2.134t- 7.0445 x 10-3t2
4213.65 exp(- 4.660 x 10e3t)
3539.15 exp(- 5.040 x 10m3t)
2665.55 exp(-4.171 x 10m3t)
3290.83 exp(- 5.321 x 10e3t)
2548.10 exp(- 4.290 x 10m3t)
5447.43 exp(- 8.103 x 10m3t)
2105.15 exp(-4.537 x 10m3t)
2062.64 exp(- 4.734 x 10m3t)
2052.57 exp(- 4.457 x 10m3r)
2294.18 exp(-4.989 x 10-3t)
2682.33 exp(- 4.376 x 10d3t)
2538.03 exp(- 4.286 x 10m3t)
2666.67 exp(- 3.943 x 10e3t)
2689.04 exp(- 3.858 x 10m3t)
3236.02 exp(- 4.431 x 10m3t)
3751.68 exp(- 3.923 x 10m3t)
2595.08 exp(- 4.143 x 10m3t)
2919.46 exp(-4.611 x 10e3t)
TABLE 2. ABBREVIATIONS OF POLYMER NAMES AND THE
EXPERIMENTAL TEMPERATURE-PRESSURE RANGE FOR POLYMER
LIQUIDS
Polymer Monomer or source- P
abbreviation based Name
T (Cl (MEW
Refs.
PDMS Dimethyl siloxane
PS Styrene
PoMS b o-Methyl styrene
PMMA Methyl methacrylate
PBMAb n-Butyl methacrylate
PCHMA b CycIo hexyl met hacryl at e
PEA Ethyl acrylate
PEMA b Ethyl methacrylate
PMA Methyl acrylate
PVAC Vinyl acetate
LPEb Linear polyethylene (PE)
BPEb Branched PE
LDPE-A Low density PE-A
LDPE-B Low density PE-B
LDPE-C Low density PE-C
PBDb Butadiene
PBD8 b Butadiene with 8% 1,2
content
PBD24 b Butadiene with 24% 1,2
content
PBD40 b Butadiene with 40% 1,2
content
PBDSO b Butadiene with 50% 1,2
content
PBD87 b Butadiene with 87% 1,2
content
25-70 O-100 34,35,36
115- 196 O- 200 37
139- 198 O- 180 37
114-159 O- 200 38
34-200 O- 200 38
123,198 O- 200 38
37-210 O- 196 34
113- 161 O- 196 34
37-220 O- 196 34
35- 100 O- 80 39
142-200 O- 200 38
125- 198 O- 200 38
112- 225 O- 196 40
112- 225 O- 196 40
112- 225 O- 196 40
4-55 O-283.5 4 1
25-200 O- 200 42
25-200 O- 200 42
25-200 O- 200 42
25 -200 O- 200 42
25 -200 O- 200 42
TABLE 2. contd
Polymer Monomer or source-
abbrevation based Name T(C)
Refs.
P B 1-Butene 133-246 O- 196 43
PArb Arylate 177-310 O-176.5 44
PCL Caprolactone lOO- 148 O- 200 34
P C Carbonate (PC) 151-340 O-176.5 44
BCPC b Bisphenol chloral PC 220-280 O- 50 45
HFPCb Hexafluoro bisphenol-A P C 220-280 O- 50 45
TMPC b Tet r amet hyl bi sphenol - A PC 210- 290 O- 50 45
PET Ethylene terephthalate 274-342 O- 196 46
PIB Isobutylene 53-110 o-00 36,47
PI8 Isoprene with 8% 3,4 25-200 O- 200 42
content
PI14 Isoprene with 14% 3,4 25-200 O- 200 42
content
PI41 Isoprene with 41% 3,4 25-200 O- 200 42
content
PI56 Isoprene with 56% 3,4 25-200 O- 200 42
content
i-PP Isotactic polypropylene 170- 297 O- 196 43
a-PP Atactic polypropylene 80-120 O- 100 34
Phenoxy b Phenoxy 68-300 O-176. 5 44
PSO Sulfone 202-371 O- 196 48
PEO Ethylene oxide 88-224 O-68. 5 49
PVME Vinyl methyl ether 30-198 O- 200 34,50
PEEK Ether ether ketone 346-398 O- 200 5 1
PTFE Tetrafluoro ethylene 330-372 o-39 52
PTHF Tetrahydro furane 62-166 O-78. 5 49
PMP 4-Methyl- 1 -pentene 241-319 O- 196 5 3
PA6 Ami de 6 236-296 O- 196 5 4
PM Properties and Characteristic Parameters for the S-C and H-H Equations of State VI / 597
TABLE 2. contd
Polymer Monomer or source-
abbrevation name T (Cl (Mia) Refs.
PA66 Amide 66 246-298 O-196 5 4
PECH Epichlorohydrine 60- 140 O-200 3 4
PVC Vinyl chloride l oo- 150 O-200 3 4
PPO Phenylene oxide 203-320 O-176.5 55
E/ P50 Ethylene/propylene 50% 140-250 O-62.5 56
EVA18 Ethylene/vinyl acetate 1
il
% 112-219 O-176.5 57
EVA25 Ethylene/vinyl acetate 2 % 94-233 O-176.5 57
EVA28 Ethylene/vinyl acetate 28% 94-235 O-176.5 57
EVA40 Ethylene/vinyl acetate 40% 75-235 O-176.5 57
SAN3 Styrene/acrylonitrile 2.7% 105-266 O-200 4 5
SAN6 Styrene/acrylonitrile 5.7% 96-267 O-200 4 5
SAN15 Styrenelacrylonitrile 15.3% 132-262 O-196 4 5
SAN18 Styrene/actylonitrile 18.0% 104-255 O-196 4 5
SAN40 Styrene/acrylonitrile 40% loo-270 O-196 4 5
SAN70 Styrenelacrylonitrile 70% loo-271 O-196 5 8
SMMA20a Styrenelmethyl 1 lo-270 O-196 5 8
methacryl ate 20%
SMMA60 Styrenelmethyl 1 lo-270 O-200 5 8
methacryl ate 60%
a See Abbreviations Table in Part VIII of this Handbook.
b Abbreviation may not be recognized by international organization.
TABLE 3. PM PROPERTIES OF OTHER POLYMERS
Polymer
P
T (C) (MPa) Note Refs.
HDPE 140-203 0- 196. 0 5 9
LDPE 121-175 0- 196. 0 5 9
HMLPE 137-200 O-200.0 3 8
i-Poly( 1 -pentene) 140-172 0.1 6 0
Poly(vinylidene fluoride) 175-240 0.1 6 1
Poly(methylene oxide) 155-185 18.3-150.9 Figure only 6 2
Poly(butylene 215-280 20.7-103.4 Figure only 6 3
terephthalate)
Qiana nylon 270-320 20.7-103.4 Figure only 6 3
Natural rubber lo-82 O-1013. 0 6 4
vulcanizated with
lO-28% sulfur
Hevea rubber lo-85 O - 8 0 . 0 Simha- 6 5
uncrosslinked Somcynsky
crosslinked parameters
(6% sulfur) only
crosslinked
. .
(11.5% sulfur)
PWPPO blends 30-350 0- 176. 5 5 5
PYPVME blends 30- 198 O-200.0 5 0
Main chain LCPs Figure only up 66
Azomethine ether LCP 20-300 O-200.0 to nematic 67
a This table lists polymers not mentioned in the earlier tables.
TABLE 4. CHARACTERISTIC PARAMETERS FOR THE
SANCHEZ-CHO EQUATION OF STATE
Polymer
PDMS
PS
PoMS
PMMA
PBMA
PCHMA
V* (cm3/g)
0.8071
0.8165
0.8368
0.7139
0.7963
0.7710
T* WI
1375.1
2277.2
2380.6
2184.2
1855.9
2195.1
P* (MPa)
6212.9
7867.6
7772.1
9873.0
9025.3
8515.1
TABLE 4. contd
Polymer V* (cm3/g) T* (K)
P* (MPa)
PEA
PEMA
PMA
PVAc
LPE
BPE
LDPE-A
LDPE- B
LDPE-C
P B D
PBD8
PBD24
PBD40
PBDSO
PBD87
PB
PAr
PCL
PC
BCPC
HFPC
TMPC
P E T
PIB
PI 8
PI 14
PI 41
PI 56
i - PP
a- PP
Phenoxy
PSO
P E O
PVME
PEEK
FTFE
PTHF
P M P
PA6
PA66
PECH
PVC
PPO
E/P50
EVA18
EVA25
EVA28
EVA40
SAN3
SAN6
SAN15
SAN18
SAN40
SAN70
SMMAZO
SMMA60
0.7398
0.7332
0.7121
0.6918
0.9491
0.9723
0.9852
0.9937
0.9869
0.9115
0.9308
0.9359
0.9357
0.9408
0.9498
0.9854
0.6839
0.7671
0.6871
0.5971
0.5264
0.7261
0.6199
0.9382
0.9453
0.9366
0.9370
0.9330
1.0116
0.9690
0.7242
0.6655
0.7441
0.8187
0.6395
0.3638
0.8561
1.0089
0.7130
0.6887
0.6269
0.6252
0.7181
1.0582
0.9585
0.9338
0.9241
0.8864
0.8030
0.7896
0.7860
0.7854
0.7853
0.7616
0.7789
0.7408
1747.4
1771.2
1829.0
1696.9
1655.0
1751.9
1865.4
1923.8
1880.5
1633.8
1798.6
1819.0
1842.9
1892.0
1905.6
1924.1
2243.9
1849.0
2070.3
2249.1
1788.2
1908.0
2022.2
2130.2
1921.0
1911.3
1912.7
1854.5
1991.5
1776.2
2103.4
2232.2
1789.1
1861.3
2126.5
1400.7
1843.0
1885.0
3140.3
2195.2
2068.9
2395.4
1810.4
2384.7
1878.9
1848.3
1812.5
1856.1
2185.7
2010.7
2170.4
2208.4
2435.2
2546.6
2105.6
2099.5
9131.8
11257.0
10623.9
10399.9
9943.5
8630.7
8214.5
7983.8
8225.3
9443.2
9136.3
8708.0
8352.0
7757.3
7241.8
6891.1
11557.3
9530.1
12106.1
9931.3
10173.1
10573.0
15278.8
7045.3
7669.6
8219.9
8112.3
8600.1
6118.1
6202.8
12728.1
13286.4
10805.4
9270.5
14335.5
9757.5
8160.2
6452.5
5718.4
8391.9
8899.3
7551.2
11776.9
6421.0
8107.5
7957.5
8622.1
8441.9
7878.5
8896.8
8602.0
8495.6
7772.6
9177.0
8531.3
8858.9
TABLE 5. CHARACTERISTIC PARAMETERS FOR THE
HARTMANN-HAQUE EQUATION OF STATE
Polymer V* (cm3/g) T* (K) P* (MPa)
PDMS
PS
0.8795
0.8754
1106 1837
1603 2956
References page VI - 601
VI / 598 PVTRELATIONSHIPS AND EQUATIONS OF STATE OF POLYMERS
TABLE 5. contd
Polymer V* (cm3/g)
T* (K)
P* (MPa)
PoMS
PMMA
PBMA
PCHMA
PEA
PEMA
PMA
PVAc
LPE
BPE
LDPE-A
LDPE- B
LDPE- C
P B D
PBD8
PBD24
PBD40
PBDSO
PBD87
PB
PAr
PCL
PC
BCPC
HFPC
TMPC
PET
PIB
PI8
PI14
PI41
PI56
i-PP
a- PP
Phenoxy
PSO
P E O
PVME
PEEK
PTFE
PTHF
P M P
PA6
PA66
PECH
PVC
PPO
E/ P50
EVA18
EVA25
EVA28
EVA40
SAN3
SAN6
SAN15
SAN18
SAN40
SAN70
SMMA20
SMMA60
0.8891
0.7582
0.8552
0.8249
0.8038
0.7976
0.7712
0.7368
1.0381
1.0677
1.0769
1.0842
1.0781
0.9855
1.0065
1.0118
1.0113
1.0157
1.0264
1.0818
0.7408
0.8418
0.7474
0.5356
0.5758
0.8010
0.6802
0.9935
1.0199
1.0098
1.0103
1.0076
1.1066
1.0292
0.7784
0.7246
0.8005
0.8836
0.7044
0.3683
0.9165
1.1228
0.7654
0.7559
0.6734
0.6559
0.7906
1.1112
1.0443
1.0171
1.0077
0.9604
0.8615
0.8545
0.8495
0.8448
0.8326
0.8140
0.8453
0.8037
1608
1467
1309
1517
1284
1298
1334
1 1 5 1
1 2 1 1
1313
1387
1426
1396
1199
1301
1317
1336
1370
1387
1452
1614
1 4 1 1
1502
1520
1306
1430
1484
1422
1389
1375
1377
1339
1475
1197
1 4 8 1
1623
1254
1342
1568
9 0 0
1276
1449
2255
1643
1456
1532
1339
1516
1380
1356
1333
1339
1534
1448
1564
1566
1630
1776
1539
1530
3096
3819
3268
3038
3076
3654
3680
3817
2 8 0 4
2 5 1 0
2516
2509
2538
3333
3109
2989
2891
2742
2 5 5 7
2 0 6 6
3709
3013
3644
3641
2920
2907
4071
2976
2733
2925
2889
2 9 9 0
1852
2383
4 3 5 7
3972
3504
3245
3668
3251
2894
1670
2 2 6 4
2453
3775
3595
3079
2247
2521
2474
2646
2716
2 8 4 0
3 0 1 0
2957
3 0 2 4
3138
3578
2 8 1 2
2912
TABLE 6. CHARACTERISTIC PARAMETERS FOR THE SIMPLE CELL
MODEL EQUATION OF STATE
Polymer V* (cm3/g) T* 6)
P* (MPa)
PDMS
PS
PoMS
PMMA
PBMA
PCHMA
PEA
PEMA
PMA
PVAc
LPE
BPE
LDPE-A
LDPE- B
LDPE-C
P B D
PBD8
PBD24
PBD40
PBDSO
PBD87
i-PB
PAr
PCL
PC
BCPC
HFPC
TMPC
PET
PIB
PI8
PI14
PI41
PI56
i-PP
a- PP
Phenoxy
PSO
PEO
PVME
PEEK
PTFE
PTHF
P M P
PA6
PA66
PECH
PVC
PPO
E/ P50
EVA18
EVA25
EVA28
EVA4
SAN3
SAN6
SAN15
SAN18
SAN40
SAN70
SMMA20
SMMA60
0.9180
0.9148
0.9302
0.7941
0.8931
0.8906
0.8394
0.8321
0.8054
0.7731
1.0978
1.1179
1.1195
1.1267
1.1210
1.0269
1.0488
1.0539
1.0532
1.0573
1.0679
1.1216
0.7745
0.8758
0.7835
0.6676
0.6116
0.8473
0.7193
1.0393
1.0617
1.0516
1.0521
1.0495
1.1470
1.0758
0.8145
0.7593
0.8447
0.9210
0.7465
0.4829
0.9609
1.1652
0.7956
0.7841
0.6997
0.6855
0.8355
1.1653
1.0874
1.0592
1.0509
1.0012
0.8995
0.8950
0.8875
0.8826
0.8696
0.8493
0.8795
0.8362
3 2 5 4
5167
5 2 1 4
4 7 8 3
4 2 3 7
4 8 7 3
4167
4 1 9 0
4 3 1 8
3781
4 1 2 4
4 3 0 9
4 4 3 0
4 5 3 7
4461
3811
4171
4 2 1 2
4 2 6 3
4 3 5 7
4 3 9 9
4 6 0 0
5257
4 4 7 8
4 9 6 9
5046
4 5 2 5
4875
5 0 7 0
4 5 9 3
4415
4 3 8 2
4 3 8 6
4277
4 7 1 2
3 8 8 4
4 8 3 7
5358
4 2 2 6
4 2 9 8
5418
4 4 8 8
4185
4721
7048
5231
4 6 6 2
4 9 3 8
4 5 8 5
4 9 8 2
4 4 3 4
4 3 6 8
4 3 1 9
4 3 2 6
4 9 6 9
4761
5069
5 0 7 0
5273
5 6 7 6
4 9 0 8
4 8 8 4
388.0
599.0
622.7
765.0
683.0
630.1
652.7
772.8
768.3
755.9
588.1
535.2
549.8
544.6
552.3
681.5
655.5
629.9
608.3
575.4
537.9
460.6
776.0
632.0
774.7
762.1
620.7
609.4
868.8
580.0
572.1
611.4
604.1
628.0
425.8
493.4
903.2
844.5
696.8
677.0
797.0
323.9
576.8
400.0
465.4
550.9
757.7
719.2
668.5
453.5
544.5
537.6
572.9
584.9
603.2
640.8
618.8
630.4
653.6
723.1
600.7
622.9
PVT Properties and Characteristic Parameters for the FOV and S-S Equations of State VI / 599
TABLE 7. CHARACTERISTIC PARAMETERS FOR THE FLORY,
ORWOLL, AND VRIJ EQUATION OF STATE
TABLE 8. CHARACTERISTIC PARAMETERS FOR THE
SIMHA-SOMCYNSKY EQUATION OF STATE
Polymer V* (cm3/g) T* (K) P* (MPa) Polymer V* (cm3/g) T* W) P* (MPa)
PDMS
PS
PoMS
PMMA
PBMA
PCHMA
PEA
PEMA
PMA
PVAc
LPE
BPE
LDPE-A
LDPE- B
LDPE-C
P B D
PBD8
PBD24
PBD40
PBDSO
PBD87
PB
PAr
PCL
PC
BCPC
HFPC
TMPC
PET
PIB
PI8
PI14
PI41
PI56
i-PP
a- PP
Phenoxy
PSO
PEO
PVME
PEEK
PTFE
PTHF
PMP
PA6
PA66
PECH
PVC
PPO
E/P50
EVA18
EVA25
EVA28
EVA40
SAN3
SAN6
SAN15
SAN18
SAN40
SAN70
SMMA20
SMMA60
0.8264
0.8277
0.8457
0.7204
0.8087
0.7772
0.7563
0.7503
0.7277
0.7090
0.9818
0.9992
0.9963
1.0025
0.9974
0.9173
0.9404
0.9438
0.9419
0.9443
0.9511
0.9867
0.6991
0.7830
0.7070
0.6065
0.5521
0.7720
0.6452
0.9455
0.9480
0.9415
0.9415
0.9400
1.0072
0.9755
0.7389
0.6847
0.7719
0.8266
0.6642
0.4215
0.8774
1.0203
0.6896
0.6885
0.6321
0.6210
0.7472
1.0650
0.9724
0.9475
0.9416
0.8985
0.8129
0.8087
0.8020
0.7974
0.7869
0.7648
0.7865
0.7494
5 1 8 4
8118
8463
7717
6 7 9 4
7 7 0 0
6599
6703
6 8 9 4
6449
6548
6 7 1 0
6 7 7 4
6 8 9 6
6809
5521
6418
6432
6453
6 5 1 4
6 4 7 4
6 8 3 8
8 4 7 0
6 7 5 4
8039
8287
7 3 6 0
8156
8215
7 3 9 6
6573
6 6 2 2
6613
6 5 1 4
7011
6351
7 8 6 9
8664
7147
6607
8667
7 0 8 8
$7006
7079
-9182
7865
7 1 9 2
7 7 5 2
7 3 6 0
8377
6 8 7 0
6 7 7 0
6 7 5 9
6 7 6 6
7897
7 6 2 2
8053
7 9 9 9
8369
8701
7521
7558
326.9
405.2
441.5
568.8
509.6
461.4
511.5
641.3
599.2
599.7
537.6
453.1
469.5
456.4
471.0
454.4
505.5
480.9
460.7
425.0
395.9
403.9
651.2
486.2
671.0
611.0
542.7
514.2
851.0
396.0
419.3
450.1
444.0
473.7
397.4
405.9
713.2
738.2
601.6
512.8
832.9
404.9
459.8
395.0
411.0
558.3
524.6
501.8
650.9
360.2
453.6
444.8
480.5
475.5
453.3
503.1
465.0
461.0
474.7
500.9
475.8
491.3
PDMS
PS
PoMS
PMMA
PBMA
PCHMA
PEA
PEMA
PMA
PVAc
LPE
BPE
LDPE-A
LDPE- B
LDPE-C
P B D
PBD8
PBD24
PBD40
PBDSO
PBD87
PB
PAr
PCL
PC
BCPC
HFPC
TMPC
PET
PIB
PI8
PI14
PI41
PI56
i-PP
a- PP
Phenoxy
PSO
PEO
PVME
PEEK
PTFE
FTHF
P M P
PA6
PA66
PECH
PVC
PPO
E/ P50
EVA18
EVA25
EVA28
EVA40
SAN3
SAN6
SAN15
SAN18
SAN40
SAN70
SMMA20
SMMA60
0.9592
0.9634
0.9814
0.8369
0.9358
0.9047
0.8773
0.8710
0.8431
0.8126
1.1406
1.1674
1.1664
1.1734
1.1679
1.0766
1.0960
1.1013
1.1003
1.1049
1.1149
1.1666
0.8091
0.9173
0.8156
0.6975
0.6317
0.8794
0.7426
1.0940
1.1094
1.0997
1.1000
1.0970
1.1884
1.1274
0.8529
0.7903
0.8812
0.9632
0.7705
0.4339
1.0087
1.2050
0.8327
0.8195
0.7343
0.7320
0.8602
1.2227
1.1341
1.1040
1.0949
1.0446
0.9416
0.9352
0.9299
0.9255
0.9124
0.8906
0.9186
0.8739
7 8 6 4
12840
13080
11940
10310
12030
11040
10190
10460
9348
9793
10390
10580
10860
10660
9225
10029
10122
10229
10450
10502
10920
12390
10870
11830
12190
10550
11540
11800
11360
10578
10541
10547
10284
11060
9 4 9 4
11730
12770
10150
10360
12580
8 1 2 6
10280
11030
16870
12640
11370
12350
10580
12220
10630
10440
10310
10360
12070
11490
12360
12380
12900
13790
11800
11780
501.4
715.9
746.1
926.4
856.0
772.2
830.8
987.0
969.1
947.4
786.4
692.3
716.2
703.6
718.8
815.0
827.0
792.3
763.7
716.8
671.2
603.7
1003.0
784.5
1020.0
987.8
851.0
819.2
1194.0
686.6
711.5
760.1
750.7
786.9
573.0
627.7
1139.0
1116.0
914.5
848.1
1086.0
658.1
725.5
545.3
549.9
706.9
913.1
849.5
929.4
572.0
705.6
697.8
747.2
753.9
764.2
823.8
779.2
785.3
811.8
874.7
764.0
791.1
References page VI - 601
VI / 600 PVT RELATIONSHIPS AND EQUATIONS OF STATE OF POLYMERS
TABLE 9. CHARACTERISTIC PARAMETERS FOR THE
SANCHEZ-LACOMBE EQUATION OF STATE
Polymer V * (cm3/g)
T* WI
P* (MPa)
TABLE 10. CHARACTERISTIC PARAMETERS FOR THE AHS +
vdW EQUATION OF STATE
Polymer V * (cm3/g) T* (K)
P* (MPa)
PDMS
PS
PoMS
PMMA
PBMA
PCHMA
PEA
PEMA
PMA
PVAc
LPE
BPE
LDPE-A
LDPE-B
LDPE-C
P B D
PBDS
PBD24
PBD40
PBDSO
PBD87
PB
PAr
PCL
PC
BCPC
HFPC
TMPC
PET
PIB
PI8
PI14
PI41
PI56
i-PP
a- PP
Phenoxy
PSO
P E O
PVME
PEEK
PTFE
PTHF
P M P
P A 6
PA66
PECH
PVC
PPO
E/ P50
EVA18
EVA25
EVA28
EVA40
SAN3
SAN6
SAN15
SAN18
SAN40
SAN70
SMMA20
SMMA60
0.9022
0.8929
0.9142
0.7805
0.8789
0.8444
0.8216
0.8189
0.7908
0.7768
1.0734
1.0878
1.0827
1.0878
1.0835
0.9851
1.0167
1.0194
1.0161
1.0169
1.0224
1.0739
0.7632
0.8477
0.7737
0.665 1
0.6077
0.8493
0.7102
1.0213
1.0196
1.0141
1.0139
1.0141
1.0958
1.0658
0.8032
0.7496
0.8492
0.8930
0.7310
0.4515
0.9587
1.1153
0.7406
0.7502
0.6803
0.6686
0.8220
1.1652
1.0580
1.0307
1.0259
0.9772
0.8860
0.8841
0.8733
0.8672
0.8556
0.8222
0.8520
0.8125
4 6 6
6 8 8
7 2 5
6 6 8
5 9 6
6 7 5
581
6 0 2
6 0 6
5 8 2
5 9 6
601
6 0 3
6 1 0
6 0 6
4 6 2
5 5 4
553
5 5 2
5 5 3
5 4 7
6 0 9
7 6 0
5 8 9
7 2 8
7 5 3
6 8 0
7 5 2
761
623
555
5 6 2
561
5 5 7
6 3 3
5 7 0
6 9 0
7 8 7
6 5 6
5 6 7
8 0 4
6 3 0
6%
6 5 0
7 8 5
7 1 3
6 0 6
6 5 6
681
7 5 3
6 1 2
6 0 2
6 0 4
6 0 0
701
6 8 6
7 1 2
7 0 3
7 3 4
7 2 6
6 5 8
6 6 2
288.5
371.5
405.7
516.9
442.1
410.0
450.6
567.5
521.9
501.3
479.8
411.3
429.9
421.4
431.8
440.2
456.0
437.1
422.5
394.8
373.6
377.5
568.7
453.4
574.4
513.6
455.4
432.4
726.1
350.4
392.3
415.6
410.7
433.1
366.4
354.2
607.4
635.3
492.2
463.0
713.7
357.2
385.6
355.7
422.5
513.7
482.4
469.0
554.1
301.4
407.7
397.0
424.1
419.8
391.6
429.7
404.1
400.1
412.1
466.4
434.7
446.0
PDMS
PS
PoMS
PMMA
PBMA
PCHMA
PEA
PEMA
PMA
PVAc
LPE
BPE
LDPE-A
LDPE- B
LDPE-C
P B D
PBD8
PBD24
PBD40
PBDSO
PBD87
i-PB
PAr
PCL
PC
BCPC
HFPC
TMPC
PET
PIB
PI 8
PI 14
PI 41
PI 56
i-P
a- PP
Phenoxy
PSO
P E O
PVME
PEEK
PTFE
PTHF
P M P
PA6
PA66
PECH
PVC
PPO
E/p50
EVA18
EVA25
EVA28
EVA40
SAN3
SAN6
SAN15
SAN18
SAN40
SAN70
SMMA20
SMMA60
0.5629
0.6080
0.6222
0.5264
0.5820
0.5719
0.5294
0.5 143
0.5111
0.4891
0.6471
0.6801
0.6995
0.7117
0.7017
0.6793
0.6764
0.6832
0.6865
0.6962
0.7069
0.7029
0.4779
0.5249
0.4691
0.4016
0.3627
0.4638
0.4041
0.7079
0.7030
0.6936
0.6943
0.6850
0.6987
0.6935
0.515
0.4541
0.4974
0.5991
0.4164
0.1807
0.6026
0.6857
0.5321
0.4818
0.4707
0.4747
0.4664
0.7592
0.6792
0.6669
0.6589
0.7130
0.5894
0.5662
0.5685
0.5763
0.5911
0.5745
0.5622
0.5344
7331
16542
17194
15173
12106
15573
10289
9 6 5 9
10989
9713
7955
9 3 3 6
10596
11372
10761
11913
11417
11794
12248
13112
13574
11078
12060
8788
10088
10381
8 5 9 8
7 4 4 6
8 3 4 4
16891
13661
13326
13369
12371
10082
10648
212153
10866
8 1 3 9
12258
8 6 6 6
3 1 5 6
10303
8842
23165
11705
15781
19538
7365
14530
10625
10405
9791
10665
14537
11971
13512
14760
18577
19851
12948
12855
707.2
731.7
731.6
986.3
868.5
793.6
933.1
1252.0
1105.2
1246.9
1136.2
924.9
845.6
802.4
846.0
867.5
900.7
843.1
792.9
710.5
642.2
680.3
1319.1
943.2
1439.2
1248.0
946.0
1496.6
1984.3
687.8
689.7
756.7
744.3
817.0
691.1
672.6
1377.3
1582.8
1439.8
900.3
1801.4
2185.6
965.0
718.6
533.4
896.1
820.9
673.1
1538.8
718.7
852.7
831.9
934.8
877.9
737.9
902.0
858.1
816.5
678.8
827.2
850.6
883.0
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61. K. Nakagawa, Y. Ishida, Kolloid-Z. Z. Polym., 251, 103
(1973).
62. V.-H. Karl, F. Asmussen, K. Ueberreiter, Makromol. Chem.,
178, 2037 (1977).
63. K.-Y. Wei, J. A. Cuculo, D. W. Ihm, J. Polym. Sci. Polym.
Phys. Ed., 21, 1091 (1983).
64. C. E. Weir, J. Res. Nat. Bur. Stand., 50, 153 (1953).
65. 0. Olabisi, R. Simha, Macromolecules, 8, 211 (1975).
66. D. J. Walsh, G. T. Dee, P. W. Wojtkowski, Polymer, 30, 1467
(1989).
67. Y. A. Fakhreddine, P. Zoller, J. Polym. Sci., Part B: Polym.
Phys., 32, 2445 (1994).
68. J. E. Lennard-Jones, A. F. Devonshire, Proc. R. Sot., London
Ser. A, 163, 53 (1937).
SECTION VII
SOLUTION PROPERTIES
Viscosity - Molecular Weight Relationships
and Unperturbed Dimensions
of Linear Chain Molecules
M. Kurata, Y. Tsunashima
institute for Chemical Research, Kyoto University, Uji, Kyoto, Japan
A. Introduction
1. The Viscosity - Molecular Weight
Rel at i onshi p
2. Unperturbed Dimensions of Linear
Chain Molecules
B. Effect of Molecular Weight Distribution
on the Viscosity Constant K
C. Tables of Viscosity - Molecular Weight
Relationships, [q] = KMa
Table 1. Main-Chain Acyclic Carbon
Pol ymer s
1.1. Polytdienes)
1 . 2 . Poly(alkenes), Poly(acetylenes)
1.3. Polyfacrylic acid) and
Derivatives
1.4. Polyfa-substituted acrylic acid)
and Derivatives
1.5. Poly(vinyl ethers)
1.6. Polyfvinyl alcohol),
Poly(vinyl halides)
1. 7. Poly(vinyl estersr
1.8. Poly(styrene) and Derivatives
1.9. Other Compounds
1 .l 0. Copolymers
Table 2. Main-Chain Carbocyclic Polymers
Table 3. Main-Chain Heteroatom Polymers
3.1. Polyfoxides), Polyfethers)
3 . 2 . Polyfesters), Polyfcarbonates)
3 . 3 . Polyfamides)
3.4. Poly(amino acids)
3 . 5 . Polyfureas), Polyfurethanes),
Polyfimines)
3 . 6 . Poly(sulfides)
3 . 7 . Poly(phosphates)
3 . 8 . Polyfsiloxanes),
Polyfsilsesquioxanes)
3 . 9 . Poly(heterocyclics)
VII-2
VII-2
VII-4
VII-5
VII-5
VII-5
VII-5
VII-7
VII-1 0
VII-1 3
VII-1 7
VII-I 7
VII-l 8
VII-1 9
VII-24
VII-27
VII-31
VII-32
VI l-32
VII-34
VII-36
VII-38
VII-39
VII-39
VII-39
VII-40
VII-41
3.10. Copolymers (Maleic
Anhydride, Sulfones)
3.11. Other Compounds
Table 4. Cellulose and Derivatives,
Poly(saccharides)
Table 5. Miscellaneous
D. Calculated Unperturbed Dimensions of
Freely Rotating Chains
E. Unperturbed Dimensions of Linear Polymer
Molecules
Table 6. Main-Chain Acyclic Carbon
Pol ymer s
6 . 1 . Poly(dienes)
6 . 2 . Polyfalkenes), Poly(acetylenes)
6.3. Polyfacrylic acid) and
Derivatives
6.4. Poly(a-substituted acrylic acid)
and Derivatives
6.5. Polyfvinyl ethers), Polyfvinyl
alcohol), Poly(vinyl esters),
Polyfvinyl halides)
6.6. Polyfstyrene) and Derivatives
6.7. Other Compounds
6.8. Copolymers
Table 7. Main-Chain Carbocyclic Polymers
Table 8. Main-Chain Heteroatom Polymers
8.1. Polyfoxides), Poly(ethers)
8 . 2 . Polyfesters), Polyfcarbonates)
8 . 3 . Polyfamides)
8.4. Polyfamino acids)
8 . 5 . Poly(urethanes)
8 . 6 . Poly(sulfides)
8 . 7 . Polyfphosphates)
8 . 8 . Poly(siloxanes),
Polyfsilsesquioxanes),
Polyfsilmethylenes)
8 . 9 . Poly(heterocyclics)
VII-42
VII-42
VII-43
VII-46
VI l-46
VII-47
VII-47
VII-47
VII-48
VII-49
VII-50
VII-53
VII-54
VII-56
VII-58
VII-60
VII-60
VI l-60
VII-61
VI l-63
VII-63
VII-63
VI l-63
VI l-64
VII-64
VII-64
VII/l
VI I / 2 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
8. 10. Copolymers (Maleic
Anhydride, Sulfones,
Si loxanes)
8. 11. Other Compounds
Table 9. Cellulose and Derivatives,
Poly(saccharides)
F. References
VI I - 65
VI I - 66
VI I - 66
VI I - 68
A. INTRODUCTION
1. The Viscosity - Molecular Weight Relationship
The limiting viscosity number [q] of a solution - which has
long been called the intrinsic viscosity - is defined as
[q] = lii y
(41)
in terms of the solvent viscosity, r]o, the solution viscosity,
7, and the solute concentration, c. The concentration, c, is
expressed in grams of solute per milliliter of solution or,
more frequently, in grams of solute per 100 milliliters of
solution, the limiting viscosity number being given in the
reciprocal of these units, i.e., in milliliters per gram or in
deciliters per gram. Here, following the IUPAC 1952-
recommendations (l), we adopt the former unit. The
quantity [q] of a polymer solution is a measure of the
capacity of a polymer molecule to enhance the viscosity,
which depends on the size and the shape of the polymer
molecule. Within a given series of polymer homologs, [q]
increases with the molecular weight M, hence it is a
measure of M.
Section C gives the limiting viscosity number -
molecular weight relationships for polymers, in various
solvents and at various temperatures. The table contains the
constants of the equation
[q] = KM"
( AZ)
which is known as the Mark-Houwink-Sakurada equation.
It is now well established that for linear, flexible polymers,
under special conditions of temperature or solvent, (usually
known as the Flory theta temperature or solvent, (2)), the
above equation becomes
[ & =KeM0. 50
W)
In the tables, the % sign in parenthesis (next to the
temperature data) indicates that the viscosity constants were
obtained under the theta condition. Since Eq. (A3) is
approximately valid over the whole molecular weight
range, KQ and a = 0.50 may be used without modification,
outside of the molecular weight range in which they were
determined. However, it must be noted that [n] is rather
sensitive to temperature in the vicinity of 8, especially when
M is higher than 5 x 105.
In ordinary good solvents, the constants K and a
obtained are valid only within a rather limited range of M
(3,4). It is therefore, quite probable that the tabulated
relationships are in error outside the indicated range of M
(see eighth column in the table). As for the effect of
temperature, however, both K and a mostly become in-
sensitive to the temperature when a exceeds about 0.70, and
they may be used in a lo-degree range on either side of
temperature at whichthe constants were determined.
The method of determination of the molecular weight
and the number of fractionated samples (Fr.) or whole
polymer samples (WP) used to determine the ( 71- M
relationship are also given in the ninth and the sixth or
seventh columns, respectively. The abbreviations used are
as follows:
(A) Methods Yielding the Number-Average Molecular
Weight ( M, )
CR cryoscopy
EG end-group titration
v o s vapor pressure osmometry
EB ebullioscopy
OS osmotic pressure
(B) Methods Yielding the Weight-Average Molecular
Weight ( M, )
LS light scattering
LLS low-angle laser light scattering
SE sedimentation equilibrium
SEC, GPC size exclusion chromatography
SA
gel permeation chromatography
approach to the sedimentation equilibrium
(Archibalds method)
(C) Empirical or Semi-Empirical Methods
EM electron microscopy
GPC gel permeation chromatography
LV limiting viscosity number - molecular weight
relationship
P R analysis of polymerization rate (yielding M, )
DV diffusion and viscosity
MV melt viscosity - molecular weight relationship
SD sedimentation and diffusion
s v sedimentation and viscosity
Thus, for example, the constants tabulated are for the [VI-
M relationships, expressed in terms of M, or M, , if the
method is specified as OS or LS, respectively; i.e.,
[rl] = K&f, @4)
or
[VI = K&f: C- 45)
The values of K, and K, , especially the former, are greatly
influenced by the molecular weight distribution (MWD) of
the polymer samples, and caution must be taken in using
these relationships.
To illustrate this effect, let us assume that
(i) Equation (A2) is applicable to the molecule i with
molecular weight Mi over the whole range of M, i.e.,
[rj] i = KM;
646)
(ii) The weight fraction wi of the molecules i in a given
sample can be represented by a continuous exponential
function,
wi (Mi ) = l yh /J?(h + l)] Mf exp(-yMi) (A7)
y = h/M, = (h + l)/Mw
C-48)
or by the log-normal function,
wi(Mi) = AMi exp[-p2(lnMi/Ma)2]
(A91
where h, A, p, and MO are constants, and I represents the
gamma function.
Then, since [q] = Ci wi [q] i, we obtain
K, = Kl?(a + h + l)/hF(h + 1)
(410)
K,=KI(a+h+l)/(h+l)aI(h+l) ( A l l )
for the exponential MWD, and
K, = K(M,/M,) 0.5a(a+1)
(412)
K, = K(M,/M,) 0.5a(a-1)
(Al31
for the log-normal MWD (5). The values of K,/K and
K,/K calculated by these equations are shown in Section
B. This table may be used for estimating an error due to
MWD in the determination of M.
As an example, let us assume that a given polymer
sample has the exponential MWD with M,/M, = 2.0,
while an available [VI-M, equation has been obtained for
samples with a narrow MWD, e.g., M,/M, = 1.1. Further,
let a be 0.70. Then, to find the correct value of M, of the
given sample from [q], we must, use Eq. (A4) with
K, = 1.54K, instead of the available equation with K, =
1.06K. Use of the latter would lead-to an overestimate M,,
which is related to the correct M, by
[q] = 1.54KMf7 = 1.06KMf
( fw
The error amounts to about 70%, i.e., MA = 1.7M,. Thus,
application of the viscosity equation written in M, is to be
restricted to within a narrow class of samples, unless an
appropriate correction is made. On the other hand, if an
[VI-M, equation is available for the same pair of working
and reference samples as above, we have
[q] = 0.951KM;70 = 0.991KM;
W)
instead of Eq. (A14). Hence, the error M, amounts to only
6% (Mk = 0.94M,), which will be negligible for more
practical purposes.
I nt r oduct i on VI I / 3
Based on the above consideration, we classify the
heterogeneity of polymers into four classes, A-D, as shown
in the last column of the table in Section B, and indicate it
in the tenth column of the tables in Section C, as a measure
of the heterogeneity of the reference samples used.
It is desirable that readers select their own relationship
by inspecting these data on heterogeneity as well as those
on the number of samples and the molecular weight range.
Generally speaking, a good [q--M relationship is one
that has been obtained on the basis of M, for at least four
samples of classes A and B (exceptionally C) or on the
basis of M, for those of class A (exceptionally B), whose
molecular weights range over at least one half orders of
magnitude.
In the Remarks column of Section C, we have
occasionally indicated by the letter R, a recommended
relationship for the convenience of readers. In the range
of low molecular weight (mostly less than 104), the
constant a becomes 0.50 irrespective of the solvent. This
type of relationship cannot be used, even approximately, at
higher molecular weights. This case is noted by the letter L.
High conversion polymers are also marked by the letter H,
where the [VI-M relationships are less reproducible due to
chain branching than are ordinary ones. The abbreviations
used are as follows:
A Narrow MWD polymers, or well-fractionated
polymers, M,/M, < 1.25
B Ordinary fractionated polymers,
1.30 I M,/M, 5 1.75
C Poorly fractionated polymers or most probable
MWD polymers, 1.8 5 M,/Mn < 2.4
D Wide MWD polymers, M,/A4,, 2 2.5
H High conversion polymers, including branches
L Limited to low-molecular-weight polymers
R Recommended relationship
In Section C, polymers are arranged according to their
structure in subgroups. Within each subgroup, the polymers
are, in principle, given in alphabetical order. Within each
polymer, the solvents are also arranged in alphabetical
order, followed by the mixed solvents.
Chain configurational data are occasionally given in the
first column. The data given in parentheses refer to only one
set of viscosity constants listed in the same row, while the
data given without parentheses refer to a series of sets listed
in the same and succeeding rows. Thus, for example, the
data N content, 13.9 wt.% are effective only for the sixth
row of cellulose trinitrate, and the data 95%-c& I%-truns,
4%-1,2 are effective for the fourth to eighth rows of
polybutadiene.
The tables in Section C are essentially based on the table
published by Kurata and Stockmeyer (3). Data were also
taken from tables published by Peterlin (7), Meyerhoff (8),
Elias (9), and Krause (lo), the last one including a number
of unpublished data on acrylic and methacrylic polymers.
We are also grateful to these authors. Thanks are also due to
J. Brandrup and K. Kamide for their help with this
compilation.
References page VII - 68
VI I / 4 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
2. Unperturbed Dimensions of linear Chain Molecules
The mean-square end-to-end distance (r2) of a linear chain
molecule in solution is usually expressed in terms of two
basic quantities, the unperturbed mean-square end-to-end
distance (r2)a and the expansion factor a; i.e.,
(r) = (r2)OQ2
Gw
The latter quantity Q represents the effect of long-range
interactions which can be described as an osmotic
swelling of the chain by the solvent-polymer interactions,
while the unperturbed dimension (I-~) a represents the effect
of short-range interactions such as bond angle restric-
tions and steric hindrances to internal rotation. The steric
hindrances are also influenced by the torques exerted on the
chain by solvent molecules, but the effect is rather small in
many cases (11).
For sufficiently long chain, (r)a becomes proportional
to xi nil? where ni is the number of the ith-kind bond of
length Zi. The quantity C,, defined by
(Al?
is often called the characteristic ratio and it serves as a
measure of the effect of short-range interactions.
The freely rotating state is a hypothetical state of
the chain in which the bond angle restrictions are
retained, but the steric hindrances to internal rotation are
released. The mean-square end-to-end distance of the
freely rotating chain (r2) af can be readily calculated from
the given basic structure of the chain. For instance, if the
chain consists of only one kind of bond of length 1, we
obtain
(r2)0f = n12[(1 + cos@/(l -cos0)]
W8)
where y1 is the number of bonds and 8 is the supplement of
the valence bond angle. For vinyl polymer chains, 1 =
0.154 [nm], cos0 = l/3, and n = M/p = 2M/M,; and
hence
Ur) Of/M) ]I2
= 0.308/MAj2 = 0.218/~/~ [nm] (A19)
where M, is the molecular weight of the repeating unit and
m is the average molecular weight per skeletal link. Similar
expressions for t-of (= (r) ,$) can be also obtained for
more complicated chains. The results are summarized in
Section D.
The ratio of (r2) o to (r2),,, then, represents the effect of
steric hindrance on the average chain dimensions:
0 = r0Ir0f = ((r2)O/(r2)0f) I2 WO)
The quantity 0 is independent of n. Section E gives a list of
the unperturbed dimensions of linear chain molecules
which were obtained under various conditions of solvent
and temperature. The values of ro/M12, rof/Mi2, CT and
C, are given, together with the experimental values of
SOJM~~, up,
or Kc from which 10 was computed. Soz
which is the abbreviation of (S):! is the z-average value
of the unperturbed radius of gyration, up is the persistence
length, and Ka is the viscosity constant corresponding to Ke
in Eq. (A3). The methods used to determine these quantities
are also indicated in the tenth column of the tables by using
the following abbreviations:
(A) Light scattering
LT Zimms plot in a theta solvent yielding
Soz/M~~. After a heterogeneity correction
is made, the tabulated value of
,r,o/@&= 6 12SowlMy2)
LD dissymmetry method in a theta solvent. Less
reliable for heterogeneous samples than the
former method.
LG Zimms plot in good solvents yielding
S,/My2. After corrections for the excluded
volume effect and heterogeneity are made,
the tabulated value of ro/M1i2 is obtained
(3,121.
(B) X-ray small-angle scattering
x s the persistence length up is obtained
irrespective of the solvent nature. The
tabulated values of ro/M112 are the
asymptotic values for infinitely high
molecular weight (13,14).
(C) Limiting viscosity number
VT viscosity - molecular weight relationship
in a theta solvent. Equation (A3)
ro/M II2 is calculated by the Flory
and Fox relation Ko = @o(ro/M/2) 3.
The following values of @a were used:
2.7 x 1O23 for well-fractionated polymers
(class A in Section C)
2.5 x 1O23 for ordinary fractionated
polymers (class B)
2.1 x 10 23 for poorly fractionated or
unfractionated polymers (class
C or D)
VG viscosity - molecular weight relationship in
good solvents. Kc was estimated by using
the Kurata-Stockmeyer-Fixman plot (3,4)
or other analogous plots (12).
VWC viscosity analyzed by the wormlike cylinder
model.
VA viscosity in good solvents. The correction of
excluded volume effect is made by using the
Flory-Krigbaum-Orofino theory of the
second virial coefficient A2 or other analo-
gous theories (12).
Viscosity - Molecular Weight Relationships of Main-Chain Acyclic Carbon Polymers VI I / S
(D) Method yielding the temperature dependence of ro. LT or XS. The listed values of r0/A4/~ sometimes
ST stress - temperature coefficient of undiluted scatter appreciably, reflecting the difficulty involved, both
or swollen samples. experimental and theoretical, in the determination of
VTe viscosity - temperature coefficient of the this quantity. Especially in the case of cellulose chains,
intrinsic viscosity the right magnitude of ro is yet in controversy (542,
549,3,691,696,688,678,686,12). In recent papers, emphasis
The polymers are arranged in Section E in the same order has often been put on the effect of temperature or solvent on
as in Section C. For each polymer, smoothed values of the unperturbed dimensions. These data are put together
ro/M/2, CT, and Cm, which were mostly obtained by VT at the end of the tabulation for each polymer. Section E
or VG, are given in the first line, followed by some is also based on the tables published by Kurata and
typical values obtained by more direct methods such as Stockmeyer (3).
B. EFFECT OF MOLECULAR WEIGHT DISTRIBUTION ON THE VISCOSITY CONSTANT K
a = 0.5 a = 0. 6 a = 0. 7 a=0.8 a = 0. 9 a = 1.0
MwIMn KnIK KwIK KnIK KwIK KnIK KwIK K,IK KwIK K./K K,/K K,/K K,/K Class
MOLECULAR WEIGHT DISTRIBUTION: EXPONENTIAL TYPE (Eq. (A7))
3 0 4.87 0.890 6.91 0.897 9.85 0.911 14.18 0.933 20.56 0.963 30 1 D
1 5 3.46 0.893 4.57 0.900 6.08 0.914 8.16 0.935 11.02 0.964 15 1 D
1 0 2.83 0.896 3.59 0.903 4.59 0.917 5.91 0.937 7.67 0.965 10 1 D
5 2.03 0.907 2.40 0.913 2.85 0.925 3.42 0.943 4.12 0.968 5 1 D
3 1.60 0.921 1.79 0.926 2.02 0.936 2.29 0.952 2.62 0.973 3 1 D
2 1.33 0.940 1.43 0.943 1.54 0.951 1.68 0.963 1.83 0.979 2 1 C
1.75 1.25 0.948 1.33 0.951 1.42 0.958 1.51 0.968 1.63 0.982 1.75 1 B
1.50 1.18 0.959 1.23 0.961 1.28 0.967 1.35 0.975 1.42 0.986 1.50 1 B
1.25 1.09 0.975 1.12 0.977 1.15 0.980 1.18 0.985 1.21 0.991 1.25 1 A
1.10 1.04 0.989 1.05 0.989 1.06 0.991 1.07 0.993 1.09 0.996 1.10 1 A
MOLECULAR WEIGHT DISTRIBUTION: NORMAL TYPE (Eq. (A9))
3 0 3.58 0.654 5.12 0.665 7.57 0.700 11.58 0.762 18.32 0.858 30 1 D
1 5 2.16 0.713 3.67 0.723 5.01 0.753 7.03 0.805 10.13 0.885 15 1 D
1 0 2.37 0.750 3.02 0.759 3.94 0.785 5.25 0.832 7.16 0.902 10 1 D
5 1.83 0.818 2.17 0.824 2.61 0.845 3.19 0.879 3.96 0.930 5 1 D
3 1. 51 0.872 1.69 0.877 1.92 0.891 2.21 0.916 2.56 0.952 3 1 D
2 1.30 0.917 1.39 0.920 1.51 0.930 1.65 0.946 1. 81 0.969 2 1 C
1.75 1.23 0.932 1. 31 0.935 1.40 0.943 1.50 0.956 1.61 0.915 1.75 1 B
1.50 1.16 0.951 1.21 0.953 1.27 0.958 1.34 0.968 1.41 0.982 1.50 1 B
1.25 1.09 0.973 1.11 0.974 1.14 0.977 1.17 0.982 1.21 0.990 1.25 1 A
1.10 1.04 0.988 1.05 0.989 1.06 0.990 1.07 0.992 1.08 0.996 1.10 1 A
C . TABLES OF VISCOSITY - MOLEdULAR WEIGHT RELATIONSHIPS, [q] = KM
TABLE 1. MAI N- CHAI N ACYCLI C CARBON POLYMERS
No. of samples Mol. wt.
Temp. K(x103) range
Polymer Solvent
(C) Wk9 u Fr. W.P. (x 10-q Method(s) Remarks Refs.
1. 1. POLY(DIENES)
Poly(butadiene)
linear Dioxane 12. 1 1 3 9 0.52 4 - 2.1-23.2 LG B - C 8 8 9
Tol uene 3 5 16. 9 0.765 6 - 2.1-23.2 L G B - C 8 8 9
r i ng Tol uene 3 5 11.8-10.6 0.765 3 - 3.8-6.1 L G B - C 8 8 9
98%-c& 2%-1,2 Benzene
30 (@
33. 7 0.715 9 - 5- 50 O S 0
1 5
Isobutyl acetate 20. 5 1 8 5 0 . 5 0 6 - 5- 50 O S A 1 5
Tol uene 3 0 30. 5 0.725 9 - 5- 50 O S A 1 5
95%-c& I%-trans, 4%.1,2 Benzene 3 0 8. 5 0.78 4 - 15-50 LS A 1 6
Cyclohexane 3 0 11. 2 0.75 4
-
15-50 LS A 1 6
5-Methyl-2-hexanone 12.6 (8) 1 5 0 0 . 5 0 4 - 15-35 LS B 1 7
References page VII - 68
VI I / 6 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 1. contd
Polymer Solvent
Temp.
(0
K (x 103)
Whit)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-4) Method(s) Remarks Refs.
3.Pentanone
T0luene
94%-c& 4%-trans. 2%-l ,2 Benzene
Dioxane
92%-h, 3%-rrans, 5%-1,2 Benzene
51%- trans, 43%-c& 6%-1,2 Tol ue ne
57%-rrans, 36%~cis, I%-1,2 Tetrahydrofuran
71%-tram, 4%~cis, 25%-1,2 Cyclohexane
19%-tram, 21%~cis Cyclohexane
97%-trans. 3%-I,2 Cyclohexane
Tol ue ne
ca. lOO%-cis Benzene
Heptane/hexane
(l/l, w
65%-1,2, 25%~mm, lo%-& Toluene
SC-emulsion, randoml y 3-Pentanone
branched
50C-emulsion, randomly Benzene
branched
Poly(butadiene-co-acrylonitrile), Buna-N rubber
Acetone
Benzene
Chloroform
Tol ue ne
Poly(butadiene-co-styrene), Buna-S, GR-S, or SBR rubber
Benzene
Cyclohexane
2-Pentanone
Tol ue ne
linear fraction Tol ue ne
branched fraction Tol ue ne
Poly( 1 -butenylene-co-vinylethylene)
43%-1,2 1,4-Dioxane
Tetrahydrofuran
Poly(2-terr-butylbutadiene) Benzene
Octane
Poly(chloroprene)
Neoprene CG Benzene
Neoprene GN Benzene
Neoprene W Benzene
type, unspecified
Poly(isoprene)
natural rubber
Bu t a n o n e
Butyl acetate
Carbon tetrachloride
Cyclohexane
Tol ue ne
Benzene
Cyclohexane
4-Methyl-2-pentanone
2-Pentanone
Tol ue ne
synthetic cis
85-91%-cis
Hexane
Tol ue ne
Tol ue ne
2,2,4-Trimethylpentane
Heptane/propanol
(78122, v/v)
10.3 (8) 152 0.50 4
30 33.9 0.688 8
25 41.4 0.70 8
20.2 (0) 205 0.50 8
32 10 0.77 13
30 39 0.713 6
30 25.6 0.74 2
25 12 0.77 8
20 36 0 . 7 0 12
40 28.2 0 . 7 0 7
30 29.4 0.753 6
32 14.5 0.76 8
20 138 0.53 5
25 110 0.62 8
24 (0) M*l3[7J] = 7.15 + 3.47M 10
5 (@ M2j3 kl I3 = 4.61 + 0.3287M 16
25
25
25
25
25
25
3 0
21 (0)
2 5
3 0
3 0
3 0
3 0
15.7 (0)
3 0
21
21
25
25
25
25
25 (0)
25
25
45.5 (0)
25
3 0
27
35
14.5 (0)
25
35
2 0
3 0
3 0
3 0
3 0
3 0
5 0
13
5 4
4 9
52.5
5 4
31.6
185
52.5
16. 5
31.9
21.4
535 \
173
32.3
4 . 2
4 . 2
2.02
14.6
15.5
15.5
113
37.8
22.1
107
5 0
18.5
3 0
60.7
119
50.2
17.4
68.4
8.51
20.0
15
22.2
37
0.64
0.55
0.68
0.64
0.66
0.66
0.70
0 . 5 0
0 . 6 6 7
0.78
0.71
0.74
0.48
0 . 5 0
0.72
0 . 8 0
0 . 8 0
0.89
0.73
0.71
0.72
0.50
0.62
0.69
0 . 5 0
0.615
0.74
0.70
0.57
0.50
0.667
0 . 7 4
0.58
0.77
0 . 7 2 8
0.74
0.683
0.63
2 4
8
6
6
2 5
-
6
15
2 0
6
6
10
16
8
9
7
I
7
7
13
-
-
-
-
-
-
9
8
7
-
-
-
4
1
4
12
16
8
6
lo-25
lo-65
9-120
9-120
lo-160
11-25
l -57
230-880
23-130
4-17
5-16
18-50
?
7-70
10-100
5-124
2.5-10
2.5-10
2.5-10
2.5-40
l -160
1-165
5-25
5-25
2.5-50
3-35
5-25
3-20
20-100
0.88-22
0.88-22
6-90
6-35
6-150
2-96
5-100
5-80
15-300
15-300
15-300
15-70
4-120
8-28
ca. 185
5-100
8-28
7-100
5-100
5-80
20- 100
14-580
2-15
23-580
43-580
LS
OS
OS
OS
LS
OS
LS
LS
LS
LS
OS
LS
S D
OS
OS
OS
OS
OS
OS
OS
OS
OS
OS
OS
OS
OS
O S
OS
OS
B
A
A
A
BJ
A
A
C
RR
B
A
A
A
A
AR
B
LLS, SEC, OS A
LLS, SEC, OS A
S D
S D
OS
LS, SD
LS
OS
OS
LS
S D
LS
LS
P R
LS
LS
B
B
B
RR
A
A
A
B
B
C
C
B
C
RR
B
A
A
AR
A
A
A
17
18
19
19
2 0
21
7 3 3
22
23
2 4
25
2 6
2 7
28
2 9
2 9
28
28
28
2 8
45
4 6
4 7
41
28
4 8
4 7
41
41
8 9 0
8 9 0
3 0
3 0
31
32
33
34
35
35
35
34
28
37
38
698
37
39
698
4 0
41
42
43
42
42
TABLE 1. contd
Viscosity - Molecular Weight Relationships of Main-Chain Acyclic Carbon Polymers VI I / 7
Polymer Solvent
Temp.
(Cl
K (x 103)
W@
No. of samples Mol. wt.
range
a Fr. W.P. (x10-d) Method(s) Remarks Refs.
84%-c& 14%~rrans, 2%-1,2 Benzene
Dioxane
II%-cis, 22%.trans. 7%-3,4 Cyclohexane
Dioxane
4-Methyl-2-pen&none
Tol ue ne
gutta percha Benzene
Dioxane
Propyl acetate
synthetic iruns Benzene
synthetic tram (98%) Benzene
Cyclohexane
Hexane
Tol ue ne
98% 1 ,Ctrans Benzene
Cyclohexane
n-Hexane
Tol ue ne
70% c&1,4, 23% tmns-1.4 Cyclohexane
1% 3,4
16% c&1,4, 19% tram-l,4 Cyclohexane
5% 3,4
star type
70% &s-1,4, 23% trans-1,4
1% 3,4
(mol. wt. of arm=various)
3arm Cyclohexane
4arm Cyclohexane
8arm 1,4-Dioxane
Tol ue ne
12 ar m 1,4-Dioxane
Tol ue ne
16 ar m 1,4-Dioxane
Tol ue ne
tram 1.4 Benzene
Cyclohexane
Hexane
Tol ue ne
Poly(isoprene)-block-poly(styrene), Ak-B n
k/n, (50/50, w/w) Cyclohexane
Dioxane
4-Methyl-2-penta6one
Toluene .
k/n, (25115, w/w) Cyclohexane
Dioxane
4-Methyl-2-pentanone
Tol ue ne
25
25
34 (@I
35
35
35
35
25
41.7 (S)
60 V-9
3 2
3 0
3 0
3 0
3 0
3 0
3 0
3 0
3 0
25
2 5
2 5
25
3 4
3 4
3 4
3 4
3 4
3 4
3 0
3 0
3 0
3 0
35
35
35
35
35
35
35
35
13.3
11.2
1 4 . 5
20.2
9 4
16
17.5
35.5
191
2 3 2
43.1
18.1
16.2
13.8
17.6
18.1
16.2
13.8
17.6
20.5
18.0
12.5
11.6
15.5
9 . 4 7
53.9
5.70
37.4
3.04
18.1
16.2
13.8
17.6
21.8
32.6
53.1
14.6
39.3
24.8
62.8
14.3
Poly(isopropenylethylene-co-l-methyl-l-vinylethylene) 20-25%-1,2,70-75%-3,4
2-Octanol 30.5 (0) 102
Tetrahydrofuran 3 0 11.6
Poly(l-methyl-1-butylene-co-isopropenylethylene) 51%-1,4,49%-3.4
2-Octanol 41.3 7 8
Tetrahydrofuran 3 0 14.6
Poly(l,l,2-trichlorobutadiene) Benzene 25 31.6
1.2. POLY(ALKENES), POLY(ACETYLENES)
Poly(alkene) C 10-C 1s
Poly(alkene) C 12-C 1s
Poly( 1-butene)
atactic
Tol ue ne
Cetane
2-Octanol
Tetrahydrofuran
Ani s ol e
Benzene
25 12.7
38 21
23.6 60.5
25 8.24
86.2 (8) 123
3 0 22.4
0.78
0.78
0 . 5 0
0.73
0.53
0.56
0.74
0.71
0 . 5 0
0.50
0.65
0 . 7 2 2
0 . 7 3 6
0.711
0 . 7 2 9
0 . 7 2 2
0 . 7 3 6
0.711
0 . 7 2 9
0 . 7 3 0
0 . 7 4
0.757
0.753
0.493
0 . 7 2 6
0.501
0.741
0.502
0 . 7 6 4
0 . 7 2 2
0 . 7 3 6
0.711
0 . 7 2 9
0.68
0.63
0.57
0.73
0.60
0.65
0.55
0.72
0.50
0.77
0.52
0.75
0.66
1.04
0.61
0.52
0.76
0.50
0.72
2 0
25
3 0
5
5
5
5
9
9
2 4
8
7
6
8
7
5
1 1
5
-
-
7
7
8
8
1 1
2-80
2-60
2-50
2-32
2-32
2-32
2-32
0.2-5
0.2-5
10-20
8-140
14-77
14-77
14-77
14-77
14-69
16-130
16-105
14-77
1.5-342
33-724
-
-
-
-
14-70
14-70
14-70
14-70
3-54
3-54
3-54
3-54
3-48
3-48
3-48
3-48
1.3-27
1.3-27
1.1-14
1.1-14
25-130
2-18
4-700
2.7-55
2.7-55
10-130
0.03-0.5
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
OS
OS
OS
OS
O S
O S
OS
OS
LLS, SEC, OS
LLS, SEC, OS
LLS, SEC, OS
LLS, SEC, OS
LS
LS
LS
LLS, SEC
LLS, SEC
LS
EG
B
B
B
A
A
A
A
AR
A
C
C
B
B
B
B
B
B
B
B
A
B
B
A
A
C
B,L
4 4
4 4
4 4
7 8 6
7 8 6
7 8 6
7 8 6
19
19
3 7
2 6
6 9 9
6 9 9
6 9 9
6 9 9
8 8 7
8 8 7
8 8 7
8 8 7
891
8 9 2
8 9 3
8 9 3
8 9 3
8 9 3
8 9 3
8 9 3
8 9 3
8 9 3
8 9 4
8 9 4
8 9 4
8 9 4
7 8 6
7 8 6
7 8 6
7 8 6
7 8 6
7 8 6
7 8 6
7 8 6
8 9 0
8 9 0
8 9 0
8 9 0
3 6
8 6
87
8 9 6
8 9 6
81
82
References page VII - 68
VI I / S VI SCOSI TY - MOLECULAR WEI GHT RELATI ONSHI PS AND UNPERTURBED DI MENSI ONS OF LI NEAR CHAI N MOLECULES
TABLE 1. contd
Polymer Solvent
Temp.
(Cl
K (x 103)
Wk)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-4) Method(s) Remarks Ref s.
i s ot act i c
Ethylcyclohexane
Phenyl ether
Anisole
Decalin
Ethylcyclohexane
Heptaue
Nonane
Phenet ol e
Phenyl ether
1,2,4,-Trichlorobenzene
Cyclohexane/propanol
(80/20, v/v)
(70/30, v/v)
(65135, v/v)
Poly(ethylene)
low pressure Bi phe nyl
1Chloronaphthalene
Decalin
Decanol
Diphenyl ether
Diphenylmethane
Dodecanol
Octanol
Tet r al i n
1,2,4-Trichlorobenzene
3,5,5-Trimethylhesyl
acetate
p-Xylene
7 0
141 (8)
89 (@I
115
7 0
35
6 0
8 0
64.5 (0)
148 (8)
135
35
3 5
35
127.5 (0)
130 (0)
125
125
125
129
135
135
135
135
135
153.3 (8)
161.4 (0)
142.2 (0)
137.3 (6)
138 (0)
144.5
180.1 (B)
105
120
120
130
130
130
135
135
135
121
105
105
105
Paraffin wax (M, = 390 zt 10)
150
high pressure Decalin 7 0
p-Xylene 75
81
(normal paraffin) Carbon tetrachloride 20 [q] =
Poly(ethylene-air-tetrafluoroethylene)
Diisobutyl adipate 2 4 0
Poly(ethylene-co-isopropylethylene)
n-Hexyl acetate 6 5
Tetrahydrofuran 3 0
Poly(ethylene-co-propylene) Benzene 19.0
21.4
n-Decyl acetate 5 . 0
n-Heptyl acetate 38.0
7.34
104
111
9.49
7 . 3 4
4.73
15.0
5.85
113
103
11.8
102
2 5 3
4 9 7
3 2 3
3 0 2
138
18.4
4 3
27.1
67.7
4 6
6 2
58.5
6 2
3 0 2
2 9 5
315
3 0 7
3 1 6
2 8 6
16.2
23.6
32.6
43.5
51
37.8
95.4
51
51.6
16.5
17.6
51
(42)
38.73
135
105
1.14+0.104M
2.3
171
71.3
201
136
162
156
0 . 8 0
0 . 5 0
0 . 5 0
0.73
0 . 8 0
0.80
0.69
0 . 8 0
0.50
0 . 5 0
0.729
0.59
0.51
0 . 4 4
0 . 5 0
0 . 5 0
0.58
0.78
0.67
0.71
0.67
0.73
0 . 7 0
0.725
0 . 7 0
0 . 5 0
0 . 5 0
0 . 5 0
0 . 5 0
0 . 5 0
0.61
0 . 5 0
0.83
0.78
0.77
0.76
0.725
0.72
0 . 6 4
0 . 7 0 6
0.691
0.55
0.83
0.83
0.725
( 0 . 6 5 )
0.738
0.63
0.63
0.71
0.51
0 . 6 4
0 . 5 0 2
0.543
0.523
0 . 5 2 2
5
5
5
6
4
6
6
4
5
5
6
6
6
4
5
?
10
10
2 6
6
?
4
3 6
2 0
6
9
-
4
19
4
6
4
8
?
9
8
7
-
-
-
-
-
-
?
-
> 10
-
-
-
8
-
-
-
-
10
-
-
-
2 2
7
3
-
4-130
2-66
4-57
4.5-90
8-94
4.5-90
4.5-90
11-94
4-57
4-57
3-73
3-73
3-73
2-30
5.7-27
?
5-100
5-100
5-100
3-100
3-64
2-105
0.4-50
3-120
2-105
2-105
2-105
2-105
8-32
0.8-59
2-105
13-57
5-100
0.3-50
2-30
0.4-50
8-17
3-45
0.8-123
l -59
13-50
1-18
0.4-50
0.04-l 1
0.2-3.5
0.2-7.6
l -10
0.024-0.048
54-116
L S
O S
OS
L S
LS
LS
LS
LS
OS
OS
G P C
LS
LS
LS
LV
LS, GPC
LS
LS
LS
LS
LS
LS
LS
OS
GFC, L S
LV
LS
LV
LV
LS
LS
LV
LS
LS
LS
OS
OS
LS
LS
GPC, LS
GPC
LS
LS
OS
LV
LS
OS
OS
OS
C R
LS
0.92-23 LLS, SEC, OS
0.92-23 LLS, SEC, OS
2.8-39 LS
2.8-39 LS
2.8-39 LS
2.8-39 LS
A
A
B
B
B-C
B-C
B-C
B
?
CD
D
D
RR
B
B
B
B
B
B
F
B
C
B
B
RR
D
A
B
C
C
RR
D
B
D
D
A
B
A
A
A
A
A
A
81
7 0 0
7 0 0
83
81
83
83
81
7 0 0
7 0 0
701
7 0 2
7 0 2
7 0 2
58
7 0 3
59
6 0
61
6 2
63
64
65,66
67,68
7 0 4
5 8
65
5 8
58
6 9
7 0 5
58
7 0
6 0
71
71
7 2
7 3
7 0 6
7 0 4
701
7 0 5
7 0
7 4
75
7 6
77
78
7 9
80
898
8 9 0
890
897
897
897
897
TABLE 1. contd
Viscosity - Molecular Weight Relationships of Main-Chain Acyclic Carbon Polymers V I I / 9
Polymer Solvent
Temp.
(Cl
K (x 103)
(mlk)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-q Method(s) Remarks Refs.
Poly(ethylene-co-propylene-co-diene), EPDM rubber
Cyclohexane
Poly(isobutene) Ani sol e
Benzene
Carbon tetrachloride
Chl orof orm
Cyclohexane
Cyclohexane
Cyclohexane
Decalin
n-Heptane
Isooctane
Phenetol e
Tol uene
oligomer-polymer Benzene
Isoamyl isovalerate
Poly(isobutene-co-isoprene),
butyl rubber
Benzene
Carbon tetrachloride
5-Methyl-3-heptanone
Tol uene
Poly(methylbutylene) n-Hexyl acetate
Tetrahydrofuran
Poly(isopropylethylene-co-l-methyl-l-ethylethylene)
2-ocmnol
Tetrahydrofuran
Poly(3-methyl-1-butene) Di i sobutyl ene
Poly( 1-methylbutylene-co-isopropylethylene)
2-Octanol
Tetrahydrofuran
Poly(4-methyl-1-pentene) Biphenyl
Decalin
Di phenyl ether
Diphenylmethane
Poly( 1-octene) Bromobenzene
Cyclohexane
Phenetol e
4 0
1 0 5 (B)
2 4 (0)
2 5
3 0
4 0
6 0
2 5
3 0
2 5
1 0
2 0
3 0
4 0
5 0
2 5
3 0
3 0
2 5
2 5
2 0
2 5
2 5
1 0
2 0
3 0
4 0
5 0
86 (@
0
1 5
2 5
3 0
5 0
6 0
9 0
2 5 (0)
25 (0)
22.8 (0)
2 5
55.5 (8)
2 5
3 0
60. 9
3 0
26. 2
3 0
2 0
53. 3
3 0
194.6 (8)
1 3 0
210.0 (8)
176.6 (0)
2 5
3 0
50.4 (8)
53. 1
9 1
1 0 7
8 3
6 1
4 3
2 6
1 0 0
2 9
7 1
25. 6
24. 2
23. 3
22. 9
22. 4
4 0
27. 6
26. 5
13. 5
2 2
3 6
1 3 0
15. 8
38. 1
36. 8
36. 2
34. 6
33. 6
9 1
4 0
2 4
8 7
2 0
2 0
13. 5
12. 6
(M,>los)
(M,<105)
(M, > 105)
(M, < 105)
1 1 5
10. 7
1 0 9
6 6
21. 4
1 6 9
4 2 . 2
9 2
10. 3
4 2
7 4
29. 8
1 5 2
19. 5
1 5 8
1 6 0
2 . 9 0
5.75
65. 5
0.75
0 . 5 0
0.50
0.53
0.56
0 . 6 0
0.66
0 . 5 0 4
0.68
0.55
0 . 6 3 9
0.697
0 . 6 9 9
0.701
0.702
0.72
0.69
0.69
0 . 7 4 0
0 . 7 0
0 . 6 4
0 . 5 0
0.697
0 . 6 2 4
0 . 6 2 6
0.627
0.63 1
0.633
0 . 5 0
0 . 6 0
0.65
0 . 5 6
0.67
0.68
0.71
0 . 7 2
0 . 5 0
Not const.
0 . 5 0
Not const.
0.50
0.78
0 . 5 0
0.60
0.678
0.5 1
0.68
0.49
0.75
0.63
0.52
0.68
0.50
0.75
0 . 5 0
0.50
0.78
0.78
0.50
2 0
1 5
9
9
9
9
1 2
1 2
-
6
7
1 2
6
2 3
5
-
4
8
6
6
5
6
4
3
1 9
1 9
7
7
6
-
9
-
1 8
-
-
-
3-30
18-188
18-188
0.05-126
0.05-126
0.05-126
0.05-126
1.35-148
0.05-126
5.7-490
2.6-110
2.6-110
2.6-110
2.6-110
2.6- 110
14-34
4-71
0.05-126
6.4-161
530-1680
l - 130
0.4-2.5
0.84-148
2.6-110
2.6-l 10
2.6-110
2.6- 110
2.6- 110
5-188
1-146
1-146
14-34
1-146
1-146
11-146
46- 146
0.011-179
0.011-179
15-72
10-30
15-72
15-30
10-30
0.84-60
0.84-60
1.5-28
1.5-28
l - 20
1.1-43
1.1-43
6- 30
6- 30
6- 30
6- 30
25-400
25-400
60-400
OS
LV
LV
OS, CR
OS, CR
OS, CR
OS, CR
SEC, LLS
OS, CR
LS
LV
LV
LV
LV
LV
OS
OS
OS, CR
SEC, LLS
LS
OS
OS
SEC, LLS
LV
LV
LV
LV
LV
LV
LV
LV
OS
LV
LV
LV
LV
LS
LS
LS
OS
LS
OS
OS
LLS, SEC, OS
LLS, SEC, OS
LLS, SEC, OS
LLS, SEC, OS
LS
LLS, SEC, OS
LLS, SEC, OS
OS
OS
OS
OS
LS
LS
LS
A
B
B
B,R
B
B
B
A - B
B
A(?)
A - B
A - B
A - B
A - B
A - B
B
.%R
B
A- E
A - B
A3
A,J-
A - B
A- E
A - B
A - B
A - B
A - B
B
B
B
B
B,R
B
B
B
A
A
A
A
A
A
A
A
A
A
A
A
A
A
B
B
B
B
A
A
A
4 1
4 9
4 9
5 0
5 0
5 0
5 0
1 0 1 0
5 0
8 9 9
9 0 1
9 0 1
9 0 1
9 0 1
9 0 1
5 1
5 2
5 0
1 0 1 0
53,54
55,52
5 6
1 0 1 0
9 0 1
9 0 1
9 0 1
9 0 1
9 0 1
4 9
5 0
5 0
5 1
5 0
5 0
5 0
5 0
904
904
7 8 7
5 7
7 8 7
5 7
5 7
8 9 0
8 9 0
8 9 0
8 9 0
8 5
8 9 0
8 9 0
7 0 7
7 0 7
7 0 7
7 0 7
8 4
8 4
8 4
References page VII - 68
VII / 10 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 1. co&d
Polymer Solvent
Temp.
(C)
K (x 103)
Wk)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-q Method(s) Remarks Ref s.
Poly(pentenamer)
80-85%-trails,
19-12%-cis
Poly(l-phenyl-1-propyne)
Cyclohexane
Isopentyl acetate
Tol uene
Cyclohexane
Tol uene
Poly(propylene)
atactic
n-Octyl acetate
3-Nonanol
I-Octanol
Benzene
Bi phenyl
I-Chloronaphthalene
Cyclohexane
Cyclohexanone
Decalin
Isobutyl acetate
Isopentyl acetate
Phenyl ether
i s ot a c t i c
Te t r a l i n
Tol uene
Bi phenyl
1- Chl or onapht hal ene
Decalin
Dibenzyl ether
Diphenyl ether
Te t r a l i n
s yndi ot act i c
head-to-head
94%-tram, 6%-1,2
89%-tram, 1 l%-1,2
p-Xylene
Heptane
Cyclohexane
Cyclohexane
1.3. POLY(ACRYLIC ACID) AND DERIVATIVES
Poly(acrylamide) Wa t e r
Aq. NaCl (1 N)
Aq. NaCl (0.12 M)
Poly(N-acryloyl-m-aminobenzoic acid)
N,N-Dimethylacetamide
N,N-Dimethylformamide
Dimethyl sulfoxide
Poly(N-acryloyl-o-aminobenzoic acid)
N,N-Dimethylformamide
Dimethyl sulfoxide
Tetrahydrofuran
3 0 5 6 . 9
38 (6 2 3 4
3 0 5 2 . 1
36(6) -
(wormlike behavior)
2 5
(wormlike behavior)
2 7 . 0
5 . 0
7 7 . 0
2 5
3 0
1 2 9 (8)
74 No
2 5
3 0
92 (0)
135
1 3 5
1 3 5
58 (0)
34 (0)
145
1 5 3 (0)
1 3 0
3 0
125. 1 (0)
1 2 5 (8)
1 3 9
1 4 5
1 3 5
1 3 5
183. 2 (0)
142. 8 (0)
1 4 5 (8)
153
135
1 3 5
1 3 5
8 5
3 0
3 0
3 0
3 0
3 0
3 0
3 0
3 0
2 5
3 0
3 0
3 0
3 0
2 5
2 5
2 5
1 7 5
1 1 3
1 1 0
2 7 . 0
3 3 . 8
128. 3
1 8 2
1 6 . 0
2 0 . 9
1 7 2
1 5 . 8
1 1 . 0
5 4 . 3
158. 5
168. 5
1 9 2
1 2 0
1. 24
2 1 . 8
1 5 2
141. 0
2 1 . 5
4 . 9
1 1 . 0
1 0 . 0
1 0 6
1 3 7
1 3 2
1 1 2
2 . 5
9. 17
1 9 . 3
9 6
3 1 . 2
4 9 3
4 . 1 6
2 9 5
3. 82
6. 31
6 8
6 . 5
1 9 . 1
5. 31
9 . 1
8 . 9
1 0 . 6
3. 74
3. 83
3. 39
0. 68
0 . 5 0
0. 69
0.5-0.8
Not const
0 . 5 1 2
0 . 5 3 6
0 . 5 0 4
0. 71
0. 67
0. 50
0 . 5 0
0 . 8 0
0. 76
0. 50
0. 77
0 . 8 0
0. 65
0. 50
0. 50
0. 47
0. 50
0. 96
0. 725
0. 50
0. 50
0. 67
0. 80
0. 80
0. 80
0 . 5 0
0 . 5 0
0 . 5 0
0 . 5 4
1 . 0
0 . 8 0
0. 74
0. 63
0. 71
0. 39
0. 86
0. 43
0 . 9 0
0. 80
0. 66
0. 82
0. 71
0. 79
0. 84
0. 83
0. 80
0. 93
0. 92
0. 89
5
8
1 0
1 2
1 2
6
7
7
6
6
3
3
6
6
4
6
6
7
4
5
1 1
9
6
4
4
4
4
4
5
9
5
1 2
5
7
-
7
7
7
I
7
-
-
-
-
-
-
-
-
1 0
-
-
-
-
-
-
-
-
-
-
-
-
-
-
2 1
-
5
-
-
-
-
3.6-63
3.6-63
3.6-63
1.6-145
1.6-145
2.8-39
2.3-42
2.3-42
6-31
2-34
4-71
4 - 3 3
6-31
2 - 3 4
1.5-33
2 - 3 9
2 - 6 2
2 - 7 2
4-71
2 - 3 4
3.7-21
3.7-21
?
2-34
5 - 4 2
5 - 5 0
lo- 170
5-63
2-62
10-100
5 - 4 2
5 - 4 2
3-48
3-48
2-11
4 - 5 4
5 - 5 0
?
9-45
0.2-1.1
2.1-4.2
0.3-0.8
1.7-3.2
2 - 5 0
l - 2 0
4-127
49-320
15-153
1.3-5.5
1.3-5.5
1.3-5.5
0.7-2.9
0.7-2.9
0.7-2.9
L S
L S
LS
L S , S E
L S , S E
LS
L S , S E C
L S , S E C
OS
OS
LV
OS
OS
OS
OS
OS
LS
LS
LV
OS
OS
O S
?
OS
LV
OS
L S
LS
LS
LS
LV
LV
OS
OS
OS
OS
OS
OS
LS
v o s , OS
v o s , OS
v o s , OS
v o s , OS
S D
P R
OS
LS
LS
vos, GPC
VOS , GP C
vos, GPC
VOS , GP C
C OS , GP C
C OS , GP C
B
B
B
A
A
A
A
A
A
A
B
A
A
A
A
A
.%R
D
B
A
A
A
A
A
B
AR
&R
AR
A
A
A
A
.%R
B
A
L
L
A- B
A- B
A- B
A- B
A- B
A- B
7 8 8
7 8 8
7 8 8
9 0 2
9 0 2
8 9 7
8 9 7
8 9 7
8 8
8 9
7 0 8
9 0
8 8
8 9
9 0
9 1
8 8
9 2
7 0 8
8 9
9 0
9 0
9 3
8 9
9 4
7 0 8
9 5
9 6
8 8
9 7
9 4
9 4
9 0
9 0
9 8
9 6
7 0 8
9 9
1 0 0
7 0 9
7 0 9
7 0 9
7 0 9
101
1 0 2
7 1 0
9 0 5
9 7 2
9 0 8
9 0 8
9 0 8
9 0 9
9 0 9
9 0 9
TABLE 1. contd
Viscosity - Molecular Weight Relationships of Main-Chain Acyclic Carbon Polymers
Polymer Solvent
Temp.
(C)
K (x 103)
WM
No. of samples Mol. wt.
range
a Fr. W.P. (x10-4) Method(s) Remarks Refs.
Poly(acrylamide-co-N,N,N-trimethyl ami noethyl chl ori de acrylate)
70% acrylamide
Poly(acrylic acid)
-. sodium salt
Aq. NaCl (1 N)
1,4-Dioxane
Aq. NaOH (2M)
Aq. NaCl
(0.012 M)
(1M)
2 5
30 (0)
2 5
2 0
2 5
Poly(acrylic acid)
-. sodium salt
Poly(acrylonitrile)
(polymerized at - 30C)
(polymerized at 60C)
(polymerized at - 30C)
(polymerized at 60C)
Aq. NaCl
(0.05 M)
(0. 1 M)
(0. 3 M)
(0. 5 M)
(l.OM)
Aq. NaBr
(1.5M)
(1.5M)
(0. 5 M)
(0. 1 M)
(0.05 M)
(0.025 M)
(0.01 M)
(0.005 M)
(0.0025 M)
Aq. NaSCN
(1.12M)
y-Butyrolactone
Dimethylformamide
( Dei oni zed DMF)
Dimethylacetamide
Dimethyl sul foxi de
Ethylene carbonate
Ethylene carbonate/ water
(85/15, w/w)
2 5
2 5
2 5
2 5
2 5
1 5
15 (@
15 ((3
1 5
2 5
1 5
2 5
1 5
1 5
2 5
1 5
2 5
1 5
1 5
30 m
30 (0)
2 0
3 0
3 0
3 0
5 0
2 0
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
3 0
3 0
3 0
3 5
3 5
5 0
2 0
3 5
5 0
2 0
5 0
1 4 0
5 0
2 5
10. 5
7 6
4 2 . 2
-
15.47
1.35
14. 6
16. 9
18. 6
41. 5
1 4 5
1 6 5
1 2 4
52. 7
50. 6
25. 4
31. 2
28. 1
16. 3
17. 6
13. 6
13. 2
(44.2)
(24.9)
l54
121
34. 3
51. 2
34. 2
4 0 . 0
28. 7
17. 7
16. 6
24. 3
39. 2
52. 0
15. 5
5 7 . 4
39. 6
44. 3
69. 8
29. 6
20. 9
33. 5
27. 8
31. 7
30. 0
30. 7
27. 5
27. 4
32. 1
28. 3
20. 9
29. 5
2 6 3
0.73
0.50
0.64
0.93
0 . 9 0
0.88
0.80
0.75
0.72
0.63
0.50
0 . 5 0
0.50
0 . 6 2 8
0 . 6 5 6
0.755
0.755
0.77
0.84
0.85
0.89
0.91
0.83
0.89
0 . 5 0
0.50
0 . 7 3 0
0.67
0.70
0.69
0 . 7 4 0
0.78
0.81
0.75
0.75
0 . 6 9 0
0.80
0.73
0.75
0.70
0.65
0.74
0.75
0.72
0.76
0 . 7 4 6
0.752
0.761
0.767
0 . 7 6 4
0 . 7 5 0
0.758
0.75
0.718
0.49
-
1 2
I
1 2
4
4
4
4
4
4
5
4
7
7
7
7
7
7
7
7
7
7
7
5
4
5
6
5
-
5
5
5
-
-
7
3
-
-
-
7
7
-
9
1 2
2 2
6
6
6
9
9
1 3
7
6
4
-
-
-
-
-
-
-
-
-
-
-
5
-
4
1 6
-
5
8
7
7
2 1
-
6
-
45-270
13-82
4- 50
7-180
4- 50
9.4-60
9.4-60
9.4-60
9.4-60
9.4-60
9.4-60
6-64
12-83
l - 50
2- 80
l - 50
2- 80
l - 50
l - 50
2- 80
l - 50
2- 80
l - 50
l - 50
6- 64
12-83
4- 40
4- 30
6- 30
15-53
4- 40
7- 30
5-27
3-25
3-100
5-52
3- 10
0.3-1.5
4- 30
2-20
8-140
4- 30
6-30
16-48
3-58
9- 76
4-102
2- 40
2- 40
2- 40
9- 40
9- 40
4- 40
7- 40
5.2-52
L S
OS
O S
LV
O S
LLS, GPC
LLS, GPC
LLS, GPC
LLS, GPC
LLS, GPC
LLS, GPC
LV
LS
LV
LV
LV
LV
LV
LV
LV
LV
LV
LV
LV
LV
LS
LV (LS)
S A
S A
LS
LS
LS
S D
LS
OS
L S
LS, SD
E G
OS
LS
LS
SA
SA
LS
D V
LS
LV
LV
LV
LV
LV
LV
LS
LV
LS, OS
D
B
C
B
C
B - C
B - C
B - C
B - C
B - C
B - C
C
C
C
CR
C
C
C
C
C
C
C
C
C
C
C
AR
B
B
D
A
B
B
C
C
RR
B - C
L
C
C
C
B
B
D
B
AR
A
A
A
A
A
A
A
A - B
9 0 5
1 0 4
105
1 0 6
1 0 5
9 0 6
9 0 6
9 0 6
9 0 6
9 0 6
9 0 6
1 0 7
1 0 8
1 0 9
1 1 0
1 0 9
1 1 0
1 0 9
1 0 9
1 1 0
1 0 9
1 1 0
1 0 9
1 0 9
1 0 7
111
1 3 4
1 3 5
1 3 5
1 3 6
1 3 4
1 3 7
1 3 8
1 3 9
1 4 0
7 1 1
141
1 4 2
1 4 3
1 4 3
1 4 4
1 3 5
1 3 5
1 3 6
1 4 5
1 3 4
1 3 4
1 3 4
1 3 4
1 3 4
1 3 4
1 3 4
1 4 6
1 3 4
9 5 1
References page VII - 68
VII / 12 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 1. contd
Polymer Solvent
Temp.
(0
K (x 10)
Wk)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-d) Method(s) Remarks Ref s.
Hydroxyacetonitrile
Aq. HNOa (60%)
Poly(benzy1 acrylate) Bu t a n o n e
Poly(buty1 acrylate) Acetone
Poly(terr-butyl acrylate) Acetone
Bu t a n o n e
Hexane
Methanol
Pentane
Poly( l,l-dihydroperfluorobutyl acrylate)
Benzofluoride
Methyl perfluorobutyrate
Poly(N,N-dimethylactylamide) Methanol
Wat er
Poly(ethy1 acrylate) Acetone
Benzene
Butanone
Chloroform
Ethyl acetate
Poly(2-fetrocenylethyl acrylate) Benzene
Poly(ferrocenylmethy1 acrylate) Benzene
Poly(hexadecy1 acrylate) Methanol
Heptane
Poly(N-isopropylacrylamide) Tetrahydrofuran
Wat er
Poly(isopropy1 acrylate) Acetone
Benzene
i s ot act i c
atactic
s yndi ot act i c
i s ot act i c
atactic and syndiotactic
Poly(methy1 acrylate)
Chloroform
2,2,3,3-tetrafluoro-
pr opa nol
Acetone
Benzene
Butanone
Dimethyl malonate
Ethyl acetate
Isopentyl acetate
2-methylcyclohexanol
Tol ue ne
20
5 0
0
20
35
25
25
25
24. 2 (8)
25
25
26. 6
26. 6
25
25
40
25
30
30
30
30
30
25
25
30
20
27
20 m
30
25
25
30
25
60
30
25
25
25
60
60
20
25
25
25
30
25
30
30
30
35
20
25
30
35
30
35
62. 5 (8)
56. 0 (8)
30
35
40. 9
35. 4
33. 9
30. 7
0. 587
6. 85
4. 1
3. 2
49. 0
16. 0
22. 0
13
12
17. 5
23. 2
20. 0
51
20. 0
27. 7
2. 68
31. 4
26. 0
4. 68
6. 84
48. 7
1. 74
9. 59
145
13. 0
14. 9
12. 4
11.8
11.3
11.6
14.1
19.7
17.3
15.9
17.9
14.7
( 7. 40)
5. 5
19. 8
5. 20
28. 2
2. 58
4. 5
3. 56
4. 59
12. 8
3. 5
14. 1
3. 97
( 34)
3. 51
1 1
68
68
1. 79
21
0. 697
0. 707
0. 740
0. 747
0. 883
0. 75
0. 75
0. 80
0. 50
0. 61
0. 57
0. 56
0. 60
0. 68
0. 81
0. 65
0. 59
0. 66
0. 67
0. 80
0. 68
0. 66
0. 70
0. 75
0. 55
0. 82
0. 65
0. 50
0. 69
0. 70
0. 701
0. 71
0. 704
0. 698
0. 72
0. 697
0. 703
0. 708
0. 693
0. 704
( 0. 76)
0. 77
0. 66
0. 77
0. 52
0. 85
0. 78
0. 798
0. 795
0. 71
0. 81
0. 67
0. 772
( 0. 61)
0. 793
0. 69
0. 50
0. 50
0. 697
0. 60
8
8
6
5
?
-
5
5
5
5
5
-
I
5
-
5
-
-
6
8
8
6
9
20
4
20
20
5
I
-
8
9
1 1
7
4
I
6
6
-
13
4
6
-
-
-
-
6
-
-
-
-
-
-
-
-
7
4- 34
4- 34
2- 40
4- 40
?
5- 27
7- 31
7- 31
7- 31
7- 31
7- 31
20- 200
20- 200
5- 122
5- 122
11-122
35- 450
16- 50
5- 67
48- 700
9- 54
9- 54
1. 4- 2. 7
0. 7- 2
6- 70
l -10
I O- 100
lo- 100
6- 30
7- 70
4- 100
7- 20
4- 100
4- 100
7- 30
l o- 65
8-110
20-110
lo-65
20-110
l - 32
28- 160
30- 250
4- 183
4- 45
20- 130
7- 160
25- 190
15- 140
5- 30
6- 240
17- 68
25- 190
5- 47
50- 190
24- 148
20- 160
40- 105
25- 190
12- 69
LV
LV
LV
LV
OS
L S
L S
L S
LS
LS
L S
LS
LS
LS
L S
LS
LS
OS
OS
LS
OS
O S
vos, GPC
vos, GPC
OS
L S
OS
O S
LS
OS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
OS
LS
LS
LS
OS
OS
L S
LS
OS
OS
LS
LS
LS
LV
LS
LS
LS
LS
LS
LS
A
A
A
A
B
B
C
C
C
RR
W
C
B-C
C
C
D
C-D
C
B
A
A
B
B
RR
B
B
B
B
B
B
B
B
B
B,R
B
B
B
RR
B
C
A-B,R
B
B
C
B
A
B
B
B
A
134
134
134
134
337
112
712
712
712
712
712
113
113
103
103
103
114
115
116
117
116
116
713
714
116
118
975
915
119
120
121
119
121
121
122
121
121
121
121
121
123
124
125
715
126
127
128
129
129
130
128
131
129
132
129
133
129
129
129
133
TABLE 1. contd
Viscosity - Molecular Weight Relationships of Main-Chain Acyclic Carbon Polymers VII / 13
Polymer Solvent
Temp.
(C)
K (x 103)
OW3)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-d) Method(s) Remarks Refs.
Butanone-2-propanol
(42158, v/v)
(l/l, v/v)
branched (42158 v/v)
Poly( 1- met hyl phenyl acr yl at e) Butyl acetate
Poly(morpholinocarbonylethylene)
Dimethylformamide
Aqueous NaCl (0.1 M)
Poly(piperidinocarbonylethylene) Dimethylformamide
Poly(propy1 acrylate) Bu t a n o n e
20 (Q)
27.5 (0)
30 (@
20 (0)
25
25
2 0
25
3 0
81
54.4
7 2
2 9 0
14.7
18
6 4
3 2
15.0
1.4. POLY(a-SUBSTITUTED ACRYLIC ACID) AND DERIVATIVES
Poly(benzy1 methacrylate)
Poly(buty1 methacrylate)
Benzene
Acetone
Benzene
Benzene
Butanone
Chloroform
Cyclohexane
Dioxane
Methyl ethyl ketone
2-Propanol
Poly(terf-butyl methacrylate) Butyl acetate
ani oni c Bu t a n o n e
Cyclohexane
Tetrahydrofuran
free radical Bu t a n o n e
Cyclohexane
n-Heptane
Tetrahydrofuran
Poly(2-fert-butylphenyl methacrylate)
Benzene
Bu t a n o n e
Cyclohexane
Poly(4-fert-butylphenyl methacrylate)
Acetone
Bromobenzene
Carbon tetrachloride
Chloroform
Cyclohexane
Tetrahydrofuran
Poly[l-(N-carbethoxyphenyl)-methacrylamide]
Acetone
Dimethylfonnamide
Ethyl acetate
Poly(2-chloroethyl methacrylate) o-Dichlorobenzene
Tetrahydrofuran
Poly(4-chlorophenyl methacrylate)
Benzene
Carbon tetrachloride
Dioxane
Poly(cyclobuty1 methacrylate) 1- But a nol
Poly(cyclododecy1 methacrylate) Cyclohexane
n-Hexyl acetate
Tol ue ne
3 0
2 5
3 0
25
23
25
3 0
2 0
25
2 5
25
25
21.5 (0)
21.5 (6)
23.7 (0)
2 5
25
10.0
3 0
25
10.0
6 4 . 0
3 0
25
25
18.4 (6)
2 0
25
2 0
2 0
2 0
25
25
Uric.
Uric.
Uric.
35.7 (0)
3 0
37.5
3 0
35
3 0
1.03
18.4
( 4 . 0 )
3.82
1.56
9.7
( 1 . 1 5 )
2.9
4.37
21.0
23.1
6.13
29.5
3 8
36.6
22.0
12.0
62.0
15.2
5.91
4 6 . 0
62.1
5 . 8 4
7.8
9 . 0
35.5
5.75
16
4.1
4.1
2.4
41
9.4
0.00115
This relation
not followed
0 . 0 0 4 4 6
47.4
6.83
9.2
20.0
6.1
4 9 . 2
8.84
35.4
6.03
0 . 5 0
0.50
0.50
0 . 4 0
0.63
0.65
0.68
0.56
0.687
0.82
0.62
( 0 . 7 7 )
0 . 7 7 4
0.81
0.68
( 0 . 8 9 )
0.78
0.80
0.648
0 . 6 3 0
0.726
0 . 5 0
0 . 5 0
0 . 5 0
0.63
0.675
0.499
0.66
0.73
0.505
0.476
0 . 7 6
0.68
0.64
0.50
0.68
0 . 6 0
0.71
0.71
0.78
0.49
0.68
1.35
1.25
0.50
0.72
0.66
0.58
0.70
0 . 4 9 4
0.65 1
0 . 4 9 4
0 . 6 8 7
-
5
6
10
5
3
8
6
6
6
10
8
9
5
6
6
6
6
4
5
7
6
4
5
5
6
6
-
-
-
-
9
-
3
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
29- 140
14-83
50-190
37-250
2-l 10
?
?
?
71-181
17-120
100-600
S-300
1270-2070
25-260
1 l-670
67-132
4-800
S-80
1230-2450
1330-2070
959-2160
30-260
4-800
40- 170
46-870
2.8- 107
2.8-107
2.8-107
14-155
6.8- 155
3.4-155
3.4- 155
4-113
4-113
4-113
6-350
1 l-204
15-2500
20-2500
6-300
1 l-204
7-88
26-74
48-140
26-11
3.2-54
3.2-54
lo-610
lo-610
lo-610
4.8-31
5.1-475
5.1-475
5.1-475
LS
L S
L S
L S
S D
LS
LS
LS
LS
LS
LS
LS
-
LS
LS
OS
LS
OS
LS
LS
LS
LS
LLS, SEC
LLS, SEC
LLS, SEC
LLS, SEC
LLS, SEC
LLS, SEC
LLS, SEC
LS
LS
LS
LS
LS
LS
LS
LS
LS
L
LS
LS
LS
LLS, SEC
LLS, SEC
LS
LS
LS
B
RR
B
A
A
A
A
A
A
A
A
A-B
B
B
A-B
A-B
A
A
A
A-B
B-C
B-C
B-C
124
108
129
125
3 4 6
3 3 8
3 3 8
3 3 8
117
3 3 9
1 5 0
151
9 1 2
152
150
153
154
155
9 1 2
9 1 2
9 1 2
152
154
1 5 6
157
9 1 7
9 1 7
9 1 7
9 1 7
9 1 7
9 1 7
9 1 7
3 4 0
7 1 6
341
341
3 4 2
7 1 6
7 1 6
3 6 9
3 6 9
3 6 9
9 1 4
9 1 4
References page VII - 68
VI I / 14 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 1. contd
Polymer Solvent
Temp.
(0
K(xl0')
(mh)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-d) Method(s) Remarks Ref s.
Poly(cyclohexy1 methactylate) Benzene
But a nol
Bu t a n o n e
Cyclohexane
Poly(cyclohexylthioltnethacrylate)
Cyclohexane
Tetrahydrofuran
Poly(cycloocty1 methacrylate) 2-Butanol
1,4-Dioxane
Tol ue ne
Poly(cyclopenty1 methactylate) Cyclohexane
1,4-Dioxane
Ethyl acetate
Methyl ethyl ketone
Tol ue ne
Poly(2,6-dimethylphenyl methacrylate)
Chlorobenzene
Tetrahydrofuran
Tetrahydrofuran/water
Tol ue ne
Poly(diphenylmethy1 methacrylate)
3-Heptanone
Tol ue ne
Poly(decy1 methacrylate) Ethyl acetate
Tetrahydrofuran
Poly(dodecy1 methacrylate) Amy1 acetate
Tetrahydrofuran
Poly(dodecyI methacrylate) Butyl acetate
Isopropyl acetate
Pent anol
Poly(2-ethylbutyl methacrylate) Butanone
2-Propanol
Poly(ethy1 methacrylate) Bu t a n o n e
Ethyl acetate
2Propanol
Butanone-2-propanol
(l/7, y/y)
Ethyl acetate/ethanol
(219, V/V)
(l/6, VW
Poly(2-ferrocenylethyl methacrylate)
Benzene
Poly(fetrocenylmethy1 methacrylate)
Benzene
Poly(hexadecy1 methacrylate) Benzene
Carbon tetrachloride
Heptane
Poly[4-(4.hexadecyloxybenzoyloxy)-phenyl methacrylate]
Carbon tetrachloride
Poly(hexy1 methacrylate) Bu t a n o n e
2.Propanol
Poly(2-hydroxyethyl methacrylate)
Dimethylfotmamide
Dimethyl sulfoxide
Methanol
30
25
23 (0)
22. 5 (0)
25
25
30
25
25
35
45
30
30
36
30
30
30
30
25
25
25 (0)
25 (0)
45
25
11 (0)
30
31
30
23
13 (0)
29. 5 (0)
25
27. 4 (0)
23
35
36. 9 (0)
23~0)
35
35 (0)
25
21
21
21
25
23
32. 6 (0)
30
30
30
Poly[l-(2.hydroxyethyl) pyridiniutnbenzene sulfonate methacrylate]
Aq. KCL ( 0. 5 M) 25
8. 4
3. 54
33. 1
45. 2
31. 8
5. 79
7. 0
8.8
8. 65
4. 07
43. 2
26. 0
8. 70
54. 8
10. 9
19. 4
13. 6
8. 38
18. 4
33. 1
75. 0
78. 0
38. 6
3. 61
34. 7
4. 56
36. 6
1.05
8. 64
32. 2
34. 8
2. 21
33. 7
2. 83
8. 6
41. 5
41. 3
41. 6
56. 4
3. 12
27. 5
5. 9
2. 31
3. 92
35. 1
10. 6
12. 9
52. 4
2. 62
0. 69
0. 77
0. 50
0. 50
0. 533
0. 68
0. 66
0. 67
0. 63
0. 74
0. 488
0. 549
0. 677
0. 487
0. 659
0. 588
0. 63 1
0. 696
0. 65
0. 59
0. 50
0. 50
0. 485
0. 712
0. 50
0. 73
0. 53
0.64
0.64
0. 50
0. 50
0. 77
0. 50
0. 79
0. 7 1
0. 50
0. 76
0. 58
0. 7 1
0. 78
0. 75
0. 56
0. 5
0. 78
0 . 5 0
0. 70
0. 69
0.51
6
5
9
8
8
7
8
8
8
8
9
9
9
9
7
10
10
10
10
8
7
7
8
8
10
4
10
6
6
20
8
8
6
5
7
SO- 200
10- 419
57- 445
l o- 125
l o- 125
57- 560
SO- 200
10- 419
4- 60
4- 60
6. 6- 418
3. 1- 418
3. 1- 418
4. 6- 358
2. 9- 358
2. 9- 358
2. 9- 358
2. 9- 358
3. 4- 33
3. 4- 82
5. 7- 33
3. 4- 82
8. 7- 575
42- 575
2. 9- 92
2. 9- 92
10- 135
10- 135
26- 360
26- 360
27- 240
48- 332
48- 332
20- 263
65- 1200
22- 130
20- 263
78- 500
60- 420
2- 9
0. 6- 3. 6
130-440
130-440
130-440
20- I 10
10-2000
6-41
6-41
4- 52
4- 52
4- 52
OS, SEC
OS, SEC
OS, SEC
OS, SEC
LLS, SEC
LLS, SEC
LS, OS, SEC
LS, OS, SEC
LS, OS, SEC
LS, OS, SEC
LS
LS
LS
LS
LS
LS
LS
LS
vos, GPC
S D
S D
S D
LS
S D
LS
LS
B
B
A-C
A-C
A-C
A-B
A-B
A-B
A-B
A-B
A-B
A-B
B
B
B
B
A
A
A
A
A
A
C
B
CD
CD
B
B
B
AB
A3
A,B
344
717
345
718
718
345
344
717
923
923
923
923
911
911
913
913
913
913
158
158
159
160
160
161
162
156
161
162
162
714
163
163
163
164
730
165
165
720
720
720
721
TABLE 1. contd
Viscosity - Molecular Weight Relationships of Main-Chain Acyclic Carbon Polymers
Polymer Solvent
Temp.
(Cl
K(x103)
Cm%)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-q Method(s) Remarks Refs.
Poly[l(2-hydroxyethyl) trimethylammoniumbenzene sulfonate methacrylate]
Aq. KC1 (0.5 M)
Poly[N-(2.hydroxypropyl) methacrylamide]
Aqueous KC1 (0. 1 M)
Poly(D,L-isobomyl methacrylate) I-Octanol
Tetrahydrofuran
Poly(isobuty1 methacrylate) Acetone
Acetone
BelIzelIe
Benzene
But anone
Carbon tetrachloride
1,4-Dioxane
2-Hydroxymethyl-
tetrahydrofuran
Poly(S-p-methyl methacrylate) Benzene
Cyclohexane
2-Pentanone
Tetrahydrofuran
Poly(methacrolein) Dimethylfotmatnide
Poly(methacrylic acid) N,N-Dimethylformamide!
1,4-dioxane (5/7, v/v)
Methanol
Aq. HCl (0. 002 M)
Aq. NaNOx (2M)
Poly(methacrylonitrile) Acetone
Dimethylfortnamide
Poly(2methoxyethyl methacrylate)
Poly(methy1 butacrylate)
Poly(methyl cx-chloroacrylate)
Poly(methy1 ethacrylate)
Poly(methy1 methacrylate)
atactic
But anone
Tetrahydrofuran
Butanol
But anone
Chloroform
Benzene
But anone
2,6-Dimethyl-4-heptanone
Acetone
Acetonitrile
Benzene
2 5
2 5
39.6 (0)
3 0
2 5
2 5
6 0
2 5
2 5
2 5
2 0
2 5
3 0
4 4
2 5
2 5
2 5
2 5
2 5
25 (0)
2 5
2 0
26.9 (0)
2 6
3 0
2 5
2 0
2 9 . 2
2 5
2 5
13 (0)
3 0
3 0
3 0
3 0
11. 4 (8)
2 0
2 0
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
3 0
3 9
4 6
3 0
45 (0)
5 0
6 5
2 0
2 0
2 5
2 5
4 . 0 4
1 1 . 0
3 1 . 7
3. 68
0. 199
2 3 . 4
1 8 . 2
8. 41
3. 88
7. 03
5. 56
8. 61
7. 47
2. 18
4. 88
6. 89
8 5 . 8
9 . 6
1 1 . 5
4 3 . 6
1 1 . 5
2 . 8
103
2 4 2
6 6
4 4 . 9
9 5 . 5
3 0 6
7. 34
7. 57
5 7 . 0
5. 43
3. 08
2. 35
4. 29
6 7 . 6
5 . 5
3. 90
7 . 5
6. 76
7 . 5
5 . 3
9 . 6
7 . 5
2. 45
6. 59
7 . 7
6. 40
6. 18
3 9 . 3
4 8
2 9
9 . 8
8. 35
1 5 . 1
7. 24
5 . 5
0. 70
0. 67
0. 50
0. 73
0. 94
0. 66
0. 68
0. 66
0. 74
0. 77
0. 73
0. 70
0. 71
0. 79
0. 72
0. 68
0. 56
0. 67
0. 65
0. 50
0. 65
0. 97
0. 50
0. 5 1
0. 50
0. 65
0. 56
0. 503
0. 71
0. 71
0. 50
0. 73
0. 78
0. 82
0. 75
0 . 5 0
0. 73
0. 76
0. 70
0. 71
0. 70
0. 73
0. 69
0 . 7 0
0. 80
0. 71
0 . 7 0
0. 72
0. 72
0. 50
0. 50
0. 54
0. 64
0. 73
0. 70
0. 76
0. 76
-
1 2
6
6
6
6
6
6
5
6
6
7
6
6
6
6
6
-
-
-
1 2
1 2
4
10
8
6
1 0
IO
7
7
9
1 0
1 4
7
4
4
9
6
6
6
6
6
6
6
5
7
7
IO
I1
8
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
?
-
-
-
-
-
-
-
6
-
-
-
-
15-400
2-500
9-120
9-120
300-1100
50-116
50-116
1020-3460
1020-3460
50-116
300- 1100
300- 1100
300-1100
300- 1100
1020-3460
1020-3460
50-116
12-230
12-230
12-230
12-230
0.5-2
27.5-101
4 - 2 0
10-90
8 - 7 0
35-100
0.6-8
4-220
4-220
6 - 6 0
7-430
20-780
16-110
4-200
4-200
7-700
7-700
8-137
3-700
2-740
2-780
180-350
3-98
6-210
5-41
6-263
5-41
5-41
10-86
lo-260
lo-260
lo-260
7-700
S-90
6-100
2-740
L S
G P C
G P C
LS
O S
O S
-
-
OS
LS
LS
LS
LS
O S , C R
L S
OS
LV
OS
OS
LV
LS
LS
LS
LS
LS
LS
LS
LS
S D
S D
LS
S D
L S , S D
LS
LS
L S
OS
OS
LS
OS
OS
LV
LV
LV
LV
S D
S D
OS
LS
-
-
B
C
B
C
C,H
A- B
A- B
A
A
D
A
A
A
A-B,R
A- B
B
A- B
A- B
A-B,R
A- B
B- C
B- C
B
A- B
B
B
A- B
A-B,R
A- B
A- E
A- B
B
A-B,R
7 2 1
7 2 2
7 2 3
7 2 3
1 6 6
7 2 4
7 2 4
9 1 9
9 1 9
7 2 4
1 6 6
1 6 6
1 6 6
1 6 6
9 1 9
9 1 9
7 2 4
7 7 1
7 7 1
7 7 1
7 7 1
2 0 4
9 0 7
1 4 7
1 4 8
1 4 9
2 0 2
2 0 3
7 2 5
7 2 5
1 6 8
1 6 8
7 2 6
1 6 8
1 6 8
168
1 6 9
1 6 9
1 7 0
171
1 7 2
1 7 3
1 7 4
1 7 5
1 7 6
1 7 7
1 7 8
1 7 7
1 7 7
178
1 7 9
1 8 0
1 8 0
1 6 9
181
1 8 2
173
References page VII - 68
VI I / 16 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 1. contd
Polymer Solvent
Temp. K(x 103)
(C) (mW
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-q Method(s) Remarks Ref s.
plasma initiated
But yl c hl or i de
Chloroform
living type
p-Cymene
1,2-Dichloroethane
Ethyl acetate
3-Heptanone
4-Heptanone
Methyl isobutyrate
Methyl methacrylate
Methyl methacrylate
Nitroetbane
3-Octane
Propanol
Tetrachloroethane
2,2,3,3-Tetrafluoro-
propanol
Tetrahydrofuran
Toluene
Butanone/2-propanol
(55145, v/v)
(SO/SO, v/v)
oligomer-polymer
atactic, fracem = 0.79
Methanolkoluene
(915% v/v)
Acetonitrile
Benzene
n-Butyl chloride
i s ot act i c Acetone
Acetonitrile
2 5 3.80 0.79
25 83 0.52
3 0 5.2 0 . 7 6
3 0 6.27 0 . 7 6
3 0 104 0 . 5 0
3 0 195 0.41
39 6.74 0.75
53 6.52 0.76
25 6.8 0.72
25 7.1 0.72
25 6.8 0.72
25 9.39 0.68
25 l l f 2 0.69
35.4 (8) 50.5 0 . 5 0
2 0 9 . 6 0.78
2 0 4.88 0.82
2 0 4.85 0.80
2 0 6.0 0.79
2 5 4 . 8 0.80
25 3.4 0.83
2s 5.81 0.79
3 0 4.3 0 . 8 0
3 9 5.02 0 . 8 0
53 3.90 0.79
Uric. 5.1 0.79
159.7 (8) 57.5 0 . 5 0
25 17.0 0.68
3 0 5.3 0.77
2 0 21.1 0.64
33.7 (8) 63.1 0 . 5 0
33.8 (6) 4 8 0 . 5 0
3 0 9 . 9 0.67
2 0 16.2 0.65
4 0 11.3 0.68
6 0 21.2 0.64
30 6.75 0.72
2 5 5 . 7 0 0.74
72 (8) 5 0 0 . 5 0
84.4 (8) 67.9 0.50
25 12.8 0.73
53 12.2 0.73
25 7.2 0.79
5
7
9
5
9
5
6
6
9
7
4
15
4
18
8
9
12
9
6
6
-
8
4
5
6
9
9
9
3
2
3
4
6
6
7
25 7.5 0.72
25 7.1 0.73
25 8.12 0.71
25 7 8 0.50
3 0 7.0 0.71
3 9 7.24 0.72
53 6.63 0.73
23 4 7 . 0 0.55 6
25 (8)
59.2 0 . 5 0 7
25 (0)
42.8 0 . 5 0 5
26.2 (8) 55.9 0.50 3
4 4 . 0
30.0
40.8
3 0
2 0
27.6 (0)
-
-
23.0
130
75.5
Not const 2 2
Not const 15
Not const 21
0.63 7
0.448 5
0.500 5
-
-
-
-
6
-
-
-
-
8
-
-
-
6
7
3 4
6
24-450 L S
0.03-I EB
6-250 LS
4-73 O S
0.02-2 O S
0.3-2 LS
5-41 O S
5-41 O S
8-137 LS
41-330 LS
3-98 LS
16-910 LS
1610-3000 LS
13-68 S A
1.4-60 OS
6-100 OS
E-200 S D
3-780 LS
8-137 LS
40-330 LS
5-41 OS
13-263 LS
5-41 OS
5-41 OS
7-400 LS
6.6-171 LV
3-98 LS
6-263 LS
6-110 S D
6.6-171 LV
1-172 LS
19-260 LV
1.8-160 LS
1.8-160 LS
1.8-160 LS
13-170 LV
IO-200 LS
13-260 LV
6.6-171 LV
5-41 OS
5-41 OS
7-95 LV
4-330
5-41
0.2-7
19-263
5-41
5-41
40-300
30-280
77-490
60-300
0.032-283
0.032-75.8
0.032-283
5-128
3-19
3-19
LS
LS
OS
OS
LV
OS
OS
LS
LS
LS
LS
LS
LS
LS
LS
LV
LV
AJ -
A-B,R
A
AL
A-B,L
B
B
RR
A-B
B-C
A-B
A-B
B
A-B,R
A-B
B
A-B
B
A-B
B
B
B
A-B
B-C
A-B,R
A-B
A-B,R
A-B
A
A
A
A-B
C
A-B
A-B
B
B
A
183
184
178
185
185
178
177
177
170
174
175
186
727
187
188
182
169
173,189
170
174
177
178
177
177
190
1 9 1
175
178
192
1 9 1
179
178
918
918
918
178
193
179
191
177
177
194
A 732
A-B 174
B 177
AL
195
A-B 178
B 177
B 177
A-B 174
A-B 196
A-B 186
A-B 156
A 916
A 916
A 916
A-B 199
A 198
A 198
TABLE 1. contd
Viscosity - Mol ecul ar Wei ght Rel at i onshi ps of Mai n- Chai n Acycl i c Carbon Pol ymers
Polymer Solvent
Temp.
(C)
K(x103)
(mW
No. of samples Mol. wt.
range
a Fr. W.P. (x10-d) Method(s) Remarks Refs.
35 4 6 0 . 5 4 6
5 0 26.2 0.602
21.5 (8) 16.2 0 . 5 0
Benzene 3 0 5.2 0.76
p-Cymene 152.1 (0) 56.6 0.50
3-Heptanone 40.0 (8) 87.0 0 . 5 0
Propanol 75.9 (0) 76.1 0 . 5 0
2,2,3,3-Tetrafluoro- 25 7.05 0.78
pr opa nol
ButanonelZ-propanol 30.3 (0) 90.0 0 . 5 0
(l/l, v/v)
5%-iso, 5 1 %-hetero,
43%~syndiotactic Acetonitrilekhlorobenzene
(4.41956, v/v) 25 (8) 68.3 0.50
(91.2/8.8, v/v) 25 (8) 63.5 0 . 5 0
Poly(cc-methyleneglutaronitrile) Dimethylformamide 25 31.6 0.65
Poly(methy1 phenylacrylate), see 1.9 Other Compounds poly( I-methoxycarbonyl-l-phenylethylene)
Poly(P-naphthyl methacrylate) Benzene 2 0 27.2 0.55
Tet r al i n 20 @) 47.5 0 . 5 0
Poly[4-(4-nonyloxy-phenyl methacrylate], Poly(phenylmethacrylic ester of nonyloxybenzoic acid)
Poly(octadecy1 methacrylate)
Poly(octy1 methacrylate)
Carbon tetrachloride
Tetrahydrofuran
But a nol
Bu t a n o n e
Butyl acetone
Poly(N-phenyl methactylamide) Acetone
n-Propyl acetate
Tetrabydrofuran
Poly(2-selenolylmethyl methacrylate)
Chlorobenzene
Tetrahydrofuran
Poly(steary1 methacrylate) Tetrahydrofuran
Poly(tetrahydrofurfury1 methacrylate)
Acetone
Poly(tetrahydro-4H-pyranyl 2.methacrylate)
I s obut a nol
Poly(2-thiophenmethyl methactylate)
Chlorobenzene
Tetrabydrofuran
Thiophen :
Poly(N,N,N-trimethyl aminoethyl chloride acrylate)
Aq. NaCl (1 N) I
Poly(tridecy1 methacrylate) Ethyl acetate
Tetrahydrofuran
Tetrahydrofuran
Poly[2-(triphenylmethoxy)ethyl methacrylate]
Mesitylene
1.5. POLY(VINYL ETHERS)
Poly[(hexadecyloxy)ethylene] Heptane
Poly(methoxyethylene) Benzene
Bu t a n o n e
Poly[(octadecyloxy)ethylene] Benzene
Tetrahydrofuran
Poly(viny1 methyl ether), see Poly(methoxyethylene)
3 0
16.8 (0)
23
10.5 (S)
2 0
3 0
2 0
36 (0)
3 0
25
25
3 0
25 (8)
25
25
25
27 (0)
3 0
3 0
21
3 0
3 0
25
3 0
1.6. POLY(VINYL ALCOHOL), POLY(VINYL HALIDES)
Poly(chlorotrifluoroethylene) 2,5-Dichlorobenzo- 130
trifluoride
24.3
2.5
26.8
4.47
-
-
-
28.2
37.1
8.95
36.3
18.1
9 . 0
24.0
31.9
4.35
6.95
9 . 0 0
2.3
32.2
4 . 7 4
2.93
3 0
70.8
7 6
137
170
2 2 4
6.15
0.5
0.75
0 . 5 0
0.69
0.45
0.53
0 . 5 4
0.75
0 . 5 0
0.67
0 . 5 6
0.65
0.67
0.66
0 . 5 0
0 . 5 0
0.72
0.66
0.82
0 . 5 0
0.71
0 . 7 6
0 . 5 0
0 . 5 0
0.60
0 . 5 6
0.47
0.35
0.74
4
4
4
6
4
2 0
10
10
4
4
4
8
1 1
1 1
5
5
12
7
6
6
6
6
10
10
6
6
13
13
-
-
7
8
3-19
3-19
13-68
5-128
7-131
7-131
7-131
2-100
73-232
73-232
17-262
57-262
20-220
20-170
33-1250
33-1250
62-320
62-320
62-320
lo-320
1.5-93
1.5-93
3.6-21
3.6-21
1.5-94
16-62
4-85
48-59
48-59
48-59
85-510
8.2- 138
8.2-138
4-85
0.5-3
l -45
l -45
0.1-1.5
9.4-l 1
7-51
LV
LS
L S
L S
LS
LS
S D
LS
LS
LS
LS
LS
LS
LS
LS, OS, SEC
LS, OS, SEC
VOS, SEC
VOS, SEC
LS
OS
WC
S E C
S E C
S E C
LS
LS, OS, SEC
LS, OS, SEC
WC
LV
S D
LS
LS
LS
LS
OS
A
A
B
A-B
A-B
A-B
A-B
B
A-B
CA
B
B
C
C
C
A-B
A-B
B
A-B
A-B
A-B
B,L
B
B
D,H
D,H
B
198
198
7 2 8
199
191
191
191
194
7 8 5
7 8 5
7 3 1
7 2 9
7 2 9
7 3 0
2 0 0
201
201
9 2 0
920
9 2 0
3 7 0
9 1 3
9 1 3
9 2 2
9 2 2
733,751
921
921
921
7 3 6
2 0 5
2 0 6
2 0 6
2 0 0
2 0 0
234
References page VII - 68
VII / 18 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 1. cont d
No. of samples Mol. wt.
Temp. K (x 103) range
Polymer Solvent (C) (mVgf a Fr. W.P. (x 10-q Method(s) Remarks Ref s.
Poly(tetrafluoroethylene-alt-ethylene), see also Poly(ethylene-air-tetra-fluoroethylene) in group 1.2
Poly(viny1 alcohol) 6
-
0.6-2.1 OS B 2 0 8
4
-
0.9-17 S D 2 0 9
3
-
l - 7 S D B 2 1 0
8
-
0.6-16 OS B 2 1 2
-
1 4 l - 8 0 LS C 2 1 3
- -
l - 8 0 LS AR
2 1 3
7
-
3 - 1 2 LV B 7 3 7
-
5 lo-46 LS B 2 1 4
-
2 1 3-12 LV B 2 1 5
7 4 . 3 0. 63 7
-
DP=815-2830 VG C 9 2 4
-
Not clear 5
-
DP=815-3400 VG C 9 2 4
Poly(viny1 bromide) 3 2 . 8 0. 55 7
-
2 - 1 0 LS B 2 1 7
1 5 . 9 0 . 6 4 I
-
2 - 1 0 LS B 217
7
-
B 2 1 8
Poly(viny1 chloride) 9
-
B 2 1 9
7
-
B 2 2 0
-
6 C 2 2 1
7 5 C,D
2 2 2
5 3 D,H 2 2 2
1 1 2 2 3
1 3
- 2 2 4
? C 2 2 5
6
-
C 2 2 6
5
-
B 2 2 7
2 8
-
MO
2 2 8
6
-
B 2 2 0
2 0
-
B 2 2 9
2 2
-
-0 2 2 8
2 3
-
A.B,R 2 3 0
5
- A- B 2 3 1
9
- 2 3 2
7
-
B 2 2 0
1 6
-
2 3 3
Poly(viny1 fluoride)
-
9 D 2 3 5
Poly(vinylidene chloride)
-
7 C 7 3 8
-
7 C 7 3 8
- 7 C 7 3 8
Poly(vinylidene fluoride)
4 5 0. 70
-
7
-
LS
-
9 2 5
Wa t e r 2 5
2 5
2 5
3 0
3 0
3 0
3 0
8 0
Phenol/water (85/15, v/v) 30
Water/dimethylsulfoxide
(100/0, v/v) 3 0
(90/10, v/v) 3 0
Cyclohexgone 2 5
Tetrahydrofuran 2 5
Methanol/tetrahydrofran
(17/83, v/v) 2 0
Benzyl alcohol 155. 4 (0)
Chlorobenzene 3 0
Cyclohexanone 2 0
2 0
2 0
2 5
2 5
2 5
2 5
2 5
2 5
3 0
Tetrahydrofuran 2 0
2 5
2 5
2 5
3 0
3 0
3 0
Dimethylformamide 9 0
Hexamethylphos- 2 5
phoramide
1-Methyl-2-pyrrolidone 2 5
Tetramethylene sulfoxide 2 5
N,N-Dimethylacetamide,
N,N-dimethylformamide,
N-methylpyrrolidone.
N,N-dimethyl-NJ+tri-
methylene urea 2s
2 0 0. 76
3 0 0 0 . 5 0
1 4 0 0. 60
6 6 . 6 0. 64
4 2 . 8 0. 64
4 5 . 3 0. 64
7 3 . 4 0. 63
9 4 0. 56
2 4 . 6 0 . 8 0
3 8 . 8 0. 50
1 5 6 0 . 5 0
7 1 . 2 0. 59
1 1 . 6 0. 85
1 3 . 7 1 . 0
112. 5 0. 63
1 2 . 3 0. 83
2 4 0. 77
2 0 4 0. 56
1 7 4 0. 55
8 . 5 0. 75
1 3 . 8 0. 78
1 6 . 3 0. 77
3. 63 0. 92
1 5 . 0 0. 77
1 6 . 3 0 . 7 6 6
4 9 . 8 0. 69
6 3 . 8 0. 65
8 3 . 3 0. 83
2 1 9 0 . 5 4
6. 42 0. 80
2 5 . 8 0. 65
2 - 1 0 LS
4-35 LS
3-19 S A
2 - 1 0 O S
7-13 O S
9-15 OS
2-14 OS
3 - 1 4 OS
2-15 OS
6 - 2 2 L S
4 - 2 0 LS
l - 1 2 LS
3-19 S A
2 - 1 7 O S
l - 1 2 LS
2 - 3 0 LS
4 - 4 0 LS
3 - 3 2 LS
3 - 1 9 S A
5 - 3 0 LS
14-66 SV
0.8-12 LS
1 3 . 1 0. 69
1 3 . 9 0 . 6 9
0.8-12 LS
0.8-12 LS
1.7. POLY(VINYL ESTERS)
Poly(allyl acetate) Benzene
Poly(viny1 acetate) Acetone 2 7 6 6 0. 53 6 [T/I =0.104M +0.00725M090 2:
1 8 2 4 . 5 0. 67 6
2 0 1 5 . 8 0. 69 6
2 5 2 1 . 4 0. 68 6
2s 1 8 . 8 0. 69 ?
2 5 1 4 . 6 0. 72 -
2 5 1 0 . 8 0. 72 1 0
3 0 1 7 . 6 0. 68 1 6
3 0 8 . 6 0. 74 8
3 0 1 7 . 4 0. 70 ?
3 0 1 0 . 2 0. 72 -
3 0 1 0 . 1 0. 73 II
-
?
6
-
-
8
-
0.1-0.3 C R
0.3-150 LS
4 - 3 4 OS
19-72 LS
4 - 3 4 OS
? LS
0.7- 1.3 E G
0.9-2.5 E G
2-163 OS
8-66 LS
7-68 OS
3-126 LS
6- 150 LS
A
B
B
CL
W
A- B
A- B
C
A
2 1 6
2 3 6
2 3 7
2 3 8
2 3 7
2 3 9
2 4 0
2 4 0
2 4 1
2 4 2
2 4 3
2 4 4
2 3 6
TABLE 1. contd
Viscosity - Molecular Weight Relationships of Main-Chain Acyclic Carbon Polymers VII / 19
Polymer Solvent
Temp.
(C)
K (x 103)
(ml&
No. of samples Mol. wt.
range
a Fr. W.P. (x10-d) Method(s) Remarks Refs.
30 [v] = 0. 097 M0.50 + 0. 00723 M 9o 2 2
4 6
2 5
3 0
3 0
3 0
3 0
3 5
2 5
2 5
3 0
2 5
2 5
5 3
6 7
2 0
2 5
5 3
2 5
53, 60
56. 9 ( 0)
3 0
26.8 (0)
29 (0)
6 @I
2 5
3 0
5 3
66 @I
66 (8)
3 0
2 5
3 5
2 5
6 7
3 5
1 3 . 8
1 6 . 2
4 1 . 5
2 2
5 6 . 3
5 6 . 3
2 1 . 6
1 3 . 4
4 2
1 0 . 7
1 1 0
9 4 . 4
5 3 . 7
2 8 . 9
1 5 . 8
2 0 . 3
1 4 . 7
1 1 . 4
1 0 . 2
9 0
3 2
8 2 . 0
9 2 . 9
101
3 8 . 0
3 1 . 4
3 6 . 6
8 2 . 0
7 8 . 0
4 4 . 9
1 6
1 5 . 6
1 0 8
1 5 6
3 3 . 0
0. 7 1
0. 71
0. 62
0. 65
0. 62
0. 62
0. 675
0. 71
0. 62
0. 71
0. 50
0 . 5 6
0 . 6 0
0. 65
0 . 7 4
0. 72
0. 74
0. 74
0. 75
0. 50
0. 65
0. 50
0 . 5 0
0 . 5 0
0. 59
0. 60
0. 59
0. 50
0. 50
0 . 6 0
0 . 7 0
0. 708
0. 53
0. 49
0. 623
6
-
4
5
2 4
1 2
1 4
6
1 5
9
6
6
6
?
5
5
5
5
5
4
5
1 8
5
-
5
9
3
5
1 1
9
4
4
-
-
-
-
-
-
-
-
-
1 3
-
-
-
?
-
-
-
-
-
1 3
-
-
-
-
-
-
-
-
0.3-150
4 - 3 4
24-215
97-153
34- 102
3-86
7-54
5 - 4 0
25-346
2-120
3-120
0.15-7
4 - 3 4
4 - 3 4
4 - 3 4
7-68
4 - 3 4
4 - 3 4
4 - 3 4
4 - 3 4
4-150
16-154
4-150
5-83
0.3- 150
4 - 2 2
3-120
4 - 2 2
14-83
9- 150
12-69
5 - 5 0
1.7-117
4 - 1 5
4-15
5 - 4 0
L S
O S
L S
LS
L S
OS
LS
LS
LS
SD,LS
LS
OS
OS
OS
OS
OS
OS
OS
OS
OS
O S , LS
LS
OS, LS
LS
OS, LS, vos
OS
LS
OS
L S
OS, LS
LS
G P C
GPC
OS
OS
LS
A
A
B
A- B
A- B
B
B
A- B
A
AB
C
A
A
A
A
A
A
B
B
A
A- B
A
A- B
B
C
B
A- B
A
BC
B
B
B
2 3 6
2 3 6
2 4 6
2 4 7
2 4 8
2 4 9
2 5 0
2 5 1
2 5 2
2 5 3
2 4 4
1 9 5
2 3 6
2 3 6
2 3 6
2 4 3
2 3 6
2 3 6
231
2 3 7
2 3 6
241
2 3 6
2 5 5
236, 245
2 3 7
2 4 4
2 3 7
2 5 5
2 3 6
2 4 7
7 3 9
740
231
231
2 5 1
Acetonitrile
Benzene
But anone
Chlorobenzene
Chloroform
Dioxane
Et hanol
Ethyl formate
3-Heptanone
Methanol
6-Methyl-3-heptanone
4-Methyl-2.pentanone
Tetrahydrofuran
Tol uene
1,2,4-Trichlorobenzene
Poly(viny1 benzoate)
Poly(viny1 butyrate)
Poly(viny1 caproate)
Poly(vinyl 4-chlorobenzoate)
Heptane/3-methyl-2-butanone
(27.3172.7, v/v) 2 5
Xylene 32.5 (8)
Benzene 3 0
Benzene 3 0
Wa t e r 3 0
Butanolibutanone
60 (0)
(47153, v/v) .
Acetone 3 0
Acetonitrile 3 0
Dioxane 3 0
Methyl acetate 3 0
Methyl formate 3 0
Benzene 3 0
Benzene 3 0
Acetone 2 5
Butanone-methanol 2 0
( 0. 897 g/ ml )
Aq. NaCl (0.5 M) 2 0
9 2
6 2 . 0
11. 15
15. 47
6 4 . 0
7 3
0 . 5 0
0 . 5 0
0. 735
0. 689
0. 64
0. 50
25-281
lo-24
3-15
3-126
6-35
6-35
LS
OS
OS
OS
LV
LV
2 4 4
3 3 4
2 5 6
2 5 6
3 3 6
3 3 6
-
4
4
-
Poly(viny1 formate) 2 9 . 3
1 4 . 1
2 0 . 7
3 1 . 6
1 4 . 1
11. 05
5 1 . 0
2. 88
5 3
0. 63
0. 717
0. 68
0. 61
0 . 7 2 2
0. 711
0. 575
0. 77
0. 50
2 5 7
2 5 7
2 5 7
2 5 7
2 5 7
2 5 6
2 5 6
2 5 8
2 5 8
3-41
3-41
3-41
3-24
3-24
5 - 2 0
3-17
40-217
222-344
LV
LV
LV
LV
LV
OS
OS
LS
LS
-
Poly(viny1 isobutyrate)
Poly(viny1 isocaproate)
Poly(viny1 pivalate)
-
4
2
-
Poly(viny1 sulfate) 0. 55 1. 06 6 l - 6 LV C 2 6 1
-
1.8. POLY(STYRENE) AND DERIVATIVES
Poly(4-acetoxystyrene) Butyl acetate
Dioxane
Isopropyl acetate
Tetrahydrofuran
26. 8 ( 6)
2 5
19. 7 (0)
2 5
5 2 . 0
1 6 . 7
5 2 . 0
1 7 . 5
0. 50
0. 65
0 . 5 0
0. 64
1 3
2 2
1 3
2 0
15-219
0.91-352
15-219
0.91-352
LS
LS
LS
LS
A- B
A- B
A- B
A- B
9 3 7
9 3 7
9 3 7
9 3 7
References page VII - 68
VII / 20 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 1. conrd
Polymer Solvent
Temp. K(x 103)
c-3 (mW
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-q Method(s) Remarks Ref s.
Poly(4-bromostyrene) Benzene
Poly@-rut-butylstyrene)
Chlorobenzene
Tol uene
Benzene
Benzene
Cyclohexane
Cyclohexane
1- Hexanol
Cyclohexane
1,4-Dioxane
Poly(2-chlorostyrene)
I-Nitropropane
1- Ni t r opr opane
3-Nonanol
2-Octanol
2-Octanol
Tetrahydrofuran
Butanone
Tol uene
Poly(4-chlorostyrene) Benzene
Poly(4-cyclohexylstyrene)
Poly(2,5-dichlorostyrene)
Poly(3,4-dichlorostyrene)
Poly(2,4-dimethylstyrene)
Poly( 1,4-divinylbenzene)
Poly(3-fluorostyrene)
Poly(4-fluorostyrene)
Poly(4-hydroxystyrene)
Benzene&methanol
(4.5/l, v/v)
But anone
Chlorobenzene
Chloroform
Dioxane
Ethylbenzene
Tol uene
Heptane
Tol uene
Tol uene
Ethanol/ethyl acetate
(l/15, w/w) i
Chlorobenzene
o-DiChlorobenzene
Butanol/butyl acetate
(l/13, wlw)
Benzene
Butyl acetate
Cyclohexane
Tol uene
trans-Decalin
Benzene
But anone
Carbon tetrachloride
Chloroform
Benzene
Butanone
Carbon tetrachloride
Chloroform
Dioxane
Ethyl propionate
Isobutyl acetate
Tetrahydrofuran
1-Chloro-n-hexane
20 (Q)
9 5 . 5 0. 53
26.3 (8) 5 0 . 0 0. 50
3 0 7. 43 0. 69
3 0 1 8 . 2 0. 57
3 5 7 . 1 0. 74
3 5 6. 58 0 . 7 3 9
2 5 8. 52 0. 717
3 5 9 . 9 0. 7 1
6 5 . 0 6 4 . 7 0 . 4 8 0
3 5 . 0 1 1 . 1 0 . 6 9 4
2 5 . 0 2 1 . 4 0 . 6 0 4
3 8 . 0 1 4 . 3 0 . 6 4 4
3 1 . 0 6 0 . 0 0 . 4 8 9
31 (8) 6 1 0. 49
1 0 . 9 6 6 . 5 0 . 4 9 0
3 2 . 1 6 0 . 8 0 . 4 9 2
3 2 . 1 6 1 . 0 0 . 4 8 9
3 0 . 0 1 0 . 4 0. 70
24.5 (6) 4 6 . 8 0. 50
25 (0)
4 6 . 0 0 . 5 0
2 5 1 1 . 5 0. 66
3 0 1 4 . 3 0. 65
3 0 3 0 . 6 0 . 5 6
2 6 . 7 2 9 . 3 0. 56
41.6 (8) 5 6 . 8 0 . 5 0
2 5 2 9 0. 59
3 0 3. 52 0. 75
3 0 2. 19 0. 80
3 0 1 4 . 8 0. 65
3 0 1 7 . 6 0. 62
3 0 2 1 . 8 0 . 6 0
2 0 2 4 . 1 0. 605
2 5 1 3 . 2 0. 645
3 0 1 3 . 0 0. 64
3 0 1 1 . 8 0. 65
3 0 5. 37 0. 7 1
3 0 3 2 . 3 0. 54
3 0 1 0 . 6 0. 69
2 1 1 2 . 6 0. 69
30.5 (0) 3 5 . 5 0. 50
3 0
3 0
32.9 (0)
4. 39
4. 11
0. 72 7
-
8-51 OS
0. 73 7
-
8-51 OS
0 . 5 0 8
-
40-540 LS
2 0 3 . 8 0. 79
2 0 1 0 . 2 0. 68
2 0 1 4 . 8 0. 65
3 0 9. 52 0. 70
25.0 (8) 2 8 6 0. 32
2 5 1 5 . 3 0. 69
2 5 1 3 . 8 0. 70
2 5 6 5 . 6 0. 53
2 5 1 2 . 8 0. 70
2 5 4 0 . 8 0. 58
2 5 1 1 . 1 0. 73
2 5 8 2 . 8 0. 50
2 5 1 6 . 1 0. 69
2 5 2 0 . 3 0. 66
2 5 6 3 . 7 0. 52
2 5 5 9 . 4 0. 53
2 5 3 7 . 2 0 . 6 0
5 . 7 9 1 . 6 0. 468
10
5
5
5
4
7
1 0
4
6
7
4
4
7
4
6
6
7
7
I
5
6
1 0
5
5
6
8
7
-
7
-
1 1
1 1
1 1
1 0
9
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
8
-
3-30
84-250
59-400
63-400
1.8-640
1.3-174
1.3-240
1.8-640
16-240
2.7-45.5
9.3-45.5
9.3-45.5
2.7-45.5
1.8-640
16-240
16-240
2.7-45.5
2.7-45.5
20-80
20- 100
14-101
23-143
10-200
34- 180
34- 180
-
-
8
8
-
7
I
-
-
-
-
-
-
-
3-140 LS
17-270 OS
17-270 OS
10-200 LS
10-200 LS
lo-180 LS
2 - 4 0 LS
l - 2 4 4 L S
3-140 LS
21-140 LS
17-270 OS
4 - 3 0 OS
2 - 3 0 OS
7 - 6 6 LS
50-130 LS
-
9
-
3-22 LS B,C
3-22 LS B,C
3-22 LS BC
5-120 LS C
0.7-180 L S , S E Br anchi ng
8
0.5-8
1-15
8 0.2-13
-
3.8-583
- 3.8-583
-
3.8-583
-
3.8-583
-
5.9-90.3
OS B
L S AR
L S A
L S A
L S A
L L S , S E C , O S A
L L S , S E C , O S A
LS A
L L S , S E C , O S A
OS, LLS A
O S , LLS A
O S , LLS A
OS, LLS A
LS A
L L S , S E C , O S A
L L S , S E C , O S A
O S , LLS A
OS, LLS A
LS AR
LS A,B
LS AB
LS A
LS C
LV B
LV B
B,R
B
B
C
C
B
B
B
RR
A
B
A- B
A- B
A
A
LS
LS
LS
LS
LS
LS
LS
L S , S E C , O S A
3 4 7
3 4 8
3 4 8
3 4 9
7 4 1
9 3 4
9 3 4
7 4 1
9 3 4
9 3 8
9 3 8
9 3 8
9 3 8
741
9 3 4
9 3 4
9 3 8
9 3 8
7 4 2
7 4 3
7 4 3
3 5 0
351
7 4 4
7 4 4
3 5 2
3 5 3
3 5 3
3 5 1
3 5 1
7 4 5
3 5 4
3 5 5
3 5 2
3 4 9
3 5 3
2 6 6
2 6 6
3 5 6
3 5 7
3 5 8
3 5 8
3 5 9
7 4 6
7 4 6
7 4 6
3 3 3
8 9 5
7 4 7
7 4 7
7 4 1
7 4 7
7 4 7
741
7 4 7
7 4 1
9 4 0
9 4 0
9 4 0
9 4 0
8 8 8
TABLE 1. contd
Viscosity - Mol ecul ar Wei ght Rel at i onshi ps of Mai n- Chai n Acycl i c Carbon Pol ymers VII / 21
Polymer Solvent
Temp. K(x103)
(C) (mW
No. of samples Mol. wt.
range
a Fr. W.P. (x10-4) Method(s) Remarks Refs.
Poly(Ciodostyrene) Dioxane 2 0
Poly((p-isopropyl-cc-methylstyrene)
Tetrahydrofuran 25
Poly(p-isopropylstyrene) Tol ue ne 25
Poly(o-methoxystyrene) Bu t a n o n e 3 0
Tol ue ne 3 0
MethanoUtoluene 30 (0)
(25175, v/v)
Poly@-methoxystyrene) Bu t a n o n e 3 0
35
Chlorocyclohexane 25
Pentyl acetate 25
Tol ue ne 25
3 0
3 0
Methanokoluene 30 (8)
(28.1/71.9, v/v)
Poly(cc-methylstyrene) anionic, (ca. 50%-hetero, ca. 40%syndio)
Benzene
Cyclohexane
frans-Decalin
Tol ue ne
cationic
(lo%-hetero, 90%-syndio)
(19%-hetero, SO%-syndio)
Benzene
Cyclohexane
Tol ue ne
Benzene/methanol
(79.4/20.6, v/v)
1 -Chloro-n-heptane
I-Chloro-n-octane
n-Hexyl acetate :
Cyclohexane
trans-Decalin .
n-Butyl chloride
Carbon tetrachloride
Chloroform
Tetrahydrofuran
Tol ue ne
n-Butyl chloride
Poly(m-methylstyrene) Benzene
Cyclohexane
Ethyl acetate
Poly(p-methylstyrene) Diethyl succinate
Tol ue ne
Poly(methylstyrene), position of substituent, unspecified
Cyclohexane
Poly[(2,3,4,5,6-pentafluorostyrene)]
4-Methyl-2.pentanone
Poly(styrene) Benzene
atactic
3 0 10.3 0.72
3 0 9.15 0 . 7 2 6
34.5 (8) 73 0.50
37 (0) 78 0.50
38 (0) 7 6 0.50
38.6 (8) 76.0 0.50
39 71.3 0.51
9.5 (B) 6 7 0 . 5 0
25 7.06 0 . 7 4 4
25 7.81 0.73
3 0 10.8 0.71
3 0 24.9 0 . 6 4 7
32.5 (8) 6 6 . 0 0 . 5 0
33.3 (8) 72.7 0.50
30 (8) 2 . 2 0.80
3 0 76.8 0 . 5 0
10.0
20.0
27.0
4 3 . 0
53.0
80.0
85.0
34.5
10.0
35.5
4 5
25
25
25
5
25
5 0
3 0
3 0
30
16.4 (0)
3 0
71.8
94.9
79.6
94.8
65.1
74.6
86.4
74.0
83.0
4 0 . 0
19.4
13.3
11.1
10.1
33.6
27.0
26.5
7 . 3 6
11.76
17.42
7 0
8.86
0.49 1
0 . 4 5 9
0.477
0.461
0 . 4 9 7
0 . 4 8 4
0 . 4 7 4
0.493
0 . 4 8 0
0.56
0.67
0 . 7 0
0 . 6 9
0.71
0 . 5 7 0
0 . 5 9 0
0 . 5 9 4
0 . 7 6
0.70
0.64
0.50
0.74
2 0
2 0
2 0
2 0
22 0.68
4.37
6.3
12.3
0.736
0.78
0.72
33 0.51 10 6 lo-118 LV B - C 3 6 0
4 5 0.55
12.3 0.69
18.6 0.59
6.40 0.71
57.5 0 . 5 0
8
-
5
5
4
l -63 L S A-D 7 4 8
14-75 L S B,C 2 6 5
13-35 LS A-B 3 6 2
13-35 LS A-B 3 6 2
15-30 LS A-B 3 6 2
3.75 0.73 5
8.6 0.68 6
17.7 0.63 16
55 0.52 16
10.5 0 . 7 0 16
5.28 0.73 5
18.0 0.62 6
62.1 0.50 5
-
-
-
-
13-75 LS A-B 3 6 2
l-100 LS B 3 5 2
22-220 LS A 3 6 3
22-220 LS A 3 6 3
22-220 LS A 3 6 3
13-75 LS B 3 6 2
I-100 LS B 3 5 2
7-180 LS B 3 6 2
-
-
-
-
-
-
9
6
10
9
6
9
9
9
9
6
13
4- 170 LS A 3 1 9
37.5-685 LS A 8 7 3
4-750 LS, OS A 3 2 0
9-400 LS A 321
2-66 LS A 3 2 2
4-170 LS A 3 2 3
3-140 LS A 3 2 4
S-750 LS, OS A 3 2 0
8-750 LS, OS A 3 2 0
3-60 S D A 325
2-66 LS A 322,326
14-91 OS B 3 2 7
2-370 LS B 3 2 8
2-18 LS B 3 2 8
l -100 LS B 3 2 9
14-91 OS B 3 2 7
9
9
9
9
9
9
9
1 1
1 1
16
16
16
16
16
8
1 5
8
9
7
7
6
9
5.9-90.3 LLS, SEC, OS A 8 8 8
5.9-90.3 LLS, SEC, OS A 8 8 8
5.9-90.3 LLS, SEC, OS A 8 8 8
5.9-90.3 LLS, SEC, OS A 8 8 8
5.9-90.3 LLS, SEC, OS A 8 8 8
5.9-90.3 LLS, SEC, OS A 8 8 8
5.9-90.3 LLS, SEC, OS A 8 8 8
2.01-90.3 LLS, SEC, OS A 8 8 8
2.01-90.3 LLS, SEC, OS A 8 8 8
0.2-130 OS, GPC B 9 2 7
0.2- 130 OS, CPC B 9 2 7
0.2- 130 OS, GPC B 9 2 7
0.2-130 OS, GPC B 9 2 7
0.2-130 OS, GPC B 9 2 7
6.0- 107 LLS, LS A 9 3 5
5.4-354 LLS, LS A 9 3 5
6.0- 107 LLS, LS A 9 3 5
8-115 OS A 3 3 0
15-83 O S A 3 3 0
15-83 OS A 3 3 0
16-200 LS A 331
19-180 LS A 331
6
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
21
-
-
11-133 s v A 3 3 2
-
18
7
lo-260 OS C 3 6 4
l -300 S D A 2 7 0
0.6-520 S D AR 271
References page VII - 68
VII / 22 VI SCOSI TY - MOLECULAR WEI GHT RELATI ONSHI PS AND UNPERTURBED DI MENSI ONS OF LI NEAR CHAI N MOLECULES
TABLE 1. contd
Polymer Solvent
Temp. K (x 103)
(0 Wk)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-A) Method(s) Remarks Refs.
Bu t a n o n e
But yl c hl or i de
n-Butyl chloride
Carbon tetrachloride
Chlorobenzene
Chloroform
Cyclohexane
cis-Decalin
Decalin (100%~trans)
Decalin (73%~rrans)
Dichloroetbane
1,2-Dichloroethane
Diethyl malonate
Dietbyl oxalate
Dimethylformamide
Dioxane
Ethyl acetatekyclohexane
(100/O-10/90)
25
25
25
25
25
25
34
25
25
25
30
34
35
40.8
25
50
10
20
30
40
50
25.1
25
25
30
28
34(Q)
34 (0)
34.5 (0)
35 (0)
35 (8)
35 @I
40
45
50
50
25
20
23
23.8 (8)
25
30
60
18 (Q)
30
40
60
loo
25
35
35
34.2 (0)
55.8 (0)
35
34
-
10
25
40
55
65
22.1 0.72
-
41.7 0.60 9
34.0 0.65 11
9.52 0.744 6
9.18 0.743 6
11.3 0.73 10
9 . 8 0.737 10
39 0.58 16
30.5 0.60 5
19.5 0.635 7
23 0.62 7
28.9 0.60 10
17.1 0 . 6 4 13
15.1 0.659 5
17.4 0.662 8
(M,>3.7 x 104)
1 6 . 2 0.665 8
(M,.>3.7 x 104)
12.6
12.0
11.4
11.2
11.0
1 . 4
7.16
11.2
4.9
108.0
82
90.2
84.6
80
70
76
41.6
34.7
26.9
36.4
40
149
98
-
61
61
22
17
36
37
22
15.7
21.0
14.3
14.3
71.8
73.0
31.8
15.0
0.717
0.720
0.724
0.725
0.726
0.749
0.76
0.73
0.794
0.479
0.50
0.503
0.50
0.50
0.50
0.50
0.554
0.575
0.599
0.584
0.574
0.44
0.48
0.50
0.52
0.53
0.63
0.50
0.58
0.58
0.64
0.67
0.66
0.69
0.69
0.50
0.50
0.603
0.694
18.2-43.8 0.54-0.67
11.0 0.733
9.32 0.738
9.07 0.739
8.79 0.742
8.90 0.740
-
-
-
4
8
5
4
7
15
9
8
3
8
10
10
10
10
J
8
I
7
7
6
4
4
4
4
4
6
7
1 1
1 1
3
3
5
10
5
7
-
0.2-0.8 C R
CL
212
0.1-I C R
B,L
272
0.04-0.8 EG AL 273
3-61 OS A 274
3-70 LS A 275
J-180 OS A 276
S-80 DV A 277
I-180 LS AR
278
J-150 OS A 276
12-280 LS A 279
40-370 L S B 280
S-80 DV A 28 1,282
4-640 LS A 752
29-106 LS B 283
0.97-67.5 LLS, SEC A 933
-
0.97-67.5 LLS, SEC A 933
-
-
-
-
-
-
-
1.8-180
1.8-180
1.8-180
1.8-180
1.8-180
62-424
12-280
7-150
19-373
0.6-69
l -70
0.6-69
14-200
8-42
3-200
4-137
4-137
4-137
4-137
4-52
4.8-2360
14-200
14-200
-
-
-
14-200
14-200
14-200
14- 140
14- 140
14-140
14- 140
14-200
l -180
10-500
9-540
39-400
39-400
0.4-87
S-80
LV A-B 901
LV A-B 901
LV A-B 901
LV A-B 901
LV A-B 901
LS B 283
LS A 279
OS A 276
OS B 284
OS A 285
LV A 274
OS A 285
LS A3 286
LS A 287
S D B 288
LS B 283
LS B 283
LS B 283
LS B 283
LS A 289
LS A 936
LS A 290
LS A 290
LS A 290
LS A 290
LS A 290
LS A 290
LS A 290
LS A 290
L S A 290
LS A 290
LS A 290
LS A 278
LS A 689
LS A 752
LV B 291
LV B 291
LS A 754
DV A 282
II-96
1.8-180
1.8-180
1.8-180
1.8-180
1.8-180
LV
LV
LV
LV
LV
A 939
A-B 901
A-B 901
A-B 901
A-B 901
A-B 901
TABLE 1. contd
Viscosity - Molecular Weight Relationships of Main-Chain Acyclic Carbon Polymers VII / 23
Polymer Solvent
Temp.
P - 3
K (x 103)
(mh)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-41 Method(s) Remarks Refs.
Ethylbenzene
Ethylcyclohexane
Methylcyclohexane
4-Methyl-2-pentanone
Tetrahydrofuran
Toluene
2 5 1 7 . 6 0. 68
70 (0) 7 5 0. 50
70 (0) 7 6 0 . 5 0
70.5 (0) 6 9 . 6 0. 50
3 5 6 1 . 9 0. 53
2 5 1 1 . 0 0. 725
2 5 1 4 0. 70
2 0 4. 16 0. 788
2 5 7 . 5 0. 75
2 5 8. 48 0. 748
2 5 1 0 . 5 0. 73
2 5 1 7 0. 69
2 5 7. 54 0 . 7 8 3
2 5 1 3 . 4 0. 71
2 5 4 4 0. 65
2 5 (a increases with M)
atactic, anionic
Trichloro benzene
Benzene/methanol
(74 126, v/v)
Butanone/methanol
(97.512.5, v/v)
(95.915.0, v/v)
(92.517.5, vlv)
(89/l 1, v/v)
Butanone/2-propanol
(6/L W
(82.6117.4, v/v)
Chloroform/methanol
(90/ 10, v/v)
(80/20, v/v)
(75125, v/v)
(74.7124.3, v/v)
Dioxane/methanol
(65.1134.9, v/v)
Toluene/methanol
(90/ 10, v/ v)
(80/20, v/v) I
(76.9124.8, v/v)
(75.2/24.8, v/v)
Benzene
Cyclohexane
Cyclohexene
Decalin (66%.cis)
Decalin (99%.rrans)
Dichloroethane
Dioctyl phthalate
Tetrahydrofuran
2 5
3 0
3 0
3 0
3 4
3 5
3 5
135
34 (0)
2 5
2 5
2 5
25 (0)
23 co)
34 (@
2 5
2 5
2 5
25 (0)
34 (0)
2 5
2 5
2 5
34 (0)
2 5
2 5
3 0
3 0
3 0
34 (0)
34.5 (8)
34.5 (0)
34.5 (8)
34.6 (8)
35 (0)
2 5
12. 2 ( 0)
20.4 (fl)
3 0
22.0 (H)
2 5
100
9 . 2
1 2 . 0
1 1 . 0
9 . 7
1 2 . 6
1 2 . 9
1. 75
8 9
2 2 . 4
2 6 . 3
3 5 . 7
7 3
7 3
7 1 . 8
7 . 7
1 2
4 6
7 3
7 2 . 6
1 0 . 4
2 6
9 2
8 8
1 0 0
7 . 8
8 . 5
1 1 . 5
9. 50
7 4 . 5
8 5
8 8
8 8
91
8 6
1 6 . 3
8 0
8 1
8. 38
8 0
13. 63
0. 50
0. 72
0. 71
0. 725
0 . 7 3 3
0 . 7 1
0. 71
0. 67
0. 50
0. 62
0 . 6 0
0. 57
0. 50
0. 715
0. 612
0 . 5 0
0. 50
0 . 5 0
0. 75
0. 75
0. 73
0. 74
0. 50
0 . 5 0
0. 50
0. 50
0. 50
0. 50
0. 68
0. 50
0. 50
0 . 7 4
0. 50
0 . 7 1 4
-
10
8
7
6
9
?
5
-
1 0
8
9
8
7
1 0
1 6
8
8
1 2
10
-
1 7
-
-
-
7
-
7
-
-
-
-
-
?
-
9
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
7
7-150
36-127
?
39-400
5-100
l-100
4-137
12-280
4-52
16-100
I-160
5 - 8 0
7-150
0.5-4.5
0.08-3.7
0.05-0.5
4-146
40-370
8-85
8 - 8 0
3-650
5-100
8-80
12-280
12-280
12-280
12-280
4-146
8 - 8 0
12-280
12-280
12-280
12-280
8-80
12-280
12-280
0.07-3.5
S-80
0.04-l
40-6000
2.5-150
25-300
31-500
?
0.04- 150
31-970
l-6000
25-300
2 - 5 0
20-107
2 - 5 0
31-760
25-300
40-160
2-4000
O S
LV
?
LV
L S
G P C
L S
LS
L S
LS
L S
L S
OS
OS
OS
C R
C R
LS
LS
O S
DV
LS
LS
DV
LS
LS
LS
LS
LS
D V
LS
LS
LS
L S
DV
L S
LS
DV
DV
V O S , E B
LS
v o s
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
L S , O S , S D
A
B
B
B
A
C
B
A
A
A3
A
A
L
A N -
A
B
A- B
A
A
B
A
A
A
A
A
A
A
A
A
AL
A
AL
AR
A
A
A
B
AR
A
A
A
A
A
A
A
A
A
AR
2 7 6
2 9 2
2 9 3
2 9 1
6 9 8
7 4 9
7 5 6
2 8 3
2 7 9
2 8 9
2 9 4
2 7 8
2 9 5
2 7 6
2 9 6
2 9 7
2 9 8
2 9 9
2 8 0
3 0 0
2 8 2
7 5 2
6 9 8
6 9 7
2 7 7
2 7 9
2 7 9
2 7 9
2 7 9
2 9 9
2 8 2
2 7 9 , 2 7 8
2 7 9 , 2 7 8
279, 278
279, 278
2 8 2
219
2 7 9
298, 297
2 8 2
3 0 1
7 5 0
3 0 1
3 0 2
6 4 9
3 0 4
301, 303
6 4 9
7 5 0
3 0 2
3 0 5
3 0 6
3 0 3
6 4 9
3 0 2
3 0 3
7 5 3
References page VII - 68
VII / 24 VI SCOSI TY - MOLECULAR WEI GHT RELATI ONSHI PS AND UNPERTURBED DI MENSI ONS OF LI NEAR CHAI N MOLECULES
TABLE 1. cont d
Polymer Solvent
Temp. K (x 103)
((3 OWi9
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-q Method(s) Remarks Ref s.
Thiophenol
Tol ue ne
i s ot act i c Benzene
Chloroform
o-Dichlorobenzene
Tol ue ne
branched, random type
head-to-head
Butanone
Cyclohexane
Tol ue ne
Tetrahydrofuran
ring
star type
three branches
four branches
regular H-shaped
star type 3 arm
star type 15 arm
20 arm
star type, anionic
Cyclohexane
Tetrahydrofuran
Tol ue ne
Cyclohexane
Tol ue ne
Benzene
Cyclohexane
Cyclohexane
Tol ue ne
Cyclohexane
Tol ue ne
Cyclohexane
Tol ue ne
Cyclohexane
Cyclohexane
Cyclohexane
Decalin _
Tol ue ne
Poly(styrenesulfonic acid)
-, sodium salt
Aq. KC1
Aq. HCI (0.52M)
Aq. NaCl (0.52 M)
Aq. NaCl
(4.17M)
(0.5 M)
(0.1 M)
(0.05 M)
(0.02 M)
(0.01 M)
(0.05 M)
(3.1 M)
2 5
2 0
2 0
25
25
3 0
30.3
3 0
3 0
3 0
25
3 0
3 0
2 5
35 m
3 0
2 5
35 (not 0)
4 0
35
34.5
35
3 0
25
2 5
4 0 . 0
35.0
25
3 5
35 (@
5 0
3 5
35 (0)
35
16.6-30.1 (0)
(depend on M,)
35
34.5 (not 8)
34.5 (not 0)
14.6 0.70 6
10.69 0 . 7 2 4 2 0
11.2 0.72 -
9.77 0.73 -
34.5 0.62 -
8.81 0.75 -
10.4 0.73 -
9.5 0.77 6
10.6 0.735 7
25.9 0 . 7 3 4 3
17.9 0.677 5
11.0 0.725 7
9.3 0.72 5
(a decreases with M) 5
(a decreases with M) 9
(a decreases with M) 9
5 3 0.61
0.465
0.5
0.67
53 0 . 5 0
- 0.52
12.0 0.68
-
6.38 0 . 7 3 4
55.6 0 . 5 0
12.4 0.67
5.7 0.76
3 6 0.55
63.1 0.50
26.5 0.58
7.4 0.73
66.5 0 . 5 0
74.7 0.73
- -
Not const.
3 0 0.5
2 4 0.5
8
12
3
12
8
10
8
8
10
10
-
4
3
34 (0)
15
25
3 4
2 5
25
25 (0)
25
25
25
25
25
25
25
g = 0.94 (3 branches) *
8 = 0.82 (4 branches) *
8 = 0.48 (9 branches) *
8 = 0.90 (3 branches) *
8 = 0.84 (4 branches)*
( 0 . 3 4 4 ) (1.0)
( 0 . 3 1 2 ) (1.0)
20.4 0 . 5 0
18.6 0 . 6 4
17.8 0.68
13.9 0.72
10.1 0.78
2 . 8 0.89
2.3 0.93
20.4 0 . 5 0
a g = [VI of branched molecules/[~] of linear molecules with same mol. wt
1.9. OTHER COMPOUNDS
Poly(2-acrylamino-2-methylpropanesulfonamide)
Wat er
Wat er / l ,Cdioxane
(81.5/18.5, v/v)
25 12.3 0.757 10 85-122 OS, LS B 1011
25 (0) 172 0.50 10
-
85-122 OS, LS B 1011
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
0.69-43.6
16.1-43.6
0.69-43.6
3-27
4.4-27.6
3-27
?-18
3-27
0.7-44
0.7-44
LS
LS, OS, SD
S D
S D
S D
LS
OS, LS
OS
OS
OS
LV
OS
LS
LS
LS
LS
LS
GPC
GPC
G P C
LLS, GPC
LS
LLS, GPC
LS
LLS, GPC
LS
LS
A-B,R
C - D
C
A-B
A-B,R
B - C
A
A
C
B
B
B
A-B
A-B
A-B
A-B
A-B
778
7 5 3
3 0 7
3 0 8
3 0 9
3 0 2
3 1 0
311
3 1 2
2 8 4
313
3 1 2
3 1 4
3 1 5
316
3 1 6
756
9 2 6
9 2 6
9 2 6
9 2 8
9 3 0
9 2 8
9 3 0
9 2 8
7 5 5
755
3-96
3-96
5-140
5-140
5-140
11-170
11-170
OS, GPC
OS, GPC
OS, LS
OS, LS
OS, LS
LS
LS
LS
-
7 5 7
7 5 7
7 5 8
7.58
7 5 8
7 5 9
7 5 9
931
86-302
26-148
LS
-
LS, OS, GPC A-B
LS, OS, GPC A-B
3
-
18-46 LV
3 18-46 LV
931
941
941
3 0 4
3 0 4
318
3 0 4
3 0 4
3 6 5
3 6 5
4 49-228 LS B 3 6 6
6 39-234 LS
B,R
3 6 6
6 - 39-234 LS B 3 6 6
6 - 39-234 LS B 3 6 6
6 - 39-234 LS B 3 6 6
5 - 39-234 LS B 3 6 6
5 49-234 LS B 3 6 6
4 49-234 LS B 3 6 6
-
6
12
2 5
5
15
-
-
-
42-842
3-4000
3-24
l -104
0.4-230
25-300
2.6-50
4-75
4-37
9-32
2-100
3-37
15-71
30-200
S-300
8-300
A
.%R
AS
B
A
A
TABLE 1. contd
Viscosity - Mol ecul ar Wei ght Rel at i onshi ps of Mai n- Chai n Acycl i c Carbon Pol ymers VII / 25
Polymer Solvent
Temp. K (x 103)
(0 (mlk)
No. of samples Mol. wt.
range
a Fr. W.P. ( x10- 4) Method(s) Remarks Refs.
Poly(allylammonium chloride) Aqueous NaCl (0.05 M) 2.5 2.40
(0.2M) 25 7.18
(OSM) 25 7.19
(l.OM) 25 13.9
Poly[(biphenyl-4-y&ethylene] Benzene
Poly(rerr-butyl crotonate) But yl c hl or i de
Tol ue ne
Poly(carbanilinoxyethylene),
(Poly(vinyl carbanilate)) Dioxane
Dioxane/methanol
(28f 72, v/v)
Poly(dibuty1 itaconate) Tol ue ne
Poly(dicyclohexy1 itaconate) Tetrahydrofuran
Tol ue ne
Boly(didecy1 itaconate) Tol ue ne
Poly(diethy1 fumarate) Benzene
Poly(didodecy1 itaconate) Tol ue ne
Poly(diethy1 itaconate) Tol ue ne
Poly[di(ethylcyclohexyl) itaconate]
Tol ue ne
Poly(dihexadecy1 itaconate) Tol ue ne
Poly(dihexy1 itaconate) Tol ue ne
Poly(diicosay1 itaconate) Tol ue ne
Poly(diisopropy1 fumarate) Benzene
Poly(dimethy1 itaconate) Benzene
Poly[di(methylcyclohexyl) itaconate]
Tol ue ne
Poly(diocty1 itaconate) Tol ue ne
Pol y( di phenyl met hyl ene) Benzene
Poly(dipheny1 itaconate) Tol ue ne
Poly(dioctadecy1 itaconate) Tol ue ne
Poly(dipropy1 itaconate) Tol ue ne
Poly[di(propylcyclohexyl itaconate]
Pentyl acetate
Tol ue ne
Poly(ditetradecy1 itaconate) Tol ue ne
Poly(diundecy1 itaconate) Tol ue ne
Poly( I-methoxycarbonyl-1-phenylethylene)
Benzene :
Chloroform
Ethylbenzene _
Poly(monodecy1 itaconate) Tetrahydrofuran
Poly(monododecy1 itaconate) Tetmhydrofuran
Poly[bis(phenylethyl) itaconate] Toluene
Poly[bis(phenyl-n-propyl) itaconate]
Tol ue ne
Poly(9-vinyladenine) Aq. NaCl (0.1 M)/
2 0 21.4
3 0 29.5
75 27.7
25 7.7
25 1.7
2 0 13.7
0.975 9
0.815 7
0 . 7 9 4 6
0 . 7 1 4 9
0.619 5
0.59 6
0 . 5 8 9 5
0.82
-
0.82 10
0.68 1 1
-
6-200 L S
20 (Q)
64.5 0.5 1
25 5.70 0.70
25 23.3 0.58
25 13.1 0.623
25 8.01 0 . 6 4
3 0 1.62 0.87
25 11.7 0.59
25 1.48 0 . 8 0
2 5 2.62
25 11.4
25 3.71
25 14.3
3 0 0.753
(Wormlike behavior)
25 5.15
25 2.02
25 3.67
2 1 8
25 4.47
25 13.1
25 1.62
25 14.0
25 2.23
25 9.91
25 10.01
0.73
0.60
0.72
0 . 5 6
0.98
0.68 8 4-120 LS
0 . 7 6
0.7 1
0.328
0.69
0.59
0.78
0.56
0.73
0.61
0.61
3 0 35.6
3 0 12.7
15 m 51.4
25
(Wormlike behavior)
25 11.2
(Wormlike behavior)
25 5 . 2 6
25 5.97
0 . 5 6 6 8
0.661 8
0.507 8
Not cons1 1 1
0.65 9 1.7-233 LS, SEC
0 . 6 6 8 9.0-45
0.65 12 6.5-52
NaAs(CH s) z(O.1 M); pH7 2 6
4 0
Poly(l-vinyl-3-benzyhmidazolium chloride)
Aq. NaCl (0.2 M) 25
MethanoVN(CH s) 4 25
Br(O.01 M)
Poly(4-vinylbenzyl trimethylammonium chloride)
Aq. NaCl (0.5 M) 25
(0.1 M) 25
(0.01 M) 25
(0.002 M) 25
241 0.35 3
29.2 0.53 3
5.89 0 . 7 4 4
13.4 0.63 5
19.6 0.67
18.6 0 . 7 0
7.87 0.85
5.77 0.88
-
-
-
-
1 1
-
-
-
-
-
-
8
-
-
-
1 1
8
-
8
?
9
-
6
-
4.1-18 L S
2.8-18 L S
2.8-18 LS
4.1-18 L S
7-170 L S
l -110 LV
7-170 LS
0.2-32 OS, GPC
0.6-35 OS, GPC
6-200 LS
20- 105 LS
5-56 OS
5-56 OS
13-82 L S
?-20 OS, GPC
-
LS
5-61 LS
16-170
12-122
4.7-30
LS
LS
LS
LS
OS, GPC
13-102 LS
11-163 LS
l -90 ?
5.7-57 LS
-
LS
13-109 LS
16-91
16-91
9-250
6-40 LS
6-40 LS
6-40 LS
3.3-12.4 LS, SEC
LS
LS
9-51 OS 8 3 0
9-51 OS 8 3 0
18-130 LS B 8 1 3
18-160 LS B 8 1 3
1-21 OS, GPC 7 6 4
1-21 OS, GPC 7 6 4
1-21 OS, GPC 7 6 4
1-21 OS, GPC 164
9 0 0
9 0 0
9 0 0
9 0 0
2 6 4
2 6 4
2 6 4
7 6 0
7 6 0
3 3 5
A 3 3 5
B 7 6 2
B 761
B 761
B 7 6 2
A-B 1009
-
945
B 7 6 2
B
-
A-B
763
945
7 6 2
945
1009
162
7 6 3
7 6 2
2 6 7
9 4 3
9 4 5
7 6 2
7 6 3
7 6 3
9 4 5
7 6 2
361
361
361
1006
9 4 9
9 4 3
9 4 3
References page VII - 68
VII / 26 VlSCOSlTY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 1. contd
Polymer Solvent
Temp. K (x 103)
(C) (mlk)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-d) Method(s) Remarks Ref s.
Poly(vinylcarbazole) Benzene
Bromobenzene
Chlorobenzene
Chloroform
Cyclohexanone
1,2-Dichlorobenzene
1,3-Dichlorobenzene
Nitrobenzene
Tetrachloroethane
Tetrahydrofuran
Tol ue ne
Poly(N-vinyl-3,6-dibromo carbazole)
p-Chloro-m-crew1
o-Chlorophenol
Poly(l-vinylimidazole) Aq. NaCl (0.1 M)
(5.0 M)
Aq. NaSCN (0.1 M)
Methanol/N(CH 3 ) d
Br(O.01 M)
protonated Aq. HCI (0.1 M)/
NaCl (1 M)
Poly(S-vinyl-2-methylpyridine) Bu t a n o n e
Dimethylformamide
Methanol
Poly(l-vinylnaphthalene) Benzene
Poly(2-vinylnaphthalene) Benzene
Poly(3-vinylpyrene)
Poly(2-vinylpyridine)
Decalin/toluene
(13/10, w/u.)
Chloroform
1,2-Dichlorobenzene
Tetrahydrofumn
Benzene
Benzene
Benzene
Poly(2-vinylpyridine l-oxide)
Bu t a n o n e
Dimethylformamide
Dioxane
Methanol
Methyl ethyl ketone
Pyr i di ne
2-Propanol
Pyr i di ne
Pyr i di ne
Ethanol/water
(92/8, w/w)
Benzyl alcohol
1- But a nol
Chloroform
Methanol
25 30. 5 0. 58 II
25 5.14 0. 76 I
30 5. 23 0. 755 6
45 4. 44 0. 776 6
25 5. 93 0. 74 7
25 13. 6 0. 67 8
25 20. 0 0.61 9
25 11.0 0. 68 7
25 5. 6 0. 75 6
25 9. 25 0. 69 6
30 7. 19 0. 716 6
45 6. 03 0. 739 6
25 12.9 0. 68 9
25 14. 4 0. 65 10
37( O) 76. 2 0. 50 7
112.9 (0) 30. 2 0. 50 7
60. 0 ( 0) 21. 5 0. 50 8
25 122 0. 5 1 5
25 ( 0) 121 0. 50 8
25 ( 0) 105 0. 50 5
25 48. 5 0. 63 6
25 ( 0)
169 0. 50 5
25
25
25
25
25
25
20
75
1 7
20
75
30. 2 ( 0)
13.9
19
13.0
18. 0
18. 6
8. 0
2. 20
1. 03
1.7
6. 90
8. 69
0. 65 5
0. 64 15
0. 76 6
0. 83 8
0. 70 9
0. 76 9
0. 82 4
0. 88 4
0. 80 11
0. 719 6
0. 695 6
0. 50 8
25( H) 51.0 0. 500
25 11.7 0. 655
25 31. 8 0. 547
25 6. 6 0. 72
25 17. 0 0. 64
I O 151 0. 445
10 149 0. 43
11. 4 ( 0) 82 0. 50
12 56. 0 0. 53
15 31. 8 0. 59
25 97. 2 0. 47
25 14.7 0. 67
25 30. 9 0. 58
25 11.3 0. 73
25 93. 3 0. 480
25 9. 84 0. 727
25 18. 4 0. 67
25 9. 9 0. 73
25 13. 8 0. 69
25 12.2 0. 73
25 9. 35 0. 73
25 7. 78 0. 72
25 15. 8 0. 64
25 7. 55 0. 72
9
9
9
3
14
5
5
5
5
5
14
14
14
14
5
5
5
4
14
14
14
14
14
14
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
0. 7- 45 L S A 367
7- 49 G P C A-B 765
I - 57 G P C A-B 766
7- 57 WC A-B 766
7- 49 G P C A-B 765
3- 45 L S A 367
2- 45 LS A 367
4- 44 G P C A-B 767
7- 49 G P C A-B 767
7- 49 G P C A-B 765
7- 57 G P C A-B 766
7- 57 G P C A-B 766
2- 45 L S A 367
1- 45 LS A 367
4-107 OS A 368
4.8-125
4.8-125
9- 90
5- 90
9- 90
9- 130
-
942
942
813
813
813
813
9- 90
-
-
LS
L S
LS
LS
LS
LS
LS
OS
OS
L S
LS
LS
LS
L S
LS
LS
LS
L S
LS
LS
LS
L S
LS, OS
LS, OS
LS, OS
LS, OS
LS, OS
LS
L S
LS
LS
LS, OS
LS, OS
LS, OS
LS, OS
LS
LS
LS
LS
LS
LS
B 813
13- 88
6- 100
4- 40
4- 40
7- 80
13-88
4-17
4-17
10-100
6- 68
6- 69
10-100
A
A
A-B
A-B
A
A
B
B
B
B
375
376
377
377
376
375
264
264
268
264
264
269
3- 50
3- 50
3- 50
3-11
3- 93
9. 4- 196
9. 4- 196
9. 4- 196
9. 4- 196
9. 4- 196
3- 93
3- 93
3- 93
3- 93
9. 4- 196
9. 4- 196
9.4-196
9.4-196
3- 93
3- 93
A
A
A
B,C
A
A
A
A
A
W
B,C
W
BC
A
A
A
A
B,C
BC
768
768
768
769
371
944
952
952
952
952
207
371
371
371
944
944
952
952
207
371
1.3-34
1.3-34
1. 3- 34
1.3-34
A-B 946
A-B 946
A-B 946
A-B 946
TABLE 1. contd
Viscosity - Molecular Weight Relationships of Main-Chain Acyclic Carbon Polymers
Temp.
(C)
K (x 103)
Wk)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-d) Method(s) Remarks Refs. Polymer Solvent
1-Propanol
2-Propanol
Et hanol
Wa t e r
Butanone/Z-propanol
Ethanol/water
(9218, w/w)
Chloroform
Methanol
water
2 5
2 5
2 5
2 5
2 . 5
2 5
2 5
2 5
3 0
2 0
2 5
2 5
3 0
3 0
25 (0)
25 (0)
2 5
2 5
5.7 (0)
1 5
3 0
5 0
5.5 (0)
2 5
26.0 (0)
44.5 (0)
- 0.6 (0)
10
2 0
3 0
40.1 (B)
32.4 (0)
2 0
2 5
1 0 . 3
1 2 . 0
( 1. 51)
2 5 . 0
2 2 . 0
3 8 . 0
1 2 . 0
1 9 . 4
2 3
6 4
6 1 . 6
4 . 1
1 4
3 9 . 3
7 5 . 0
5 8 . 0
8. 86
6 4
6 8 . 8
3 0 . 8
2 4 . 5
2 6 . 6
6 8 . 2
1 6 . 7
7 9 . 5
8 0 . 3
9 5 . 5
2 6 . 8
2 5 . 1
2 2 . 0
9 4 . 5
96. I
2 1 . 5
8 . 2
0. 70
0. 68
( 0. 52)
0. 68
0 . 6 8 7
0. 57
0. 73
0. 64
0. 65
0. 58
0. 55
0. 85
0. 70
0. 59
0. 50
0 . 7 4
(Mixed)
0. 53
(Mixed)
0. 50
0. 61
0. 75
0. 76
0 . 5 0
0. 79
0. 50
0. 50
0. 50
0. 73
0. 76
0. 79
0. 50
0. 50
0. 65
0. 7 I
9
6
2
6
-
-
6
-
1.3-34
I .3-34
l - 4
IO-185
lo-185
7-224
7-224
2-23
2-23
l - 9
0.7-10
l - 4
l - 2 0
8-110
1.2-108
4-220
0.2-4
4 - 3 9
8-39
8-39
8-39
4 - 3 9
4 - 3 9
4 - 3 9
4 - 3 9
4 - 3 9
8-39
8-39
8-39
4 - 3 9
4 - 3 9
0.3-3
59-213
LS
LS
S D
LS
S D
S D
OS
LS
LS
S D
LS
A- B
A- B
C
A- B
A- B
B
B
B
B
B
RR
CD
B
A3
B
9 4 6
9 4 6
3 7 2
3 7 3
313
3 7 4
3 7 4
3 7 8
3 7 8
3 7 9
3 7 8
2 1 1
3 8 1
3 8 3
3 8 4
9 4 8
9 4 8
2 5 9
2 5 9
2 5 9
2 5 9
259
2 5 9
2 5 9
2 5 9
2 5 9
2 5 9
2 5 9
2 5 9
2 5 9
2 5 9
2 6 0
6 1 0
Poly(4-vinylpyridine)
Poly(vinylpyrrolidone)
Acetone/water
(66.8133.2, v/v)
Aq. Na2S04
( 0. 55 M)
Aq. sodium acetate
( 0. 1 M)
Aq. sodium acetate
( 0. 1 M)
Aq. KBr (0.347 M)
Poly(l-vinyl-2.pyrrolidone)
high M
low M
Poly(vinylsulfonic acid)
A q . K C I
(0. 349 M)
(0. 650 M)
( 1. 001 M)
Aq. NaBr
( 0. 346 M)
(1.008M)
Aq. NaCl
(1.003M)
( 0. 5 M)
Cyclohexane Poly(vinyltrimethylsilanef
1.10. COPOLYMERS
Poly(acrylonitrile-co-butadiene), see also Poly(butabiene-co-acrylonitrile) in group 1.1
(18/82, w/w, random) Tol uene 2 5 2 5 1
(26 174, w/w, random) Tol uene 2 5 2 6 0
Poly(acrylonitrile-co-glycidyl methacrylate)
Dimethylformamide 3 0 175
Poly(acrylonitrile-co-methyl acrylate)
Dimethylformamide 2 0 1 7 . 9
Poly(acrylonitrile-star-methyl acrylate), (91.5/8.5, w/w)
Dimethylformamide 2 5 2 1 . 3
Ethylene carbonate/water 2 5 (0) 1 5 2
(82.5117.5, w/w)
Poly(acrylonitrile-co-styrene)
(38.3/61.7, mol/mol,) But anone 3 0 3 6
Tetrahydrofuran 2 5 2 1 . 5
azeotropic
(62.6/37.4, mol/mol, random) But anone 3 0 5 3
Dimethylformamide 3 0 12
Poly(acrylonitrile-srat-styrene)
(27.4/72.6, mol/mol) Dimethylformamide 3 0 1 2 . 0
0. 50
0. 50
0.06- 1.26
0.15-0.40
OS
OS
A
A
5 9 0
5 9 0
0. 65 5 9 1
0. 79 6
1 1
2-21
2-53
LS
LS
B 5 9 2
0. 743
0. 502
7 7 2
7 7 2
0. 62
0. 68
16
4
15-120
lo-78
LS
LS
0 . 6 1
0. 77
1 1
1 1
19-56
19-56
LS
LS
0. 74 6 14-58 LS
References page VII - 68
VII / 28 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 1. contd
Polymer Solvent
Temp. K(x 103)
(0 Wg)
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-q Method(s) Remarks Refs.
(38.5/61.5, moYmo1) Dimethylformamide 3 0 16.2 0.73 6
(47.5/52.5, mol/mol) Dimethylformamide 3 0 17.2 0.73 6
Poly(acrylonitrile-a/r-styrene) (I/1, mol/mol)
Bu t a n o n e 3 0 24.3 0.67 10
Dimethylformamide 3 0 7.63 0.76 9
Butanonelmethanol 30 (0) 140 0.50 10
(63.6136.4, v/v)
Poly(acrylonitrile-co-vinylidene chloride) 58 wt.% AN
y-Butyrolactone 25 112 0.576 8
Dimethylacetamide 25 99.9 0.603 8
Dimethylformamide 25 102 0.591 8
N-methyl-2-pyrrolidone 2 5 114 0.595 8
70 wt.% HNO, 2 5 142 0.52 1 8
Poly@-aminobenzoic acid-smt-6-aminohexanoic acid) ( 1 / 1, mol/mol)
Dichloroacetic acid 3 0 23.7 1.13 4
Trifluoroacetic acid 3 0 132.5 0.99 4
Poly(butadiene-co-methactylamide) (90/10, w/w, random)
Tol ue ne 25 4 3 7 0.50 5
Poly(butadiene-co-2.methyl-5.vinylpyridine)
Tol ue ne 25 3 0 9 0.50 5
Poly(butadiene-co-styrene), see. also Poly(butadiene-co-styrene) in group 1.1 (84/ 16 mol/mol, random)
Benzene 25 39.4 0 . 7 0
Dibutyl phthalate 5 6 4 7 2 0 . 4 0
2-Pentanone 23.8 (0) 167 0.50
Poly(buty1 itaconate-co-dibutyl itaconate), (40/60, mol/mol, random)
Acetone 2 5 5 7 5 0.32
Methanol 25 3 5 4 0.32
m-Xylene 25 1040 0.21
Poly(buty1 methacrylate-alt-styrene)
Bu t a n o n e 25 5.3 0.76
Poly(buty1 methacrylate-star-styrene) ( 1 / 1, mol/mol)
Bu t a n o n e 25 4 . 9 0.77
35 5.98 0.75
Cyclohexane 35 7.88 0 . 7 0
Poly(rerr-butylphenyl methacrylate)-sraf-vinylpyrrolidone)
(33.7/66.3, mol/mol) Benzene 25 118 0.53
Chloroform 25 105 0.57
(60.4/39.6, mol/mol) Benzene 25 130 0.55
Chloroform 25 2 4 7 0.5 I
Poly@-tert-butylstyrene)-block-poly(dimethyl-siloxane)-b~~c~-poly~-~err-butylstyrene) 28 wt . % PBS
Methyl ethyl ketone 10 2 5 2 0.39
15 58.9 0.50
2 0 40.5 0.54
31 19.3 0.61
38 10.7 0.66
Benzene 35 15.4 0.66
Methyl ethyl ketone
15 (0) 58.9 0 . 5 0
2 0 40.5 0.54
31 19.3 0.61
Poly@-chlorostyrene-srar-methylmethacrylate), (52/48, mol/mol)
Benzene 27 7.94 0.72
Benzene/hexane 22.3 (8) 64 0.50
(60/40, v/v)
Poly(4-chlorostyrene)-b[ock-poly(styrene)-b~~c~-poly(4-chlorostyrene), Ak-B .-Ai
2k/n, (33/67, mol/mol) Carbon tetrachloride 4 0 6.24 0.76
Cume ne 4 0 5.88 0.76
2k/n, (50/50, mol/mol) Carbon tetrachloride 4 0 6.63 0.74
Cume ne 4 0 5.76 0.75
Poly(diethy1 fumarate-co-isobutene)
50/50, mol/mol Benzene/petrol ether 2 0 3 4 0 0.44
Poly(diethy1 fumarate-co-vinylcarbazole)
Benzene 25 14.6 0.67
4
6
5
6
7
7
10
10
8
6
9
8
-
-
-
4
6
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
5
5
10
10
-
22-106 L S B 7 7 3
14-78 L S B 173
5-100 L S B 714
8-100 LS B 7 7 4
5-100 LS B 7 7 4
4.2-50 L S
4.2-50 LS
4.2-50 L S
4.2-50 L S
4.2-50 LS
-
-
-
961
961
961
961
961
12-60 LS 7 7 5
12-60 LS 7 7 5
0.09-0.11 OS A 5 9 0
0.08- 1.04 OS A 5 9 0
2-51 OS A 5 9 6
2-51 OS A 5 9 6
7-51 OS A 5 9 6
9-70
11-110
11-110
LS
LS
LS
B
B
B
5 9 7
5 9 7
5 9 7
32-320 LS B 7 7 6
15-208 LS B 7 7 6
22-56 LS B 7 7 7
34-50 LS B 7 7 7
33-96
33-96
OS
OS
OS
OS
C
C
C
C
7 7 9
7 7 9
7 7 9
7 7 9
12-129 OS, GPC C-D 9 5 7
12-129 OS, GPC C-D 9 5 7
12-129 OS, GPC C-D 9 5 7
12-129 OS, GPC C-D 9 5 7
12-129 OS, GPC C-D 9 5 7
9.3- 128 OS, LS B 9 6 0
9.3-128 OS, LS B 9 6 0
9.3-128 OS, LS B 9 6 0
9.3-128 OS, LS B 9 6 0
15-120 LS
15-120 LS
598
598
14-61 O S
14-61 OS
19-74 OS
19-74 OS
780
780
780
780
1-14 S D 599
2-13 LS 789
Viscosity - Molecular Weight Relationships of Main-Chain Acyclic Carbon Polymers VII / 29
TABLE 1. contd
Polymer Solvent
Temp.
Pa
K(x 103)
(mVs)
No. of samples Mol. wt.
range
a Fr. W.P. (x10-d) Method(s) Remarks Refs.
Poly(p-diethylphosphonomethylstyrene-co-styrene), (l/4, mol/mol, random)
Benzene 2 0 I .95 0.90
Tetrachloroethane 2 0 0.0836 1.18
Poly(dimethy1 itaconate-co-styrene)
(15125, w/w) Tol ue ne 25 6.6 0.68
(67133, w/w) 25 9 . 0 0.67
(59/41, w/w) 25 9.1 0.67
(4915 1, w/w) 25 11.7 0.67
(29.5170.5, w/w) 25 12.8 0.67
(27173, w/w) 25 10.9 0.69
(O/ 100, w/w) 25 11.45 0.712
Poly(dimethy1 siloxane-co-diphenylsiloxane)
(54/45, mol/mol) Benzene 2 5 4 0 . 7 0 . 6 0
Dimethyl phthalate 82.5 5 1 2 0.31
Ethanolltoluene 29.5 (8) 78 0 . 5 0
(37163, w/w)
(66/34, mol/mol) Benzene 25 15.6 0.68
Hexane 36 (6) 141 0.44
Benzene/Z-propanol 42 (0) 7 4 0.50
(44156, w/w)
Poly(divinylstyrene-co-styrene), see also Poly(styrene), branched, random type, in group 1.8.
Benzene 25
Octane 21
Poly(ethy1 acrylate-star-methyl methacrylate), (80/20, mol/mol)
Acetone
Poly(ethy1 methacrylate-a&styrene)
Bu t a n o n e
Poly(ethy1 methacrylate-star-styrene)
(l/l, mol/mol) Bu t a n o n e
Poly(ethylene-co-cc-methyl-styrene), [(ET),(MS) n]p
m/n = 314 Cyclohexane
Di oxa ne
Tol ue ne
Butanonekyclohexane
(60/40, v/v)
m/n = 514 Cyclohexane
Dioxane
Tol ue ne
Butanonekyclohexane
(75125, v/v)
m/n = 517 Cyclohexane
Dioxane
Tol ue ne
Poly(hexadecy1 methacrylate-co-methyl methacrykte)
(25/75, mol/mol, random) Heptane
Propyl acetate
(38/62, mol/mol, random) Chloroform
Heptane
Propyl acetate
(50/50, mol/mol, random) Chloroform
Heptane
Propyl acetate
25
25
25
3 0
30
3 0
30 (0)
3 0
3 0
3 0
30 (@I
30 (0)
3 0
3 0
25
25
25
25
25
25
25
25
37.2
162
6 2
9.3
12.0
92
16
3 2
135
65
8 9
37
140
112
123
5 6
85.0
17.1
36.3
6.9
53.6
53
32.0
91.3
Poly(l-hexene-co-sulfur dioxide), see Poly[sulfonyl(butylethylene) in group 3.10.
Poly(isobutene-co-isoprene), see group 1.2.
Poly(isoprene)-b/ock-poly(styrene), see group 1.1.
Poly(maleic acid-al?-styrene)
DNb=9.5 Aq. NaCl ( 0. 02 M) 25 395
0.50 25 37.3
0 . 2 0 25 0.5 1
0.10 25 0.01
Poly(methacrylic acid-co-methyl)methacrylate) (7.4/92.6, w/w)
Acetone 2 0 3.4
b DN-Degree of neutralization
0 . 7 0
0.50
0.57
0.72
0.70
0.56
0.58
0.68
0.50
0.60
0 . 5 6
0.66
0.50
0.50
0.49
0.58
0.38
0.62
0.57
0.65
0.50
0.54
0.52
0.43
0.59
0.67
0.87
0.98
0.74
5
1 1
4
4
4
5
6
10
9
10
4
4
4
7
9
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
15-50
9-51
6-22
4-19
5-38
6-24
7-36
6-40
3-58
l -57
11-57
7-35
3.7-100
3.7-100
3.7-100
5-80
5-80
65-800
19-470
3-185
0.7-6
0.7-6
0.7-6
0.7-6
0.8-7
0.8-7
0.8-7
0.8-7
1.5-7
1.5-7
1.5-7
4-47
4-47
16-195
4-47
4-47
10-154
4-47
4-41
29-130
29-130
29-130
29-130
26- 105
sv
sv
S D
S D
S A
S A
S A
S A
S A
S A
S A
S A
S A
S A
S A
LS
LS
LS
LS
LS
LS
LS
LS
LV
LV
LV
LV
LS
B
B
A
A
A
A
A
A
A
A
A
A
A
A
A
B
B
B
B
B
B
B
B
B
B
B
B
B
B
A
A
A
A
A
A
A
A
B
B
B
B
6 8 3
6 8 3
6 8 3
6 8 3
6 8 3
6 8 3
6 8 3
5 9 6
5 9 6
5 9 6
5 9 6
5 9 6
5 9 6
6 0 2
6 0 2
114
7 7 6
7 7 6
6 0 4
6 0 4
6 0 4
6 0 4
6 0 4
6 0 4
6 0 4
6 0 4
6 0 4
6 0 4
6 0 4
6 0 5
6 0 5
6 0 5
6 0 5
6 0 5
6 0 5
6 0 5
6 0 5
8 4 2
8 4 2
8 4 2
8 4 2
6 0 7
References page VII - 68
VII / 30 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 1. contd
Polymer Solvent
Temp. K(xlOj)
(C) Wk)
No. of samples Mol. wt.
range
a FE-. W.P. (x 10-4) Method(s) Remarks Refs.
Poly(4-methoxystyrene-srur-styrene)
(24.4/75.6, mol/mol) T0hlene
(26.4/73.6, mollmol) Bu t a n o n e
T0luene
(46.2/53.8, mol/mol) Tol ue ne
(53.0/47.0, mol/mol) Bu t a n o n e
Tol ue ne
(74.0126.0, mol/mol) Tol ue ne
(75.6/34.4, mol/mol) rerr-Butylbenzene
Tol ue ne
Poly(methy1 acrylate-sr&methylmethacrylate)
(17/83, w/w) Bu t a n o n e
(29171, w/w)
(67133, w/w)
Poly(methy1 acrylate-co-styrene)
(22/78, mol/mol, random) Benzene
Bu t a n o n e
2-Methylcyclohexanol
(33/67, mol/mol, random) Benzene
Bu t a n o n e
2-Methylcyclohexanol
(47/53, mol/mol, random) Bu t a n o n e
(50/50, mol/mol, random) Ethyl acetate
(59/41, mol/mol, random) Benzene
Bu t a n o n e
2-Methylcyclohexanol
(76124, mollmol, random) Benzene
Bu t a n o n e
2-Methylcyclohexanol
25 7.0 0.75 9
25,50 4 0 0.585 8
25 18.6 0.68 8
25 7.3 0.755 13
25 (0) 100 0.49 7
2 5 3 7 0.615 7
25 8.2 0.755 9
25 (0) 83 0.49 6
25 16.9 0.673 7
-
-
-
-
-
-
-
4-42
7-80
7-80
3.5-70
7-80
7-80
5-35
7-80
7-80
25 11.7 0.70 4
-
56-208
25 11.1 0.63 4
-
37-137
25 36.6 0.60 4
-
71-187
3 0 8.93 0 . 7 4 4 16
3 0 21.1 0.640 12
43.5 (0) 77 0.50 8
30 7.18 0 . 7 5 9 9
30 11.4 0.696 4
35.0 (B) 7 6 0.50 7
30 10.7 0.724 9
35 41.6 0.57 9
3 0 6.15 0 . 7 8 0 6
3 0 11.3 0.703 4
36.6 (0) 7 6 0.50 6
30 7.42 0.766 6
30 9.16 0.728 5
29.4 (0) 75 0.50 5
2.6-80
2.6-80
2.6-80
6.6-36
6.6-36
6.6-36
6.7-24.4
18-116
7-40
12-40
7-40
7.2-28
8.9-28
6.5-24
Poly(methyl methacrylate-co-p-isopropylstyrene), 2/3, mol/mol, graft
Bu t a n o n e 25 0.021 1.11
-
6 31-65
Poly(methy1 methacrylate-co-2-methyl-5vinylpyridine) (85/15, mol/mol, random)
Acetic acid 25 170
Poly(methyl methacrylate-co-styrene)
(10/90, mol/mol, random) 1Chlorobutane 40.8 16.6
(30/70. mol/mol, random) I-Chlorobutane 30 17.6
Cyclohexanol 64.0 (0) 71.6
. Tol ue ne 30 8.32
(44/56, mol/mol, random) 1- Chl or obut a ne 3 0 24.9
Cyc l ohe xa nol 64.0 (0) 70.0
Tol ue ne 3 0 13.2
(50/50, mol/mol, random) Bu t a n o n e 25 15.4
(52/48, mol/mol, random) Khlorobutane 40.8 49.0
(71/29, mol/mol, random) 1Chlorobutane . 3 0 24.9
Cyc l ohe xa nol 68.0 (0) 97.3
Tol ue ne 30 11.4
(94/6, mol/mol, random) 1- Chl or obut a ne 40.8 27.6
nearly equimolar,
0.51 3
0 . 6 0 9 5
0.67 9
0.51 4
0.75 10
0.63 10
0.51 4
0.71 1 1
0.675 11
0.575 5
0.63 10
0.47 5
0.70 8
0.617 5
three blocks (MSM) Cyclohexanol
PS% 86.1-90.4, graji (S on M;
Mps =0.7-1.0 x 104)
Benzene
Bu t a n o n e
&TM Bromoform
Poly(methy1 methacrylate)-block-poly(styrene), Ai
Bu t a n o n e
1 Chlorobutane
Tol ue ne
81.0 (0) limM,--O[njH/MZ = 63
-
25 [7/] = O.O0918M~,7~~g~
25 [q] = o.o390Mssgr~59
PS
- 5 6 0.6
-B,, k/n, (54146, wlw)
3 0 9.4 0.69
30 22.4 0.60
30 7.3 0.73
6
6
6
6
Poly(2-methyl-1-pentene-co-sulfur dioxide), see Poly[sulfonyl( I-methyl-1-propylethylene)], group 3.10.
Poly(cc-methylstyrene-co-styrene)
Benzene 2 0 14.4 0.69 5
Poly(l-octadecane-alt-maleic acid)
Ethyl acetate 25 55 0.48 6
-
-
-
-
-
-
-
-
-
-
-
-
7
-
-
-
-
37-150
20-82
5-55
5-55
5-55
5-81
lo-81
4.8-81
5-227
18-115
4.8-81
155106
7-106
20- 100
3.4- 147
83-121
53-285
180-320
5.8893
5.8-93
5.8-93
18-80
2.4-9.9
OS
LV
LV
OS
LV
LV
OS
LV
LV
LS
LS
LS
LS
LS
LS
LS
LS
LS
O S
LS
LS
LS
LS
LS
LS
LS
LS
LV
LS
L S
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LV
LV
LV
LS
L S
LS
s v
LS
B
B
B
B
B
B
B
B
B
B
B
B
A
A
A
A
A
A
A
A
A
A
A
A
A
A
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
A
A
A
A
-
781
782
7 8 2
781
7 8 2
782
781
7 8 2
7 8 2
1 3 1
131
131
129
129
129
129
129
129
129
133
129
129
129
129
129
129
611
6 1 2
6 1 3
6 1 4
6 1 4
6 1 4
6 1 4
6 1 4
6 1 4
615
6 1 3
6 1 4
6 1 4
6 1 4
6 1 3
6 1 6
6 1 7
6 1 7
6 1 8
783
7 8 3
783
332
9 5 6
TABLE 1. contd
Viscosity - Molecular Weight Relationships of Main-Chain Carbocyclic Polymers VII / 31
Polymer Solvent
Temp. K(x103)
PC) WM
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-d) Method(s) Remarks Refs.
-
Poly(octy1 methacrylate-a[?-styrene)
But anone 2 5 7 . 4
Poly(octy1 methacrylate-star-styrene), (l/ 1, mol/mol)
But anone 2 5 1 . 8
Poly(styrene)-block-poly(butadiene)-bloc~-poly(styrene) 50 wt.7c-PS
Tol uene 3 0 7 1 . 3
Poly(styrene)-block-poly(4-chloro-styrene)-~~oc~-poly(styrene), B ,, -A i -B , )
k/2n, (33161, mol/mol) Carbon tetrachloride 4 0 6. 10
C u m e n e 4 0 3. 99
k/2n, (50/50, mohmol) But anone 3 0 8. 14
Carbon tetrachloride 4 0 5. 58
C u m e n e 4 0 6. 84
Tol uene 3 0 4. 62
k/2n, (66134, mollmol) Carbon tetrachloride 4 0 5. 94
C u m e n e 4 0 5. 21
Poly(styrene-co-sulfur dioxide), see Poly[sulfonyl(phenylethylene)], group 3.10.
0. 72 11
0. 71 1 0
0. 62 7
0. 77
0. 79 -
0. 72 -
0. 76 -
0. 74 -
0. 79 -
0. 74 -
0. 75 -
Poly(styrene)-grafr-poly(methy1 methacrylate), MMA content, 13 wt.%
Bromoform
Poly(styrene)-block-poly(dimethylsiloxane) 12.627c PS
Methyl ethyl ketone 2 5
Poly(styrene-co-monoethyl maleate)
Acetone 26.4 (0)
Di oxane 2 5
Tetrahydrofuran 2 5
-, sodium salt Aq. NaCl
( 0. 005 M) 2 5
( 0. 01 M) 2 5
( 0. 03 M) 2 5
( 0. 05 M) 2 5
(0. 075 M) 2 5
( 0. 15 M) 2 5
( 0. 3 M) 2 5
(0.6M) 2 5
Poly(styrene)-block-poly(2-vinylpyridine) 5 0 w t . %- P S
Benzene 1 0
Methyl ethyl ketone 2 5
Pyt i di ne 2 5
( 16. 5) (0.58) 5
Various
5 1 . 1 0. 50 9
1 1 . 2 0. 702 9
7. 50 0. 695 9
5 . 8 0. 87 4
5 . 5 0. 85 5
6 . 3 0. 80 5
II 0. 73 5
I O 0 . 7 1 5
1 5 0. 65 5
2 1 0. 60 5
5 5 0. 50 5
3 5 . 2 0.605 4
3 1 . 9 0. 587 4
9. 02 0 . 7 3 4 4
Vari ous Various
- 12-450
- lo- 198
- 5.7-140
4 20-82
4 20-82
8 31-89
8 31-89
8 31-89
8 31-89
4 15-54
4 15-54
- 17-196
- Various
- 20-180
- 20- 180
- 20-180
- 40- 130
- 40-180
- 40-180
- 40-180
- 40-180
- 40-180
- 40-180
- 40-180
- 6.5-153
- 6.55153
- 6.5- 153
LS B 7 7 6
LS B 7 7 6
OS, LS A- B 9 5 8
OS A 7 8 0
OS A 7 8 0
OS A 7 8 0
OS A 7 8 0
OS A 7 8 0
OS A 7 8 0
OS A 7 8 0
OS A 7 8 0
S D A
OS , GP C B - C
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS, OS
LS, OS
LS, OS
A
A
A
A
A
A
A
A
A
A
A
A
A
A
7 8 4
9 5 5
3 1 7
3 1 7
3 1 7
3 1 7
3 1 7
3 1 7
3 1 7
3 1 7
3 1 7
3 1 7
3 1 7
9 4 4
9 4 4
9 4 4
TABLE 2. MAIN- CHAIN CARBOCYCLIC POLYMERS
Polymer Solvent
Temp. K(x103)
(C) Wk)
No. of samples Mol. wt.
range
a Fr. WP M (x 104) Method Remarks Refs.
Poly(acenaphthenylene) Benzene 2 5 30. 04 0. 594 I I 2-100 OS B 2 6 2
2 5 2. 82 0. 74 4 4-100 LS AB 2 6 3
Ethylene chloride 2 5 2 0 . 0 0. 54 6 6-125 LS AB 2 6 3
Dioxane 2 5 1 1 . 5 0. 61 7 6-145 LS
AB
2 6 3
Methylene chloride 2 5 6. 92 0. 66 5 6-145 LS
A,B
2 6 3
Tol uene 2 5 6. 76 0. 66 1 7 3-175 LS &B 2 6 3
Poly(4,7-dimethylindene) Benzene 2 5 3 . 5 0. 77 9 5.8-140 LS CD 8 1 1
Poly(6methylindene) Benzene 2 5 3 4 0. 60 I3 30-1320 LS
C,D
8 1 1
References page VII - 68
VII / 32 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 3. MAIN-CHAIN HETEROATOM POLYMERS
Polymer Solvent
Temp. K ( x 103)
v-3 Wk)
No. of samples Mol. wt.
range
a Fr. WP M (x 10m4) Method(s) Remarks Refs.
3.1. POLYCOXIDES), POLY(ETHERS)
Poly(butene oxide), see Poly[oxy(ethylethylene)]
Poly(ethylene oxide), see Poly(oxyethylene)
Poly[oxy(terr-butyl-ethylene)] Benzene 25
i s ot act i c Xylene 8 0
Poly(l,2-cyclohexylene) Tol ue ne 35
Poly(oxydecamethylene) Benzene 35
Chloroform 3 0
Poly(2,6-dichlorophenylene oxide)
from 2,4,6-trichlorophenol Tol ue ne 37
from 4-bromo- Tol ue ne 37
2,6-dichlorophenol
Poly(oxy-2,6-dimethyl-l A-phenylene)
Benzene 25
Carbon tetrachloride 25
Chlorobenzene 25
9 0
Chloroform 25
Tol ue ne 25
Poly(dioxolane), see Poly(oxymethyleneoxyethylene)
Poly[2,2-@,p-oxydi-p-phenylene)6,6-oxybis(4-phenylquinoline)]
Chloroform
Poly(oxy-2,6-diphenyl-1,4-phenylene)
Benzene
Chlorobenzene
Poly(oxyethylene)
Chloroform
Tol ue ne
Acetone
Benzene
Carbon tetrachloride
Chloroform
Cyclohexane
Diethylene glycol
diethyl ether
Dimethylformamide
Dioxane
Methanol
4.Methylpentan-2-one
Tol ue ne
Wat er
Wat er
25 2 5 0 0.57 9 7.6-32.5 LLS, SEC B 9 6 2
5 0 19.72 0.638
25 13.9 0.68
9 0 15.5 0.67
25 32.1 0 . 6 0 9
25 21.4 0.635
25 3 2 0.67
2 5 156 0 . 5 0
2 0 4 8 0.68
25 39.7 0 . 6 8 6
25 129 0.50
2 0 6 9 0.61
25 6 2 0.64
25 2 0 6 0.50
2 0 [q] = 0.5 + 0.035 M o

64
5 0 140 0.5 1
25 [$ = 2.0 + 0.024M0,73
2 0 [q] = 0.75 + 0.035 MO.
25 138 0.50
20 [q] = 2.0 + 0.033 MO.72
25 85.2 0.57
5 0 120 0.52
35 14.5 0 . 7 0
20 [q] = 2.0 + 0.016M076
25 156 0 . 5 0
3 0 12.5 0.78
35 6 . 4 0.82
35 16.6 0.82
4 5 6.9 0.81
3 60.2 0.67
5 61.7 0.66
10 56.8 0.67
1 5 50.5 0.68
25 49.9 0.67
35 48.8 0 . 6 6
5 5 77.7 0.61
75 76.3 0.57
85 118 0.54
-
-
-
10
IO
10
15
10
5
7
12
9
12
9
5
6
1 1
5
-
-
-
l -110 LS A 7 9 2
4-145 LS C 4 7 3
4-145 LS C 4 7 3
l -110 LS A 7 9 2
4-145 LS C 4 7 3
7-100 LV 45 3 8 7
0.02-0.3 E G AL
3 8 8
0.01-1.9 EG A 3 8 9
S-520 LS AR 3 8 5
0.02-0.8 E G AL
3 8 8
0.02- 1.1 E G A 3 8 9
7-100 LV A 3 8 7
0.02-0.15 E G AL 3 8 8
0.006-1.1 EG A 3 8 9
7-100 LV A 3 8 7
10
13
7
12
?
5
1 1
5
-
-
-
-
-
-
-
-
-
-
-
-
-
-
4
6
5
4
5
6
6
6
6
6
6
6
6
6
0.1-3 LS, SD A 3 9 0
0.006-1.1 EG A 3 8 9
0.02-0.15 EG AL 3 8 8
0.006-1.9 EG A 3 8 9
? LS, SD A 391
7-100 LV A 3 8 7
0.04-0.4 E G CL
3 9 2
0.006- 1.1 EG A 391
0.019-0.1 EG A&
3 9 3
2-500 LS, SD C 3 9 4
3-700 LV C,R 395
0.04-0.4 EG CL
3 9 2
3-700 LV C 395
0.31-3.0 G P C A-B 9 6 3
0.31-3.0 G P C A-B 9 6 3
0.31-3.0 G P C A-B 9 6 3
0.31-3.0 G P C A-B 9 6 3
0.31-3.0 GPC A-B 9 6 3
0.31-3.0 GPC A-B 9 6 3
0.31-3.0 GPC A-B 9 6 3
0.31-3.0 GPC A-B 9 6 3
0.31-3.0 G P C A-B 9 6 3
39.7 0 . 6 8 6 9 S-520 L S
1.48 0.56 8 67-640 L S
3.5 0.83 2 2 2-50 O S
195 0.53 7 0.1-0.9 S E
172 OS6 9 0.05-0.9 S E
150 0.327
207 0 . 3 2 0
-
6(?) 1.6-25 L S Branching 9 6 4
W) 1.6-25 L S Branching 9 6 4
26.0 0.69 8
75.5 0.585 5
37.8 0.66 7
51.4 0.63 7
48.3 0.64 8
28.5 0.68 15
-
-
-
3-17 L S B 4 7 3
7-17 L S B 4 7 3
2-42 LS B 474
3-18 LS B 4 7 3
2-42 L S B 4 7 4
2-42 LS B 474
A-B
B
B
B
3 8 5
7 9 0
4 7 2
3 8 6
3 8 6
TABLE 3. contd
Viscosity - Molecular Weight Relationships of Main-Chain Heteroatom Polymers VII / 33
Polymer Solvent
Temp. K(x103)
c-3 (mUg)
No. of samples Mol. wt.
range
cl Fr. WP M (x 10 -4) Method(s) Remarks Refs.
Poly[oxy(ethylethylene)]
Aq. KOH ( 0. 96 M)
(l.lOM)
(1.24M)
(1.48M)
Aq. KzS04
(0.45 M)
Aq. MgS04
(0.39 M)
Benzene
But a nol
Butanone
HfXaIle
2-Propanol
Poly[oxy(hexamethylene)]
Poly(oxymethylene)
Benzene
Dioxane
Dimethylformamide
Hexafluoroacetone-
sesquihydrate (I/ 1.7,
mol/mol, with
triethylamine I%, v/v)
PhenoVtetrachloroethane
(l/3, ww
(l/3, v/v)
Poly(oxymethyleneoxyethylene) Chlorobenzene
p-Chlorophenol
lH,lH,SH-octafluoro-
pentanol-I
Tetrahydrofuran
Poly[oxy(phenylethylene)] Benzene
Tol ue ne
25 144 0.53
25 165 0.5 1
25 185 0 . 5 0
25 3 0 9 0.43
35 m 130 0 . 5 0
35 2 8 0 0.45
45 (Q) 1M) 0.50
25 15.9 0.75 10
3 0 3.39 0.84 9
2.5 19.6 0.69 10
3 0 4.08 0.79 9
25 14.3 0.73 10
30 va 86.5 0.50 9
30 NV
1 1 1 0.50 9
25 86.9 0.62 1
25 131 0.55 1
130 22.4 0.7 1 7
140 18.1 0.73 I
25 4 6 . 0 0 . 7 4 7
25 87 0.69
-
9 0 27.5 0.80
9 0 5.22 0.93
25 2 0 0 0.50
6 0 41.3 0 . 7 2 4
110 13.35 0 . 8 1 0
25 17 0.73 4
-
3-11 OS
3 0 92.2 0 . 7 5 8 10
-
1.4-81 LS
25 67.9 0 . 7 6 6 10
-
1.4-81 LS
Poly(oxy- 1,4-phenylene-oxy- 1,4-phenylene-carbonyl- 1 $phenylene), (PEEK)
i s ot act i c
ol i gomer
Poly(oxytetramethylene)
Poly(oxytrimethylene)
p-ChlorophenoV
o-dichloro-benzene
(60140, w/w)
Methanesulfonic acid
Acetone
Benzene
Hexane
Methanol
Tetrahydrofuran
Tol ue ne
Toluene/2,2,4+imethyl.
pentane (5/7, v/v)
Acetone
Benzene
Benzene
Ethyl acetate
Tol ue ne
Ethyl acetate/hexane
(22.1177.3, w/w)
Acetone
Benzene
Carbon tetrachloride
35 58.6 0.702
3 0 22.6 0.818
25 75.5 0.56
2 0 11.1 0.79
25 11.2 0.77
25 14 0.8
25 38.5 0.73
2 5 41.3 0 . 6 4
25 41.5 0.65
4 6 19.7 0.67
2 0 40.6 0 . 6 4
25 76.9 0.55
2 0 55.0 0.62
2 0 20.8 0.72
25 12.9 0.75
39.5 (0) 107.5 0 . 5 0
2 0 75.5 0.56
2 0 41.5 0.65
3 0 131 0 . 6 0
3 0 42.2 0.65
28 25.1 0.78
31.8 (0) 2 0 6 0.49
3 0 76.0 0.59
3 0 21.9 0.78
3 0 26.1 0.75
-
-
-
?
4
-
7
1 1
5
6
6
10
6
5
3
6 0.31-3.0 GPC A-B
6 0.31-3.0 GPC A-B
6 0.31-3.0 CPC A-B
6 0.31-3.0 GPC A-B
5 3-700 LV C
5 7-100 LV A
5 3-700 LV C
-
-
-
-
-
8
10
-
5
5-120 L S B-C
20-210 L S B
5-120 L S B-C
20-210 LS B
5-120 LS B-C
20-210 LS B
5-120 LS B-C
0.01-1.5 SE, CR C
0.01-1.5 SE, CR C
0.15-1.5 E G B
0.15-1.5 E G B
0.15-1.5 EG B
2-16 LS C
18 OX-10 EG
? OS
9-100 LS
7-13 LS
7-13 LS
CD
14
3
3
D
C
C
BC
KC
-
0.86-S LS B
-
-
B
A
A
A-B
8
-
10
-
-
-
-
12
12
1 1
7
15
1 1
0.46-S LS
0.1-0.4 LS
0.07-0.33 S E
3-70 LS
? ?
0.5-92 LV
l - 8 LS
0.05-0.4 LS
3.4-367 LS
0.05-0.33 S E
l - 7 LS
0.05-0.33 S E
0.07-0.33 S E
3-70 LS
C
A
A
A-B
A
A
A
A-B
l -7
0.1-0.4
0.04-0.4
2.6-113
2.6-113
3-12
LS
LS
LS
OS
LS
LS
LS
LS
A
L
L
A
A
A-B
2.6-113
2.8-20
2.8-30
2.8-25
A
A
A
A
9 6 3
9 6 3
9 6 3
9 6 3
3 9 5
3 8 7
3 9 5
3 9 6
3 9 7
3 9 6
3 9 7
3 9 6
3 9 7
3 9 6
3 9 8
3 9 8
3 9 9
3 9 9
3 9 9
4 0 2
4 0 0
4 0 3
4 0 4
4 0 5
4 0 5
791
3 8 5
385
9 9 3
9 9 3
4 0 6
4 0 7
4 0 8
4 0 9
410
4 1 1
4 0 6
4 0 8
4 0 7
411
4 0 7
4 0 7
4 0 8
4 1 1
193
7 9 3
412
4 1 2
4 1 3
4 1 2
414
4 1 4
4 1 4
References page VII - 68
VII / 34 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 3. contd
Polymer Solvent
Temp. K (x 103)
((3 Wk)
No. of samples Mol. wt.
range
a Fr. WP M ( x 10 -4) Method(s) Remarks Refs.
Poly(phenyl ether-alt-phenyl ketone), (PEK)
Sulfuric acid (96.4%)
Poly(propylene oxide), see Poly(oxypropylene)
Poly(tetrahydrofuran), see Poly(oxytetramethylene)
? 5 6 0. 73
-
6 1.2-5 L S , S E C C- D 1008
3.2. POLY(ESTERS), POLY(CARBONATES)
Poly(butylene isophthalate) Chloroform ? 3 . 3 0. 92 6
Poly(butylene adipate-co-butylene isophthalate)
( I 00 mol% BADP) Chloroform 3 0 7 3 . 1 0. 69 6
(80 mol% BADP) Chloroform 3 0 4 7 . 4 0. 73 4
(50 mol% BADP) Chloroform 3 0 2 6 . 7 0. 78 4
(20 mol% BADP) Chloroform 3 0 1 1 . 2 0. 80 4
Bisphenol A poly(carbonates), see Poly[oxycarbonyloxy- I ,4-phenyleneisopropylidene- 1,4-phenylene]
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
1.4-3.7 V O S , E G
- 9 6 6
0.67- 1.45 v o s C 9 6 7
0.92-I .9 v o s C 9 6 7
0.80-1.8 v o s C 9 6 7
0.88-2.3 v o s C 9 6 7
Poly(N-decanoyldehydroalanine methyl ester)
Tetrahydrofuran 2 5
Poly(ethylene terephthalate), see Poly(oxyethyleneoxyterephthaloy1)
Poly(o-P-hydroxybutyrate), see Poly(o-oxy-I-oxo-3.methyl-trimethylene)
Poly(4,4-isopropylidene-diphenyl carbonate)-block-poly(styrene)
2 6 w t . %- P S Chloroform 2 5
Diethyl carbonate 2 5
1,4-Dioxane 2 5
Methylene chloride 2 5
Tetrahydrofuran 2 5
4 8 w t . %- P S Chloroform 2 5
Diethyl carbonate 2 5
1,4-Dioxane 2 5
Methylene chloride 2 5
Tetrahydrofuran 2 5
5 0 w t . %- P S Chloroform 2 5
Diethyl carbonate 2 5
1.4.Dioxane 2 5
Methylene chloride 2 5
Tetrahydrofuran 2 5
13 wt.%-PS Chloroform 2 5
Diethyl carbonate 2 5
1 ,6Dioxane 2 5
Methylene chloride 2 5
Tetrahydrofuran 2 5
2 6 . 3 0. 63 6
3 1 . 1 0. 74 9
2 2 8 0. 54 9
6 0 . 8 0. 68 9
2 1 . 2 0. 77 9
1 3 6 0. 57 9
6 5 . 1 0. 71 8
3 7 8 0. 53 8
8 0 . 5 0. 68 8
2 8 . 6 0. 79 8
3 5 2 0. 54 8
6 2 . 1 0. 7 I 6
3 1 6 0. 55 6
7 9 . 8 0. 68 6
2 0 . 4 0. 8 I 6
2 4 3 0. 56 6
5 2 . 2 0. 74 9
3 4 7 0. 55 9
117 0. 67 9
3 1 . 5 0. 80 9
143 0. 65 9
IO-254 LLS
-
9 6 8
6-17 OS, LS A 9 5 9
6-17 OS, LS A 9 5 9
6-17 OS, LS A 9 5 9
6-17 OS, LS A 9 5 9
6-17 OS, LS A 9 5 9
3-11 OS, LS A 9 5 9
3-11 OS, LS A 9 5 9
3-11 OS, LS A 9 5 9
3-11 OS, LS A 9 5 9
3-11 OS, LS A 9 5 9
6-27 OS, LS A 9 5 9
6-21 OS, LS A 9 5 9
6-27 OS, LS A 9 5 9
6-27 OS, LS A 9 5 9
6-27 OS, LS A 9 5 9
6 - 1 7 OS, LS A 9 5 9
6-17 OS, LS A 9 5 9
6-17 OS, LS A 9 5 9
6-17 OS, LS A 9 5 9
6-17 OS, LS A 9 5 9
Poly(o,L-P-methyl-P-propiolactone), see POly(o,L-B-methyl-P-prOpiOlactOne), see ~O~y(~,~.O~y.~~O~O.~.~e~hy].~~~e~hy~e~e)
Poly(oxyadipoyloxydecamethylene)
Chlorobenzene 2 5 1 1 . 7
Diethyl succinate 7 9 5 . 8
Poly(oxybutynedioyl- Benzene 2 0 151
oxyhexamethylene) Chloroform 2 0 9 1
Poly[oxycarbonyl(bicyclo-[2,2,2]octan-2,5-dion)carbonyloxyhexamethylene]
Chloroform 2 0 -
Poly(oxycarbonyloxy-1,4-phenyleneisopropylidenel,4-phenylene]
Butyl benryl ether 1 7 0 (0) 2 1 0
Chloroform 2 0 2 7 7
2 5 1 2 . 0
2 5 30. I
Dichloromethane 2 5 2 9 . 9
Dioxane/cyclohexane 25 (0) 2.5-2.8
(68/W
Ethylene chloride 2 5 2 0 . 4
Methylene chloride 2 5 11.1
2 5 Il.9
2 5 3 8 . 9
Tetrachloroethane 2 5 1 3 . 4
Tetrahydrofuran 2 5 3 8 . 9
2 5 3 9 . 9
2 5 3 7 . 8
0. 84 - 7 0.3-3 LV C 4 1 5
0. 86 - 12 1-3 LV C 4 1 5
0. 55 ? -
0.1-0.5 OS B 4 1 6
0. 61 ? -
0.1-0.5 OS A 4 1 6
-
-
4 1.4-3.9 OS C 4 7 5
0. 50 8 -
0. 50
0. 82 8 -
0. 74 1 2 -
0. 74 1 2
Vari ous 9 -
4-31
1.5-6
1-7
0.4-47
0.4-47
LS
LS
LS
LS
LS
S E C
B
-
A
AR
A
B
4 7 6
4 7 7
4 7 8
7 9 6
7 9 6
9 6 5
0. 76 8 -
1-7 LS A 4 7 8
0. 82 6 -
l - 2 7 S D B 4 7 9
0. 80 1 2 -
1-76 LS B,R 4 7 6
0. 70 8 -
1-7 LS A 4 7 8
0. 82 8 -
1-7 LS A 4 7 8
0. 70 8 -
l - 7 LS A 4 7 8
0. 70 - 6 l - 2 7 S D CR 4 7 9
0. 71 1 2 -
0.4-47 LS A 7 9 6
TABLE 3. contd
Viscosity - Molecular Weight Relationships of Main-Chain Heteroatom Polymers
Polymer Solvent
Temp.
(a
K (x 103)
bUg)
No. of samples Mol. wt.
range
a Fr. WP M (x 10e4) Method(s) Remarks Refs.
Tetrahydrofuran Room t emp. 31.4
Cyclohexane/dioxane 25 2 1 0
(36.1163.9, w/w)
Poly(oxy- 1,4-cyclohexyleneoxysebacoyl)
c i s Chloroform 2 0 27.8
tram Chloroform 2 0 18.3
Poly[oxy-l,lO-di-oxoperfluorodecamethyleneoxydecamethylene)
Chloroform 25 15.5
s-Tetrachloroethane 25 (0) 88
Poly(oxyethyleneoxycarbonyl-1,4-phenyleneoxyethyleneoxy-1,4-phenylenecarbonyl)
o- Chl or ophe nol 35
Phenol-tetrachloroethane 35
(l/Z w/w)
Poly(oxyethyleneoxyterephthaloy1)
o-Chlorophenol 25
25
25
25
25
55
m-Cresol 25
Dichloroacetic acid 45
Tetrachloroethane 5 0
Trifluoroacetic acid 25
3 0
35
55
Dichloroethane/phenol
(614, v/v)
Phenoketrachloroethane 25
(40/60, w/w) 35
(315, VW 3 0
(50/50, v/v) 2 0
25
25
Phenolketrachlorophenol 25
Phenolkichlorophenol 29.8
(10/7, v/v)
3 0
Poly(oxyfumaroyloxyhexamethylene)
Chloroform 2 0
Poly[oxy(hexahydro-3,6-endomethylenephthaloyl)-o~yhexamethylene]
c i s B e n z e n e 2 0
Chl oroform . 2 0
trllns Benzene 2 0
Chloroform 2 0
Poly[oxy(hexahydroterephthaloyl)oxyoctamethylene]
c i s Chloroform 2 0
trails Chloroform 2 0
Poly(oxyhexamethyleneoxy-2,9-dibutylsebacoyl)
Benzene 2 0
Poly(oxyhexamethyleneoxysebacoy1)
Benzene 2 0
Chloroform 2 0
Poly(oxymaleoyloxyhexamethylene)
Benzene 2 0
Chloroform 2 0
Tetrahydrofuran 2 0
Poly(oxy-1-oxo-dimethyltrimethylene)
Trifluoroacetic acid 2 0
Poly(oxy-I-oxohexamethylene) Benzene 25
3 0
145
112
17
19
3 0
42.5
65.6
2 6
0.77
4 0 0
13.8
140
43.3
130
105
9.2
140
125
22.9
75.5
21
12.7
46.8
28.0
6 3 0
27.1
4 . 6 4
9.33
17.4
17.9
22.9
18.9
37.4
62.7
72.5
76.3
36.2
43.7
24.2
72
9.94
0 . 7 0
0.50
0.78
0.86
0 . 7 0
0 . 5 0
0.59
0.63
0.83
0.81
0.77
0.69
0.73
0.77
0.95
0 . 5 0
0.87
0.64
0.68
0.66
0.69
0.8
0 . 6 4
0.65
0.73
0.685
0.82
0.86
0.68
0.775
0.47
0.80
0.86
0.83
0.75
0.77
0.79
0.84
0.74
0.69
0.70
0 . 6 0
0.73
0.66
0.74
0.63
0.82
9
4
-
7
7
9
9
-
5
13
13
10
1 1
6
6
?
9
9
7
7
7
1 1
6
9
-
-
5
9
-
-
-
7
3 4
-
5
-
5
-
6
-
9
-
-
9
38
9
4
8
-
-
-
-
-
-
-
-
-
-
-
30-75
2.1-4.6
1.1-3.7
0.8-S
0.8-8
1.3-11
1.3-11
0.8-2.0
1.5-3.8
1.1-2.9
2-15
1.2-2.5
1.5-3.8
0.04- 1.2
1.5-3.8
0.04-0.1
1.5-3.8
2.5-12
1.5-3.8
1.5-3.8
1.5-3.8
1.5-3.8
2.5-12
0.3-3
0.5-3
0.1-0.4
1.1-4
2-4.3
2.3-7.5
2.3-7.5
3.3-11
3.3-15
3.3-5.5
2.4-4.4
0.9-2.4
0.6-1.8
2-10
1.3-6.6
1.3-6.6
1.3-6.6
5-54
3.4-12
1.4-15
S E C
LS
OS
OS
LS
LS
OS
OS
E G
E G
E G
S D
OS
EG
EG
EG
E G
EG
LS
E G
E G
E G
EG
E G
LS
E G
E G
LS
E G
OS
OS
OS
OS
OS
OS
OS
OS
OS
OS
OS
OS
OS
OS
G P C
LS
s v
C
C
C
B
C
S
C
B
AL
B
AJ-
B
C
B
B
C
C
B
B
B
B
B
B
B
B
B
B, C
A
B
9 6 5
4 7 6
4 8 0
480
7 9 5
7 9 5
801
801
481
482
4 8 3
484
4 8 5
482
486
4 8 2
4 8 7
4 8 2
4 8 8
4 8 2
4 8 2
4 8 9
4 8 2
4 8 2
4 8 8
490
4 9 1
492
4 9 3
494
4 9 5
4 1 7
4 9 6
496
4 9 6
496
480
480
4 1 8
4 1 8
4 1 9
4 1 7
4 1 7
4 1 7
8 0 0
808
4 4 7
References page VII - 68
VII / 36 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 3. contd
Polymer Solvent
Temp. K (x 103)
(C) Wk)
No. of samples Mol. wt.
range
a Fr. WP M (x 10 -4) Method(s) Remarks Refs.
Dimethylformamide 3 0 1 9 . 1
Dioxane 2 5 9 0
Ethyl acetate 2 5 1 8 0
Poly(oxy-I-oxo-3.methyl- Chloroform 3 0 1.1
trimethylene) 2,2,2-Trifluoroethanol 3 0 2 5 . 1
D- Chloroform 3 0 1 1 . 8
D,L- Ethylene dichloride 3 0 9. 18
Trifluoroethanol 2 5 1 2 . 5
But yl chl or i de 1 3 m 1 0 0
Chloroform 3 0 1 6 . 6
1- Chl or onapht hal ene 4 0 3 9 . 6
Ethylene dichloride 3 0 1 6 . 8
Tr i f l uor oet hanol 2 5 2 2 . 2
3 0 1 7 . 5
Poly(oxysebacoyloxyhexadecamethylene)
Chloroform 2 0 7 4 . 7
Poly(oxysuccinyloxyhexamethylene)
Benzene 2 0 4 3 . 3
Chloroform 2 0 2 4 . 4
Tetrahydrofuran 2 0 4 4 . 3
Poly[oxytetra(ethyleneoxy)carbonyl(l-methylethyleneoxy)thio(2-methylethylene(carbonyl]
Chloroform 7 3 4 . 1
0. 73 9
0. 61 6
0. 52 6
0. 82
-
0. 74
-
0. 78 9
0. 78 9
0 . 8 0 9
0. 50 4
0. 76 5
0. 62 4
0. 74 6
0 . 7 6 8
0. 78 8
0. 70
0. 70 2 2
0. 79 1 8
0. 69 1 3
0. 714
-
-
-
1.4-15 sv B 4 4 7
3.4-12 L S A 8 0 8
3.4-12 LS A 8 0 8
2-78 S D C, D 6 6 0
2-101 LS C D 6 6 1
11-164 LS B, C 7 9 7
11-164 LS B, C 7 9 7
11-164 LS B, C 7 9 7
2-15 LS A 7 9 8
2-15 LS A 7 9 8
2-15 LS A 7 9 8
2-15 LS A 7 9 8
2-15 L S A 7 9 8
2-15 LS A 7 9 8
4
-
2 - 1 0 OS B 4 1 9
-
-
1.5-5
1.5-5
1.5-5
OS
OS
OS
B
B
B
4 1 7
4 1 7
4 1 7
-
? < 1. 5 EG ? 4 2 1
Poly[oxy-( 1,1,3-trimethyl-3-phenylindan-5,4 -dicarbonyl)oxy- 1.4.phenyleneisopropylidene- 1,4-phenylene]
Tetrahydrofuran 25 30.5
Poly(oxyundecanoyl) Chloroform 20 21.4
25 36.3
Poly(phenylhydroquinone-co-terephthalic acid)
o-Dichlorobenzenelp-chlorophenol (1 /I, w/w)
25 30
( Wor ml i ke behavi or )
Poly(P-propiolactone) Chloroform 30 28.2
1,4-Dioxane 30 17
2,2,2,-Trifluoroethanol 30 17.2
3 . 3 . POLY(AMIDES) ( F O R COPOLY(AMIDES), see 3.10 COP OL YME RS )
Poly[(butylimino)carbonyl], [P%ly(butyl isocyanate)]
Benzene 20 1.10
Carbon tetrachloride - 31.6
22 7.81 x IO-
Tetrachloromethane 2 0
Tetrahydrofuran 20 0.457
40 -
40 -
Poly[(chlorohexylimino)-carbonyl], [Poly(chlorohexyl isocyanate)]
Carbon tetrachloride 21 0.22
Poly(rrans-2,5-dimethylpiperazo-IJphthaloyl)
m-Cresol 25 -
Tr i f l uor oet hanol 2 5
Poly[(hexyliminocarbonyl], [Poly(hexyl isocyanate)]
Carbon tetrachloride 25 0.0152
Chloroform 25 0.0499
Hexane 25 1.0
25 88
25 5.4
Tetrahydrofuran 25 0.0220
Tol uene 25 0.0248
0. 691 7
-
2.6-30 LS A 7 9 4
0. 60 7
-
3 - 4 9 O S B 4 1 9
0. 82
-
6 0.5-1.3 E G C 420
0.869 5 5.0-16 LS
-
9 6 9
0. 71 1 3
0. 71
-
0.78 13
-
-
7
2
7
-
-
-
-
-
-
-
-
-
-
-
0.68-86 LS B-D 9 9 1
0.68-86 LS B-D 9 9 1
0.68-86 LS B-D 9 9 1
1. 11
-
1 . 2 9
2 . 0 8
-
1. 18
-
1.8-2.0 4
0 . 2 6 - 0 . 3 7 4
1.8-21 S D
l - 3 0 S D
2.5-14 OS, LS
6.6-16 S D
1.8-21 S D
< 10 S E
>lOO S E
AR
B
A
D
A
4 4 1
8 2 3
8 2 5
4 4 2
4 4 1
8 2 1
8 2 1
1. 21 1 0 1.4-31 S D B,C 8 2 6
0. 75 9
0. 75 1 0
6-237 LS 8 2 8
3-237 LS 8 2 8
1. 10 1 0
0.97 10
1 . 2 8
0. 77 8
0. 97 6
1. 06 1 0
1. 05 1 1
3.8-43 LS A
3.8-43 LS A
6.8-39 LS A
> 106 LS A
9.1-230 LS A, B
3.8-43 LS A
3.8-43 LS A
0.44-724 L S , S E A
8 2 2
8 2 2
8 2 4
8 2 4
8 2 7
8 2 2
8 2 2
9 7 0
9 8 4
Poly(hexy1 isocyanate) But yl chl or i de
Dichloromethane
Tol uene
2 5 (Wormlike behavior) 3 1
2 0 - N o t cons t . 1 3
(Wormlike behavior)
1 0 - N o t cons t . 1 3
(Wormlike behavior)
2 5 - N o t cons t . 1 3
(Wormlike behavior)
0.44-91 LS, OS, SE, LV A
0.44-91 LS, OS, SE, LV A
0.44-91 LS, OS, SE, LV A
9 8 4
984
I
!
I
j
!
/
!
,
j
I
TABLE 3. contd
Viscosity - Molecular Weight Relationships of Main-Chain Heteroatom Polymers VII / 37
Polymer Solvent
Temp. K(x 103)
(a (mUf4)
No. of samples Mol. wt.
range
a Fr. WP M (x 10m4) Method(s) Remarks Refs.
Poly(iminoadipoyliminohexamethylene), (Nylon 66)
o- Chl or ophe nol
m- Cr esol
Dichloroacetic acid
2,2,3,3-Tetrafluoropro-
panolKF3COONa
(0.1 M)
Aq. HCOOH
(90%, v/v)
Aq. HCOOH
(90% vol)/HCOONa
(0.1 M)
Aq. HCOOH
(90%, v/v)/KCI (2.3 M)
Aq. HzS04
(95%, v/v)
(96%, v/v)
Poly(iminocarbonyl-1,4-phenylene), Poly@-benzamide)
Sulfuric acid (96%)
Poly(imino-4,6-carboxyisophthaloylimino-1,4-phenylene)
Dimethylformamide
Poly(iminohexamethyleneiminosebacoyl), (Nylon 6-10)
m-Cresol
4 0
-
Not const 13
-
0.44-91 LS, OS, SE, LV A 9 8 4
(Wormlike behavior)
25 168 0.62
25 2 4 0 0.61
2 5 [ ~J =0. 5+0. 0353M0792
25 [a] =0.5 +0.352M0.55
25 114 0.66
25 35.3 0 . 7 8 6
25 110 0.72
2 5 [~]=2.5+0.0132M0873
25 32.8 0 . 7 4
25 87.7 0.65
25 [v] = 1.0+0.0516M0~687
25 (0) 2 2 7 0.50
25 (8) 2 5 3 0 . 5 0
25 [a] = 2.5 +0.0249M0.832
2 5 115
2 0 1.6
3 0 2 5 2
25 13.5
Poly(iminohexamethyleneiminoterephthaloyloxyhexamethyleneoxyterephthaloyl)
PhenoVtetrachloroethane 2 5
(l/l, w/w)
Poly(iminohexamethyleneiminothiocarbonylhexamethylenethi~~bonyl)
36.4 0.75 8 1.6-7.4 G P C D 8 0 6
\
Dimethylformamide/ 2 0
LiCl (5%)
Poly(iminohexamethyleneiminothiocarbonyltetr~e~ylenet~oc~bonyl)
22.8 0.76 12
Dimethylformamide/
LiCl (5%)
Poly[imino(l-oxododecamethylene)], (Nylon 12)
mCreso1
2 0 99.1 0.65 12
Sulfuric acid (96%)
Poly[imino(l-oxohexamethylene)], (Nylon 6)
m- Cr esol
Trifluoroethanol
25 81 0.74 38
25 46.3 0.75 16
25 69.4 0.64 15
Aq. HCOOH (85%)
Aq. HCOOH (65%)
Aq. H2S04 (40%)
ring oligomer m- Cr esol
Ethylene chlorohydrin
Monochain, polymerized with stearic acid
Cont. H2S04
Dichain, polymerized with sebacic acid
Cont. H2S04
25 3 2 0 0.62
- 20 53.3 0.74
25 53.6 0.75
5 0 58.2 0.73
- 10 26.8 0.82
0 24.8 0.82
10 23.4 0.82
2 0 75 0 . 7 0
2 5 22.6 0 . 8 2
25 2 2 9 0 . 5 0
25 59.2 0.69
25 2100 0.22
25 8 7 0 0.27
25 6 3 0.76
25 4 2 0 . 7 9
0.67 2 1.4-5 LV C 4 4 3
1.7 10 0.7-2.3 DV 807
0.56 14 0.9-2.5 LS 802
0.96 5 0.8-2.4 S D B 4 5 4
-
5
5
-
-
-
-
-
-
-
-
4
3
7
14
0.7-4.8 EG 8 0 5
0.8-2.2 E G 8 0 5
0.3-13 LS B,R 8 0 3
1-13 L S B 8 1 2
1-13 LS B 8 1 2
0.05-0.5 EG
1.3-10 LS
1.3-10 LS
1.3-10 LS
0.7-12 L S
0.7-12 LS
0.7-12 LS
0.45-1.6 EG
0.7-12 LS
0.7-12 LS
0.3-1.3 E G
0.02-0.06 v o s
0.03-0.06 v o s
B,R
B
0.2-1.4 EG
0.2-2.3 EG
4 4 8
450
450
450
4 5 0
450
450
451
450
450
4 5 2
4 4 9
4 4 9
4 5 3
453
-
13
13
-
2 1.4-5 LS, EG C 4 4 3
2 1.4-5 L S , G C 4 4 3
-
0.015-5 LS,EG B 444
-
0.015-5 LS,EG B 444
2 1.4-5 LV C 4 4 3
3 1 1 0.6-6.5 LS, EG C 4 4 3
-
2 0 0.5-2.5 EG C 446
13
-
0.015-5 L S , E G B 4 4 4
-
19 l -5 E G 4 4 5
-
6
2 1.4-5 LS, EG
0.015-5 L S , E G
4 4 3
4 4 4
2
7
12
1.4-5 LS, EG
0.015-5 LS, EG
0.015-5 LS,EG
CR
C
B, R
C
B - C
B
4 4 3
444
4 4 4
References page VII - 68
VII / 38 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 3. contd
Polymer Solvent
Temp. K (x 10)
(C) Wk)
No. of samples Mol. wt.
range
n FT. WP M (x 10 -4) Method(s) Remarks Ref s.
Tetrachain, polymerized with a tetrabasic acid
Cont. HzS04 2s 55 0 . 7 4
Octachain, polymerized with a octabasic acid
Cont. H~SOI 25 13.5 0.86
Poly(iminoterephthaloylhydrazocarbonyl-1,4-phenylene), [Poly(terephthaloyl-p-aminobenzhydrazide)]
Dimethyl sulfoxide 2 s - 1.3-0.9
2 s 1.05 0 . 7 9 s
Poly(iminoterephthaloylimino-1,4-phenylenefluoren-9-ylidene-1,4-phenylene)
Dimethylfonnamide 2 s 110 0.66
Poly(iminoterephthaloylimino-1,4-phenylene-phthalidylidene-1,4-phenylene)
Dimethylformamide 25 2 7 7 0.59
Poly[iminoterephthaloylimino(trimethylhexamethylene)], 2,4,4-/2,2,4-trimethyl (l/ 1, mol/mol)
Dimethylformamide 2 s 21.4 0.71
Poly(isophthaloyl-rrans-2,5-dimethylpiperazine)
N-methyl-2.pyrrolidone 2 5 Not const
( Wor ml i ke behavi or )
Poly[(octylimino)carbonyl], [Poly(octyl isocyanate)]
Carbon tetrachloride 22 2.02 x 10-s 2.0
Poly( 1,4-phenyleneterephthalamide), (Kevlar)
96% Sulfuric acid 3 0 1.09 1.25
Poly(terephthalamide-p-benzohydrazide)
Dimethyl sulfoxide 2 s (Wormlike behavior)
3. 4. POLY(AMIN0 ACIDS)
Poly(P-benzyl-L-aspartate), see Poly(iminocarbonyl-L-benzyloxycarbonylethylidene)
Poly(y-benzyl-L-glutamate), see Poly(iminocarbonyl-L-benzyloxycarbonylpropylidene)
Poly[(benzylimino)carbonylethylene], (Poly(N-benzyl-p-alanine))
Dichloroacetic acid 2 s 120
Poly(iminocarbonyl-t.-benzyloxycarbonylethylidene), (Poly(P-benzyl-L-aspartate))
m- Cr esol 1s
7 0 -
Hexamethylphos- 2 s
phoramide
ChloroformIdichloro- 2 s -
acetic acid (98/2, v/v)
Poly(iminocarbonyl-L-benzyloxycarbonylprpylidene),
Dichloroacetic acid 25 2.78
25 8.8
(Poly(y-benzyl-L-glutamate)) Dimethylformamide 2 s 0.0056
2 s 0 . 0 0 0 2 9
Dichloroacetic acitieptane
(55/45, v/v) 21 116
(90/10, v/v) 21 25.4
D,L-glutamate Dichloroacetic acid 25 2.85
Dimethylformamide 2 s 37.7
Poly(iminocarbonyl-L-hydroxycarbonylpropylidene), [Poly(cc-L-glutamic acid)]
Sodium phosphate buffer 25.5 1.55
(1.01 M, pH, 6.8)
0.525 6 0.15-1.8 E G BJ- 455
1.15 5
-
0.8-24 LS B 4 5 6
0 . 7 4 5
- 0.8-24 LS B 4 5 6
0 . 8 0 4
-
2-24 L S B 4 5 6
1.30 5 0.8-24 L S B 4 5 6
0.87
0.77
1.45
1.70
8
8
-
6
-
5
2-34 LS C 4 5 7
6 - LS B 8 1 4
6 - LS B 8 1 4
7-34 LS C 4 5 7
0.53
0.68
0.85
0.55
4 1.5-10 LS C 4 5 8
4 1.5-10 LS C 4 5 8
6 1.5-10 LS C 459
6 1.5-10 LS C 4 5 9
0.96 4-15 LS C 8 1 5
-
1 1 0.2-I .9 EG B 4 5 3
-
5 0.4-2.6 E G B 4 5 3
15
-
0.2-5.8 LS B 8 0 9
8 1.2-65 LS B 8 1 0
7
-
1.5-7.8 LS B 5 0 3
8 1.4-6.9 LS B 5 0 3
17 1.2-28 LS, SA B 8 0 4
18
-
0.26-237 LS, SE A 971
4
-
5.9-20.0 OS, LS A 8 2 5
3 1.6-3.8 LS
-
9 7 3
6
-
0.94-5.8 LS, SE A 9 7 4
Poly[iminocarbonyl-~-(N-hydroxy-ethylcarbamoylpropylidene)], (Poly[N-(2-hydroxyethyl)-L-glutamine]]
Sodi um phosphate buffer 25 26.2 0.65 6
(0.05 M, pH, 7.4)
Wat er 3 0 - 0.55 4
Poly[iminocarbonyl-L-(N-hydroxypropylcarbamoylpropylidene)], (Poly(N5-(3-hydroxypropyl)-L-glutamine))
Methanol 25 - 1.6 4 -
Wat er 25 - 0.61.0 5 -
Poly(iminocarbonyl-L-methoxycarbonylpropylidene), [Poly(y-methyl-L-glutamate)]
mCreso1 25 >l
Dichloroacetic acid 25 2 9 0 . 7 4 - 6
D,L-glutamate m-Cresol 2 s 1 1 0.78 - 6
Dichloroacetic acid 2 s 5.9 0.85 - 6
0.8-15 S E C 8 1 6
1.7-7.2 OS C 817
20-40 LS B 4 6 0
2-33 LS B 4 6 0
3-21 OS C 4 6 3
3-21 OS C 4 6 3
3.2-8.2 OS C 4 6 4
3.2-8.2 OS C 4 6 4
Poly(iminocarbonyl-~-methoxyethylideneimin~arbonyl-~-hydroxyethylideneiminoc~bonylmethylene), [Poly(Asp(OCH,)-Ser(H)-Gly)]
Dichloroacetic acid 3 0 868 0.367 - 9 0.25-1.1 S A
8.C
4 6 7
TABLE 3. contd
Viscosity - Molecular Weight Relationships of Main-Chain Heteroatom Polymers VII / 39
Polymer Solvent
Temp. K(x 103)
(C) (mlk)
No. of samples Mol. wt.
range
n Fr. WP M ( x 10 -4) Method(s) Remarks Refs.
Poly(iminocarbonyl-L-methylthiopropylidene), [Poly(r-methionine)] acid (l/l, mol)
Dichloroacetic acid 3 . 0 0. 87
Dichloroacetic acid/trifluoroacetic
3 6 0 . 6 2 -
Poly(iminocarbonyl-~-p-nitrobenzyloxycarbonylpropylidene), [Poly(r-p-nitrobenzyl-L-glutamate)]
Dichloroacetic acid 2 5 1 1 . 5 0. 72
Dimethylformamide 2 5 0. 0170 1. 36
Poly(iminocarbonyl-phenylethylidene), [Poly(phenylalanine))]
L- Chloroform 2 5 0. 00346 1. 48
W Chloroform/dichloro- 2 1 1 1 8 0. 55
acetic acid (2/3, v/v)
Poly(y-hydroxy-L-proline) Wa t e r 3 0 9 2 0. 68
Poly(r,a-L-lysine) Dimethylformamide/ 2 0 2 5 0 0 0
LiCl (1%)
Poly[(methylimino)carbonylmethylene], (Poly[sarcosine)]
Wa t e r 2 0 5 6 0. 88
Poly( I-proline), see Poly[(L-1,2-pyrrolidindiyl)carbonyl] in group 3.9.
3.5. POLY(UREAS), POLY(URETHANES), POLY(IMINES)
Poly(ethylene imine), see also Poly(iminoethylene)
Methanol 2 5 1 0 . 4 0. 95
Poly(iminoethylene) Wa t e r 2 5 [q]=2.14P35
P: number of
N a t o m s
Poly(oxytetramethyleneoxycarbonylimino-2,4-tolyleneiminocarbonyl)
Dimethylformamide 3 0 5 4 0. 74
Poly[oxytetramethyleneoxycarbonylimino-(6-pentyloxy-1.3-phenylene)-iminocarbonyl]
Dimethylformamide 2 0 8 . 1 0. 86
- 5
4 3 - 5 0
- 1 0
- 10
- 1 1
3 -
- 5
8 -
4 -
- 5
- 5
number of F atoms
4 Acetone 2 0 7 . 1 0. 81
8 Acetone 2 0 4 . 3 0. 785
12 Acetone 2 0 1 3 . 5 0. 67
1 6 Acetone 2 0 2 5 . 6 0. 615
Poly(terephthalic acid-4-aminobenzohydrazide)
Dimethyl sulfoxide 2 5 ( Wor ml i ke behavi or )
Poly(urethane)with methylene bis(4.phenyl isocyanate), tetramethylene glycol and ethylenediamine
Poly(ureyleneheptamethylene)
Dimethylacetamide
Dichloroacetic acid
Sulfuric acid (90%)
(96%)
(98%)
3. 6. POLY(SULFIDES)
Poly(thiopropylene) Benzene
Poly(trimethylene sulfide) Chloroform
3. 7. POLY(PHOSPHATES)
Lithium-potassium copoly(phosphate)
Li/K (9/l, mol/mol) Aq. NaBr (0. 035 N)
(S/2, mollmol) Aq. NaBr (0. 035 N)
(7/3, mol/mol) Aq. NaBr (0.035 N)
(6/4, mol/mol) Aq. NaBr (0.035 N)
(5/5, mol/mol) Aq. NaBr (0.035 N)
Poly[oxy(hydroxyphosphinylidene)]
Aq. NaBr ( 0. 35 M)
( 0. 415 M)
sodi um sal t Aq. NaBr ( 0. 035 M)
2 5 101 0. 59 8
-
3.2-35 LS
4 6 3 3 8 0. 505
- 10 0.3-2.4 LS
2 5 5 0 . 0 0. 714
-
14 0.13-2.4 LS
4 6 2 2 3 0. 506
-
7 0.06-2.4 LS
2 5 3 7 . 5 0. 757
- 5 0.4-2.4 LS
4 6 2 4 0 0. 53
-
7 0.2-2.4 L S
2 0 3 . 3 0. 86 7
-
3.8-20.4 LS
3 0 5 . 0 0. 78
-
10 3.6-73 L S
2 5 3 1 . 0 0. 76 6
-
l-4.7 OS
2 5 6 . 5 0. 69
25 (0) 4 9 . 4 0. 50
2 5 . 5 6 9 0. 61
0. 073 1. 17
0. 63 0. 93
7 . 3 0. 89
2 7 0. 75
2 5 0. 74
-
5 0.5-4 s v
-
5 2-16 s v
- 5 1.7-28 s v
-
5 0.9-9 s v
I1
-
0.38-26 LS
6 0.4- 1 E G
6 0.4- 1 E G
6 0.4-l E G
5 0.4-i EG
6 0.4-I EG
1 6 I-125 LS
9 1-125 LS
5 0.09-l EG
3 - 5 0 L S B 8 2 0
L S B 8 2 0
l - 5
l - 5
LS
LS
6 0 8
6 0 8
2.2-14 LS
L S
B
B
B
B
A
A
C
-
D
C
C
C
C
C
C
-
-
C
C
C
C
C
B
B
-
-
-
-
C
C
C
4 6 5
4 6 6
1.6-3.5
0.05-23
G P C 8 1 8
8 1 9
0.7- 1 . 6 E G 4 6 8
0.24-2.8 L S
P=4-13 C R
9 7 6
4 7 0
0.35-1.6 LS 4 9 7
0.9-4.3 S V 4 9 8
4 9 8
4 9 8
4 9 8
4 9 8
9 7 7
9 7 8
4 7 1
4 7 1
4 7 1
4 7 1
4 7 1
4 3 6
8 3 9
9 7 9
9 8 0
9 8 0
9 8 0
9 8 0
9 8 0
4 2 2
4 2 2
4 2 3
References page VII - 68
VII / 40 VI SCOSI TY - MOLECULAR WEI GHT RELATI ONSHI PS AND UNPERTURBED DI MENSI ONS OF LI NEAR CHAI N MOLECULES
TABLE 3. contd
Polymer Solvent
Temp. K(x103)
((-3 Wg)
No. of samples Mol. wt.
range
a Fr. WP M (x 10e4) Method(s) Remarks Ref s.
Poly(phosphoric acid), see Poly[oxy(hydroxyphosphinylidene)]
Sodium-potassium copoly(phosphate)
Na/K (9/ 1, mol/mol) Aq. NaBr (0.035 N)
(S/2, mol/mol) Aq. NaBr (0.035 N)
(l/3, mol/mol) Aq. NaBr (0.035 N)
(6/4, mol/mol) Aq. NaBr (0.035 N)
(5/5, mol/mol) Aq. NaBr (0.035 N)
(4/6, mol/mol) Aq. NaBr (0.035 N)
3.8. POLY(SILOXANES), POLY(SILSESQUIOXANES)
3.6 0.93
1 1 0.81
12 0 . 8 0
51 0 . 6 0
7 3 0.57
150 0 . 5 0
Poly(dimethy1 siloxane), see Poly[oxy(dimethylsilylene)]
Poly[( I-isobutyl-3-phenylsilsesquioxane)]
Benzene
Butyl acetate
Poly(3-methylbutenesilsesquioxane)
Benzene
Poly(methylphenylsiloxane)
Butyl acetate
Cyclohexane
Poly[oxy(dimethylsilylene)]
Methylcyclohexane
Tetrahydrofuran
Benzene
Bromobenzene
Bromocyclohexane
Bromocyclohexane
Bromocyclohexanel
phenetole (611, v/v)
Butanone
CsFdCzCWz
(33.17/66.83, w/w),
low cohesive
21 1.4 0 . 9 0
21 110 0.54
2 4 Same as above two data
21 5 . 4 0.88 5
21 1.6 0 . 9 0 ?
2 4 5.4 0.88 13
25 27.3 0 . 6 0 4
5 0 15.6 0.65 4
2 0 30.6 0.58 4
25 16.5 0.69 4
2 0 12 0.68 4
18.1 (0) 7 6 0.50 3
28 (0)
78 0 . 5 0 5
28 @I 79.5 0.50 6
29.0 (0) 7 4 0 . 5 0 5
37 (0) 78 0.5 I
36.3 (8) 75.5 0 . 5 0 4
2 0
20 (0)
3 0
22.5 (S)
6 4 0 . 5 2 5 6
81 0.50 5
4 8 0.55 8
106 0 . 5 0 4
energy density mixture
Chlorobenzene/dimethyl 57.5 (8)
phthalate (45/6, v/v)
Cyclohexane
Et hyl i odi de
Phenet ol e
Tol ue ne
Tol ue ne
Tol ue ne
star type, 3 branches Tol ue ne
star type, 4 branches Tol ue ne
Poly[oxy(dimethylsilylene] 1,4-phenylenedimethylsilylene]
Tol ue ne
Poly[oxy(dipropylsilylene)] 2-Pentanone
Tol ue ne
Poly[oxy(methylsilylene)]
Me/Si = 1.5
Me/Si = 1.8
Chlorobenzene
Chlorobenzene/dimethyl
phthalate (90.7/9.3, w/w)
35 10.2 0.735
2.1 (8) 7 0 0 . 5 0
83 (@ 7 9 0 . 5 0
89.5 (8) 7 3 0 . 5 0
2 0 20.0 0.66
25 2.43 0.84
25 8.28 0.72
25 21.5 0.65
25 75 0 . 5 0
2 5 13.6 0 . 6 9
25 18.7 0.66
35 12.5 0.703
2 0 23.9 0.64
2 0 64.5 0.54
8
2
4
-
5
-
5
13
18
8
10
10
2 5 11.2 0.75 6
76 @I 87.1 0.50 4
10 m
109 0.50 6
25 43.5 0.58 15
20 @) 3 2 6 0.21 12
20 (0) 2 4 0 0.28 3
7 6 0.50
-
-
?
?
3
4
4
4
4
4
4
-
-
-
-
-
-
-
-
-
-
-
-
-
2
?
7
?
-
-
-
-
-
0.4-0.8 E G
0.4-0.8 E G
0.4-0.8 E G
0.4-0.8 E G
0.4-0.8 E G
0.4-0.8 EG
-
-
-
9 8 0
9 8 0
9 8 0
9 8 0
9 8 0
980
1.2-15 S D ?
20-230 S D ?
6 1 9
6 1 9
6 1 9
9-60 S D B 6 0 3
0.35-74 S D B 6 1 9
9-60 S D B 6 0 3
12-46 LS C 9 8 3
12-46 LS C 9 8 3
12-46 LS C 9 8 3
12-46 LS C 9 8 3
5.5-12 LV A-B 4 2 4
S-106 LS A 4 2 5
lo-92 S D A 426
4-90 LS A 8 3 8
3.3- 106 LS AR 4 2 5
4.5-32 LS
-
9 8 2
4.5- 106 LS A 4 2 5
4-90 LS A 8 3 8
5-66 OS A 4 2 7
5-66 OS A 4 2 7
55- 120 LS A-B 424
S-106 LS A 4 2 5
1.7-90 LS
34- 106 LS
5-66 OS
4.5- 106 LS
0.3-20 OS, LS
1.9-13 LS
lo-92 S D
2-130 OS
0.2- 1.0 OS
0.26-63 OS, LS
0.2-30 LS, SA
1.7-90 LS
4-35 LS
0.8-25 LS
A
A
A
AR
C
C
A
8 3 8
4 2 5
4 2 7
4 2 5
4 2 8
4 2 9
4 2 6
430
5 6
981
8 3 7
8 3 8
431
431
7-40
2.5-27
2.5-30
1.7-43
LS
OS
OS
OS
LS
LS
499
4 3 3
4 3 3
4 3 3
0.1-500
5-100
4 3 2
432
TABLE 3. contd
Viscosity - Molecular Weight Relationships of Main-Chain Heteroatom Polymers
Polymer Solvent
Temp.
(C)
K (x 103)
Wk)
No. of samples Mol. wt.
range
a Fr. WP M (x 10A4) Method(s) Remarks Refs.
Poly[oxy(methylphenyIsilylene)] Cyclohexane
Diisobutylamine
Tol ue ne
Poly[oxy(y-triRuoropropyImethylsilylene)]
Cyclohexyl acetate
Ethyl acetate
Methyl hexanoate
Poly(phenylsilsesquioxane) Benzene
25
30.4 (8)
25
25.0 (8)
25
72.8 (0)
21
21
21
21
25
21
21
21 (8)
21 (@
50.5 (Iv)
30.0
25
3 0 . 0
25
4 0
5.52
51.5
3.90
41.0
5.92
44.5
0.77
2.38
0.13
7.6
Not linear
0.13
2.38
2.38
2 2 0
2.12
0.72
0.50
0.78
0.50
0.70
0.50
0.92
0.90
0.85
1.10
0.70
1.09
0.85
0.85
0 . 5 0
0.87
7
14
8
5
8
12
5
?
4
6
1.8
4
-
-
-
-
-
-
8
6-124
6-124
6-124
12-451
20-45 1
44-451
1.7-6.1
0.4-88
3. 7- 1. 5
10-31
3.7-15
3.6-88
14-71
60-340
5-30
0.36-l 1
59-668
LS
LS
LS
LS
S D
S D
S D
S D
LS
S D
S D
S D
S D
OS
LLS
LS
LLS
LS
LS
B
B
W-
B
4 3 5
4 3 5
4 3 5
500
501
5 0 2
5 0 1 , 6 0 3
6 0 3
8 4 3
501
5 0 2
5 0 2
6 1 9
601
9 8 9
833
9 8 9
8 3 6
845
Bromofotm
cis-syndiotactic
Benzeneibromoform
(60/40, w/w)
1 ,ZDichloroethane
3.9. POLY(HETEROCYCLICS)
Poly(2,6-benzothiazole) Methanesulfonic acid
Poly(benzobisthiazole-2,6-diyl-1,Cphenylene)
Methanesulfonic acid
Poly[2,5-benzoxazole) Methanesulfonic acid
Poly[bis(m-chlorophenoxy)phosphazene]
Chloroform
Poly[6,6-bis(3-phenylquinoxaline)-2,2-diyl-l,4-phenylene)]
m- Cr esol
12.6 1.0
0 . 0 1 4
10.9 1.02
0.67
86 0.63
Poly[( 1,3-dihydro-3-oxoisobenzofuran- I-ylidene)- 1,4-phenyleneiminoterephthaloylimino- l,4-phenylene]
Dimethylformamide 25 2 7 7 0.59 7
Poly[( 1,3-dihydro-3-oxo-2-phenylisoindole-l-ylidene)-l,4-pbenyleneoxyterephthaloyloxy-1,4-phenylene]
Tetrachloroethane 2 0 4 1 . 0 0 . 6 8 4 10
Tetrahydrofuran 2 0 2 5 9 0.488 5
515
9 8 6
Dimethylformamide 2 0
Poly(3,3-dimethylthietane) Tetrahydrofuran 25
Poly( l-isobutyl-2,5-oxopyrrolidine-3,Cdiyl)
Butyl acetate 21
Poly[Z-methoxy-4,6-di@,p-isopropylidene diphenyloxy)-s-triazine]
Chloroform 3 0
1 ,2-Dichloroethane 3 0
1,2-Dichloroetha& 3 0
n-butanol (80/15, v/v)
Poly(methylene-NJ-dimethylpiperidinium chloride)
Aq. NaCl (0.1 M) 2 0
(0.4 M) 2 0
Poly[N-(n-octadecyl)maleimide] Benzene 25
1- Chl or ona pht ha l e ne 25
o-Dichlorobenzene 25
Tetrahydrofuran 25
Tol ue ne 25
1-Decanol 39.4 (0)
I-Hexanol 79.0 (0)
I-Octanol 53.7 (0)
Poly(N,N-(p-phenylene)-3,3,4,4-biphenylteuacarboxylic acid diamine]
N-methylpyrrolidinone 25
Dimetbyl sulfoxide 2 5
3 2 8 0 . 5 1 6
11.0 0.79
2 2 0.65
16.8 0.74
21.6 0.71
27.9 0.68
2 6
7
13
6
4
4
5
5
17
7
7
15
8
6
6
6
-
0.4- 17 LS B
3.8-12.9 OS B
19-340 S D A
9-55.2 OS, LS B-C
14-55.2 OS, LS B-C
14-55.2 OS, LS B-C
5 1 2
9 8 5
9 8 5
9 8 5
8-195
8-195
1.2-33
1.5-12
1.8-12
1.3-33
1.2-17
2-19
1.4-9
1.1-12
LS
LS
OS, vos, GPC
OS, vos, GPC
OS, VOS, GPC
OS, vos, GPC
OS, VOS, GPC
LV
LV
LV
A
A
B
B
B
B
B
B
B
B
8 2 9
8 2 9
9 8 7
9 8 7
9 8 7
9 8 7
9 8 7
9 8 8
9 8 8
9 8 8
39.8 0 . 6 6 0
13.9 0.542
5.38 0.74
2.89 0.77
4.03 0.75
9.61 0.67
6.04 0 . 7 0
18.3 0 . 5 0
37.0 0.50
23.5 0.50
9.5 0.90
3 8 0.77
0.59-7.5
0.58-5.6
LLS, SEC
LLS, SEC
Poly(4-phenylquinoline-2,6-diyloxy-4-phenylguinoline-2,6-diyl- 1 ,Cphenyleneoxy- 1,4-phenylene)
Chloroform 25 9 0 0.66
Poly[(4-phenyl-l,2,4-triazol-3,5-diyl)-1,3(or 1,4)-phenylene]
Phenol/water (90/10, w/w) - 8 4 5 0.56
Poly[(~- 1,2-pyrrolidindiyl)-carbonyl]
Water, acetic acid 25 No simple relation
4-8 OS
1.3-2.7 OS
-
l -5 OS C
8 3 2
5 1 6
5 0 7
References page VII - 68
5
5
VII / 42 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 3. contd
Polymer Solvent
Temp. K(x103)
(C) Wk)
No. of samples Mol. wt.
range
a Fr. WP M (x 10 -4) Method(s) Remarks Refs.
Poly(quinoline-2.4.diyl- I ,4-phenyleneoxy- 1,4-phenylene-quinoline-4,2-diyl- 1,4-phenyleneoxy- 1,4-phenylene)
Chloroform 2 0 5 5 0 0.44 3 -
Poly(l-p-tolyl-2,5-oxopyrrolidine-3,4-diyl)
Dimethylformamide 21 15.5 0.7 6 -
3.10. COPOLYMERS (MALEIC ANHYDRIDE, SULFONES)
Poly[3,9-bis(ethylidone-2,4,8,10-tetraoxaspiro(5,5)undecane)-r~~-(~ru~~-cyclohexane-dimethanol)/( 1,6-hexanediol)]
rrans-CDM/l,6-ND (100/O) Tetrahydrofuran 30 49.2
(70/30) Tetrahydrofuran 3 0 22
(50/5(X Tetrahydrofuran 3 0 17.2
W/71)
Tetrahydrofuran 3 0 11.9
(O/100) Tetrahydrofuran 3 0 3.78
Poly[(tetrahydro-2,5-dioxo-3,4-furandiyl)( 1 -isobutyloxyethylene)]
Acetone 3 0 124.7
Bu t a n o n e 3 0 119.4
Tetrahydrofuran 3 0 75.6
Poly[(tetrahydro-2,5-dioxo-3,4-furandiyl)( 1-methoxycarbonyl-1-methylethylene)]
Acetone
Dimethylsulfoxide
Dioxane
Tetrahydrofuran
Poly[(tetrahydro-2,5-dioxo-3,4-furandiyl)( I-phenylethylene)]
Acetone
Tetrahydrofuran
Poly[sulfonyl(bicycloheptene)] Chloroform
Cyclohexane
Poly[sulfonyl(butylethylene)] Acetone
Benzene
Chloroform
Dioxane
Hexylchloride
Butanone/2-propanol
(29.8/70.2, v/v)
(37/63, v/v)
Dioxane/hexane
(40/60, v/v)
Poly[sulfonyl( 1-methyl-1-propylethylene)]
Chloroform
Butanonel2.propanol
(39.5J60.5, v/v)
Butanone/hexane
(35.4164.6, v/v)
Poly[sulfonyl(phenyleneoxyphenylene)]
Dimethylformamide
Poly[sulfonyl(phenylethylene)] Tetrahydrofuran
3.11. OTHER COMPOUNDS
30
30
30
30
3 0 8.69
3 0 5.07
25 1.58
25 3.05
2 0 5.9
25 8.9
25 5.8
25 6.2
13 (0) 33
8 (0)
53
24 (8)
20 m
65
2 0 5 . 9
22.5 (6) 91
11.5 (8)
25 33
3 0 3.89
Poly(di-n-hexylsilane) Tetrahydrofuran 25
Poly(oxy-l,4-phenylene-oxy-l,4-phenylene-N-phenylimine-1,4-phenylene)
Tetrahydrofuran 25
12.4
7.5
26.1
13.4
53
91
17.0
63.4
Poly[oxythiocarbonyloxy-1,4-phenylene(methyl)phenylmethylene-1.4-phenylene]
Chloroform 25 71.0
Dichloromethane 25 1 4 1
1,4-Dioxane 25 153
Tetrahydrofuran 25 61.7
Poly[tran.~-bis(tributylphosphine)platinum-1,4-butadiynediyl]
Heptane 25 Wormlike
/
0.57 ?
0.65 ?
0.68 ?
0.74
7
0.81
7
0.506 5
0.512 5
0.552 5
0.69 6
0.77 6
0.64 6
0.69 6
0.74 6
0.81 6
0.79 4
0.73 4
0.74 7
0.70 5
0.75 6
0.76 5
0.55 5
0.50 6
0.50 6
0.50 7
0.81 6
0.50 6
0.50 6
0.64 6
0.78 5
0.672 7
0.617 8
0.60
0.55
0.50
0.61
Cyl i nder
Tetrahydrofuran 25
Poly[tmns-bis(tributylphosphine)platinum-l,4-phenylenediethynylene]
Tetrahydrofuran 25
Poly(hexamethylenedimethylammonium bromide)
Aq. KBr (0.4 M) 25
Poly(hexamethylenedimethylammonium chloride)
Aq. KCI (0.4M) 25
6.5 x lo- 1.7
2.0 x 10-e 1.7
62.2 0.58
1.02 1.00
?
?
?
?
?
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
3-8 O S 831
4-56 S D B 5 1 3
LLS
LLS
LLS
LLS
LLS
9 5 4
9 5 4
9 5 4
9 5 4
9 5 4
21-111
21-111
21-111
L S
L S
LS
B
B
B
5 0 4
5 0 4
5 0 4
20-71 LS B 505
20-71 LS B 5 0 5
20-71 LS B 5 0 5
20-71 LS B 5 0 5
13-75 O S A 5 0 6
13-75 OS A 5 0 6
27-227 L S D 8 4 0
27-227 LS D 8 4 0
5-60 LS, SD B 4 3 7
9-107 OS .%R 4 3 8
7-54 OS A,R
4 3 9
9-107 OS A 4 3 8
lo-60 LS, SD B 4 3 7
7-54 OS A 4 3 9
7-54 OS A 4 3 9
9-107 OS A 4 3 8
4-50
4-50
O S
OS
A
A
4 3 9
4 3 9
4-50 OS A 4 3 9
3-25 L S C 841
15-40 OS A 4 4 0
18-960 LS B-D 9 9 5
0.58-10 LS 9 9 3
1.5-14.2 OS, SEC
1.5-14.2 OS, SEC
1.5-14.2 OS, SEC
1.5-14.2 OS, SEC
9 9 2
9 9 2
9 9 2
9 9 2
4-10
1 . 3 3 5
1.3-3
G P C
8 3 4
835
G P C 835
LS
LS
8 4 4
844
Viscosity - Molecular Weight Relationships of Cellulose and Derivatives, Polysaccharides VII / 43
TABLE 4. CELLULOSE AND DERIVATIVES, POLY(SACCHARIDES) (See also table Properties of Cellulose Materials)
Polymer Solvent
Temp.
(C)
K (x 103)
(mW
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-q Method(s) Remarks Refs.
(Acetoxypropyl) cellulose Dimethyl phthalate
Amylose Dimethyl sulfoxide
Ethylenediamine
F o r m a m i d e
Water
Acetone/dimethyl sulf-
oxide (43.5/56.5, v/v)
Aq. KC1 (0. 33 M)
Amylose triacetate
( 0. 50 M)
Aq. KOH (0. 15 M)
( 0. 2 M)
(0. 5 M)
(IM)
Aq. NaOH (0.5 M)
Chloroform
Methyl acetate
Amylose tributyrate
Amylose tricarbanilate
ChlorofornVcyclohexane
(X0/20, v/v)
(SO/SO, v/v)
Methanol/nitromethane
(70.7129.3, v/v)
(50/50, v/v)
(25175, v/v)
Nitromethane/propanol
(43.31X.7, v/v)
(50/50, v/v) i
But anone
Carbon tetrachlotide
Ethyl acetate
Tetrahydrofnran
Acetone
Di oxane
Di oxane
Pyr i di ne
Amylose tricarbethoxymethylcarbamate
Acetone
Amylose tripropionate Ethyl acetate
Tetrahydrofuran
Amylose, carboxymethyl Aq. NaCl
-, sodium salt ( 0. 35 M)
(0.5 M, pH 8)
2 5
1 0 5
150
2 0
2 5
2 5
2 5
2 5
2 0
2 5
2 0
20 (0)
2 2 . 5
25 ((1)
25 (0)
25 (0)
2 5
2 5
2 5
2 5
2 0
3 0
3 0
5 0
2 5
2 2 . 5
2 5
3 0
3 0
5 0
3 0
3 0
30 (0)
3 0
3 0
25 PJ)
2 5
2 5
2 5
2 5
2 5
2 0
2 0
-
2 0
2 5
2 0
2 5
2 5
3 7 . 5
3 5
Amylose, diethylaminoethyl
-, hydrochloride
Ar gi ni c aci d, s odi um s al t
(0.78 M; 0.024 NaNa) 3 5
Aq. NaCl 3 5
(0.78 M; 0.02% NaN 2)
Aq. NaCl (0.2 M) 2 5
- 0. 88 6
- 0. 75 5
- 0. 57 6
(Wormlike behavior)
3. 97
1. 25
1 5 . 1
3 0 . 6
1 5 . 5
2 2 . 6
3 0 . 5
1 3 . 2
8 3 . 1
3 3 . 9
1 1 2
115
6 1 . 1
8. 36
6 . 9 2
8. 50
1. 18
3. 65
1. 06
4 . 9 0
5. 20
5. 60
8. 50
3. 58
2. 18
9. 93
8. 71
4 . 6 4
7. 41
9 8 . 4
6. 49
10. 23
9 1 . 6
1 7 . 0
3. 39
3. 46
5. 59
1. 66
0. 814
0. 906
0. 82
0. 87
0 . 7 0
0. 64
0. 70
0. 67
0. 62
0. 68
0 . 5 1
0. 59
0. 50
0. 50
0. 50
0. 77
0. 78
0. 76
0. 89
0. 85
0. 92
0. 85
0. 83
0. 80
0. 73
0. 78
0. 82
0. 76
0. 76
0. 85
0. 79
0. 51
0. 75
0. 76
0. 50
0. 66
0. 77
0. 79
0. 74
0. 86
0. 90
0. 92
(Wormlike behavior)
0. 589 0. 92
2. 00 0. 83
2 7 . 6 0. 63
3 1 . 3 0. 58
2 4 . 8 0. 61
2 5 . 2 0 . 6 4
2 0 9 0. 53
3 7 . 1 0. 61
8 2 . 8 0. 55
7. 97 1 . 0
-
9
5
5
6
7
5
6
5
-
1 2
4
4
-
1 2
6
6
4
4
4
4
4
4
4
7
-
II
1 3
8
6
6
6
5
-
-
-
-
1 4
-
-
-
-
-
-
-
-
1 6
-
-
-
3
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
2 6
2 5
-
2 0
2.2-43
7.6-43
2.2-43
2-217
22-310
8-180
27-220
31-310
2-157
8-180
36-217
2-157
16-230
16-230
27-220
S-180
16-229
27-220
31-310
2-217
12-480
21-102
21-102
7-19
14-310
4-100
4-100
21-102
21-102
21-102
21-102
21-102
21-102
21-102
14-310
14-310
7-160
7-160
7-160
7-160
4-490
4-360
21-290
4-360
30-244
9-380
1-61
1-61
5-21
7-29
4 - 2 3
5-19
S E C , L L S
S E C , L L S
S E C , L L S
LS
LS
LS
LS
LS
LS
LS
L S
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
S D
LS
LS
LS
LS
L S
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LV
OS , GP C
OS , GP C
LS
OS
LS
LS
OS
A- C
A- C
A- C
B
B
B
B
B
B
B
B
C
B
A
A
D
B
W
BC
A
A
A
A
A
A
A
B
B
B
B
B
B
B
B
A
B
B
B
B
B
A
B
B
B
C
1001
1001
1001
5 1 7
518
5 1 9
5 2 0
5 1 8
5 1 7
5 1 9
5 1 7
5 1 7
5 2 1
5 2 2
5 2 0
5 2 3
5 1 9
5 2 2
5 2 0
5 1 8
5 1 7
5 2 4
5 2 5
5 2 5
5 2 6
5 19, 527
8 4 6
8 4 6
5 2 5
5 2 5
5 2 5
5 2 5
5 2 5
5 2 5
5 2 5
5 1 9
5 1 9
8 4 7
8 4 7
8 4 7
8 4 7
5 2 8
5 2 8
9 9 7
5 2 8
848, 849
5 2 9
8 5 0
8 5 0
6 0 9
5 3 0
5 3 1
5 3 1
5 3 2
References page VII - 68
VII / 44 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 4. contd
Polymer Sol vent
Temp. K (x 103)
(C) (mW
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-4) Method(s) Remarks Refs.
Cellulose, see also table Properties of Cellulose Materials
Cadoxen
Cuprammonium
Cellulose acetate
DS a 0 . 4 9
DS 1.75
Cellulose acetate butyrate
Cellulose diacetate
AC. a c i d c ont e nt , 55. 5 wt . %
Cupriethylene
NJ-Dimethylactamide/
97~ LiCl
N,N-Dimethylacetamide
Dimethyl s&oxide
Formamide
Wa t e r
NJ-Dimethylacetamide
Acetic acid
Acetone
Ethyl acetate
Nitromethane
Acetone
Dimethylacetamide
NJ-Dimethylactamide
Cellulose nitrate
Cellulose triacetate
Tetrahydrofuran
Trifluoroacetic acid
Tetrahydrofuran
Acetone
Chloroform
o-Cresol
Dichloromethane
Dimethylacetamide
Tetrachloroethane
Trifluoroacetic acid
Acetone/water
(80/20, v/v)
Cellulose tributyrate
EthanoUmethylene
chloride (20/80, v/v)
B u t a n o n e
Tributyrin
Cellulose tricarbanilate
Dodecane/tetralin
(75125, vlv)
Acetone
Acetone
Ani sol e
But anone
Cyclohexanol
Cyclohexanone
2 5 3 3 . 8 0. 77
2 5 3 8 . 5 0. 76
2 0 105 0. 66
2 5 8 . 5 0. 81
2 5 1 3 . 3 0. 905
3 0 0. 128 1. 19
5
4
9
-
3 2
9
5
20-100 S D
1.0-3.4 S E , L S
2-25 O S
8-96 O S
1-54 O S
12.5-70 LLS
2 5
2 5
2 5
2 5
2 5
2 5
2 5
3 0
3 0
2 5
2 5
3 0
1 9 1 0. 60
171 0. 61
2 0 . 9 0 . 6 0
2 0 . 9 0. 60
9 5 . 8 0. 65
1 4 . 6 0. 83
1 3 . 7 0. 85
1 1 . 3 0. 83
1 6 . 5 0. 78
133 0. 616
3 9 . 5 0. 738
1 1 . 0 0. 848
(Wormlike behavior)
1 0
10
1 0
1 0
7
5
1 1
4-15 L S
4-15 L S
4 - 1 5 L S
4 - 1 5 L S
3-14 LS
l-21 OS
l-21 O S
3-14 L S
3-14 LS
6-27 L S
6-19 LS
3.58-17.0 S E
2 5
2 5
2 5
2 0
2 5
2 5
2 5
2 5
2 0
2 5
3 0
3 0
3 0
2 0
2 5
2 5
2 5
2 0
5 1 . 3
5 2 . 7
2. 38
1 4 . 9
8. 97
3 3 . 0
2 8 . 9
2 . 2
4 5 . 4
1 4 . 4
4 . 5
6. 15
2 4 . 7
2 6 . 4
3 9 . 3
3 9 . 6
2. 65
0. 688 6
0. 696 5
0.80-0.84
-
1 . 0 5
0. 82 8
0. 90 1 4
0 . 7 6 0 9
0. 725 9
0. 95 13
0. 649 7
0 . 8 0 0 6
0 . 9 5
0 . 9 5
0 . 7 0 4 7
0 . 7 5 0 IO
0. 662 IO
0 . 7 0 6 8
1 . 0 9
9
7 - 3 0 LS A 8 5 4
6 - 1 9 LS A 8 5 5
2.6-27 LLS, OS D 1 0 0 4
2 - 1 4 S D B 5 3 9
2-39 OS A(?) 5 4 0
1-18 OS RR 5 4 1
2 - 3 0 OS C 5 3 5
8-69 L S A 8 5 5
1-13 LS A 8 5 6
8-69 LS A 8 5 5
lo-18 L S A 8 5 7
3-18 LV C 5 4 2
3-18 LV C 5 4 2
6 - 6 9 LS A 8 5 5
6 - 6 9 LS A 8 5 5
6 - 6 9 L S A 8 5 5
6 - 6 9 LS A 8 5 5
2-11 S D B 5 3 9
2 5 2 1 . 0
1 3 . 9 0 . 8 3 4
0. 803
-
2
2 - 3 0
- 30
3 0 4 . 3 0. 87 7 6 - 3 2
3 0 1 8 . 2 0. 80 7 8-32
0 5 . 3 0. 87 4 6 - 3 2
2 5 5 . 6 0. 85 4 6 - 3 2
5 0 6 . 1 0. 82 4 6-32
7 0 6 . 2 0. 80 4 6-32
130 (0) 8 2 0. 50 3 11-21
0
2 0
2 5
3 5
2 5
1. 10
4 . 6 6
1. 43
1. 31
0. 93 6
0. 84
-
0. 9 1 6
0. 90 6
Not const 9
-
1 6
-
31-220
7-270
31-220
31-220
22-770
94 (0)
1 5
3 0
73 (0)
2 5
3 5
(Wormlike behavior)
1 3 0 0. 50
2. 02 0. 89
3. 42 0. 84
1 5 6 0 . 5 1
1. 91 0. 86
2. 02 0. 85
1 0
1 0
5
31-220
21-110
21-110
21-110
31-220
31-220
O S
OS
LS
OS
LS
LS
LS
LS
OS
LS
LS
LS
LS
LS, GPC
LS
LS
LS
LS
LS
LS
CR
B-C,R
C
C
B - C
-
5 3 3
5 3 4
5 3 5
5 3 6
5 3 7
1000
B
B
B
B
B
B-C
B-C
A
A
A- B
851
851
8 5 1
8 5 1
8 5 2
5 3 8
5 3 8
8 5 3
8 5 3
8 5 4
8 5 5
1007
C
C
5 3 5
5 3 1 5
RR 5 4 3
C- D 5442
B 5 4 3
B 5 4 3
B 5 4 3
B 5 4 3
C- D 544,2
B- C 5 4 5
B 5 2 8
B-C, R 5 4 5
B- C 5 4 5
B- C 9 9 6
B- C 5 4 6
D 8 5 8
D 8 5 8
D 8 5 8
B- C 5 4 5
B- C 5 4 5
TABLE 4. contd
Viscosity - Molecular Weight Relationships of Cellulose and Derivatives, Polysaccharides VII / 45
Polymer Sol vent
Temp. K (x 103)
(f-3 bk)
No. of samples Mol. wt.
range
a Fr. W.P. (x10-4) Method(s) Remarks Refs.
Cellulose trihexanoate
Ce l l ul os e t r i ni t r a t e
Dioxane
Pyr i di ne
Tetrahydrofuran
Dimethylformamide
Dioxane
Acetone
(N content, 12.9 wt.%)
(N content, 13.9 wt.%)
Butyl acetate
Butyl formate
Cyclohexanone
Ethyl acetate
Cellulose trioctanoate
(Cyanoethyl)(hydroxypropyl)
cel l ul ose
Et hyl cel l ul os e
Ethyl hydroxyethyl cellulose
Hydroxyethyl cellulose
DS 0.88
Methyl cellulose
DS 1.74
Ethyl butyrate
Ethyl formate
Ethyl lactate
2-Heptanone
Methyl acetate
Nitrobenzene
Pentyl acetate
Dimethylformamide
y- Phenyl pr opanol
Toluene
Tetrahydrofuran
Acetone
Benzene
But anone
Butyl acetate
Chloroform
Ethyl acetate
Methanol
Nitroethane
Wa t e r
Cadoxen
Wa t e r
Aq. HCl (4 M)
Wa t e r 2 5
Aq. HCl (4M) 2 5
2 0
2 5
3 5
50
1 5
2 1
3 0
7 0
2 0
2 5
41 (0)
3 5
2 0
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
3 0
2 5
2 5
2 5
2 5
2 5
2 5
2 5
1 4 0 (0)
48 (@
3 0
2 5
2 0
2 0
2 5
6 0
2 5
6 0
2 5
6 0
2 5
4 6
2 5
6 0
2 5
2 5
6 0
2 5
2 5
2 5
2 5
4 . 2 0 0. 88
0. 813 0. 97
0. 865 0. 96
0. 849 0. 95
0. 89 0. 97
0. 95
1. 04 0. 95
2. 51 0 . 8 6
3. 46 0. 86
-
Not const
( Wor ml i ke behavi or )
2 4 5 0 . 5 0
125 0. 57
2. 80 1. 00
1. 69 1. 00
1. 66 0. 86
1 0 . 8 0. 89
5. 70 0. 90
6. 93 0. 91
7 . 0 0 0. 933
1 1 . 0 0. 91
2 3 . 5 0. 78
5. 68 0 . 9 6 9
2 3 0 . 8 1
2. 24 0 . 8 1 0
3 . 8 1. 03
8 . 3 0 . 9 0
1. 66 0. 86
2. 50 1. 01
3. 64 1 . 0
3 0 0. 79
1 2 . 2 0. 92
5 . 0 0. 93
1 8 . 3 0. 835
6 . 1 0. 945
1 . 1 1. 04
113 0. 50
1 2 9 0. 50
1 7 . 3 0. 70
1. 14 0. 99
( Wor ml i ke behavi or )
1. 51 1. 05
1. 34 1. 07
2 9 . 2 0. 81
3 5 . 8 0. 78
1 8 . 2 0. 84
2 6 . 7 0. 79
1 4 . 0 0. 87
1 8 . 1 0. 83
1 1 . 8 0. 89
9 . 3 0 . 9 0
1 0 . 7 0. 89
1 4 . 0 0. 85
5 2 . 3 0. 65
4 . 2 0. 96
2 2 . 6 0. 79
3 7 0. 80
1 7 . 4 0. 79
9. 53 0. 87
-
5
5
4
-
1 1
-
-
1 2
7
7
1 3
1 1
6
4
4
6
9
3 3
6
9
6
6
3 3
6
7
6
7
6
1 0
6
6
6
6
3
3
6
8
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
4
4
5
1 5
-
-
1 5
10
-
1 0
1 0
1 2
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
7-270 L S
31-220 LS
31-220 L S
31-94 LS
21-110 LS
l-11 S D
21-110 LS
21-110 LS
7-270 LS
2.7-370 L S , G P C
6-130 LS
4-130 LS
l - 2 5 0 S D
8-265 LS
68-250 LS
4 - 3 2 LS
15-200 LS
8-400 LS
5 - 5 0 OS
3-100 OS
7 - 2 6 OS
5 - 5 0 OS
7-26 OS
7 - 2 2 OS
3-100 OS
7 - 2 6 OS
68-250 LS
4 - 5 7 LS
5 - 5 0 OS
7-26 OS
3-65 OS
7 - 2 6 OS
7 - 2 2 OS
7 - 2 2 OS
7 - 2 6 OS
lo-32 OS
8-32 OS
8-35 OS
5.4-27 L L S , S E C
1.1-8 S D
1.1-8 S D
4 - 1 4 OS
4 - 1 4 OS
4 - 1 4 OS
4 - 1 4 OS
4 - 1 4 OS
4 - 1 4 OS
4 - 1 4 OS
4 - 1 4 OS
4 - 1 4 OS
4 - 1 4 OS
10-41 LS
4 - 1 4 OS
4 - 1 4 OS
5 - 1 8 S D , L S
8-61 LS
8-63 LS
[q] = 1.2 DPt8 (DP,; weight-average degree of polymerization)
3 1 6 0. 55 - 5 12-57 LS
[a] = 1.6 DPts6 LS
B 5 2 8
B- C 5 4 5
B- C 5 4 5
B- C 5 4 5
D 8 5 8
B 8 5 9
D 8 5 8
D 8 5 8
B 5 2 8
B- C 9 9 6
C- D 5 4 7
C- D 5 4 7
B 5 4 8
B- C 5 4 9
C 5. 50
C- D 5 5 1
AR 5 5 2
AR 5 5 2
B- C 5 3 5
B-C 5 3 7
B-C 5 5 3
B- C 5 3 5
B- C 5 5 3
B-C 5 5 4
B-C 5 3 7
B- C 5 5 3
C 5 5 0
B- C 5 5 5
B- C 5 5 6
B-C 5 5 3
B- C 5 3 7
B- C 5 5 3
B- C 5 5 4
B- C 5 5 4
B- C 5 5 3
B- C 5 4 4
B- C 5 4 4
B- C 5 4 4
C- D 1 0 0 2
A 5 5 7
A 5 5 7
B- C 5 5 8
B- C 5 5 8
B- C 5 5 8
B- C 5 5 8
B- C 5 5 8
B- C 5 5 8
B- C 5 5 8
B- C 5 5 8
B- C 5 5 8
B- C 5 5 8
B- C 5 5 9
B- C 5 5 8
B- C 5 5 8
B 5 6 0
B 5 6 1
B 5 6 1
B 5 6 2
C- D 5 6 3
B 5 6 2
References page VII - 68
VII / 46 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 4. contd
Polymer Sol vent
Temp. K (x 103)
(C) (mhd
No. of samples Mol. wt.
range
a Fr. W.P. (x 10-q Method(s) Remarks Refs.
Sodium carboxymethylcellulose Aq. NaOH
DS 0.2-1.0
DS I 0.96
DS 0.62-0.74
DS 1.06
Sodium cellulose xanthate
Dextran
linear fraction
branched fraction
Guaran triacetate Acetonitrile
Hyaluronic acid Aq. HCI (0.1 M)
Aq. NaCl (0.2 M)
(0.5 M)
Wat er Pul l ul an
Salep glucomannan triacetate
Shizophyllan (P-1,3-o-glucan)
Xanthan
(0.78 M)/NaNj(O.l M) 35 37 0.61 6
-
7-30 OS, LS
Cadoxen
Aq. HCl (4M)
Aq. NaCl (0.001 M)
25
25
33.4 0.73 - 5 5-106
[q] = 0.97 DPkv3
LS
(0.01 M)
(0.1 M)
(0.005 M)
(0.01 M)
(0.05 M)
(0.2 M)
Aq. NaOH (1 M)
For mami de
Wat er
Methanol/water
(40.5/59.5, v/v)
Wat er
Ni t r o e t h a n e
Dimethyl sulfoxide
Aq. NaOH
Cadoxen
Aq. NaCl (0.1 M)
25 0.100 1.40 8 - 4.5-35
25 0.646 1.20 3 - 4.5-35
25 12.3 0.91 8 - 4.5-35
2 5 7.2 0.95 4 - 14-106
25 8.1 0.92 4 - 14-106
25 19 0.82 4 - 14- 106
25 4 3 0.74 4 - 14-106
0 [r/] =1.67 DP;8z +0.62 DS2.j-0.20 DS,DPO,
DS I, Degree of substitution at the i( = 2, 3 or 6) positions in glucose unit
S D
S D
S D
LS
LS
LS
LS
25 165 0.49
5 -
0.2-3.2 OS C 5 6 8
25 97.8 0.50
IO -
2-10 LS CR 5 6 9
25 49.3 0.60
10 -
0.04-4.5 E A C 5 7 0
5 0 39.3 0.61
6 -
0.2-3.2 OS C 568
34 (f3
10.3 0.25 - 6 7-51 LS C 8 6 0
25
32.7
25
25
25
25
25
25
25
3 0
- 0 . 2 0
2.62 0.87
311 0.52
27.9 0.763
22.8 0.816
31.8 0.777
22.1 0.66
- 0.65
This relation
not followed
0.69
- 1.8
- 1 . 1
- 0.87
0.70
0.17 1.14
Double strand helix
9 -
6 -
4 -
5
5 -
8 -
5 -
9 -
8 -
I1 -
6 -
4 -
3 -
5 -
8 0 LS C
7-85 LS A
206-534 LS B
7-103 LS A
7-103 LS A
11-103 LS A
11-236 LS A
0.53-102 S E A
0.06-0.4 LS A-B
5 6 9
571
5 7 2
5 7 2
573
573
573
998
1003
5 7 4
25
25
25
25
25
25
25
3-190 SE, LS
1 O-25 LS
300-570 LS
3-15 LS
20-360 LS
30-700 LS
3-360 LS
A
A
A
862,863
863
863
865
865
866
865
B 531
C 5 6 4
B 5 6 2
C-D 565
C-D 565
C-D 565
CD 5 6 6
C-D 5 6 6
C-D 5 6 6
C-D 5 6 6
C 567
DS : Degree of substitution.
TABLE 5. MISCELLANEOUS
Polymer
Imogolite
Sol vent
Aqueous acetic acid/
0. 02 wt . % NaN3
No. of samples Mol. wt.
Temp. K ( x 103) range
(Cl Wg)
a Fr. WP M(xlO-4) Method Remarks Ref.
IllI=
6
30 9.35 x 10~0M2/ln M (sonic wave) - 59-208 LS A 1005
D. CALCULATED UNPERTURBED DIMENSIONS OF FREELY ROTATING CHAINS
r,f/M 1/Z
Chai n type (nm mol //g!) Refs.
Poly(methylene) chain 0. 308/ 1W, ): ~ 0. 218/ 1n' / ~ 2
*Amylosic chain 0. 426/ M; : 2 0. 191/ m' / 2 518
Cellulosic chain o.790/b4,,i2 0.353/m Q 620
Gutta-percha (tram polydiene) 0. 580/ M; / 2 0. 290/ m' i 2 620, 621
Natural rubber (cis poiydiene) 0. 383/ M, ' , / ' 0. 201/ m"~ 620
Poly(peptide) 0, 383/ M, j J 2 0. 221/ m' J 2 620
Unperturbed Dimensions of Linear Polymers: Main-Chain Acyclic Carbon Polymers VII / 47
E. UNPERTURBED DIMENSIONS OF LINEAR POLYMER MOLECULES
TABLE 6. MAIN-CHAIN ACYCLIC CARBON POLYMERS
Polymer Sol vent
Temp.
((3
Sk/MY
(x104) Ko ror/M/
or ap (x10) ro/M12 (x104)
bm) Wg) x lo4 (nm) (nm) c = ro/rm C, = ri/n12 Method(s) Refs.
6. 1. POLY(DIENES)
Poly(butadiene)
I 00%~cis Di oxa ne
98%-c& 2%.1.2 Isobutyl acetate
95%.cis, 4%. I ,2 2.Pentanone
3-Pentanone
92%-c& 5%.I,2 Benzene
7I%-rrans, 25%-l,2 Cyclohexane
79%-tram, 21%.1,2 Cyclohexane
97%.tram, 3%-1,2 Cyclohexane
100%~cis Various solvents
Undi l ut ed
100%~mans Decalin
Undi l ut ed
I ,4-walls Oligomeric
1,4-Poly(butadiene)
linear Di oxa ne
Tol ue ne
PoIy( I-butenylene-co-vinylethylene) 43%-I,2
1,4-Dioxane
Poly(chloroprene) 85%.rrans Benzene
Bu t a n o n e
Cyclohexane
Butanone
Poly(2,3-dimethylbutadiene) 85%-tram-1,4, 3%-I,2
20.2
20.5
59.1
10.3
32
25
2 0
4 0
5 0
5@90
5.5
25.0-105.8
12.1
35
15.7
25
25
45.5
25
Poly(isoprene) lOO%-cis
100%~rrans
trans. I,4
11%~cis, 22%-rrans,
7%-3,4
Cyclohexane/n-propanol 2 5
Benzene; 2-pentanone - 2 0
Diisopropyl ether 22
2-Pentanone 14.5
Undi l ut ed - 10 to 70
30-70
Propyl acetate 6 0
Dioxane 47.7
Undi l ut ed - 6 0
Benzene, cyclohexane,
Tol ue ne 30
Hexane 3 0
Cyclohexane; dioxane; 35
4-methyl-2-penianone;
toluene .
- 205 9 2 0 5 4 7
- 185 8 8 0 5 4 7
- 157 835 5 4 6
- 152 825 5 4 6
- 150 zt 20 820 i 40 5 4 5
- 3OOzt40 1030f50 7 0 2
- 28Oi25 1010130 7 4 2
2OOf30 935i40 7 6 8
dln ri/dT = 0.4 x 10m3 (deg-)
dln ri/dT = -0.6 x lo- (deg-)
dln ri/dT = -0.10 x 10-j (deg-)
- 155
- -
- 1 5 0
-
- 173
-
- 115f20 750 i 80 5 3 5
- 113 7 5 0 5 3 5
- 107 7 5 5 5 3 5
3 1 3 7 5 0 5 3 5
- 2 2 6
- -
- 130f20 810145 4 8 5
0.76 - 8 4 7 4 8 5
119
din ra/dT = 0.41 x 10m3 (deg-)
dln ri/dT = 0.56 x lo- (deg-)
2 3 2 9 7 0 7 0 3
191 9 1 0 703
dln ri/dT = -0.27 x 10m3 (deg-)
198 8 8 4 -
- 135 7 7 8
-
- 126 7 6 6
-
Poly(isopropenylethylene-co-I-methyl-l-vinylethylene) 20-25%.1,2,70-75%-3,4
2-Octanol 30.5 -
Poly[isoprene-block-poly(styrene)], Ak-B,
k/n, (75125, w/w) 4.Methyl-2.pentanone; 3 0 -
t o l u e n e
k/n, (50/50, w/w) Cyclohexane; dioxane: 35
4.methyl-2.pentanone;
t o l u e n e
Bu t a n o n e 44 -
Cyclohexane 4 6 -
4.Methyl-2.pentanone 3 0 -
Tol ue ne 3 0 -
k/n, (25175, wlw) Cyclohexane; dioxane; 35 -
4.methyl-2.pentanone;
t o l u e n e
Poly(methylbutylene) 43%.I,2 n-Hexyl acetate 60.9 -
Poly( I-methyl-l-butylene-co-isopropenylethylene) 51%-1,4,49%-3,4
2-Octanol 41.3 -
102 -
128 7 8 2
110 741
116 7 5 7
116 7 5 6
124 773
I15 7 5 4
97 711
189 -
9 6 -
* References in parentheses include data used for the calculations of end to end distance in Ref. 3.
-
-
-
1.68
1.61
1.53
1.51
1.50 IC 0.08
1.45 i 0.08
I .36 f 0.05
1.22 * 0.07
1.63
1.23
-
-
-
1.4010.15
1.40
1.41
1.40
-
1.67 i 0.09
I .74
1.38
1.30
1.26
1.11
-
-
-
-
-
-
5.15 VT
4.75 V T
4.3 VT
4 . 2 VT
4.15 VG
7.3 VG
6.9 VG
5.4 VG
4.9 V T
S T
5.8 VA
S T
VG
6.15 VG
- VG
6.0 V T
5.6 VG
5.6 V T
5.65 V T
5.6 L T
8.59 f 0.14 VG,VT
5.0
5.5
4.7
7.2
6.35
5.99
4.64
-
7.9
-
6.2
5.3
VT,VG
X.5
V T
S T
ST,VT
V T
V T
S T
VG
VG
VG
V T
VG
VG
V T
VG
VG
VG
VG
VG
VG
I9
1 5
17
17
3(20)
3(22)
X23
2 4
6 2 2
6 2 2
6 2 3
6 2 3
8 8 8
8 8 9
8 8 9
8 9 0
3(32,33)
35
3 4
6 2 4
8 8 3
3,37
6 2 5
6 2 6
6 2 6
6 2 7
37
19
6 2 3
8 9 4
8 9 4
7 8 6
8 9 0
8 6 7
7 8 6
8 6 7
8 6 7
8 6 7
8 6 7
7 8 6
8 9 0
8 9 0
References page VII - 68
VII / 48 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 6. contd
Polymer Sol vent
Temp.
(C)
Soz/MY2
(x104) Ko rQf/M/2
or lip (x10) rolM12 (x104)
Mm) bUg) x lo4 (nm) (nm) o = rofrm C, = r:fn12 Method(s) Refs.
6. 2. POLY(ALKENES), POLY(ACETYLENES)
Poly( 1 -butene)
atactic
i s ot act i c
Poly(ethylene)
2-Octanol 23.6
Tetrahydrofuran 25
Anisole; ethylcyclo- - 7 0
hexane
Nonane 35
Phenyl ether 141
Undi l ut ed 140-200
Ani s ol e 89
Nonane 8 0
Phenet ol e 64.5
Phenyl ether 148
Undi l ut ed 140-200
160
1- Chl or onapht hal ene; t et r al i n;
p-Xylene -100
Decalin 140
Bis-Z-ethylhexyl adipate 145
145
Bi phe nyl 127.5
Dodecanol 137.3
138
Diphenylmethane 142.2
Decanol 153.3
Diphenyl ether 161.4
Oct anol j 180.1
Bi pbe nyl 127.5
Diphenylmethane 142.2
Dipbenyl ether 163.9
Undi l ut ed; di l ut ed 14ck190
with triacontane;
dotriacontane
Hexadecane 140
low pressure Bi phe nyl 130
Decalin 120
1,2,4-Trichlorobenzene 135
Poly(ethylene-co-isopropylethylene)
n-Hexyl acetate 65
Poly(ethylene-co-propylene) Benzene 19.0
21.4
n-Decyl acetate _ 5.0
n-Heptyl acetate 38.0
n-Octyl acetate 27.0
Poly(isobutene) Ani s ol e 105
Benzene 2 4
Benzene 25
Phenetole 86
Heptane/propanol 25
(80/20, v/v)
Undi l ut ed; di l ut ed 6 0
with hexadecane
Poly(isopropylethylene-co-l-methyl-l-ethylethylene)
2-Octanol 26.2
Poly( 1-methylbutylene-co-isopropylethylene)
2-Octanol 53.3
Poly(l-octene) Bromobenzene 25
Cyclohexane 30
Phenet ol e 50.4
Poly(pentenamer)
80-85%-trans.
19-12%-k Isopentyl acetate 38
- 7 4
-
- 7 4
-
- 123flO 775525 4 2 7 1.82 f 0.05
590*50 - 1180f70 4 2 7 2.76 f 0.20
- 104 7 4 7
- -
dln ri/dT = (0.5 i 0.04) x 10m3 (deg-)
111 7 6 3 -
510f50 - 1290f90 4 2 7 3.00 f 0.20
- 113 7 6 7 -
- 103 7 4 4 -
-
dln ri/dT =(0.09 zk 0.07) x 10e3 (deg-)
dln ri/dT = -0.1 x 10m3 (deg-)
2 3 0 950 + 40 5 8 2 1.63 k 0.08
1070 5 8 2 1.84
- 2 2 5 940*40 5 8 2 1.61
6901+ 100 - 13201t 150 5 8 2 2.27 f 0.26
- 323 1085 5 8 2 1.87
- 307 1070 5 8 2 1.84
- 31617 1080 5 8 2 1.86
- 315 1080 5 8 2 1.86
3 0 2 1065 5 8 2 1.83
295 1060 5 8 2 1.79
- 2 8 6 1040 5 8 2 1.79
- 3 3 0 1095 5 8 2 1.88
- 3 2 2 1085 5 8 2 1.87
3 0 9 1070 5 8 2 1.84
dln ri/dT = -(1.15 f 0.1) x lo- (deg-)
dln ri/dT = -1.2 x 1O-3 (deg-)
3 0 2 1130 -
3 6 0 1200 - -
- 3 6 0 1200
-
- 188
-
- 2 0 6 9 3 8
-
- 203 9 3 3
-
- 2 0 3 9 3 3
-
- 194 9 1 9 -
- 198 9 2 5
-
- 91f5 700120 4 1 2 1.70 i 0.05
- 107f5 740 f 20 4 1 2 1.80 i 0.05
- 105 7 4 9
-
- 91*5 7OOf20 4 1 2 1.70 f 0.05
3 9 0 166 7 8 0 4 1 2 1.9
dln ri/dT = -(O.l i 0.05) x 10m3 (deg-)
83 -
- 91
-
5 0 570 i 50 291 1.96f0.15
- 100 710160 291 2.44 + 0.20
6 5 625 i 30 291 2.14ztO.10
- 2 3 4 991 - 1.26
5.3 VG 8 9 6
5.3 VG 8 9 6
6 . 6 VT, VG 3(81)
15.1
-
-
18.0
-
-
L T 81
V T 7 0 0
S T 6 3 3
V T 7 0 0
L T 81
VT 700
V T 700
S T 6 3 4
S T 6 3 4
5.3 VG
6.8
5.2
10.3
7 . 0
6.8
6.9
6.9
7.6
6 . 4
6 . 4
7.1
7 . 0
6.8
VA
V T
L T
VT
VT
VT
VT
VT
VT
VT
VT
VT
VT
S T
3(61,67,
7 4 )
65
6 3 0
6 3 0
5 8
5 8
6 9
58
6 5
5 8
5 8
631
631
631
6 2 9
-
VA 6 3 2
V T 703
VG 703
VG 703
6.3 VG 8 9 0
6.85 VG 897
6.78 VG 897
6.78 VG 897
6.57 VG 897
6 . 6 6 VG 897
5.8 VT 4 9
6.5 VT 4 9
6.7 VG 1010
5.8 VT 4 9
1.2 L T 628
S T 629
7 . 2 VG 890
5 . 0
7.7
11.9
9.1
-
VG 890
VG 84
VG 84
V T 84
V T 788
TAB
-
POI]
-
POl)
a l
ir
Pal:
a
P O
6 . :
P C
:efs.*
-
8 9 6
8 9 6
3W)
8 1
7 0 0
6 3 3
7 0 0
8 1
700
7 0 0
6 3 4
6 3 4
11,67,
7 4 )
6 5
6 3 0
6 3 0
5 8
5 8
6 9
5 8
6 5
5 8
5 8
631
631
631
6 2 9
6 3 2
703
7 0 3
7 0 3
8 9 0
8 9 7
8 9 7
8 9 7
8 9 7
8 9 7
4 9
4 9
1010
4 9
6 2 8
6 2 9
8 9 0
8 9 0
8 4
8 4
8 4
7 8 8
TABLE 6. contd
Unperturbed Dimensions of linear Polymers: Main-Chain Acyclic Carbon Polymers VII / 49
Polymer Sol vent
Temp.
(a
ShJM;12
(x104) Ko riJf/M~2
or ap (x103) r~lM/~ (x104)
0) (mQ9
x 104 (nm) (nm) d = rolrm C, = riln12 Method(s) Refs.
Poly( 1 -pentene)
atactic
i s ot a c t i c
Poly(propylene)
atactic
Undi l ut ed 40-140
2-Pentanol 6 2 . 4
Undi l ut ed 86140
- 9 0
- 6 0
3-Nonanol 5 . 0
I-Octanol 7 7 . 0
Isoamyl acetate; benzene; 30
i s ot a c t i c
cyclohexane; toluene
Decalin
1Xhloronaphthalene
Cyclohexanone
Diphenyl ether
Di phenyl
Isoamyl acetate
Isobutyl acetate
Phenyl ether
Above 4 solvents
I-Chloronaphthalene;
decalin; tetralin
Diphenyl ether
s yndi ot act i c
head-to-head
94%~trans. 6%-1.2
89%~rrans, 11%-1.2
Poly(vinylethylene)
atactic
Bi phenyl
Diphenyl ether
Dibenzyl ether
Di phenyl
Phenyl ether
Above 2 solvents
Heptane
Isoamyl acetate
Cyclohexane
Cyclohexane
2-o&no1
6.3. POLY(ACRYLIC ACID) AND DERIVATIVES
Poly(acrylamide) Wa t e r
Poly(acrylic acid)
3 0
3 0
3 0
50% neutralization
l OO%- neut r al i zat i on
-, sodium salt
Poly(acrylonitrile)
( pol ymd. at - 30C)
1,4-Dioxane .
Aq. N&l C, =O.O2mol/l 30
O.lOmoYl 3 0
0. 50 mol/l 3 0
Aq. NaCI, C, =O.O2mol/l 30
0. 10 moV1 3 0
0. 50 moV1 3 0
1. 50 mol/l 3 0
Aq. NaBr (1.5M) 1 5
1 5
Aq. NaSCN (1.25 M) 3 0
Dimethylformamide 2 5
y- But yr ol act one; 3 0
135
7 4
9 2
153
1 2 9
3 4
5 8
1 4 6
-
1 4 0
145
145
1 4 5
125. 1
142. 8
183. 2
1 2 5
1 4 3
3 0
4 5
3 0
3 0
3 2 . 8
( pol ymd. at 60C)
dimethyl f or ma mi de 30
Ethylene carbonate/water 25
(85/15, w/w)
Dimethylformamide/
0.1 wt.% LiCl 2 5
dln ri/dT = (0.53 k 0.05) x 10e3 (deg-)
-
121 7 9 0 3 6 8 2. 14
din ri/dT =(0.34 f 0.04) x 10m3 (deg-)
d l n ri/dT = -0.3 x 10m3 (deg-)
dln ri/dT = -0.2 x 10m3 (deg-)
1 5 8 8 5 7 -
- 1 1 5 7 7 3
-
- 156 zk 15 835 f 25 4 7 5
- 125 f 20 755 + 35 4 7 5
1 8 2 8 8 0 4 7 5
1 7 2 8 7 0 4 7 5
1 2 0 7 6 5 4 7 5
128. 3 8 2 0 -
- 168. 5 9 0 0 -
158. 5 8 8 0 -
- 125. 6 8 2 0 -
dln ri/dT = 1.8 x 10m3 (deg-) -
- 12Ok20 765f40
- 1 3 2 7 9 0
9 4 7 1 0
370*30 - 685 i- 30
1 5 2 8 0 9
1 3 7 7 8 2
1 0 6 7 1 8
141. 0 8 5 0
- 130. 4 8 3 0
dln ri/dT = 3 x lo- (deg-)
-
-
-
-
-
-
-
-
-
-
-
-
-
1 6 4 8 3 0
1 7 2 8 4 3
8 0 6 7 4
7 0 6 4 6
1 2 0
260&40 100150
- 8 6 2
7 6 6 6 5
9 5 6 9 2
121 7 5 0
1 1 4 7 3 5
1 1 2 7 3 0
121 7 5 0
1 3 3 7 7 4
1 2 0 7 5 0
1 2 4 7 5 6
- 1 0 3 0
121 7 5 2
210* 1 5 93Ozt20
2 5 0 9 7 0
2 5 0 9 0 0
- 9 5 0
4 7 5
-
-
-
1. 61 ztO.08
-
-
5 . 2
4 7 5
4 7 5
4 7 5
4 7 5
4 7 5
4 7 5
-
-
-
4 7 5
4 7 5
1. 66
1. 49
1. 44 i 0. 07
1. 70
1. 62
1. 51
5 . 5
4. 45
4. 15
5 . 8
5. 25
4. 55
-
-
1. 75 6 . 1
1. 77 6. 25
-
1. 42 4 . 0
-
1. 36 3 . 7
- -
7 . 0
3 6 7
-
3 6 3
-
-
2.72f0.10
2. 36
1. 83
-
-
-
-
3 1 8 2. 38
3 1 8 3. 24
3 1 8 2. 36
4 2 2 2. 20 * 0. 05
4 2 2 2. 30
4 2 2 2. 13
1 4 . 8
11. 14
6 . 7
-
-
-
-
-
-
-
1 1 . 3
2 1
1 1 . 1
9 . 7
1 0 . 6
9 . 1
2. 25 1 0 . 1
2. 51 1 2 . 6
-
1. 76 f 0. 05
1. 63 +z 0. 08
1. 85
1. 83
1. 61
-
9 . 2
6 . 6
5 . 4
6 . 2
5 . 3
6. 85
6 . 1
5 . 2
-
-
S T 6 3 3
VT 6 3 3
S T 6 3 3
S T 6 3 4
S T 6 3 5
VG 8 9 7
VG 8 9 7
VT,VG 3;88,89)
VG 3(88,91)
VT 9 0
V T 9 0
VT 9 0
V T 7 0 8
VT 7 0 8
VT 7 0 8
V T 7 0 8
V T 7 0 8
VG 3(88,96)
V T 9 0
V T 630
L T 6 3 0
V T 9 4
V T 9 4
VT 9 4
VT 7 0 8
V T 7 0 8
V T 7 0 8
VG 100
VT 1 0 0
VG 7 0 9
VG 7 0 9
V T 8 9 6
VG 3(101)
VG 7 1 0
V T 1 0 4
VG 8 6 8
VG 8 6 8
VG 8 6 8
VG 868
VG 868
VG 868
VG 8 6 8
VT 108, 109
LD 1 0 8
VT 1 1 1
V G 3(138,139)
VG 1 3 5
VG 1 3 5
Various 9 5 1
various 9 5 1
References page VII - 68
VII / 50 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 6. contd
Polymer S o l v e n t
T e mp .
(Cl
S@JMA12
(x104) Ke roflMJ2
or lip (x103) I.0 JMJ2 (x104)
(nm) (ml@ x lo4 (nm) (nm) 0 = ro/rof C, = rg/n12 Method(s) Refs.
55 wt.% HNO,
61 wt.% HNO?
Poly(N-acryloyl-m-aminobenzoic acid)
N,N-dimethylacetamide,
N,N-dimethylformamide,
Dimethyl sulfoxide
Poly(N-acryloyl-o-aminobenzoic acid)
NJ-dimethylfonnamide,
Dimethyl sulfoxide,
Tetrabydrofran
Poly(butyl acrylate) Undi l ut ed
Poly(sec-butyl acrylate) Undi l ut ed
Poly(rert-butyl acrylate) Undi l ut ed
Acetone; butanone;
me t h a n o l : pentane
Poly(N,N-dimethylacrylamide) Methanol; water
Poly(dodecy1 acrylate) Undi l ut ed
Poly(ethy1 acrylate) Acetone; methanol
Acetone
Undi l ut ed
Poly(hexyl acrylate)
Poly(isopenty1 acrylate)
Poly(isopropy1 acrylate)
i s ot act i c
s yndi ot act i c
Poly(methy1 acrylate)
Undi l ut ed
Undi l ut ed
Benzene
Bromobenzene
2,2,3,3-Tetrafluoro-
propanol
Undi l ut ed
Bromobenzene
Bromobenzene
Various solvents
Isopentyl acetate
2-Methylcyclohexanol
Butanone/2-propanol
(42158, v/v)
( SO/ SO, v/v)
Undi l ut ed
Poly(octy1 acrylate) Undi l ut ed
Poly(morpholinocarbonylethylene)
Dimethylformamide
Poly(piperidinocarbonylethylene)
Dimethylformamide
Poly(propyl acrylate) Undi l ut ed
- -
1060
-
- -
1290 -
2.51 12.6 valious 951
3.06 18.5 various 951
3 0
-
85 6 7 0 2 2 3 3.0 18.1 VG 9 0 8
25 - 85 6 6 0 223
6 0 dln ri/dT = -0.2 x lo- (deg-)
7 6 dln ri/dT = 0 (deg-)
6 0 dl n ri/dT = -0.2 x 10-j (deg-)
6 0 dln ri/dT = -0.2 x lo- (deg-)
2.96 18.3 VG 9 0 9
S T 6 3 5
S T 6 3 4
S T 6 3 5
S T 6 3 5
25
2 s
6 0
3 0
25
6 0
76
6 0
6 0
25
6 0
2 s
2. 2- 2. 3 -
2.1710.14 9.15
2.34~kO.10 10.9
2.78 15.4
1.88 i 0.08 7.1
1.88+0.08 7.1
2.42iO.10 11.7
VG 7 1 2
VG 3(103)
S T 635
V G 3(115,116)
VG 114
S T 6 3 5
S T 6 3 4
S T 6 3 5
S T 6 3 5
VA 120
VA 120
VG 121
6 0
6 0
6 0
30
62.5
56.0
- 4111 607f3 -
- 78zt 15 670f40 3 0 9
din ri/dT = 1.0 x lo- (deg-)
- 9OilO 720+30 3 0 8
- 8 5 6 3 0 8
dln ri/dT = -0.2 x 10m3 (deg-)
d In r;/dT = -0.4 x 10 -3 (deg -)
dl n ri/dT = -0.3 x lo- (deg-)
dl n ri/dT = -0.2 x 10m3 (deg-)
-
-
540f25 2 8 7
-
-
54052s 2 8 7
- 9 2 700*30 2 8 7
dl n ri/dT = -0.3 x 10m3 (deg-)
-
-
630f30 2 8 7
- 546f35 2 8 7
81110 680f30 3 3 2
- 6 8 6 5 0 3 3 2
- 6 8 6 5 0 3 3 2
2.20f0.10 9.7
1.90f0.12 7.2
2.05 i 0.10 8.4
1.96 7.7
1.96 7.7
2 0
3 0
27.5
6 0
6 0
- 81 6 8 0 3 3 2
72 6 6 5 3 3 2
-
-
7 2 0 3 3 2
din ri/dT = -0.2 x lo- (deg-)
din ri/dT = -0.2 x lo- (deg-)
2.05 8.4
2.00 8.0
2.17 9.4
25 7OilO 63Oi40 2 6 0
- S8ilO 6OOi40 261
dl n ra/dT = -0.3 x 10m3 (deg-)
2.42 ho.15 11.7
25
6 0
2.30f0.15 10.6
S T 6 3 5
VA 120
VA 120
V G 3(123,132)
V T 129
V T 129
VT 124
VT 129
LD 108
S T 6 3 5
S T 6 3 5
VG 3(338)
VG 3(338)
S T 6 3 5
6. 4. POLY(a-SUBSTITUTED ACRYLI C ACI D) AND DERI VATI VES
Poly(buty1 methacrylate) Butanone; 2.propanol 23 -
3415 510120 2 5 8
Dimethylformamide
2-Propanol
Undi l ut ed
Poly(sec-butyl methacrylate) Undi l ut ed
Poly(terf-butyl methacrylate) Butyl acetate
ani oni c Cyclohexane
free radical Cyclohexane
n-Heptane
Butanone, cyclohexane,
n-Heptane.
Tetrahydrofuran
Poly(ferr-butylphenyl methacrylate)
Acetone
23.6
23
6 0
6 0
25
10.0
10.0
6 4 . 0
25-64 din ri/dT = 0 (deg-)
- -
2 0 351s Sl5+20 2 0 8 2.48 210.10
3 0 9 - 6 5 9 -
- 5 3 0 2 5 8
dln ri/dT = 2.5 x lo- (deg-)
dln r;;/dT = -0.2 x lo- (deg-)
-
-
8 9 4 2 5 8
- 60.8 -
-
- 4 8 . 9 -
-
- 4 8 . 6 -
-
1.98iO.10 7.85
- -
2.06 8.5
3.45
-
-
23.8
Il.8
10.2
10.2
VT,VG 3(152)
( 1 5 4 , 1 5 6 )
L T 9 1 0
LD 152
S T 6 3 5
S T 635
VA 157
VG 9 1 7
VG 9 1 7
VG 9 1 7
VTe 9 1 7
VG 3(340)
TABLE 6. contd
Unperturbed Dimensions of linear Polymers: Main-Chain Acyclic Carbon Polymers
Polymer Sol vent
Temp.
(C)
S@J M:i2
(x10) Ko rQflM/
or (Ip (x103) 1.0 J Mj2 (x104)
(nm) (ml/g) x104 ( n m) (nm) o = rofrm C, = ri/n12 Method(s) Refs.
Poly(2-w-r-butylphenyl methacrylate)
Benzene; butanone 25
Cyclohexane 18.4
Poly(4-rerr-butylphenyl methacrylate)
Acetone; cyclohexane; 25
tetrahydrofuran
Poly(Zchloroethy1 methacrylate) o-Dichlorobenzene 35.7
Poly(cyclobuty1 methacrylate) 1- But a nol 31.5
Poly(cyclohexy1 methacrylate) Butanol 23 .
Benzene; butanol; 25
butanone; cyclohexane;
dioxane
Poly(cyclododecy1 methacrylate) Cyclohexane,toluene 3 0
Butanol 22.5
n-Hexyl acetate 35
21-27
Poly(cyclohexy1 thiolmethacrylate)
Cyclohexane 25
Tetrahydrofuran 35
Poly(cycloocty1 methacrylate) 2-Butanol 4 5
1,4-Dioxane, t o l u e n e 3 0
Pol y( cycl opent y1 met hacr yl at e) Cyclohexane 3 6
1 ,CDioxane,ethyl acetate,
methyl ethyl ketone,
Toluene
Poly(decahydro-B-naphthyl methacrylate)
-
Pol y( decy1 met hact yl at e) Ethyl acetate
Poly(2,6-dimethylphenyl methacrylate)
Chlorobenzene,
tetrahydrofuran
TetrahydrofuranIwater,
t o l u e n e
Poly(diphenylmethyl methacrylate)
3-Heptanone
Poly(dodecy1 methacrylate) Isopropyl acetate
Pent anol
Undi l ut ed
Poly(docosy1 methacrylate) Amy1 acetate,
tetrahydrofuran
Poly(2-ethylbutyl methacrylate) Butanone; 2-propanol
2-Propanol .
Poly(ethy1 methacrylate) Bu t a n o n e
2.Propanol
ButanoneR-propanol
(l/7, w
Poly(hexadecy1 methacrylate)
Poly(hexy1 methacrylate)
Heptane
Bu t a n o n e
2-Propanol
Undi l ut ed
Poly[N-(2.hydroxypropyl) methacrylamide]
Aq. NaCl (10%); water
Et hanol
Dimethylformamide
Poly(isobuty1 methactylate) 2-Hydroxymethyl-
tetrahydrofuran
Acetone
Benzene
3 0
-
1 1
25
25
4 5
13
29.5
29.5
6 0
31,30
25
27.4
23
36.5
23
23
21
3 0
32.6
32.6
6 0
5 0
10
25
19.5
25
25
-
-
-
-
2 2 4
-
2 2 8
-
-
-
-
-
-
2 2 2
35
3 5
4 5
47.5
47.7
3 4
4 5
33.0
45.2
33.0
-
30.0
3 0 . 0
37.7
31.1
47.8
47.8
4 3
35.1
17
II
33.1
32.2
34.8
-
5 5 0
5 5 0
5 6 5
-
5 1 0
5 9 0
5 4 9
-
5 5 8
4 9 0
4 9 0
6 0 0
-
6 7 5
6 7 5
5 1 0
4 9 0
5 0 0
5 0 0
-
-
-
231
2 4 0
-
2 3 6
2 3 6
2 3 0
2 3 0
-
-
-
2 1 0
-
2 2 3
2 2 3
-
193
193
193
din ri/dT = 2.6 x 10e3 (deg-)
- 31.9
- -
- 36f5 510f30 2 3 6
33.7 5 0 0 2 3 6
- 49.3 565 zt 15 2 8 8
- 47.5 5 7 5 2 8 8
- 41.3 5 6 0 2 8 8
- 5 6 0 2 8 8
- 6 0 6 2 0 175
41 f4 530 f 20 2 3 6
- 4 3 5 4 0 2 3 6
- 5 8 0 2 3 6
din ri/dT = 2.2 x 10m3 (deg-)
- 5 2 5 9 0 -
5 2 5 9 0 -
- 5 2 5 9 0 -
- 26.5 501 -
- 89.8 2 9 0
-
113 3 1 3 -
2.6
2 . 6
-
2.15
2.5
2.33
-
2.37
2.13
2.13
-
-
2 . 9
3.02
3.02
2.54
2.59
2.59
2.16&0.13
2.12
1.96 zt 0.05
2.00
1.94
1.94
3.54
2.25 3~ 0.08
2.29
2.46
10.5
10.0
9.25
-
14.2
-
14.2
-
-
12.1
12.1
11.2
11.2
-
13.0
18.3
18.3
14.0
12.9
13.4
13.4
23.6
9.3
8.95
1.7
8.0
1.55
7.55
25.1
10.1
10.5
12.1
-
-
-
VG
VG
VG
VT
VG
VT
VG
VG
V T
VG
LG
VG
VG
VG
VG
VG
VG
V T
VG
V T
VG
VT
VT
LD
S T
VG
VG,VT
VT
VG
VT
V T
LD
VG
VT,VG
V T
LD
S T
VG
VG
VG
V T
VG
VG
7 1 6
9 1 4
915
3 4 5
7 1 7
9 1 5
7 1 8
9 1 5
7 1 8
7 1 9
7 1 9
9 1 5
9 1 5
9 1 5
9 1 5
7 1 7
9 1 3
9 2 3
9 2 3
911
158
159
159
6 3 5
9 1 3
3(160)
160
3(161)
156
161
161
163
3(165)
165
165
6 3 5
122
122
7 2 2
7 2 4
9 1 9
9 1 9
References page VII - 68
VII/52 VI SCOSI TY - MOLECULAR WEI GHT RELATI ONSHI PS AND UNPERTURBED DI MENSI ONS OF LI NEAR CHAI N MOLECULES
T ABL E 6 . c o n t d
Polymer Solvent
Temp.
(C)
s&fY2
(x104) Ko rof pi/=
or tap (x103) ro jM12 (x104)
(nm) (mW x lo4 (nm) (nm) d = ro/rm C, = r:/n12 Method(s) Refs.*
Carbon tetrachloride 2 5 1 0 . 5 3 0 5 -
1,4-Dioxane 2 5 9 8 . 4 2 9 9 -
Poly(isopenty1 methacrylate) Undi l ut ed 60 dln r;/dT = 1.4 x 10-j (deg-)
Poly(isopropy1 methacrylate) Undi l ut ed 6 0 dln ri/dT = 2.5 x 10m3 (deg-)
Poly(S-p-menthyl methacrylate) Benzene; cyclohexane; 2 5 4 4 . 0 6 3 0
2-pentanone;
tetrahydrofuran
Poly(methacrylic acid) Aq. NaCl 2 5 2 0 0 900
N,N-Dimethylformamide/ 2 6 . 9 (0) 2 8 4 103
Poly(methy1 butacrylate)
Poly(methy1 ethacrylate)
Poly((methyl methacrylate)
atactic
1,4-Dioxaie(5/7, v/v)
But anol 1 3
2,6-Dimethyl-heptanone 1 1 . 4
Various solvents 2 5
5 7 5 9 0 2 5 8 2. 28 1 0 . 4 VT
6 7 . 6 6 2 0 2 8 8 2. 15 9. 25 V T
7 0 1 2 0 6401t60 3 0 8 2. 08 zt 0. 20 8. 65 VT,VG
Acetonitrile
But yl chl or i de
i s ot a c t i c
Benzene, toluene
Benzene; chloroform;
etc. (various)
2-Methyl-4-pentanone
Methyl isovaleriate
Butyl acetate
ButanoneR-propanol
(58.2141.8, v/v)
(55145, v/v)
(50/50, v/v)
(46.8153.2, v/v)
But yl chl or i de
4-Heptanone
Isoamyl acetate
4-Heptanone
3-Octanone
Undi l ut ed
Acetonitrile
ButanoneR-propanol
(50/50, v/v)
3-Heptanone
Propanol
p-Cymene .
4 5
3 5 . 4
4 0 . 8
2 1
- 4 2 3 6 . 0 5 0 0 3 0 8 1. 62 5. 25 VT 6 3 6
- 3 7 4 1 . 5 5 2 5 3 0 8 1. 70 5 . 8 V T 6 3 6
- 20 4 0 . 6 5 2 0 3 0 8 1. 69 5 . 7 VT 6 3 6
4 . 0 4 7 . 2 5 5 0 3 0 8 1. 78 6. 35 VT 6 3 6
1 2 . 8
2 2 . 8
2 8 . 5
3 5 . 4
4 0 . 4
5 7 . 5
3 3
7 2
1 6 8
2 7 . 6
2 7 . 5
3 0 . 3
4 9 . 8 5 6 0 3 0 8 1. 82 6. 65
5 0 . 4 6 1 0 3 0 8 1. 98 7. 85
5 0 . 8 6 1 0 3 0 8 1. 99 7. 95
5 2 . 6 6 2 0 3 0 8 2. 00 8 . 0
5 3 . 2 6 2 0 3 0 8 2. 01 8 . 1
5 3 . 5 6 2 0 3 0 8 2. 01 8 . 1
4 7 1 4 5 5 0 1 1 5 3 0 8 1.78f0.05 6. 35
5 0 1 3 56Oi 1 0 3 0 8 1. 82 zk 0. 03 6. 65
dln ri/dT = 0.1 x 10m3 (deg-)
1 5 . 5 6 7 0
2 7 3 7 6 . 2 6 6 9
9 0 7 1 5
3 0 8 2. 17
3 0 8 2. 32
9 . 4
-
1 0 . 8
VT 6 3 6
VT 6 3 6
VT 6 3 6
V T 6 3 6
V T 6 3 6
V T 6 3 6
V T 1 7 9
V T 1 7 9
S T 6 3 4
V T 1 9 8
V T 7 2 8
V T 191
4 0
7 5 . 9
152. 1
8 7 7 1 0
7 6 . 1 6 8 0
5 6 . 6 6 1 0
3 0 8
3 0 8
3 0 8
2. 30
2. 21
1. 98
1 0 . 6
9. 75
7. 85
V T
V T
V T
4 9 1 5
2 1 9
292f6
0. 72 f 0. 05 -
46f9
555 f 15 3 0 8
5 3 7 3 0 8
620f 15 3 0 8
653 k 25 3 0 8
Poly(methy1 methacrylate)-block-poly(cc-methylstyrene)-b~oc~-poly(methylmethac~late)
0 . 0 w t . % P MS Chloroform, toluene, 25,
tetrahydrofuran. 4 5 6 6 0
carbon tetrachloride
6 . 1 w t . % P MS ibid. 25. 45 600-690 -
8 . 3 w t . % P MS ibid. 25. 45 670-770 -
2 1 . 0 w t . % P MS ibid. 25,45 630-720 -
3 1 . 8 w t . % P MS ibid. 25,45 680-780 -
7 8 . 1 w t . % P MS ibid. 25,45 710-810 -
1 0 0 w t . % P MS ibid. 25. 45 6 5 3
Poly(methyl-phenylacrylate), (see group 1.7 Poly(methoxycarbonyl-I-phenylethylene)
Poly(P-naphthyl methacrylate) Benzene various 4 7 . 2 5 7 4
Tetralin various 4 7 . 5 5 7 5
Toluene various 3 9 . 0 5 3 8
- 5 4 6 6 0
Poly(octadecy1 methacrylate) Butyl acetone 10.5,20,30 - -
Poly(octy1 methacrylate) But anol ; but anone 2 0 3ozt5 480 3~ 20
But anol 1 6 . 8 - 5 0 0
Undi l ut ed 6 0 dln ri/dT = 2.2 x 10m3 (deg-)
-
3 . 1
3 3 4 2 . 7
-
2. 13
-
1. 80 + 0. 05
1. 74
2. 01 + 0. 05
2. 12 zt 0. 08
-
-
-
-
-
-
-
2 1 0
-
2 1 9
2 1 9
-
-
-
-
-
-
-
-
3 . 1
2. 19 xt 0. 09
2. 28
-
1 4 . 6
6 . 5
6. 05
8 . 1
9 . 0
2. 08
1.98-2.28
2.24-2.54
2.17-2.45
2.27-2.82
2.48-2.80
2. 30
-
-
-
-
1 4 . 5
9 . 6
1 0 . 4
VG 9 1 9
VG 9 1 9
S T 6 3 5
S T 6 3 5
VT,VG 7 7 1
VG 1 1 0
LT,VT 9 0 7
VT
L T
L T
x s
VG
1 6 8
1 6 8
3(170,
173,
174, 181,
193, 196)
1 7 9
6 3 6
2 8 3
631
8 6 9
V A 921
V A
VA
V A
V A
V A
V A
9 2 7
9 2 7
921
9 2 7
9 2 7
9 2 7
VG
VG
VG
VG
VT, VG
L D
S T
7 2 9
7 2 9
7 2 9
7 1 7
9 2 0
3(201)
201
635
TABLE 6. contd
Unperturbed Dimensions of linear Polymers: Main-Chain Acyclic Carbon Polymers VII / 53
Polymer Sol vent
Te mp .
(C)
&/My=
(x10) Ko QfIM12
or lzp (x103) ro/M 1 (x104)
(nm) (mUi x104 (nm) (nm) u = ro/ror C, = r:/nl* Method(s) Refs.
Poly(N-phenylmethacryylamide) Acetone
Poly(pheny1 methacrylate) Acetone; benzene;
butanone; dioxane
Poly(2-selenolylmethyl methacrylate)
Chlorobenzene
Tetrahydrofuran
Poly(steary1 methacrylate) n-Propyl acetate
Poly(tetrahydrofurfuryl)methacrylate)
2-Hydroxymethyl-
tetrahydrofuran
Poly(2-thiophenmethyl methacrylate)
Chlorobenzene
Tetrahydrofuran, thiophene
Poly(tridecy1 methacrylate) Ethyl acetate
Poly[2-(triphenylmethoxy)ethyl methacrylate]
Mesitylene
2 0
2.5
25
2 5
3 6
31.2
2 5
25
27
4 7
-
-
38f9 520 zt 40 2 4 2 2.15ztO.16
5 7 6 7 0 2 4 0 2.8
5 6
6 5
38.2
34.9
4 5 . 0
4 5 . 0
33.3
3 0
5 8 0 2 0 4
6 0 7 2 0 4
- -
573 -
5 9 4 2 2 8
5 9 4 2 2 8
- -
4 8 7
-
6.5. POLY(VINYL ETHERS), POLY(VINYL ALCOHOL), POLY(VINYL ESTERS), POLY(VINYL HALIDES)
Poly(chlorotrifluoroethylene) 2,5-Dichlorobenzo- 130
trifluoride
Benzene; butanone 3 0
Mixed digomers of poly- 340
(chlorotrifluoroethylene)
Pertluorokerosene 300
Various solvents 25
- 52f3 580f 1 5
- 195 * 30 900 zt 50
330 i 50 In this solvent poor
- -300 1070
93510 7 0 5 f 1 0
2 8 6 2.03 zt 0.07 8.25 VG 3(234)
Poly(methoxyethylene)
Poly(tetrafluoroethylene)
Poly(viny1 acetate)
Poly(viny1 alcohol)
Poly(viny1 benzoate)
Poly(viny1 bromide)
Poly(viny1 butyrate)
Poly(vinyl chloride)
Poly(viny1 4-chlorobenzoate)
Poly(viny1 fluoride)
Poly(viny1 hexanoate)
Poly(viny1 isobutyrate)
3-Heptanone 2 9
Heptane/3-methyl-2- 25
butanone (26.8/73.2, v/v)
Methanol 6
3-Heptanone 26.8
Et hanol 56.9
6-Methyl-3-heptanone 6 6
Tetrahydrofuran 35
Wat er 3 0
Undi l ut ed 5 0
9 0
Xylene 32.5
Cyclohexane; tetrahydro- 20
furan; methanol/THF
(17/83, v/v)
1-Methylnaphthalene - 2 0
Benzene 3 0
Cyclohexanone; - 2 5
tetrahydrofuran
Benryl alcohol 155.4
Tetrahydrofuran 25
Butanolibutanone 6 0
(47153, v/v)
Dimethylformamide 9 0
Benzene 3 0
Benzene 3 0
Poly(viny1 methyl ether), see Poly(methoxyethylene)
Poly(viny1 pivalate) Butanonelmethanol 2 0
(0.897 g/ml)
Poly(vinylidene chloride) 1 -Methyl-2-pyrrolidone; 25
Tetramethylene sulfoxide
0.95 f 0.05 - 790 + 20
318110 - 745 i 20
- 101 720
- 82.0 670
- 90 690
- 78 660
- 116+9 774 f 20
- 222 i 25 950 f 40
d In ri/dT = 0.0 (deg -)
4 0 4 2.23 + 0.13 9.95 VG 3(206)
71-2 L T 885,886
3 0 8 N 3.5 - 2 4 VG
3 3 2 2.12&0.09 9 . 0 VT, VG
3 3 2 2.38 + 0.07 11.3
3 3 2 2.24 i 0.07 10.0
2 5 2 , 2 5 5 )
X S 641
L T 2 5 2
3 3 2
3 3 2
3 3 2
3 3 2
4 6 4
2.17 9 . 4
2.02 8.15
2.08 8.65
1.99 7.9
- -
2.04ztO.10 8.3
V T 2 3 6
V T 2 3 6
VT 2 3 6
V T 2 3 6
VG 7 4 0
V G 3(208,210,
2 1 2 )
S T 6 3 8
S T 6 3 9
V T 3 3 4
VT, VG 3(217,
2 1 8 )
dln ri/dT = 0.5 x lo- (deg-)
- 62 i 8 620 f 25 2 5 2
- 40f5 540 i 20 2 9 8
1.09 - 7 6 3 2 9 8
801 10 67Oi35 2 8 8
- lOOf 393
- 156 8 2 0 393
- 103 7 1 7 3 9 0
- 73 6 6 5 2 2 8
128 7 8 7 4 5 7
- 91+ 10 700+30 2 5 8
- 801 10 67Oi35 2 8 8
- 53f5 580 + 20 2 5 3
- 60f 10 62Oi30
-
9.25 VG 3(370)
VG 117
2.84
2.98
-
VG 9 2 2
18.0 VG 9 2 2
20.4 VT 9 1 3
- -
VT 7 3 4
2.45 10.8 VT 9 2 1
2.45 10.8 VG 921
-
14.7 V T 9 1 3
-
18-19 V T 7 3 6
6 9 0
3(242,
244,
2.46 3~ 0.10
1.82 + 0.07
12.1
6 . 6
2.56
2.32zt0.12
1.83f0.15
13.1
6.7
2.08
1.84
2.92
8.65
-
17.1
1.72
2.71 f0.12
2.32f0.12
5.9
2.29 h 0.08
-
8 1 1
X S 6 4 0
VG 3(256)
V G 3(221,223,
2 2 4 , 2 2 9 )
VT 2 1 9
VG 8 7 9
VT 3 3 6
VG 2 3 5
VG 3(256)
VG 3(256)
V T 2 5 8
VG 7 3 8
References page VII - 68
VII 154 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 6. contd
Polymer Sol vent
Temp.
(C)
s&4~~2
(x104) K( rorpf12
or ap (x103) rolMJ2 (x104)
me Wig) x 104 (nm) (nm) 0 = ro/rm C, = ri/n12 Method(s) Refs.
Poly(vinylidene fluoride) NJ-dimethylacetamide, 2 5
NJ-dimethylformamide,
N-methylpyrrolidone,
NJ-dimethy-iV,N-tri-
methylene urea
6.6. POLY(STYRENE) AND DERIVATIVES
Poly(4-acetoxystyrene)
Poly(4-bromostyrene)
Poly(p-tert-butylstyrene)
Poly(2-chlorostyrene)
Poly(4-chlorostyrene)
Poly(4-cyclohexylstyrene)
Poly(2,5-dichlorostyrene)
Poly3,4-dichlorostyrene)
Poly(2,4-dimethylstyrene)
Poly(4-hydroxystyrene)
Poly(o-methoxystyrene)
Poly(p-methoxystyrene)
Butyl acetate,
Isopropyl acetate,
Dioxane, tetrahydrofuran
Benzene
Chloroform
Dimethylformamide
Dioxane
T0heIle
Benzene; cyclohexane
I-Nitropropane
Benzene
Cyclohexane
1-Hexanol
3-Nonanol
2-Octanol
I-Nitropropane
2-Octanol
Bu t a n o n e
Butanone; chloro-
benzene; toluene
Benzene; benzene/
methanol (5.5/ 1, v/v)
Tol ue ne
Heptane; toluene
Tol ue ne
Ethanol/ethyl acetate
(l/15, w/w)
Butanohbutyl acetate
(l/13, w / w )
Chlorobenzene; o-
dichlorobenzene
Cyclohexane; 1,2-
dichloroethane; dioxane
n-Decane; n-heptane
p-Dichlorobenzene
Tol ue ne
Dioxane
Ethyl propionate
Isobutyl acetate
Tetrahydrofuran
Methanohtoluene
(25 115, vlv)
Amy1 acetate
Amy1 acetate; cyclo-
hexane; toluene
But a none ; 20, 50,
chlorocyclohexane;
toluene
MethanoVtoluene
(28.1/71.9, v/v)
26.8
19.7
25
26.3
3 0
3 0
3 0
3 0
3 0
3 0
35
31
31
35
25
65.0
10.9
32.7
31.0
32.7
24.5
24.5
3 0
26.7
-
3 0
3 0
3 0
6 0
30.5
32.9
3 0
2 0
5 0
6 0
3 0
25
25
25
25
3 0
75.0
23.4
75
3 0
3 3 0
-
-
-
-
-
2 3 7
-
2 5 5
2 8 6
-
-
-
-
237
2 3 6
2 7 2
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
- - 8.9 LV 9 2 5
5 4 593
5 4 5 9 3
5 0 5 7 0
28.5 -
4 6 . 0 -
4 4 . 0 -
30.0 -
4 5 5 6 4
- 5 5 4
6 2 6 1 2
61+5 610f15
-
-
2 2 8
-
-
2 2 8
2 2 8
2.37
2.37
2 . 5 0
2.05
2.41
2.37
2.09
2.48
2.43
-
11.2
11.2
12.5
-
-
12.3
11.8
-
13.4 + 0.7
-
58.2 -
51.7 -
51.1 -
59.5 -
55.7 -
54.2 -
46.8 5 8 0
- 5 8 0
50f5 56Oi20
-
-
11.9
13.1
12.6
12.3
-
261
-
2.22
2.22
2.15 at 0.07
-
9.25
V T 931
VG 9 3 7
VT 3 4 8
VG 8 7 0
VG 8 7 0
VG 8 7 0
VG 8 7 0
VG 3 4 9
LG 3 4 9
VG 741
VT 741
L T 741
VG 9 3 4
VG 9 3 4
VG 9 3 4
VG 9 3 4
VG 9 3 4
VG 9 3 8
VT 7 4 2
L T 7 4 2
V G 3(352,355),
5 9 5 9 0
5 8 6 1 5
- 6 1 5
53f3 57Oi-20
5113 56Oi20
35.5 5 1 0
71 640
38f5 510+20
-
2.25
-
VG
353
7 4 4
261 2.36 11.1 VG 3 4 9
261 2.36 11.1 LG 3 4 9
2 2 6 2.52 dr 0.07 12.7 VG 2 6 6
2 2 6 2.48 zt 0.07 12.2 VG 2 6 6
2 3 4 2.18 9.5 V T 3(357)
2 3 4 2.7 14.6 VT 3 5 9
2 3 4 2.18 z!z 0.08 9.5 VG 3 5 8
5960 635-640
48-l9 595600
48.5 5 9 5
6015 630% 15
82.7 -
90.0 -
90.0 -
83.7 -
57.5 6 0 0
6 9 635 i 15
71 6 4 0
66-73 -
- -
VG 7 4 6
2 6 8
-
-
-
2 6 6
-
2.35 zt 0.07
2.38
2.45
2.45
2.39
2.26
VG 146
VG 7 4 6
VG 3 3 3
VG 9 4 0
VG 9 4 0
VG 9 4 0
VG 9 4 0
VT 3 6 2
2.40 3~ 0.06
-
-
-
-
11.0
11.3
12.0
12.0
11.4
10.2
-
11.2
VT 871
VG 363
VG 7 8 2
62.1 6 3 0 2 6 6 2.37 VT 362
TABLE 6. contd
Unperturbed Dimensions of linear Polymers: Main-Chain Acyclic Carbon Polymers VII / 55
Polymer Sol vent
Temp.
PC)
S@JMy
(x104) Ko Qf J M' / =
or ap (x103) Q/M2 (x104)
(nm) (mh)
x lo4 (nm) (nm) d = ro/ror C, = r~/nE* Method(s) Refs.
4-Methyl-2.pentanone 2 3 . 4 - 6 4 62Oi I5
2-Methyl-2. 5 2 . 2 - 7 4 6 5 0 f2 0
phenylpropane
Tol uene 2 5 - 14 6 5 0 i 2 0
Poly(methy1 methacrylate).block-poly(a-methylstyrene).~/~c~- poly(methyl methaqlate), see also group 1.4
Poly(r-methylstyrene) IChloro-n-hexane
Khloro-n-heptane
1-Chloro-n-octane
n-Hexyl acetate
Cyclohexane
trans-Decalin
5 . 1
1 0 . 0
2 0 . 0
2 7 . 0
4 3 . 0
5 3 . 0
8 0 . 0
8 5 . 0
3 4 . 5
1 0 . 0
-
-
-
6 6 . 0 -
6 5 . 2 -
6 2 . 5 -
6 2 . 7 -
6 3 . 8 -
63. I -
6 3 . 8 -
6 6 . 5 -
6 8 . 9 -
6 8 . 0 -
7 6 1 5 65Oi 15
6 7 1 2 625f5
76f2 650 zt 10
anionic (atactic)
ca. 50%-hetero, ca. 40%-
syndi o
cationic (syndiotactic)
Poly(m-methylstyrene)
Poly@-methylstyrene)
Poly(styrene)
atactic
Benzene; cyclohexane - 3 0
truns-Decalin 9 . 5
Cyclohexane - 3 8
3 4 . 5
3 4 . 5
3 4 . 9
3 4 . 9
trans-Decalin (100%) 9 . 5
9 . 5
9 . 6
9 . 6
Toluene; benzene/ 3 0
methanol (79.4120.6, v/v)
Cyclohexane - 3 3
Benzene; cyclohexane; 30
ethyl acetate
4 0
5 0
Butanone; cyclohexane; 3 0
to1uene
Diethyl succinate 1 6 . 4
1 6 . 4
wious solvents - 3 0
n-Buy1 chloride
Cyclohexane
trans-Decalin
Ethylcyclohexane:
methylcyclohexane
Cyclohexane
Benzene; toluene
Benzene/ethanol
(7 I .5/28.5, v/v)
ButanoneR-propanol
(87113. v/v)
Khloroundecane
Cycl ohexane
Dimethyl malonate
25, 50
3 4 . 5
16-80
- 7 0
3 4
3 5
3 5
3 5
2 5
2 5
6 7
3 2 . 8
3 4 . 8
3 5 . 9
-
-
2 9 0
-
2 6 3
-
2 8 3
-
2 5 0
-
-
-
-
-
-
-
2 9 1
-
-
2 9 7 i 3
-
282i5
3 0 6
3 0 0
- 7 1 0
7 3 6 4 5
6 4 5
7 4 . 2 6 5 0
- 6 9 0
6 7 6 3 0
6 1 5
6 2 . 5 6 1 5
74zt 10 67Oi25
69+3 655 f 10
8 4 . 0 6 6 4
8 6 . 8 6 7 1
8 9 . 7 6 7 8
6 8 1 5 62Oi 15
7 0 6 5 5
- 6 8 0
82 * 5 670 i 15
7 7 -
8 1 . 4 -
7 5 1 5 650+ 15
- 690+ IO
- 7 3 0
6 7 0
0. 92 i 0. 03 - 705* 15
0. 91 i 0. 02 - 7ooi 15
2 9 6 - 6 4 5
3 1 7 - 151
- 7 7 5
- 7 6 8
- 7 6 2
-
-
-
-
-
-
-
-
-
-
-
-
2 8 4
2 8 4
2 8 4
-
-
-
-
-
2 8 4
2 8 4
2 8 4
2 8 4
2 8 4
2 8 4
2 8 4
2 8 4
3 0 2
-
-
-
3 0 2
3 0 2
3 0 2
3 0 2
3 0 2
3 0 2
3 0 2
3 0 2
3 0 2
3 0 2
3 0 2
2. 33 i 0. 07
2. 45 i 0. 06
2. 45 i 0. 06
-
-
2. 29 i 0. 05
2. 20 It 0. 02
2. 29 + 0. 03
-
-
-
-
-
-
-
2. 36 i 0. 10
2.3 1 + 0.03
2. 34
2. 37
2. 39
2. 18 + 0. 05
2. 3 I
2. 39
2. 22 i 0. 05
-
-
-
2.151kO.05
2. 28 * 0. 04
2. 42
2. 22
2. 33 zt 0. 05
2. 32 i 0. 04
2. 14
2. 50
2. 56
2. 54
2. 52
-
-
-
1 0 . 4
1 0 . 3
1 0 . 0
1 0 . 0
1 0 . 1
1 0 . 1
1 0 . 1
1 0 . 4
1 0 . 7
1 0 . 6
1 0 . 5
9 . 7
1 0 . 5
-
-
1 1 . 1
1 0 . 7
1 1 . 0
1 1 . 2
1 1 . 4
9 . 5
1 0 . 7
1 1 . 4
9. 85
-
-
-
9. 25
1 0 . 4
1 1 . 7
9. 85
1 0 . 9
1 0 . 8
9. 15
1 2 . 5
1 3 . 1
1 2 . 9
12.7
VT 8 7 1
VT 8 7 1
VT 871
VG 8 8 8
VG 8 8 8
VG 8 8 8
VG 8 8 8
VG 8 8 8
VG 8 8 8
VG 8 8 8
VG 8 8 8
VG 8 8 8
VG 8 8 8
VT, VG 319, 323
V T 3 2 0
V T 320, 321
322, 323
L T 8 7 2
V T 8 7 2
L T 8 7 3
VT 8 7 3
L T 8 7 2
V T 8 7 2
L T 8 7 3
V T 8 7 3
VT, VG 3(329,
327)
V T 3 2 8
VG 3 3 0
VG 3 3 0
VG 3 3 0
VG 651, 331
V T 3 3 1
L T 3 3 1
V T , V G 3(274,
277,
2 7 9 , 2 8 2
286, 299,
301, 304)
VG 9 3 3
L T 8 7 5
Monte Carlo, G 8 7 6
3(292,293)
L T 6 4 3
L T 2 7 8
L T 6 4 4
X S 6 4 5
X S 6 4 5
L T 6 2 8
L T 2 7 8
V A 6 4 6
V A 6 4 6
V A 6 4 6
References page VII - 68
VII / 56 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 6. contd
Polymer Sol vent
Temp.
(C)
srpiy2
(x10) KS rM/M/2
or ap (x103) roJMt12 (x104)
(nm) bW
x lo4 (nm) (nm) a = ro/rw C, = r:/n12 Method(s) Refs.
atactic, anionic
i s ot a c t i c
head-to-head
head-to-tail
s t ar t ype
four branches
six branches C y c l o h e x a n e
star type 12.3 arm Cyclohexane
16. 8 ar m Cy c l o h e x a n e t
regular H-shaped Cyclohexane
Poly(styrene-p-sulfonic
-, sodium salt
acid) Aq. NaCl (4.17 M)
73%~rrans-Decalin 1 8
lOO%-?rans-Decalin 2 4
Butyl formate - 9
Hexyl - m- xyl ol 1 2 . 5
Decalin 2 9 . 5
Diethyl malonate 3 1
Cyclohexane 3 4
Diethyl oxalate 5 1 . 5
Methylcyclohexane 6 8
Cyclohexanol 8 3 . 5
I-Chlorodecane 6 . 6
1Chloroundecane 3 2 . 8
I-Chlorododecane 5 8 . 6
Cyclohexane/methylcyclohexane
(1 /o, v/v) 3 4 . 5
(2/l, v/v) 4 3 . 0
(l/l, v/v) 4 8 . 0
(l/2, v/v) 5 4 . 0
co/ 1, v/v) 7 0 . 5
Diethyl malonate 3 4 . 2
Diethyl oxalate 5 5 . 8
Undi l ut ed 1 5 0
Benzene/isopropyl alcohol
(64136, v/v)
Cyclohexane
Decalin; dioctyl
phthalate
Benzene; toluene
12-22
-
80fl 665zk5 3 0 2 2. 20 zt 0. 02 9 . 7 V T
3 0
-
9 0 1 1 0 695 IL 25 3 0 2 2. 30 + 0. 08 1 0 . 5 VG
Chlorobenzene 2 5 . 3
-
1 7 6 8 9 0 3 0 2
Tetrahydrofuran 2 5
-
1 3 5 8 0 5
-
Tetrahydrofuran 2 5 7 8 6 6 0
-
Cyclohexane 3 5
3 4 . 5
3 4 . 5
3 4 . 6
3 4 . 6
3 5
3 5
2 5
-
6 3 . 1 6 6 1
2 8 0
-
6 8 5
1 9 0 4 6 5
<S2>02/<S2>02.,,=0.276 -
<S2>n,/<S2>~~.,,n=0.228 -
-
-
-
-
6 6 . 5
- -
2 3 5
- -
2 0 . 4 4 2 5 2 1 4
6.7. OTHER COMPOUNDS
Poly(2-acrylamino-2-methyl-propanesulfonamide)
Watedl,4-dioxane
(81.5/18.5, v/v)
Poly[(biphenyl-4-yl)ethylene] Benzene
Poly(carbanilinoxyetbylene) Dioxane/methanol
(28172, v/v)
2 5 . 5 3 1 2 7 6 4
2 5 . 5 1 0 7
3 4 . 5 2 8 8 7 0 6
3 4 . 5
-
89.7 -
3 4 . 5 2 8 0
-
6 8 5
- 3 4 . 5 88 * 3 685 f 10
-
-
-
-
-
3 0 2
-
2. 27 + 0. 03
-
-
-
-
1 0 . 3
L T
V T
LV
V T
L T
VT
8 7 4
8 7 4
8 7 7
8 7 7
8 7 8
301, 302.
303,305,649
303, 649
2. 94
-
1 7 . 3 VG
-
VG
-
VG
3(311,312,
3 1 4 )
6 5 0
7 5 6
7 5 6
-
-
-
-
-
-
-
-
1. 98
-
-
7. 85
V T 7 5 8
L T 8 7 8
L T 8 7 8
L T 9 2 9
L T 9 2 9
VT 7 5 9
L T 7 5 9
V T 3 6 6
2 5
-
1 7 2 8 8 0
-
4 . 0 3 2 VT 1011
3 0
20-75
2 0
-
6 3 . 0 6 0 5 2 3 0 2. 63 1 3 . 8
d In ri/dT =(0.23 i 0.01) x 10m3 (deg
7 5 6 8 0 2 4 1
-I
1
2. 82 1 5 . 9
-
-
-
VG 2 6 4
VG 2 6 4
VT 3 3 5
Poly[l-(9-c~bazyl)-2,3-(diethoxycarbonyl)-butane-1,4-diyl]
Benzene 2 5
Poly(dibuty1 itaconate) Tol uene 2 5
Poly(dicyclohexy1 itaconate) Tetrahydrofuran; toluene 25
Poly(didecy1 itaconate) Tol uene 2 5
7 7
- 8 2
1 7 . 4
- 7 7 . 0
7 7 . 9
- 7 0 . 5
- 7 9 . 5
- 7 2 . 2
- 7 8 . 0
5 0 . 8
7 8 . 0
7 8 . 7
- 8 0 . 7
7 7 . 9
7 7 . 6
7 4 . 8
7 3 . 0
6 9 . 6
7 1 . 8
- 7 3 . 0
6 5 5 3 0 2 2. 17 9 . 4 VT
6 7 0 3 0 2 2. 22 9. 85 VT
6 5 5 3 0 2 2. 17 9 . 4 V T
6 5 5 3 0 2 2. 17 9 . 4 VT
6 5 5 3 0 2 2. 17 9 . 4 V T
6 3 5 3 0 2 2. 10 8 . 8 V T
6 6 0 3 0 2 2. 18 9 . 5 VT
6 4 0 3 0 2 2. 12 9 . 0 VT
6 5 5 3 0 2 2. 17 9 . 4 VT
5 7 5 3 0 2 1. 90 7 . 2 V T
6 5 5 3 0 2 2. 17 9 . 4 V T
6 6 0 3 0 2 2. 18 9 . 5 V T
6 6 5 3 0 2 2. 20 9 . 7 V T
6 5 5 3 0 2 2. 17 9 . 4
6 5 5 3 0 2 2. 17 9 . 4
6 5 0 3 0 2 2. 15 9. 25
6 4 5 3 0 2 2. 14 9. 15
6 3 5 3 0 2 2. 10 8 . 8
6 4 0 3 0 2 2. 12 9 . 0
6 4 5 3 0 2 2. 14 9. 15
VT
V T
V T
VT
V T
VT
VT
S T dln rz/dT = 0.4 x lo- (deg-)
54f2 5 7 3 2 2 8
3 5 . 4 5 0 8 1 9 8
- 44f2
- -
3 3 . 8 5 0 3 1 5 2
2. 51
2. 60
2. 99
3. 30
2 9 0
2 9 0
6 4 7
6 4 7
6 4 7
6 4 7
6 4 7
6 4 7
6 4 7
6 4 7
6 4 8
6 4 8
6 4 8
2 9 1
2 9 1
2 9 1
2 9 1
2 9 1
2 9 1
2 9 1
6 3 4
VG 7 8 9
VG 7 6 2
VG 7 6 1
VG 7 6 2
TABLE 6. contd
Unperturbed Dimensions of linear Polymers: Main-Chain Acyclic Carbon Polymers VII / 57
Polymer Sol vent
Temp.
(C)
S&/MY2
(x104) Ko rQf/M/2
or lap (x103) roIM12 (x104)
(4 (mh)
x 104 (nm) (nm) n = ro/rm C, = r:/nl Method(s) Refs.
Poly(didodecy1 itaconate) Tol ue ne
Poly(diethy1 itaconate) Tol ue ne
Poly(diethylcyclohexy1 Tol ue ne
itaconate)
Poly(dihexadecy1 itaconate) Tol ue ne
Poly(dihexy1 itaconate) Tol ue ne
Poly(diicosay1 itaconate) Tol ue ne
Poly(dimethy1 itaconate) Benzene
Poly(dimethylcyclohexy1 itaconate)
Tol ue ne
Poly(dioctadecy1 itaconate) Tol ue ne
Poly(dipheny1 itaconate) Tol ue ne
Poly(dipropy1 itaconate) Tol ue ne
Poly(dipropylcyclohexy1 itaconate)
Amy1 acetate
Tol ue ne
Poly(ditetradecy1 itaconate) Tol ue ne
Poly(diundecy1 itaconate) Tol ue ne
Poly( 1-methoxycarbonyl-1-phenylethylene)
Benzene; chloroform
Ethylbenzene
Poly[bis(phenylethyl)itaconate] Tol ue ne
Poly[bis(phenyl-n-propyl)itaconate]
Tol ue ne
Poly(N-vinyl-3,6-dibromo carhazole)
pChloro-m-cresol
o- Chl or ophe nol
Poly(vinylcarbazole) Benzene; chloroform;
tetrachloroethane;
tetrahydrofuran
Bromobenzene; chloro-
form; nitrobenzene
Chlorobenzene;
nitrobenzene
1,2-Dichlorobenzene
1,2-Dichloroethane
Tol ue ne
Poly( 1 -vinylimidazole) Aq. NaCl (0.1 M);
(5 M); aqueous
NaSCN (0.1 M)
pr ot onat ed Acetate (0.1 M)
Acetate (0.1 M)/NrkI
(1W .
Aq. HCl (0.1 M)/
NaCl (1 M)
Pr opi onat e ( 0. 1 M)
Poly(l-vinyl-3-benzyl-imidazoliumchloride)
Aq. NaCl (0.01 M);
(0.02 M); (0.05 M);
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
3 0
15
25
25
112.9
6 0 . 0
25
25
3045
25
25
31
25
25
2 5
25
25
25
Poly( 1 -vinylnaphthalene)
Poly(2-vinylnaphthalene)
Poly(3-vinylpyrene)
acetate (0.1 M); aqueous
NaH2POd (0.1 M)
Benzene 3 0
75
20-75
Benzene 3 0
65
20-75
Decalinkoluene 30.2
(13/10, w/w)
Chloroform; 1,2-dichloro- 25
benzene; tetrahydrofuran
33.6 -
22.3 4 4 7
27.5 -
33.5 -
34.8 5 2 8
26.7 -
30.2 4 9 4
21.5 -
30.7 -
28.4 -
27.3 4 7 8
27.0 -
24.8 -
33.6 -
33.9 5 1 4
5411 585f5
54*1 585f5
28.1 -
29.1 -
30.2 470
27.5 481
68f2 6 1 9
59.2 5 9 0
56.8 5 8 3
58.5 5 8 9
59.6 5 9 2
76.2 i 5 6 3 3
116flO 774 It 22
4 1 4 1180
183 9 0 0
169 8 8 0
3 9 2 1160
6 3
2 2 6
3.6
1.98
2.83
25
-
VG 9 4 5
VG 7 6 2
VG 163
-
3.9
179 2.90
-
3.9
2 4 5 2.02
3 0
31
VG 9 4 5
VG 7 6 2
VG 9 4 5
VG 7 6 2
2.83
4 . 0
2.69
2.27
-
31
14.6
VG 7 6 3
VG 9 4 5
VG 9 4 3
VG 7 6 2
2.93
-
VG 7 6 3
2.84
-
VG 7 6 3
3.7 21 VG 9 4 5
3.50
-
VG 7 6 2
2 4 2 2.42 LIZ 0.02 11.7 VG 361
2 4 2 2.42 + 0.02 11.7 V T 361
-
2.78 14.8 VG 9 4 3
2.91 15.6 VG 9 4 3
2.89 16.7 V T 9 4 2
2.96 17.5 VT 9 4 2
2.82 15.9 VG 3 6 7
2.66 VG 7 6 5
-
VG 766
-
2.85 16.2
-
12-15
VG 7 6 7
VG 7 6 7
V T 3 6 8
VT 8 1 3
15-28 VT 8 1 3
15-28 VT 8 1 3
15-28 VT 8 1 3
15-28 VT 8 1 3
18 VG 8 1 3
24.2 4 3 5 2 4 8 1.76
- 4 0 5 2 4 8 1.63
dln ri/dT = -(1.87 f 0.04) x 10m3 (deg-)
64.7 6 1 0 2 4 8 2.45
5 9 5 2 4 8 2.40
dln ri/dT = -(0.83 i 0.03) x 10m3 (deg-)
-
- -
2 4 8 ca. 3.1
52.0 577 - 2.84 VG 7 6 8
6 . 2
5.3
12.0
11.5
ca. 19.2
VG 2 6 4
VG 2 6 4
VG 2 6 4
VG 2 6 4
VG 2 6 4
VG 2 6 4
VT 2 6 9
References page VII - 68
VII / 58 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 6. contd
Polymer Sol vent
Temp.
(C)
I,2
So./Mw
(x104) Ko rof/M:2
or lx&, (x103) ro/M12 (x104)
(nm) (mW x 10 (nm) (nm) IJ = ro/rnf C x = r~/nl Method(s) Refs.*
Poly(2-vinylpyridine) various solvents 2 5
Benzene 1 5
2 5
3 0
4 0
5 0
6 0
Benzene; chloroform; vatious
Poly(2-vinylpyridine l-oxide)
Poly(4-vinylpytidine)
Poly(5-vinyl-2-methylpyridine)
Poly(vinylpyrrolidone)
Poly(l-vinyl-2-pyrrolidone)
Polyfvinyl sulfate)
Poly(vinylsulfonic acid)
6.8. COPOLYMERS
etc. (various)
Chloroform
Benzene,
2-propanol, pytidine
Benzyl alcohol,
1- but anol , chl or of or m,
methanol, I-propanol,
2.propanol
Ethanol; water
But anone; met hanol
Butyl acetate
4-Methyl-2-pentanone
Pentyl acetate
Wa t e r
Acetone/water
(66.8133.2, k/v)
Butanone/2-propanol
(9414, V/V)
Aq. Na2SOd
(0.55 M); 2.propanol
Chloroform
Chloroformlacetone
(40/60, v/v)
Water; water/acetone
(80/20. v/v)
Water/acetone
(33.2166.8, v/v)
MethanoV3-heptanone.
ethanol&heptanone,
propyl alcohol/
3.heptanone
Aq. NaCl (0.5 MI
Aq. KBr (0.349 M)
Aq. KCI (0. 349 M)
(0. 650 M)
( 1. 001 M)
Aq. NaBr ( 0. 347 M)
Aq. NaCl (1.003 M)
Aq. NaBr ( 1. 008 M)
0
2 5
IO-15
2 5
2 5
2 5
2 5
2 1 . 8
3 7 . 4
4 8 . 2
.- 25
2 5
2.5
2 5
2 5
2 5
2 5
2 5
2 5
2 0
5.1
5 . 5
2 6 . 0
4 4 . 5
- 0 . 6
3 2 . 4
4 0 . 1
Poly(acrylonitrile-stat-a-methylstyrene) ca. (46/54, mol/mol)
Tetrahydrofuran
-
Poly(acrylonitrile-co-styrene)
(38.3/61.7, tnol/mol) But anone 3 0
azeotropic
(62.6/37.4, mol/mol. random) Butanone; 3 0
dimethylfotmamide
(38.5/61.5, molhnol) But anone
-
azeotropic Tetrahydrofuran
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
4 0 9
3 5 4
3 9 0
821 IO 66Oi30
12 6 3 5
7 1 6 3 3
5 9 5 9 5
5 2 5 7 0
5 7 5 9 0
6 2 6 0 5
7 2 1 1 1 660 It 30
8 8 6 9 0
8 7 . 5 6 8 9
8 1 -
5 5 5 7 6
941 IO 7lOf30
69 * 5 652zk 15
8 3 6 7 5
8 3 6 7 5
8 0 6 6 5
1OOi 15 72Oi40
7 5 650
6 1 6 3 0
5 8 . 0 6 5 0
3 0 . 0 5 2 0
6 6 . 0 6 8 0
2 3 . 0 4 8 0
7 4 . 0 7 1 0
61 -
251 15 46Oi80 2 7 8 1. 65 xt 0. 30 5. 45 VG 3(26 I)
6 8 . 8 650(788) i 2 9 6 2.19(2.66) i 9 . 6 V T 259, 642
6 8 . 2 650(786) 2 9 6 2.19(2.66) 9 . 6 V T 259, 642
7 9 . 5 685(830) 2 9 6 2.31(2.80); 1 0 . 6 V T 259, 642
8 0 . 3 690(832) + 2 9 6 2.33(2.81)+ 1 0 . 8 V T 259, 642
9 5 . 5 730(882) 2 9 6 2.46(2.98) + 1 2 . 1 V T 259, 642
96. I 730(880) 2 9 6 2.46(2.97)+ 1 2 . 1 VT 259, 642
9 4 . 5 725(875) 2 9 6 2.45(2.96) i 1 2 . 0 VT 259, 642
-
1 2 4 7 7 0
1 7 0 8 4 0
- -
- -
3 0 0
3 0 0
3 0 0
3 0 0
3 0 0
3 0 0
3 0 0
2.20f0.10 9 . 7
2. 12 9 . 0
2. 11 8 . 9
1. 98 7. 85
1. 90 7 . 2
1. 96 7. 65
2. 02 8. 15
- -
3 0 0 2. 24 1 0 . 0
3 0 0 2. 24 1 0 . 0
3 0 0 2 . 3
-
2 7 8 2. 07 8 . 6
VG 3 7 1
VG 6 5 2
VG 6 5 2
VG 6 5 2
VG 6 5 2
VG 6 5 2
VG 6 5 2
VG 8 6 9
VG 6 5 2
VG 6 5 2
VT,VG 9 5 2
VG 9 4 6
3 0 0 2.37fO.10 1 1 . 2 V G 3(373,374)
2 8 2 2.3 I i 0.05 1 0 . 6 VG 3 7 5
2 8 2 2. 39 11.4 V T 381
2 8 2 2. 39 1 1 . 4 V T 381
2 8 2 2. 36 1 1 . 1 V T 381
2 9 2 2. 48 i 0. 12 1 2 . 3 V G 3(380,382)
2 9 2 2. 22 9. 85 V T 3 8 4
2 9 2 2. 16 9 . 3 V T 6 5 3
2 9 0 2. 24
-
VT,VG 7 7 0
2 9 0 1. 79
-
VG 7 7 0
2 9 0 2. 34
- VG 7 7 0
2 9 0 I .66
-
VG 7 7 0
2 9 0 2. 45
-
V T 110
- -
VG 9 4 7
- - -
LG 8 7 8
3 3 5 2. 30 i 0. 05 1 0 . 6 VG 593, 595
3 6 2 2. 32 1 0 . 8 VG 5 9 5
-
-
- -
L G 8 7 8
- -
L G 8 7 8
+ The values of ro/M and CT given in parentheses were obtained by usmg @a = 1.39 x 101, while for the others @a = 2.5 x 10 was used.
TABLE 6. contd
Unperturbed Dimensions of linear Polymers: Main-Chain Acyclic Carbon Polymers VII / 59
Polymer Sol vent
Temp.
(C)
ShIMi !=
(x104) K@ Qf/Mf2
or lip (x103) Q/M (x104)
(nmf W&i9 x lo4 (nm) (nm) d = ro/rw C, = r:jnl Method(s) Refs.
(I /I, mol/mol, alternating) Butanone; dichloroethane: 30
dimethylformamide
Butanone/methanol 3 0
( 63. 6 136.4, v/v)
Poly(acrylonitrile-co- y-Butyrolactone 25
vinylidene chloride) Dimethylacetamide 2 5
5 8 w t . %- A N Di me t h y l f o r ma mi d e 2 5
N-Methyl-2-pyrrolidone 2 5
70 wt.% HNO? 25
Poly(butadiene-stat-styrene) (84/16, mol/mol)
2-Pentanone 23.8
Poly(buty1 itaconate-star-dibutyl) itaconate) (40.5/59.5, mol/mol)
Acetone 25
Methanol/m-xylene
(100/O, v/v) 25
(80/20. v/v) 25
(65135, v/v) 25
(50/50, v/v) 25
(30/70, v/v) 25
(10/90, v/v) 25
(O/ 100, v/v) 25
Poly@-chlorostyrene-srat-methyl methacrylate) (5 1.6/48.4, mol/mol)
Benzene/hexane 22.3
(960/40, v/v)
poly(dimethy1 itaconate-co-styrene)
(I 00/o, w/w) Benzene 2 5
(75125, w/w) Tol uene 2 5
(67133, w/w) 2 5
(59141, w/w) 2 5
(4915 I, w/w) 2 5
(29.5170.5, w/w) 2 5
(27173, w/w) 2 5
(O/ 100, w/w) 2 5
Poly(ethyl acrylate-star-methyl methacrylate) (80/20, mol/mol)
Acetone 25
Poly(ethylene-co-cc-methyl-styrene), [(ET),,,(MS) ,,I,
m/n = 314 Butanonelcyclohexane
(60/40, v/v) 30
m/n = 5 /4 Butanonelcyclohexane
(75125, v/v) 30
m/n = 517 Cyclohexane 30
Poly(4-methoxystyrene-stat-styrene)
(24.4/75.6, mol/mol) Toluene . 25
(26.4/73.6, mol/mol) Butanone; chlorocy- 25. 50, 75
clohexane; toluene
(46.2/53.8, mollmol) Tol uene 2 5
(53.0/47.0, mol/mol) Butanone; chlorocyclo-
hexane; toluene 25, 50, 75
(74.0/26.0, mollmol) Tol uene 2 5
(75.6124.4, mol/mol) Butanone; chlorocyclo-
hexane; toluene 25, 50, 75
Poly(methy1 acrylate-stat-styrene)
(50/50, mol/mol) Ethyl acetate 3 5
(22178, mol/mol) Var i ous sol vent s - 3 0
(33-76, mol/mol) - 3 0
(47153, mol/mol) - 3 0
(59/41, mol/mol) - 3 0
(76124, mol/mol) - 3 0
Poly(methyl methacrylate-co-styrene)
(100/O, mol/mol, random) 1- Chl or obut ane 4 0 . 8
(94/6, mol/mol, random) 4 0 . 8
(58/42, mol/mol, random) 4 0 . 8
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
1 3 9 7 8 5 - 2. 25
1 4 0 7 8 5
-
2. 25
9 4 0
9 8 0
9 5 0
1 0 0 0
8 6 0
-
-
-
-
2. 46
2. 57
2. 49
2. 62
2. 31
2 3 . 8 460
-
-
1 3 . 2
1 4 . 4
1 3 . 5
1 5 . 0
1 0 . 8
VG
VT
Various
various
Various
Various
Vari ous
VT
8 3 3 . 2 VG
51 2 . 7 VG
6 2 2 . 8 VG
7 8 3 . 1 VG
9 8 3 . 4 VG
101 3 . 4 VG
8 2 3 . 2 VG
4 2 2 . 5 VG
6 4 6 6 0 V T
3 0 . 4 4 9 5 245 2. 02 VT
3 5 . 4 5 0 8 2 6 0 1. 96 VT
4 0 . 3 5 4 4 2 6 6 2. 04 VT
4 5 . 7 5 5 3 2 7 0 2. 05 V T
5 5 . 3 5 9 0 2 7 8 2. 12 V T
6 3 . 4 6 1 7 2 8 7 2. 15 V T
6 3 . 7 6 1 8 2 8 8 2. 15 V T
7 8 . 0 6 6 1 3 0 2 2. 17 VT
-
8 2 3 3 0 8 2. 67 VG
135 8 2 0 3 4 5 2. 38 V T
1 4 0 8 3 0 3 7 3 2. 22 V T
1 1 2 7 7 0 3 4 3 2. 24 VT
8 1
95-100
-
-
- -
VG
VG
1 0 9
- -
86-109
9 8
-
-
-
-
75-83 -
-
VG
- VG
-
VG
- VG
VG
V T , V G
VT
VG
VT,VG
VT
10412 1010120
7 5 6 5 0
7 6 6 5 0
7 7 6 5 5
7 6 6 5 0
7 5 6 5 0
5 0 5 8 3
5 9 6 1 6
9 5 7 2 8
3 1 4 3. 22
3 0 8 1. 89 VT
3 0 8 2. 00 VG
3 0 5 2. 39 VG
9 6 1
9 6 1
9 6 1
9 6 1
9 6 1
596
6 8 2
6 8 2
6 8 2
6 8 2
6 8 2
6 8 2
6 8 2
6 8 2
5 9 8
6 8 3
6 8 3
6 8 3
6 8 3
6 8 3
6 8 3
6 8 3
6 8 3
6 0 4
6 0 4
604
7 8 1
7 8 2
7 8 1
7 8 2
7 8 1
7 8 2
1 3 3
1 2 9
1 2 9
1 2 9
1 2 9
1 2 9
6 1 3
6 1 3
6 1 3
References page VII - 68
VII / 60 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 6. contd
Polymer Sol vent
Temp.
(C)
s&/My2
(x104) K() rorJM12
or op (x103) ro/M12 (x104)
(nm) Wk) x lo4 (nm) (nm) c = ro/ror C, = r~/n12 Method(s) Refs.
(10/90, mol/mol, random) 40.8
-
(O/100, mol/mol, random) 40.8
-
(7 I /29, moI/mol, random) Various solvents - 3 0
-
(44/56, mol/mol, random) Various solvents - 3 0
-
(30/70, mollmol, random) Various solvents .-. 30
-
three blocks (MSM) Cyclohexanol 81
nearly equimolar
Poly(styrene)-block-poly(butadiene)-b[oc~-poly(styrene) 50 wt.%-PS
Tol ue ne 3 0
-
Poly(styrene-stat-vinylpyrrolidone)
(87/ 13, w/w) Bu t a n o n e 25
-
ButanoneR-propanol 25
-
(75125, v/v)
( 13/87, wlw) Butanone/2-propanol 25 341
(9713, v/v)
Poly(styrene-co-monomethyl maleate)
Acetone 26.4
-
Aq. NaCl (0.6 M) 25
-
Poly(trifluoronitrosomethane-co-tetrafluoroethylene)
35
Poly(vinylchloride-srat-diphenylpropene)
Tetrahydrofuran 25
-
(77.3/22.7, mol/mol) Tetrahydrofuran 25
-
(62/38, mollmol) Tetrahydrofuran 25
-
(33/67, mol/mol) Tetrahydrofuran 25
-
(I l/89, mol/mol) Tetrahydrofuran 25
-
(4/96, mol/mol) Tetrahydrofuran 25
(O/ 100, moVmol) Tetrahydrofuran 25
-
8 9 7 0 7 3 0 2 2.34 VG 613
8 0 6 8 5 3 0 2 2.27 VG 613
66 It 2 625 i 95 2.05 VG,VT 6 1 4
7512 655 3~ 95 2.15 VG,VT 6 1 4
771t2 660 f 95 2.17 VG,VT 6 1 4
6 3 6 1 7 3 0 5 2 . 0 4 V T 6 1 6
-
970-986
9 6
7 6
75
51.1 5 7 5 2 8 5 2.02 8.15 V T 3 1 7
55 5 8 5 2 8 5 2.05 8.4 V T 3 1 7
3 8 51Ozk25 3 0 4 1.68 zt 0.08 V T 3(685)
127 7 6 8 3 2 0 2.40 VG 8 7 9 2
123 761 2 9 0 2.62
- VG 8 7 9
100 7 0 7 2 5 0 2.82
-
VG 8 7 9
7 0 6 3 0 233 2.70
-
VG 8 7 9
6 2 6 0 5 2 3 0 2.63 - VG 8 7 9
5 6 5 8 5 2 2 4 2.61 VG 8 7 9
5 0 5 6 3 221 2.55
-
VG 8 7 9
VG
V T 6 8 4
V T 6 8 4
LT,VT
958
6 8 4
TABLE 7. MAIN-CHAIN CARBOCYCLIC POLYMERS
Polymer Sol vent
Temp.
(C)
112
SonlMw
(x104)
or lip
(nm)
Ko
(x103)
Wg)
ro/M I2
x lo4 (nm)
rof/M12
(x104)
(nm) c7 = ro/rm Method Ref.
Poly( 1,2-acenaphthenylene)
tram Var i ous s ol ve nt s 25 3613 5 2 0 i 2 0 3 5 4 1.47 It 0.05 VG 2 6 3
TABLE 8. MAIN-CHAIN HETEROATOM POLYMERS
Polymer Sol vent
Temp.
(C)
S&M;/
(x104) Ko rof/M/
or ap (x103) ro/Mf2 (x104)
(nm) (mVg) x104 (nm) (nm) 6 = ro/ror C, = riln12 Method(s) Refs.
8.1. POLY(OXIDES), POLY(ETHERS)
Poly(butene oxide), see Poly[oxy(ethylethylene)]
Poly(ethylene oxide), see Poly(oxyethylene)
Poly[oxy(rert-butylethylene)] B e n z e n e 25 2 3 0 9 3 0 377 * 2.47 13.6 VG 385
isotactic Xyiene 8 0 - 1040 15.9 VG 7 9 0
Poly(oxy-1,2-cyclohexylene) T o l u e n e 35 - 53 5 9 2 3 5 9 1.65 VG 4 7 2
Poly(oxydecamethylene) Be n z e n e ; c h l o r o f o r m - 3 0 2 4 0 9 6 0 5 7 0 1.68 7.5 VG 3 8 6
Poly[oxy(2,6-dimethyl-1,4-phenylene)]
Chlorobenzene; toluene 25 - 16615 833 i 10 7 1 5 1.16f0.02 2.7 VG 4 7 4
Benzene: carbon 25 - 175i8 850f 10 7 1 5 1.13iO.02 2.6 VG 4 7 3
tetrachloride
TABLE 8. contd
Unperturbed Dimensions of linear Polymers: Main-Chain Heteroatom Polymers VII / 61
Polymer Sol vent
Temp.
(C)
S&/M?
(x104) KIJ Qf/M/
or ap (x103) rolM/2 (x104)
fnm) (mk) x IO4 (nm) (nm) 0 = ro/rof C, = r~lnl Method(s) Refs.
Poly[oxy(2,6-diphenyl-1,4-phenylene)]
Chlorobenzene; toluene 2 5
Poly(oxyethylene) Var i ous sol vent s - 2 0
Aq. KzS04 (0.45 M);
aq. MgS04 - 4 0
( 0. 39 M)
Benzene 2 5
Acetone 2 5
Various poor solvents 5 0
Undi l ut ed 6 0
Wa t e r 2 5
3-85
Aq. KOH (1.24M) 2 5
(0.96- 1.48 M) 2 5
Poly[oxy(ethylethylene)] Benzene; butanone; 3 0
2-propanol
2-Propanol 3 0
Poly(oxyhexamethylene) Benzene; dioxane 2 5
Poly(oxymethylene) Hexafluoroacetone sesquihydrate
(l/1.7, mol/mol) 2 5
Poly[oxy(2-methyl-6-phenyl-1,4-phenylene)]
Dioxanelmethyl- 2 5
cyclohexane ( 1 / 1, v/v)
Poly[oxy(phenylethylene)] Tol uene 2 5
Poly(oxypropylene) Benzene; methanol 2 5
Toluene/2,2&methylpentane
Poly(oxytetramethylene)
(517, v/v)
2,2,4-Trimethylpentane
Diethyl malonate
Ethyl acetate
Ethyl acetatehexane
(22.1/11.3, w/w)
2-Propanol
Undi l ut ed
Poly(oxytrimethylene) Acetone; benzene;
carbontetrachloride
Poly(propyleneoxide), see Poly(oxypropylene)
Poly(tetrahydrofuran), see Poly(oxytetramethylene)
8 . 2 . POLY(ESTERS), POLY(CARRONATES)
Poly(butylene adipate-co-butylene isophthalate)
(100 mol% BADP) Chloroform
(80 mol% BADP) Chloroform
(50 mol% BADP) Chloroform
(20 mol% BADP) Chloroform
3 9 . 5
5 0
3 3 . 5
3 0
3 0 . 4
3 1 . 8
4 4 . 6
6 0
3 0
3 0
3 0
3 0
3 0
- 8 0 1 5 660 f 20 5 0 0
- 1lOi 1 0 750+30 5 4 1
- 115115 775i30 5 4 1
1 2 9 7 9 0 5 4 1
- 1 7 0 8 4 0 5 4 1
1 7 0 8 4 0 5 4 1
dln ri/dT = (0.23 & 0.02) x 10m3 (deg
-
-
-
-
-
-
-
-
-
-
3 7 5
-
-
-
-
1 7 5 8 8 8 5 6 6
201-156 - -
1 7 7 8 8 8 5 6 6
183-180 - -
8 7 7 0 0 4 2 3
1 1 0 7 3 0 421
185 9 1 0 5 6 5 *
43Oi40 1200f80 5 2 2
1 1 0 1 5 790 i 20 5 8 0
7 5 6 4 0 344 *
1151t 10 750f25 4 7 2
107. 5 7 3 5 4 7 2
- 8 0 0 4 9 4 *
2 4 3 9 4 5 5 5 6
180120 860f30 5 5 6
2 6 7 9 7 5 5 5 6
2 1 0 900 f 20 5 5 6
2 3 1 9 3 0 5 5 6
dln ri/dT = -1.33 x 10mi (deg-)
-
1 2 6 7 9 5 5 5 0
- 2 4 7 9 5 0
-
2 2 5 9 2 3 -
- 1 6 0 8 2 3
-
- 9 9 7 0 0
-
Bisphenol A poly(carbonate), see Poly(oxycarbonyl-l,4-phenyleneisopropylidene-1,4-phenylene)
Poly(ethylene terephthalate), see Poly(oxyethyleneoxyterephthaloy1)
Chlorobenzene 2 5 1OOi 1 0 720f25 5 4 0
Poly(P-hydroxybutyrate) Chloroform/n-heptane.
(50.2/49.8, v/v) 2 5
-
1 5 7 8 6 0
-
2,2,2-TrifluoroethanoV
water (52.6147.4. v/v) 2 5
-
1 4 9 8 4 0
-
2,2,2-Trifluoroethanol 2 5 380-390 145-160 830-960 -
Poly(4,4-isopropylidenediphenyl carbonate)-block-poly(styrene)
2 6 w t . %- P S Chloroform, diethyl
carbonate, 1,4-dioxane,
methylene chloride,
tetrahydrofuran 2 5
- -
910-1040 -
1. 45
-
-
-
-
1. 33 zt 0. 05
-
-
-
4 . 2 VG 414
-
-
3. 55
-
-
-
-
VG 9 6 7
VG 9 6 7
VG 9 6 7
VG 961
V T
VT,LT
VT,LT
VG,LG
VG
3(415)
9 5 0
9 5 0
9 5 0
9 5 9
* These values of r~f of poly(epoxide) chains were calculated by 0.377/M! [nm.mol 12/gram I*], while those given without asterisk were calculated by 0.360/M:/*. The
former is due to Allen et al. (Ref. 695). The latter is based on the assumption that all valence angles of skeleton are tetrahedral.
1. 32 i 0. 04 3 . 5 VG 4 7 3
1. 38 f 0. 06 3 . 8 V G 3(389,390)
1. 43 f 0. 06 4 . 1 VT 395, 655
1. 46
1. 55
1. 55
1
I .51
4. 25
4 . 8
4 . 8
1. 57
-
1. 66 zt 0. 05
-
-
-
-
5 . 5
VG 6 5 6 , 3 8 8
VG 3 8 7
VG 3 8 7
S T 6 5 5
VG 9 6 3
VG 9 6 3
VG 9 6 3
VG 9 6 3
VG,VT 391
1. 71 5. 85 V T 3 9 6
1. 61 5. 15 VG 3 9 8
2. 3 f 0 . 2 1 0 . 5 VG 4 0 2
1.36ztO.04 3 . 7 V T 6 7 3
1. 85 6. 85 VG 3 8 5
1. 59 i 0. 05 5. 05 VG 3(411)
1. 56 4. 85 VT 4 1 1
1. 62 5. 15 L T 654
1. 70 5 . 8 V T 6 5 8
1. 55 It 0. 05 4 . 8 VG 412
1. 75 6 . 1
1. 62 +z 0. 03 5. 25
1. 61 5 . 6
V T 6 5 8
V T 4 1 2
V T 6 5 8
S T 6 5 9
References page VII - 68
VII / 62 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 8. cont d
Polymer Sol vent
Temp.
((3
s@JM;12
(x104) Ko Qjf/Mf2
or up (x103) ro/Mj2 (x104)
(nm) (mUs)
x lo4 (nm) (nm) 5 = ro/rof C, = r&n12 Method(s) Refs.
48 wt . %- PS ibid. 25
50 wt . %- PS ibid. 25
13 wt . %- PS ibid. 25
Poly(oxybutynedioyloxyhexamethylene)
Benzene: chl oroform 20
Poly[oxycarbonyloxy- 1,4-phenyleneisopropylidene-1,4-phenylene]
Met hyl ene chl ori de; 2. 5
tetrahydrofuran
Butyl benzyl ether 170
Cyclohexaneldioxane
(36.1163.9, w/w) 25
Chloroform; 25
tetrahydrofuran
Hexanektrachloroethane
(54146, v/v) 30
Various 25
Poly(oxy-1,4-cyclohexyleneoxysebacoyl)
c i s Chloroform 20
tram Chloroform 20
Poly(oxyethyleneoxyterephthaloy1)
Phenolketrachloroethane 2 5
(l/L v/v)
ochlorophenol 25
Tri fl uoroacet i c aci d 30
Poly(oxyfumaroyloxyhexamethylene)
Chloroform 20-50
Poly[oxy(hexahydroterephthaloyl)oxyoctamethylene]
ci s Chloroform 20
tram Chloroform 20
Poly(oxyhexamethyleneoxy-2,9-dibutylsebacoyl)
Benzene 20
Poly(oxyhexamethyleneoxysebacoy1)
Benzene; chl oroform 20
Poly[oxyisophthaloyloxy-l,4-phenylene (fluoren-9.yildene)-1,4-phenylene]
Tetrachloroethane; 20
tetrahydrofuran
Poly(oxymaleoyloxyhexamethylene)
Benzene; chloroform; 20-50
tetrahydrofuran
Poly(oxy-1-oxo-dimethyltrimethylene)
Ttifluoroacetic a c i d . 2 0
Poly(oxy-1-oxo-hexamethylene) Benzene; dioxane; 25
ethyl acetate .
IOOO- 1200
-
1040-1200
-
1120-1270
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
180120 870 i 30 6 2 7
180120 880 i 20
2 1 0 9 4 0 7 9 6 .18 V T 4 7 6
2 1 0 9 4 0 7 9 6 .18 VT 4 7 6
150113 8 4 0 7 9 6 .05 VG 4 7 8
2 3 0 9 3 0 7 9 6 1.16
210+ 17 920 f 50
-
1.35
140120 8OOf30 4 9 5 1.62 zt 0.05 VG 3(480)
160 i 20 840 f 30 6 3 3 1.33f0.05 VG 3(480)
1601 15 840 i 25 6 8 7
2 1 0 9 1 0 6 8 7 1.33 3.7 VG 484
2 4 2 9 7 5 6 8 7 I .42 4.25 VG 4 8 8
180120 870 i 30 5 9 2
140120 800 i 30 4 9 5 1.62 k 0.05 VG 3(480)
160120 840 i 30 6 3 3 1.33 i 0.05 VG 3(480)
155125 835 i 70 4 5 7 1.82f0.15 6 . 6 3(418)
215160 9101100 5 4 0 1.7010.17 5.8 3(418,419)
2 1 0 9 0 2 VG 6 7 4
135115 790 i 30
2 3 8 9 5 0
- -
- - -
Poly(oxy-1-oxo-3-methyltrimethylene), D,L
Chl oroform; et hyl ene 30
dichloride
Ttifluoroethanol 25
Poly(oxypetiuorosebacoyloxydecamethylene)
Ch l o r o f o r m; s-tetra- 2 5
chloroethane
Poly(oxysebacoyloxyhexadecamethylene)
Chloroform 20
Poly(oxysuccinyloxyhexamethylene)
Benzene; chloroform;
tetrahydrofuran 20-60
133 875
133 875
-
270 + 40 lOOf 5 5 5 1 . 8010.10 6.5 VG 3(419)
165530 850 i 60 5 2 2 1.621kO.14 5.25 VG 3(417)
Poly[oxy-( 1,1,3-trimethyl-3-phenylindan-5,4-dicarbonyl)-oxy- I ,4-phenyleneisopropylidene- I ,4-phenylene]
Tetrahydrofuran 25 - 15612 850f 10
Poly(oxyundecanoy1) Chloroform 2 0 - 185i60 88Oi 100
Poly(P-propiolactone) Chloroform, 1,4-dioxane,
2,2,2,-trifluoroethanol 3 0 146 -
7 9 6
5 1 0
-
-
-
-
-
5 5 0
-
-
-
-
I .39 f 0.05
l . 10f0. 05
I .22 f 0.03
1.47 f 0.05
55 i 0.05
-
-
-
-
-
-
1.6OzkO.16
-
-
-
VG
VG
VG
9 5 9
959
9 5 9
3.9 VG 3(4 16)
VG 3(479)
-
VT 6 9 4
VG 8 8 0
3.15 VG 3(491)
4.3 VG 3(417)
4.8 VG 3(417)
5.9zto.3
VG 8 0 0
VG 8 0 8
5.6 881
-
VG 7 9 9
- VG 7 9 9
6.3 + 0.5 VG,VT 7 9 5
-
5.1
-
VG 794,882
V G 3(419,420)
VG 991
i
TABLE 8. contd
Unperturbed Dimensions of linear Polymers: Main-Chain Heteroatom Polymers VII / 63
Polymer Sol vent
Temp.
(C)
S&J MV
(x104) Ko ,()flM12
or BP (x103) r,,/Mi 2 (x104)
(nm) (mW x lo4 (nm) (nm) o = ro/rof C, = r~/n12 Method(s) Refs.
8.3. POLY(AMIDES)
Poly(iminoadipoyliminohexamethylene), (Nylon 66)
Aq. HCOOH (90%. v/v) 2 5
-
Aqueous HCOOH (90%, v/v)
KC1 (2. 3 M) 2 5
-
2 5
-
Poly(iminohexamethyleneiminoterephthaloyloxyhexamethyleneoxyterephthaloyl)
Phenolketrachloroethane 2 5
-
(l/l, w/w)
Poly(iminohexamethyleneiminothiocarbonylhexamethylenethiocarbonyl)
Dimethylformamide/ 2 0
-
LiCl (5%)
Poly(iminohexamethyleneiminothiocarbonyltetramethylenethiocarbonyl)
Dimethylformamide/ 2 0
-
LiCl (5%)
Poly[imino( I-oxododecamethylene)], (Nylon 12)
nr-Cresol 2 5
-
2 5
-
Sulfuric acid (96%) 2 5
Poly[imino( I -oxohexamethylene)], (Nyl on 6)
Sulfuric acid 2 5
-
Aq . HC OOH 2 5
-
(65-85%)
Poly[iminoterephthaloylimino-I,4-phenylene(Auoren-9-ylidene)-1.4-phenylene]
Dimethylformamide 2 5
-
Poly[iminoterephthaloylimino(trimethylhexamethylene)], 2.4,4-/2.2.4-trimethyl (I/l,
Ani l i ne 142
-
Dimethylformamide 2 5
-
Pyr r ol i ne 6 2
-
Poly(isophthaloyl-rrans-2,5-dimethylpiperazine)
N-methyl-2.pyrrolidone 2s 355
8.4. POLY(AMIN0 ACIDS)
Poly(p-benzyk-aspartate), see Poly(iminocarbonyl-r-benzyloxycarbonylethylidene)
Poly(y-benzylglutamate), see Poly(iminocarbonyl-benzyloxycarbonylpropylidene)
Poly(iminocarbonyl-~-benryloxycarbonylethy~idene)
m-Cresol 100
-
Poly(iminocarbonyl-benzyloxycarbonylpropylidene)
L Dichloroacetic acid 2 5
2 5
-
D,L Dichloroacetic acid: 2 5
-
dimethylformamide
Poly(iminocarbonyl-r-carboxypropylidene), [Poly(r-glutamic acid)]
Phosphate buffer I7
(Na+, 0.3 M; pH 7.85)
Poly(iminocarbonyl-L-hydrocarbonylpropylidene), [Poly(a-L-glutamic acid)]
Sodium phosphate buffer
(pH, ca. 7) 2 5 . 5
-
19Ozt20 890 f 40 5 4 5 1. 63 + 0. 08 5 . 3 V G 3(445,446)
2 5 3 1 0 1 0 5 4 5 1. 85 6. 85 VT 4 4 4
1 9 2 9 3 5 5 4 5 I .72 5. 93 VT 6 6 8 , 6 6 9
2 5 0 1 0 0 0 - -
4. 76 VG 8 0 6
1 4 2
-
2 7 9
-
2 6 6
-
2 3 8 9 7 0
2 2 2 9 4 9
- -
-
6. 29
-
6. 01
6. 71 VG 8 0 3
- VG 8 1 2
-
VG 8 1 2
190110 890 * 20 5 4 5 1. 63 zt 0. 04 5 . 3 VG 3(453)
2 2 9 9 7 0 5 4 5 I .78 6. 35 V T , V G 4 5 0
4 0 9
mol/mol)
1 4 8
1 7 4
151
- 1 2 0 0 VG 5 0 3
8 5 0 6 4 0 1. 33
-
VG 8 0 4
- - - -
VG 8 0 4
8 5 0 6 4 0 1. 33 - VG 8 0 4
- - - -
VG 9 7 1
-
6 0 0 2 6 8 2. 24 f 0 . 1 9 . 6 V A 6 7 0
58i5 600 i 20 2 5 9
58f5 600 i 20 2 5 9
2. 32 i 0. 08 1 0 . 3 VG 3(457)
2. 14 8 . 8 V A 670(457)
2. 32 i 0. 08 1 0 . 3 VG 3(459)
-
7 2 0 2.14fO.l 8 . 8 V A 6 7 0
9 8 . 4 7 7 5
3 3 7
- - -
VG 8 1 5
Poly(iminocarbonyl-~-(N-hydroxyethylcarbamoylpropylidene)], (Poly[N-(2.hydroxyethyl)-L-glutamine]]
Wa t e r 3 0 - - -
Poly(y-hydroxy-r-proline) Water 3 0 - -
Poly[(methylimino)carbonylmethylene], (Poly(sarcosine)]
Wa t e r 2 0 5 0 1 2 0 57Oi90
8.5. POLY(URETHANES)
Poly(oxytetramethyleneoxycarbonylimino-2,4-tolyleneiminocarbonyl)
Dimethylformamide 3 0 - - 1 0 3 0
8 . 6 . POLY(SULFIDES)
Poly(thiopropylene) Benzene 2 0 6 0 6 0 0
Poly(trimethylene sulfide) Chloroform 2 5 - 1 5 0 7 8 3
- -
VG 8 0 5
- -
VG 8 0 5
-
4 5 5
5 1 5
1.25f0.20
2 . 0
IOfl
1 5 . 8
3 . 0
4 . 0
Compl ex 8 1 7
V A 8 1 8
VG 3(468)
VG
VG
4 9 7
4 3 6
9 7 9
References page VII - 6X
VII/64 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 8. contd
Polymer Solvent
Temp.
(C)
SC/M;/=
(x104) Ko rQf/M/2
or ap (x103) r,,lM I2 (x104)
(nm) (ml49 (x lO%m) ( n m) u = ro/ror C, = r~/n12 Method(s) Refs.
8. 7. POLY(PHOSPHATE.5)
Poly[oxy(hydroxyphosphinylide.ne)]
Aq. NaBr
( 0. 35- 0. 415 M)
Aq. LiBr
Aq. CsCl (0.96 M)
Aq. LiCl (2.9 M)
Aq. NaCl (0.96 M)
25 5013 560+20 370
30
30
30
-
8. 8. POLY(SILOXANES), POLY(SILSESQUIOXANES), POLY(SILMETHYLENES)
1.51 Ito. 6. 6 VT, VG 3( 422)
3. 93
2. 25
2. 19
7.1 L T
L T
L T
662
663
663
663
25 540 988 450 2. 2 L T 671
25
-
25 580
1200 480 2. 5
- LG 671
1160 322 3. 6
-
L T 671
~25 8015 670+20 482 1.39zto.05 6. 25 VT,VG
2- 90
22. 5
266i 10
-
612zt 13 482 1.271kO.03 5. 2 L T
106 740 482 1.54 1. 6 VT
3( 427,
428)
664
425
424
2
29
28
28
31
36
-
-
294i 14
-
70 640
74 655
19. 5 [6551
482
482
78
15
-
685
660 482
1.33
1.36
-
-
-
1. 37
5. 1
6. 0
6.1
VT 425
VT 425
VT 838
L T 838
VT 982
VT 42. 5
51. 5
78. 5
89. 5
25
30
40-100
30- 105
76 660
76 660
13 650
15 670
78 678
482
482
482
1.37 6. 1
1. 37 6.1
1. 35 5. 9
- -
- -
V T 425
V T 425
VT 425
VG 981
VG 953
S T 665
VT 665
din ri/dT = -(0.78 i 0.06) x 10m3 (deg-t)
dln ri/dT = -(0.71 zkO.13) x 10e3 (deg-)
1.89
2. 04
1.58
-
-
12.0 V T 433
14. 0 VT 433
8. 35 VT 434
10.8 VG 983
10.8 VG 983
10.2 VG 983
13.4 VG 983
1. 61( 1. 90) * 6. 3
1.66( 1.96) * 6. 65
VT 435
VT 43s
VT 615
-
1 . 1
-
VG 986
-
VG 985
16.6 VG 987
16.2 VG 987
15.4 VG 987
Poly(dimethy1 siloxane), see Poly[oxy(dimethylsilylene)]
Poly(dimethylsilmethylene) HeptaneJpropanol
(68.8/31.2, v/v)
Poly(dimethylsi1trimethylene) Heptane
Poly(diphenylsiltrimethylene) CyclohexanolAoluene
( 63. 5136. 5, v/v)
Poly[oxy(dimethylsilylene) But a none , t ol ue ne
Various theta solvents
CsF1s/CzC14Fz
( 33/ 67, w/ w)
Et hyl i odi de
Bromocyclohexane
Bromocyclohexane
Bromocyclohexane/
phenetole (6/7, v/v)
Chlorobenzene/dimethyl
phthalate (45/6, v/v)
76
10
30. 4
25
50
20
25
25. 0
72. 8
50. 5
25
Bromobenzene
Phenet ol e
Tol ue ne
Undi l ut ed
Di l ut ed wi t h l i qui d
s i l i c on
Poly[oxy(dipropylsilylene)] 2-Pentanone
Tol ue ne
Poly[oxy(methylphenyIsilylene)] Di i sobut yl ami ne
Cycl ohexane .
Methylcyclohexane
Tetrahydrofuran
Poly[oxy(y-trifluoropropylmethylsilylene)]
Cyclohexyl acetate
Methyl hexanoate
Poly(phenylsilsesquioxane) 1,2-Dichloroethane
8. 9. POLY(HETEROCYCLICS)
Poly(3.3 -dimethylthietane) Tetrahydrofuran
87.1 703 372
109 759 372
51.5 575 363
71.5 - -
71.5 - -
65. 0 - -
96. 0 - -
41. 0 550( 648) * 341
44.5 565( 667) ' 341
1160 -
120 7 4 4
-
Poly[2-methoxy-4,6-di@,p-isopropylidene diphenyloxy)-s-triarine]
Chl or of or m,
1,2-dichloroethane,
1,2-dichloroethane/n-
butanol (80/15, v/v) 3 0
Poly[N-(n-octadecyl)maleimide] Benzene 25
1- Chl or ona pht ha l e ne 25
o-Dichlorobenzene 25
16.5-17.5 850- 863 778
28
27
25 - -
* The values of rc/M/* and D given in parentheses were obtained by using Cps = 1.39 x 10z3, while for the others @a = 2.5 x 10z3 was used.
T ABL E 8. contcf
Unperturbed Dimensions of Linear Polymers: Main-Chain Heteroatom Polymers VII / 65
P o l y m e r Sol vent
Te mp .
(C)
SQJM;J2
(x104) Ko ri)fIM/
or ap (x103) rO/M I2 (x104)
b) (mUg)
x lo4 (nm) (nm) 0 = ro/rw C, = r:/n12 Method(s) Refs.
Tetrabydrofuran 25 3 7
Toluene 25 2 4 -
I-Decanol 39.4 18.3 -
1-Hexanol 79.0 - 37.0 -
1- Oct anol 53.7 23.5 -
Poly[6,6-bis(3-phenylquinoxaline)-2,2-diyl-l,4-phenylene]
m- Cr esol 4 0 2 1 3 1000
Poly[( 1,3-dihydro-3-oxo-isobenzofuran-l-ylidene)-l,4-phenyleneoxyisophthaloyloxy-1,4-pbenylene]
Tetracbloroethane; 2 0 - 195 8 8 0
tetrahydrofuran
Poly[(l,3-dihydro-3-oxo-isobenzofuran-l-ylidene)-l,4-phenyleneiminoterephthaloylimino-1,4-phenylene]
Dimethylformamide 25 - 5 5 8 - 1500
Poly[(o,~-1,2-pyrrolidindiyl)carbonyl]
Wat er 25 - ca. 25 ca. 570
Poly(l-isobutyl-2,5-dioxopyrrolidin-3,4-diyl)
Butyl acetate 21 - 132 7 9 0
Poly(l-p-tolyl-2.5.dioxopyrrolidin-3,4-diyl)
Dimethylformamide 21 - 7 5 6 7 0
-
-
-
-
3 9 0
-
-
-
2 0 . 0 VG
15.0 VG
11.7 VT
18.8 VT
13.8 V T
VG
-
VG
VG
ca. 1.5 VT
VG
VG
9 8 7
9 8 7
9 8 8
9 8 8
9 8 8
8 4 9
6 7 4
3(507)
5 1 2
8.10. COPOLYMERS (MALEIC ANHYDRIDE, SULFONES, SILOXANES)
8.10.1. MALEIC ANHYDRIDE COMPOLYMERS
Poly[3,9-bis(ethylidone-2,4,8,1O-tetraoxaspiro(5,5)undecane)-ran-rrans-cyclobexane-dimethanol)/( 1,6-hexanediol)]
rrans-CDMU ,6-ND (100/O) Tetrahydrofuran 3 0
(70/30) Tetrabydrofuran 3 0
(50/50) Tetrahydrofuran 3 0
W/71) Tetrahydrofuran 3 0
(O/100) Tetrahydrofuran 3 0
Poly[(tetrahydro-2,5-dioxo-3,4-furandiyl)-I-phenylethylene]
Tetrahydrofuran 3 0
8.10.2. SULFONES
Poly(sulfonylbicycloheptene) Chloroform 25, 40
Cyclohexane 25
Poly[sulfonyl(butylethylene)] Hexyl chloride 13
13
Benzene/cyclohexane 25
(43157, v/v)
ButanoneR-propanol 8-24
(30-37 / 70, v/v)
Dioxane/hexane 2 0
(40/60, v/v)
Poly[sulfonyl(l-methyl-1-propylethylene)]
Butanoneihexane
(35.41646, v/v) 11.5
Poly(sulfonyl-p-phenoxyphenylene)
Dimethylformamide 25
Poly[sulfonyl(phenylethylene)] Tetrahydrofuran 3 0
8.10.3. SILOXANES
-
-
-
-
87.0
-
67.0 -
61.5 -
50.0
-
30.0 -
-
-
-
-
LS
-
LS
-
LS
-
LS
-
LS
9 5 4
954
954
9 5 4
9 5 4
-
82.6 7 3 2 3 8 3 1.91 VG 5 0 6
-
-
296f9
2 9 . 0 488
2 9 . 0 4 8 8
67f2 625 f 10
- 725 f 22
6612 642zk7
5 3 5 8 0
65 + 2 638&7
3 5 0 1.79 It 0 . 0 2
3 5 0 2.07 + 0.07
3 5 0 1.84 f 0.02
4 . 2 VG
4 . 2 VG
V T
L T
VG
840
8 4 0
6 6 6
6 6 6
3 4 8
3 5 0 1.66 VT 4 3 9
350 1.83 =t 0.02 VT 4 3 8
91 700
106 7 5 3 +20
57.4 6 4 9
VT 4 3 9
771 0.98 zk 0.10 VG 841
4 2 5 1.53 VG 4 4 0 , 6 6 7
Poly(p-~erf-butylstyrene)-block-polydime~ylsiloxane)-b~oc~-poly~-~e~-butylstyrene) 28 wt.% PBS
Methyl ethyl ketone 15 - 58.9 6 2 0
Benzene 35 6 8 6 5 0
Methyl ethyl ketone 15 - 5 9 6 2 0
2 0 6 2 6 3 0
31 6 2 6 3 0
Poly(dimethy1 siloxane-co-diphenyl siloxane)
(95/5, mol/mol) Bromobenzene 9 - 100 7 4 2
(66/34, mol/mol) BenzeneR-propanol 4 2 7 4 6 7 0
(44156, w/w)
-
VT 9 5 7
-
VG 9 6 0
V T 9 6 0
VG 9 6 0
-
VG 9 6 0
1.56 VT 5 9 6
1.70 VT 5 9 6
References page VII - 68
VII / 66 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 8. c ontd
Polymer Sol vent
Temp.
c-3
SQJM;J
(x104) Ko r(f/M I2
or ap (x103) Q/M/= (x104)
(nm) (mlk) x lo4 (nm) (nm) d = rg/r~f C, = riln12 Method(s) Refs.
(55/45, molImo1) Di met hyl pht hal at e 8 2 . 5
Ethanol/toluene 2 9 . 5
(31163, w/w)
Poly(styrene)-block-poly(dimethyl siloxane) 68% PS
But anone 3 0
Decalin 3 0
Tol uene 3 0
Poly(styrene)-block-poly(dimethy1 siloxane)-block-poly(styrene) 68% PS
Tol uene 3 0
8.11. OTHER COMPOUNDS
Poly(2-acrylamino-2.methylpropanesulfonic acid)
cesium salt Aq. CsCl (I N)
sodi um sal t Aq. CsCl (1 N)
Aq. NaCl
t et r abut yl ammoni um s al t Aq. NaCl
(O.lN; IN; 5N)
Organic solvents
Tet r abut yl ammoni um
bromide (0.5 N)
Poly(dihexoxyphosphazene) Tetrahydrofuran
Poly(di-n-hexylsilane) Tetrahydrofuran
Poly(hexamethylenedimethylammonium bromide)
Aq. KBr (0.4 M)
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
-
7 8 6 7 5 1. 81 VT 5 9 6
-
7 8 615 1. 81 VT 5 9 6
-
8 1
-
8 0
-
8 2
-
8 0
6 8 7
6 8 7
6 8 7
VG 9 5 3
VG 9 5 3
VG 9 5 3
6 8 7
-
VG
- 1 6
- 3 2
- 3 0
- 1 0
- 2 3
3 0
-
1 1
-
1 2
-
1 2
-
1 1
VG 8 6 4
VG 8 6 4
VG 8 6 4
VG 8 6 4
-
-
1 9 VG 864
2 3 VG 8 6 4
- 3 0 . 8
- -
- 117. 4
-
7 4 0
-
-
C, = 13.2 VG 9 9 4
-
1 9 VG 9 9 5
8 2 5
- VG 8 4 4
1 9 0 9 1 3
-
5. 26 VG 9 9 2
2 2 5 9 6 5
-
5. 89 VG 9 9 2
175 8 8 8
-
4. 98 VG 9 9 2
165 871
-
4 . 1 9 VG 9 9 2
Poly[oxythiocarbonyloxy-l,4-phenylene(methyl)phenylmethylene-l,4-phenylene]
Chloroform 2 5 -
Dichloromethane 2 5 -
1,4-Dioxane 2 5 -
Tetrahydrofuran 2 5 -
TABLE 9. CELLULOSE AND DERIVATIVES, POLY(SACCHARIDES)
Polymer S o l v e n t
Temp.
((2
Sk/MY
(xl09 Ko ror/M I2
or lip (x103) olM/2 (x104)
(nm) (mVf$
x lo4 (nm) (nm) d = ro/rof C, = ri/n12 Method(s) Refs.
Amylose
Amylose acetate
Amylose triacetate
Dimethyl sulfoxidC;
ethylene diamine
Var i ous sol vent s
Aq. KC1 (0.33 M);
dimethyl sulfoxide
Aq. KC1 (OS M)
Aq. KOH (0. 15 M)
Aq. KCI (0. 33 M)
Nitromethane
Water/dimethyl sulfoxide
(40160, v/v)
Wa t e r
Nitromethane
Chloroform; nitromethane
2 5 5 6 1 1 2 6OOi50 3 3 5 1.79*0.15 VG 3(518)
2 5
-
7 0 0 3 3 5 2. 08 VT,VG 5 1 7
2 5 110*5 750 k 25 3 3 5 2. 24 f 0. 08 VT,VG 3(520)
2 5
2 5
2 5
2 2 . 5
61 6 2 5
1 6 4
- -
9 2 0
3 3 5 1. 87 V T 5 2 3
VG 5 1 9
5. 2 V T 5 3 0
LG 5 2 7
- -
3 3 5 2. 75
2 5
2 4
2 5
3 0
3 0
3 0
2 5
2 5
4 . 1 VA,LG 8 8 4
1 1 . 7 VG,LG 9 9 9
VG 8 4 6
VG 3(524)
VG 6 7 6
VG 617
LG 8 4 7
6. 83 VG 8 4 7
-
- -
5 1 5 8 9
47+ 1 0 580 f 60
4 8 5 8 0
800f 15
- 5 5 7
- 614
2. 22
-
2 5 0
2 5 0
2. 50
2. 32 + 0. 24
2. 32
3. 2 + 0. 06
Amylose tributyrate But anone
Butanone; carbon
tetrachloride
Ethyl acetate 2 5 5 9 5 L G 8 4 7
TABLE 9. contd
Unperturbed Dimensions of linear Polymers: Cellulose and Derivatives, Poly(saccharides) VII / 67
Polymer Sol vent
Temp.
(C)
S@JM;12
(x104) Ko Q/M/=
or or (x103) rCJjM/2 (x104)
(nm) hW x lo4 (nm) (nm) o = ro/rm C, = ri/n12 Method(s) Refs.
Amylose tricarbanilate
Amylose tripropionate
Carboxymethyl amylose,
sodi um sal t
Diethylaminoethyl amylose
hydrochloride
Cel l ul ose
Cellulose diacetate
AC. a c i d c ont e nt , 55. 5 wt . %
Cellulose triacetate
Cellulose tributyrate
Cellulose tricarbanilate
Cellulose trihexanoate
Cellulose trinitrate
(N%, 13.9) Acetone
(N%, 12.9) Acetone
(N%, 13.5) Ethyl acetate
( N%, 12. 0) Acetone
Ethyl acetate;
tetrahydrofuran
Acetone; dioxane;
pyr i di ne
Dioxane/methanol
(4915 1, v/v)
Pyr i di ne
Ethyl acetate
Aq. NaCl (0.65 M)
Aq. NaCl
(0.5 M; pH 8)
Aq. NaCl
( 0. 78 M; 0. 02% NaN X)
Aq. NaCl
( 0. 78 M; 0. 02% NaN j)
Cupriethylene diamine
Cadoxen
NJ-dimethylacetamide/
9% LiCl
Acetone
Tetrahydrofuran
Acetone;
chloroform; o-cresol
Ethylacetate; dioxane;
methyl acetate;
tetrahydrofuran
Chloroform
But anone
Dodecaneketralin
(75 125, v/v)
Acetone; dioxane;
pyr i di ne
Acetone
Acetone
Cyclohexane
Dioxane
Dioxane/methanol
(42.5j51.5, v/v)
Ani sol
Cy c l o h e x a n o l
Dioxane
Tetrahydrofuran
Dimethylformamide
Dioxanelwater
(100/7, v/v)
Acetone; ethyl acetate
Acetone
2 5
2 0
2 0
2 5
2 5
3 7 . 5
3 5
3 5
3 5
2 5
-
180f80 9ooi 1 5 0 6 2 0 1. 45 z!z 0. 25
2 5 0. 24 4 9 5 1 2 5 0 6 2 0 2 . 0
3 0
-
6. 71
2 5
2 5
25-30
-
-
- -
- -
1 0 8 1 1 0 750f30 4 6 5
3. 59
2. 56
1. 61 +0.07
2 5 73&740 4 6 5 1. 57- 1. 59
3 0
-
1 1 8 0
3 0
-
97f 1 5 730f40
1 3 0 -
8 2 6 9 0
- -
4 0 8 1.79f0.10
4 0 8 1. 69
2 0
-
130f30 s10*70 3 4 6 2. 34 f 0. 20
- 2 5
2 5
- 2 5
- 2 5
-
65f3 6 3 5 3 4 6
1 4 5 0
-
83. 5 f 3 6 9 0 3 4 6
4453 5 6 0 3 4 6
1. 83
-
-
1. 99
1. 61
2 0
9 4
7 3
7 3
1 5
3 0
4 5
6 0
7 0
2 5
4 1
6 3
-
ca. 1000
ca. 1050
3 4 6
3 4 6
3 4 6
-
-
3. 24
2. 32
2. 52
-
-
-
-
1 1 2 0
1 3 0 8 0 5
-
8 7 5
1 5 6 1 0 9 0
7 6 8 6 0
6 8 8 3 0
6 1 8 0 0
5 6 7 8 0
5 1 7 5 0
1 4 1 0
2 4 0 9 8 0
2 2 4 9 6 0
-
-
-
-
-
-
-
3 7 0
3 7 0
-
2. 65
2. 60
- 2 5
-
1 3 0 1 3 0 810f50 4 5 8 1.77f0.11
2 5 3 6 0 - 7 2 0 4 5 8 1. 57
2 2 0. 26 i 0. 01 - 930+ 1 5 4 5 8 2. 03 f 0. 03
- 2 0 0.40-0.70 - 1180- 1590 4 5 8 2.58- 3. 46
2 0 0.22-0.28 - 850- 9 7 5 4 5 8 1.85- 2. 12
2 5 9 7 0 - 2 4 1 0 4 6 2 4 . 7
2 5 5 3 0 - 1 7 8 0 4 7 5 3 . 4
3 0 7 0 0 - 2 0 5 0 4 6 7 3 . 9
2 0 0. 48
-
4 8 6 2 . 5
6 1 1
- -
- - -
-
27f5 470 f 30
-
2.21-2.24
1 8 7 2.51 f0.16
- -
2 1 8 0
471-478
- -
-
-
-
1 1 . 7
-
2. 32
2. 62
2. 95
-
5 7 5 8 3
2. 15
5. 63
-
6. 21
1.9y
10. 0
6. 4
9 1 . 9
2 6 . 3
1 3 . 5
VG 8 4 7
VG
8 6 1
3(528)
L T 6 7 8
LG 8 4 8
V T ? 8 5 0
V T 609
V A 5 3 0
V A 5 3 1
V A 5 3 1
VG 3(537)
VG 6 9 1 , 5 3 4
L G 1 0 0 0
LS 8 5 4
LS 8 5 4
V G 3(541,542)
VG 6 8 0
VG 8 5 7
VG 3(544)
V T 5 4 4
VG 3(528)
VG 6 9 3
v w c 9 9 6
VG 6 9 3
VG 6 9 3
L T 6 7 8
LT,VT 5 4 6
L T 5 4 6
VT 8 5 8
VG 8 5 8
VG 8 5 8
VG 8 5 8
VG 8 5 8
VG 8 5 8
v w c 9 9 6
V T 5 4 7
V T 5 4 7
VG
LG
x s
x s
x s
LG
L G
LG
x s
3(535,537
548, 549)
3(549)
6 4 1
6 7 9
6 7 9
6 8 6
6 8 6
5 5 5
6 8 7
References page VII - 68
VII / 68 VISCOSITY - MOLECULAR WEIGHT RELATIONSHIPS AND UNPERTURBED DIMENSIONS OF LINEAR CHAIN MOLECULES
TABLE 9. contd
Polymer Sol vent
Temp.
(C)
S@J M; j 2
(X104) Ko r or l M' 12
or np (x103) r O/ M' i 2 ( x 104)
mw Wk) x lo4 (nm) (nm) Q = ro/rm C, = r$/n12 Method(s) Refs.
Cellulose trioctanoate TlJhlene 3 0 - 12lf 15 800 + 40 3 4 0 2. 35 i 0. 12 VG 3(544)
Dimethylformamide 1 4 0 - 113 770 3 4 0 2. 27 V T 5 4 4
y-Phenylpropanol 4 8 - 129 805 3 4 0 2. 37 V T 5 4 4
(Cyanoethyl)(hydroxypropyl) Tetrahydrofuran 2 5 dln ri/dT = 3 . 8 x 10m3 (deg-) - - VTe 1 0 0 2
cel l ul ose
Et hyl cel l ul os e Methanol 2 5 232i 1 0 970f20 5 2 0 1. 87 f 0. 03 VG 3(559)
Ethyl hydroxyethyl cellulose Wa t e r 2 5 - 55Oi80 13OOf50 5 4 5 2. 38 f 0. 09 VG 3(560)
2 5 - 335 1100 5 4 5 2 . 0 VG 691, 560,
6 9 2
Hydroxyethyl cellulose Cadoxen; water 2 5 - 250 loo0 5 1 4 1 . 9 VG 691, 561
Methyl cellulose Wa t e r 2 5 - 92Oi 100 15OOzt60 5 8 1 2. 58 f 0. 10 VG 3(563)
Pullulan Wa t e r 2 5 3 6 0 9 1 - VG 1 0 0 3
Sodi um car boxymet hyl Cadoxen 2 5 - 357 1130 5 6 3 2 . 0 VG 69 1, 565
cellulose
Aq. NaCl 2 5 420 1190 5 0 2 2 . 4 VG 69 1, 565
(0.005-0.2 M)
Sodium cellulose xanthate Aq. NaOH (1 M) 3 0 290 1380 VG 6 8 1
Hyaluronic acid Aq. HCl (0.1 M) 2 5 - 2 . 5 V A 6 8 8
a These values of the characteristic ratio C, of cellulosic chains were obtained by C, = ri/DP I 2, where DP is the degree of polymerization and I = 0.425 (nm).
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922. L. Gargallo, M. I. Munoz, F. R. Dias, D. Radic, Polym., 29,
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923. L. Gargallo, N. Hamidi, D. Radic, Polym., 31, 924
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924. K. Yamaura, K. Hirata, S. Tamura, S. Matsuzawa, J. Polym.
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925. G. Lutringer, G. Weill, Polym., 32, 877 (1991).
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929. J. Roovers, N. Hadjichristidis, L. J. Fetters, Macromole-
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930. G. B. McKenna, G. Hadziioannou, P. Lutz, G. Hild,
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molecules, 20, 498 (1987).
931. N. Khasat, R. W. Pennisi, N. Hadjichristidis, L. J. Fetters,
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932. Y. Einaga, H. Koyama, T. Konishi, H. Yamakawa, Macro-
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933. M. E. Lewi s, S. Nan, J. W. Mays, Macromol ecul es, 24, 197
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934. J. W. Mays, S. Nan, D. Whi t fi el d, Macromol ecul es, 24, 315
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935. J. W. Mays, S. Nan, M. E. Lewis, Macromolecules, 24,
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936. W. -M, Kulicke, M. Prescher, Makromol. Chem., 185,2619
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937. S. Arichi, N. Sakamoto, S. Himuro, M. Miki, M. Yoshida,
Polymer, 26, 1175 (1985).
938. J. W. Mays, W. F. Ferry, N. Hadjichristidis, W. G. Funk,
L. J. Fetters, Polym.er 27, 129 (1986).
939. A. A. Abdel-Azim, S. A. Moustafa, M. M. E. Dessouky,
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940. S. Arichi, N. Sakamoto, M. Yoshida, S. Himuro, Polymer,
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941. T. Masuda, Y. Ohta, T. Yamauchi, S. Onogi, Polym. J., 16,
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942. J. M. Barrales-Rienda, P. A. G. Gomez, Europ. Polym. J.,
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943. J. Velickovic, J. Filipovic, Macromolecules, 17,611 (1984).
944. Y. Matsushita, Y. Nakao, K. Shimizu, I. Noda, M. Naga-
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945. J. Velickovic, J. Filipovic, Makromol. Chem., 185, 569
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946. N. Sakamoto, H. Tanaka, K. Yamaguchi, M. Yasuda,
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947. R. Gavara, A. Campos, J. E. Figueruelo, Makromol. Chem. ,
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948. G. M. Pavlov, E. F. Panarin, E. V. Komeeva, C. V Kur-
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191, 2889 (1990).
949. A. Leon, L. Gargallo, D. Radic, A. Horta, Polym., 32, 761
(1991).
950. M. B. Huglin, M. A. Radwan, Polym., 32, 1293 (1991).
951. K. Kamide, Y. Miyazaki, H. Kobayashi, Polym. J., 17, 607
(1985).
952. Y. Matsushita, K. Shimizu, Y. Nakao, H. Choshi, I. Noda,
M. Nagasawa, Polym. J., 18, 361 (1986).
953. M. Benchabane, R. Van Leemput, J. Polym. Sci., Polym.
Phys. Ed., 23, 991 (1985).
954. D. B. Cotts, J. Polym. Sci., Polym. Phys. Ed., 23, 2217
(1985).
955. S. L. Malhotra, T. L. Bluhm, Y. Deslandes, Europ. Polym.
J., 22, 391 (1986).
956. K. Matsuo, W. H. Stockmayer, F. Bangerter, Macromole-
cules, 18, 1346 (1985).
957. Z. Kucukyavuz, S. Kucukyavuz, Makromol. Chem., 187,
2469 (1986).
958. Z. Kucukyavuz, Makromol . Chem, 191, 2205 (1990).
959. A. Dems, G. Strobin, Makromol, Chem., 192, 131 (1991).
960. S. Kucukyavus, Z. Kucukyavus, G. Erdogan, Polym., 31,
379 (1990).
961. K. Kamide, Y. Miyazaki, H. Yamazaki, Polym. J., 18,645
(1986).
962. P. M. Cotts, J. Polym. Sci., Polym. Phys. Ed., 24, 1493
(1986).
963. P. Gregory, M. B. Huglin, Makromol. Chem., 187, 1745
(1986).
964. D. Kisakurek, N. Binboga, J. F. Harrod, Polym., 28, 1767
(1987).
965. J. I. Eguiazabal, J. Areizaga, J. J. Iruin, G. M. Guzman,
Europ. Polym. J., 21, 711 (1985).
966. F. Pilati, A. Munari, l? Manaresi, G. Miloni, V. Bonora,
Europ. Polym. J., 23, 265 (1987).
967. A. Munari, P. Manaresi, E. Chiorboli, A. Chiolle, Europ.
Polym. J., 28, 101 (1992).
968. L. J. Mathias, R. E. Hermes, Macromolecules, 19, 1536
(1986).
969. W. R. Krigbaum, T. Tanaka, Macromolecules, 21, 743
(1988).
970. M. Kuwata, H. Murakami, T. Notisuye, H. Fujita, Macro-
molecules, 17, 2731 (1984).
971. T. Kitagawa, J. Sadanobu, T. Norisuye, Macromolecules,
23, 602 (1990).
972. R. A. Kulkami, S. Gundiah, Makromol. Chem., 185, 549
(1984).
973. Q. Yi ng, B. Chu, R. Qi an, J. Bao, J. Zhang, C, Xu, Pol ymer,
26, 1401 (1985).
974. K. Sakurai, K. Ochi, T. Norisuye, H. Fujita, Polym. J., 16,
559 (1984).
975. S. Fujishige, Polym. J., 19, 297 (1987).
976. K. F. Weyt s, E. J. Goet hal s, W. H. Bunge, C. J. B. Tresl ong,
Europ. Polym. J., 26, 445 (1990).
977. W. R. Krigbaum, G. Brelsford, Macromolecules, 21, 2502
(1988).
978. K. Kamide, A. Kiguchi, Y. Miyazaki, Polym. J., 18, 919
(1986).
979. A. Sanchez, A. Bello, C. Marco, J. G. Fatou, Makromol.
Chem., 189, 399 (1988).
980. H. N. Bhargava, C. B. Sharma, R. R. Srivastava, Polmer J.,
18, 619 (1986); H. N. Bhargava, R. R. Sri vast ava, M. Si ngh,
Polym. J., 19, 1285 (1987).
981. A. Lapp, J. Herz, C. Strazielle, Makromol. Chem., 186,
1919 (1985).
982. J. Horska, V. Petrus, M. Bohdankcky, Polym., 28, 1207
(1987).
983. C. Salom, J. J. Freire, I. Hernandes-Fuentas, Polym., 30,
615 (1989).
984. T. Itoh, H. Chikiri, A. Teramoto, S. M. Aharoni, Polym. J.,
20, 143 (1988).
985. P. P. Shah, Europ. Polym. J., 20, 5 19 (1984).
986. S. Lazcano, A. Bello, C. Marco, J. G. Fatou, Europ. Polym.
J., 24, 985 (1988).
987. J. M. Barrales-Rienda, C. R. Galicia, J. J. Freire, A. Horta,
Macromolecules, 16, 940 (1983).
Re f e r e n c e s VII / 83
988. J. M. Barrales-Rienda, C. R. Galicia, J. J. Freire, A, Horta,
Macromolecules, 16, 1707 (1983).
989. A. W. Chow, S. P. Bitler, P. E. Penwell, D. J. Osborne, J. F.
Wolfe, Macromolecules, 22, 3514 (1989).
990. S. A. Swanson, P. M. Cotts, R. Siemens, S. H. Kim,
Macromolecules, 24, 1352 (1991).
991. D. Rosenvasser, R. V. Figini, Makromol. Chem., 185, 1361
(1984).
992. L. Gargallo, E. Soto, L. H. Tagle, D. Radic, Europ. Polym.
J., 24, 1119 (1988).
993. J. Roovers, J. D. Cooney, P. M. Toporowski, Macromole-
cules, 23, 1611 (1990).
994. J. Bravo, M. P. Tarazona, E. Saiz, Macromolecules, 24,
4089 (1991).
995. P. M. Cotts, S. Ferline, G. Dagli, D. S. Pearson, Macro-
molecules, 24, 6730 (1991).
996. J. Danhelka, M. Netopilik, M. Bohdanecky, J. Polym. Sci.,
Polym. Phys. Ed., 25, 1801 (1987).
997. B. Pfannemuller, M. Schmidt, G. Ziegast, K. Matsuo,
Macromolecules, 17, 710 (1984).
998. T. Kato, T. Katsuki, A. Takahashi, Macromolecules, 17,
1726 (1984).
999. S. G. Ri ng, K. J. lAnson, V. J. Morri s, Macromol ecul es, 18,
182 (1985).
1000. C. L. McCormick, P. A. Callais, B. H. Hutchinson, Jr.,
Macromolecules, 18, 2394 (1985).
1001. G. V. Laivins, D. G. Gray, Macromolecules, 18, 1746
(1985).
1002. J. W. Mays, Macromolecules, 21, 3179 (1988).
1003. K. Nishinari, K. Kohyama, P. A. Williams, G. 0. Phillips,
W. Burchard, K. Ogino, Macromolecules, 24, 5590
(1991).
1004. A. Wirscn, Makromol. Chem., 189, 833 (1988).
1005. N. Donkai, H. Inagaki, K. Kajiwara, H. Urakawa,
M. Schmidt, Makromol. Chem., 186, 2623 (1985).
1006. A. Leon, L. Gargallo, A. Horta, D. Radic, J. Polym. Sci.,
Polym. Phys. Ed., 27, 2337 (1989).
1007. H. Kawanishi, Y. Tsunashima, F. Horii, S. Okada, Polym.
preprints Japan 45, 3387 (1996).
1008. C. Wei-Berk, G. C. Berry, J. Polym. Sci., Polym. Phys. Ed.,
28, 1873 (1990).
1009. A. Mat sumot o, T. Tarui , T. Ot su, Macromol ecul es, 23,5 102
(1990).
1010. L. J. Fetters, N. Hadjichristidis, J. S. Lindner, J. W. Mays,
W. W. Wi l son, Macromol ecul es, 24, 3127( 1991) .
1011. S. R. Gooda, M. B. Huglin, Macromolecules, 25,
4215(1992).
Note: References 508-511 and 575-589 are for biological polymers such
as collagen, gelatin and poly(nucleotides), which do not appear in the
present tables.
Sedimentation Coefficients, Diffusion
Coefficients, Partial Specific
Volumes, Frictional Ratios, and
Second Virial Coefficients of
Polymers in Solution*,**
M. D. Lechner, E. Nordmeier, D. G. Steinmeier
Physical Chemistry, University of Osnabruck, Osnabruck, FR Germany
A. Sedimentation Coefficients, Diffusion
Coefficients, Partial Specific Volumes, and
Frictional Ratios of Polymers in Solution
1 . Introduction
1 .l. Sedimentation Coefficient
1.2. Diffusion Coefficient
1.3. Molar Mass Averages Determined
from Sedimentation and Diffusion
Coefficients
1.4. Partial Specific Volumes
1.5. Frictional Ratios
1.6. List of Symbols and Abbreviations
1.7. Miscellaneous
B. Tables of Sedimentation Coefficients,
Diffusion Coefficients, Partial Specific
Volumes, and Frictional Ratios of Polymers
in Solution
Table 1. Polyfalkenes)
Table 2. Poly(dienes)
Table 3. Acrylic Polymers
Table 4. Vinyl Polymers
Table 5. Styrene Polymers
Table 6. (0, 0Heterochain Polymers
[Polyfethers), Polyfesters),
Polyfcarbonates)]
VII-86
VII-86
VII-86
VII-87
VII-89
VII-89
VII-89
VII-90
VII-91
VII-92
VII-92
VII-94
VII-96
VII-1 05
VII-1 09
VII-1 34
* Based on a table in the second edition, by P. E. 0. Kllmer, and H. A.
Ende, BASF AG, Ludwigshafen, Germany.
** Particular thanks are due to B. Hartmann, Cl. Kerrinnes, and
L. Schloesser for checking and preparing the manuscript.
Table 7. (N, Cl- and (0, N, Cl-Heterochain
Polymers [Polytamides), Polyfureas),
Polyturethanes)] VII-1 37
Table 8. Other Synthetic Polymers VII-1 40
Table 9. Inorganic Polymers VII-1 41
Table 10. Polyfsaccharides) VII-I 44
Table 11. Other Biopolymers [Proteins,
Polyfnucleotides)] VII-I 57
C. Second Virial Coefficients of Polymers in
Solution VII-l 63
1 . Introduction VII-l 63
1 .I. Colligative Properties VII-l 63
1.2. Scattering Methods VII-l 63
1.3. Sedimentation Velocity VII-l 63
1.4. Sedimentation Equilibrium VII-l 64
1.5. D- V-T Measurements VII-l 64
1.6. Averages of the Second Virial
Coefficient VII-I
1.7. Second Virial Coefficient - Molar
Mass Relationship VII-I
1.8. Temperature Dependence, Pressure
Dependence VII-1
6 4
6 4
6 4
1.9. Abbreviations
1.10. Miscellaneous
D. Tables of Second Virial Coefficients of
Polymers in Solution
Table 12. Polytalkenes), Polyfalkynes)
Table 13. Polytdienes)
Table 14. Poly(acrylics)
VII-l 64
VII-l 64
VII-l 65
VII-l 65
VII-1 68
VII-I 70
VII / 85
VI I 186 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
Table 15. Poly(vinyls) VII-I 77
Table 16. Polyfstyrenes) VII-I 79
Table 17. (0, 0Heterochain Polymers
[Poly(ethers), Polyfesters),
Poly(carbonates)l VII-I 88
Table 18. (N, Cl- and (0, N, 0Heterochain
Polymers [Poly(amides), Polyfureas),
Poly(urethanes)l VII-I 91
Table 19. Other Synthetic Polymers VII-I 92
Table 20. Inorganic Polymers VII-I 92
T a b l e 2 1 . Poly(saccharides) VII-I 94
Table 22. Other Biopolymers [Proteins,
Polyfnucleotides)] VII-l 96
E. References VII-I 98
A. SEDIMENTATION COEFFICIENTS, DIFFUSION
COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, AND
FRICTIONAL RATIOS OF POLYMERS IN SOLUTION
(2, 349-357, 799, 800)
1. Introduction
1.7. Sedimentation Coefficient The sedimentation
coefficient s is defined as the sedimentation velocity in a
unit force field
s = (dr,dt)/(w*r)
(Al)
where r is the distance from center of rotation, and w, the
angular velocity. For a given polymer-solvent system, the
sedimentation coefficient is dependent on temperature T,
pressure p, and polymer concentration C. Experimentally,
sedimentation coefficients can be determined only with an
ultracentrifuge.
Concentration Dependence
For polymer solutions studied by ultracentrifugation, the
following concentration dependence of the sedimentation
coefficient holds:
l/s = (l/so) (1 + k,C + k;C2 + . . .)
(A21
where SO is the sedimentation coefficient at zero concentra-
tion. In Section B the concentration dependence of s
according to Eq. (A2) is listed. In some cases, special
extrapolation procedures are used. The tables in Section B
also refer to the appropriate reference. For special treat-
ments, see, e.g., Gehatia (358,359).
Sector shaped cells are normally used in an ultracen-
trifuge. In these cells, the square-dilution rule has to be
taken into account (360):
et/co = (rolrJ2 (A31
where ru and rI are the distances of the meniscus and of the
boundary from the axis of rotation and CO and C, the
concentrations at zero time and at time t at the boundary,
respectively.
Averages of the Sedimentation Coejjicient
The average of a function X(M) is defined as
with so W(M) dM = 1, where W(M) denotes the prob-
ability density function (in our case the molar mass
distribution). The average with ,D = 0 is called the number
average X,, with p = 1, the mass average X,, and with
/? = 2, the z-average X,.
In principle it is possible to evaluate the various averages
of the sedimentation coefficient from the distribution of the
concentration gradient, aC/ar, in the cell:
03
S=M
J
W(M)Ks(M) dhl
0
s, = (l/M,) i W(M)Ms(M)dM
(fw
0
where W(M) = C(M)/ so C(M) dM = C(M)/Co is the
mass distribution of the polydisperse polymer in the cell
and s,,, s,, and s, the number average, mass average and
z-average of the sedimentation coefficient. In many
cases the migration of the maximum of the quantity
aC/ar is determined, which leads to a sedimentation
coefficient st, that in turn is related, in a complicated
manner, to the averages of s in Eq. (A5). Another method of
evaluating the sedimentation coefficient is by observing the
median, that is the line dividing the gradient curve in two
equal areas, yielding a value s, which is also a rather
complicated average. Provided the skewness of the molar
mass distribution is not very pronounced, s, can be
calculated by (Ref. 259)
S
w = (3sIn - St)/2 W)
Most ultracentrifuges measure the refractive index
difference between polymer and solvent, dn, or the
refractive index gradient an/&- versus r (Schlieren optics).
With certain assumptions an/& can be related to the
concentration gradient (Ref. 14)
an/ ar =R( ac/ ar )
( A?
Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, and Frictional Ratios of Polymers in Solution VII / 87
where R is called the specific refractive index increment.
The interference optics measure the deflection of the
parallel interference lines in the solution. This deflection
is directly proportional to the concentration of the polymer.
The absorption optics measure the optical density of the
system as a function of the rotor distance, which, according
to the Lambert-Beers law is proportional to the concentra-
tion of the polymer. The intensity is measured with a
photoelectric scanner.
A multiplexer is used in order to measure several
concentrations during one run (869-871).
Sedimentation CoefJicient - Molar Mass Relationship
The dependence of s on the molar mass can be given by a
power law expression:
s= K,May
(48)
where K, and a, are empirical constants determined for
each polymer-solvent system at given values of tempera-
ture and pressure. In Section B, relationship (A8) is listed
whenever quoted in the literature, in preference to single s
values,
Temperature Dependence, Pressure Dependence
Svedberg and Pedersen (2) and Mosimann and Signer (361)
derived expressions for the temperature and pressure
dependence of the sedimentation coefficient with restricted
validity:
s/s8 = (rl?lrll) (1 - &fw(l - V2PI) (A91
where s*, qf, U! and py denotes the values at the reference
temperature and/or pressure. Equation (A9) holds in the
case of an incompressible medium and if no changes of
size, shape and solvation state of the dissolved molecules
in the temperature and pressure region take place. From
these assumptions it may be deduced that Eq. (A9) can be
applied with sufficient accuracy only on proteins in aqueous
solvents.
Due to the high centrifugal fields applied in the
ultracentrifuge, pressure gradients with pressures up to
200 bars are encountered in the cell and change appreciably
the viscosity and the density of the solvent and the partial
specific volume of the polymer. Thus the sedimentation
coefficient, s, measured at a pressure p differs from the
sedimentation coefficient, s, measured at 0 bar. Applica-
tion of Eq. (A9) for the calculation of s requires the know-
ledge of ~7 I (362), pi (given in a number of Handbooks) and
~2 (148). More precise equations for the calculation of the
pressure influence on the sedimentation have been worked
out by several authors (363,364,365,800). The equation of
0th and Desreux (Ref. 363)
s = sO(l - /Lp)
(AlO)
has very often been used for the calculation of so (800). The
coefficient p depends on the polymer-solvent system and
varies only slightly with pressure.
In Section B, the intrinsic sedimentation coefficient, [so],
instead of so, has been occasionally listed. [so] is related to
Eq. (9): [so] = sorl~/(l - ~2~1).
1.2. Diffusion Coefficient The translational diffusion
coefficient D is defined by Ficks first law:
J = -DVC
Gw
where J is the flow of substance (total number of particles
transported in unit time across unit surface) and VC the
concentration gradient. For one dimensional diffusion,
Eq. (Al 1) reduces to
(l/A) (&z/i%) = -D(X/ar)
W2)
where A denotes the area and n the number of moles.
The negative sign in Eqs. (All) and (A12) indicate that
diffusion takes place in the direction of decreasing
concentration. For practical reasons, Ficks second law is
prefered
(X/at) = DAC
(w
where A denotes the Laplace operator. Eq. (A13) reduces to
(X/at) = D(a2C/ar2)
(Al4
for the one dimensional case. Eqs. (A13) and (A14) allow
the determination of D when solved with consideration to
certain initial and boundary conditions.
Experimentally translational diffusion coefficients can be
determined with an ultracentrifuge (see Section 1.3) in
special diffusion cells using Eqs. (All)-(A14) (800) and
with dynamic light scattering (DLS). Since 1970, when the
dynamic light scattering became available, nearly all
diffusion coefficients have been measured by this
method. Based on the theory of Pecora (853,854), the
experimentally measured autocorrelation function g 2 (t)
is linked with the diffusion coefficient in polymer solutions
(Refs. 730,855):
MW(M)p(q, M)
\ 2
(A15)
exp(-q2D(M)t)dM
)
where n = 1 for the heterodyne procedure and n = 2 for the
homodyne one. Eq. (A15) reduces, in the case of a
monodisperse polymer solution, to
F?. 82(t) = A + B(p(q,M) exp(-q2D(M)t)) (A16)
References page VII - 198
VII / 88 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
A and B are measurable constants. Extrapolation of q
against zero yields P(q,M) = 1. Note that gz(t) is the
z-average of the function, exp(-qzD(M)t). In this way
one obtains the direct measurable quantity D, from
dynamic light scattering on polydisperse polymer
solutions.
For polydisperse polymer solutions, Eq. (A16) may be
expanded in a series (Ref. 856):
l& g(t) =exp(-q2D,t) (1 + (bz/2!)t2 - (ps/3!)t3 + . .)
q-0
(Al?
where the moments, pi, are related to the molar mass
distribution of the polymer (671).
More general methods for the determination of the
distribution of the diffusion coefficient and of the molar
mass are given elsewhere (857,858).
As has been pointed out, only the translational diffusion
coefficient is listed in the tables. For higher modes of the
autocorrelation function (e.g. rotation, vibration) see the
appropriate literature (853,854).
The entire description of the translational diffusion of
a polymer molecule in solution requires the determination
of the mutual or cooperative diffusion coefficient, D,,
which characterizes the relaxation of a concentration
gradient and the self-diffusion coefficient, D,, which
describes the Brownian or random motions of the polymer
molecule (860-863).
D, =(RT/f) (1 - v2pi) (1-t 2A2MC+ 3A3MC2 + . ..)
D, = RT/f
At infinite dilution, D, =D, x D, is normally measured
with classical diffusion cells or dynamic light scattering
whereas D, can be studied by measuring the migration of
labeled solute molecules (864), by pulsed field gradient
NMR (865), and by forced Rayleigh scattering (866).
Normally, D ,,, is given in the tables. In some cases,
especially where D, is extrapolated to zero concentration,
D, = D, is given in the tables. .
Concentrati on Dependence
The concentration dependence of the diffusion coefficient
may be described as
D =DO( 1 + koC + kbC2 + . .)
Gw
where Do is the diffusion coefficient at zero concentration.
In Section B a concentration dependence of D according to
Eq. (A18) is listed. In some cases, special extrapolation
procedures are used. In these cases Section B refers to the
appropriate references.
Averages of the Diffusion Coeficient
Similar considerations as made on sedimentation coeffi-
cients hold for diffusion coefficients. From measurements
in a diffusion cell, one obtains the various averages of the
diffusion coefficient from the distribution of the concentra-
tion gradient, aC/ar, in the cell:
DC)
D, =M,,
s
W(M)M-D(M) dM
0
D, = 9 W(M)D(M) dM
0
D, = (l/M,) i W(M)MD(M) dM
(A 19)
0
where W(M) = C(M)/Co.
The diffusion cell may be combined in the same manner
as in the case of the ultracentrifuge with Schlieren optics,
interference optics, and absorbtion optics. In most cases, the
mass average and the area average of the diffusion co-
efficient are determined. They can be calculated with the
help of Eqs. (A14) and (A19):
D, = (I r2(Xjir)dr)/(2t[(X/&-)dr) (A20)
DA =i ((X/at-) dr) 2/(47rt(X/&-),,,)

2
0
ww
@Cm-) max
is the maximum height of aC/&. The integral
in Eq. (A21) is the area of the curve.
As has been pointed out, dynamic light scattering
measurements normally yield the z-average of D. Never-
theless it might be possible to determine averages other
than D, with the help of Eqs. (A19) and (A21). In Section B
the different averages of D are quoted. In some cases
unusual averages are listed. In these cases Section B refers
to the appropriate references.
Diflusion Coefficient - Molar Mass Relationship
The diffusion coefficient - molar mass dependence fre-
quently takes the form
D = KDM-@
(A221
where KD and aD are constants for each polymer-solvent
system at given values of temperature and pressure. In
Section B relationship A(22) is listed whenever quoted in
the literature, in preference to single D values.
Temperature Dependence, Pressure Dependence
A similar expression as Eq. (A9) holds under the same
restricted conditions for the temperature and pressure
dependence of the diffusion coefficient:
(~23)
Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, and Frictional Ratios of Polymers in Solution VII / 89
where De and r7 f denote the values at the reference
temperature To and/or pressure po. As has been pointed out
in Eq. (A9), Eq. (A23) can be applied with sufficient
accuracy on proteins in aqueous solvents only.
The temperature dependence of the diffusion coefficient
is often described by the following exponential function
D =D, exp(-Eo/RT)
(-w
where ED denotes the apparent activation energy of the
diffusion and D, the diffusion coefficient at the limit
T = cc. In Section B we have listed the temperature
and pressure dependence of D whenever quoted in the
literature.
1.3. Molar Mass Averages Determined from Sedimen-
tation and Diffusion Coefficients For the experimental
determination of the molar mass from sedimentation and
diffusion measurements, the Svedberg Eq. (A2) is used:
M = (~o/(l/v2~l))/(Do/RT) G425)
Here SO and Do are the corrected and standardized
coefficients for zero polymer concentration. For polydis-
perse polymers the various averages of the sedimentation
and diffusion coefficient s and D are inserted, obtaining
certain molar mass averages MD,-,. Thus Eq. (A25) acquires
the more general form:
MA, = (~O,Pl(l - u2P 1 MDo.dRT) VW
For /3 = n, w, z, . . . and y = n, w, z, . . . Eq. (A26) defines
several different molar mass averages M,,,, M,,,, M,,, etc.
The averages, M,,,, and M,,,, are different from M, and
M, respectively (859). The coefficients with p = n and z
and y = n are determinable only with large error. Instead,
the coefficients with /3 = t and m (see under Section 1.1.)
and y = A and w (see under Section 1.2.) are usually
evaluated. Thus, rather peculiar averages, e.g. Mr,A, M,,,,
and Mm,A,
result. The more straightforward molar mass
averages M,,,, M,,,, M,,,,
etc., in relation to the familiar
averages, M,, M,, and M,, are found elsewhere in the
literature (369-371,859).
7.4. Partial Specific Volumes The volume, Vid, of an
ideal two component system can be expressed in terms of
the masses ml and m2 and the specific volumes, WY and wi,
of the two components by the equation
Vid = rnlvy + rn2vi
(A271
Most components do not behave ideally upon mixing;
i.e. they react with each other in a way so that the total
volume deviates from Vid. The total volume can then be
written as
V =mlvl + m2v2;
vi = (aVlami)p,r,m,p, (AW
where Vi (i = 1,2) is the partial specific volume of
component i. When component 2 is polymer and compo-
nent 1 solvent, then, for practical reasons it is convenient to
introduce the so-called apparent partial specific volume w;
which is defined by
V=mlvy+m2vi
(A291
where vy denotes the specific volume of the solvent. The
quantity, v;, now contains the parameter of nonideal mixing
of both the solvent and the polymer. In practice, however v;
differs not much from 212 if the polymer concentration is
kept low (up to 1%). Dividing Eq. (A29) by the total mass
ml t m2 leads to
v=w1wy+w22/;
WO)
where v is the specific volume of the solution and
wi = mi/ c mi are the mass fractions of the solvent
(i = 1) and the polymer (i = 2).
With v = l/p and vy = l/pi, p and pi being the
densities of the solution and the solvent, respectively, it is
readily found that
4= Ww2) bl - wdlbPl> W)
Eq. (A31) demonstrates that v; can be determined by
measuring pi and p. Numerous methods for determining
densities are described in the literature (268,372-379).
In order to determine the partial specific volume from
the apparent specific volume, Eq. (A29) yields
(a(m2v;)/am2),l = m2@;/am2),, + v; = (av/am2),,
(A=)
where (aV/am2),l is, according to definition, equal to 212.
In terms of mass fractions, Eq. (A32) can finally be written
a s
212 = v ; + w~w@v;/aw2)
VW
Most values reported in the literature are @-values rather
than vz-values, since extrapolation according to Eq. (A33)
is usually omitted. The differences between v; and 212 are,
however, often small.
1.5. Frictional Ratios The molar frictional coefficient,
fsP, of an unsolvated spherical molecule may be computed
by the formula based on Stokes law:
fsp = ~TT?$&A = 6~r?#N~Mv2/(&r)]
113
(A341
where q is the viscosity of the solvent and NA is Avogadros
number. When the shape of a molecule deviates from a
sphere, or when it is solvated, then the frictional coefficient,
fo, of such a molecule is larger than that of the spherical
molecule. The frictional ratio, fo/fsp, thus permits to draw
conclusions concerning either solvation or shape of the
References page VII - 198
VII / 90 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
molecule. It is possible to calculate the dimensions of the
nonspherical molecule, provided a particular model (ellip-
soid, cylinder, etc.) for the molecule is adopted and either
the degree of solvation is known or assumed to be
negligible. The molar frictional coefficient can be deter-
mined either from sedimentation velocity data, provided the
molar mass is known from independent measurements
according to the Svedberg equation
foso = M(l - VZPI) (A351
or from diffusion measurements, using the relation
fo = RT/Do (436)
Eqs. (A34)-(A36) are most frequently used for calculating
the frictional ratio. fa/fsp is listed in the tables. Other
relationships for the determination of fo/fs, are quoted in
the literature (2). In these cases special reference to the
literature is made in the tables.
In few cases, only the molar frictional coefficient fa,
rather thanfo/fsr, was quoted in the literature. These values
are inserted in the same column as the values for the
frictional ratio.
1.6. List of Symbols and Abbreviations
Symbols
C
CO
C,
D
DA
D,, Dw, Dz
Concentration
D
Do
rll
4
f sp
f o
k, , ks
kD, kD
Initial polymer concentration
Polymer concentration at time t
Diffusion coefficient
Area average of the diffusion coefficient
Number average, mass average, and
z-average of the diffusion coefficient
Diffusion coefficient at reference
temperature and/or pressure
Diffusion coefficient at zero concentration
Viscosity of solvent
Viscosity of solvent at reference temperature
and/or pressure .
Molar frictional coefficient of a spherical
molecule
Molar frictional coefficient at zero
concentration
Concentration coefficients defined by
Eq. W)
Concentration coefficients defined by
Eq. (A18)
M Molar mass of the polymer
M,, M,, M, Number average, mass average and z-average
of the molar mass of the polymer
M Molar mass determined by Mark-Houwink
equation
MMW
Molar mass determined by equations from
Mandelkem and Flory, or Wales and Van
Holde (see Section 1.7)
M :j.A,
Molar mass average determined by
Eq. (A26) from sup and Dosy
M M.T.A, s.w,
Molar mass average determined from
undefined sedimentation coefficient s and
D,, DA and undefined diffusion coefficient
D, respectively
Refractive index or number of moles
Angular velocity
Distance from center of rotation
Distance of meniscus from center of
rotation
Distance of boundary from center of
rotation at time t
Density of solution
Density of the solvent
Gas constant
Sedimentation coefficient
Number average, mass average, and
z-average of the sedimentation coefficient
Sedimentation coefficient at reference
temperature and/or pressure
Sedimentation coefficient at pressure p = 0
bar
Sedimentation coefficient at zero
concentration
Intrinsic sedimentation coefficient (see
under Section 1.1)
Sedimentation coefficient determined from
migration of gradient curve median
Sedimentation coefficient determined from
migration of gradient curve maximum
Temperat ure
Theta temperature (A2 = 0)
Ti me
Partial specific volume of component
i (i = 1, solvent; i = 2, solute)
Specific volume of component i
Apparent specific volume of solute
Abbreviations
A
approx.
CLS
DLS
NBS
OS
PCC
RT
SE
S RM
s v
T S
V
Archibald method
approximately
Classical light scattering method
Dynamic light scattering method
National Bureau of Standards, USA (now
National Institute of Standard and
Technology, NIST)
Osmomet ry
Pressure Chemical Co., Pittsburg, PA,
USA
Room temperature
Sedimentation equilibrium
Standard reference material
Sedimentation velocity
Toyo Soda Co., Japan
Number of single values given in Ref.
ci t ed
Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, and Frictional Ratios of Polymers in Solution
VII / 91
1.7. Miscellaneous With certain assumptions it is pos-
sible to determine the molar mass from a combination of
the intrinsic viscosity [q] and the limiting sedimentation
coefficient SO. In this way, Mandelkern and Flory (128) and
Wales and Van Holde (134) derived an expression. An
expression similar to the equation between M, [q], and SO
was derived between M, [q], and DO (128). The molar
masses determined from either one of these relationships
are refered to as MW.
References page VII - 198
B. TABLES OF SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, AND FRICTIONAL RATIOS OF
c
3
POLYMERS IN SOLUTION
\
E
TABLE 1. POLY(ALKENES)
L4
0
z
Polymer
-
Sol vent
f ((3 M ( x 10 -3) (g/mol) sg (x 103) (s) k s (cm 3/g) DO (x 10) (cm2/s) kn (cmlg) fo/fsp w (cm3/g) Remarks
%
Refs. z
I
Poly(ethylene)
branched
linear
I-Bromonaphthalene 1 1 0
I-Bromonaphthalene 1 1 0
1 2 0
Khloronaphthalene
1 2 0
1 2 0
branched, fractions
branches per molec
1 . 9
2.6
3 . 0
2 . 9
4.6
5 . 7
6.4
1 3 . 7
1 6 . 1
2 6 . 3
Di phenyl
110
1 2 3
1 3 0
branched Tetralin 8 0
Poly(l-butene) Ethyl octanoate 2 2 (T=O)
Poly(isobutene) Cyclohexane 3 4 (T=@
2 0
4.1 1. 42
1 4 . 2 2. 03
2 1 . 8 2. 39
55.0 3. 39
3.5-274 S = 7.74 x 10-15 M0.3M
6 9 - 4.09
1 3 6 - 5. 14
8 8 - 5. 18
- 1.61
- 2.37
- 3. 31
- 1.06
- 1. 91
- 2.85
- 2.77
- 3.57
- 4. 11
- 4. 52
- 7. 30
- 7.87
- 11.37
2 6 9. 80
60
7 9
9 9
2 6 1
4 9 3
2 5 . 7
5 0 3
8 0 0 1. 30 5 5 . 5
6.4 721+ 159
3 0 . 9 0. 925 5 4
8 6 . 7 1. 49 1 2 8
1 7 2 1. 94 191
612 3. 33 5 1 0
6. 42
6. 42
4. 73
3. 13
2. 15
0. 87
0. 20
MV
MMW
Muw
[ r j ] =51 cm/g
90
[v] = lScm/g
3 3
5 6
60
6 6
7 4
8 8
1 1 8
1 2 9
1 3 9
(1
a
DA. M, , D, given
in Ref.
1. 1066
Do..; MwIMn = 3
&I,,; MwIMn =5
MM&;
M,; Oppanol B 100
1. 091 M,
:
32,621,622 VI
.-.-- -.
Ethyloctanoate
n-Heptane
Tetralin 2 4 3 8 8 0. 68
TClhene 2 4 3 8 8 2 . 7
Poly(isobutylene) Benzene 2 4 . 5
Chloroform 2 5
Cyclohexane 2 5
lsoamyl isovalerate
(IAIV)
2 5 &=/I) 1 8 . 1
Do= 1.27 x IO-* M,04;
Do =6.22 x IO-* M,
&=1.78x 1O-4 Mm0572 CLS and DLS
1.33 x lOiM,<;4.8 x 105g/mol
5 . 1 - 8.7
n-Heptane
1 4 2 0 4. 45 8 3 6
2.5 2 1
7 8
1 2 2
1 7 6
490
6 9 8
1 8 0 0
2 2 7 5 0 1 . 3
2 5 1 4 5
5 5 . 5
6. 32 4.8
2. 99 4 1
2. 26 5 3
1. 84 7 9
1 .Ol 1 6 7
0.79 3 7 9
0. 43 3 4 8
1. 106
2 5 65.2-308
2 0 . 9 5 2
2 3 . 2 1 6 0 0
2 0 . 7 , 1 6 0 0
2 5 1 9 0 0
4 8 . 5
1 3 9
4 2 2
6 3 4
8 1 9
1 7 6 0
2 5 1 8 . 1
4 8 . 5
1 3 9
4 2 2
6 3 4
8 1 9
1 7 6 0
2 5
Isoamyl isovalerate (IAN) 22.1
2 5 (Z=8) 4 2 0
6 3 4
8 1 9
1 7 6 0
D,, =5.01 x IO4 Moss5
1. 072
1. 069
I.075
5 . 8
3 . 1 - 16
1 . 9 - 24
1 . 1 - 4 7
0. 86 - 6 4
0. 75 - 80
0. 52 - II0
1 6 . 3 - 1.5
9 . 5 3 . 5
5 . 5 1 3
2 . 8 5 6
2 . 3 6 8
2.0 8 8
1 . 3 1 8 0
Do=4.1OX 10-4M,O560;
0.64 x lo5 5 M, 5 14.8 x lOg/mol
&=5,94x 10-S M,O?
O.&l x 10s 5 M, 2 14.8 x lo5 glmol
1. 06
0. 86
0. 75
M, , so, C=3.461 gl
dm3; 25V; C from
623 %
0
3.461 to 16.293g/dm3
-.
p from 0 to 46 x 10 Pa I
624 s Oppanol B 50;
M, I M. =3. 0
Oppanol B 50;
M,fM, =3.0
M, I M, = I.2
M, / M, , = 1.2
990
0
6 2 4 3
-.
0.
M, / M. = 1.08
M, f M. =1. 06
M, f M, = 1.07
M, / M, =1. 09
M, / M. = 1.06
M,/M,= 1.09
M, f M, = 1.09
MW
MW
MW
MW
MW
MW
MW
CLS and DLS
CLS and DLS
[rj] = 70.9 cm3/g
[q] = 88.2 cm 3/g
[v] = 99.8 cm3/g
[q] = 146 cm 3/g
M, ; M, f M, =3. 2 6 2 0
M, ; M,fM,=2.1
M,; M,/M, = 2.0
M, ; M, / M, =2. 7
M, ; M, / M, =4. 5
M, ; M, f M, =5.1
M, ; M, / M, = 10.8
St
2 3 7
M , , , ; C from 0.53
to 2.95g/dm3;
M, , DA given in Ref. 511
if
n
M,; CLS 449 3
M I48 2
D
d
s
References page VII - 198
TABLE 1. contd
Polymer S o l v e n t
c
e:
\
T C-2 M ( x 10 m3) (g/mol) so ( x 103) (s)
k, (cm3M
Do ( x 10) (cm */s)
kD (cm49 fo,!fsp ~2 (cm3/g) Remarks Refs. P
Poly(l-hexene) Acetone 2 0 46.8 1 1 . 5 1 6 . 2
sr; DA; M,,A
2 2 2 2 1 . 5 6.4
53 g
5 7 1 3 3 . 8 3.0
E
2 0 0. 793 54 F
Poly(tetrafluoroethylene) Perfluorotetracosane 3 2 5 2 6 0 3. 66 - 35.2 1004 ;
2 1 0 0 1. 21 - 130.0
See Ref.for various methods applied and values obtained.
$
h Corrected for pressure influence.
See Ref. for def. of s. 8
i
3
TABLE 2. POLY(DIENES)

0
G
Polymer Solvent T (C) M ( x 10 -) (g/mol) so ( x 103) (s) k, (cm3k) DO ( x 107) (cm/s)
kD (cm349 fo/ fsp 1~2 (cm3k)
Remarks Refs. z
,n
Poly(butadiene) Diethyl ketone
CL-4 Dodecane
cis-4 Hexafluorobenzene
95%, I,4 cis Di et hyl ket one
IO.3 6 0
1 8 7
3 5 0
4 3 6
7 7 8
1 3 8 0
8 0
8 0
10.3 (T= 0)
90%, I ,4 cis (TiJ 4) Hexane/heptane (1 / I ) 2 0 55- 1080
90%, 1.4 cis (CoCl2) Hexane/heptane (I/ 1) 34.7- 1040
h-4 Hexatriacontan 8 0
linear Cyclohexane 2 5
18-armed star
Dioxane 26.5 (T=6)
Cyclohexane 2 5
Dioxane 26.5 (T=0)
Poly(butadiene- Methyl ethyl ketone/ 2 2 (T=B) 34.8-780
stat-acrylonitrile) cyclohexane (47.5/52.5)
Methyl ethyl ketone/ 2 0 (T=B) 4 7 5
isopropanol (60/40)
2 0 5
101
Poly(butadiene-co-styrene)
branched Benzene 2 5 81.9-168
Methyl n-propyl ketone 2 1 (T=fl) 49-514
21 mass% styrene Methyl n-propyl ketone 2 1 (T=@ 49-514
Poly(chloroprene) Methyl ethyl ketone 2 5 56-380
1. 76
2. 76
3. 45
4. 28
4. 52
5. 15
sg =0.53 x IO- Mos
s0=2.80x IO- M48 M
s.
s,, =2.33 x IO-Ii M5 M
5.D
7. 58 1 9 . 7
4. 65 1 6 . 0
3. 43 2 0 . 6
1.21-4.63
SIJ = 1.04 x 10-15 MO.5
s0=0.83 x lo- MO
s=3.1 x lo-l5 Mo5

5 9 0 P
2 3 . 8
1 6 . 3
s,, s,, s,, sm.0 given
in Ref.
4. 78
Do= 1.45 x 10m4 M-O;
11000 < M w 5 760000~/mo1
Dp6.34~ lO-5 M;O%;
11000 < M w < 760000 g/m01
D,, = 2.39 x 10m4 M,05;
99000 $ M, 5 1900000 g/mol
Do=8.87x lo- M;0497;
99000 5 M w 5 1900000 g/mol
Do= 1.38 x lO-4 Wo5; DA; M,.o, ks
given in Ref.
DA; M,,D
0.995 i 0.005
0. 773
See Ref.
Mn
M,; OS; SE
g
5
625 .J
625 9
514 2
z
3 2 3
3 2 3
%
3
625 4
987 i=,
5
E
3
.I
5 5 2
2
E
5 5 2
2
2
4 0 6
5 7 3
3 4 4
444
Poly(isoprene)
linear
4-armed star
I8-armed star
3-armed star
4-armed star
8-armed star
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
Cyclohexane
5
50
50
50
-
5
5
21. 2- 122
61. 1~630
137
173
380
195
1760
4400
96
810
3900
5280
93
218
384
800
1480
3570
270
M, I M, = 1.05-1.11
M,/M,=1.02-1.07
MW
Mw
[r/J ~0.958 dL/g
[+0. 973 dL/g
[y/l = 1.74 dL/g
[r/J = I .83 dL/g
[r/J = 3. 30 dL/g
[q] = 6. 37 dL/g
[q] = 0.294dUg 12.armed star
0. 89
0. 37 560
0. 305 331
2. 4
I . 88 35
1. 06 IO0
0. 7 1 169
0. 455 303
2. 24
[rj]=4,33dL/g
[r/l = 5. 63 dL/g
lr/]=O.i82dLlg 18-armed star
[r/ j =I . 02 dL/p
1r/l = I . 58 dL/g
[r/j =2.90dL/g
M,%.,); Determ. of
,f,,/f\,,see Ref.
natural rubber, crepe Chloroform 20 1 5 . 5 3. 32
485
930
125
1 5 . 5
21. 5
1. 26
1. 16
2. 63
5. 10
5. 26
3. 82 M,; OS; Determ.
of f,,/f,p see Ref.
I . 64
1. 55
1. 41
1. 44
0. 48
0. 46
0. 41
0. 48
3
1. 01
Do=3. 98x I O- ? M- Or 5
215
330
450
760
1 6 0 0
1750
1800
1600
270
1660
4.1 I
4. 61
4. 64
3. 82
Cyclohexane
HexalE
Hexane
Hexalle
20 4. 6
4. 16
4. 35
4. 6
9
21
A-,, ~5. 01 x 10 ~I 5 M4
. so=l . 76x lO-2 M" @
M&D
1. 10
1. 54
natural rubbe 20
20
25
I ,4-h
I , 4- ci s (TiCI ,/AL
(CTH 15)d
M, 11
M, I M, =1.8-2.9
460- 970
References page
TABLE 3. ACRYLIC POLYMERS
c
q
\
Polymer Sol vent T (C) M ( x 10m3) (g/mol) so (x 103) (s) k s (cm k) DO (x 10) (cm*/s) ko (cm3@J fo/f, 7~2 (c&i!)
Remarks Refs.
z
Poly(acrylamide) Water 2 0 19.4-534 s,=8.17 x lo-l5 I@ DA = 8.46 x 1O-4 Mm0.69 0.769
2 0
Water&XI (0.2 moi/dm3) 20 250, 610 0. 687
2 0
Water/NaCl (0.5 mol/dm3) 20
2 5
Water/NaCI
WaterMaCl (0.1 mol/dm )
Water/NaCl (0.1 mol/dm )
H-acrylamide Water/NaCl (I M) 2 5
2.3.3.Dx- acrylamide 1 7 1 0
Water/NaCl (2 g/dm ) 2 0
Water/NaCl ( 2 0 g/dm 3, 2 0
Water/N&JO3 (0.5 mol/ 2 5
dm3)
partially hydrolyzed Water 2 6
Posher 700
(Dow Chemical) Water/NaCl (0. I mol/dm )
Water/NaCI (0.2 mol/dm 3,
Poly@-ethoxycarbonyl Acetone
phenylmethacrylamide)
Dimethylformamide
Dimethylformamide/
formamide (90/10)
Poly(N-isopropyl-
acrylamide)
Ethyl acetate
Water
Poly(N-isopropyl
methacrylamide)
Water
1 5
2 0
2 5
2 7 . 5
3 0
3 2
3 3
2 0
.-
130-8200
s
w
= I.07 x 10-E M48*0.01
w
D,,o= 1.24 x 10m4 M,
0 53*0.01
0. 708
5 0 0 0 0. 693
250, 610 0. 696
490-5150
8400
so = 8.17 x lo-l5 MyA &=8.46x 10m4 M-Oh
so=9 x lo-5 MO32
sa =4.9 x lo-5 ;037
w
1. 570 0 . 3 8 8 0.697
0.710
IO&8000
8 2 0 0
2 3 3 0
8OOQ
1 6 0
2 6 0
0. 505
0.630
1 . 6 9 7
0. 14 1 3 7 0
1.29f0.05 7 2
460 1.15+0.10 2 7 7 Mw; Dz,o
0.280 D,; C=0.5g/dm3
4 7 9
0.562
0. 383
7. 05
5 7 5 7. 59
9 5 5 3. 90
1060 2. 52
1 0 0 0 2. 18
7 4 0 1. 16
1 1 0 0 1.11
260-740 DA=2.8 x lO-4 M-0.69
w
2 9 0 99 M n 6b%%loroform 498
2. 48
3. 04
3. 55
4. 17
4.76
5. 08
D,, = 2.02 x 10m4 M-0.57
D measured in 266,154
H 2 O/KC1
(0.2 mol/dm ); M,,A
Sv; 15v; M,/M, = 6 2 8
1.15-1.4
C=O.O6, l.2g/dm3 6 2 9
M,; M,IM, = 1.5; 6 3 0
C=5, lOg/dm
M,; M,fM, = 1.5; 6 3 0
C=5, 10g/dm3
6 3 2
M,IM, =2.5 6 3 3
Mw; D,,o 6 3 1
7 9 0
634, 635
c
M,; see Ref. for 6 6 7
P
SO and k,
1008
Mw; D,,o
634 $
Mw; D,,o 634 3
Mw; Dz.0 6 3 6
3
6 3 6
E
637 2
r
D,; C=0.5g/dm3; 4V %
1
D,; C=0.5g/dm-; 4 V
Mw; DA
2 6 7
f
F
0.896 M, in chloroform
0.902
1 0 0 5
_--- -~.-..
Poly(N-isopropylmethacrylamide-co-acrylamide)
IPAM- Deionized water - 3 0 0 0
lPAM-85 3100
IPAM- 4 5 0 0
IPAM- 3 9 0 0
IPAM- 2 2 0 0
IPAM 5 2 0 0
Poly(acrylamide-co-sodium-3-acrylamide-3-me~ylbutanoate-c~-(2-(ac~lamido)-2-me~ylpropyl) trimethylammonium chloride)
0.490
0. 439
0. 394
0.42 1
0.524
0. 335
AM NaAMB AMPTAC
ATABAM 0.5-0.5 Water/NaCI (1 M) 2 5 3 4 3 0
ATABAM 2.5-2.5 1 3 9 0 0
ATABAM 5.0-5.0 3 4 5 0
ATABAM IO-10 10800
ATABAM 15-15 * ,I2200
ATABAM 5.0- 10 11200
ATABAM 10-5.0 1 9 4 0 0
Poly(acrylamide-co-3-(2-acrylamido-2-methylpropane dimethylammonio).1-propane-sulfonate) (AM-co-AMPDAPS)
0. 498
0. 313
0.476
0.264
0. 313
0. 361
0. 389
DAPSAM-I Water/l M NaCl
DAPSAM5
DAPSAM-IO-2
DAPSAM-IO-3
DAPSAM-25-2
DAPSAM40-2
DAPSAM-40-3
DAPSAM-60-2
DAPSAM-75-2
DAPSAM-100
Poly(acrylamide-co-NaAMPS-co-AMPTAC)
ATASAM 0.5-0.5 Water/l M NaCl
ATASAM 2.5-2.5
ATASAM 5-5
ATASAM lo- 10
ATASAM 15-15
ATASAM IO-5
Poly(NaAMPS-co-AMPTAC)
A T A S - O
ATAS-IO-2
ATAS-25-2
ATAS-40-2
ATAS-50-2
ATAS-70-2
ATAS-
Poly( 1 ,Cbenzamide)
Poly( 1 ,Cphenylene
terephthalamide)
Water/l M NaCl
Dimethylacetamide/
3% (g/mol) LiCl
96wt.% HzS04
2 5 3 2 0 0 0. 505
1 2 4 0 0 0.316
7 0 0 0.40 I
21500 0.320
8 2 0 0 0. 397
15100 0.362
1 7 5 0 0 0.324
5 4 0 0 0.360
6 2 0 0 0. 490
3OOa 0. 628
2 5 6 0 3 0 0. 423
2 7 8 0 0. 577
5 0 7 0 0. 381
5 8 7 0 0.449
6 7 7 0 0. 433
3 8 8 0 0. 413
2 5 6 1 2 0 0. 387
8 2 2 0 0.419
6 2 0 0 0. 473
7 9 2 0 0. 385
7 6 8 0 0. 463
4 9 8 0 0. 406
1 4 7 0 0. 637
2 5 5 5 &=4.38x 1O-4 M- ' . "
w
3 0 4 8 . 3 0.072
3 8 . 4 0. 088
2 2 . 1 0. 113
1 5 . 9 0. 159
CLS, DLS 1 0 0 6
Terpolymer
composition mol%
AM: NaAMB:
AMPTAC
99 : 0.5 : 0.5
89.1 : 5.1 : 5.8
85.9: 7.9: 6.2
80.5 : 9.7 : 9.8
74.6: 11.5: 14.0
75.7: 13.6: 10.7
85.3 : 4.5 : 10.2
AMPDAPS in the
copolymer mol%
5
9.6
10
27.7
38.9
40
58.8
70. I
1 0 0
dn/dC = 0.1426 cm /g
dn/dC = 0.148 I cm /g
dn/dC=O.l5lOcm/g
dn/dC=O.l395cm/g
dn/dC=0.1344cm3/g
dn/dC = 0.1376 cm /g
AMPTAC in the
copolymer mol%
0.0
1 4 . 7
3 6 . 1
45.4
51.7
65.7
100. 0
References page VII - 198
TABLE 3. contd
Pol ymer S o l v e n t
c
E
\
is
- v1
T (C)
M ( x 10 -3) (g/m4 S (x 109 (s) k, (cm349 DO (x 10) (cm/s) ko (cm3fg) f~/f$~ 1-2 (cmk) Remarks Refs. 5
z
14.5
96 wt.% HzSOJ 3 0 42.6
0.05 M KzSOJ 29.8
Poly(n-phenylene
isophthalamide)
Dimethylacetamide
Dimethylacetamidel
3 % LiCl
Dimethylformamide
4.2-230 2 6
25
20
2s
0.196
Dr.0 =2.72 x 10m5 M,
0.074
0.093
DI_(,=1. 51 x IO5 M,Z
D,,=1.13xI O- M-
D,l=o.55x IO-I M ~a%
0. 66 s v
0. 7 I
8
1082 q
See Ref. for ! , and MM\\
0.83 .s,; D,,M,,,
7x.7
67- 1030
48
113
IS5
270
IO.5
210
16
28
63
I93
214
28-575
980
320
I .72
I .65-4.6X
I52
2.0x
2.36
2.95
2.04
2.48
Poly(acrylonitrile)
3.6
2 . 1
I .7s
1.25
0 . 8 3 0 s,; M,
D,;D,, given in Ref.
2s
7. 14
5.72
5.08
4.03
3.91
Do=2.19x IO M 3s kn=
Dimethylfonnamide/
benzene 30% RI-
Dimethylformamide/
benzene 37% RT
Dimethylfomwmide/
tetrahydrofuran ( I / I)
4.6
3.08
2.31 x IO- x D-
0
C= 1.5-lOg/dm
M T.n
7000 13x
I200
2 1 0
Dimethylformamidelmethanol 1200 4.03 ~
Butanone 330 1 2 . 1
M,,, calculated from
s,, = 0.025
M, ; C=O. 648g/
dm2; SV
M, ; C= 1. 323gl
dm; l2V
M, ; C= 1. 270d
dm; 4V
C = 1.5-IOgldm
Butanone 1 7 0 10.2 C = 1.5-10g/dm7
Poly(acrylonitrile-
star-styrene)
Poly(acrylonitrile-
ult-styrene)
Poly(amidobenzimi-
dazole)
Dimethylacetamide 25 74.7 I .33 537
72.3 1.32 525
6 3 . 1 I .28 550
55.7 1.25 42X
46.9 I.1I 285
39.6 0.99 183
27.3 0.93 142
I O. 1 0.80 5 1
_.- ._-.- .._.
- ---
Dimethylacetamide/
0.3% LiCl
2 5 79.3 1.45 900
60.6 1.33 8 9 0
41.1 1.12 7 2 0
29.3 0.88 4 6 0
Poly(benzyl acrylate-co-methyl acrylate)
different camp. Methyl ethyl ketone
Poly(n-butyl-acrylate) Methyl isobutyl ketone
Poly(tert-butyl-acrylate) Methyl ethyl ketone
Acetone
Methanol
Pe nt a ne
Methyl ethyl ketone
Acetone
Methanol
Pentane
Acetone
Methanol
Pe nt a ne
Methyl ethyl ketone
Acetone
Methanol
Pe nt a ne
Methyl ethyl ketone
Acetone
Met hanol
Pentane
Poly(n-butyl Methyl isobutyl ketone
methacrylate)
Propan-2-01
Microgels Ethyl acetate
0.944
u2 and M given 5 0 6
MV 148
Mw; so 5 1 2
2 0
23.3 4 6
2 5 3 0 6 17.7
0.207
0.237
0.266
0.160
0.194
0.230
0.244
0.182
0.203
0.228
0.139
0.162
0.94
0.84
0.53
0.22
0.88
0.74
0.49
0.21
0.64
0.43
0.20
0.65
0.55
0.39
0.19
0.59
0.32
0.22
0.13
2 5 2 3 7
Mw; so
25 .
180
25 149
0.191
0.109
0.117
0.127
0.137
25 75
8 2 0 21.2
21.5
2 0
0.922 M 148
40- 8000 6.3 x 10ms M- " ' "
2 5 4 0.174
3 9 9
1
M, , C=O.l-0.5g/dm ; 646
see Ref.
M, , C=O.l-0.5g/dm?
see Ref.
M, , C=0.1~0.5g/dm~;
see Ref.
M, , C=O.l-0.5g/dm;
see Ref.
1052
C = 0.5 g/dm 3 551
DA; M , . D given in Ref.
M\ . D, DA 5 6 0
M
s. 0 580
2 5 4 0.14s
Tetrahydrofuran 3 4 0 0.181
3 8 0
s=0.12M03
so ~3.02 x 10ms Mo. 4'
w
sg = 1.42 x lo-l4 x M" . " 6
140-780 ~~~1.9 x 10mL5 Mo. 4b
0.191
2 5
2 0
21
21
21
Poly(tert-butyl
methacrylate)
Poly(cetyl methacrylate)
Poly(cholestery1
acrylate)
Poly(2.6.diisopropyl-
phenylmethacrylate)
Poly(2.6~dimethyl-
phenylmethacrylate)
Poly(acrylic acid)
Butyl acetate
D, , =2. 51x 10m4 Mm" " "
D, , =1. 74x 10-j Mwo"
Do=3. 2x l O- 4 M- 0. 54
Heptane
Benzene
Toluene 25 0.789 1053
0.894
1100 5.6 4.71 0.73 Ms, Di
Toluene 25
Water/NaCI
(0.2 moVdm3)
(0.02 mol/dm)
(O.O12mol/dm)
(0.006mol/dm3)
20-22
35.0 20.0
0.65 f 0.02d 28.2
49.0
7.3 h 0.5 81.0
114.0
References page VII - 198
TABLE 3. conrd
Polymer Sol vent T (3 M ( x 10e3) (g/mol) s ( x 10 3) (s) k, (cm349 Do (x 10) (cm/s) ku (cm@ folfsp ~2 (cm 3k) Remarks Ref s.
(l.0moVdm3)
(0.2 mol/dm)
(0.012 mol/dm3)
(0.006 mol/dm 3,
(O.O012mol/dm)
(l.Omol/dm)
(0.2 mol/dm )
(0.012 mol/dm )
(0.006 mol/dm )
Poly(ethyl actylate) Methyl isobutyl ketone 2 4 . 3
n-Propanol 2 8
Poly(ethyl acrylate-co-acrylic-acid)
sodium salt WatedNaCl (0.05 mol/dm )
(0. I mol/dm )
(0.3 mol/dm3)
(0.5 mol/dm )
(0.7 mol/dm )
( I .Omol/dm )
(I .2 mol/dm )
2-Heptanone
420
6.5 f 0.5
2 . 4 0.2
4.2 1 . 0
3 2 . 0 1. 35 i 0. 05 d 1 0 . 0
6 0 . 0 2 1 . 4
1 4 6
2 2 . 3
0.0 2 2 . 3
2. 15 3.2i0.1d 1 5 0
8 . 0 2 8 6
MF. D
0.95 I M 1 4 8
MMW 4 5 6
M, / M, =1.8-2.3
7 0
2. 4f 0. 1
3 4
18-155 s,j= 1. 05 x 1oF @4
165-1300 D.,=5.76x 10m4 Mm" "
D,,, ~8.55 x lO-4 M-Oh7
D
0. 1
=3. 73x 10m4 M- OS9
D
0.1
= 1 . 5 4 x 10-4 M-s2
Do,, = 1.41 x 10m4 M- ' j 5'
D
02
=1.24x 10 4M-5
D, , , =l . 10x10- 4 M 04'
D =1. 35~l O- ~M- " "
Cl , ,
Poly(ethyl actylate-co-methylacrylate)
different camp. Methyl ethyl ketone
Poly(ethyl methacrylate) Acetone
02 and M given 5 0 6
f
,p ~.,,+f~ 0. 798 M,.A 5 9
0.798 IV,,~; s,; See Ref. I8
0. 7942 extrapolated value 2 6 8
M, , w; s, ; D~, See Ref. 5 2
0. 863 M
148
0.900 A 4 2 7
1053
2 0
2 0
Methyl isobutyl ketone 2 2 . 9
(theta-solvent) 2 5
77-7440 s , ) - M
" 47
34. I-9350 8.95% 120
&,-M-57
17.4-0.85
7.45- 107 23-60 20.0-0.95 O-63 24.6-7440
4 1 0
1 0 3 6 Poly(isoocty1
methacrylate)
63.0-67.5
C=2.5&ms; s,
(Trautmann)
8 7 5
2 5
2 5 3 0 6
0.789 Poly(phenyl Toluene
methacrylate)
Poly(sulfoalkyl methacrylate)
alkyl : hexyl 0.1 M NaCl
octyl
decyl
e t hyl
Poly(metbacrylic acid) Dimethylsulfoxide
M, / M. =1. 5; dn/dC= 100
0.135cmlg
M,/M, =2.0; dn/dC=
O.l40cm/g
M, I M, = 1.8; dn/dC=
0.149cm3/g
M, j M, =2. 1; dn/dC=
0.170cm3/g
MtVlW
6 3 8
I .22 1. 54 x 10-4
1. 02 1. 72 x 1O-4
1. 00 1. 99 x 10-d
0. 975 2.07 x 10 -
4 9 4
7 0 1
134
3 4 0. 46
1 3 0 I .02
2 6 0 1. 27
4 2 9 1. 66
4 3 2 1. 85
3 8 1 1. 60
2 5
_-.---.. -.-~-.
Poly(methacrylic acid) Sodium salt
Water/NaCl, Yf = 4 20
5
9
14
19
29
39
49
59
co
WatedHCl (pH = 2.0) 21. 3
Water/NaOH (pH = 12.0) 2 1 . 4
Water/NaCl (0.01 mol/dm)/
NaOH(pH = 12.0) 21.8
Poly(methyl acrylate-co-styrene)
different camp. Methyl ethyl ketone 20
Poly(methy1 Acetone 20
methacrylate)
20
20
Acetonitrile
20
20
25
30
38
4 4
Acetonitrile-d 3
Benzene 20
25
25
Benzene-d6
30
7 7 7 2. 80
1 4 0 4 3. 02
237
339
442
530
690
768
880
943
986
1014
1112
62
7 8
78
115
201
1380
6350
65- 1980
65- 1980
2. 90
3. 87
4. 36
4. 73
5. 46
5. 66
6. 04
6. 28
6. 43
6. 50
7. 22
20. 3
4 6 . 1
88. 5
16 27. 06f0. 70
29 17. 20f0. 17
so= 18. 6 x 10-15 MO.51
1. 16
1. 80
2. 95
4. 18
7. 55
10. 9
20. 2
35. 3
74. 0
119
218
1.1
1 1 5
1.9-77
1.1 42. 8 NMR-self diffusion
1. 150
1. 072
0. 923
0. 838
0. 742
0. 692
0. 643
0. 621
0. 611
0. 602
3. 45 M of uncharged polymer
0. 712 Mv
0. 385
M
0. 412 M
10. 25 1. 19 x 10-5cmR
12 6. 8 18 1. 97 x 10-5cmR 0.789
224 2. 2 5. 35 x 10m5 crng
614 0. 92 14. 1 x 10-5cm~
D, ~, =(8. 09*0. 68)x10~4 M-57h*om
- 0. 4L73. 05
101
82. 1
68. 0
51. 5
40.8
36. 4
25. 6
21. 0
14. 3
11. 6
8. 9
14. 1
- 6. 97
- 4.17
0. 798
0. 825
- 0. 7
- 2. 1
- 3. 1
- 3. 1
- 3. 1
- 4. 1
- 5. 1
- 8. 1
- 11. 4
- 13. 2
- 24. 2
5. 05 1. 25 x 1O-5 cm8
0. 8213- 0. 8077
0. 8069+39. 4/ M
0. 818
0. 879
s,; apparent M 124
~2 and M given
MMW
M,,A; SI; DA
M,.A; s,; DA
MI,A; st; DA
M,/M. = 1.20- I .44
M, / M. = 1. 20- 1. 44;
see Ref.
D, , &M, / M. = 1. 18
D~, ~; M, I M. =1. 29
See Ref. for range
of M,
MW
M,/M. = 1.08 for all
NMR-selfdiffusion
MMW
Mm; (AIBN) See Ref.
(B~02) See Ref.
if
B
t
g.
3
148 g
148 :
148 z
s
506 2
460 $a
15 5:
15 J
15 ?
639
639
f
g
VI
639 ;
3
0
1054
494 s
=
570 3
-!
1 0 5 1 2.
P
CL
-.
s
L
c
c
s
4
R
-z
z
1 0 8 0 0
460 -g
268
268
$
211
494 i-5
1 0 8 0 T
E
References page VII - 198
TABLE 3. cont d
Polymer Solvent T (0 M ( x 10 -3) (g/mol) so ( x 103) (s) k, (cm%) DO (x 10) (cm*/s)
ko (cm%) fO/fsp ~2 (cm3/g) Remarks Refs.
Butanone
n-Butyl acetate
n-Butyl chloride
2 5 0.799
2 5
3 4 . 5 65-1980 Do,. = (3.08 f 0.68) x 10m4 M,.498*o~7
3 4 . 5 65-1980
1 0 5 4
2 0 8 Value for infinite
molar mass
M,IM.= 1.20-1.44
M,IM, = 1.20-1.44;
see Ref.
Do. , ; M, f M, =1.18
D0. L; M, / M. = 1.29
See Ref. for def. of s
M,.A; s,; DA
6 3 9
6 3 9
6 3 9
6. 15
3 4 . 5 1 6
3 4 . 5 2 9
3 5 (T=O)
35.6 2 0 0
1 3 0 0
6 5 5 0
4 0 . 8 1. 80
2. 95
4. 18
7. 55
1 0 . 9
2 0 . 2
3 5 . 3
74.0
1 1 9
2 1 8
22.38 f 0.01 - 6.2
14.92 f 0.05 - 6.52
- 30 1.65 x 10m5 cmR 0.82
- 5 5 4 . 0 9 x 10m5 cm8
- 35 9. 38 x 10mScm
- 3. 0
- 4.0
- 3.8
- 5. 1
- 6. 1
- 9.0
- 10.7
- 14.6
- 18.8
- 22.4
0. 8038
0. 8118
0. 7942
4 0 . 1 2 5 1 +53
1 5 . 7 2 2
3 9 . 1 4 1
8 6 . 0 107
7. 18
2. 91
1. 15
62.4
5 1 . 5
44.0
3 2 . 7
2 8 . 1
2 1 . 8
1 6 . 4
I l . 2
9 . 1
6.8
MW
M, / M, n. 1. 08 for all
1 0 5 7
Carbon tetrachloride
Chlorobenzene
Chloroform
Chloroform-d
Cyclohexanone
2 5
2 5
25-65
Value for infinite
molar mass
Value for infinite
molar mass
Value for infinite
molar mass
NMR-self diffusion
See Ref. for Do
and kD-values
Value for infinite
molar mass
Value for infinite
molar mass
Value for infinite
molar mass
M,,A; sr
2 6 8
2 6 8
2 6 8
1.1
3 1
46.7 1 0 8 0
6 4 0
o-Dichlorobenzene 2 5
Diethyl ketone
8 0. 8187
0. 8015
1,4-Dioxane 2 5 0. 8181
2 5
Ethyl acetate
1300
6 5 5 0
2. 11 1 3 4
4 . 5 4 1 2
8. 55 1 0 4 0
2.17 x 10-j cmg
6. 35 x 10 -5 cmg
1 7 . 6 x 10-5cmg
0. 7963
2 0 7 9 7 . 6 2 . 5 7. 21 0 0. 787
1 2 7 8 . 8 0 . 8 5. 66 0
2 6 8
2 6 8
2 6 8
1 5
1 5
1 5
2 6 8
2 1 1
2 1 1
Value for infinite
molar mass
M,,o; Dw
so=-0.06+
0.026 M ' . '
Ethyl acetate 2 0 7 1 1 . 7 1 . 8 4. 36
3 1 5 1 4 . 1 1 . 9 3. 73
--
3 8 1 1 6 . 3 2 . 4
4 7 3 1 9 . 4 5 . 2
7 0 1 2 1 . 5 5 . 2
9 3 1 2 5 . 0 6.0
1 8 0 9. 86 0. 59
1965 3 4 . 0 3 . 1
18-1965 S() = 1.51 x lo-5 MO48
3. 79
3. 38
2. 54
2. 34
2 1 2
2 6 8
148
641
641
2 6 8
6 4 2
1056
4 6 0
2 6 8
6 4 5
148
1058
1 0 5 8
Methyl ethyl ketone 0. 7993
0.816
Value for infinite
molar mass
M,
Mw; Dz; MwIMn =2,
C = 1.34gldm
Mw; D,; MwIMn 4
C = 0.859 g/dm
Value for infinite
molar mass
Methyl isobutyl ketone 2 1 . 8 4 8 0
Methyl methacrylate 3 7 0 I .95
1.51
9 4 3
4 5 4
Tetrahydrofuran 0. 8085
Thi ophenol 2 5
45-448
107
2 6 0
2 6 5
4 0 1
8 4 4
1 1 0 0
2 1 4 0
4 0 5 0
II5
1. 15
I .63
1. 66
2. 08
2. 56
3. 06
3. 94
4. 88
Do, , =2. 27 x I O ~' M" " j
8 7
126
150
201
3 1 5
3 7 5
6 1 5
9 5 5
5. 80
S,) = 1.17 x lo-
M (1 40
w
k,-2.50x IO *M" "
w
Toluene 2 0 1.19x IO~crn~
0. 807
M
Value for infinite
molar mass
Value for infinite
molar mass
MV
MV
MV
M
MV
MW
MwIMn =
I .08 for all
0. 8101
m-Xylene
2 5 1400
17 1 9 0
22. 15 190
2 9 . 5 1 9 0
4 5 . 0 1 9 0
2 5 I .83
4. 18
7. 55
2 0 . 2
5 0 . 4
7 4 . 0
119
2 0 4
3 1 2
4 8 2
9 5 2
4 4 (T=B) 1. 83
4. 18
7. 55
2 0 . 2
5 0 . 4
20. 62
0. 8063
0. 8019
0. 8190
0. 8143
atactic 6 9 . 2 - 1.6
48.2 - 1.8
3 6 . 5 - 2.9
2 2 . 4 - 1.1
1 4 . 3 1 . 8
1 1 . 5 1 . 9
9 . 1 7.4
6 . 7 1 9
5.5 1 3
4 . 3 2 9
2 . 9 6 4
78.0 - 1.7
5 7 . 5 - 3. 1
40.8 - 3.7
2 6 . 9 - 6. 1
1 7 . 6 - 8.0
M, ; M, / M, - - 1. 08
for all
References page VII - 198
TABLE 3. contd s
-F
Polymer Solvent T ((3 M ( x 10m3) (glmol) so ( x 10) (s) k, (emJ Ig) DO (x 10) (cm*/s) kl, (cm%) folfsp u2 (cm3k) Remarks Refs.
E
Acetone
Acetonitrile
Acet oni t r i l e
Poly(methacrylic acid)/Foly(vinylpyrrolidone)
complex Water
Dimethylsulfoxide
2 5
2 8 (T=8)
2 5
2 5
Poly(methy1 methacrylate-co-ethylene dimethylacrylate)
randomly branched Ethyl acetate 2 0
Mesitylene 4 7 (T=B)
74.0 1 4 . 3 - 11
1 1 9 1 1 . 6 - 13
204 8.9 - 16
3 1 2 7.3 - 15
4 8 2 5.9 - 33
9 5 2 4.2 - 38
3. 04 52.4 - 1.5
7. 21 3 4 . 5 - 2.5
3 0 . 9 1 6 . 6 - 2.8
70. I I O. 9 - 1.5
1 5 4 7 . 1 2 . 3
319 4.3 1 5
686 3.2 3 7
9 7 8 2.6 51
3. 04 49.9 - 2.6
1. 21 33.0 - 4.9
3 0 . 9 1 6 . 2 - 9.8
70. I 1 0 . 6 - 14
1 5 4 1.2 - 21
3 7 9 4.6 - 36
6 8 6 3.4 - 5 2
9 7 8 2.9 - 6 6
looa
1 3 8 4
1 3 2 4
1313
1 2 6 2
1335
1 1 3 6
1 1 3 8
1 0 6 5
9 3 6
7 4 6
6 9 2
5 3 6
4 2 8
3 1 1
1 3 0
3 8 0 2 0 . 7
8 0 0 3 0 . 8
1 0 5 0 3 6 . 0
2 6 3 0 5 8 . 6
2 4 . 4
3 0 . 3
2 8 . 5
3 0 . 3
2 8 . 5
3 3 . 3
2 5 . 0
2 6 . 6
2. 63
2. 50
2. 30
2. 20
2. 10
1. 79
1. 60
1. 08
M,; M,IM, = 1.06
for all
0
M,; M,/M, o 1.06 1058 i
for all C
r
P
MHW
Mh4W
6 3 8
d
E
3
.E
0.680
M,; see Ref. for 5 4 9
polymerization
conditions, SO, k, and
5
v,
M values
M, (measured in 6 4 3
dioxane); togs,
-.-- .- .-_
47 (T= 8) 380-2630 so=3.1 x 103 ws
2 5 1000 20.57
1350 26.39
170
12.6
51 6.7
3 8 0 16.6
8 0 0 24.3
1050 26.5
2 6 3 0 42.7
0.702
Mw
Mw
MW
M,; (measured in
dioxane); vzq 1
6 4 4
6 4 5
6 4 3
For all temoeratores.
b See Ref. -
See Ref.
d See Ref. for def. of D
See Ref.
Y = total concentration (mol/dm ) of Na-ions divided by concentration (mol/dm ) of poly(methacrylic acid).
8 f;= kT/(Dom).
TABLE 4. VINYL POLYMERS
Polymer Sol vent
F
n
3
J
P
S
s
J
%
z
ra.
s
ii
9.
J
P
T (C) M ( x lo-) (g/mot) so ( x 10) (s)
k. km349 Do ( x 10) (cm%) k D (cm49 /o/f- v2 (cm49 Remarks Refs. $
-.
L
Poly(hydroxyetber) composed of 1,4-arthydroerythritol and diglycidyl ether/bisphenol A
VI
1085 j.
z
16
13
9.6
8.0
1.5
6.7
5.8
5.5
[q] = 8.7 cm /g
[q] = 9.9 cm 3/g
[q] = 10.0 cm 3/g
[q]=ll.lcm3/g
[q]=ll.9cm3/g
[q] = 12.2cm3/g
M
2 0 3.1
2.5
4.9
6.95
8.26
11.8
12.3
14.2
15
148 2
2
148 3
148 &
Poly(methoxy ethylene) Amy1 alcohol
Poly(viny1 acetal) Toluene
Poly(viny1 acetate) Cyclohexanone
Diethyl ketone
23.5
20.9
23.8
13
40
2 0
13
40
2 5
2 5
2 0
0.983
0.848
0.849
0.821
0.833
4 8
M
60 k
S.
s
1 1 0 , 1 2 2 0
6 0
2
6 4 7
3
6 4 7
B
129
2
129 ;:
Methyl ethyl ketone
1,2,3-Trichloropropane
17-1200 so =9.8 x IO-l5 MO*
w
Do =I.8 x lO-4 M.63
w
M~,A; st: DA
0.83
0.841
microgels
Poly(viny1 alcohol)
Methanol
Methanol
Water
2360-17500
31700-422900
22.4
13
3 4
7 4
9 0
Do,, = 9.78 x 10 -s M,
0 478
0.16
0.765
0.96 7.46
1.26 3.17
1.96 2.68
1.86 2.16
so =4.4 x lo- MO.32 &=5.5x lo-0 M-a.68
0.765 130 >
0.750
M 148 g 21.6 21
References page VII- 198
-
TABLE 4. cont d
Polymer Solvent T ((3
M ( x 10m3) (g/mol) so ( x 103) (s)
k, (cm3/g)
Do (x 107) (cm*/s)
ko (cm3k) fo/fsp w (cm3k) Remarks Refs. 2
5
2 5 8 . 5 0. 61 6. 89 2 2 8
2 3 . 3 0. 96 3. 91 2 8 2
6 4 . 1 I .54 2 . 3 3 4 7 l.o4xM-1
2
f
119
r
=I
2 5
2 5
2 5
2 5
2 5
3 0
Wateriborax
(0.0060 mol/dm )
(O.O100mol/dm~)
(O.O149mol/dm)
(0.0299 mol/dm )
(0.0498 mol/dm)
2 5
Water/NaCI
(0.2 mol/dm )
DzO/NaCI
(0.2 mol/dm)
Wat er / n- Pr opanol
(IO mass%)
Water/n-Propanol
(20 mass%)
Wat er / n- Pr opanol
(30 mass%)
Wat er / n- Pr opanol
(35 mass%)
Poly(4-vinylbiphenyl) 2 s
Poly(vinyl butyral) Amy1 alcohol 2 0
Poly(4-vinyl-N-butyl- Water/NaCl 2 0
pyridinium bromide) (0.2moUdm) 2 5
-_--. --
2 5 2. 14
1. 22
2 5
2 0
2 5
2 5
2 5 (T=Q)
9 0. 90 5. 45
1. 14 4. 10 3. 82
6 3 I .82 3. 55
2 0 0 2. 33 2. 45
1 3 0. 63 4.00
3 0 0. 95 2. 15
14 1. 25 1. 65
2 3 0 I .45 1. 05
I O 0. 62 3. 25
2 1 0. 92 2. 85
14 I .05 I .55
2 0 0 1.15 0. 85
1 4 0. 82 3. 25
2 1 0. 92 2. 80
16 1. 32 I .55
2 1 7 I.64 1. 05
1 1 5 3 . 0
2 5 1. 10
1 6 7
1 0 7
9
2 8
130
4 9 2
9 4 . 5
18
4 3
6.4
1 9 . 8
5 4
9 4 . 5
2. 52 I .45
3. 06
1.10 1. 56
2. 13 5. 45
3. 22 2. 65
4.3s I .I5
1 2 . 3
9.8
2 . 8 2. 38
4 0 0
- 8
4.02
4. 39
4. 62
3. 45
3. 22
4. 00
5. 08
5. 30
3. 45
4. 25
4. 70
3. 42
4. 15
4. 23
0. 754
0.769
0.766
0. 763
0.767
M, ; C= lOg/dm
M, ; C= IOg/dm
M
0. 768
0. 775
0.77 I
0. 111
0.79
M,.; s,; c=2-10
g/dm
M5.0; St; c=2-lOg/
dm
M,.o; s,; c=2-log/
dm
M, Q; s, ; c=2- l Og/
dm
0.82 See Ref. for solvent
0. 883 [q] = 122 cm 3/g
0. 77 C=1g/dm3
DA; M, I M, = 1.01
M.,,o; s , ; c=2-lOg/
dm
6 4 8
P
6 4 9 8
i
650 5
.m
6 5 8 Q
i
151 2
z
s
6 5 0 8
i
5
Y
4 8 0
I48
135
131
Poly(N-vinylcarbazole) B.?lZelle 2 0 3 3 . 3 0.786 CLS 4 5 7
1 6 . 3 CLS
0.793 [q]= 122cm~/g 148
0. 711 M 148
0. 6926 6 0 2
0. 622 0. 705 M 7 5
I.075
1. 18
1. 56
Poly(vinyl chloride)
Chlorobenzene
Cyclohexanone
2 3 . 1
2 3 . 4
2 5
9 4 0
1 9
5 3
6 6
1 2 0
2 9 - l IO
100-180
3 9
97- 105
6 4 0
MW 6 5 1 it

6 4 0 $f
Mw: M MW given 5 4 4 2
i n Re f z.
0. 7429 181 s
0. 6951 6 0 2 ;
MW 6 0 2 o
5
M 5 9 6 5.
0. 723 [r/1=72.2cm3/g 148 =
h
b
0. 703 [q]=77.4cm/g 148 3
0
-.
M,; Muw 4 2 1 8
.!
0. 72 from 441 3
sg .Y,) a
-.
=s(l+ 1.66[7#?); MMW L
g
0. 82 4 8 0 4
0
,sg=2.195 x IO- M49 120
I-Dioxane
Tetrahydrofuran 2 0 7.69-5.32 247- 132
2 5
9 0
4 6
20.2- 183
Fr act i onat ed 6 . 8
5. 41
s,, =6.50 x IO- M 5 5
Poly(vinyl chloride- Cyclohexanone 2 3 . 5
w-vinyl acetate)
Poly(vinyl chloride-co- Cyclohexanone 2 3 . 5
vinylidene chloride)
Poly(vinyl fluoride) Dimethylformamide/ 100
LiBr (0. I molldm )
114-521 . Y, I =0. 101 x M" " '
143-654 .x0=9.29x I O- ' MO4
0.84 480 2
F
Poly(vinyl methyl ether) See Poly(methoxy ethylene)
Poly( I-vinyl- Toluene 2 5
naphthalene)
Poly(2-vinyl- Toluene 2 5
naphthalene)
Poly(vinylpyridine) Et hanol 2 5 MHW; Ref. 134 132
3
B
s,; See Ref. for A4
J
116 EL
and D
n
a .
&
0
5
9 7
4 3 0
3 . 6 179 0.682
6. 45 6 2 9 0.689
2 1 . 3 0.410 Poly(vinyl sulfonic acid) Sodium salt
Water/NaCl
(0.5 mol/dm)
2 0 3 1. 57 1 5 . 0
5 1. 96 1 I.0
9 2. 32 9. 75
1 2 . 5 2. 94 5. 95
2 9 . 5 4. 27 6. 40
2 9 . 5 4. 46
5 0 0
1.0 (1.04)
0. 428
0.430
0.424
0.408
0.424
Poly(vinyl
trimethylsilane)
Cyclohexane RT
2 5
Poly(vinylpyrrolidone) Methanol 2 5
Water 2 0
M, I M, = 1.4-2.1; 652 <
C = 0.5 g/dm 3
7 6 1 3
0.730 M,,D; SV 1 5 0 3
0.776 1 4 4 f
0. 783 1 4 4
Mr,~i DA
1 4 3 , 1 4 4 c
er
\
5
s= 1.02 x 10-s Mo4j
w
D = 2.4 x 10 A M - " A'
w 2 3 3. 41 9. 60
2 0
500
12-74 so=8.81 x lo-l6 Moso D, , = 1.0 x lO-4 MO. "
References page VII - 198
-
TABLE 4. cont d
4
E
\
Polymer Solvent
T C-3 M ( x 10 -3) (g/mol) so (x 103) (s) k s (cm3k) Do ( x 107) (cm%) kD ( cm3@ fo/fsp 21~ ( cm3h! )
Remarks Refs. oG
unfractionated
23. I
2 5
Water/CaBr (1 mol/dm ) 2 0
Water/KBr (I mol/dm )
Water/LiBr ( I mol/dm )
Water/MgBrZ (I mol/dm)
Water/NaCl (0.2 mol/dm)
(Luviskol K 30) Phosphate buffer 2 0
(0. I mol/dm ; pH = 7)
Water/NaSCN 2 5
(0.6 mol/dm )
Water/NazS04
(0.2 mol/dm)
Water/NaAc (0. I M) 2 5
13-41.5 0.82-1.42 7.55-4.14 1.70-2.11 0.802 s,; IV, s ee Ref. for 4 0
MandD
E
u2 at 24.85C; DA
f
2. 12
2. 94
0. 775
0. 781
0.820
0.780
0.784
0. 801
given in Ref.
M, , A; s, ; DA
M, . A
M.,,o; c = 50%
M@; C=5%
M,,a; c = 5%
9 4 . 5 I O 1. 17 1. 17
2 7 0 0 12. 20 0. 50 0.50
1 0 . 6 0. 85 8. 66 8. 66
4 2 1. 66 4. 3 I 4.3 I
8 6 1. 94 2. 44 2. 44
1. 66 1 5 3 5
2
I78
H
1 7 8
1 7 8
178
$
148
150
g
3
487 .m
144 0
144 z
6 1 1 , 6 1 3 5
6 1 1 , 6 1 3 5
6 1 1 , 6 1 3 =
61 1,613
8
144 In
I44 fi
I44
g
1 4 4
f
I44 .w
I44 2
I44 7
144 z
I44 w
144 a
153 Y
5
2 9
ta. 32
3 0
5 0
2 4 . 5
2 4 . 5
2 4 . 5
2 4 . 5
1 2
2 5
3 9 . 2
5 5 . 6
3 1 0
5 8 4
II29
1900
3 4 2 0
9 4 5
2 0
5 . 5
4. 78
4.06
4. 01
1 . 0
I .43 6 8
I .59 8 5
I .I6
4. 77 391
7. 13
7. 13 7 2 0
1 2 . 5 1310
1 6 . 7 I630
sg = 8.81 x 10-h M5
7. 15
I .46
2. 09
2. 38
2. 8 I
4.36
0.772
0.77 I
MMW
C = lOg/dm
C = 10g/dml
C= IOg/dm
C = IO.03 g/dm
M,,A
M,,A; s,
MHW
MMW
4 8 7
d
E
487 3
.JJ
s,, =2.14 x I O- " Mn4* D,,=2.42~10-~ M- OS8 M,>4x 104g/mol 1059 ;
so= I.15 x lo-5 M4* &=1.29x 10~4M~052 M,<4x 104g/mol
?
See Ref.
TABLE 5. STYRENE POLYMERS
Polymer Solvent T (C) Y ( x 10m3) (gjmol) so (x 103) (s) k s (cm%)
DO (x IO) (cm2/s)
ko (cm349 fo/f, uz (cm3k) Remarks Refs.
Poly(styrene)-poly(dimethylsiloxane)
THF
7.5 ~01% PDMS/THF
15 ~01% PDMS/THF
Poly(styrene)-b-poly(ethylene/propylene)
2.Pentanol
5% 2-PentanoVS-
methyl-2.hexanone
10% 2-Pentanol/S-
methyl-2.hexanone
15% 2-PentanolA-
methyl-2.hexanone
Poly(o-chlorostyrene) Benzene
Poly(p-chlorostyrene) Benzene
Poly(p-isopropyl- Toluene
a-methylstyrene)
1 0 6 4
PS : M, = 321OOg/mol
PS : M, =32lOOg/mol
PS : M, =32lOOg/mol
1067
[q] = 16.2 cm j/g
P
B
[q] = 15.5 cm 3/g 3
(D
2
[q]= 13.6cm/g B
0
,
[q] = 12.9cm/g J
n
u
0.792 5 8 5 3
2 5 4 6 . 8
2 5 4 6 . 8
2 5 4 6 . 8
7. 28 1 9
I .32 3 6
0. 72 8.4
7. 03
7. 10
2 5 105
2 5 105
2 5 105 6. 96
2 5 105
3 0
3 0
2 1 . 5 18-625
6. 73
0.797 5 8 5
M,,,; M,/M,= 1.1-3.1; 6 5 3
i.
C=O.Ol-0.3gIdm
a
M, ; corrected for 6% 3
pol ydi s per s i t i y 0.
(Log-Non-n distribution) 2
.g
D, =(5+2)x IO8 M1;6*004)
2 1 . 5 18-625
Poly(a-methylstyrene)
narrow distribution Benzene M, from SE,LS; k,,,
Do, k. given in Ref.
M, (CLS); M,/M, =
1.59; D&O
M, (CLS); M, f M. =
I .22; D r,
M, (CLS); M, / M, =
I .03; Dr.
M, (CLS); M, / M, =
1. 04; DL. 0
M, (CLS); M, / M. =
1.26; D,,o
M, (CLS); M, / M. =
1.10; D,,o
M, (CLS); M, / M, =
1.1-1.6
Mw; Dw
l.O3<M,/M, 5 1.15
1.03<M,/M, Il.15
ML/ M, = 1.04-1.2
5 2 2 2
;\
cl
6 5 4 g.
$
5 5 8 4
1 0 7 0 !$
1 0 7 0 2
651 2
6 5 5 0
6 5 6 3
%
3 0 48.4-1670 ~~~3.61 x I O- " Mo4'
3 0 8. 64 19. 88 f 0. 28
3 2 . 7 10.65fO.lI 4.67 f I .98
9 1 . 7 6.02 f 0.02 14.5 f 0.4
145. 3 4. 80f 0. 05 20.8 f I .4
394.6 2.74 f 0.12 52.2 k I .O
976.4 I .58 f 0.07 101.4f 1.6
100-1000 D,,~ = (5.24 f0.48) x 10m4 M W9*" " 1
Poly(a-methylstyrene)
Chloroform
Cyclohexane
2 1 5 0 0
2 0
2 8
3 2 1 lo-3280
3 4 . 5 2 0 4
2 0 4
444
7 6 8
II90
1 8 2 0
3 . 1
D ~4.78 x 10-5M-.425
of z6.49 x 10-5M%42s
~~~1.36~ IO- M, 05
3. 00
so= 1.67 x lo-l5 MO, '
w
8. 06
1 1 . 7
1 6 . 5
2 1 . 6
2 4 . 3
3 3 . 0
2 0
3 6
3 8
9 1
6 8
119
fo~1.78~ IO-cm
Mw;fo ql
2.60 x IO-cm
3.41 x 10-s cm
3.87 x 10e5 cm
5.21 x 10-s cm
7.03 x lo- cm
References page VII - 198
TABLE 5. STYRENE POLYMERS
c
E
\
Polymer Sol vent T (C) A4 ( x 10 -3) (g/mol) so ( x 103) (s) k, (cm3k) DO ( x 10) (c m2/s) kI, (cm3/g) fO/fSP 212 (cm3/g) Remarks Refs. 5
7 4 7 0
204-7470
narrow di s t r i but i on Cyclohexane 3 9 48.4- 1670
3 5 (T=l9) 37-621
7 3 0
1 5 2 0
3 7
3 8 . 2
35-125 6 5 0 0 ,
3 9 42.7-1430
3 9 42.5-l 170
trans-Decalin 9.5 (T=0) 2 0 4
trans-Decalin 3 3 0 0
2 0
4 0
Toluene 2 5
3 5
25-120
42.5-l 170 S = 3.01 x lo-5 M.M
1 9 . 8 II.37
40. I 17. 78
6 5 0 0 2.38-8.0
3 7 2 0 s,,=4.02 x IO- M43
w
2 5 8. 64
444
7 6 8
II90
1820
6. 85
7 4 7 0
204-7470
II90
1 8 2 0
3 3 0 0
7 4 7 0
I .74
2. 42
3. 40
4. 41
5. 15
8 9
1 0 . 6
sn=3.9x IOmh M;
4. 98
5. 7 I
7. 4 I
II.4
2 9
2 7
3R
6 2
5 7
IO6
109
137
I78
3 5 3
2 0 4 2. 7 I 4 5
4 4 4 3. 38 8 2
7 6 8 5. 26 134
II90 6. 41 167
1820 7. 41 2 0 7
3 3 0 0 1 0 . 3 3 5 6
7 4 7 0 1 4 . 3 6 2 8
3 2 . 7
4 9 . 8
so= 1.8 x lOm5 z&f;
s,,=2.0 x 10-15 WS
s,j= 1.72x IO- M49
13. 89
19. 47
S = 1.86 x lo-~5 M;
sg= 1.93 x lo- M5
w
134
s,,=2.ox lO~5 MC5 k, =6.2x IO4 M
10.6 x 10 - cm
0.886
fo=4.1 x 10-x M$5cm
0. 889
I .886
fo=1.62x IO-cm
2. 47 x IO-cm
3. 12 x 10mScm
3. 72 x IO cm
4. 82 x IO-cm
fx6.65 x IO-cm
9. 73 x IO-cm
0.894
f0=4.19x I O scm
5. 53 x IO-cm
7.82 x IO -cm
11.5x 10-5cm
0.892
f.= 1.99 x IO-cm
2. 95 x IO-cm
3.68 x IO- cm
4.91 x IO- cm
6. 43 x IO-cm
8.74 x IO - cm
13.8 x IO m5 cm
0.892
0. 873
19.551LO.18 1.1210.30
10. 67 f 0. 05 4.63 zt 0.30
M, (SE); k, given
in Ref.
M,; A; M, given
in Ref.; s ,,,
so
MW
M,; Do given in Ref
M, dep. of k, given
in Ref.
C= 16.4g/dm; see
Ref. for so-values
M w; pressure dep.
of s given in Ref.
M,; CLS; k, given
in Ref.
Mw;fo T/I
M,; A; LS
M
M
C= 16.4g/dm3; s ee
Ref. for so-values
M,; DO andfo
given in Ref.
Mw; (CL3 Mwl
M, =1.59
M,; (CLS) M,IM, = 1.22
.
6 5 6
5 2 2
g
5
3 2 1
5
s
6 1 6 3
6 8
5 9 4 8
=
n
5 5 0 5
.i
601 0
Y
4 7 2 2
!e
4 7 2 z
6 1 6 f
F
5 5 0 5
0
v,
6 8
6 5 4
9 1 . 7
145. 3
394. 6
792.9
976.4
100-1000
2 0 4
4 4 4
7 6 8
I190
1 8 2 0
3 3 0 0
1410
204-7470
M,; (CLS) M,/M = 1.03
M,: (CLS) M,/M = 1.04
M,; (as) M,/Mn = 1.26
M, ; (CLS) M, / Mn= 1. 20
M,; (CLS) M,/Mn = 1.10
6 5 4
Mw;f;, 71 6 5 6
6.1OzkO.02 1 3 . 5 i o . 4
4.76 * 0.07 19.7 f 2.4
2.77 i 0.02 46.0 f I .8
1. 80 It 0. 02 8 8 . 9 f 4.9
1.61 iO.02 105. 3 f 7 . 2
D,,o =(5.24f0.48) x 10m4 Mm" ' 9*0" '
91 f,] = 2.25 x 10-5 cm
167 3.49 X IO- cm
2 4 7 4. 78 x lo-Scm
3 5 3 6.04 x 10~5cm
4 5 7 7 . 8 1 x -5cm IO
7 4 3 10.9 x IO-cm
1450 16.5 x m5 IO cm
6. 76
9. 26
1 2 . 0
1 5 . 1
1 7 . 2
2 2 . 7
3 3 . 8
s,j ~3.6 x IO -Is Mo4
w
Poly(cc-methylstyrene- Toluene
block-butadiene)
Poly(cc-methylstyrene-stat-butadiene)
different camp. Cyclohexane
0. 873
sg and M, given
in Ref.
5 6 7
3
$.
2
3 7
1200-2450 Poly(styrene) Acetone 2 0
2 5
2 0
2 5
2 5
11.9-16.7 l.lX-0.80
,y,; Dw; Mt,,
50 g
Extrapolated val ue 2 6 3 3
M,; M, T450.10 606 i:
See Ref. for v2 532 =
4 8 0 F
I80 2
i;
0. 899
0.91 I
Benzene I50
9 . 2
I .32
I .95
2 . 8
3 . 9
1 0 . 6
6 7
6 0 6
2 7 . 9
25.0
2 1 . 1
1 7 . 2
Il.7
4 . 1
I .50
2s
SV; M,
2 . 5
7. 14
2 5
2 5
0. 91
0.9 I75
I50
2 6 8
4 3
2 6 8
Benzene cc
1.18-520
2.3-222
D, , - Mo5"
0.9078-0.9177
0. 917
MMW; vz=u2. m- 23/ M;
BzOz
Mw; DA
Mw; DA
Mw; DA
5 7 7
M, ; CLS
M,; see Ref. for so
and k,
M w ; see Ref. for SO
and k, ,
C = l.5-lOg/dm
D, ; C= 1%89g/dm3
DZ
DL
DZ
DZ
NBS 705
NBS 419
Styron 683-7
3 5 179
411
2 7 7
3. 29 2 2
I .57 5 9
3. 26 4 5
Do=3. 05 x 10m4 Mm" =
100. 4
517
517
517
PCC
4 0 4 0 0 0
2 5 392. 1700
four branched star 2 5 312, 2210
19. 89 1 7 2
193
7 9 3
1 4 0
2 4 . 8
8 6 . 6
1 6 2
4 1 1
1 1 1 0
4 . 3
192
661
2 5 12.4iO.l
5.750.1
3.6fO.l
2. 5f 0. 1
1.1 fO.l
References page VII - 198
TABLE 5. contd
Polymer solvent f t-3 Y ( x 10-3) (g/mol) S@ (x 109 (s) k, (cm349 Da (x 10) (cm%.) ko tcm3k) folf, w (cm31g) Remarks Refs.
E
four branched star Benzene
PCC, 4b
Pee, Ic
PCC, 3b
Pee, 13a
PCC, 4b
FCC. Ic
PCC, 3b
Pee, 13a
FCC. 4b
Pee, Ic
PCC, 3b
FCC. 13a
FCC, 4b
FCC, Ic
PCC, 3b
PCC, 13a
FCC, 4b
F-cc, Ic
FCC, 3b
PCC, 13a
PCC, 4b
Pee, lc
FCC, 3b
FTC, 13a
PCC, 4b
FCC, Ic
FCC, 3b
FTC, 13a
Benzenekyclohexane
W10)
Benzenekyclohexane
@O/W
Benzenekyclohexane
170/30)
Benzenekyclohexaoe
ww
Benzenekyclohexane
(50/50)
Benzenekyclohexane
w/w
PCC, 4b
FCC, l c
Benzenekyclohexane
W/60)
Benzenekyclohexane
(30/70)
4 3 3 0
8 8 7 0 0
3 0 7 9 . 8
3 0 7 7 5
2 4 2 0
5 5 3 0
9 7 0 0
1 3 4 0 0
2 0 24-3800
2 5 7 8 5
24-24000
2 0 1 1 7 4. 17
1 8 6 3. 26
3 7 2 2. 29
5 9 6 1. 92
2 0 1 1 7 4. 23
1 8 6 3. 42
3 7 2 2. 30
5 % 1. 84
117 4.14
1 8 6 3. 33
3 7 2 2. 27
5 % 1. 80
1 1 7 4. 15
1 8 6 3. 26
3 7 2 2. 24
5 9 6 1. 74
1 1 7 4. 15
1 8 6 3. 31
3 7 2 2. 26
5 % I .82
1 1 7 4. 18
1 8 6 3. 24
3 7 2 2. 15
5 9 6 1. 69
1 1 7 3.96
1 8 6 3. 12
3 7 2 2. 25
5 9 6 1 .I5
1 1 7 3. 86
1 8 6 2. 96
0.6fO.l
0.7 f0.1
5.18f0.02 15. 44
1. 41 1 2 0
0. 745 3 1 0
0.512 490
0. 353 6 4 0
0.284
D,,,,=(2.18f0.32) x 10~~;(0~s5+n~mi
I .30 1 5 0
D,,o=(2.18+z0.32) x 10m4 MJ(.55*o02)
DZ
DZ
Mw; Dz,o
M,/M, = 1.01
M,/M = 1.04
M,/M, = 1.04
M, I M, =l . 03
M, ; M, / M. =I . 13 6 6 2 0
M,; M,IM, =I.01 663 z
M,; M,/M,=0.02-1.2; 6 6 4 5
=
k, given in Ref.
M,; D,; C=4g/dm
3
M, ; D, ; C=4g/dm
M, ; D, ; C=4g/dm3
M, ; D, ; C=4g/dm3
M, ; D, ; C=4g/dm
M, ; D, ; C=4g/dm
M, ; D, ; C=4g/dm3
M, ; D, ; C=4gldm3
PCC, 3b
Pee, 13a
PCC, 4b
FCC, Ic
PCC, 3b
Pee, 13a
FCC, 4b
FCC, Ic
PCC, 3b
Pee, 13a
Poly(styrene)
Polyscience
waters
Benzenekyclohexane
(20/W
Benzenekyclohexane
(10/90)
Benzene/methanol
(l/3.27 vol)
Benzene/propane-2-01
W/36)
Bmmoknzene
Butanone
5 9 6
1 1 7
1 8 6
312
5 9 6
1 1 7
1 8 6
3 7 2
5 9 6
2 5
2 5 . 5 (T=8) 3 3
111
1 8 0
3 9 2
6 7 0
8 6 0
loo0
1 8 0 0
2 0 5 0
33-2050
5 . 0
1 0 . 0
1 7 . 5
3 5 . 5
5 0 . 0
10. 000
2 5
2 0
3 8 0 0
1 1 0
3 3 1
9 8 5
7 2 0
5 2 8
2 5 0
5 5 0
800
1 3 0 0
9 0
1 8 0
7 5 0
9 6 0
1 7 0 0
2 8 0 0
3 4 0 0
7. 13
13. 41
2 6 . 0
2 3 . 8
1 8 . 4
1 2 . 6
1 8 . 2
2 1 . 3
26.0
12
21
2 1
2 2
3 1
4 5
3 0
13
1 3 0
1 7 0
2 3 0
2. 00
1. 75
3. 64
2. 88
I .99
1. 57
3. 39
2. 64
I .88
I .48
Mw; D,; C=4g/dm
M,; D,; C=4g/dm3
0.660
6 6 5
6 6 5
150
8 . 2
4. 14 - 21. 0
3.367f0.012 -31.6f 1.2
2.266 zk 0.006 - 34.4 f 0.6
1.75 I f 0.007 -45.0f 1.0
1. 512f 0. 014 - 48. 7f 2. 6
1.41 I f0.001 - 5.03 f 0.8
I .I365 f 0.004 -58.4& 1.0
0.942 rt 0.006 - 64.6 zt I .7
D r, N &f -0.497-t co6
1 0 . 4
1 . 5 2
5 . 1 3
3 . 5 7
2 . 8 10
3. 25
1 2
6.4
2 . 6
2. 04
1. 70
1. 48
0. 83
I .38
2. 05
3. 18
3. 75
3. 71
3.59
6. 05
Mw; D,,o
DLS
DLS
DLS
DLS
DLS
M,; see Ref. for so
and k,
M,; see Ref. for
sg and k,
CLS; M: av. of 6 obs.
CLS: M: av. of 6 obs.
CLS; M: av. of 6 obs.
CLS; M: av. of 6 obs.
Mw; s,; DA
M u,w; sw; Dw
6 6 6
666
1 0 3 8
6 6 7
667
I I
3
1 2 5
126
References page VII - 198
2
\
TABLE 5. contd
E
Polymer Sol vent T ((3 M ( x 10 -3) (g/mol) sg (x 103) (s) k, (cm349 De (x 10) (cmls) k D (cm49 .f~/f.~ 1~2 (cm3/g) Remarks Ref s.
v,
!
But anone
2.Butanone
2 3 . 4
2 5
2 5
5000 4 5
5 5 0 0 4 8
4 5 0 1 7 . 9
5 2 8
I800
0. 84 5.24
0. 81 5. 25
3.4
3. 75
[0=3.12x 10e5cm
I .56
&=3.l x 10-4 Ae5
D, =4. 58x 10-4 M,55
z
3
52
D, ; a" . of 4 ohs. 4
D,; 4
2
fo= k7/(D 11 71, ) 3
g
CLS 5 6 8
CLS 5 6 8
8
3.7<M, x lo+<302 1071 =:
l.O3<M,/M,< 1.15
D L S
1071 f
9 9 5
D L S
5
n
D L S
D L S
:
D L S
z
M,.,; See Ref. for D, j 8 9 7
z
and k, ,
g
MW 6 6 9
8
M, ; M, I M, < 1. 06; 4V 670 q
M, ; M, / M, = 1. 04; I ) , , 0 671
M, ( SE) ;
g
;
M, / M, i I . 1 I ; D, , I ,
f
M, ; Mw/ Mn <1. 17; D, , o
Y
M, ( SE) ; M, / M. <~. I ; D, , I , 2
M, ; (DLS); 7
Mw/Mn 5 1.4; D/J
F
Mw; MwIMn 672 VI
= 1.3-1.6; 4V
2
n
M, ; M, / M, = 1.06; 673 =
M, ; M, I M, = 1.06; D, , o
I 5
M, . , ; M, / M, = 1.06: D, . , ,
d
M, ; M, / M, = 1.06; DL. 0
E
M, ; M, I M, = 1.1; Dl . , , 3
M, . , ; M, / M, =1. 2; D, , o 9
M, ; Mw/ Mn=1. 1; DL. 0
M, ; M, I M, =1. 3; DL. 0
;
n
M, ; M, / M, = 1.3; Dr . 0
Mw; MwI Mn
:
673 z
= 1.06&1.3 g
M, : M, / M, = 1.06 6 7 4
M, ; M, I M, =1. 06 2
M, ; M, / M, = 1.06
9
M, ; M, I M, =l . l 5
M, ; M, I M, = I.3
MW 6 7 5
Extrapolated value 2 6 8
[so] = 1.385 x lo-
2 0
S 1 6 9
PCC, 4b, I3a, 6 1208 But anone
PCC
PCC- I c
NBS 705
PCC-50 I24 2 5 4 4. 89 i 0. 06
NBS 706 2 8 8 4. 37 * 0. 03
bl end 2 3 3 5. 22 f 0. 06
PCC, 2b
PCC, 7b
PCC. 4b
PCC, Ic
PCC, 3b
PCC, 5a
PCC, 13a
PCC, 14b
JVC, 7M
PCC, 2b
PCC, 4b
PCC. Ic
PCC, 13a
PCC. 14b
3 0
2 5
2 0
2 1 - 2
2 5
2 5
2 5
2 5
2 5
2 5
2 3 8
4 2 6
1210
3 8 5 0
5 4 7 0
I IO, 670, 950
5. 13 5. 89
3. 83 1 3 . 4
2. 21 5 5 . 3
I.19 140
0. 976 140
20.x- 1700 D,,,=(3.1 +0.2)x 1orJ Ml [~r~~2
100~1800 D,o=4.1 x I O 4 I@~4
200 5. X6 f 0. 06
190 5.66 zk 0.09
5400- I5300
2 0 . 8 22.5 f I .O -25*5
3 3 16.0 + 0.6 -26f5
I I I 8.1 io.3 -II+4
2 0 0 5.95iO.l -2+3
3 9 2 3.95f0.15 9f4
5 0 7 3.3010.10 19+4
6 7 0 2.9 f 0. I 27+4
2 7 0 0 I .30 f 0.03 72f5
8 7 0 0 0.70 It 0.03
20.8-8700 Dr, = (5.5 It 0.2) x 10 -4 M - 5h* (
w
2 1
1 1 0
2 0 0
6 7 0
2 7 0
1 0 0 0 0
m
325-2800 log s,, = 17.845 + 0.455 log M,
2 2 . 5
7. 90
5. 96
2. 95
1. 37
0. 62 f 0. 01
0. 9078
NBS 706
NBS 705
Waters sample W-61970
2 5
2 5 (T=B)
2 7
2 5
2 5
Butanone 2 7
Butanonebutanol
(74/W
2 5
Butyl acetate
Carbon tetrachloride
2 5
2 3
2 4
2 5
2 5
2 5
21
Chlorobenzene
Chloroform
3 0
2 5
2 5
2 0
2 5
standard sample no. 706 2 1
2 5
257. 8
179. 3
2 1 4 5
127
8 2
1 4 0
107
45-448
2 . 2
480
7 7 0
I l oo
200
372. 5
8 3 0
1065
2 3 0 0
m
600
2 8 8 0
loo00
2 0 0 0
8 2
1 4 0
4 8 0
1100
7 9 . 8
Co
2 5 0
5 5 0
8 0 0
1 3 0 0
5 4 0
2 7 8
115-2800 log so= 17.992f0.415 log M,
3. 88
5 . 4
1. 62
Do= 1.96x 10m4 M-.49
35.76-37.82
9 . 8 4 3 9 . 4 - 8 6
1 3 . 3 4 8 5. 14 - 1 2
so ~4.62 x 1O-5 Mo.452 0.107 MO.55
k
I
= 8. 08 x 10 -* M.70
7. 44 5
D,o=5.85 x 10m4 M-0.5s
( 5 0
6. 18
2 0 . 0 I I I 3. 32 4 9
2. 5 1 0
2 5 . 0 175 2. 64 4 0
IS.05
2 6 . 6
3 2 . 0
4 7 . 1
9.2
1 3 . 1
1 5 . 4
1 7 . 8
- 15.1
123
162
2 7 2
1 8 0
3 2 0
4 0 0
5 0 0
0. 9162
1. 0
0.7
0.179f0.012
0.93 I
0. 63
4. 43
2. 21
1. 41
1. 04
D, =kM; t s9
3. 70 f 0 . 2
- 1.31
0
0
0.5
38.92
(1.84) fo = 3.86 x 10e5 cm
5.8
0. 9087
0. 9207
0.912
0. 908
0.924
0. 9100
M,; CLS 5 7 1
M,; CLS 5 7 1
M, ; CLS 5 7 1
5 7 1
For solvents See Ref.; 4 2 7
s,; A; C=2g/dm3
M, ; D, ; D, =kM; $zs3 1 2
M, / M, =1. 6- 2. 3 7 4 5
v
B
M, ; M, / M, =l . Ol ; 6 4 8 3
DA; C=15. 1 g/dm3 8
M,; DLS 642 g.
M, ; D, , o; C=7. 9 716 s
gldm 3 5
Mw; D,,o; C= 1.7g/dm3
P
M,; CLS
Mw; Dz,o; kl,
given in Ref.
DLS; M, I M. =l . @l
Mw; Dqo
A. Paar Digital
Densitometer
M,; M,/M, < 1.3;
C=20g/dm3; 3 V
M.; Dw
Extrapolated value
Mw; Dz,o
Extrapolated value
2 6 8 g
6 7 7 E
g
9 9 1 g
6 7 6 3
o
1 0 6 0 o<
F
7 9 9 3
1 2 i
s
a
3
sr ; Mw; f o=kT/ ( Do. , ) 3
M&D,
558 4
Extrapolated value
268 5
[sol = - 1.595 x IO-* s,, 268
=
WI
References page VII - 198
TABLE 5. contd
c
E
\
Polymer Solvent T (C) M ( x 10-3) (g/mol) so (x 103) (s) k, (cm%)
DO (x 10) (cm%) k. @d/ g) f~/f.~ 2) ~ ( cm' @
Remarks Refs. E
PCC, 4b
Cyclohexane
Cyclohexane
Styron 683-7 125
NBS 705
Styron 683-7
NBS 705
NBS 419
2 2 1 1 0
2 1 5 0 0
50@3
1 3 3 0 0
1 6 4 0 0
2 5 00
181-1040
2 8 1 8 0
3 0 1 8 0
9 0
2 3 7
3 4 (T=B) 1 1 5 0
34. 5 (T=O) 0. 37
0. 58
0.90
I .78
3. 48
1 0 . 1
40.0
191. 0
732.0
1320. 0
35.1 (T=O) 7 0 2
2 3 0 0
3 5 32-1640
5 4 0
11.4-1040
3 0 9
9 7 5
4 9 0 0
3 5 2 7 7
1 7 9
4 1 1
194-929 so = 1.50 x 10-15 MO.5 0. 928
1 5 0 0. 933
- 12.30
- 20.80
- 27.10
- 33.3
so = 3.85 x IO-l5 MO.+*
w
16.9
3 3 0
6 9 0
9 5 0
I420
72 22
6 . 1
ca. 2.2
ca. 2.5
4.0
ca. 3.1
67.4
5 8 . 2
43. I
3 2 . 9
2 1 . 7
1 3 . 0
6. 58
3. 04
I .57
I.17
1. 69
0. 93
0. 9293
- 1.03
- 1.67
- I.91
- 3.45
- 3.78
- 6.07
- 10.0
- 21. 7
- 38.9
- 68.4
1 2 . 1 I .92 fo=2.95 x 10m5cm
0.934
so= 1.69 x IO-l5 Mo.48
A-= 1.35 x 10-15 MS
w
Do = 1.21 x 10-d M,49
28. I 5.06 0.928
3. 86 - 7
2. 7 I
3. 19 5
2. 88
8. 43
1 6 . 2 0. 943
3 4 . 5
3. 86 - 6
3. 19 - 4
2. 67 - 4
so = 1.50 x lo-5 MO.5 Do = 1.21 x 10-4 M-O.5
M, ; M, I M. =1. 06
M,; flotation
Extrapolated value
M s,ci
M.
Mn
C = 17.8g/dm3
C= 1.47-17.9g/dm3
M
M,/M. N 1.02
M,/M. = 1.02
M,IM, N 1.02
M,/M, x 1.02
M,IM. zz 1.02
M,/M,- 1.02
M, / M. = 1.02
M,/M, z 1.02
M,/M, N 1.02
M,/M, = 1.02
DLS
DLS
Mwfo=kT/(hm~)
given in Ref.
Mw; f o=kT/ ( DoqO
M,; CLS
See Ref. for ~2
M,; M. given in
Ref.; D,
DW
D A
M.
Mw; DA
Mw; DA
Mw; DA
M, ; dep. of k,
given in Ref.
M
s.D
M,; M, =450.000
6 7 8
7 4 8 b
f
s
2 6 8
2
6 0 5
$
4 1 4
4 1 4 a
5 8 7 ;:
5 8 7
5 7 6
g
1069 5
.yl
:
2
z
P
8
=
2
1061 f
1061 c
6 3
1
3 E
5
4
107 g
9 6 i
1 7 2 z
5 3 2 d
5 9 2 E
3
5 9 2 .g
5 9 2 ;
5 9 2 5
4 8 6 :
f
5 7 7 g
5 9 4
6 0 5
6 0 6
-.-
waters sample no. 25 170
1 6
2 2
2 8
3 5
3 2
3 4
3 6
3 8
40
4 2
28-40
4 5
55
3 5
3.5
3 5
3 5
1 3
1500
1 8 0
4ooa
4ooo
7 9 . 8
4 9 8
179, 1050
1 7 9
NBS 705
Waters sample no. 25167
Waters sample no. 61970
3 8
40.4
4 5
5 5
4 5
5 5
35 (T=0)
40
3 5
FCC, 4a
Pee, l a
FTC, Ic
FCC, 3a
PCC, 6a
Cyclohexane
900
4500
34.5 (T = 0) 91
4100-48ooO
2 0 0
179. 3
5 1
2. 42
2. 61
2. 88
3. 26
1 6 . 8
1 7 . 2
1 7 . 6
1 8 . 0
1 8 . 6
1 9 . 0
2. 28 - 4.3
M~;Mw=51.000, 5 4 3
- 1.4 M,=49.000
- 0.8
5 . 8
1 2 . 1
2 4
4 6
7 1
8 6
105
125
ca. 2.9
M
0.934 Mw (CL%
0.936 Mw (CW
4 1 4
1 7 2
1 7 2
6 5 9
6 7 9
6 7 9
6 8 0
2 9 . 0 1 5 7 0
3 4 . 0 3 5 7 0
4.61 f 0.2 - 17.62
1 . 5
M, ; D, ; see Ref. M,
M, ; D, given in Ref.
M,; M,/M.=l.W
D&o
Given in Ref.
3.23 3~ 0.02
3. 37 f 0. 05
3. 64f 0. 01
3. 83 f 0.04
4. 61 f 0. 08
1. 49 f 0.02
1. 83 f 0. 03
D, , o= 1.39x 1O-4 M-O5
2.9
2. 62
I .20
0.80
0.34
6 8 0
6 8 1
6 8 2
6 8 4
6 8 5
6 8 5
6 8 6
MW
M, C = lOg/dm
M,; M,IM, = 1.07; D,
M, ; M, I M, = 1.12; D,
M,; M,/M. = 1.21; D,
M, ; D, ; C=5.4g/dm3
M, ; M, I M. = 1.06
M,; M,IM, = 1.06
M, ; M, I M, = 1.06
M, ; M, / M, = 1.06
M, ; M, / M. = 1.15
M,/M. = 1.20
8 6 7
2 1 4 5
4.64 f 0.04 19* 1.5
5.93 f 0.03 21.5f 1
6.44 f 0.03 26fl
9.68 f 0.08 38f4
14.05 f 0.08 58f4
1 6 0
1 9 0
410
8 6 0
1 8 0 0
97-1800
so z(1.51 xkO.02) x lo-s MO5
s , - , zz (0.062 f 0.003) M .
7 . 3
9 . 7
1 1 . 6
1 8 . 2
2 9 . 4
4 0 . 8
6 6 . 7
so=(l.50f0.01) x IO-s Mo.5
sn = (0.052 f 0.010) M.
M, ; M, / M. = 1.15
MW
MW
M, ; M, I M. = 1.04
M, ; M, / M. = 1.1
M, ; M, I M, = 1.05
M, ; M, / M, =1. 05
M, : M, / M. = 1.19
MW
35.4 2 3 3
422
6 0 0
1 2 6 0
3 8 4 0
8 4 2 0
2 0 6 0 0
233-20600
TS-6
Pee, 60914
TS-8
TS-34
TS-3 1
TS-33
6 8 6
110-4100
Mw; MwIMn =
1.06-1.15, k,
given in Ref.
6 8 7 PCC, 4b, 13a.
PS-705; F-4
3 5
References page VII - 198
TABLE 5. contd
Polymer Sol vent T C-3 M ( x 10m3) (g/mol) so (x 1013) (s) k, (cm3M Do (x 10) (cm/s) ko (cm/& folf, vt (cmk) Remarks Ref.% $
5
35 f 0.2 110-4100
Mw; MwIMn =
1.06-1.15, k, ,
given in Ref.
M,; C=2.5g/dm; so
given in Ref.
MW
PCC
SRM 1478
PCC
PCC
PCC
FCC
PCC
PCC
-
Cyclohexane 3 5 6 7 0 1. 66
3 5 . 4
2 8
3 5
3 5
1 0
1 5
2 0
3 0
35 ( T=@
4 0
5 0
1 5
2 0
3 0
35 (T= 0)
40
5 0
6 0
7 0
8 0
9 0
1 0 0
2 0
3 0
35 (T=O)
4 0
5 0
6 0
7 0
8 0
9 0
100
3 5 (T=O)
3 5 107-775 so=1.49x 10-15 w.5 D,o=1.4Ox 1O-4 M-0.5
2 3 0 7.3 f 0.2
2 3 0 7 . 2 f 0 . 2
3 7 . 4 0.9320 f 0. 0007
5 I f 2.5 2. 07 f 0.02
410f20 5. 86 f 0. 22
186f 10 2. 56 f 0. 07
254f 13 2. 56 f 0. 03
3 7
1 1 0
3 5 0
37-350
3. 69
4. 08
4. 5 1
5. 44
5. 01
6.36
7. 27
ca. 2.5 I
2. 78
3. 38
3. 69
3. 97
4. 57
5. 17
5. 91
6. 67
7. 47
8. 28
1. 72
1. 99
2. 12
2. 26
2. 61
2. 96
3. 36
3. 80
4. 25
4. 71
D z,. = (1.24 zk 0.05) x 10 - M;.498*o-02
M, ; MJ M, < 1.1; D,
M, ; M, f M, < 1.1; D,
M, ; M, f M, = 1.87; D,
M, ; MJ M, = 1.24;
0.05; D,
M, ; M, / M, =1. 06;
Da. 0
M, ; M, / M. = 1.06;
D,,o
M, : M, / M, , = 1.1;
DL,O
Mw; Mw/Mn =
1.06-1.1; D, , o
Mw; Dz, o; C=
4.2-79.9 gldm3
M,; C=O.9-8.08
6 8 9
g/dm 1; 7v;
corrected f or
polydispersity
Mw; MzIM, =
I .6 I + 0.05; D;
C=2g/dm3
M, ; M, / M, =1. 59+
0.19; D; C=2g/dm
MW
M,; D, ; C= IOg/dm7
M, ; D, ; C= lOg/dm
D, given in Ref.
M, ; M, =l l 1000;
D, , , , ; see Ref.
M, ; M, =l 82000;
Dw,o; see Ref.
M, ; M, =202000;
D, , " ; see Ref.
M, ; M, =l 68000;
Dw,,,; see Ref .
Mw; MwIM, =
I .02-I. I7
35 (T= 8) 2.41 f0.20
2.43 310.05 6 9 5
6 6 5
6 9 3
7 9 6
791
6 9 6
2.45 i 0.26
2.46 f 0.09
3.14
2.25
1.95
PCC, 4b 2 0
3 7
117
2 5 0
2 6 9
6 7 0
3 4 0
3 5
3 5 Styron 683-7 7.14
1.76
9.23
8.25
2 4 3.69 - 8. 4
2 6 5
4 2 5
3 6 5
35f 0. 1 4 I OO-48000
3.23 - 5. 4
3.07 - 7. 1
3.35 - 9. 4
D, , j =l 39x I O- Mm' j r
D, =DL. , j - 7. 76 x I O' C 6 9 6
6 9 7
7 4 3
9 9 5
6 9 8
34. 5 9 8 4.64io.04
M, ; M, / M, <l . 06;
PKSSUK
dependence of sg
gi ven i n Ref .
M, ; M, / M, <1. 06
M, ; M, I M, <1. 06
M, ; M, j M, <1. 15
D L S
D L S
D L S
D L S
D L S
D L S
D L S
D L S
D L S
D L S
Mw; M, / M, = 1.14
1 6 0 5.93 + 0.03
190
411
8 6 0
3 5
34.5 (T= 8) 2 3 8
4 2 6
1210
3 8 5 0
5 4 7 0
44. 5 2 3 8
4 2 6
1 2 1 0
3 8 5 0
5 4 7 0
6 7 7 0 35. 6
38. 7
35. 6
36. 6
39. 0
35. 6
36. 6
38. 0
39. 0
35. 4
8 4 2 0
2 0 6 0 0
100-20600
6.44 f 0.03
9.68 f 0.08
14.05 + 0.08
0 . 9 3 4
2.14 ~ 22.0
2.09 - 26. 6
1.24 - 48. 6
0.67 - 50. 0
0.58 - 85. 6
3.22 - 10. 6
2.46 - 8. 3
I .42 1.21
0.75 8.67
0.612 43. 5
T S - 3 2 Cyclohexane
TS-3 I
38.02
38.06
4 1 . 1 9
4 0 . 7 9
4 0 . 7 0
64.36
64.75
63.19
61.75
so = 1.50 x lo- M" . "
M, ; M, / M. = 1.17
T S - 3 3
MW
M,
References page VII - 198
TABLE 5. contd
c
E
\
Polymer Sol vent
T (0 M ( x 10 -3) (glmol) s 0 ( x 10 3) (s) k, (cm349 DO (x 10) (cm2/s) kI , (cm3/g) fo/fsp v2 (cm3/g)
Re ma r k s Refs. 5
NBS-705 3.5 1 7 9
Pee, 8a 3.5 1 0 . 3
3 0 3 7 6.4 z!z 0.02
20.3 (T=T,) 8 5 3. 00
3 4 . 5 (T=0) 3 . 7
2 4 . 3 (T= T,) 1 4 0 4.96
3 4 . 5 (T= 0) 5.0
2 7 . 0 (Ty T,) 3 2 0 7. 60
3 4 . 5 (T= 0) 8 . 8
3 0 . 0 (T=T,) 7 0 0 12. 60
3 4 . 5 (T== 8) 1 2 . 0
3 1 . 0 (T= T,) 1100 13. 20
3 4 . 5 ( T=%) 1 4 . 2
3 4 . 5 (T=@ 85-1100 so= 1.58 x IO-l5 M@
F 10 3 5
Styron 683-7
FTC, 7a
waters, 4 I 995
PCC, 4b
NBS-705
FTC, 3b
Waters, 25 166N
Wat er . 25 166
FCC, 5a
Waters, 25 I67
PCC, 14a
Waters, 61970
3 5
3 4 . 5
3 4 . 5
3 4 . 5
3 4 . 5
PCC, 2b 3 5
PCC, 4b
Pee, Ic
PCC, 13a
PCC, 14b
0.9280
0. 9219
0.9260
0. 9 195
0. 9220
0. 9179
0.9200
4. 33 - 4
- 8 107 2. 81
3 0 2 6. 10
5 1 3. 28 4.50
9 8 . 2 4.66 4. 03
I IO 5. 09 3. 36
183 6-33 2. 33
3 9 0 9. 26 2. 26
4 7 0 9.34 2. 20
411 9. 62 2. 05
4 9 8 11. 16 1. 64
8 6 7 13. 64 1. 12
1 8 0 0 19. 41 1. 09
2 1 4 5 19. 41 D,,,,=(1.388+0.42) x 10m4 M-O.
51-2145 so=(1.514~0.077) x IO- Mn5
k, =( 0. 65f 0. 17)
1 . 2 3 5 . 0 - 2.0
3 . 1 2 2 . 3 - 2.8
4.0 19. 45 - 3.9
1 0 . 7 12. 30 - 5.7
3 0 . 2 7. 31 - 10.8
2 1 8. 97 - 9
110 4.20 - 18
2 0 0 3. 05 - 16
6 7 0 1. 66 - 3 4
2 7 0 0 0. 84 - 5 6
21-2700 Dzo=(1.3~0.2)x 10-4xM-0.497*0.006
w
M, ; M, I M, =1. 07;
DL, ~, kD given in Ref.
M,; M,/M, = 1.06;
D, , o, kD given in Ref.
M, ; M, / M, =1. 03;
Dz, o; DLS
0.9214 M, ; M, ~M, ~1. 06;
T, critical temp.
0. 9285
0. 9225
0.936
0.936
MU.
M,; M,/M, = 1.01;
7 0 0
z
7 0 0 s
3
7 0 1
4
3
DA; C= 15.3gIdm
M, ; M, / M. =: ; Dp, ;
C = 13g/dm7 =
M,; M,/M, 5 1.06; s,, 7 0 3
2
5
.Y
M,; M,IM, = 1.2; so
M,; M,/M. = 1.2
DLS 9 9 3
DLS 9 9 3
D L S 9 9 3
DLS 9 9 3
D L S 9 9 3
M,; M,IM, < 0.06; 6 7 4
D L S
M,: M,/M, <0.06; DL S
M, ; M, / M, <0. 06; DLS
M, ; M, / M. <O.l5;DLS
M,; M, / M, <0. 3; DLS
M,; M,/M. = 1.6-2.3; 6 7 4
D L S
__- -._..._ ^ . . ,....
-7
l i near , S 102
linear, PS lOOf
l i near , S 108
linear, PSBOOf2
linear, PSlOOOt2
s t ar
branched
branched
branched
branched
branched
branched
branched
branched
branched
branched
Cyclobexane
3 5
3 5
3 5
3 4 . 5
4 4 . 5
branched, 4-armed stars, S I3 1 A
branched, 4-armed stars, S 12 I A
branched, 4-amxed stars, S 111A
branched. 4-armed stars, S161A
branched, 4-armed stars, S141AA
branched, 4-armed stars, S181A
branched, 4-armed stars, Sl91A
branched, 6-armed stars, HSO61A
branched, 6-armed stars, HSOSIA
Comb, C612
Comb, C622
Comb, C632
Comb, C642
Comb, C652
Comb, Cl32
Comb, C742
Comb, C752
PCC, 3b
PCC, 14a
branched, Carmed stars
branched. 3-armed stars
branched, 12-armed stars
3 5
3 5
3 5
3 5
3 5
21-2700
500
5 0 0 0
1 6 4 0 0
8 4
1 1 6
2 3 8
6 7 5
1 7 0 0
9 6 0
9 8 0
1 7 3 0
2 3 9 0
4 7 8 0
1 4 3 0 0
9 8 0
1 7 3 0
2 3 9 0
4 7 8 0
1 4 3 0 0
5 0 . 7
9 3 . 5
1 5 4
3 5 1
5 2 1
1 0 2 7
1 3 9 0
1 1 0
1 0 9 0
4 7 5
624
9 1 3
1 6 3 0
3 1 3 0
1 5 3 0
2 2 3 0
3 6 2 0
3 9 2
1 7 0 0
312
2 2 1 0
1 2 . 4
9 2 0
1190
5 5
1 4 9
4 6 7
ro= 1.46 x 10-15 MO.501 ko=(4.1+0.3)x 10-4xM~*0.
ks =5.69 x 1O-z Mo.5o
11. 50 40
24. 40 104
50.00 1 5 0
4. 29
4.94
7. 66
1 2 . 2
20. 15
3. 38
4.72
6. 17
9. 34
1 2 . 0
1 6 . 2
1 8 . 7
5. 51
1 7 . 4
1 0 . 8
1 3 . 7
1 7 . 4
25.0
3 5 . 6
20.6
2 6 . 5
3 6 . 3
so= 1.49 x 10-15 Mp
1.66 f 0.04 -4100+4OO
1. 63
1. 28
1. 09
0. 767
0. 509
1. 82
1. 37
1. 18
0.860
0.569
11. 73
I .47
1. 28
6. 61
4.04
2. 42
M,; M,/M. = 1.6-2.3 7 4 5
MW
7 4 8
M ,,,; s D corrected for
pressure influence
6 8 3
M,; D,,o; DL S
M,IM, = 1.17
M,IM,=1.24
M,JM,, = 1.19
M,/M, = 1.06
M,/M. = 1.03
Mw; so
M,; so
Mw; so
SO
683 d
i
6 8 3
E
P
-.
0
a
L
c
c:
683 2
84,; M,/M,L 1.10
5
so and k, given 793 2
in Ref.
-z
2
M,; M,/M. I 1.20 793 7
M,:M,/M.< 1.15 793 3
M,: M,/M, 5 1.2
3
M,;D,
705 2
References page VII - 198
c
Z
\
T A B L E 5 . contcf ii
N
Polymer S o l v e n t T ((3 M ( x lOma) (g/mol) S ( x 103) (s) k, (cm3/g) Do (x 10) (cm2/s)
kD (cm3k) fo/ fsp 7~2 km3k9
Remarks Refs.
is
branched, I R-armed stars
branched, 9-armed stars
KC Cyclohexanone
PCC, 4b Cyclopentane
PCC, 2b
PCC, 3b
PCC, 61208
TS-12 2 0 (T=B) 4 4 8 0
8. 07 2.og/g
8. 40 10. 9 g/ g
8. 84 16. 1 g/ g
8. 90 17.1 g/g
9. 94 22.9 g/g
11. 03 27. 0 g/ g
3. 97 9.7 g/g
16. 12 36.5 g/g
26. 60 64.9 g/g
$0 = 8. 7 x IO M;
k, = 1.9 Mty
34. 85
P C C 20.4 (T=H) I IO 5. 91
Polym. kc. (Japan), trans.Decalin
stand. sample
TS, F80
TS, FF33
TS, FF35
TS, FF36
8 0 8
1 1 1 0
I690
8 7 7 0
3 5 9 5 0
2 5 2 0 0
5 I I I
1 1
15
20 I
3 0
4 0
2 0 (T=B) 2 0 . 8
2 0 (T=O) 3 9 2
2 0 (T=H) 9 0 0
2 0 (T=H) 20.X-900
2 4 . 8
2 9 . 0
3 4 . 0
1 8 . 2 1 5 0
3 0
4 0
5 0
6 0
7 0
8 0
9 0
1 0 0
1 1 0
1 8 . 2 4 5 0
4 0
6 0
8 0
1 1 0
2 7 7 7 0
20.4 (T=6) 7 7 5
2 4 2 0
5 5 3 0
9 7 0 0
2 0 . 4 775-9700
2 5 (T=fJ) 1 8 0 0
2. 73 7 3
5. 43
1. 85
I.61
1. 35
0.62 I
I .66 i 0.04
5 . 2
4. 54
5. 27
6. 13
0. 85
1. 16
0. 93
I .43
I .52
I .82
1. 96
2. 69
3. 30
3. 59
0. 69
0. 76
1. 10
I .45
2. 23
0. 50
0. 5223
0. 3035
0. 1935
0. 1458
g
3
z
- 41 f4 Mw; Dz.0 7 0 6
M, ; M, / M, <1. 06 6 2 4
M, ; M, / M, I 1. 06 7 0 7 8
g
5
.Y
M, ; M, / M, i 1. 06 7 0 7
:
M, ; M, j M, <1. 10 7 0 7
z
M, ; M, J M, <I.10 7 0 7
:
707 2
7 0 7
M, ; M, / M, - 1. 14;
o^
708 71
C = 4.448 gldm ; 4V
Mw; MwIM
z
n-1.06; D, 756 ;
C = 0.55 mass%: 6V
f
D,; C=5.95 mass%; 3V
.m
D,; C= 5.95 mass%; 3V
D,; C= 5.95 mass%; 3V
5
4
M, ; DA; D, ; M, ;
MMWgiven in Ref.
M, ; DA; Dw; Mw;
Muw given in Ref.
- 15 Mn; Dw
- 38.8 f 2.4 MW
- 82.2 i 7.3
-104xt11
-119f19 0. 13 MV#
Do=( 4. 60+0. 08) ~ I O- ' Mm" . 5 0.43 + 0.02 M,
M, ; M, / M, x 1.20
2 0 3 9 0
2 5
3 0
3 5
4 0
2 0 179. 3
2. 34 2 7 . 3
M, ; M, / M, <1. 10 7 1 2
2.60 5 8 . 8
2. 78 6 5 . 6
3. 06 79. I
3. 34 9 4 . 9
1. 11 1.72 x IO-
1. 33
1. 59
6. 95
1.77 x 10-j
1.82 x 10m5
M, ; M, . , / M, = 1.07, 7 1 3
Dr,oi DLS; fo/r/o
NBS-705
3 0
4 0
20.5 (T=0) 3 7
Mw; M, / M, = 1.06; 7 1 4
DL. 0; DLS
M, ; M, I M, =1. 06;
Dz, o; DLS
Mw; M, / M, = 1.15;
D
o; DLS
M, ; M, I M, =1. 05;
Dr . o; DLS
M, ; M, / M, =l . 09; 7 1 4
D,,o; DLS
M, ; M, / M, = 1.02;
D,,o; DLS
Mw; MwIM, =
I .02- 1.15; DLS
M, ; I OV; 724, 725
C = O-84.5 g/dm z
M,; 9V; C= O-86.7 g/dm
M,; 9V; C=O-83.0g/dm3
Mw; D,,o; DLS 7 1 5
1 8 0 3. 13
6 7 0 I .65
1260 1. 172
trams-Decalin 2 8 8 0 0. 736
0.566
20.5 (T= 0) 37-5050 D, . , j = 1. 309x 10m4 M- " '
w
PCC, 3b 2 0 3 9 0 0.70 0. 9259
0.9282
0. 9308
0.9336
0. 9357
0.9289
0. 9106
0.930
Dibutyl phthalate
o-Dichlorobenzene
Dichloroethane
2 5
3 0
3 5
4 0
2 5
1 2 0
2 5
2 1
0. 86
1. 01
6 8 0
Extrapolated value 2 6 8
M, ; flotation 7 4 8 - 4.26 2 9 2
- 8.35 8 8 0
- 13.30 1330
- 16.70 1960
Methyl ketone 2 5
Dimethylformamide 2 1
Extrapolated value 2 6 8
MW 7 4 8 3. 60 103
6. 70 167
7. 70 190
Dioxane 2 5
1,4-Dioxane 5 0
Taylor dispersion
method
1060
1 0 6 2 2 2 7 . 7
4 1 9 . 8
9 1 4 . 9
1 7 . 5 9.9
5 0 5 . 8
1 0 0 4 . 1
2 41.8
4 30.0
9 21.3
1 7 . 5 1 4 . 1
7 5
References page VII - 198
TABLE 5. contd
Polymer solvent
K
g
T ((3 M ( x 10m3) (g/mol) so ( x 10) (s)
k. (cm3k)
Do (x 10) (cm*/s)
ko (cm349 fdsp vz (cm3@ Remarks Refs.
E
5
I ,CDioxane 9 5
Dioxane
Epichlorohydrin
Epichlorohydrin/
dimethyl maleate
(I.3/l.OmoVmol)
Ethyl acetate
FCC, 4b
Pee, Ic
PCC, 3b
PCC, 13a
Ethyl acetate/
cyclohexane (90/ 10)
Ethyl acetate/
cyclohexane (80/20)
Ethyl acetate/
cyclohexane (70/30)
9.5
1 0 5
2.5
3 0
2 1
2 5
2 7
2 0
2 0
2 0
2 0
50
100
2
4
9
1 7 . 5
5 0
loo
2
4
9
1 7 . 5
5 0
1 0 0
00
7 9 . 8
5 0 0
5000
13300
1 6 4 0 0
5 0 0
5oOQ
1 3 3 0 0
1 6 4 0 0
co
I17
1 8 6
3 7 2
5 9 6
1 1 7
1 8 6
3 7 2
5 9 6
117
1 8 6
3 7 2
5 9 6
1 1 7
1 8 6
3 7 2
5 9 6
8.2
5.9
52.7
3 9 . 1
28.0
1 8 . 4
1 0 . 8
7.6
5 9 . 5
4 4 . 1
3 2 . 5
20.9
1 2 . 4
8 . 7
3.10 zt 0.2
- 1.97 145
- 3.85 4 6 0
- 7. 15 1 1 6 0
- 11.10 2 1 7 0
- 1.35 3 6
- 2.63 9 7
- 3.03 168
- 5.26 2 7 8
2. 64
6. 23
5. 05
3. 31
2. 45
6. 05
4.54
3. 21
2. 38
5. 81
4. 55
3. 05
2. 45
5. 73
4. 36
2. 89
2. 20
Taylor dispersion
method
1 3 . 7
0.9270 Extrapolated value
Mw; Dz,o; DLS
M,; flotation
M,; flotation
1 2
0. 9132 Extrapolated value
Mn; Dw
Mw: D,
Mt.,; D,
Mw; Dz
Mw; Dz
6 6 5
i
2 6 8
6 5 9
a
=
7 4 8 f
.I-
E
=!
7 4 8 g
vl
2
n
i
2 6 8 E
1 2 5
6 6 5 E
3
.F
n
6 6 5 R
a
f
6 6 5 F
=!
9
1
Ethyl acetate/
cyclohexane (60/40)
2 0
Ethyl acetate/
cyclohexane (50/50)
2 0
Ethyl acetate/
cyclohexane (40/60)
2 0
Ethyl acetate/
cyclohexane (30/70)
2 0
Ethyl acetate/
cyclohexane (20/80)
2 0
Ethyl acetate/
cyclohexane (10/90)
2 0
Ethyl benzene 2 7
3 0
1 3 0
Ethyl n-butyrate 2 5
Mesitylene 2 5
Methylethylketone 2 5
Methyl isopropyl ketone 20
Nitrobenzene 2 5
Tetrahydrofuran 2 5
linear
Tetmhydrofuran 2 5
2 5
cyclic
1 1 7
1 8 6
3 7 2
5 9 6
1 1 7
1 8 6
3 7 2
5 9 6
1 1 7
1 8 6
3 7 2
5 9 6
117
186
3 7 2
5 9 6
1 1 7
1 8 6
3 7 2
5 9 6
1 1 7
1 8 6
3 7 2
5 9 6
7 7 0
42.5- 1430
9 . 5
so=3.28 x IO-l5 M.42
5. 28
4. 11
2. 76
2. 15
4. 95
3. 92
2. 53
1. 99
4.12
3. 68
2. 39
1. 92
4. 27
3. 54
2. 31
1. 81
4. 08
3. 09
2. 10
1. 53
3. 69
2. 73
1. 79
1. 49
3. 55 0.96
Mw; Dz 6 6 5
Mw; Dz
6 6 5
Mw; D,
Mw; Dz
Mw; D,
Mw; Dz
1 3 0 Mn; Dw
M, ; 12V; k,
given in Ref.
D given in Ref.
0.919
0.9260
0.919
Extrapolated value
94- 1200 7.2-34 6.95-2.5 7V;s,; DA =D, ; M, >w
0.904
3 8 4 0 0. 682 5 7 1
5 4 8 0 0.53 1 1114
8 4 2 0 0. 432 1071
2 0 0 0 0 0. 241 1501
1 0 . 5
45.0
7 9 . 5
182. 0
1 5 . 8 8
8 . 1 2 0
6. 15 3 8
3. 95 4 6
Dp = (1 .L$c) * 0.20) x 10 4 M,o.48*0.02
6
1 4
2 0
0. 9102
M, / M. = 1.04
M, f M, = 1.15
M,fM, = 1.17
M, / M. = 1.20
Extrapolated value
M, / M, = 1.15
M, / M, = 1.19
M, / M, = 1.08
M, I M, =l . l O
1 1 . 1
3 7 . 8
79.4
M, / M, = 1.20
M,IM, = 1.21
M, / M, = 1.14
6 6 5
if
P
3
2
6 6 5 g.
s
J
665 4
3
0
-.
m
2
.!
a
I2 a
6 1 2 $
B
7 9 4 a
,@jo 2
2 6 8 d
1 0 6 0 F
6 6 ;
1 0 6 0 *;
9 9 2 2
9 9 2 7
-.
I
-.
s
2 6 8 =
9 9 6 z.
s
a
3
2
z
1
v1
References page
VII - 198
TABLE 5. contd
Polymer Sol vent
ii
T (C)
M ( x 10m3) (g/mol) so ( x 103) (s) k, (cm%) Do ( x 10) (cm2/s)
ko fcm3k) fdfsp v 2 (cmk)
Remarks Ref s.
%
0
181. 5 M, f M, = 1.11 s
30
linear 30 .
star
linear 3 0
3 0
3 0
2 4
atactic 4.rert-Butyltoluene 5 0
atactic Toluene 1 5
1 9 8
3 7 0
5 7 0
1 1 0
3 9 0
411
3000
1 0 0 0 0
1 8 0
3 9 0
3 0 0 0
IO@30
9 6 0
ISO-IOOOO
1 9 . 8
3 7
51
I IO
411
20-41 I
2 0 . 4
5 1
9 7 . 2
1 6 0
411
8 6 0
1800
20- I800
5. 38
2 0 . 2
3 5 9
7 3 2
1 2 7 0
3 8 4 0
0. 92
5. 38
9. 98
4 0 . 0
9 7 . 3
191
3 5 9
7 3 2
1 2 7 0
3 8 4 0
13. 41
8. 81
8. 02
4. 92
2. 47
2. 51
0. 813
0. 435
3. 25 3 6 1 8
2. 48 96f7
0. 813 390 f 90
0. 435 620 i 30
I .7 1 xt 0.04 5 100 f 500
D,~j=(3.21t0.1) x IO 4 M, 5h*2
13. 41 7 6
8. 81 2 4
8. 02 1 4 . 9
4. 92 3 2
2. 5 I 7s
D, , , j =( 3. 0+0. 4) x I O - 4 M- 4* 3
12.7 7
7. 65 I6
5. 43 2 8
3. 99 44
2. 35 9 1
1. 59 136
1. 01 2 6 4
D,,p(3.45fO.l8) x 10-4 M,1*4
1 9 . 2 - 2.69
9. 31 - 2.44
2. 01 20.4
I .38 57.0
1. 02 7 7 . 1
0. 53 129
52.0 - 1.22
20.0 0. 525
1 4 . 1 2. 38
6. 85 1 0 . 7
4. 15 2 1 . 8
2. 82 40.6
I .96 71.2
1. 33 1 3 0
0. 978 2 0 6
0. 502 3 1 9
M, ; D, , " ; kD given
in Ref.: DLS
Mw; D,,o; DLS
M,; D,,o; DLS
M,; DLS
M, ; M, / M, =l . O6
D, I , ; DLS
D L S
M,; D,.II; DLS
M, ; DLS
DLS
DLS
DLS
D L S
DLS
DLS
M, / M, =I.01
M, I M, = 1.03
M, / M, =1. 03
M, / M, = 1.02
M, / M, =l . 02
M, I M, =l . 02
M, / M, = 1.01
M, / M, = 1.03
M, / M, = 1.03
M, / M, =1. 05
7 2 3
5
1068 E
3
F
2 0 5 3 6 8. 75 I .95 fOT3.55 x 10-5cm Mw; St; DA;
.fr+kTlVhw,)
Av. of 3 ohs.
3
M, ; M, =450000
M, ; s, ; DA
Mn; sw; D,
M
, , A; . y, ; DA
4
5
6 0 6
4 3
I
4V; k, y given in Ref.
4V; M,,A C= Ig/dm
M
s ,
MMW
Extrapolated value
02 given in Ref.
DA; C=0.79g/dm
DA; C= 1.19gldm
D L S
D L S
D L S
D L S
M, (Ref. 13); D,
s ,
1 6
if
EL
3
125 g
4 4 g.
I48 s
2 3 7 s
4 0 9 ;
2 6 8 3
5 9 1
5 3 2
$.
511 A
511 i %
q
1078 i:
1078 s
IO78
.g
1078 9
z
5 7 g
I2 g
I7 g
17 3i
0
Mn
1.237 2
467 =
M, ; M, I M. < 1.06 624 ;
M, ; M, / M, = 1.14; 708 Z
C=0.429g/dm; l2V
J
P
(C= 0.429-37.02 g/dm
M, ; C=0.487g/dmJ; 6V 708
z.
2
(C= 0.487-4.445 gldm) 5
M, ; M, =l OOOOO; 721 =
D
L. 0; DLS P
Mw; M, =59000; D, , " ; DLS
c
$
M, ; M, =388000;
0,
D
r , o; DLA r s
D L S 995 3
DLS 995 7
DLS 995 0
DLS 995 -
DLS
3
Mw; Dz,o; DLS
995 5
6 5 9
450 7. 92 2. 02
0.910
0.917
D N ,,,, -,,.53
2.50
2. 85
4. 03
I.17
0.74
150
1.2-520
3 0 0
4 5
140
960
2 8 5 0
250- I300
s, , - Mo4'
6. 25
7. 20
4. 75
9. 65
18.1
5.9-l 1.2
57.5-226 Szwarc living polymer
22.7
2 3 . 5
3.7-5.20 8.05-3.29
0.918
3 6 . 4
3 6 . 4 0.917
0.916
D=2.15 x lW4 M,
190
3. 24
3. 24 75.0
25
7 4 4.13
3. 78
I.265
0. 8 I
0. 43
0.3 I
2 5
2 7
I260
2 9 5 0
8000
1 5 0 0 0
0.917
I .22 9 6
0. 66
0. 44 L
4 0
13.3
200
4 4 8 0
0.917
0.948 3 0
2 5
2 5
c
q
\
5
References page VII - 198
PCC
TS-I2
3.4
14. 01
TS-33 2 5 2 0 6 0 0 15. 47
3 0 2 5 0 2.57
2 6 9 2. 37
411 I .982
3 0
3 0
2 3 8 3. 19 5 6 . 7
426
2.32 7 4 . 2
1210
I .28 190
3 8 5 0 0. 68 361
5 4 7 0 0. 55 5 4 6
7 9 . 8 6.32 + 0.2 20. 57
93.46 5.22 f 0.2 10. 476
347.22 2.20 f 0. I 61.36
1136. 36 1.20fO.l 173. 3
3802. 28 0.85 f 0.05 1552. 94
4
H
\
CL
TABLE 5. contd
!I2
P o l y m e r Sol vent
T ((3 M ( x 10 -3) (glmol) so ( x 10) (s) k, (cm%) DO (x 10) (cm2/s) kD (cm349 fo/fs* v2 (cm343
Remarks Refs.
E
3 0 31 12.6 f 3. 8 M,; M,IM, = 1.03; 701 g
Dz,o; DLS
ii
M,; D, given in
Ref . ; DLS
796 2
5
Mw; Dz,o C=
4.2-79.9gIdm; DLS
195 p
M,; M,IM,, = 1.06; 6 8 0
Dz,o; ko =ko D,,o; DLS
8
M,; M,fM, =1.06; 680 z
Dz,o; kD = kD Dz,o; D L S
=
M,; M,IM. = 1.06;
5
678 .w
D,; C=28.7gldm3, DLS
0
M,; M,/M, = 1.07; 121 ;
D,,o; D L S
C
Mw; Dz,o; DLS
M,; D+o; DLS
p
Mw; &,o; DLS
M,; M,IM. = 1.16;
8
730 71
D,,o; C=O.O715-0.3511 9
n
PCC
PCC
Tol uene 2 3 1 7 9 3.59 zk 0.25 85.9 f 73. 7
FCC, 4b
20 610
2 0 610 1.58
5 5
10
2 0
1 7 9 5.09 f 0.03 198.1 f 10. 1
I IO 2. 3
9 9 . 5 4 . 4 5
1.34
1.01
0 . 5 3
0 . 2 0 7
F 80
F 1 2 6
F 288
2 0
2 0
TClllMle
Tol uene
4.ring-shaped
2 0
2 5
2 5
2 5
7 8 3
1 2 8 0
2 8 9 0
1 8 8 0 0
31 8.027
I10
200
422
7 7 5
1 2 3 0
2 4 2 0
1. 2
3. 1
4 . 0
10. 1
30. 2
4 8 . 5
9 7 . 0
424
2 5 . 6
3 8 . 6
6 4 . 9
2 3 8
so = 3.43 x lo-5 MO43
k
s
=8.08 x 10 -* M.74
4 . 1 8 0
3.175
1.900
1.360
I .083
0 . 7 2 0
40. 1
2 8 . 5
2 5 . 8
15. 7
8.82
6.78
4 . 3 9
I.96
2.56
1. 95
1. 32
0 . 8 0
3 0 2.554
78. 5 3.869
1 2 3 4.808
19
113
173
4 3 2
- 0. 8
1 .I
5 . 0
10. 0
2 1 . 0
7 0 . 9
0 . 9 1 6
0 . 9 2 2
g/dm3, DLS
M,; M,/M. = 1.03;
Dz,o; DLS
M,/M,= 1.03
M,IM. = 1.03
M,/M,= 1.04
M,IM,= 1.01
M,IM, = 1.02
M,IM.= 1.04
D L S
D L S
D L S
D L S
D L S
D L S
D L S
D L S
M,; M,IM. = 1.1;
Dz,o; DLS
A
7 3 1 2
.3
2
7
E
VI
2
G
9 9 3 5
d
E
3
.E
B
g
144 0
f
5
7 4 5 g
1075
1 0 7 5
1075
1 0 7 5
M,/M, = 1. 6-2. 3
sv
sv
sv
2 7 2 6. 909
3 . 1
4.0
1 0 . 7
5 0 0 7. 30
5 o o o 15. 20
1 3 3 0 0 18. 50
1 6 4 0 0 25. 00
4 5 9 0
9 5 0 0
16100
37-16100
SV 1075
DLS 1076
DLS 1 0 7 6
DLS 1 0 7 6
Mw 7 4 8
2 8 . 5
2 5 . 8
1 5 . 1
2 1 2 7 0
8 4 0
loo0
1490
0.491
0.310
0. 205
&=3.32x 10m4 Mn.s74
MJM, = 1.05 7 3 1
MJM. = 1.03
!$
MJ M, = 1.16
n
3
M w ; extrapolated 7 2 8 , 7 2 9 , 8
for C=O and 7 3 1
B
C.
M,/M,= 1.0; DLS s
M,; D,,o; DLS 732 J
Mw; D,,o; DLS 7 3 2
G
Mw 7 3 3
Cross link ratio I:20 1 0 6 6 $
s
Mw; DI IDzSD,; 7 3 4
C < 0.45 g/dm )
P
M,; 23V;
C=O-120g/dm
724 2.
1
M,; M,IM, = 0.03; 735 F
D given in Ref.
J
a
M,; M,IM.=0.04;
-.
Iu,
D given in Ref.
g
M, ; M,/M. =0.04; a
D given in Ref.
3
n
Taylor dispersion
d
technique 1074 =
3
M,; M,/M. = 1.06; 7 2 6
a
D,,o; p =I bar
J
n
M,; M,/M. = 1.06;
n
z.
D,,o;p=960bar
2
M,; M,IM, = 1.06;
3
D,,n;p= 1940bw
L
M,; M,IM, = 1.06; P
D z,o; /J = 2900 bar
E
s
M,; M,/M,, = 1.06;
4
D,o; p = 3870 bar
!c
M,; M,IM, =1.06;
-e
z
D r,o; p = 4840 bar :
2 0
2 0
microgel
2 5
2 4
1 1 0 4.25f0.10
2 0 0 3.25 f 0. IO
I I I 3.954 f 0.002 2 5 . 8 + 0. 003
4 1 0 2. 07
NBS 706
Toluene
2 5 2 6 0 D, = 3.38; D2 = 2.96; Dz = 2.86
FCC, 4b 2 5 I10 4.00 4.25, 4.50
TS, F870 9 5 0 0
TS, F225 2 4 2 0
TS, F510 5 5 3 0
Toluene 2 5
2 5
1 7 . 4 1 4 . 4
I10 4.42
9 0 0 1. 34
I I I 4. 35 30f3
2.48 22f6
1. 52 20f6
0.92 20f5
0.56 20+6
0. 35 23f 10
PCC, 7a 2 5 5 1 2. 98 7.20
Waters, 41995 9 8 . 2 3. 94 5.3 1
PCC, 4b 110. 0 4. 32 4.58
NBS 705 183 5. 12 3. 48
M,; M,IM, = 1.06; 736 3
so: DI =DA
j
VI
References page VII - 198
TABLE 5. contd
Polymer Sol vent
2
\
5
T ((3 M ( x 10 m3) (g/mol) so (x 109 6) k, (cm349 DO (x 107) (cm*/s) kD (cm3k) fdfsp 2~2 (cm3k) Remarks Ref s.
NBS 705
NBS 1479
TS 550
TS 2000
PCC, 3b
Waters, 25 I66 N
Waters, 25 166
PCC, 5a
Waters, 25 161
PCC, 14a
Waters 6 I970 Toluene
2 5
2 5
RT
l i ne a l
branched TOIUEXE 3 0
branched, 4.armed stars 3 5
branched, 6-armed stars
comb
3 5
3 5
3 5
191
9 3 9
5 8 5 0
1 5 9 0 0
3 9 0
470
411
4 9 8
861
I800
7. 15
1. 20
1. 32
1. 93
9. 92
13. 70
3. 49
I .44
0. 62
0.3 I
2.46
2. 33
2.24
2. 05
I .52
I .oo
2 1 4 5
51-2145
51-2145
1 0 0 0
13. 53 I .oo
k, / [ r / j = 1.65fO.l.S
s,) - 2 . 8 4 x 10 MI!;
1 . 3
1 3 0 0 0 0.6
I I6
2 1 6
215
615
8 6 0
1700
980
I730
2 3 9 0
4780
14300
5 0 . 7
9 3 . 5
1 5 4
3 5 1
521
1027
1 3 9 0
I I O
1 0 9 0
415
6 2 4
9 1 3
1 6 3 0
3 1 3 0
1 0 5 0
1 1 9 0
1 5 3 0
4. 80
6. 22
7. 06
9. 97
II.1
15.0
I .88
I .39
I .28
0. 895
0. 595
3. 60
4. 59
5. 81
8. 33
9. 15
1 3 . 2
1 4 . 5
5. 41
1 4 . 6
9. 91
II.8
1 4 . 6
2 0 . 4
2 9 . 0
1 2 . 9
1 4 . 6
1 6 . 4
DLS
D L S
D L S
D L S
M, ; M, J M, =1. 2;
so: DI =DA
0.917 MW
MW
M, ; D, ; C=O. O5%;
D L S
M, ; D, ; C=O. O5%;
D L S
Mw; so
1019
1019
g
1 0 1 9
f
1 0 1 9
4
136
2
g
g
III
s
6 8 3 8
71
;
5
.!!
P
9 9 4 7
9 9 4 ji
9 9 4 g
9 9 4 ;;
9 9 4 =i
6 8 3 E
5
E
3
F
z
6 8 3 g
0
6 8 3 E
F
-. _.--
2230
3620
21 500
5OOil
13300
16400
T0lllene 25
Toluene/butanone (3/l) 2 0 528
(l/l) 553
U/3) 554
m- Xyl ene
p-Xylene
halomethylated, Tetrachloroethane
containing 5.66% P
latex Water
latex, DCC, 481 nm
latex
latex, 481 nm
latex, 109 nm
latex, 109 nm
latex
latex
latex
latex
latex Water/NaCI
(0.01 mol/dm )
20
24.7
40.2
55.2
70.4
25
25
25
25
0.415
0.43 1
0.637
0.865
1.15
0.439
0.652 f 0.007
0. 654 f 0.007
0.687 f 0.007
0. 696 f 0.008
0. 856 +0.043
PMMAknzene
CPMMA =0&m
CPMMA =0.91 g/cm
20
30
8420 0.38
8420 0.0594
CPMMA = I .29 g/cm 3 8420 0.0330
Cpt.q~~ = 2.72 g/cm 3 8420 0.0055
CPMMA = 3.65 g/cm 3 8420 0.0021
CPMM,P+ =0.91 g/cm3 8420 0.125
CPMMA = I .28 g/cm 3 8420 0.0837
CPMMA = 2.69 g/cm3 8420 0.028 1
CPMMA = 3.67 g/cm3 8420 0.0148
CPMMA = 3.70g/cm3
8420 0.0258
CPMM,+ = 3.67 g/cm3
CPMMA = 0 g/cm 3
CPMMA = 3.65 g/cm 3
CPMMA = 3.65 g/cm 3
8420
1260
1 2 6 0
0. 0364
1. 10
0.0347
1 2 6 0 0.0727
20
25
20
2 0 0.08 1
20 0.475
RT 0.41
RT 0.089
21.3
27.6
7.30
15.20
18.50
25.00
9.9 2.1 I
12.9 2.45
15.6 2.82
90.7-507 so=9.77 x I O- " Mo2hh
270
840
l oo0
M, ; D, ; C=O.O5%; 748
D L S
0. 919
fo = 3.65 x 1O-5 cm
fo= 3.43 x 10m5 cm
fo=3.29x 10-5cm
0.9205
1060
s~; D~; f o=kT/ ( Dcm, ) 3
SA; DA; . ~O=~T/ ( DO~, ) 3
~~;D~;fo=kT/@oq,) 3
ff
n
268 3
532 1
Extrapolated value
2)~ given in Ref.
MMW
561 g.
s
737 J
727
738
%
739 F
2.
s
739 8
See Ref.
D, ; DLS
D, ; DLS
D, ; DLS;
C=0.05g/dm3
D, ; DLS;
C=O.O5g!dm
D, ; DLS
D, ; DLS
D, ; DLS; C=O.ll%
D, ; DLS; C=O.O04%
D, ; DLS; C=O.O22%
D, ; DLS; C=O.O04%
D, ; DLS; C=O.O23%
D,,o; DLS
MPMM~=4. 05 x
IOh g/m01
Mp~~~c1. 93 x
I06g/mol
MPMMA = 1.09 x
I O6 g/ m01
c
740 3-.
723 3
.e
3
;I
-.

684 g
741 a
741 2
741 o<
741 =
746 ;
.m
J
P
1077 7
-.
2
3
ii
D
1077
c
p
0
,
-2
2
I
1077 2
-z
MPMMA = 8.5 x 10 g/mol ii
;:
MPMMA = 4.05 x 1077
106g/mol
Mp~~~=1. 93 x 106g/mol ,
E
References page VII - 198
TABLE 5. contd
Polymer Solvent T (C) M ( x 10m3) (g/mol) so (x 1013) (s) ks (cm%9 Do ( x 10) (cm%) k D (cm 3k) fo/fsp 21 z (cm 3k)
Remarks Refs.
CPMMA = 3.65 g/ cm 3 1260 0. 11 I MpMMA = I .09 x 1077
lo6 g/m01
CpMMA =3.70g/cm~ 1260 0.137 MPMMA = 8.5 x 105 g/m01
Poly(styrene- Methyl n-propyl ketone 2 I 125-985
co-hutadiene)
24 mass% St. 21 (T=O) 49-514
Poly(styrene)-block- THF 2 5 46.8
(dimethylsiloxane) 7.5 ~01% PDMS/THF 2 5 46.8
15 ~01% PDMSITHF 2 5 46.8
Poly(styrene)-block-(hydrogenated polybutadiene)-block-polystyrene
1,4-Dioxane/O-30 ~01% 2 5 4800
n-heptane
,444O
Poly(styrene)-block-(hydrogenated polyhutadiene)-block-polystyrene
I ,4-Dioxane/O-30 ~01% 4 2 0 0
n-heptane
3 7 7 0
Poly(styrene-co-divinylhenzene)
3w70 n- Oct ane 21 65-710
Poly(styrene-c&sooty1 methacrylate)
20/80 Theta-solvent (see Ref.) 2 5 (T=b) 59.6
53.5
Poly(styrene-block-methyl methacrylate)
Poly(u-methylstyrene)
Butyl acetate
Toluene
n-Butylchloride
RT 600
2 5
2 5 53.8
Poly(styrenesulfonic
acid)
PCC
Water/KC1 (0. 2 mol/dm3) 20
Water/NaCl 2 5
(0.005-0.2 mol/dm3)
WaterINaCl
(0.01 mol/dm3)
74.3
171
303
6 6 6
881
3 5 4 0
670- 1150 8.6- 1 I .5
350-2650 4.95-16.4
se=3.31 x lo-h MO.62
so = 8.3 x IO-l6 M" . '
7.280 19
1.320 - 36
0.715 - 8.4
Mn
Tracer diff. coef.
so= 1.59x IO-l5 Ma,
25.87-28.42
4.02
6.63
7.54
II.95
Do = 1.49x I O - 4 M - .
1.6
D,,,=3.14x 10m4 M-0.556
w
11.4 - 24.8
10.1 - 22.3
6.38 - 24.3
4.56 - 23.2
3.04 -26. 1
2.67 - 25.4
1.26 -21. 9
0.90
1.05
0. 76 I
0 ~01% n-Heptane
10 ~01% n-Heptane
20 ~01% n-Heptane
30 ~01% n-Heptane
M
r,D
sw; A
C = 1.67g/dm3
M,; D,; C=O.O5%;
DL S
7000_<M,<
114Oog/mol
[q] = 17.0cmVg;
9 9 8
Do=3. 81 x 1O- 4 M- . 53
w
[q] = 20.5 cm 3/g; 9 9 7
Da=3.81 x lO-4 M-0.53
w
[q] = 32.5 cmlg; 9 9 7
Do =3. 81 x 10m4 M- 0. 53'
w
[q] = 46.4 cm )/g; 9 9 7
Do = 3. 81 x 10 -4 M-.53
w
[q] = 74.1 cm3/g; 9 9 7
Do=3. 81 x 1O- 4 M- 0. 53'
w
[q] = 86.2 cm/g; 9 9 7
Dac3.81 x lO-4 M-0.53
w
[q] = 198cm3/g; 9 9 7
D,,=3.81 x lO-4 M-O.
w
Mm; single data 127
given in Ref.
MMW; single data 4 5 2
given in Ref.
M, ; M,/M.<l.l; 7 4 2
Dz,o; 1OV
C=O.Ol-17.5g/dm3
1018
1018
3 2 2
4 2 7
P C C
P C C
P C C
P C C
P C C
P C C
Water/NaCl (0.01 mol/dm 3,
Water/NaCl (0.025 moVdm 3,
Water/NaCl (0.05 mol/dm 3,
Water/NaCl (0.10 mol/dm ))
Water/NaCl
(0. I moVdm )
Sulfonated Poly(styrene) Ionomers
DMF/I x 10m4 M salt
DMF/I x IOm3M s a l t
DMF/I x 10 -* M salt
DMWl x IO- M salt
Poly(sodium-styrene-
sulfonate-co-2-vinylnaphthalene)
Poly(styrene) P M P S
1 2 3 4 0 1. 05
1 5 1. 20
2 0 1. 65
2 5 2 . 7
2 5 4 0 0 I .63 8 2 8
1. 58 2 3 7
I .68 2 1
1. 77
D,,. = (I .5 f 0.8) x 10 -3 h&-
5 0 2 0.415*0.041 1 0 5
1 0 . 2 0.321 zt 0.028 46
6 5
1 2 . 2
1 7 . 5
2
1 0 . 2
1 2 . 2
1 7 . 5
0.289 f 0.026 9 4
0. 265 f 0. 032 1 2 2
0. 728 + 0. 041 1 2 1
0.554 It 0. 033 4 9
0. 448 f 0. 059 8 0
0. 419 zt 0. 045 121
6 5 0 0. 75 M, ; M,/M.<I.I; 7 4 2
Dqo; 9v
C = 0.049-26.4g/dm3
6 5 0 0.727 f 0.007
6 5 0 0.864 + 0.09
6 5 0 0. 92 z!z 0. 01
6 5 0 1. 01 zko.01
See Ref.
b See Ref. for def. of s.
0. 40 M, ; M, / M. <I . I ;
D, , o; 12v
C=O.Ol-27.0g/dm3
M,; D,; C=O.O5
g/dm3; 9V; DLS
M, ; D, ; C=O. O75
g/dm3; 14V. DL S
M,; D,; C=O.28
gldm; 9V, DLS
M,; D,; C=O.O5
g/dm; 1 IV; DLS
M,; D,; c= 13.1
g/dm; DLS
M, ; D, ; C=13. 1
g/dm; DLS
M,; D, ; C=13. 1
gJdm3; DLS
M, ; D, ; C=13. 1
g/dm3; DLS
Ion content: 2.6%
1073
PC-spectroscopy;
P MP S :
M, = 2600 g/mol;
M,fM, = 1.5
References page VII - 198
TABLE 6. (0,CkHETEROCHAIN POLYMERS (POLY(ETHERS), POLY~ESTERS), POLYKARBONATES))
c
H
\
Polymer Solvent
T (C) M ( x 10m3) (g/mol) so (x 10) (s)
k. (cmk) Do ( x 10) (cm2/s)
ko (cm3k) fO/fsp ~2 (cm3k9
Remarks Refs. 5
Poly(carbonate)
PMC If-Dioxane 2 5 4 1 . 8
PMC Methylene chloride 2 0 4 1 . 8
PMC Tetmhydrofuran 2 0 4 1 . 8
PPhC Benzene 2 5 47.0
Poly(thiocarbonate)
PHTC Benzene 2 5 1 9 . 1
PHTC 1,CDioxane 1 9 . 1
PMTC- 1 9.4
PMTC-2 63.0
PetTC Benzene 1 4 . 0
PiBuTC 40.0
PPhTC - 93.0
P3CIPhTC-1 5 . 8
P3ClPhTC-2 3 4 . 0
P4CIPhTC-1 5.0
3 5 5.0
5 0 5.0
P4ClPhTC-2 2 5 3 1 . 0
P34CIPhTC- I 4 . 5
I ,CDioxane 4 . 5
Chlorobenzene 4 . 5
P34CIPhTC.2 Benzene 2 8 . 0
Poiy(ethylene terephthalate) See Poly(oxyethyleneoxyterephthaloy1)
Poly(oxycarbonyloxy-I,4-phenyleneisopropylidene-l ,Cphenylene)
Methylene chloride 2 0
Tetrahydrofuran 2 0 8.5-266
Poly(oxycarbonyl- Chloroform 2 0 7 8 0
propylene)
3 7 0
1 5 6
8 3 . 5
2 1 . 1
Poly(oxyethylene) Acetone 2 5 4 . 3
Formamide 2 5 4 . 3
Methanol 2 5 4 . 3
2 3 . 8
1 9 . 2
4 0
7 4 5. 92
145 4. 05
5 9 4 1. 63
1 2 0 0 I.10
2 0 0.29 37.0
0. 625 2 9 . 2
sg= 1.33 x lo-4 IV:62
- 9 . 9 5
- 8. 16
- 4.96
- 3.50
- 2.00
3. 18
l/D0 = 1.569 x 10m3 .&f?
r.0
3 7 . 8
5. 76
2 3 . 5
1 0 . 7
1 0 . 7
8. 23
0.804 M,/M, = 1.10
0. 8999 M,/M, = 1.10
0. 7738 M, / M, = 1.10
0.762 M,/M, = 1.09
0. 753
0. 795
0.790
0. 808
0.790
0.834
0.780
0.719
0.718
0.738
0.724
0.729
0.732
0.700
0.704
0. 705
0.694
M, / M, = 1.23
M, I M, = 1.23
M,IM, = 1.34
M,/M, = 1.30
M, / M, =1. 40
M, / M. = 1.24
M, / M, =2. 07
PAAR DMA 55
0.8099
0.812
0. 785
M
1.w; St
M, from 5 3 5 , 5 3 7 vl
Scheraga-Mandel-
2
kern-Eq. (Ref. 536) z
i5
d
E
3
M, ; CLS 1 8 4 .F
M,; CLS I84 ;
M, ; CLS I84 E
M,,D; st
:
150 z
T0 = 16.lC: 1003 g
[T7]=79.5 x 10-J MO.58
for T= 25C
F
T,j = 17.2C
T,j = 16.7C
To = 17.oc
Te = 16.5C
DZ
1 7 7
- -..
Water
TS, SE I5
TS, SE 30
TS, SE 70
TS, SE 150
TS, SE 8, SE 30,
SE 150
Poly(ethylene glycol) D20
20
22.8
23
25
25
25
25 + 0.02
12 0.59 7.35
23.8 0.93 4.85
37.3 1.09 3.95
17.7 I .33
30.0 I .08
67.9 0.79
II9 0.63
17.7-I 19 D, = K1, M- 039
1130 3.73 I .58
1470 4.16 I .33
1490 4.18 1.36
1900 4.67 1.15
2000 4.78 1.12
2610 5.39 0.93
2630 5.42 0.93
2670 5.34 0.94
1130-2670 so=6.40x IO-l6 My4 Do= 1. 86x 1O-4 I+-.~
D
25 5.7-1200
25 320 2.15 I .o
5
Do = k M -0 597f 20
25
Do = k M-.s4*021
D~O/diethylene 25
glycol l/l
Poly(oxy-2,6-dimethyl- T0hene 40- 54
1,Cphenylene) 55-65
69- 78
1. 25 24.0
3.3 13.3
5.8 11.6
8.8 1 0 . 3
10.6 7.2
1.426 23.6
I .470 22.6
1.778 19.7
I.822 20.1
470
0.24
4.3 11.5
177 1.33
300 1. 08
679 0.79
* .I190 0.63
20
0.0206-0.025 1
0.0463-0.0509
0.0556-0.0624
26.8
29. I
28.4
30.9
31.2
34.4
34.2
33.8
180
0.834
0.846
0.9058
0.8689
0.8420
M
M, I M, =1. 04
M, I M, =1. 05
M, / M, =l . l O
M, / M. =1. 12
Forp=lMPa
Forp= IOOMpa
For = 200 Mpa p
148
184
1002
1001
184
M, ; CLS 150
M, ; M, / M. =1. 04; 744
D, ; C= l.O03g/dm; DLS
M, ; M, / M. =l . O5; D, ;
C = I.003g/dm ; DLS
M, ; M, / M, =l . l O; D, ;
C = I.003g/dm ; DLS
M, ; M, I M, =l . l 2; D, ;
C = I .003 gldm ; DLS
M, ; M, / M, =l . l 2 144
C=l.O03g/dm; DLS
Mw; Do,A; Ma; Mw 749
given in Ref.; f o =RT/ Do, A
f
B
MW 149 2
M, ; M, / M, = 1.12; D 750 3
given in Ref. 3
M
s, ~; M, , DI M, = 1.1 751 2
1088 -
3
v)
c = 30 mass% 765 4
c = 40 mass% 765 5
C = 50 mass% 765 t;
01
References page VII - 198
TABLE 6. contd
Polymer Solvent
c
q
\
T ((3 M ( x 1O-3) (g/mol) so (x 103) (s) k, (cm%) Do (x 10) (cm*/s)
ko (cm%) fo/fsp 7~2 (cm %)
Remarks Refs. 2
Poly(oxyethyleneoxyterephthaloyl)(polyethylene terephthalate)
m-cresol 2.5
unfractionated
50
unfractionated
Poly(oxypropylene)
TS, SE 5
TS, S E 8
TS, SE I5
TS, SE 3 0
TS, SE 7 0
TS, S E 15
TS, SE 15
Acetone 2 0
Benzene 2 0
Water 2 5
15
3 4
4 3
2 5
30.3
35.4
40.5
45.5
111
17.3
61.0
41.3
36.8
23.0
60.2
87.3
0.103
0.153
0.138
0.132
0.125 180
0.120
0.155
0.186
0.263
0.280
0.365
0.205
0.130
Do =KD I +- ' . ' ~
111
11.3
61. 0
41.3
36.8
23.0
60.2
87.3
0.074-3.375
0.134-3.375
so =K, Mo. 26
0.435
0.405
0. 39 I
0.372
0.338
0.439
0.408
so =K, , M" . 22
140 0.992 8 0
0. 38 I
Do= KD M-s2
Do= K. ,$.-OS5
4 0 3.73
7 3 2.09
148 1.66
2 7 8 I .72
661 1.07
148
148
I .73
2.47
2.88
2.63
2.72
3.08
3.25
3.49
A 2 given in Ref.
0.678 MS,D
f o=4. 4x 10- J MO=
fO =3.2 x IO- M.55
$
4
DA;fo=kT/(Doq,)
465
DA; Mfrom condensa-
8
465 q
tion and boiling
temperature elevation
;
M, ; M, I M. =1. 03; 765
5
D, ; C= 14gldm; DLS
.w
M, ; M, I M, =l . O2; D, ;
2
C=4.8g/dm; DLS r:
M, ; M, I M, =l . O4; D, ;
E
C=3.2gIdm3; DLS
M, ; M, I M. =l . O5; D, ;
%
C= 10.6g!dm3; DLS
i
M, ; M, / M. =l . l O; D, ;
zi
C=3.6g/dm3; DLS
5
M, ; M, I M, =l . WD, ;
E
C= 10.5g/dm3; DLS 3
.F
M, ; M, / M. =l . O; D, ;
C=25.6g/dm1; DLS
z
5
a
f
T
TABLE 7. (N,C)-AND (O,N,C)-HETEROCHAI N POLYMERS (P~LY~AMIDES), POLY(UREAS), POLY(URETHANES))
n
3
8
Polymer Solvent T (C) M ( x 10m3) (g/mol) so ( x 10) (s) k, (cm3k) DO ( x 10 ) (cm2/s)
k D (cm3hd f0lf.p v2 km%!) Remarks Refs. g.
s
Poly(ethylenimine)
linear IOOmM NaCl
25 mM NaCl
IOmM N&l
25 mM NaCl
Poly(n-butyliminocarbonyl) (Poly(butylisocyanate))
Tetrahydrofuran
Poly(hexyliminocarbony1) (Poly(hexylisocyanate))
Hexane
2 5 41.5
41.5
41.5
88.2
J
2.48 2.3 DLS 1090
1.92 9.2
%
I .39 25 if-
D.
I.12 I5 s
2 0 18-21 I so =3.05 x 10-14 MO.h
2 5 52.1
2 0 2
* ,411
Do=1.69x IO-M-.s5
6
I44 \.D 3 2 5 3
8.11 27.3 Mw; Do,z; 152 z
1
3.17 - 263 C=O.2-6.0&g r
I .85 - 242 2
a
B.
E
0.890 M I48
f
Poly(iminohexamethyleneiminoadipoyl) (Nylon 66)
Formic acid (98- 100%)
Poly(iminoisophthaloylimino-l,3-phenylene)
22.4 16
Dimethylformamide 2 5 30.2-156 so = 1.9 x 1o-5 MO-
LiCl (2.5 g/dm 3 + 96% H$Ob) 20.7- 142 so=2.8 x IO-l5 h4o-39
in dimethylfomwnide
Poly(iminoisophthaloylimino-1,3-phenylene-sulfonyI-1.3-phenylene) (Poly(3,3-diphenylsulfonisophthalamide))
2 5 19 2.2
8 2 2.5
I IO 2.6
130 2.8
I75 3.3
240 3.5
360 4.4
2 5 79-360 so =2.56 x 1O-5 ,+I.
Poly(iminoterephthaloylimino-I ,4-phenyleoe-sulfonyl-1,3-phenylene) (Poly(4,4-diphenylsuIfonterephthalamide))
2 0 25.0
33.4
50.0
68.5
72.0
90.0
98.0
109.0
25-109
Poly(iminoterephthaloylimino-1,4-phenyleneanthron-9-ylidene-1,4-phenylene)
Dimethylformamide 2 5
Poly(l-lysine)
branched by benzyl aspartate and benzyl glutamate
Dimethylfomuunide 2 0
I .50
1.71
2.00
2.40
2.51
2.10
2.11
2.86
so = 2.34 x lo-5 Mo.4*
so = 3.0 x lo-5 MO.
Poly(4,4-oxydiphenylene) pyromellitamic acid)
Dimethylformamide/
LiBr (0. I mol/dm))
2 5 so=3.9 x 10-15 IV.39
0.578
0.678
0.682
5 8 9 9
5 8 9 ::
f
7 6 4 8
J
P
P
2
3
k
0.141
F
=.
164 g
s.
763,764 5
n
7
5
0
5
i
n
M,IM. c 1.5 7 6 3 ;
From dn/dc (see Ref.) 532 3
w
5 7 9 5
3
B
SO, L DA as 4 4 8
function of composition
3
;:
and M given
153 $
\
5
References page VII - 198
TABLE 7. contd
Polymer Sol vent
T (C)
M ( x 10m3) (g/mot) so (x 103) (s) k, (cm3k)
5
DO (x 107) (cm2/s) kD (cm3/g) fo/fsp wz (cm3k)
Remarks Ref s.
Poly(4,4-phenylene) pyromellitamic acid)
Dimethylformamide/ 2 5
LiBr (0. I mol/dm )
Poly(oxy- I ,4-phenyleneiminocarbonyl-2,5-dicarboxy- I ,4-phenylenecarbonylimino-I ,Cphenylene)
Dimethylacetamide/ I5 9.9-266 0.99-3.22
LiBr (0. I mol/dm ) I5 18.4-45.4 ~0~3.72 x 1O-5 Mo36
w
Poly(iminoisophthaloylimino-1.3.phenylene)
Dimethylformamide/ 2 5 (3.30-3.70)
LiCl (0.25%)
Dimethylformamide/ 2 5 4.3 0. 33
LiCl (3%) 5.9 0. 33
* .7.7 0. 39
1 0 . 6 0. 43
11.2 0. 37
1 5 . 5 0. 57
2 0 0. 66
2 4 0. 53
2 5 0. 76
2 7 0. 76
3 7 0. 86
3 8 0. 77
41 0. 86
4 3 0. 73
4 7 0. 78
4 8 0. 8 I
5 0 0. 82
5 5 0. 88
5 7 0. 89
6 5 0. 92
6 9 0. 90
7 0 0. 95
7 2 0. 95
7 4 0. 96
7 5 0. 98
8 0 0. 98
8 2 I .08
9 6 1. 14
II2 1.15
unfractionated I12 I.18
1 1 3 1. 24
II3 1. 24
118 1. 19
1 2 4 1. 18
1 3 3 1. 25
143 1. 23
1 4 7 1. 36
1 5 4 1. 33
0. I8
4 9
107
160
2 1 0
9 0
190
2 8 3
2 7 0
2 5 0
315
2 9 0
4 6 5
6. 19
4.47
4. 03
3. 24
2. 65
2. 95
2. 65
I .78
2. 47
2.00
1. 85
I .62
I .67
I.37
I .33
I .35
1.31
I .28
I .26
I.13
I .04
I .08
I .05
1. 04
1. 05
0.98
1. 06
0. 95
0.82
0.84
0. 88
0. 88
0.8 I
0. 76
0. 75
0.69
0. 74
0. 69
sg given in Ref.
l7V; CLS
M
C=0.55-l.lOg/dm;
See Ref.
M \,I)
-_
Dimethylformamide/
LiCl (0.005 g/dm)
Dimethylformamide/
LiCl (0.010 g/dm )
Dimethylformamide/
LiCl (0.030 g/dm )
Poly(iminoisophthaloylimino-1,3-phenylene)
Dimethylformamidel
LiCl (0.040 g/dm )
Dimethylformamide/
LiCl (0.050 g/dm )
Poly(naphthoylene imidohenzimidaLole)
sulfuric acid 96%
163
1 8 4
2 0 9
2 3 3
231
2 9 6
3 0 5
2 5 4.3-305
2 5 I I2
2 5 231
124
2 5 3 0 5
231
1 2 4
* ,112
2 5 3 0 5
124
2 5 3 0 5
I12
3 0
I .47
I .54 515
1. 67
I .95 661
I.81
I .82 815
2. 06 8 7 0
s=o.88x lo-5 M4
Poly(urethane) from Poly(oxycaproyl) (A) diphenylmethanediisocyanate, ethylenediamine
l i ne a r
A:M, = 1.3 x IO
AM, = 2.8 x IO
A:M,= 1.8 x IO
branched
Dimethylfommmide 2 5
branched
Poly(ureylenehepta-
methylene)
Dimethylformamide
Formic acid (97%)
Sulfonic acid (96%)
Poly(ureylene-2,4,4-trimethylpentamethylene)
Dimethylformamide
5 5
9 0
2 5
2 5
6 0
2 3 . 5
s,, = 1. 36 x IO- M 0. 848
s,,=9.86x I O Ih ML4h 0. 8745
S,) = I.18 x IW M4 0 . 8 5 8 I
2. 9 I 2 9 2
2. 10 I76
2. 50 2 4 3
I .85 159
0. 955
0.949
0. 915
0.974
0. 965
5 5 0. 955
9 0 0.949
2 5 0. 915
26.2- I28
266-306
146.4- 17.9
2 0 0
9 6 . 1
137
7 1 . 2
0. 72
0. 67
0. 64
0. 67
0. 61
0. 49
0. 54 2 2 7
&=0.71 x IO- M-OS7
I.91
0. 88
1. 20
0. 50
0. 68
1. 08
I .28
0. 40
0. 7 I
0. 30
0. 97
.0,,=3.9 x 10-h hr M>50x IOg/mol
D,j-3.4x I O M
0 7 4
M<80x IOglmol
0.7 I f 0.02 M,g
M,g; c = 0.3-0.4 g/
dm)
M
LDi
C=0.3p0.4g/dmZ
M \.I);
C=0.3-0.4g/dm
MS/Ii
C = 0.3-0.4 g/dm
MHW
607,608
7V; k, given in Ref.
7V; k, given in Ref.
MMW
MMW
MMW
183
183
M,; CLS I83
183
Formic acid (97%)
References page VII - 198
TABLE 8. OTHER SYNTHETIC POLYMERS
2
\
ii
Polymer Solvent T (C) M ( x 10 -j) (g/mol) so ( x 109 (s) k s (cm%)
0
DO (x 10) (cm2/s)
kD (cm%9 fo/fsp vz (cm%)
Remarks Refs.
Poly(bibenzoate):
Poly(heptamethylene p,p-bibenzoate)
CI,CH
ClzCHz
C1KzHz
Poly(oxybis(ethylene oxide) p,p-bibenzoate)
Cl,CH
C14CzHz
Poly(oxytris(ethylene oxide) p,p-bibenzoate)
Cl $H
C14C2H2
Poly(oxytetraquis(ethylene oxide) p,p-bibenzoate)
Cl +ZH
CWzHz
Phenol novolac Acetone
Phenol resol Acetone RT
Poly(terephthalic acid-4-aminobenzohydrazide)
Dimethylsulfoxide
Poly(acenaphthylene)
Poly(o-methyl-
phenylene)
Benzene 2 5
Toluene 2 0
2 5
2 5
2 5
2 5
RT
2 3
0.770 70.2
I.300 6 3 . 7
I .930 5 3 . 5
2.280 43.6
4.030 3 4 . 2
0.370 106.8
0.740 8 8 . 3
I.500 7 1 . 1
2.800 46.0
7. 530 27. I
3. 78 4. 02
5. 67 2. 97
7. 06 2. 28
9. 16 2. 25
9. 79 1. 75
1 6 . 6 I .32 - 16.2
2 8 . 5 1. 00 - 31. 0
4 7 . 1 0.806 - 101
8 3 . 9 0. 665 - 192
155 0. 393 - 349
2 6 0 0. 255 - 588
5 . 6 1. 10 1 8 . 5 I .68
9 . 3 1. 36 1 2 . 5
1 2 . 6 1. 55 II.1
1 5 . 8 1. 73 1 1 . 0
1 6 . 8 2. 20 1 2 . 1
2 3 . 4 2. 35 9. 41
3 6 . 7 2. 87 8. 38
7 7 . 2 4.40 5. 34
2 7 0 8. 25 3. 52
1. 94
2. 04
2. 06
2. 04
2. 26
2. 42
2. 97
0.814
0.820
0. 835
0. 733
0.768
0. 745
0. 761
0.759
0. 783
M.; Dw; Mw; DA
given in Ref.
M,; Dw; Mw; DA
given in Ref.
7 6 2
7
CLS, DLS
0. 77
0. 841 M
t,w; Dw; ~2
independ. of M
4 8 0
4
1 4 0
5
DW
DA
M Dw ,,W.
DW
Mt,w; DA
DW
M
D::
; D,
. ____
- .-.__ .~ -- -. .- ..--.
Poly(L-p-tolyl-2,5dioxopyrrolidine-3.4-diyl) (Poly-p-tolyl-maleimide)
Dimethylfonnamide 2 1 40-560 s, , =2. 16 x I O- l 4 Mo. 42 Do = 3. 47 x 1 0 -3 M -ws 0.74
MS.D
Poly(N-phenylmaleimide-co-styrene)
Tetrahydroforan
.~
2 5
0.9064
WNPI =o
0.8040 wNp, = 0.430
0. 7768 WNP, = 0.528
0. 7584 wp,p~ = 0.569
0.7400 w~,a, = 0.702
0. 6988 wj.Jp, = l.ooo
5 6 3
1047
TABLE 9. INORGANIC POLYMERS
Polymer Sol vent
T (C)
M ( x 10m3) (g/mol) so ( x 103) (s) k, (cm3k) DO ( x 10) (cm*/s) k D (cm /g) fo/fsp 21 I km /g) Remarks Refs. 8
s
Poly(bis(m-chlorophenoxy)phosphazene)
Chloroform 25+0.01
Poly(metaphosphoric acid)
magnesium complex Water/NaCI (0.4 mol/ 3 8
dm)
potassium salt Water/NaCI (0. I mol/ 14
dm3)
WaterINaCI (0.4 mol/ 3 2
dm)
Water/NaCI (0. I mall 2 0
dm)/ethaool (5%)
Water/NaCI (0. I moV 2 5
dm3)/ethanol (8%)
Poly(3-methyl-I-butene-I-silsesquioxane), cyclolinear
Butylacetate 2 4
Poly(oxydimethylsilylene) (polydimethyl siloxane)
Bromocyclohexane 2 8
3450 f 240
looa
4 8 0
I loo
5 7 0
6 5 0
92-600
101
165
5 5 0
I .40 f 0.01 II6
DO,,
$
Do = (2.08 f 0.06) x IO -4 M -.s7
757 i
757 =
F
1. 39 2 . 8 0.370
1. 05
I .08
I .25
I .36
5 . 2 0. 311 Mr.w; st;
D, 1 3 9 0
3.
3 . 8 0.316 g!
4. I 0.315
3 . 6 0.318
s,,= I.1 x IO-l4 M D,,= I.1 x IO- M-O@
- 2.40 1. 66
- 2. 70 1. 15
- 4.60 0.59
2 8 . 2
2
0. 863 f 0. 003 M, , D; s (13V); D (13V) 5 8 3 2.
2
MI . D
326 i
1. 025
hi
Cc
$
326 s.
M. ; M, / M. = 1.0; D; 758 7
C= 0.69 mass%
4
M, ; M, / M. =1. 0;
%
2.
D, C = 0.77 mass%
0
M, ; M, / M, =l . Ol ; B
D, C = 0.80 mass%
M, ; M, I M. = 1.04;
1
UI
D, C = 0.76 mass%
M,; M,/M, = 1.11;
D; C=O. 72 mass%
s
M,; M,IM, = 1.03;
7
D, C = 0.98 mass%
E
linear 2 8 (T=O) 0.312
0.386
0.700
1. 130
2.130
5.280
2 3 . 5
1 7 . 4
13.3
9. 69
5. 96
References page VII - 198
T A B L E 9 . contd
Polymer Sol vent
6
\
T ((2 M ( x 10 -3) (g/mol) so (x 103) (s) k, (cm3k) DO (x 107) (cm2/s) kD (cm/g) folfsp vz (cm%)
Remarks Refs. g
28 (T=@ 4 . 0 3 0 9.61
IO.240 5.75
14.980
cycl i c 15 0 . 2 2 2
4.41
DOEKD M-054+002
33. 7
2 8 3.710 Il.5
Butanone IO
2 0
3 5
T0helK 2 0
22. 4
linear 2 5
10.240 4.32
14.980 3.27
0 . 2 9 6 2 7 . 4
0 . 5 2 0 21. 7
I .070 15. 0
2.080 10. 9
3.710 8.30
X.480 5.56
17.380 3.53
8.480 7.67
17.380 4.8 I
1 6
3 0 1
9 2 0
9 . 4
0.3 122
4.09 3.00
6.07 I .60
124.00
0.3863 107.10
0 . 6 0 8 6
1.053
80.00
58.92
I.018
I .0282
I .0468
1.024
M, ; M, I M, =1. 20;
D; cxo.71 mass%
M, ; M, I M, =1. 14;
D; C = 0.80 mass%
M, ; M, / M, =l . 08;
D; C=O.68 mass%
M, ; M, / M. =1. 20;
D; CrO.71 mass%
M, ; M, j M, = 1. 12;
D; C= 0.63 mass%
M, ; M, / M. =1. 0;
D; C = 0.74 mass%
M. ; M, / M, =1. 0;
D; C=0.78 mass%
M, ; M, / M. =1. 02;
D; C = 0.76 mass%
M. ; M, I M, =l . O4;
D; C=0.79 mass%
M. ; M, / M. =1. 01;
D; C~0. 76 mass%
M, ; M, / M, =l . O4;
D; C~0. 73 mass%
M, ; M, I M, = 1. 14;
D; C~0. 73 mass%
M, ; M, / M, =1. 08;
D; C=O. 73 mass%
M. ; M, I M, =l . O4;
D, C = 0.77 mass%
M, ; M, / M, =1. 06; D;
C = 0.72 mass%
M, ; M, / M, =1. 08; D;
C = 0.73 mass%
M
Mr , D
MV
M, ; M, / M, =l Q
D, C= 1.405 mass%
M. ; M, / M. =l . O;
D, C = 1.375 mass%
M, ; M, I M, =1. 03;
D; C=1. 388 mass%.
M, ; M, I M, = 1.02;
D; C= 1. 333 mass%
__---.
49.42 M.; M,/M,= 1.02;
D; C= 1.371 mass%
Poly(oxydimethylsilylene) (polydimethyl siloxane)
linear Toluene 3. 573 33. 52 M, ; M, / M, =1. 04;
D; C = I .243 mass%
M, ; M, / M, = 1. 05;
D; C= 1. 337 mass%
M. ; M, / M, =1. 07;
6. 018 26. 65
14. 460 15. 03
D; C = I.249 mass% F
a
3
Poly(oxydimethylsilylene) (polydimethyl siloxane)
23. 570 10. 88 M, ; M, / M, =1. 08;
f
D; c= 1. 750 mass%
c
M, ; M, / M, - - 1. 08
g.
759 ,
M, ; M, / M, = 1. 0;
s
D; C= 1.483 mass% 759 =
M, ; M, f M, = 1. 0;
0
3
D; C = I.294 mass%
E.
M. ; M, I M, = 1.07;
s
D; C= I.180 mass%
M.; M,/M,= 1.08;
6
D, C= I.512 mass%
ii
s1.
M.; M,/M, = 1.05; 8
D; C= I.180 mass% .g
M, ; M, / M, = 1.06; 2
D; c = I .504 mass%
;5
-.
L
M, ; M, / M, = 1.04;
D; c= I.351 mass%
g
M. ; M, / M, = 1.06;
8 .
22
0
D; C= 1.237 mass%
M, ; M, . , I M, =1. 07;
s
F
D; C= 1.432 mass% 3
M. ; M, I M, - 1.08 7 5 9 a
8. 18
Mw; Do,,
760 k
3. 36
n
0 41hf 002
Do=K, , Mm
145. 20 cyclic Toluene
0.3-23.6
0. 2223
0.2964 123. 30
0.7410 78. 00
1. 189 64. 73
I.534 57. 13
3.171 40. 95
37. 07 4.172
9. 077 24. 22
17. 673 16. 26
0.2- 17.1
linear 2 5 23. 30
12.40
0. 627
cyclic 23. 20
~-M-43*om
I I.15
17. 35
82. 05
13. 05
- 2.08 +
2. 33 Mw; D0.L 7 6 0
c
g
11. 50 21. 75 - 2.00
0.296 125. 4 - 1. 503 P
Poly(oxydiphenylsilylene) (Poly(phenyl siloxane))
c
P
Benzene 2 1 4-3350 so=9.16x IO- Mox7 D" x6. 16 x 1O- 4 Mmohx 0. 807 M s.0. DA 5 5 6 e
-h
Poly(oxymethylphenylsilylene)
5
Toluene 2 2 0.006 [VI = 132 cm /g 1 4 8 4
%
g.
z
3
VI
References page VII - 198
TABLE 10. POLYtSACCHARIDES)
Polymer Solvent
c
E
\
T ((3
M ( x lo-) (glmol) so ( x 103) (s) k. b3k) Do (x IO) (cm%) k0 (cm3k) fO/fsp ~2 (cm%) Remarks Refs.
z
Amylose I ,4dioxane 2 0 2 . 8
5 . 8
9 . 2
1 7 . 3
3 2 . 9
49.0
8 3 . 5
121
3 5 6
8 6 0
1 1 3 0
1280
Carboxymethyl
celhdose
Water RT
sodium salt WaterflVaOH(O.01 mol/ 2 0 . 6
dm; pH = 12.0)
Water/NaCl(O.OOl moU 2 5
dm)
Water/NaCl(O.O05 mol/dm )
WaterMaCI(O.0 I mol/dm )
Cel l ul os e.
absorbent cotton
aged, alkali cell.
overaged
cotton (Georgia)
Holo cellulose
(spruce)
Water/NaCl
Cuprammonium
hydroxide
2 0
2 7 3 0
0. 303
0.642
0. 805
I .27
1. 44
I .86
I .92
2. 29
3. 13
4.16
4.16
4.54
5. 40
5. 85
$0=6.6x lo-5 M;$
7 0 0
44.1 2. 40
4 6 2. 30
90.6 2.50
9 4 . 2 2. 58
163 2. 65
1 9 4 2. 62
2 8 0 2. 85
3 4 6 2.%
7 0 2. 54
1 0 4 3.00
I75 3. 14
2 9 0 3. 97
7 0 2. 76
I04 3. 18
I75 4. 25
2 9 0 4.28
4 4 . 7 2. 70
163 3. 11
3 4 6 4.53
1 5 0
4 4
1 7 5 0
3 4 0
4.28
3 . 8
I.9
1 0 . 4
1.2
6 2
3 3
41
7 7
I41
I60
183
2 8 0
2 8 4
110
2 0
9 0 0
3 9 0
II. 4 - 3
I O. 8 0
8 . 2 I
6 . 9 - 4
4 . 1 I O
3. 56 5
2. 15 1 7
I .77 2 2
0. 825 3 6
0.452 5 2
0.344 142
0.332 I66
0. 247 3 4 6
0. 20 4 4 7
Do =6.6 x 10-4 M?
r.0
1 . 2
2 . 8
3 . 1
1 2 . 0
0.505
5 1 . 5
2. 64
0. 84
I .54
0 . 2
0. 72
3 0 5 . 3 0.508
4 5 4.6 0. 508
3 5 0 9 . 8 0.508
1 4 5 4 . 1 0. 508
Mw; soi Dz,o
C=O.l mas s %
C=O.S mass%
C= 1.0 mass%
C = 2.0 mass%
M
M.
M.
s , ; C= I.Og/dm
Mr.w; 8,; Dw
0
768 a
766 c
r
P
2 7 1 , 2 1 8 ;
n
ir
2 7 7 , 2 7 8 3
.=
767 F
6 3
-~ _- ---- ,.-. --~
^_-.
7
Iinters, unbleached
Iinters, bleached
linters, cotton
filter paper
Cellulose
flax fiber
nettle fiber
ramie fiber
sulfate cell.
sulfate cell.,
acetylated
sulfate cell., precipit-
sulfite cell.
sulfite cell., bleached
viscose staple fiber (sulfate cellulose)
-. (spruce)
-. (pine)
wood cellulose (Cross
and Bevan aspen)
-Cellulose, cotton
t i nt er s
-Cellulose, holo
cellulose
p Cellulose
Cellulose Cupriethylenediamine
Cadmium
ethylenediamine
linters hydrol.
sulfite pulp
Iron-tartark acid
Complex Na salt
Cellulose acetate Acetone
2 5
12
2 5
2 0
2 0
1 5 0 0
490
1200
1 0 . 3
7.2
9.2
3.94
6 0 0
5 2 0
6 9 0
0. 23 3 2 0
0. 43 I30
0. 26 2 5 0
2. 83
9 . 0
6 . 1
8 . 6
0.508
0.508
0. 508
5 9 0 0 1 7 . 5
1900 1 4 . 0
2 0 0 0 1 0 . 8
400 6 . 5
5 7 0 6.3
I700
1000
8 6 0
3 9 0
0 . 1 1200 1 3 . 1 0. 508
0. 25 3 2 0 7 . 7 0. 508
0. 18 2 5 0 I O. 4 0.508
0. 54 105 5 . 9 0.508
0. 37 1 9 0 7 . 7 0.508
s , ; C= 1 g/dm3
Mr,w; s,; D,
Mr.& s,; Dw
3 2 0
5 0 0
6 . 3
6 . 3
4. 28
5 . 2 0. 508
3 8 0
2. 13
0. 66 I65
0. 45 I15
2. 12
3. 67
s,; constituent A
s,; constttuent B
7 5
2 3 0
5 0
170
4 . 8 0.508
6 . 4 0. 508
5 3
2.6
4 . 1
4.28
2. 13
4.6
1. 04 0
0. 54 7 5
2. 70
3. 53
5 . 4 0.642
M,,,; s,; Dw
s,; constituent A
s,; constituent B
SI
6 8 0 6 . 5 3 2 0 0. 32 2 9 5 8 . 4 0.508
Mt.w; 3,; Dw
2 7 1 . 6
175 5 . 5
9 . 5 8 . 3
5 0 I .97 5 0
1 . 2
0. 95
4.0 0.508
0. 65
3 3 . 6 1. 25
2 4 . 5 I.13
1 8 . 8 1. 04
IO.1 0.74
0.50
4 3 1. 80 I53 I .77
I55 2. 75 3 7 0 0. 75
2 1 0 3. 17 4 6 5 0. 64
2 7 5 3. 80 7 1 0 0. 58
4 3 5 4. 53 loo0 0. 44
7 4 5 5. 49 1410 0. 3 I
115 2. 87 3 6 7 I.06
M,,,; st; Dw
111
201.4
3 6 4
5 3 9
1 0 0
10. 35
5 1
143
I .I5
2. 17
2. 98
3. 35
0. 89
0. 60
0. 46
0. 35
5 . 4
2 0 . 7
7 . 7
4.0
0.654
M.A; SC DA
4. 07
7.5
1 0 . 9
6 0 0
5 6 0 0
1 4 3 0 0
DW 1 3
Mt.,; st; D A 3 9
I4
I4
I4
6 3
1 4
I4
I4
I4
1 4
f
l
1 4 B
C
1 4 8
6 3 :
6 3 ;
1 4 2
1.
I4 s
6 3
63
F
1
6 2 z.
f
I4 .!
9
%.
I4 g
234 m
a
9 7
2
425 2
E
9 7 %
97
9 7
z
a
9 7 4
9 7 =
g7 g
97 I
97 0,
References page
c
z
.
K
VII - 198
T A B L E 1 0 . contd
Polymer Sol vent
c
z
\
z
T C-3 M ( x 10 -j) (g/mol) sg (x 103) (s)
k, (cm3k)
DO (x 10) (cm*/s)
kD (cm49 fo/fsp v (cm3/g) Remarks Ref s.
z
1 9 1 0 0 3 . 4
0. 68 M,,,s,; M,/M, = 1. 27 39, 769
P
0. 687
z
Mn; OS; Mmv 554, 557 2
given in Ref
1 9 4
IO.4- 194
1 5 0
1 2 . 5
so= 1.22 x 10-14 MOXX
1 6 . 7 from cotton linters Acetone 2 5
136 1 6 . 0
6 6 1 0 . 5
I45 1 4 . 7
II0 1 2 . 8
2 6 7.0
24.2-249 s,~= 1.2x IO-l4 M9
0. 687
0.692
0. 698
0. 697
0.690
0. 700
0.700
M, / M, = 1.15-1.99
2 0
Cellulose acetate
from wood cellulose Acetone 1 0 . 0
8 . 4
s,,=2.21 x 10~4 Ml?>
4 0
21.2-122 M, . ni MwI Mn =
1.12-2.44
MW degree of
s ubs t i t ut i on: 2. 46
2 5 2 4 . 2 5. 28
3 7 . 6 6. 26
5 9 . 0 7. 31
7 5 . 0 7. 67
I I I 9. 80
I59 II.60
2 4 9 12. 50
24.2-249 s,, = 1.02 x 10~ I4 M
2 4 . 3
43.8
6 5 . 1
6X. 3
I04
169
188
M, : M, / M, =1.2-1.3
MW
degree of substitution: 2.92
N,N-Dimethylacetamide 2 5 3 6 . 1
8 2 . 2
137
3 0 8
5 0 0
2 5 0
9 7
2. 27 7 1 . 7
2. 83 IO1
3. 32 I31
4.04 2 0 5
4. 17 2 2 8
0. 744
0. 777
0. 72
M
M,
Cellulose triacetate
Cellulose acetate-co-
butyrate
Cellulose carbanilate
sym-Tetrachloroethane
sym-Tetrachloroethane
Acetone
Dioxane
2 1 . 9
2 2 . 7
3 9 3 0 45.4
I .35-2580 s,,=2.35 x lOm5 Mox6 Mr , ~~; DA, k, and kD
given in Ref.
M
$8
2 0
2 3 I4
2 4
2 8
3 4
3 9
4 6
4 4
6 6
61
8 4
1 0 7
4 . 7
4 . 9
4 . 1
3 . 4
3 . 6
3 . 2
2 . 6
2 . 8
2 . 5
2 . 3
,~ ..- -- .~ -_-.- .~- - --
Dioxane 2 0 4. 43
8. 70
1 1 . 9
1 7 . 8
42.0
8 0 . 8
141
2 1 5
2 7 8
1 0 4 0
1570
2 5 8 0
2 0 4.43-2580
23 , 1 4
2 4
2 8
3 4
3 9
4 6
4 4
6 6
6 1
8 4
1 0 7
14-107
Ethyl acetate
Cellulose carbanilate Ethylacetate
Z = degree of
polymerization
M, ; so; D, , o; DLS
7 7 1
7 6 8
Cellulose glycolate
sodium salt
Methyl cellulose
WaterINaCI(O.2 mol/dm ) 2 0
Water/NaCl(O.S mol/dmg)
Water/NaCI( I .O mol/dm 2,
Water 2 5
Cellulose nitrate
13.8% N
Acetone 2 0
5 5
5 5
1 9
31
3 9
5 8
91
8 9
8 7
102
163
1 9 0
2 5 2
4 0 8
6.2
3 0
8 0 . 2
199
6 1 3
100
1 9 0
0.520
0. 743
0. 823
0. 95
I .25
1. 51
I .88
2. 18
2. 34
4. 00
4. 35
5. 50
s,,=2.35 x 1O-s M.3
3 . 9
4 . 7
4 . 8
5 . 3
5.4
6. I
5 . 5
6 . 9
7 . 0
7.0
8 . 3
SZ 1.3 x 10-13 zZ
1 1 . 0 - 5
8.0 0
6 . 5 0
5.0 5
2. 80 2
1 7 7 I .75 1 0
145 1. 25 8
150 0. 95 6 0
164 0. 79 6 4
3 8 0 0. 36 188
5 7 4 0. 26 2 6 2
8 6 3 0.20 4 0 0
Do = 2.2 x 10-d M,;p
1 9 . 4
13.8
1 2 . 1
I O. 9
9.6
9 . 3
8 . 8
7 . 3
8 . 0
5 . 8
5.4
D = 2.2 x 10-z z;;ja
3.4
3. 44
2. 62
2. 57
2. 50
2. 07
1. 90
1. 80
1.71
1. 62
I .40
1. 36
0.94
1 2 . 0
3 0 . 0
1 3 . 9
1 4 . 0
3.30
1 . 3
7 8
140
2 7 0
5 4 0
6 2 0
7 4 0
3. 08 185
215
3. 22
4.34
3. 80
3. 12
2. 44
1. 63
i .75
I .75
1. 33
I.17
0.90
0. 73
6.5
3. 29
3 . 2 0.53
0.72 M.%D
7 7 1
0.72
1 . 7 0.5 I
3 . 2
4.6
5 . 4
6 . 9
3. 74
0.57
Z = degree of
polymerization
M . Dw f , W.
DW
M, , w; s, ; Dw
[q]=67cm3/g
[Q] = I lOcm/g
[v] = I38 cm /g
[v] = 242 cm /g
[q] = 238 cm3/g
Eq] = 260 cm /g
[q] = 270 cm /g
[q]=310cm3/g
[q] =450cm3/g
[a] = 500 cm 3/g
[q] = 760 cm /g
[q] = 830 cm /g
M,,D
SE
SE
M
s.D
M&D
M&D
s, ; DA =D,
References page VII - 198
14
14
I4
IO83
2 2 3
276
6 4
6 5
T A B L E 1 0 . contd
4
E
\
Polymer Solvent T ((3
M ( x 10m3) (g/mol) so (x 103) (s) k, (cm%) DO (x 10) (cmls) k 0 (cm 3k) f O/f q v 2 (cm 3k) Remarks Refs.
E
cotton (13.8% N)
cotton (13.5-14% N)
Acetone
holo cellulose (spruce)
holo cellulose (-cellulose)
Iinters
Mets, bleached
linters, bleached
and unbleached
rayon pulp
sulfate pulp
sulfite pulp
13.9% N
2 4 2
1 3 . 8
1 6 . 3
2 7 . 8
ICIQ
1 5 3
1 8 7
2 6 7
4 9 5
1175
1 3
2 3
4 6
7 4
90
1 7 8
2 6 2
4 5 6
6 3 0
2 4 9 0
7 4
1 7 8
2 6 2
4 5 6
5 9 3
1 1 3 0
3 4 0
7 8 0
2 3 0
2 5 0
3 4 4
7 8 0
400
6 0 0
6 8 0
6
3 0
8 0
1 9 9
6 1 3
2 4
3 0 0
3 5 0
5 1 0
5 7 0
4 1 0
430
5 3 3
1 4 . 2
6 . 5
7 . 1
8 . 3
1 2 . 6
1 5 . 3
1 4 . 5
1 6 . 8
2 5 . 3
2 6 . 2
7 . 2
8 . 8
11.1
1 0 . 8
1 2 . 8
1 5 . 2
1 7 . 1
2 0 . 5
2 1 . 5
3 7 . 5
1 0 . 8
1 5 . 2
1 7 . 1
2 0 . 5
2 0 . 0
3 0 . 5
2 1 . 6
1 3 . 4
1 6
1 5 . 8
1 9 . 0
1 4 . 0
1 9 . 0
5 . 2
8 . 7
1 2 . 0
1 8 . 0
3 0 . 0
1 7 . 6
1 5 . 5
1 6 . 7
1 8 . 3
2 3 . 3
1 6 . 2
1 6 . 4
4 2 0
2 1 0
4 2 0
2 8 0
4 2 0
480
2 6 0
3 6 0
4 8 0
1150
3 5 0
3 6 0
2.60
20.9
19.3
1 3 . 3
5.6
4.5
3 . 5
2.8
2.3
1 .o
25.0
1 6 . 5
1 0 . 8
6. 45
6.30
3.80
2.90
2. 00
1. 50
0.66
6. 45
3. 80
2.90
2.00
1. 50
1. 20
2. 57
2.4
2 . 8
2. 05
1 . 0
1. 44
1.11
3 5
3 . 7
2.0
3. 01
2. 15
1. 94
I .48
1. 66
1. 56
1. 56
1. 46
175
6 5
2 1 0
1 2 0
2 2 5
2 3 5
IQ0
2 8 0
2 6 5
6 . 3
7 . 7
1 2 . 2
1 0 . 6
11.5
6.0
7 . 9
8 . 2
9.6
8 . 2
9 . 6
9.6
0.572
0.570
0.566
0. 51
0.5 I
0.510
0.510
0.510
0. 51
0.5 1
0. 51
0. 5 1
0.5 I
0. 51
0.5 1
M
,.W
MWV; s,; D,
M,,,; s,; D A =Dw
M,,,; s,; DA =Dw
M r,wi s,; Dw
M
r,w; s,; Dw
M t,w; s,; DA =D,
M
r,w; s,; Dw
M
s,D
SE
SE
M.&D
M&D
M
r,w; s,; Dw
M
r,w; s,; Dw
14
M r,w; st: Dw
1 4
Mw; Dz.o; DLS 7 7 2
Butyl acetate
Cyclohexanone
chemical cotton
Ethyl acetate
raw cotton (Delfos variety)
t i nt er s
viscose rayon
purified chemical
linters
Met hanol
Pentyl acetate
unfractionated
fractionated
Water
2 1 . 3
2 0
8 7 0 1. 03
1 7 5 0 0. 69
3 6 0 0 0. 43
430-3600 D, , =Ko I W" ' ~
8 0 . 2
6 1 3
3 5 0
3 7 0
6 9 0
I.1
2 . 0
195
9 3
2 0 1 7 . 5
2 0 z, = 3 3 0 0 (CLS)
3 0 4 1 . 3 6. 34
7 6 7. 10
I28 8. 65
I10 9. 62
2 4 8 II.13
5 7 3 12. 66
41.3-573 s,)=3.04 x 10-14 lw29
w
2 0 8 0 . 2
\ 2 0 2 7
91
1 0 0
I53
I86
2 8 2
8 0 . 2 4.0
6 1 3 6 . 5
21 3 3 5 1 0 . 2
6 3 5 . 8
1 0 6 6 . 4
143 7 . 2
I91 8 . 2
2 2 8 8 . 7
2 6 0 9 . 5
3 0 0 9 . 7
3 4 2 9 . 8
444 II.1
600 1I.8
6 5 8 1 2 . 4
8 2 2 1 3 . 9
Z, = 2800 (CLS)
Z, = 2400 (CLS)
1 1 . 4
1 3 . 1
I500
9 . 3
9.26
5 4 0
100
120
2 2 0
3 2 0
4 0 0
4 7 0
5 0 0
6 1 0
6 9 0
8 7 0
8 7 0
1 2 5 0
1. 49
0. 91
2. 40
4. 77
0. 59
0. 77
0. 97
13.3
5.8
5.6
4.5
3 . 5
2 . 9
0.47
M,; DLS
0.584
0.59 SE; [so] given in Ref.
Ms,D
0.556 M
Mr . u; s, ; D,
M, , , ; J - , ; D, t =D,
Mr . w; s, ; Dw
0.545 M
Z, = 2600 (OS);
Dw, o; DLS;
Z = degree of
polymerization
z,=2100 (OS);
D, , O; DLS
Z, = 1600 (OS);
Dw. 0; DLS
M,; M.=34600
M,; M, =60600
M, ; M. =89000
M.
MW
M, ; M. =257000
0.54
MW,,
0.55 SE
M.\,D
M.\,D
M
r.
7 7 2
2 5 9
2 2 3
I48
91
91
6 5
91
91
7 7 3
9 0
9 0
2 2 3
2 5 9
2 2 3
References page VII - 198
T A B L E 1 0 . contd
c
q
\
Polymer Solvent T ((3 M ( x 10-3) (g/mol) sg (x 103) (s) k s (cm 3k) DO ( x 10) (cm*/s) kD (cm3k) fo/fsp 7~2 (cm3/g) Remarks Refs. 5
9 8 3 1 5 . 1 1220
Cellulose xanthate
2 1
Water/NaCI (1 mol/dm ) 0 Z= 1460 2. 10
0.59
f,j=1.16x IOgs-ml
Z= 1060 2. 25 f=l.ol x IO~gs~mol
See Ref. for degree
of subs.
Z = degree of
polymerization
z=590 1. 68
z=450 1.81
2=360 I .22
z=350 I .a5
35- 126 2.3-4.4
f,)=0.73 x I06gs- mol
f=0.57x I06gsrmol
fo=0.52 x 10gsm mol
f0=0.49x I06gs-mol
20-O 3.4-4.3 0.530 M Dw , . w*
sodium salt
wcyclodextrin
Pullulan
WatedNaOH (0.2 mol/ 2 0
dm Z)/NaCI (I .O mol/dm )
Water 25 f 0.01
Water + 0.02% (m/m)
Sodium azide 2 5
4 0
6 0
8 0
2 5
40
6 0
8 0
2 5
4 0
6 0
8 0
2 5
40
6 0
8 0
Water 2 5
70-280 3.35-I .83
3 2 . 0
2. 36 - 32.0
3. 20 - 37. 1
4.30 - 35.3
6. 70 - 46.3
1. 80 0
2. 50 0
4. 10 5 . 1
5. 00 1 2 . 8
I .40 2 3 . 6
2. 00 28.0
3. 00 2 6 . 7
3. 80 2 7 . 5
1. 00 55.0
I .40 6 5 . 7
I .90 8 4 . 2
2. 95 54.9
2. 56 - 20. 1
I .94 - 22.7
1. 34 - 30.5
1.12 - 40.2
0. 92 - 36.4
0. 787 - 35.0
0. 630 76.2
0. 567 3 0 . 2
0. 530 1 1 4
[r/l =42.5cm/g 167
3 0 3
5 1 3
iv]= 154.2cmlg 1000
[q]=44cm/g
[rj] = 70 cm Ig
[q] = 102 cm Ig
(71 = 145 cm/g
[v] = 175 cmlg
[q] = 225 cm /g
[v] = 250 cm3/g
[q]=310cm/g
[q] = 338 cm /g
1 0 7
188
3 8 4
5 7 2
811
1 0 5 0
1 4 9 0
2 1 0 0
2 3 6 0
De&an
T 500, linear Et hanedi ol 5 154. 3 4. 40 M, ; M, / M. =1. 26;
C= I g/dm3
M, ; M, f M, =1. 17;
C= 1 g/dm3
M, ; M, I M, = 1.17;
C = 1 g/dmi
M, ; M, I M, =1. 25;
C= I g/dm
191. 4 4. 26
242. 1 4. 34
309. 6 3. 66
-_-.
361.1 3.34 M,;M,/M,=1.23;
C= I g/dm3
434. I 3.48 M, ; M, / M, =1. 32;
C= I g/dm
28.9 6.01 M, ; M, f M, =1. 22; 119
C= I g/dm
51.3 4.90 M, ; M, / M, = 1.16;
C=lgldm
92.5 4.12 M, ; M, I M, =1. 16;
C= I gldm
P
142.9 4.12
5
M, ; M, I M, =1.17; 3
C = I g/dm J
185.6 2.86 M, ; M, / M, = 1.13;
G
c
C = I g/dm2 s
272.0 3.20 M, ; M, / M, = 1.24; ii
C= I g/dm
2.80
E.
M,; M,/M,= 1.31;
C= I g/dm $
branched 380.5
2.88 M, ; M, / M, = 1.20; 119 s
C= I g/dm
443. I 2.19 M, ; M, I M, = 1.24;
%
C= I g/dm
n
-.
493.3
2.71
m
M, ; M, I M, = 1.29; 2
.?
C= I g/dm
564.6 2.29 M, ; M, / M. = 1.38;
2
a
C = 1 g/d&
-e
L
617. 7 2.38 M, ; M, I M. = 1.35;
8
C = I g/dm3 x
782.5 2.53 M, ; M, / M, = 1.50;
2
C= I g/dm
s
branched 280.8 3.66 M, ; M, I M, = 1.34; 119 F
C= I g/dmx
3
324.6 3.49
$
M, ; M, I M, = 1.28;
C= I g/dmZ
J
n
360.0 2.11 M, ; M, I M, = 1.20;
E
C= 1 g/dm a
401.6 2.16
8
M, ; M, / M, = 1.28;
C= I g/dm
L
424.0
2.11 M, ; M, / M, = 1.28; F
Cc
C = I g/dm3
SI
412.5 2.49 M, ; M, I M, =1. 28;
0
C = 1 g/dm3
B
580.7 2.93 M, ; M, I M, =1. 35;
?
C = I g/dmx
5;
T 500, linear 5
E
154-434
0 2 8
D,=Kl, M- M, ; M, / M, <1. 3;
C = I g/dm3 119 c
29-434
D,=KDM-
M, ; M, f M. <1. 3;
779 2
a
C=lgldm3
branched 380-783
DXKDM-025
L M, ; M, / M. <1. 5; 179
C = I g/dm3
4
branched 280-580
D=KDM-o.40
L M, ; M, / M, <l . 4; 119 :
C = I g/dm3
5
References page VII - 198
T A B L E 1 0 . contd
Polymer Sol vent
c
E
\
T ((3 M ( x 10m3) (g/mol) so (x 103) (s) k, (cm%) Do ( x 10) (cm2/s)
ko (cm%) fo/fw ~1 (cm349 Remarks Refs. E
T 10
4 4
6 5
1 5 0
460
20. 9 160
2 0 18-400
13-200
2 0 6
so =2.45 x IO- M.
s,,=2.36x IO-l6 Mb
8. 9
T 20 16. 5 6. 7
T 70 39. 5
T 1.50 86. 0
3. 3
2. 2
Dextran
FDR 7783 120. 3 2. 2
D,,=(1.17f0.3)x 1o-4 My2*.m
Leuconostoc
mesent emi des
Water 2 0 10-200 1.1-6.0
2 0 2.02
2 5
6- 120.3
7 5 7.3 f 0. 4
2 0 9.8 + 0. 5
2 0
7.3 * 0. 3
5.8 f 0. 4
43f4 3.9zkO.l
75f4 3.1 fO.l
110*5 2.8fO.l
15oIt7 2.3fO.l
230f IO 1.90f0.05
49Of30
2 0 IO-500
1.25 $0.05
D,,. = 2.25 x 10 -4 M -.45
3.04
3.47
5.47
9. 6
3.24 + 0. 2
0.643 f 0.002
s, vs. M diagram
M determ. by Ogstons
23 vl
method (Ref. 24.25)
E
E
SI 24 y
0.60
M
Mw; Dz,o; MwIM. =
I .68; DLS
776 2
Mw; D&o; M,/M. = 1.24;
f
-55
D L S
0
Mv/; Dz,o; M,fM. = 1.76;
1
D L S
5
Mw; Dz,o; M,IM. = 1.80;
D L S
P
Mw; D,,o; M,/M. = 1.32; 8
D L S 5
M,IM, 1.8; DLS; 776 =
see Ref.
s
C = 2.72 mass%; 7 7 7 3
self diffusion; 5V
2
C=O.36 mass%; 19V 777 7
777 E
C = 2.72 mass%; self VI
diffusion; 9V
2
M,(CLS); M, / M. = G
I .6: D, , o; DLS
ii
M,(CLS); M,/M, = 1.2;
5
Dc. 0; DLS
M,(CLS); M,IM, = 1.3; 5
D,,o; DLS
.I
M,(CLS); M, I M. =1. 6;
2
D
z. 0; DL. Y A
M,(CLS); M,IM. = 1.4;
D,,o: DU
g
M,(CLS); M, / M, =1. 8; g
Dz. 0; DLS
M,(CLS); M, I M, =2. 1:
F
Dz, o; DLS
M,(CLS); M, I M. =2. 3;
Dz, o; DLS
D in mm*/s, M 7 7 8
in kg/m01
T 500 linear Water 2 5 154. 3
191. 3
242. I
309. 6
367. 7
434. I
linear 2 8 . 9
5 1 . 3
9 2 . 5
142. 9
185. 6
212.0
433.4
branched 380. 5
443. 1
493.3
564.6
617. 7
782. 5
280. 8
324.6
360.0
401.6
424.0
412.5
580.7
2. 40
2. 22
2. 08
1. 93
I .I5
1. 55
3. 17
3. 08
2. 52
2.5 I
2. 13
I .82
1. 46
I .68
I .53
I .49
I .42
I .35
I .24
1. 95
1. 83
I .72
1. 67
1. 62
1. 53
1. 41
Mw; M,/M. = 1.26:
C= I gldm3
M,; M,/M. = 1.17;
C = 1 g/dm3
M,; M,IM,= 1.17;
C = 1 g/dmz
M,; M,/M, = 1.25;
C= I g/d&
M,; M,/M. = 1.23;
C = 1 g/dm3
M,; M,/M, = 1.32;
C= I g/dm3
M,; M,/M. = 1.22;
C= I g/dm3
M,; M,IM. = 1.16;
C= I g/dm3
M,; M,IM.= 1.16;
C= 1 g/dm3
M,; M,/M.= 1.17;
C= I g/dm3
M,; M,/M,= 1.13;
C= I g/dm3
M,; M,/M, = 1.24;
C=lg/dm3
M,; M,IM,= 1.31;
C=lg/dm3
M,; M,/M,= 1.20;
C= I g/dm3
M,; M,/M, = 1.24;
C= I g/dm
M,; M,IM. = 1.29;
C= I g/dm3
M,; M,/M, = 1.38;
C= I p/dm3
M,; M,/M. = 1.35;
C=lg/dm3
M,; M,/M, = 1.50;
C=lg/dm
M,; M,IM. = 1.34;
C= I g/dm3
M,; M,IM. = 1.28;
C=lg/dm)
M,; M,IM. = 1.20;
C=lg/dm3
M,; MJM. = I .28;
C=lg/dm3
M,; M,IM. = 1.28;
C = I g/dm3
M,; M,/M, = 1.28;
C=lg/dm
M,; M,/M, = 1.35;
C=lg/dm3
References page VII - 198
TABLE 10. contd
E
Polymer Solvent T CC) M ( x 10e3) (g/mol) sg ( x 103) (s) ks (cm3/g)
DO (x 10) (cm*/s) ko km3/g) fn/fsp 11~ (cm3/g) Remarks Refs.
CA
!
T 500, linear
linear
branched 380-783
branched 280-580
T 250
DextraIl
PL IO
PL I5
PL 40
PL 100
PL 400
P L 9 0 0
pibar
2 0 0 0
I
2 5
water 2 5
Water
0.05 g/cL sodium azide 2 0
WaterlNazHP04 2 0
(0.025 mol/dm )/NaH ?POd
(0.025 mol/dm )
Water
3 0
7 0
100
3 0
7 0
100
3 0
154-434
29-434
I I ; 19; 100; 5 1 0
9 . 9
3 9 . 7
6 5 . 0
481
2 2 7 0
3 2 5 0
7 . 5
1 4 . 5
4 1 . 6
120. 7
3 7 4
I270
I4
3 6
8 4
I41
2 4 0
1990
3 0 5 0
3 8 0 0 0
1 0 0 0
1000
7 4 0 0
7 4 0 0
17500
3 . 3
1. 64
2. 64
4 . 1
5 . 3
6. 55
2 3 . 3
2 6 . 4
I50
D,=KD M-4
D, =KDM- " *'
D, =K, j M-
0 41
D, =K, >M-
0 4 4
9. 10 - IO
4. 39 - IO
3. 32 - IO
I .40 - 2 0
0. 74 - 6 0
0. 66 - 90
9. 00
6. 3 I
4. 14
2. 57
1. 30
0. 78
7. 50
4. 69
3. 12
2. 40
I .73
0. 75
0. 55
0. 25
0. 598
M, ; M, / M, = 1.3; 7 7 9
C= I g/dm3
M, ; M, I M, , = 1.3;
T
C= I g/dm
779 2
-I
M, ; M, / M, =1.5; 7 7 9
C= I g/dm
B
M, ; M, I M, =1. 4; 7 7 9
C= I g/dm
8
Extrapolated value z
(C = 0); 25V
;
C = 0.0903-O. I508 mass%
5
n
D given in Ref. 750 0
M, I M, = I.62 999 ;
M, / M, = 1.60
C
M, / M, =I.85
M, I M, =2. 69
p
n
I .04 8 1 . 5
I.00 71.4
1. 58 124. 1
I .46 100. 7
2. 60 105. 8
2. 26 112.4
0. 58 6 3 . 3
0. 53 5 9 . 2
1. 42 3 2 . 9
I.19 29.0
2. 00 3 0 . 8
I .66 3 5 . 5
0. 42 - 49.6
I .88
2. 19
2. 49
2. 79
3. 15
3. 61
4. 25
4. 03
[rj]=7.42cm/g 1015
[r/l = 10.53cmIg
g
[T/I= 18.85cm/g
5
[r/l = 29.77cmlg .v
[~]=.50.57cm/g
[a] =64.20cm7/g
5
M, . A; . v, ; DA 9 2
D L S
2 0 0 0
I 5 0
2 0 0 0
1 1 0 0
2 0 0 0
1 3 0
2 0 0 0
1 5 0
2 0 0 0
1 7 0
2 0 0 0
1 1 0 0
2 0 0 0
L.euconostoc mesmteroides
ca. 5% branched WaterlNazHPOz, 2 0
(0.05 mol/dm )/NaH 2P04
(0.05 mol/dm )
highly branched Water/NazHPOd 2 0
(0.05 molldm )/NaH *PO4
Dextran
(0.05 molldm )
2.(Diethylamino)ethyI-dextran
DEAE PL I 0.8 M sodium nitrate
DEAE PL IO
DEAE PL IS
DEAE PL 40
DEAE PL 100
DEAE PL 400
DEAE PL 900
p-De&n Water
Ethyl cellulose Acetone
sym-tetrachloroethane
Ethyl hydroxyethyl cellulose
ca. 18% ethoxyl Water
ca. 30% ethoxyl + hydroxyethyl
2 0
2 0
2 0
1. 58
11. 30
2 1
4 5 . 7
1 3 1
4 2 9
1474
1. 134
7 8 . 8
5 2 . 1
3 5 . 9
1 9 . 4
I I .45
2 0
0. 48
5. 53
4. 8 1
4. 33
3. 48
3. 02
1 7 . 6
7 . 8
5. 52
3. 56
2. 04
1. 13
0. 709
5 . 7
7 . 5
9.x
1 4 . 6
2 1 . 4
3. 46
5 3
9 0
1 9 0
1. 43
1. 05
2 1 . 9
2 0 9 2 2.0 1 . 9
1 7 5 0 0
1 7 5 0 0
2 1 1 0 0
2 1 1 0 0
2 1 1 0 0
2 1 1 0 0
1 1.2-437
0. 38 - 45. 2
0. 61 - 51. 0
0. 54 - 46. 3
I .48 - 49.3
1. 23 - 47. 1
0. 98 - 29.4
0. 35 - 31. 6
0. 85 - 37.9
0. 73 - 33.4
0. 60 - 38.2
0. 52 - 28. 1
1. 45 - 53.7
1. 15 - 54.0
1.5779.82 8.80- 1. 40 1.74-3.22 0.61 1
2X. 8 0. 603
s, - 3. 43 x Iors M42
1.A
0.627
0. 885
0.864
1 4 0 2. 32 I .4
2 0 0 2. 63 1.1
3 0 0 3 . 0 0 . 8
92-300 s=3.1 x 10-15 MO.36 D,= 10-4 M-0.
3 0 3 . 8 0. 721
3 0 4 . 1 0. 711
3 0 5 . 1 0. 703
3 0 6 . 0 0. 705
MLA; .rt; DA
see Ref. for
.f~/f,,, and Do
M ,.A; .y,; D,
see Ref. for
f;~/f\~ and Do
Irj)=3.34cm/g
[T/I = 8.72 cm/g
[7)1 = I I .59 cm q/g
[r/j= 19.45cmZ/g
17jj=31.49cm/g
1~~1=52.15cm/g
[ql=65.73cm/g
C= 1 g/dmZ
M\.01DA
Cz6.1 g/dm; see
Ref. for D
C=5.0g/dm3
C=5.16g/dm
M
Mr.w; s,; D,; D A
given in Ref.
MA,w; S,
References page
TABLE 10. contd
Polymer Sol vent
4
s
\
a
h
T ((3 M ( x 10m3) (g/mol) s0(x103)(s) k s (cm 3k) Do (x 107) (cm2/s) k. (cm3/g) fo/fsp 212 (cm3/g) Remarks Ref s.
M,;so; 11v; M,;so; 11v;
C=5.7-298g/dm3 C=5.7-298g/dm3
782 g 782 g
55
zz
MM D Msp; D Msp; w,w, w,w, W.02 W.02 7 8 1 7 8 1
DA, given in Ref. DA, given in Ref.
33
Ficoll (Pharmacia) Water 2 5 4 0 0
Galactomannan
Carob
Guar
Lotus I
Lotus II
Lucerne
Redclover
Galactomannan
S. japonica
S0ybt2n
Water 2 0 3 1 9 4. 65 0. 97 0.629
6 5 7 5. 33 0. 54 0.635
3 . 1 1. 35 2 4 . 2 0. 628
3 3 2 5. 43 I .09 0.630
2 3 9 1. 69 2. 14 0.636
4 1 6 4. 8 I 0. 77 0.630
4. 37
152 3. 02 1. 32 0.629
1 6 . 6 I .I2 6. 90 0.634
0. 76
4 7 0
125
3 3 0
4 2 0
5 4 5
0 . 1 9 0
2. 82
4. 45
4.90
5. 65
2 3 . 5 - 5 0
0.678
1. 86 3. 96 0. 701
I.1 I 4.18
0. 96 5. 12
0. 85 5. 29
125-545
1 5 0
s = 1.0 x lo-l5 M4h
I.W
2. 89
13
13
13
7 3
13
13
11
17
6 0
I10
loo0
1 . 8
1. 72
1. 87
2. 17
2. 28
2. 36
2. 54
101. 4
96.8
7 4 . 8
5 9 . 2
44.4
0.773 M,~D; M,,o/Mn < 2 sn
2
783 n
0. 332
5 . 0
5 . 0
3 . 0
2 . 1
1 . 9
0. 57
1 7 . 3
1 4 0. 83
7 0 . 6 1. 29
1 5 1 1.61
3 0 2 2.50
22.6 0.79
2 4 . 3 0.79
3 4 . 3 0.89
38. I 0.89
1. 49
0. 92
0. 7 I
3. 05
2. 34
3 . 0 0. 68 M, ; S E
M,,A; s,; DA
0.704
0.710
0.683
3 . 9 0. 717 M, ; SE
0.720 M,,A; s,; DA
4 . 5 0. 73 M, ; SE
k,. km a.,, an
given in Ref.
Mw; D,,o; DLS
M
Mr,w; s,; 7~2 at 20C
7 6 8 E
148 5
9 8 *
8
g
9 8 f
7 8 2 .m
182 E
i
g
Glucose carbanilate I ,Cdioxane
Hydroxyethyl Water
2 0
1 9 . 2
2 5
Hydroxyethyl
Natrosol 250 G 2 5
M
I.W ; S!
M,,o; so; 9v;
C = 0.4-48 g/dm
M. 9, " ; so; I I v;
C=l.l-98g/dm
Hydroxypropyl cellulose
Klucel-L Water
Water
2 5
2 5
3 0
3 4
31
4 0 ( T=O)
w
19. 20
2 2 2
19. 20
2 2 2
M, ; C= IOg/dmj
Maltotriose carbanilate I ,4-Dioxane
Methyl cellulose
22.6% methoxyl Water
27.05% methoxyl
27.44% methoxyl
28.45% methoxyl
28.8% methoxyl
2 0
2 0
3 I .I% methoxyl
3 1.8% methoxyl
ca. 28% methoxyl ~2 = 0.0560 + 0.0542 Cm, (C in%)
srJ=0.85 x Io-5 Mpi5
19,20
Do =7.9 x 1 0 ~5M,-,o.56
(
Water/N&I (0.2 mol/ 2 0 1 4 . 1 4.45 a. of M not 2 1
dm) specified; see Ref. for D
2 4 . 3 3. 05 C=5.0g/dm3; s ee
Ref. for D
3 8 . 1 2. 47 See Ref. for D
Xanthan Water (deionized) RT 2ooo 0.242 D,,; DLS 7 8 5
2 0 0 0
Water/NaCI (0.3 mol/dm))
M, ; D,,o; DL S 785 g
2 0 0 0 0.194 D
Water/NaCl (I mol/dm )
L.0; DLS 7 8 5
CL
2ooo 0.155 7 8 5
Water/urea (4 mol/dm 3,
3
Q
(heat treated) 2 0 0 0 0.280
7 8 5
c
Water 2 5 9000 0.166
s
M,; D,,o; DLS; 786,787
0.1 M NaCl C=O.O25-0.1%
J
na t i ve
2 9 4 0 0. 155 8 7 3 D L S 101 I,1012
:
pyruvate-free
1 3 7 0 0.260 2 9 6 5
acetate-free
I770 0.260
231
E.
s
6
3
-.
m
1
-Y
2
a
-.
L
TABLE 11. OTHER BIOPOLYMERS [PROTEINS, POLY(NUCLEOTIDES)]
Polymer T (C) M ( x 10 -3) (g/mol) sg ( x 103) (s) k s (cm3k$ DO (x 10) (cm*/s) kn km-k) fo/fsp ~2 (cm/g) Remarks Refs.
P-Alanine
Aldolase
Water 2 5
3 6
Poly(y-benzyl-L-
glutamate)
Dichloroacetic acid
0 to 100 vol% 2 5
NJ-Dimethylformamide 2 1
2 5
2 5
4 0
101. 4
147. 1
2. 65 D,k,, =-
5 3 0 3.8-4.2
59-364 s c
=2.8x lo-l4 Mo2 D,=2.8x lO-3 M-O8
3 0 0 100 I.1
5 5 0 1 8 0 0. 75
51-410 1.62-3.91 9-141
36.4-4350 I .77-3.95 15-141
D; C= I mass% 7 8 8
0. 07
DO.G &m/T=
789.7 I8
13. 04
0.786
0.779
Mv; s
MQ; for s, and D,
see Ref.
CLS
CLS
for sg and k,, see Ref.
CLS; for s, k,? and
MA see Ref.
5 6 6
5 5 9
581
4 3 4
450
helix to coil transition between 60 and 80 ~01%
References page VII - 198
TABLE 11. co&d
Polymer Sol vent
2
\
T (C) M ( x 10m3) (g/mol) so ( x 103) (s) k, (cm3/g) DO (x 107) (cm*/s) kn (cm3k) fo/fsp w (cm3/g) Remarks Refs. g
Poly(y-benayl-n,L-
glutamate)
Poly(L-lysine)-
hydrobromide
Benzylalcobol
Water/NaBr (3.02 x
IO- mol/dm3)
Water/NaBr (7.41 x
lO~*mol/dm)
Water/NaBr (5.75 x
10-j molldmj)
Water/NaBr (2.00 x
IO- mol/dm7)
WaterlNaBr (7.41 x
lO-4 mol/dm)
WaterlNaBr (6.92 x
IO -5 mol/dm )
Poly(adenylic acid)
Water/NaCI
(0. I mol/dm )
Water/NaCI
(0.01 mol/dm 3,
RT
2 5
3 0 3 0 0 I .33
7 0 3 1 8 0. 4763
2.5
2 0
8 3
2 2 0
3 7 0
3 8
13
8 0
9 5
200
2 1 0
5 6 0
3 2 0
2 . 2
3 . 0
3 . 5
I .30
0.84
2 . 0
6 . 8
3 . 9
4 . 9
M, ; D,
M,; M,, =29000;
Do,, given in Ref.
M,; M, =43000;
Do.~ given in Ref.
M, ; M, =48000;
Do,, given in Ref.
M, ; M, =55000;
8 4 . 8
8 4 . 8
8 4 . 8
8 4 . 8
8 4 . 8
8 4 . 8
3 5 0 0
3 5 0 0
IS.0
1 8 . 6
3 3 . 5
3. 70
II
c,=~x 10~2g/cm; Dz2. 6~ lO~cm/s
cp=l x 10-3g/cm; D=2. 2x I O cm*/s
cp=5x 10-4g/cm; D=2.Ox 10~cm2/s
cp=3x IO -g/cm; D=3.0 x 10~7cmZ/s
c,=l x IO-g/cm; D=2. 4x IO-cmls
cp =S x IO-g/cm: 0~2. 2 x lO~cm/s
(.*=5x 10~Zg/cm;D=18x 10m7cm2/s
cp= I x IO-g/cm; D=8 x 10~cm2/s
c,=l x 10-4g/cm; D=l.7x lO~cm*/s
cp=5x IO-g/cm; D=32x lO~cm*/s
cp = I x IO-g/cm; D= II x 10~cm2/s
c,=5x 10~5g/cm;D=l.6x IO-cmk
c,=3x IO-g/cm;D=30x 10m7cmZ/s
cp=7.5x 10-4g/cm7;D=12x IO-cm/5
c-,=8x 10~5g/cm;D=l.9x 10-7cm2/s
c,=5 x 10-g/cmX; 0=40x lo-7cm*/s
c,, =3 x 10m3 g/cm3; D=42 x IO-cm*/s
c,=lSx 10-3g/cm;D=30x lo-cm/s
0.84
0. 38
Do, , given in Ref.
M, ; M, = 101000;
Do,, given in Ref.
M, ; M, = 128000:
DO,, given in Ref.
M, ; M, =l 90000;
Do,, given in Ref.
M, ; IOV (C =0.5X-
15.0X gldm )
D, ; C=4,8g/dm; 8 8 3
D L S
D, ; C=2.4g/dm3; DLS
Bovine plasma albumin
Bovine serum albumin
denaturated
gl obul ar
Casein micelles
asI-casein
Chromatin subunit
Chymotrypsinogen
Col l agen
na t i ve
D N A
calf thymus
Waterkacodylate (pH = 7.4)
WaterlNaCI
(0.2 mol/dm 2,
18-22
WatedNaCI (0. I mou 2 0
dm)/phosphate
(0. I mol/dm ; pH = 7)
Water (pH = 5.2) 2 0
water 2 5
3 6
Water/N&l 2 2
(0. 10PO.lS mol/dm)
WateriTris/HCI 2 0
(0.5 mmol/dm; pH = 7.4)
( IO.0 mmolldm ;
pH = 7.4)
(100.0 mmol/dm ;
pH = 7.0)
( 120.0 mmol/dm ;
pH = 4.7)
(1000.0mmol/dm7:
pH =7.X)
Water/Gdn-HCI 3 0
Water/phosphate buffer 20
Water/phosphate 2 0
buffer (pH = 6)
Water/Gdn-HCI 2 5
2 5
0.2 M phosphate
buffer, pH = 6.7
3 5
Water/N&I (0. I-2
mol/dm )
WatedCdn-HCI 3 0
2 5
Water/NaCI (0.2 mall 18-22
dm)
water 5
Water/NaCI (0.2 mol/
dm )/Na2EDTA
(0.0 I molldm 3,
Water/N&l (0.1 mall
dm3)
I2
2 0
2 0
2 0
2 0
2 0
3 5 0 0
6 8
6 7
6 9
6 9
3 4 0 0
5 . 1
2 5 . 7
2 9
1 4 5 0 0
I56
4 . 5
2 2 . 0
0.10
5.8fO.l
Mw; Do,; DL S 8 7 6
D, M, =4.0 x 10~2cm/s g/mol C=25% 8 5 2
6.70
9. 03
1 6 . 5
5.65 + 0.35
6.00
5. 50
6 . 1
5.90
5.00
I.907 Dok D =(3.26 x IO - cmlgls
5.76 + 0.05
I.907 D,,kD=3.28 x I O cm/g/s
6. 69 DokD=-4.52x 10~hcm/g/s
0.45 * 0.03
3.4- I .8
3. 15 DokD=-0.70x 10mhcm5/g/s
3. 15 DokD=-0.70x IOmhcms/g/s
7. 4f 0. 3
4.36
4.32
4.12
0.86f0.02
0.2231tOo.06
0.080 D,; DLS
2. 06 CLS and DLS
D,; C=O.l2g/dm; DLS
Dw
D; C= I mas s %
D; c= I mas s %
DO./; DLS
DLS; Gdn = Guanidin
stLw; sv
Do,,; DLS
D,,,,; DLS; Gdn =
Guani di n
Dar; DLS
F
8 7 2 P
7 8 8
3
8
7 8 8 P
8 7 9
c
g
7 4 0
5
CL
0
7 4 0 3;
5
3
x 7 3 :,
8
8 7 4 2
:
87.5 9
2
7 1 8
8 7 7
$
8 7 8
s.

7 8 9 o
s
7 8 9
if
3
P
1048 J
0 .
n
1.
M,/M, = I .07; see Ref. 8 8 0
a
s

DLS; Gdn = Guanidin 718 p


DLS 7 8 9
c
Mw; Do.w; DLS
%
876 o
-h
D,; C = 158g/dm;
0
881 5
D L S 7
D,; C= 157g/dm; DL S E
D,; C= 147g/dm3; DL S
8
D,; C=O.4 mass%; DLS
0
D,; DLS; pH=6.5
-3
884 $
8 8 5 , 8 8 7 <
1014 F
5
References page VII - 198
TABLE 11. contd
Polymer Solvent T ((3 M ( x 10 -3) (g/mol) so ( x 103) (s) k. (cm%$ DO ( x 10) (cm*/s) kl, (cm344 folfsp vu1 (cmk) Remarks Refs.
E
Water/NaCl (0.5 mol/ 2 0
dm)
Water/NH SAC 20
(0.4 mol/dm )
Water/LiCl (5.5 mall 2 0
dm)
Water/NaCl (0.14 mol/ 2 5
dm))lIiis (0.01 moUdm)
Water/NaCI (1 .O mall 2 0
dm)
Water/NaCl (I .O mol/ 22-23
dm3)/EDTA
WaterMaCl 22-23
(I .O mol/dm )
Water/NaCl 20
(0.8 mol/dm3)
WaterMaCl (I .O mol/dm )
Water/NaCI (I .2 mol/dm )
Water/NaCl (I .4 mol/dm )
WatermaCI (I .5 mol/dm )
Water/NaCI 2 0
(0.8 mol/dm)
Water/NaCI 2 0
(0.8 mol/dm )
Water 5
10000
II700
10300
20.0 0.114
17.1 0.096
9.3 0.130-0.193
0.05
D,; DLS; see Ref. 885,887
3
D,; DLS; pH = 8 8 8 6
8
7
D,; DLS; pH=7 887 $
5
D,; C=0.04g/dm3; 8 8 8 , 8 8 7 p
DLS; pH = 9.6
0
D,; C=OMg/dm;
i
DLS; pH = 10.3
e
D,; DLS; urea (2 mol/ 8 8 9
dm ); phosphate buffer
8
8
g
D,; DLS; 889 f
C=0.7g/dm3 .F
D,; DLS; C = 0.35 g/dm
E
histone (]:I)
pure
histone FI (I:I)
histone FzA (l:I)
E. coli phage 14
Gelatin
WaterMaCl
(0.8 mol/dm )
Water/NaCI
(0.8 mol/dm )
Water
2 0
2 0
2 0
2 0
Formamide 2 5
Glycoprotein ovomucoid Water
Glycoproteins
Blood-group
specific glycoprotein (human)
Butyrylcholinesteras (horse)
Cervial (bovine)
Fibrinogen (human)
Frothrombin (human)
Submaxillary (ovine)
1500
1500
1500
1500
1500
(1.9f0.2) IO5
(1.925f0.066) IO5
2 9 2
3 4 6
371
0.118
0.15
0.14
0.265 f 0.008
0.234 f 0.009
0.183 zt 0.005
0.187f0.005
0. I86 f 0.005
0.155+0.003
0.166f0.012
4.36
0.103 f 0.004
0.259 f 0.009
0.25 x 0.03
0.295 f 0.003
0.358 35
0.324 5 0
0.311 63
4.03 DokI,=7.25 x 10-6cm5/g/s
0.731
0.707
0.635
0.725
0.713
0.685
3
D,; C = 158g/dm.;
DLS
D,; DLS
D,; DLS
Do,e; DLS
Do..: DLS
M,/M, =2.3
M,IM, =2.7
M,IM, = I.8
Do,,; DLS
Nonprotein
component 2%
20%
74%
2.5%
10%
41%
5
881 g
%
TJl
8 8 9 i
E
5
E
7 3 8 3
8 9 5 9
1000 ;
g
Submaxillary (porcine)
Tamm-Horsfall (human)
Li popr ot ei ns
HDL (human)
HDLz (human)
LDL I (porcine)
LpB (human)
VHDL I (human)
Nucleoproteins
Alfalfa mosaic virus
Bacteriophage fd (E. cd)
Bacteriophage R 17 (E. cd)
Bacteriophage T 7 (E. coli)
Bacteriophage T 2 (E. coli)
Fog virus 3
Nucleosome (chicken)
30 S Ribosome (E. cd)
Southern bean mosaic virus (cowpeas)
Tobacco mosaic virus
Metalloprotein
Ferritin (horse spleen)
haemocyanin Water/N&I (0.1 mol/dm )/
(M. trunculus) acetate buffer (0. I mol/dm x,
Haemoglobin Water 13
Histone (lysin rich)
Lysozyme
Ni t r ochi t i n
Polynucleosome
15 6.46
18
21
24
27
30
33
35
37
Water/NaCI (0.14 moV 2 5
dm3)mris (0.01 mol/dm ))
Water 20
Water/NaCI (0. I mol/ 2 0
dm3)/phosphate buffer
Dimethylformamide 26
Water/Es-HCI
(30.0mmol/dm3)
WaterEris-HCI
(10.0mmol/dm3)
Watermri-HCI
(0.5 mmol/dm 3,
WateuTris-HCl
(0.1 mmol/dm3)
20
II
$0=1.12 x 10-14 MO.29
loom<M,~17m;tnol
(1.03f0.01)-(1.08f0.01)
5.58
6.81
7.38
7.82
8.13
8.33
8.50
8.59
8.61
8.5
IO
10.6 f 0.02
&,=7.02xlO-4 M,
10000 5 M, 5 170000g/mol
0.65
0.61
0.53
0.39
0.66 54%
0.692 28%
0.884 50%
0.897 59%
0.952 72%
0.953 78. 5%
0.83 38%
0.703 16%; RNA
0.7 1 12%; DNA
0.68 I 30%; RNA
0.639 51%; DNA
0.66 55%; DNA
0.713 10% lipide
0.654 45%; DNA
0.601 70%; RNA
0.693 21%; RNA
0.728 5%; RNA
0.589 38% iron hydroxide
D,,,r;DLS; pH = 5.7
D,; DLS; C= 1.25
mass%
D, for C= 17 mass%
given in Ref.
Do,.; DLS; pH = 8
D, ; C=20g/dm3; D L S 8 9 2 F
L&; DLS; pH = 6.0 878
Cc
51
1081
D,;DLS; pH = 7.4 740 2
4
D,;DLS;
0
pH = 7.4 3
D,;DLS; pH=7.4
f
D,;DLS; pH = 7.4
References page VII- 198
TABLE 11. contd
c
E
\
Sol vent T ((2
M ( x 10 -3) (ghnol) sg (x 103) (s) k s (cm -k) Do (x 10) (cm*/s) kD ( cm349 f ol f sp uz ( cm3k) Remarks Ref s.
5
water 2 5 4 0 2. 52 D,,k =3.95 x 10-hcm5/g/s Do,,; DLS 7 8 9 , 7 1 8 v,
Phosphat i dyl choline vesicles
B
D 2O/CsCI 2 5 0. 341 D,; DLS; C= 13g/dm 893 E
(0.001 mol/dm3) 1. 24
9
Serum albumin Water/NaCI (0.2 mol/ 2 0 6 9 4.0 6.1 10.1 DO,,; D, and D, 896 2
dm )/NaF (0.005 mol/dm3) given in Ref.
water 2 5 5 2 . 3 C= I mass% 7 8 8
$
3 6 65.8 C= 1 mas s %
Water/NaCl 18-22 6 0 3.4zkO.l Mw; Do.w 8 7 6
8
(0.2 mol/dm ) ;
Virus R 17 water 2 0 4020 f I70 1.534io.015 Do.,; DLS 894 g
4550iIhO 1.423f0.014 DII.,; DLS
5
88lOf 170 1.246iO.013 &I,,; DLS
.m
47900 zt 1700 0.650 f 0.007 Do,,; DLS 0
50900+1100 0.644 f 0.007 DC,,,; DLS
%
Pr ot ei ns Water/Gdn HCI (6mol/ 2 5 D,,,, = 6. 96 x IO n DLS; n = number 7 8 9
K
dm )/mercaptoethanol (0. I molldm) of chain
5
segments: Gdn = Guanidine
8
g
5
.m
3
7
g
z
5
E
3
.z
ii
5
s
f
F
I
C. SECOND VIRIAL COEFFICIENTS OF POLYMERS
IN SOLUTION
1. Introduction
The behavior of polymers in solution can be described by
the colligative properties introducing the virial coefficients
AZ, A3, etc.
According to the theory of McMillan and Mayer (866-
868), the second virial coefficient of a monodisperse
polymer solution is defined as
A2= WA/GV~~>> j (F, (W,(2) - F&,2)) d (L2)
(Cl)
where NA is Avogadros number, V is the volume of the
system, M is the molar mass of the dissoluted polymer,
Fi(l), Fi(2), and F2 (1,2) are the molecular distribution
functions of species 1 (solvent molecule) and species 2
(solute molecule), and d(1,2) is the differential volume
element in hyperspace. The integral in Eq. (Cl) is called
the cluster integral. The distribution functions for the
molecules, F1 and F2, are to be evaluated at zero
concentration.
There are a couple of methods for the experimental
determination of the second virial coefficient.
1.1. Colligative Properties The vapor pressure depres-
sion of the solvent in a polymer solution is expressed as
Cd -P~)/PI = API/PI
=
V,0C(1/M,+A2C+A3C2+...)
cc21
where py and p t are the vapor pressure of the pure solvent
and the solvent in the solution, Vf is the molar volume of
the pure solvent, C is the mass concentration of the
polymer, M, is the number average of the molar mass, and
A2,A3, . . . are the virial coefficients. For theta conditions,
the virial coefficents are zero.
The freezing point depression, TF,t, of a polymer
solution is
and the boiling point increase, Tg, 1, is
TI - T: = ATa, = Erj C(l/M, +A2 C +A3 C2 +. .)
P-3
with Tf and T1 the boiling point (freezing point) of the pure
solvent and of the solvent in the solution, and EF and EB
are the cryoscopic and ebullioscopic constants.
Second Virial Coefficients of Polymers in Solution VII / 163
The osmotic pressure of a polymer solution can be
described as
rr=RTC(l/M,+A2C+A3C2+...)
63
where R and T are the gas constant and the absolute
temperature. In some cases B = RTA2 is given (instead of
A2).
With certain assumptions it is possible to express the third
virial coefficent, A 3, in terms of the second virial coefficient
(379-381). Especially when A2 is small, it is found that,
for example, Eq. (C5) can be approximately expressed as
(Ref. 382)
n- = (RTC/M,)(l + (A2M,/2)C)2
w
if A3 = AiM,/4.
Following Eqs. (C2)-(C6), the dimension of A2 is given
in molcm3/g2 or molm3/kg2.
1.2. Scattering Methods (Classical Light Scattering,
X-ray Scattering, Neutron Scattering) Based on the
fluctuation theory of Smoluchowski (383) and Einstein
(384), which links osmotic pressure with classical light
scattering, Debye (385) established the fundamental
equation for the light scattering of polymers in solution:
KC/R(q) = (Mwpz(q)) - + 2A2 Q(q)C + . . . P)
with q = (47r/X) sin 8/2 and
N
p(q) = (2/N*)
s
(N - a) sinqh,/q h, dn
0
Equation (C7) makes it possible to determine the virial
coefficients from classical light scattering measurements
and can also be applied on X-ray and neutron scattering. In
Eq. (C7), K is a constant and R(q) is the excess intensity of
the scattered beam at the value q, at unit distance and unit
primary intensity. M, denotes the mass average of the
molar mass and P,(q) is the z-mean of the scattering
function from which the dimensions of the dissoluted
polymer can be calculated (h, is the distance between
scattering points 0 and n). The Q(q)-function corresponds
to the q-dependence of AZ. P(q) denotes the scattering
function of a monodisperse polymer.
7.3. Sedimentation Velocity The determination of sedi-
mentation and diffusion coefficient, s and D, yields the
virial coefficients of a polymer solution (Ref. 800):
(D/s)(l -TJ~~~) =RT(1/M+2A2C+3AgC2++
CC81
where ~12 is the partial specific volume of the solute and pi
is the density of the solvent.
References page VII - 198
VII / 164 SEDI MENTATI ON COEFFI CI ENTS, DI FFUSI ON COEFFI CI ENTS, PARTI AL SPECI FI C VOLUMES, FRI CTI ONAL RATI OS
1.4. Sedimentation Equilibrium The sedimentation
equilibrium in an ultracentrifuge gives (Ref. 800)
W2r(i - V2Pl)/(ahc/ar) = RT(l/M + 2A2 C
+3A3C2+-)
(C9)
where w is the angular velocity and r is the distance from
the center of rotation.
1.5. p-V-T Measurements The virial coefficients are
related to thermodynamic quantities
A2 +A3C+... = -#(HC*h)
PO)
where VI is the partial molar volume of the solvent and ~7
is the excess chemical potential of the solvent in the
solution.
Pm
Gz is the molar excess Gibbs energy, G, is the molar
Gibbs energy, and Gz is the molar Gibbs energy of an ideal
solution. With the help of the equation
P-w
&
and consequently the virial coefficients, can be
calculated from p-V-T measurements.
1.6. Averages of the Second Virial Coefficient The
average of A2 for heterogeneous polymers is rather
complicated and depends on the measuring method. If A2
is obtained from measurements based on colligative
methods, it will give the average (Ref. 860)
cc 02
A; =
.Is
AuW(Mi)w(Mj) mi drMj = (AZ) w,w (C13)
id) j=O
This is a double mass average of AZ.
Classical light scattering measurements will give the
average (Ref. 860)
AiS = (l/M,)* T T A i Mi Mj w(Mi)w(Mj) dMi dklj
. .
(Cl41
This is a double z-average of AZ. AQ is defined as
s
(FI (WI 0) - fX4j))d(i,j)
(Cl9
where i stands for a molecule of the ith species andj for one
of the jth species.
1.7. Second Virial Coefficient - Molar Mass Relation-
ship The dependence of A2 on the molar mass can be
given by a power expression
A2 = KAMaA
W)
where KA and u A are empirical constants determined for
each polymer solvent system at given values of temperature
and pressure.
In Section C, relationship (C16) is listed whenever
quoted in the literature, in preferences to single A2
values.
1.8. Temperature Dependence, Pressure Dependence
There is no general equation concerning the temperature
and pressure dependence. The equation (Ref. 860)
A2 = (N~/2)(@&40)(1 - 8/T) W7)
where /lo is for the independent part of the excluded
volume, MO is the molar mass of a segment, and 8 is the
theta temperature, has only a restricted validity.
1.9. Abbreviations
A
approx.
CLS
DLS
Cont.
GPC
LALLS
OS
RT
SANS
SAXS
SE
s v
V
v o s
Archibald method
Approximately
Classical light scattering
Dynamic light scattering
Continued
Gel permeation chromatography
Low angle laser light scattering
Osmotic pressure osmometry
Room temperature
Small angle neutron scattering
Small angle X-ray scattering
Sedimentation equilibrium
Sedimentation velocity
Number of single values given in ref. cited
Vapor pressure osmometry
1. IO. Miscellaneous For solvent mixtures, the volume
fraction pi = vi/ C vi is used.
In some cases the second virial coefficient is replaced by
B = RTA2.
Several attempts have been made to find theoretical
explanations for the nonideal behavior of polymer solu-
tions. There exist numerous excellent books on this topic
(272,387,389-398,618,860).
The following tables give second virial coefficients for
different polymer solutions. The polymers are arranged
according to the hierarchial system in this book. In order to
indicate the number of values reported in the original
reference, a number, e.g., 5V is given in the column
Remarks. Values for solvent mixtures of different ratios,
data for different pH etc., are treated separately in some
cases. The user is asked to refer to the original references to
find the detailed data and conditions.
Second Virial Coefficients of Poly(alkenes) and Poly(alkynes) VII / 165
D. TABLE OF SECOND VIRIAL COEFFICIENTS OF POLYMERS IN SOLUTION
TABLE 12. POLY(ALKENES), POLY(ALKYNES)
Polymer Sol vent
TV3 M ( x 10 -3) (g/mol) A2 ( x 104) (mol cm3/g2) Remarks Ref s.
Poly(L-butene)
atactic
i s ot act i c
atactic
i s ot act i c
atactic
i s ot act i c
Poly(ethylene)
n-Nonane
Toluene
Toluene
I-Chloronaphthalene
Diphenylmethane 142
1,2,4-Trichlorobenzene 135
1,2,4-Trichlorobenzene 135
Trichlorobenzene 135
NBS standard
linear
branched
low pressure
Ma&X
high pressure
linear, fractions
n-Decane
1,2,3,4-Tetrahydro-
naphthalene
branched, varying degree
125
81
high pressure 81
low pressure
high pressure, fractionated
low pressure, fractionated
p-Xylene
105
81
105
105- 219
38- 735
2600- 6100
573
1980
125- 465
9- 215
11.2-160
HDPE, linear n-Decane 130 600
LDPE, branched
Lupolen 1840 D
Poly(ethylene-co-
tetrafluoroethylene)
n-Decane 130
n-Decane 130
Di i s obut yl adi pat e 240
35
80
45
45
45
125
135
135
140
135
115
105
44.1-1300
105-935
26. 3- 558
90. 1- 175
115-2160
107
113
120
141
13. 63
32. 1
119.6
82- 89
55
91
99
131
91
570
89
415
11.4-28.9
1.75-2.06
3. 53
3. 12
22. 95, 24. 8
3. 77
17. 6 (WC)
22. 7 (GFC)
26. 6 (WC)
121- 526
310
625
144- 720
20- l coo
145- 700
145- 690
2. 4
6. 05- 1.05
10.8-4.10
6. 57- 3. 73
M -0.32
-_
M -0.25
12.0-0.78
3. 5
3. 9
3. 0
5. 6
15. 9
10. 9
10. 3
- 0. 25 to 0.93
21. 0
19.0
18. 8
23. 5
19. 0
15
11. 4
9. 1
41. 1- 45. 2
20. 1 l-34.37
7. 59
6. 70
4. 17
4. 36
2. 64
2. 17
3. 22
10.5 (approx.)
11.6
10. 6
6. 3 x 1O-3 M-o.15
5. 9- 1. 6
21. 8- 6. 6
26. 8- 1.68
3. 6- 0. 9
0 (approx.)
0. 92
0. 82
23. 1- 15. 9
27. 8- 6. 54
33. 5- 26. 1
26. 2 x lO-3 M-0.24
4. 8
520 5. 0
310 5. 4
520 2. 0
310 2. 4
6 0 0 1. 9
540 1. 97
1160 1.02
321Oi290 0. 5 11 * 0.054
CLS 109
OS 109
O S 3 1 6
9V; CLS; A2M; (cm3/g) 291
CLS 820
CLS 821
CLS
CLS
CLS
CLS
4v; VOS M,/M, = 1.11-4.56
3v; VOS M, I M, =1. 39
vos
M,/M, = 1.03
VOS M, / M, = 1. 08
VOS M, / M, =1. 39
VOS M, / M, =22. 96
VOS M, f M, =9. 24
VOS M, / M, =18. 59
8v; CLS
CLS
CLS
2V. CLS; M, given in Ref.
2V; CLS: M, given in Ref.
231a
231
231
8V; CLS; A2M; (cm3/g) 291
6v; CLS 292
CLS 293
3v; CLS 293
12V, OS 292
4v; os 292
CLS, AZ. , =4. 70 x
10-3 M- o. 17
w
906
CLS
CLS
CLS
820
820
905
9 0 4
822
822
822
822
822
822
822
296
296
296
906
906
1026
References page VII - 198
VII / 166 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 12. contd
Polymer Sol vent T (Cl M ( x 10m3) (g/mol) At ( x 104) (mol cm3/gZ) Remarks Ref s.
Poly(isobutene) Ben.Zene 24-30 1260 78. 1 x 1O-4 (1-(298/T)); CLS; M,
Chloroform
Cyclohexane
Cyclohexane
Dibutyl ether
Ethyl caprylate
Ethyl heptanoate
n-Heptane
30
4 0
25
23
25
25
0
25
25-75
25-75
25-75
26-70
25-75
23
23
25
Heptane/propyl alcohol
90/10
60
25
SO/20
72128
Isoamyl isovalerate
6 0
60
21
23
25
556
722
27-16100
550
26.1
42.9
77.7
181
488
878
1580
3390
7830
14100
2400
391-4700
9lxOi1OOQ
45.0
0.52
Az=0.75x 1O-3 M-O*
A2=3.45 x 1O-3 M-*04
A2=6.88 x 10m3 M-0.203
A 2 = 6.88 x 10 -3 Mwo.203
w
260.0
10.6
9.55
8.40
7.05
5.30
4.55
3.85
3.13
2.68
2.54
5.0
4.39
1.0 (approx.)
674
56
122
230
6 1 2
1100
167-16100
27.1
42.5
81.3
179
487
890
1580
3 3 1 0
7750
50-22
41.0
0.430- 1.62
- 0.234 to 1.69
- 0.363 to 1.14
- 0.358 to 1.093
- 0.270 to 1.012
A2 =3.08 x 1O-3 M-O.**
Az=3.08 x 1O-3 M-O=
4.96
4.45
3.94
3.22
2.65
2.42
2.08
1.78
1.51
A2= 1.49 x lo-* zWo2*
400- 1 9 0 0 2.85-2.75
1900 1.75
1900 1.95
1900 0
1900 0.85
1900 - 0.25
80.4 - 0.23
178 -0. 31
482 - 0.30
872 - 0.33
1600 - 0.40
80.4 - 0. 14
178 - 0.20
482 - 0.20
872 -0. 19
1600 - 0.20
80.4 - 0.06
178 - 0.09
482 -0. 10
872 - 0.08
1600 -0. 10
A 2M; (cm 3/g)
O S
M,/M,zl.2
CLS
CLS
CLS
CLS; A 3 reported
CLS; A3 reported; M,/M, = 1.08
CLS; A3 reported; M,/M. = 1.10
CLS; A 3 reported; M,IM D = 1.09
CLS; A3 reported; M,/M, = 1.10
CLS; A3 reported; M,/M. = 1.09
CLS; A 3 reported
CLS; A 3 reported
CLS; A 3 reported
CLS; A 3 reported
CLS
CLS
CLS; graphical representation
of T-dependence given in Ref.
CLS
6v;CLS; M,/M. = 1.13
6V; CLS; M,/M, = 1.20
6v;CLS; M,IM, = 1.19
6v;CLS; M,IM, = 1.24
6v;CLS; M,IM, = 1.30
CLS
CLS; 1.14<M,/M,<2.28
CLS; A 3 reported
l7V, CLS; different methods of
polymer preparation; see Ref.
3v;CLS
CLS
CLS
CLS; see Ref. for A 3
CLS; see Ref. for A3 899
CLS; see Ref. for A 3 899
308
311
160
317
989
990
898
202
901
454
843
438
202
934
990
898
900
600
56
56
56
56
56
56
899
TABLE 12. contd
Second Virial Coefficients of Poly(alkenes) and Poly(alkynes) VII / 167
Polymer
f ((3 M ( x 10e3) (gimol) At ( x 104) (mol cm3/g2) Remarks Ref s.
2 9
3 1
3 3
Isoamyl isovalerate
Isooctane
Isooctane
n-Pentane
Poly( 1-octadecene/maleic
anhydride)
Ethylacetate
Poly( 1-octene) Bromobenzene
2 5
2 5
0
2 5
8 0 . 4
1 7 8
4 8 2
8 7 2
1 6 0 0
8 0 . 4
178
4 8 2
8 7 2
1 6 0 0
8 0 . 4
1 7 8
4 8 2
8 7 2
1 6 0 0
8 0 . 4
1 7 8
4 8 2
8 7 2
1 6 0 0
8 0 . 4
1 7 8
4 8 2
8 7 2
1 6 0 0
8 0 . 4
1 7 8
4 8 2
8 7 2
1 6 0 0
5
6 . 2
8 . 9
1 1 . 8
1 5 . 8
2 2 . 9
2 6 . 1
3 3 . 9
3 9 . 0
5 6 . 4
6 1 . 4
8 0 . 5
8 7 . 0
9 5 . 0
1 2 2
1 4 0
1 8 0
2 3 0
2 7 0
3 9 3
6 1 2
8 3 2
1100
1 3 6 0
2 4 0 0
9000 i 1000
2 8
3 7
5 1
6 8
9 9
250-4000
CLS; see Ref. for A 3
CLS; see Ref. for A 3
CLS; see Ref. for A 3
CLS; see Ref. for A 3
CLS; see Ref. for A 3
CLS; see Ref. for A 3
CLS
CLS
CLS; graphical representation
of T-dependence given in Ref.
CLS
8 9 9
8 9 9
8 9 9
8 9 9
8 9 9
8 9 9
9 0 2
4 5 4
4 3 8
9 8 1
0 0
0 . 0
0.0
0 . 0
0.0
0. 10
0.10
0. 10
0. 09
0. 08
0.20
0. 18
0. 18
0. 15
0. 13
0.30
0. 25
0. 25
0. 23
0.19
0. 35
0.30
0. 28
0. 28
0.24
0.40
0. 35
0. 35
0. 33
0.30
1. 96
8. 03
6 . 9
6. 61
6 . 2
5. 56
5. 30
5. 00
4.76
4. 42
4. 23
4. 09
3. 93
4. 08
3. 84
3. 72
3. 67
3. 57
3. 51
3. 34
3. 15
3. 14
3. 00
2. 94
1.1
1.2 (approx.)
3.0
2 . 9
2 . 8
2 . 5
2 . 1
3.12-1.62 CLS 4 2 0
References page VII - 198
VII / 168 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 12. contd
Polymer Solvent
T ((3
M ( x 10 -3) (g/mol) A2 ( x 104) (mol cm3/g2) Remarks Refs.
Poly(pmpylene) 1,2,4-Trichlorobenzene 140
isotactic a-Chloronaphthalene 147f 1
atactic Benzene 2 s
Bromobenzene 100
Carbon tetrachloride
i s ot act i c I-Chloronaphthalene
atactic
Poly( 1 -pentene)
(80% tram)
i s ot act i c
Poly(tetrafluoroethylene)
Cyclohexane
Hexane
Toluene
Poly(chlomtrifluoro-
ethylene) mixed
oligomeres
Perfluorotetracosane
Poly( 1-phenyl-1-propene) Toluene
Poly( 1 -phenyl- 1-propene) Toluene
23.0-28.0 12.0- 16.9 Sv; VOS; M,/M, = 10.00 8 2 2
44.5-49.8 12.5-15.0 3v; VOS; M,IM, =5.70 8 2 2
34.7-37.1 23.8-22.4 2v; VOS; M,/M, = 8.60 8 2 2
484 (appmx.) 4.3 (approx.) 3V. CLS; three different 4 4 6
116 (approx.) 3.65 (approx.)
2.16
37-130 2.16
37 1.25-2.50
3. 2 x 1O-3 M-O*
1.21
10.8
- 2- + 46.5
54-69.5
12s
13s
140
2 s
107-1110
4. 3 x 10-3 M-O.16
16.5 x lO-3 M-0.27
3.9 (approx.)
20 x 10-3 M-0.26
2 s 105-17200 1.8-3.2
3 0 549-25.2 0.86-2.96
340 290 zk 20 0.67 ho.13
3 2 5 260f 15% 0.19zt212
2100* 15% O.lOi20%
1450 2.91
1320 3.78
6 1 3 3.58
3 7 2 4.31
2 5 8 3.84
142 4.82
140 4.17
100 5.46
51 6.05
55.9 6.75
43.9 9.50
28.2 9.88
22.1 10.0
15.5 15.7
wavelengths used
3V. CLS; three different
wavelengths used
CLS
OS
CLS
4V; OS; E; (bar cm6/g2)
6V; OS; B; (bar cm6/g2);
values for four more
solvents given in Ref.
CLS
CLS
4v; CLS
1 Iv; CLS; MJM, = 1.1-1.9
7V; OS; (cm4/g)
CLS
CLS
CLS
SE; M,/M, = 1.06
SE; h4,/Mw =1.08
SE; M,/Mw = 1.06
SE; M,IM, = 1.09
SE; MJM, =1.06
318
518,520
518,520
518,520
518,520
3 1 8
3 1 8
31s
3 1 8
8 3 5
6 0 4
1039
1004
1034
1034
TABLE 13. POLY(DIENES)
Polymer Solvent T (C) M ( x 10m3) (glmol) A2 (x 104) (mol cm3/g2) Remarks Refs.
1,4-cis Benzene 28.6 60-293 15.3 (approx.) llV, OS 2 9 7
138 27.9 OS
Cyclohexane 2 s 2 0 16.4 (14.9) OS, (CLS) 9 0 3
4 6 25.0
70.9 13.2 (12.7)
7 6 13.6
130 11.6 (10.3)
355 9.2 (8.5)
5 4 8 (7.9)
9 2 5 (6.7)
2 9 5 0 (4.9)
3 7 4 0 (4.6)
1 6 5 0 0 (3.6)
linear 2 s 11-760 Az=1.32x IO- M-0.28
Az=5.0x 1O-3 ,&22
CLS 9 8 7
18-armed-star 99-1900 CLS
unfractionated 28.6 840-4350
2.92 (approx.) llv; CLS 291
I
TABLE 13. contd
Second Virial Coefficients of Poly(dienes) VII / 169
Polymer Solvent
T (Cl
M ( x 10 -3) (g/mot) A2 ( x 104) (mol cm/g) Remarks Refs.
fractionated
1,Crrans 69%
60-70% unfractionated
fractionated
Dioxane
Toluene
Poly(butadiene-co-styrene)
2530% styrene Benzene
25-30% Cyclohexane
24%
diblock. 32.9-3.59 mass% PST
triblock, 45.9-4.05
mass% PST
Poly(chloroprene)
Dioxane
Toluene
Cyclohexane
Dioxane
Toluene
Butanone
n-Butyl acetate
Carbon tetrachlotide
rrans-Decalin
Chlorinated rubber Butanone
Chlorinated rubber-co-poly(ethy1 methacrylate)
20.72% Butanone
Poly(isoprene)
ci s Cyclohexane
Carbon tetrachloride
natural rubber
epoxidized 10 mole% Chloroform
nitrile rubber 100% hydrogenated
Chloroform
brominated, 0% bromine Cyclohexane
5.8% bromine
7.3% bromine
25.8% bromine
41.5% bromine
43.8% bromine
Poly(isoprene)
long-arm-stars
functionality 2.9-4.0 Cyclohexane
functionality 4.9-18.1 Toluene
Poly(isoprene-co-styrene)
block copolymer Cyclohexane
Methyl isobutyl ketone
Toluene
28.6
28.6
25
25
34.2
34.2
34.2
28.6
28.6
3 0
34.2
34.2
34.2
34.2
34.2
34.2
25
2 5
25
0.4-48.7
1.1-48.7
0.4-48.7
2 9
35
2 9
2 0
25
2 5
7
2 7
7
2 7
25
25
2 5
2 0
3 0
3 0
3 0
143-1640
1070
5400-19000
3400-18000
2300-I 1000
17.4-370
17.9-434
18.2-466
58-112
800-26700
49-514
42.6-62.5
43.6-610
43.0-625
35.8-517
34-170
34.6-516
147-2920
149-3020
156-3180
5 8 7
865
1660
156
4 4 1 0
197
1600
620 f 10%
32.4
71.95
97.2
2 9 5
4 5 2
1700
1300
1300
3 0 0
4 3 0
150
1800
1850
1900
2 9 0 0
3 1 0 0
3 8 0 0
35.2-410
41-6800
221-370
221-370
221-370
7.50 to - 1.63
1.67
0.52 (approx.)
2.6 to -0.4
2.67 (approx.)
18.3-9.48
3.81-1.49
19.4-11.5
13.5 (approx.)
0.9 (approx.)
1.7-1.0
10.0-7.55
5.8-1.64
12.6-8.17
10.1-8.69
6.63-2.16
12.5-9.57
0
2.52-1.24
4.59-2.03
- 0.10 to + 1.49
- 0.074 to + 1.43
-0.05 to + 1.12
3.60
-0. 18
4.80
6.5
5.0 + 20%
0.123
0.114
0.109
0.104
0.088
14.2
14.3
11.7
12.7
6.2
3.30
3.34
14.3
9
4.5
2.6
0.4
0
7.0-12.6
1.6-9.4
5.5 l-4.40
1.25-1.74
9.04-10.2
4v; OS
4v; CLS
8v; OS
4v; OS
4V; OS
4v; OS
8v; OS
6v; OS
8v; OS
7v; CLS
7V; CLS
7v; CLS
12v; CLS
13v; CLS
12v; CLS
OS
CLS
OS
M.,o; B; (bar cm6/g2)
OS
CLS; M,IM. given
CLS; B; (bar cm6/gZ)
CLS: B; (bar cm6/gZ)
OS; values for CLS in Ref.
CLS
CLS
CLS S (bar cm6/gZ) 9 3
16v; CLS
28v; CLS
CLS; values for OS given
in Ref.
CLS; values for OS given
in Ref.
CLS; values for OS given
in Ref.
2 9 7
2 9 7
2 8 8
2 8 8
2 9 7
2 9 7
344
4 7 8
4 7 8
4 7 8
2 9
5 0 8
9 2 7
2 8
5 0 8
9 8 0
980
31
9 8 8
9 8 8
4 9 5
4 9 5
4 9 5
References page VII - 198
VII / 170 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 13. contd
Polymer Sol vent
T (C) M ( x 10m3) (g/mol) A 2 ( x 104) (mol cm3/g2) Remarks Ref s.
Poly(isoprene)/Poly(ethylenepropylene)
star polymers Cyclohexane 61 8.06 CLS 9 2 8
Methylcyclohexane - 13.5 2.91 CLS
Tetrahydrofuran - 4.2 11.1 CLS
Methylcyclohexane-d t4 - 61 8.24 SANS 9 2 8
- 13.5 3.03 SANS
4.2 5.5 SANS
TABLE 14. POLY(ACRYLICS)
Polymer Sol vent T (Cl M ( x 10 m3) (g/mol) A2 ( x 104) (mol cm3/g2) Remarks Ref s.
Poly(acrylamide) Dimethylsulfoxide 25 1100 1.3
Ethanolamine 25 1500 1.3
Water 25-60 3 9 0 217 x(1-(235/T))
25 4700 0.64
1100-2000 4.9-5.4
25 1400 1.8
Aq. NaCl 0.1 M 4 33 3.3
9.5 4.5
18 5.2
25 6.1
2 8 6.0
39 6.5
4 9 6.8
6 0 6.8
4.5 2 2 0 2.0
14 2.4
24.5 3.0
25 2.8
34.5 3.0
4 4 3.1
55.5 3.2
2.5 6700 0.3
6.5 0.5
10 0.7
18.5 1.1
26.4 1.3
3 0 1.8
Aq. NaCl 0.2 M 2 0 255-2750 3.06-2.81
Aq. NaCl 0.5M 25 900-1400 5.3-7.7
Aq. NaCl 1 M _ 25 2 3 3 0 3.66
1710 3.14
2 1 3 0 0.43
3 6 7 0 0.29
Poly(acrylamide-co-3-(2-acrylamido-2-methylpropanedimethylammonio)-l-propanesulfonate) (AMPDAPS)
AMPDAPS 1 mol% Aq. NaCl 1 M 25 3200 2.67
5 mol% 12400 1.76
9.6 mol% 7 0 0 0 1.49
10 mol% 2 1 5 0 0 1.69
27.7 mol% 8 2 0 0 1.33
38.9 mol% 15100 0.75
40 mol% 17500 1.21
58.8 mol% 5400 0.49
70.1 mol% 6200 0.48
100 mol% 3OOa 0.25
Poly(acrylamide-co-sodium acrylate) (AM)
100 mol% AM Water 25 5 0 0 0 5.1
3.7
Aq. Na2S04 0.1 M 5OOa 2.5
2.4
83 mol% AM 5 2 9 0 3.8
CLS
CLS
CLS
CLS; (J cm6/g2)
5v; CLS
5v; CLS; M, I M, =2. 5p
dependence given in Ref.
CLS
827
82-l
308
93
827
832
9 7 4
CLS; M, I M, =1. 7
CLS; M, j M, =2. 2
M, / Mw = 1.44-1.73
6V; CLS
Deuterated monomer
Microemulsion
Microemulsion, deuterated
CLS
833
8 2 7
1008
1010
CLS 1036
LALLS
CLS
LALLS
CLS
Second Virial Coefficients of Poly(acrylics) VII / 171
TABLE 14. contd
Polymer
T (C) M ( x 10 -3) (g/mol) A2 (x 104) (mol cm/g*) Remarks Ref s.
70 mol% AM 5 5 5 0 4 . 8
55 mol% AM 5 9 6 0 8 . 1
36 mol% AM 6 1 1 0 1 2 . 3
9 . 7 LALLS
9.4 mol% AM 6 4 5 0 8 . 9 CLS
1 . 7 LALLS
Poly(acrylamide-co-sodium acrylate)
5.6 mol% AM 6 1 6 0 5 . 5 CLS
6 . 8 LALLS
3.7 mol% AM NaBr 0.5 M 6500 2 . 8 CLS
Poly(acrylamide-co-sodium-3-methacrylamido-3-methylbutanoate)
(AMI (NaMAMB)
0 mol% AM 0.1 M NaCl 2 5 2 6 0 0 3 . 5 CLS
31.7 mol% AM 2 0 0 0 3 . 2
42.7 mol% AM 4 2 0 0 3 . 3
58.1 mol% AM 6 6 0 0 3 . 5
70.4 mol% AM 6900 3 . 1
87.9 mol% AM 7200 3 . 2
100 mol% AM 8 9 0 0 3 . 5
Poly(sodium-2-(acrylamido)-2-methylpropanesulfonate-c~-(2-(ac~lamido)-2-methylpropyl)t~methylammonium chloride)
(NaAMPS) (AMPTAC)
0 mol% AMPTAC Aq. NaCl 1 M 2 5 6 1 2 0 0. 92 CLS
14.7 mol% AMPTAC 8 2 2 0 0. 49
36.1 mol% AMPTAC 6 2 0 0 0 - 0.02
45.4 mol% AMPTAC 7 9 2 0 0. 59
51.7 mol% AMPTAC 7 6 8 0 0. 76
65.7 mol% AMPTAC 4 9 8 0 0. 34
100 mol% AMPTAC 1 4 7 0 2. 11
Poly(acrylamide-co-sodium-2-(acrylamido)-2-methy~propanesolfonate-c~-(2-(ac~lamido)-2-methylpropyl)t~methyl ammonium chloride)
(NaAMPS) (AMPTAC)
mol% (NaAMPS)/mol% (AMPTAC)
0.5/0.5 Aq. NaCl 1M 2 5 6 0 3 0 2. 95 CLS
2.5 12.5 2 7 8 0 I .65
515 5 0 7 0 2. 00
IO/10 5 8 7 0 1. 57
15/15 6 7 7 0 1. 31
10/5 3 8 8 0 1. 56
Poly(acrylamide-co-sodium-3-acrylamide-3-methylbutaooate-c~-(2-(ac~lamido)-2-methylpropyl)trimethylammonium chloride)
(NaAMB) (AMPTAC)
mol% (NaAMB)/mol% (AMPIAC)
0.5/0.5 Aq. NaCl 1 M 2 5 3 4 3 0 3. 61 CLS
5.1/5.8 1 3 9 0 0 1. 66
7.916.2 3 4 5 0 1. 63
9.719.8 1 0 8 0 0 2. 06
11.5/14.0 1 2 2 0 0 1. 75
13.6/10.7 1 9 4 0 0 1. 85
4.5110.2 1 1 2 0 0 1. 84
Poly(acrylamide-co-maleic Aq. Na NO? 2 1 . 5 2 4 . 4 4.0
anhydride)
Poly(acrylic acid) Aq. NaCl I M 2 5 500 2 . 8
0.1 M 1 3
0.01 M 8 8
IS: 0.102-0.994 2 7 . 5 7 7 0 5.95-196
Dioxane - 2 3 0 - 0. 1
4 2 0 0 . 1
8 9 0 0 . 2
1 5 1 0 0 . 2
2 4 4 0 0 . 0
5 6 0 0 0 . 3
I ,4-Dioxane 2 5 134-1220 28.0-18 5V, CLS; A 2M; (cm3/g)
0.2 M Hydrogen 20-68 1 1 0 0 49.9 x (l-(287/7)) CLS
chloride
sodium salt Aq. NaCl 0.01 M 2 5 6 4 7. 98 OS; B; (bar cm6/g2)
0.05 M 5 8 . 7 I .22 OS ;
0.1 M 30-644 0.68 (approx.) 6v;
l.OM 5 8 0. 07
1 0 3 6
1 0 2 5
1021
1 0 2 2
1 0 2 3
CLS 8 2 8
CLS 8 2 9
6V; CLS; IS = ionic strength
CLS
3 2 0
9 7 0
2 0 2
3 0 8
2 5 4
References page VII - 198
VII / 172 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 14. contd
Polymer Solvent
T (C) M ( x 10 -3) (g/mol) A2 (x 104) (mol cm3/g2) Remarks Refs.
Poly(acrylic acid-co-acrylamide-co-3-((2-acrylamido-2-methylpropyl)dime~ylammonio)-l-propanesulfonate)
Lw (AM) (AMPDAPS)
AA/AM/AMPDAPS mol% (in feed)
901515
80/10/10
50/25/25
20/40/40
90/10/o
75/25/O
90/o/10
15/O/25
Poly(n-butyl acrylate) Acetone
Tetrahydrofuran
2 0
3 0 0 0 2. 71
5 4 0 0 2. 95
7 9 0 0 2. 23
4 7 0 0 2. 23
4OQo 5. 76
1 9 0 0 9. 49
7 0 0 0 1. 49
8200 1. 33
32-920 5.0-2.9
2 9 4.8
7 6 4.5
1 1 0 5.0
2 0 0 3 . 9
7 9 0 3 . 4
1 4 8 0 3 . 3
118-245 0.0146-0.0197
Poly(n-butyl acrylate) Tetrahydrofuran
Poly(n-butyl acrylate-co-methyl methacrylate)
mass% 79.5/20.5 Acetone
56144
29.5170.5
Poly(ten-butyl acrylate) Butanone
Tetrahydrofuran
2 5
2 0
2 5
-
Poly(n-butyl methacrylate) Acetone
Carbontetrachloride
2 0
RT
2 0
Butanone 2 3
Isopropyl alcohol
Methyl ethylketone
2 0
2 3 . 1
2 5 . 0
3 1 . 0
4 5 . 0
2 5
Poly(tert-butyl methacrylate)
2 5 2 7 . 7 3. 81
Poly(buty1 methacrylate-co-methyl methacrylate)
50/50 mass% Acetone
Poly(rert-butylphenyl methaccylate)
PoIy(carbethoxyphenyI- Dimethylfotmamide
methacrylamide)
DMF/formamide 90/ 1 0
Ethyl acetate
Poly(cety1 methacrylate) Heptane
2 0
2 0
2 5
22-740 8.0-2.6
24-710 11.0-4.0
27-800 9.5-3.6
306-75 2.37-4.27
1 1 0 4.7
1 8 0 3 . 1
3 5 0 3 . 9
7 0 0 3 . 5
8 2 0 2 . 5
57-490 2.3-1.5
108-582 3.61-1.69
21633 i 1700 A* = 1.760x 1O-3 M,
116-613 3.04-1.33
250-2580 2.08-1.69
117-666 3.65-1.95
108-506 - 0.7 to 0.39
107-650 - 0.15 to 0.1
107-653 0.03 to 0.2
107-653 0.54 (approx.)
109-262 1.44 (approx.)
21633 i 1700 A 2 = 2.585 x 10 -3 M,.*
6 6 . 0 3. 55
1 9 0 3. 14
4 1 4 2. 73
8 3 5 2. 61
1 0 7 0 2. 56
3 4 . 2 5. 63
6 8 . 3 5. 23
1 3 8 4. 53
2 4 2 3. 34
3 4 2 3. 01
6 1 1 2. 79
1 5 5 0 2. 44
70-430
9 9 5
3.2-2.2
2 . 2
200- 1070
1 . 2
6 . 2
3.38-1.9
LALLS
lv; CLS
CLS
4v; CLS
7v: CLS
7v; CLS
7v; CLS
5v; CLS
CLS
5% CLS 5 2 5
5v; OS 2 8 0
CLS 9 1 0
5V, CLS; A 3 reported
IV; CLS
5V; CLS; A 3 reported
4v; CLS
5v
5v
5v
3 v
CLS
165, 205
2 8 0
2 7 9
9 1 0
CLS; Az = 1.25 x IO- M,.5;
anionic polymerization
9 1 2
CLS; A2=7.55 x 10m3 M,025;
free-radical polymerization
5v; CLS
CLS
9v; CLS 2 6 3
1 0 3 5
5 2 5
9 7 0
9 7 0
1 0 3 7
5 2 4
5 1 2
9 7 0
9 1 2
5 2 5
2 6 7
TABLE 14. contd
Second Virial Coefficients of Poly(acrylics) VII / 173
Polymer Sol vent T (C) M ( x lo-) (g/mol) A2 (x 104) (mol cm3/g2) Remarks Ref s.
Poly( l,l-dihydropetlluorobutyl acrylate)
Benzotrifluoride
Methyl perlluorobutyrate
Poly(ethy1 acrylate) Acetone
Tetrahydrofuran
Poly(ethy1 acrylate-co-methyl methacrylate)
50/50 mass% Acetone
Dimethylformamide
Butanone
PolyQ-ethylhexyl acrylate) Tetrahydrofuran
Poly(ethyl methacrylate)
Toluene
Ethyl acetate
Poly(n-hexyl acrylate)
Butanone
Tetrahydrofuran
Poly(n-hexyl methacrylate)
Poly(i-butyl acrylate)
Butanone
Tetrahydrofuran
Poly(isopropy1 acrylate)
highly isotactic Bromobenzene
moderately isotactic Bromobenzene
s yndi ot act i c Bromobenzene
atactic Benzene
Poly(isopropylacrylamide (IPAM)iPoly(acrylamide) copolymer
IPAM = 100 mol% Water
IPAM = 85 mol%
IPAM = 70 mol%
IPAM = 55 mol%
IPAM = 40 mol%
IPAM = 0 mol%
Poly(N-isopropyl- Water
methacrylamide)
Poly(n-lauryl acrylate) Tetrahydrofuran
25
2 0
28
3 0
23
-
23
6 0
6 0
6 0
25
2 0
-
Poly(laury1 methacrylate)
Poly(methacrylamide)
Poly(methacrylic acid)
n-Butyl acetate 23
Water 22-56
Hydrochloric acid 27-53
0.02 M
0.1 M
0.114M 25
l.OM
LiBr in ethanol 0.125 M 25
3 0
2000-38000
5200-14100
55-860
320-80
145-691
132-691
145-711
6 9
180
2 3 0
4 2 0
8 1 0
1040
220-660
2 1 0
2 8 0
4 0 0
4 9 0
8 8 0
1340
660-72
926- 11620
200-2630
100
170
3 2 0
5 9 0
1040
640-4050
2 0 0
4 9 0
7 8 0
1000
74.3-509
109-46
142-564
71.7-703
3 0 0 0
3 1 0 0
4 5 0 0
3 9 0 0
2 2 0 0
5 2 0 0
95
2 6 0
6 0 0
loo0
260-3600
3 2 0
5 9 0
146-682
200-427
84-169
42-383
34-42 1
0.2 (approx.)
0.5
5.0-3.1
10.52 (approx.)
14.6 (approx.)
18.1-14.1
13.3 (approx.)
8.1
4.1
5.3
4.1
3.8
4.3
4.3-3.5
see Ref.
see Ref.
2.6
2.4
2.1
2.4
1.7
2.0
A 2 = 0.0045 M -.*
1.45-1.01
1.38-1.20
4.9-1.83
4.1
4.5
3.4
3.2
2.4
1.77-1.17
4.5
3.6
3.0
3.0
6.21-3.52
5.83-4.12
7.06-3.71
7.27-3.60
2.94
3.01
3.31
3.46
3.62
3.78
Az=5.9x 10m3 M-0.25
w
6.5
2.3
1.6
0.9
1.10-0.47
4.49 (l- (279/T))
14.8 ((329/T)- 1)
1.76 (approx.)
16.9 (approx.)
2.2-0.4
5.2-2.3
4.9-1.8
1ov; CLS
2v; CLS
6V; CLS
1OV: OS; B; (bar cm61g2)
13V; OS: B: (bar cm6/g2)
7V; OS; B; (bar cm6/g2)
5V; OS; B; (bar cm6/g2)
CLS
2 0 3
2 0 3
5 2 5
2 0 8
2 3 3
271
2 7 0
9 7 0
5V; CLS
CLS
OS
CLS
4v; OS
9v; CLS
Calculated act. to Orofino, Flory
9v; CLS
CLS
8v; CLS
CLS
6v; OS
4v; OS
4v; OS
5v OS
CLS
CLS
CLS
5 2 5
5 1 5
5 1 5
9 7 0
5 8 6
4 7 1
162
970
2 9 5
9 7 0
4 2 9
1006
1005
9 7 0
8v; CLS 2 0 5
CLS 3 0 8
CLS: Tin K 3 0 8
3v; OS 2 4 0
5v; CLS 2 4 0
3v; OS 2 4 0
4V; CLS 2 4 9
5v: OS 2 4 9
References page VII - 198
VII / 174 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 14. contd
Polymer Sol vent
T (C)
M ( x 10 -3) (ghol) A2 ( x 104) (mol cm3/g2) Remarks Ref s.
Methanol
0.05 M NaCl
0.5 M NaCl
Water + I M NaCl
x=0.18-0.0007
Acetone
Ethyl acetate
Butanone/isopropanol
58/42
Tetrahydrofuran
PoIy(methyl acrylate-co-chlorinated rubber) 86.9/13.1
graft copolymer Butanone
Poly(methy1 acrylate-co-methyl methacrylate)
50/50 mass% Acetone
Poly(methy1 butacrylate) Butanone
Poly(methy1 ethacrylate) Butanone
Poly(methy1 methacrylate) Acetone
20-40 517 (approx.) 2.42 (approx.) 3v; CLS
20-60 505 (approx.) 1.465-O 4v; CLS
20-40 5 1 0 0.96-O. I 3v; CLS
2 5 1 9 6 O-780 5V; CLS 3 5 5
2 0 77-880 4.5-2.8 5V; CLS 5 2 5
2 5 280-2500 4.2-2.4 17V; CLS 246, 247
3 5 362- 1480 1.92 (approx.) 5v; CLS 4 8 2
2 0 290- 1720 0.1-0.06 8V; CLS 2 4 6
-
3 5
2 0
3 0
3 0
2 0
2 2
2 5
4 9 4 . 1
6 9 4.7
1 0 0 3 . 8
2 6 0 3 . 7
4 3 0 3 . 0
5 7 0 4 . 1
3 3 9 4 0
80-525
75.2-4280
46.1-1910
Poly(methylmethacrylate)
0.2-510
23-5300
200-6550
5 5 0
5 1 0
0.203-0.385
0.691-2.480
341-7800
0.613-20
0.613-50.2
0.613-496
2 0
2 5
3 0
3 5
4 0
44 (0)
4 7
5 0
Acetonitrile 5 5
28-42 20-496
Acetonitrilell -butanol 2 5 1 6 9
!+7M&-N =0.3-0.9
Acetonitrile/pentyl acetate
qMeCN = o- o. 95
atactic
Acetonitrile/l-propanol
y9MeCN = 0. 3- 0. 9
Acetonitrile/methanoI
pMeCN =0.5-l
Acetonitrilekarbon
tetrachloride
PMeCN = 0%
P hkCN = 40%
p p&CN = 100%
2 5 1 2 0
51 54.3
3670 f 50
68-1370
240-4470
27.7-7800
1 4 5 0
2.69-2500
86-1050
92-798
3 4 6
3 4 6
CLS 9 7 0
0.079 CLS 4 7 8
5.5-3.5
2.77- 1 .OO
4.78-1.72
See Ref.
1ov; CLS
1ov; CLS
1ov; CLS
Small angle X-ray scat.
varying tacticities measured
1OV; small angle X-ray scat.
1OV SE. B, ( bar cm6/gZ) 1 >1
3V; SE
CLS; identical samples;
Small angle X-ray scat.
4V; B; (bar cm6/g2); M,
3V B, ( bar cm6/g2). M
1 3 3 n
CLS
8v; CLS
9v; CLS
1 lv; CLS
llv; CLS
1 lv; CLS
1 lv; CLS
11v; CLS
1 lv; CLS
llv; CLS
17v; CLS
7V; CLS
MeCN = acetonitrile
11% CLS
5 2 5
4 4 5
4 4 5
30- 1.5
12.2-1.55
2.25-0.68
1 . 9
1 . 5
- 24.2 to 113.0
627-47.5
1 2
- 4.4 to 6.5
- 3.6 to 8.0
- 3.0 to 9.5
-2.3 to 11
- 1.9 to 12
- 1.5 to 13
-1 to 14
-0.5 to 15
0- 16.5
- 1 to - 0.08
- 0.89 to 2.24
4 9 2
5 2
1 5
4 6 9
4 6 9
4 0 8
4 0 8
8 4 2
9 1 5
9 1 5
9 1 6
- 0.76 to 2.58
- 0.16 to 2.30 7v; CLS
- 0.97 to 0.38 7V; CLS
IOV; CLS
MeCN = acetonitrile
8 2 3
0 . 6
5 . 9
- 0.65
8.2 i 0.61
2.12 i 0.05
2. 9 x 1O-3 M-02*
(7.1-3.5) x 10
2.3-1.1
0.975-0.29
1 9
0.97-390
2.90- 1.58
1.89-1.52
CLS; B; (bar cm6/g2) 4 1 9
CLS. B, (bar cm 6/g2) 3 9 4 1 9
CLS 2 7 3
7V; CLS; 981(cm*/g) 2 3 2
5v; CLS 2 6 4
12V; U-S; (J cm /g *) 9 9
CLS 2 0 2
13v 2 7 5
7v; OS 2 0 2
9v; CLS 2 0 2
TABLE 14. contd
Polymer Sol vent
Second Virial Coefficients of Poly(acrylics) VII / 175
T (C)
M( x 10m3) (g/mol) A2 ( x 104) (mol cm/g*) Remarks Ref s.
atactic Acetonitrile
Acetone
Chloroform
Nitroethane
i s ot a c t i c Acetone
Chloroform
Nitroethane
Tetmhydrofuran
unfractionated
fractionated
Acetonitrile
Acetonitrile
Benzene
fractionated
Butanone
Butanone/isopropanol
58.2141.8
55145
50/50
Butanone/isopropanol
468153.2
Butyl acetate
Butyl chloride
Carbon tetrachloride
Chlorobutane
3 0
4 4
4 7
5 0
5 5
2 5
2 5
3 0
2 5
3 5
4 5
5 5
2 5
3 0
-
-
3 0 . 5
4 0
43.3
5 0
2 5
3 0
2 5
4 - 3 6
4 - 3 6
S-40
18-40
2 5
- 18 to 60
14-48
2 5
4 - 4 8
28-48
28-48
3 5 . 6
486-6620
1 6 1
0.594-204
3 1 2
4 8 2
7 6 5
3 1 2
4 8 2
7 6 5
3 1 2
4 8 2
7 6 5
0.594-1580
2 0 4
3 1 2
4 8 2
165
1 5 8 0
2 0 4
3 1 2
4 8 2
165
1 5 8 0
0.789-1930
6 8 8
1 5 5
3 1 3
3 8 0
6 8 8
9 4 6
1 9 3 0
155
3 1 3
3 8 0
6 8 8
9 4 6
1 9 3 0
9 0
3 0 5
5 0 6
162-641
H-726
1 0
1 0
1 0
0.188-0.935
4 3 3
5-52.8
7 5 . 5
2 1 0
2 1 0
2 1 0
2 1 0
486-6620
2 1 0
2 1 0
0.202-0.155
1.160-4.625
3 0
1 1 0 0
4 6 0 0
200-6550
2.38-0.82
2.63 x 10m3 Mo7*
1. 85
- 1.5 to 12.5
0.100
0.114
0. 107
0.115
0.184
0. 117
0.256
0. 279
0. 292
1.25-47.3
5. 66
5. 06
4.39
3. 91
3. 31
3. 32
2. 97
2. 61
2. 32
1. 99
1.23-17.2
0.20
0.40
0. 51
6. 92
6. 12
5. 57
4. 91
4. 39
3. 80
4. 33
3. 66
3. 41
3. 03
2. 64
2. 33
5 . 0
3 . 9
3 . 2
28.8-88
12.3-95
- 0. 1
0
0 . 2
- 222.2 to 8.9
2. 63
1.38-2.18
2. 70
0.001-0.369
- 0.128 to 0.293
- 0.365 to 0.237
- 0.248 to 0.174
0.96-0.36
O-l.20
- 0.242 to 0.088
40.0-6.7
23.2-0.0
- 1.6 to 0.365
- 0.3 to 0.325
- 0.23 to 0.31
- 0.24 to 0.01
4v; CLS
OS; A *M; (cm /g)
O S
1ov; CLS
CLS
CLS
CLS
19v; CLS
CLS
CLS
16V, CLS; M,/M, see Ref.
CLS; M,IM, see Ref.
CLS; M,IM, see Ref
CLS; M,/M, see Ref
CLS; M,IM, given
12V; OS; A 2 M; (cm 3/g)
5V; OS; A 2 M; (cm3/g)
SAXS
SAXS
SAXS
8V; B; (bar cm6/g2); M,
OS
6v; CLS
CLS
9V 1 CLS. , (J cm3/g2)
9V, CLS; (J cm3/g2)
9V, CLS; (J cm/g*)
7V CLS. ( J cm3/gZ)
1 >
4v; CLS
6v; CLS
1OV CLS, (J cm3/g*) I ,
3V, B; (bar cm /g *); M,
4V, B, (bar cm6/gZ); M.
12v; CLS
7v; CLS
7v; CLS
3v; SD
5 5
2 7 4
4 9 4
9 1 1
9 1 8
9 5 6
2 7 4
2 7 4
4 9 2
4 9 2
4 9 2
4 0 8
4 9 4
4 1 8
4 1 8
1 3
1 3
1 3
1 3
5 5
210, 215
1 3
4 0 8
4 0 8
210, 215
210, 215
210, 215
1 5
References page VII - 198
VII / 176 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 14. contd
Polymer Solvent T (C) M ( x 10m3) (g/mol) AZ (x 104) (mol cm3/g2) Remarks Refs.
unfmctionated
1-Chlorobutane/2- 4 0
butanol pbu =0-0.7991
I-Chlorobutane/2- 40 zt 0.2
methoxy-ethanol
chloroform
Chloroformkmtyl acetate
9% butyl acetate
0
2 0
4 0
6 0
8 0
9 0
100
Dimethylformamide
Dioxane
a-Chloronaphthalene/
toluene ~CNA = 0.72
a-Chloronaphthalene/
polystyrene
(C, = 3.76 gil)
Ethyl acetate
4-heptanone
lsoamyl acetate
lsopentyl acetate
2 5 830-1370 (12-10) x 103
0.204-0.379 - 53.9 to 81.0
0.710-5.240 49.6-21.9
25
38
3 8
172 0.75
2 6 0 0.30
2 7 0 0.31
2 9 4 0.53
2 2 7 0.33
2 1 2 0.5 1
172 0.05
32.2 f 0.3 10.9-0.16
2180 60 6.2-0.08
486-6620 3.24- 1.43
1220-2000 3.1-3.0
5 6 9 0 1.82
5 6 9 0 1.75
3 8 5 6 9 0 -0. 11
16-62
20-60
20-60
25
172-3100 1.9-1.2
2100 -0.76 to 0. 52
2 1 0 -0.276 to 0. 014
2 1 0 0 - 1. 13- 0. 055
20- 1730 (4. 02- 1. 39) x lo-*
linear
Butanone/isopropyl alcohol
55145 23
58.2141.8 4-36
55145 4-36
50/50 8-50
46.8153.2 8-40
Butanone 4 0
randomly branched 48.9-4490 5.02-1.95
unfractionated Nitmethane 25
Tetmhydrofuran
Toluene 30.5
Poly(methy1 methacrylate-co-chlorinated rubber) (45.9/54.1)
graf polymer Butanone 35
Poly(methy1 methacrylate-co-ethylene dimethacrylate)
randomly branched Butanone 4 0
Poly(methyl methacrylate)/90% poly(styrene) (side chains)
gruji polymer Benzene
Poly(n-octyl methacrylate) Butanone 23
Poly(N-phenylmethacrylamide) Acetone 2 0
Poly(pheny1 acrylate) Ethyl lactate 11.55
13.65
2400-2690 O-l.28 12v; CLS
2330-2640 O-116 14v; CLS 9 1 3
2V; CLS; 981 (cm/g) 2 3 2
4V; B; (bar cm6/g2); M. 4 0 8
3V; E; (bar cm6/g2); M. 4 0 8
CLS; apparent values for M, 9 1 4
OS; B; (bar cm6/g2); M, 4 1 9
OS; B; (bar cm6/gZ); M. 4 1 9
4v; CLS 5
2v; CLS 2 9 4
CLS 9 0 8
CLS 9 0 8
CLS 9 0 8
196
210,215
13
210,215
2 7 3
130-2760 (3.04-1.07) x lo-*
760-1400 (5.4-4.2) x lo3
1220 1.6
34-9800 2.78-1.46
410-3260 1.92-1.66
3v; OS
lOv; CLS
llV; CLS; (J cm3/g2)
12v; CLS
7V; CLS; A2M; (cm3/g2);
A3 reported
4v; CLS
4% CLS; 981 (cm*/g)
CLS
1ov; CLS
7v: CLS
2 7 3
2 3 2
2 9 4
2 5 3
163
410-3260 0.08-0.02
2 1 0 0.005 - 1.44
2 1 0 - 0.57 to 1.14
2 1 0 - 1.56 to 0. 91
2 1 0 - 1.02 to 0.68
45.9-940 4.43-2.34
6X CLS
9v; CLS
1ov
1ov
8V
8V, CLS; OS results also
given in Ref.
12V. CLS; OS results also
given in Ref.
3V; CLS; OS resul ts also given
in Ref.
163
210,215
210,215
210,215
210,215
5 7 0
1470-6990 1.44-0.61
22-1710
114-564
5.51-1.68
3.38-1.73
0.67 x 10 - M -.z~
2.6 (approx.)
5.3-1.1
5.7-8.5
6V; CLS; A 3 reported
2V; CLS; A 3 reported
CLS
1220-2000
47-9300
12.3-20
2v; CLS
6V; CLS
3v; OS
2 7 3
2 7 3
2 7 3
2 9 4
121
2 7 4
8 1 5 0 0.36 CLS 4 7 8
See Ref. 11v 5 4 9
1800
3260- 12520
100-3200
1460
0.52
0.77-0.35
4.1-3.2
0.0
6.0
Iv; CLS
7V; CLS
CLS
CLS; M, = 0.90 x IO6 g/m01
8 2 4
2 0 9
2 2 9
9 1 9
TABLE 14. contd
Second Virial Coefficients of Poly(vinyls)
Polymer Sol vent T (C) M ( x 10e3) (glmol) Al (x 104) (mol cm3/g2) Remarks Ref s.
9 7 0
16.65 29.2
22.75 51.7
31.65 68.7
45.45 94.0
59.45 117
74.45 125
89.85 I41
106.15 150
Poly(n-propyl acrylate) Tetrahydrofuran 110 4.0 CLS
2 0 0 5.3
440 3.6
6 3 0 3.3
8 0 0 3.0
9 8 0 2.9
1080 2.9
Poly(sulfodecylmethacrylate) Aq. NaCl 0.1 M 25 7 3 4 1.91 CLS; M,fM,=2.1 1009
Poly(sulfoethylmethacrylate) Aq. NaCl 0.1 M 25 3 0 6 6.41 CLS; M,IM, = 1.5
Poly(sulfohexylmethacrylate) Aq. NaCl 0.1 M 2.5 4 9 4 5.61 CLS; M,fM, = 2.0
Poly(sulfooctylmethacrylate) Aq. NaCl 0.1 M 25 701 2.03 CLS; M,/M, = 1.8
TABLE 15. POLY(VINYLS)
Polymer Sol vent T (42) M ( x lo-) (g/mol) A2 (x 10) (mol cm/g*) Remarks Ref s.
Poly(acrylonittile) Dimethylformamide
highly isotactic, 73.4% iso triades
HNO ; 60-70 mass% 3
HNO ; 70 mass% 3
Dimethylsulfoxide
Poly(acrylonitrile)/vinylidene chloride
copolymer, 5 9 wt.% A N Dimethylacetamide
25
25-40
35
25
25
25
25
Butyrolactone 25
Dimethylformamide 2 5
70 mass% HNO 3 2 5
Poly(n-butoxyethylene) Butanone 25
Poly(ethoxyethylene) Butanone 25
Poly(isopropoxyethylene) Butanone 25
Poly(methoxyethylene) Butanone 25
1041
1132
1235
1371
1778
2 3 6 7
2 9 7 3
3 0 7 8
98-120
9-69
91-762
43-298
27-159
103
33-101
28-575
150-174
158-263
155-2620
4 2
6 2
9 0
140
2 0 4
2 7 0
3 4 8
5 0 0
200
196
215-861
347-409
536-894
13-450
4.217
4.064
3.988
3.589
3.63 1
3.456
3.291
3.311
A 2 = 9.44 x 10 -3 M -.*I9
w
22.9-21.4
4.94 x 10 -* h4 -OJ4
32.2-7.0
2.43 x IO-* M-**
2 1 (approx.)
16-20
18.3
19.1 (approx.)
2.74 x lo-* M -.24
0.073-0.254
0.252-0.420
- 0.002 to 0.153
0.132
0.121
0.120
0.120
0.115
0.110
0.095
0.090
0.119
0.137
0.0075
2.3-0.7
3.4-2.3
1.9-1.7
3.89 (approx.)
CLS
2 Different wavelengths used
5V; OS; (cm4/g)
CLS
7v; OS
OS
CLS
13v; OS
9V;M
4v; CLS
5v; CLS
4v; CLS
CLS; A2 =5.77 x lO-3 M,014
CLS
CLS
CLS
2v; CLS
2v; CLS
2v; CLS
l2V; CLS
603
2 4 8
9 5
199
200
9 3 8
7 4
201
9 7 3
9 7 2
149
149
149
149
References page VII - 198
VII / 178 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 1.5. contd
Polymer Sol vent
T (C)
M ( x 10 -3) (g/mol) At ( x 104) (mol cm3/g2) Remarks Ref s.
Poly(2-methyl-5.vinylpyridine) But anone 2 5
Poly( 1 -trimethylsilyl ethylene) Cyclohexane 2 5
Poly(viny1 acetate) Acetone 30 (approx.)
branched
Methanol 2 5
Benzene 3 0
Methanol
linear
branched
Butanone
linear
branched
Butanone
linear
Tetrahydrofuran
Trichlorobenzene
36 (approx.)
36 (approx.)
2 5
36 (approx.)
branched Trichlorobenzene
Poly(viny1 alcohol) Water
Poly(vinyl bromide) Tetrahydrofuran
36 (approx.)
3 0
7 3 . 5
80
RT
Poly(viny1 butyral) Dioxane 3 7
Poly(vinyl-iso-butyral)
Poly(viny1 caprolactam)
Poly(viny1 carbanilate)
Dimethylformamide
Cyclohexanol
Cyclohexanone
Diethylene glycoV
diethyl ether
Diethyl ketone
Dioxane
2 0
40-90
15-90
5-9.5
Poly(N-vinylcarbazole)
Poly(viny1 chloride) Cyclohexanone
Pyr i di ne
Benzene
Dioxane 3 7
Toluene
Poly(viny1 chloride-co-butylacrylate)
comonomer content (mol%)
1 6 . 6 Tetrahydrofuran
40.0
30 (approx.)
30 (approx.)
36 (approx.)
36 (approx.)
2 5
3 0
20-90
2 0
5-95
IO-90
2 5
37-43
37-43
2 5
3 0
30-70
2 5
2 9
2 5
67-1200
2130-590
27-845
343-722
78-660
2360-422900
258-45.2
5203-331
370-620
1620- 1900
2 9 2 0
3 5 8 0
870-3420
58-367
93-l 100
40-1268
300-772
440-3580
430- 12. 60
13.8-47.7
13x0-3760
2.8-1.2
4.85- 12. 00
8.80-3.34
3.66-3.50
6.5-2.5
7.50-0.172
4.76 (approx.)
0.208-2.066
3.5 (approx.)
1.14-1.3
0. 99
1. 06
3.51-2.43
10 (approx.)
5 (approx.)
7.00-2.95
3.93-2.90
3.2-2.74
2.99-0.66
0.160-0.280
2.29-I .75
5.94 x 10-3 M-o23o
1.69-1.18
3.9-5.2
1. 119
2.189-0.775
6-O
2.7-2.0
5.53-10.3
9.15-11.3
9.45-12.2
6.9-9.6
0.337-0.662
- 1.2 to 1.2 (approx.)
2.2-1.9 (approx.)
2.7- 1.5 (approx.)
13v; CLS
6V; CLS
9v; CLS
CLS
18v; CLS
9V; DLS
10% OS
8V; CLS
2v; CLS
2V; CLS
3V; CLS
llv; CLS
8V, OS; B; (bar cm6/gZ)
CLS. B. (bar cm6/g2) 1 ,
12v; CLS
CLS
1ov; CLS
9v; CLS
3v; CLS
12v; CLS
1610-4110
180-196
2 4 5
100-458
6 - 7 6
104-270
541-89.5
208-73.9
181-57.5
462-207
377-1670
1 1 0 0
19v; CLS
2 v; CLS
CLS
5% CLS
14v; CLS
2v; CLS
8v; OS
5V; OS
Iv; OS
6V; OS
8V; CLS
8V; CLS
6v; CLS
7V; CLS
7.2- 183
1 1 0 0
4550- 136
1 6 3 0
2 2 9 0
42.4-1070
2 9 8
5 2 2
118 (119)
59 (50)
32.3-97.4
9 0
4 8 . 8
44.9
- 0.5- 1.8 (approx.)
(3.4-1.71) X 10-b
2.7-2.2 (approx.)
2.5-2.0 (approx.)
0.57- 1.32
0. 61
0. 54
2.35-0.91
4.26 x IO- Mm*
O - O . 2 7
0.01-0.26
1 1
12 (18)
3.7 x 102
3.9 x (1 +(1613/T))
12.8 x lO-4
16.2 x 1O-4
8v; CLS
1lV; CLS; (cm/g*)
7V; CLS
4v; CLS
CLS
CLS
CLS
8V
2 4 . 8 6. 85
37-110 2.5 (approx.)
1 2 2 1 5
56 (53) 14 (17)
1 3 6 9. 03
3v; OS
3v; OS
A; (CLS)
A; (CLS)
OS; (cm/g)
CLS; M,
OS;
OS; more values for seven
dlfferent PVC-preparations
given in Ref.
OS; (J cm3/g2)
5V; OS; (J cm/g)
A
A; (CLS)
OS
173-302 0.0518-0.0649 4v; CLS
205-632 0.0156-0.0244 3v; CLS
4 3 2
5 5 3
3 3 0
3 3 1
2 8 9
8 3 1
4 5 3
3 3 1
3 3 3
3 3 3
111
1 1 2
1 1 2
3 3 0
3 3 1
3 3 3
3 3 3
1 0 3 7
3 3 3
3 3 3
3 3 3
282, 283
282, 283
282, 283
2 8 7
591
1 0 2 4
5 0 4
5 0 4
5 0 4
4 0 1
5 0 4
5 0 4
4 5 7
4 9 9
4 9 9
4 9 9
4 9 9
4 9 9
6 0 2
6 0 2
1 0 8
308, 309
4 5 1
4 5 1
7 5
7 5
6 0 2
6 0 2
4 7 8
1037
TABLE 15. contd
Second Virial Coefficients of Poly(styrenes)
Polymer T (0 M ( x 1O-3) (g/mol) AZ ( x 104) (mol cm3/g2) Remarks Refs.
Poly(viny1 chloride-co-n-butyl ether)
comonomer content (mol%)
9.2 Tetrahydrofuran
Poly(vinyl chloride-co-methylacrylate)
comonomer content (mol%)
25.5 Tetrahydrofuran
41.6
64.0
Poly(viny1 chloride-co-vinyl acetate)
comonomer content (mol%)
11.4 Tetrahydrofuran
25.0
40.0
66.0
Poly(viny1 chloride-co-vinylidene chloride)
comonomer content (mol%)
15 Tetrahydrofuran
4 2
Poly(vinylchloride-co-poly(ethy1 methacrylate))
84.55%/15.45% Tetrahydrofuran
Poly(viny1 chloride-co-poly(methy1 methacrylate))
45.1%/54.9% graji Tetrahydrofuran
copolymer
Poly(viny1 methyl ether) see Poly(methoxyethylene)
Poly(2-vinylpiridine) Aq. HzS04; 0.01 M
0.1 M
0.25 M
0.5 M
0.75 M
l.OM
5.1 M
10.3 M
Poly(4-vinylpiridine) Ethyl alcohol
Poly(vinylpyrrolidone) Cyclohexanone
Et hanol
Water
Poly(vinylpyrrolidone-co-vinylcaprolactam)
1:1 stat. Et hanol
25
25
25
25
2 9
2 9
25
RT
25
2 0
2 0
25
30-98
221-476
121-891
379-2510
29.5-96.7
21-185
43-179
loo-708
50-223
79-187
161
3 0 2
2 8 8
102-1850
24.5-37.9
63-500
3 1 0
11.6-75.4
19.5-933
3 1 0
0.077-0.115
0.0503-0.0570
0.0316-0.0803
0.014-0.033
0.089-0.119
0.050-0.148
0. 06-0. 118
0.012-0.028
0.0449-0.0910
0.0260-0.0396
4.80
9.55
1 1
2.2
2.1
1.7
1.3
1.4
3.0
3.0
4.13 (approx.)
2.6 (approx.)
1.15-5.47
4.2
3.39 (approx.)
64.7-2.52
4.2
0.457-1.89
3v; CLS 1037
3v; CLS 1037
4v; CLS
4v; CLS
4v; CLS
4v; CLS
4v; CLS
4v; CLS
4v; CLS
4v; CLS
OS
OS
CLS
1037
1037
4 7 8
4 7 8
9 7 7
1ov; CLS 2 8 6
3v; OS 191
8v; CLS 1024
M,/M, = 1.5 9 8 5
12v; CLS 191
6V; CLS
CLS; M, / M, =1.5 9 4 2
8% CLS 1024
TABLE 16. POLY(STYRENES)
Polymer Solvent
T ((3 M ( x 10 -3) (g/mol) AZ ( x 104) (mol cm3/g2) Remarks Refs.
Poly@-bromostyrene) Toluene 3 0 3860-630
Poly(p-rerr-butylstyrene)-b-poly(dimethylsiloxane)-b-poly~-fe~-butylstyrene)
anionically synthetized
diblock Toluene 3 0 92.7
t r i bl ock 115
291
8 2 9
Poly(m-chlorostyrene) Butanone 3 0 1064-322
Toluene 35 1075-145
Poly(o-chlorostyrene) n-Butyl acetate 5 4 1 5
3 0 4 0 3
55 401
Chlorobenzene 3 0 4 0 6
0.076-0.113
4.23
3.24
2.56
2.10
1.44- 1.78
AZ= 1.54 x 1O-3 M-O.
2.42-5.08
A 2 = 26. 5 x 10 -3 M -.33
0.570
0.449
0.337
1.72
5v: CLS 5 1 6
CLS; M, I M, given 9 6 6
5V; CLS 5 9 5
6V; CLS
OS 5 8 5
OS 5 8 5
OS 5 8 5
OS 5 8 5
References page VII - 198
VII / 180 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 16. contd
Polymer Solvent
T (C) M ( x 10e3) (gimol) AZ (x 104) (mol cm3/gf) Remarks Refs.
Poly@-chlorostyrene)
T0luene 25
3 0
35
Butanone
n-Butyl acetate
Chlorobenzene
Toluene
Poly(2.5dichlorostyrene)
Poly(p-methoxystyrene)
Poly(a-methylstyrene)
Dioxane 2 0
Butanone 2 5
Toluene 3 0
Benzene 25
n-Butylchloride 6.9-3540
Poly(a-methylstyrene) Cyclohexane
monodisperse
Poly(a-methylstyrene) Toluene 25
Poly(a-methylstyrene-co-acrylonitrile)
46 mo18 acrylonitrile Tetrahydrofuran
Poly(a-methylstyrene-co-styrene)
50/50 Toluene
Poly(o-methylstyrene) Toluene
Poly(p-methylstyrene) Butanone 3 0 1210-391
Cyclohexane 3 0 847-263
Dichlororethane 3 0 1180-500
21
5
3 0
5 0
3 0
3 0
3 0
2 0 60-313
2 4 61-1020
3 0 180- 1080
4 0 1220
5 0 1220
50-32 3 1 0
34.5
37
37 253- 106
3 0 430- 102
1005-142
4 0 7
1087-435
1429-2350
6V; CLS 527
OS 585
6v; CLS 500
4v; CLS 500
480-4220
180
176
165
3 1 6
472-192
300
585
585
585
585
609
1370-214
2 0 6
4 6 3
590-19600
870-220
850-220
1.45
6.76
1.78-2.70
1.73
2.18-2.70
1.96-3.00
5.22 x IO-3 M-0.23
1.29-0.752
2.96
2.39
1.90
2.17
0.96- 1.69
A2=K,$-.6
0.570-0.895
0.825
0.625
0.88-0.20
A2 =K M-0.20
A 2 = K M -.40
17.4
13.7
See Ref.
0.60-2.97
1ov; CLS
OS
OS
O S
OS
5v; OS
A 3 given in Ref.
6V; CLS
CLS
O S
7v; CLS
CLS; 6V
CLS; 6V
CLS; B; (bar cm6/g2)
CLS; II; (bar cm 6/g *)
5 1 6
516
585
250
6 1 0
Asz3.11 x 1O-3 M-.*js
A2 =2.4 x IO- Mwo.O
A2 = 6.0 x 1O-9 Mz7*
A2=5.5 x 10-l' Mos4
w
0.218
0.509
0.575 to - 0.142
15v; CLS; M,IM, , M,/M,
given
M,/M, = 1.03-1.15
CLS
CLS
CLS
4437
407
522
997
935
484
484
484
17.3 0.461 to -0.116 484
3ooo 0.406 to -0.109 484
1.45
6.76
20.1
24.7
59.0
63.1
15.9
118
177
3 0 5
313
6 6 5
9 0 3
1140
2047470
278-46.9
49
34
8.05
7.03
5.54
5.29
5.67
4.63
4.55
3.73
3.56
2.90
2 . 7 1
2.56
zi2=1.15X10-2M,0273
2.08
4.2-5.9
7V, CLS; A s-values for
mixtures of these samples
given in Ref.
7V. CLS; A s-values for
mixtures of these samples
given in Ref.
7V, CLS; A z-values for
mixtures of these samples
given in Ref.
CLS; B; (bar cm6/g2)
Ms,D; SE; B; (bar cm6/gZ)
CLS
407
407
998
CLS 845
8v:OS 584
45-417 7.70 (mean) 19v; as 819
5.9-5.2
2.64-4.80
Az=3.89x lo-* M-03*
1 .OO- 1.28
1.56-1.92
1.70-2.28
4v;os
7v: CLS
584
588
4v; CLS
3v; CLS
3v; CLS
5 1 7
5 1 7
517
TABLE 16. contd
Second Virial Coefficients of Poly(styrenes) VII / 181
Polymer Sol vent
T C-3
M ( x 10 -3) (ghol) A2 ( x 104) (mol cm3/g2) Remarks Ref s.
Diethyl succinate 60-16
Poly(styrene)
Toluene 3 0
Benzene 2 0
2 0
2 5
3 0
2 . 5
Bromobenzene
Butanone
2-Butanone
2 0
2 0
2 5
2 5
1 9 7 0
8 9 6
7 6 2
6 8 4
1800-192
1330-7100
2 7 0 0
0.207-3100
1 5 0
35.6-1750
1 6 7 0 0
125OC- 19200
8760-56800
5 8 9
1 0 . 3
1 9 . 8
9 7 . 9
2 0 0
8 4 5
1 3 8 0
3 1 5 0
8 5 6 0
1 4 5 0 0
2 0 1 0 0
35.5-1750
1 5 0
5 0
2 3 3
6 7 0
1 8 0 0
mixtures
0.589 to - 0.026
0.819 to - 0.001
0.900 to - 0.013
0.830 to - 0.046
2.18-4.37
3.6-3.3
3 . 4
54-3.1
3. 95
7.24-2.22
2. 23
1.52-1.12
1.82-1.09
A2=1.05x lo-* M,0276
3.56, 3.30
1 1 . 3
8. 80
5. 78
4. 72
3. 33
2. 85
2. 29
1. 80
1. 49
1. 38
6.38-2.15
0. 0127
0. 58
6. 90
1. 80
1. 53
1. 46
8v; CLS
8v; CLS
8v: CLS
8V; CLS
9v; CLS
4v; CLS; AzM; ( cm3/ g)
CLS; A zM; (cm 3/g); A 3
given in Ref.
9v; CLS
CLS;
M,/Mw = 1.01-1.55
CLS; A zM, (cm 3/g)
4V;CLS;Az=2.9x
10 -3 M- 0. 59
w
6v; CLS
CLS
CLS
CLS; A 3 given in Ref.
M,/Mw = 1.01-1.55
CLS
CLS; A 2M, (cm/g)
CLS
CLS
CLS
CLS
5 1 7
5 1 7
5 1 4
5 1 4
8 0 1
8 0 4
8 3 3
8 0 5
8 0 7
8 0 8
1 0 3 8
8 1 8
9 2 2
8 3 3
8 0 4
8 0 6
9 2 6
1800*/670; w=O.15-0.85 1.390- 1. 496
1800*/233; w0 =0.20-0.63 1.540- 1. 740
1800*/50; w =0.13-0.91 0.63-1.36
3 0
2 0
2 4
2 5
233-5840
1 5 0
17.5-1800
2 8 8 0
3 5
4 5
6 1
1 8 6
4 2 2
7 7 5
A2 =4. 37 x 1O- 3 M- O. " '
w
3. 58
2.23-7.69
2. 58
6. 47
5. 73
5. 57
4. 83
3. 52
2. 08
6.56
- 2.75 to 10
-2.00 to 13
- 1.20 to 15
- 0.45 to 18
0.03-21
o-o. 1
0.40-22
Carbon tetrachloride
Chloroform
Cyclohexane
2 5
15
2 0
2 5
3 0
34.5 (8)
4 0
4 4 . 5
4 5
Cyclopentane
1,4 Dioxane
5 0
2 3
2 0
0.37-40
20.7-3150
0.37-40
233-5840
1 6 0
2 6 0
4 0 0
1 5 0
6V; CLS
4v; CLS
6V; CLS
CLS; M, / M, =1. 04- 1. 16
CLS
5v; CLS; M, / M, = 1.04-1.30
CLS
CLS
9 9 5
8 0 4
9 3 4
9 9 1
9 2 7
CLS
11V; CLS; M, / M, given in Ref.
1 lV, CLS; M,/M, given in Ref.
11V; CLS; M,/M, given in Ref.
1 IV; CLS; M, / M, given in Ref.
14V; CLS; M, / M. given in Ref
6V; A 3 given in Ref.
l1V; CLS; M,/M, given
8 0 4
9 2 0
9 2 3
9 2 0
in Ref.
A 2 = 6. 30 x 10 - M-o.73
w
CLS;M,/M, = 1.04-1.16 9 9 5
0.77-24 11V. CLS; M,/M, given 9 2 0
in Ref.
1.10-26
2 8
2 3
2 0
2. 75
11V; CLS; M, / M, given in Ref
CLS; M, I M, given in Ref. 9 2 4
CLS 8 0 4
9 2 6
References page VII - 198
VII / 182 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 16. contd
Polymer Sol vent T ((3 M ( x 10 -3) (gimol) A2 (x 104) (mol cm3/g2) Remarks Ref s.
Decalin (tram)
Dimethylformamide
Dioctylphtalate
Ethylbenzene
Methyl acetate
1-Phenyldecane
Tetrahydrofuran
2 0
2 5
3 0
3 5
4 0
2 5
12 (@
2 2
2 0
2 5
3 0
4 3
5 5
7 0
1 0 0
1 1 4
1 2 5
2 1 . 6
2 7 . 0
3 1 . 3
3 5 . 0
4 1 . 3
2 5
3 0
Tetrahydrofuran/lS ~1% 2 5
Poly(dimethylsiloxane)
Toluene 1 2
2 0
Toluene 2 5
2 3
Toluene
3 0
3 0
Xylene 2 0
3 9 0 - 0.06
0. 25
0. 58
0. 85
1. 11
7 0 4 1 . 9
5 0 0 0 0
2 0 5 0 - 0.036
50-1800 3.10-8.41
A 2 = (0.011 i 0.005) M,027*o O2
179. 3 - 0.235
0
0.22
0. 39
0. 21
0
- 0.35
3 9 0 - 3.22
- 0.83
1. 54
2. 04
3. 97
90-20000 1.41-5.91
25.75 xt 1.10 10.52 i 0.20
32.09 f 1.28 9.07 zko.15
A 2 = (0.0194 i 0.004) M,.286*o~02
25.755 1.10 - 14.7 It 3.9
32.09 i 1.28 - 17.1 f9.1
622-4400 2. 27
1 2 3 0 0 2. 18
2 3 4 0 0 1. 82
2 4 4 0 0 2. 32
2 9 7 0 0 1. 75
3 5 6 0 0 1. 48
4 0 2 0 0 1. 37
1 5 0 0. 0127
1.2-424 3.5-21.7
2 1 . 6 7 . 3
1 6 0 4 5 0
2 6 0 5 1 0
4 0 0 5 4 0
2 0 . 5 0 (approx.)
9 5 . 4 1 0
9 7 0 0 1 5 9
2 2 3 0 0 3 3 6
2960 2. 24
10800-22200 1.90- 1. 28
50-2OOW 5.94- 1.4
1 8 1 0 2. 14
125-2960 3. 29
1 2 9 0 2. 35
2 5 8 0 1. 99
6 1 2 0 1. 64
1 1 1 0 0 1. 34
1 5 9 0 0 1. 21
5 8 6 3. 05
6.7-533 3.04-74
233-5840 A2 = 1.58 x lo-* M-o.zs6
w
107f5 4.810.1
CLS 8 1 5
CLS 8 1 5
CLS 8 1 5
CLS 8 1 5
CLS 8 1 5
CLS 9 3 8
Extrapolated value 9 3 0
CLS; M,IM, 5 1.30 9 2 1
5v; CLS; M,/M, = 1.06-1.30 9 3 4
CLS;0.1106~M,~8.48x106 9 2 9
DLS; M,/M, = 1. 07 8 1 1
D L S 8 1 1
D L S 811
D L S 8 1 1
D L S 8 1 1
D L S 8 1 1
DLS 8 1 1
CLS 8 1 3
9v; CLS; M,/M. = 1.04-1.20
LALLS; M,/M, = 1.03
LALLS; M,/M. = 1.02
CLS; 0 . 1 lo6 <M, 5 8.48 x lo6
LALLS; M,,M, = 1. 03
LALLS; M,/M, = 1.02
CLS
CLS
CLS
8v; CLS
SANS
CLS; M,/M, given in Ref.
CLS; microgel containing;
see Ref.
CLS; M,/M, = 1.05
9V; CLS; A 2 = 4.79 x 1O-3
M F3
8 0 3
8 0 7
IIV, CLS; M,/M, = 1.06-1.30 8 1 4
values for A 3 given in Ref.
CLS
CLS
CLS
8 1 2
8 4 7
8 0 9
CLS
IOV; OS; M,/M. given in
Ref. A2 =0.964 M-0.5-4.36x
10-3
CLS; M,/M, = 1.04-1.16
CLS
9 9 2
1031
9 2 9
1031
8 4 1
8 1 0
8 0 4
9 9 3
9 9 3
9 2 4
8 0 2
8 1 8
9 2 5
9 9 5
1032
TABLE 16. contd
Second Virial Coefficients of Poly(styrenes)
Polymer Sol vent T ((3 M ( x 10e3) (g/mol) A2 ( x 104) (mol cm3/g2) Remarks Ref s.
linear
c yc l i c
linear
Tetrahydrofuran
Xylene
Toluene (deuterated >
99%)
linear
cyclic
Mixtures A/B
mass% B: 0- 1
Mixtures C/B
mass% B: 0- 1
Mixtures D/B
mass% B: O-l
NBS 705 standard
NBS 1479 standard
Toyo Soda 550
Toyo Soda 2000
IUPAC-sample
IUPAC-sample
IUPAC-sample
branched
linear
branched
linear
atactic
Toluene
Methyl ethylketone
Cyclohexane
Toluene
Methyl ethylketone
Cyclohexane
Toluene
frans-Decalin
Toluene
Toluene
Toluene
Toluene
Benzene/ethanol
so/20
70/30
Benzene/heptane
Heptane O-56 vol.7~
Benzene/hexane
50/50
4 0 1 6 0
30170
2 5
2 4
22f5
-
-
3 0 - 4 0
-
-
25-40
2 1
2 0
3 0
4 0
-
-
-
2 5
4 0
6 0
2 5
6 0
2 5
6 0
35.0 i 0.2
2 5
6 0
2 5
6 0
6 0
10.5-182
11.1-181.5
120f5
1 3 2
143
163
1 9 6
2 1 5
127
143
163
1 8 4
1 9 4
10-390
1 1 0
15-227
4 0
105
1 3 2
2 2 7
36 (4
1600 (B)
4.9 (C)
1600 (B)
2.3 (D)
1600 (B)
179. 3
1 7 9
5 0
5 5 0 0
2 0 0 0 0
7 9
2 3 3
6 3 0
3.38 f 0.08
1 7 0
2 5 7
109-5000
3200-62
6 8 0
4 0 0 0
1 7 5 0
23.4-2370
1 7 5 0
4.62-11.0
4.37-9.33
7.0 f 1
9 . 1
9 . 2
7 . 7
6 . 8
8 . 0
7 . 8
7 . 7
7 . 1
6 . 6
7 . 0
3.9-24.4
1.48-19.5
- 0.368 to 0.446
3.87-31.7
1.69-14.8
- I .27 to 2.0
- 1.17 to 0.932
- 1.93 to 0.599
- 2.82 to 0.631
9.3-2.6
20.0-2.6
25-2.6
- 0.036
0. 593
1. 17
6. 00
4.00
2. 09
1. 61
6 . 2
5 . 0
5 . 1
23 i 3
4.9
5 . 7
3 . 3
5 . 4
3.83 (approx.)
2.9-6.0
4.9 x lo-
3 . 2
2. 30
1. 75
1. 55
0
1.1
3.06-O
1 . 0
0 . 9
0
0. 65
0
4v; CLS; M,/M, = 1.08-1.19 9 9 6
4v; CLS; M, / M, = 1.08-1.20
SANS
SANS
SANS
8v; CLS
7v; CLS
3v; CLS
1IV; CLS
1 IV; CLS
4V; CLS
4v; CLS
4v; CLS
4v; CLS
4 v
8V
7 v
CLS; M, / M, = 1.07
CLS; M, I M, = 1.05
CLS; M, / M, = 1.1
CLS; M, I M, = 1.2
CLS; M, / M, =1. 3
OS
OS
OS
9 3 7
9 3 1
9 3 1
9 3 2
9 3 2
8 5 1
8 5 1
8 5 1
8 3 0
1019. 1020
1 1
1 1
1 1
M from isothermal distillation
CLS
SV; CLS
5v; CLS
Mv ; (cm /g)
CLS
4 6 3
3 1 2
3 1 2
3 1 2
3 1 2
5 6
4 5 4
5 6 2
1 7 2
5 6
CLS 5 6
5 6
5 6
5 6
9V, CLS; A 2-values corrected
for preferential adsorption
given in Ref.
4 4 0
5 6
5 6
5 6
5 6
5 6
References page VII - 198
VII / 184 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 16. contd
Polymer Sol vent
T(C) M ( x 10 -3) (ghol) A2 (x 104) (mol cm3/gZ) Remarks Ref s.
i s ot act i c
i s ot act i c
atactic
Benzene/isopropanol
Isopropanol O-39 vol.% 35.0 f 0.2
n-Buy1 acetate 5
3 0
55
Carbon tetrachloride 25
Chlorobenzene 25
3 0
Chloroform 2 0
Chloroform/methanol
100/O 25
90/10
80/20
Chloroform 3 0
2340-4170 3.06-O
411 1.88
4 0 4 2.08
4 0 2 2.00
9 2 0 2.6
98.4 5.41
3 8 8 3.77
372-2800 8.0-6.6
3 3 0
100
7.5
5.4
1.9
5.4-5.1
I-Chloro-4-methylbenzene R T 410-1050 2.4 (approx.)
I-Chloronaphthalene 130 34.5 (approx.) 1.33 x IO2 (approx.)
o-Dichlorobenzene RT
n-Butylchloride 15
4-ten-Butyltoluene 5 0
1-Chloro-n-undecane 21.96-43.99
Cyclohexane 23-45
27-41.5
3 0
4 0
5 0
34.2
35.5-55
35-55
Cyclohexane
31.94-43.99
29.92-44.03
2 8
33
5 0
4 0
4 5
5 0
5 0
4 0
4 5
5 0
55
196-264 2.9-1.9
3 6 0 2.48
7 3 9 2.00
1270 1.81
3 9 2 0 1.35
5.37 5.12
20.2 4.18
3 6 4 2.03
743 1.74
1280 1.55
3 9 5 0 1.17
4 0 6 - 6.0 to 9.0
68.7
1610
50-203
78-210
See Ref.
3 2 0 0
4 0 0 0
4 0 6
5 0 0
100
513-45.9
3 7 0
7 4 4
1270
3 7 0
7 4 3
1280
5.48
10.3
20.5
3 7 0
146
1280
3 7 0
7 4 6
1280
- 0.410 to 0.226
- 0.37 to 0.258
- 0.276 to - 0.445
0.634-0.445
1.33-0.901
- 0.061 to 0.071
- 0.153 to 0.538
o-o.54
O-0.88
- 131 to 23.1
- 16.3 to 22.7
0.07
0
0.5
0.4-0.25
0.79-0.87
1.11-1.19
0.95- 1.29
0.320
0.304
0.321
0.526
0.537
0.509
2.50
1.62
1.20
0.764
0.738
0.674
0.887
0.854
0.797
8v; CLS 4 4 0
OS 585
CLS
OS
OS
4v; CLS
CLS 176
5V; CLS; A Z,S, A 2.~ given
in Ref.
2v; CLS
OS; AZ M/(cm/g); see
Ref. for various
extrapolation methods
3v; OS
CLS
CLS
9V; CLS; A 2M; (cm3/g); M.
given in Ref.
6V 3CLS. , (J cm3/g2)
5v, CLS
4v; OS
4v
4v
3v; OS
5v; CLS
3v; CLS
3v; CLS
5V; CLS; A 2M; (cm3/g)
5V; CLS; A 2M; (cm/g)
CLS
3V. CLS; p dependence in Ref. 5 2 8
3V. CLS; p dependence in Ref. 5 2 8
3V; CLS; p dependence in Ref. 5 2 8
Iv; CLS 5 0 3
CLS 9 6 7
2 9 4
4 0 4
5 8 5
176
5 2 8
3 2 8
5 2 3
3 2 8
961
9 6 7
133
105
166
106
106
106
4 9 7
3 2 9
3 3 4
172
133
133
4 5 4
TABLE 16. contd
Second Virial Coefficients of Poly(styrenes) VII / 185
Polymer Sol vent T ((3 M ( x 10m3) (g/mol) A2 ( x 104) (mol cm3/g2) Remarks Ref s.
atactic
IUPAC-sample
Cyclohexane 34.5 (8)
Decalin
25
3 0
4 0
Dichlomethane 2 2
25
35
67
Dichloroethanekyclohexane
65135 2 2
67
35165 2 2
6 7
6194 2 2
6 7
Dioxane 25
Dioxanekptane
Heptane O-58.5 vol.%
Ethyl acetate
Ethylbenzene
Hexyl-m-xylene
Poly(isobutene)/
cyclohexane
Toluene
34.2
35 f 0.2
25
16
2 0
25-40
3 0
35
4 0
7.5-45
15
15
RT
2 0
2 2
25
0.162
0.266
0.370
1.23
2.27
5.38
10.1
20.6
5 0 0
1800
3-17
3
439-5360
16
1610
900-920
97.3
77.6- 196
2240-2630
2 4 3
6 8 0
570-6000
14.9-39.8
84.2
38.8
68.7
5.31
20.0
191
3 5 7
723
1290
3 9 4 0
0.578
0.680
0.904
1.23
2.21
3.48
5.38
20.0
39.4
191
3 5 7
7 2 3
1290
3 9 4 0
1030
115-2800
2- 1770
3.2-980
245-540
100
4 3
33
4.10
1.33
0.41
0.28
0.10
0.8 x lO-4
0.19 to - 0.01
0.40-0.20
0.72-0.45
7-2.54
6.8
See Ref.
2.7
3.98
3.32
2.16
2.70
0.78
1.27
2.9-2.8
3.08
5.11-4.48
2.51-O
0.7
4.7 x 10-d
0
0.2-0.05
3.59
1.81
0.93
0.46
0.586
12.2
8.80
4.36
3.72
3.12
2.81
2.07
4 4
4 3
37
2 5
17
14.6
12.2
8.80
6.45
4.36
3.72
3.12
2.81
2.07
1.29
2.2-0.72
4.3-0.86
3.5-1.05
1.2-1.0
CLS; M,/M = 1.00
CLS; M,/M = 1.00
CLS; M,/M, = 1.00
CLS; M,IM, = 1.03
CLS; M, / M, =1. 05
CLS; M, / M, = 1.03
CLS; M, / M, = 1.03
CLS; M, / M. =1. 02
M, ; @m4/ g)
4V. CLS; p dependence in
5V, CLS; p dependence in
5V; CLS; p dependence in
6v; CLS
CLS
l1V; CLS
CLS
CLS
2v; CLS
OS: A 3 given in Ref
3v; OS
9v; CLS
OS
Mv; (cm4/g)
3v; CLS; SAXS
2v; CLS; SAXS
5v; CLS
CLS; (J cm3/g2)
CLS
Ref.
Ref.
Ref.
9 6 8
5 6 2
5 2 8
5 2 8
5 2 8
166
166
5 6 4
166
166
166
166
166
166
166
2 9 4
4 0 4
4 9 7
4 4 0
196
5 6 2
4 9 2
4 9 2
5 9 9
5 9 9
5 9 9
5 9 9
105
9 6 7
CLS; M,/M. = 1.00
CLS; M,/M, = 1.00
CLS; M,/M, = 1.01
CLS; M,/M, = 1.03
CLS; M, / M, =1.05
CLS; M, f M, =1.07
CLS; M, / M, =1.03
CLS; M, I M, =1.02
CLS
CLS
8% CLS
9v; CLS
av; CLS
2v; OS
9 6 8
2 5 3
176
166
166
196
References page VII - 198
VII / 186 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 16. contcf
Polymer Sol vent
T (C) M ( x 10 -3) (glmol) At (x 104) (mol cm3/g2) Remarks Ref s.
branched
3 5
6 7
Butanone/isopropyl alcohol
87/13 2 2
6 7
Tetrahydrofuran 3 0
Tetralin 25
Toluene 12
Cyclohexane 34. 5
44. 5
Toluene 30
star branched
comb branched
15
20
25
comb branched Toluene
30
30. 27
34. 2
35
31
40
22- 67
28- 67
Poly(styrene)-b-(Polyethylene/Polypropylene)
4-Methyl-2-pentaponel
2.Chlorobutane (mixtures)
100%/O% 25
90%/ 10%
80%/ 20%
70%/ 30%
60%/ 40% 20
50%/ 50% 25
Poly(styrenesulfonate)
sodium salt; degree of NaNOj-solutions; i o n i c 1 0
sulfonation = 0.84 strength 0.005-2.0
20
30
Xylene + 2% methanol 24
Poly(styrene)/Poly(acrylonitrile)
mass ratio 3: 1 Dimethylformamide 25
96. 3- 785 166-5.3 sv; OS 1 7 6
170- 257 1. 9 2 v ; CLS; OS 312
900 1 . 3 CLS 294
45. 1- 6350 See Ref. 13v: CLS 564
517- 980 0. 89- 0. 81 3v: CLS 166
16.3-17.4
24. 4- 5700
( 0. 2 to - 0. 3) 2v; CLS
0 2v; CLS
8. 32- 2. 105 6V; CLS; A 2.~~ A 2,s given
1 6 6
1 6 6
4 8 1
in Ref.
680
54- 4400
980- 14300
4. 0 x 10-b M,; (cm/.@
30- 792 8V; CLS; A zM, (cm/g)
- 0. 08- 0. 03 5v; CLS; M,IM, = 1.03-1.24
0. 02- O. I8 5V; CLS; M,/M, = 1.03-1.24
0. 38- 2. 12 5V; CLS; M,/M, = 1.03-1.24
115 CLS; A zM; (cm j/g)
380 CLS; A 2M; (cm3/g)
404 CLS; A PM; (cm/g)
520 CLS; A2M; (cm3/g)
2. 24- 2. 39 (approx.) 5v; CLS
9. 4- 4. 5 5V; SAXS
2. 27- 2. 41 5v; CLS
4. 20- 1. 84 4v; CLS
5.0 x 10-d M,; (cm4/g)
6. 5- 3. 5 7v; CLS; OS
1. 23 See Ref.; (J cm/g2)
(I I - 7. 0) x lo? 1ov; CLS; (cold/g)
4. 6 5V, CLS; A 2,~; A 2,s given
562
548
994
384
1 8 7 0
2320
3880
I800
5.85-125
1 8 0 0
209- 3920
680
99- 952
237
72- 1800
1 0 0
548
548
548
548
528
492
528
492
562
1 7 6
56
245
585
373
1 3 . 3
418- 37. 6
30. 9- 612
155-710
56- 452
77. 8- 196
33.1-6460
366- 50. 9
209- 1600
1 6 1 0
980
3. 45
4. 49
4. 54- 5. 88
7.41 x 10-j MO
4. 17- 1. 56
A2=kM-022
=4, 6x 10-3 ,,,-
z2.1 x 10-j Mm6
29-145
( 5. 43- 4. 46) x IO-
See Ref.
5. 5- 6. 9
4. 28- 2. 46
3. 12- 2. 43
20. 4 x 1( 479/ T) - I]
in Ref.
OS
OS
Iv: OS
A ?M; (cm3/g)
4v; CLS
OS
OS
OS
5V: OS; A zM; (cm Ig)
3v; os
16V; CLS
8V; OS
3v; CLS
2v; CLS
M,; CLS; A2M; (cm3/g)
585
467
503
1 6 9
290
3 1 7
319
319
321
497
564
584
121
1 6 6
308,310
50000 0. 058
48000 0. 061
35000 0. 059
29000 0. 062
20000 0. 054
100 2. 7
CLS; micelles 1033
CLS; unassociated
350
IlOi IO
538
0. 08- 34. 2 9V; CLS; M,/M, = 1.2 936
0. 3- 43. 2 9V: CLS: M,/M, N 1.2
0. 3- 64. 8 9V; CLS; M,/M, Y 1.2
3. 7* I SANS; sulfonation level
0. 005 I
1. 39 mol%
CLS
937
938
TABLE 16. contd
Second Virial Coefficients of Poly(styrenes) VII / 187
Polymer Sol vent T (Cl M ( x 10-3) (g/m@ AZ ( x 104) (mol cm3/g2) Remarks Ref s.
Poly(styrene)(PST)lPoly(p-chlorostyrene)
mixtures, mass frac. PST
1 .ooo Butanone
0. 786
0. 593
0.434
0. 272
0. 133
0.000
I .ooo Cumene
0. 786
0. 593
0. 434
0.272
0. 133
0.000
1. 000 Toluene
0. 786
0. 593
0. 434
0.272
0. 133
0.000
block-copolymer
mass frac. PST
0.650 Butanone
0. 467
0.372
0. 655
0. 509
0. 311
0.650 Cumene
0. 467
0. 372
0. 655
0.509
0.3 1 1
0.650 Toluene
0. 467
0. 372
0. 655
0. 509
0. 311
Poly(styrene)/poly Toluene
( i s obut yl ene)
Poly(styrene)-block-Poly(ethylene/propylene)
35 i 3 mass% PS Methyl ethylketone
Methyl propylketone
Methyl isobutylketone
Diethylketone
5-Methyl-2-hexanone
Poly(styrene-co-maleic anhydride)/poly(ethyl acrylate)
A B
graft copolymer
A B
56.5143.5 Acetone
77123
o/100
Poly(styrene-co-p-methoxystyrene)
random
mol% p-methoxystyrene
Toluene
5 3 . 8
3 0
5 5
3 0
3 0
5 5
3 0
2 1
2 5
2 5
2 5
3 4 1
-
-
-
-
-
3 3 0
341
-
-
-
-
-
3 3 0
3 4 1
-
-
-
-
3 3 0
3 7 9
3 2 5
3 6 8
3 7 4
3 5 6
2 9 9
3 7 9
3 2 5
3 6 8
3 7 4
3 5 6
2 9 9
3 7 9
3 2 5
3 6 8
3 7 4
3 5 6
2 9 9
194-2400 (PS)
156-2440 (PIB)
105
5 3 . 4
7 1 . 2
3 5 0
71-350
35.5-701
-
1. 15 O S 9 6 9
1. 51
1. 70
1. 78
1. 76
1. 82
1. 72
2. 90 OS 9 6 9
2. 38
1. 92
1. 39
0. 84
0. 37
- 0.20
3. 73 OS 9 6 9
3. 41
2. 99
2. 64
2. 30
I .75
1. 20
1. 68
1. 78
1. 75
1. 68
1. 82
1. 85
2. 19
1. 65
1. 37
2. 27
1. 85
1. 52
3. 02
2. 62
2. 23
3. 00
2. 73
2. 14
9.80 to 8.36
OS
O S
OS
16V. CLS; concentration and
angle dependence given in Ref.
9 6 9
9 6 9
9 6 9
8 1 7
4 2 0
3 1 0
6 8 0
9 6 0
7 8 0
Micelles; M, =47. 6 x
10 m6 g/m01
Micelles; M, = 18.2 x 10m6 g/mol
Micelles; M, = 42. 2 x 1 0 -6 g/moI
Micelles; M, = 43. 0 x 10e6 g/moI
Micelles; M, = 43. 5 x lO-6 g/mol
9 3 3
2.1 x 10-4 OS; (cm4/g)
2.1 x 10-d
5.7 x 10-e
4 8 9
5.0-3.0 7v; OS 6 1 7
4.1-3.2 12v; OS 6 1 7
References page VII - 198
VII / 188 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 16. contd
Polymer Sol vent T CC) M ( x 10e3) (g/mol) AZ ( x 104) (mol cm3/g2) Remarks Ref s.
75.6 44-421
26.4 61-665
53.0 66-1783
15.6 79-1717
Poly(styrene-co-methyl acrylate)
Dimethylformamide
Butanone
Poly(styrene-co-methyl methacrylate)
approx. 5opo Carbon tetrachloride
Dioxane
random, mol% St. 29.3 2-Ethoxyethanol
56.2 (Cyclohexanol)
70.2
block copolymer
mol% St . 27 1,4-Dioxane
33
4 6
5 6
100
mol% St. 49.6 2-Ethoxyethanol
(Cyclohexanol)
73.2
85.1
100
mass% St. 38 Benzene
2 0 See Ref. OS 5 1 5
2 0 See Ref. CLS 5 1 5
25
40.0 (68.0)
58.4 (61.3)
72.8 (63.0)
1330-1900 2.3-2.4
1330-1900 3.8-3.6
3 5 4 0
3 5 0 0
3 4 2 0
81.0 3 1 7
81.3 3 1 7
84.0 3 9 2
84.0 193
81.8 2 0 6
3 0 1530
Toluene
fractionated
unfractionated
Butanone
Isoamyl acetate
Nitroethane
Toluene
6 9
25 49-2270
9 7 0
1330-1900
Poly(styrene)-block-(hydrogenated Polybutadiene)-block-Poly(styrene)
1,4-Dioxaneln-heptane
n-Heptane 0 ~01% 25
n-Heptane 10 ~01%
n-Heptane 20 ~01%
n-Heptane 30 ~01%
5.9-3.5
5.34-4.29
A2=2.0x 1O-3 Mm0~5
5.46-3.41
A2=2.4x 1O-3 M-o35
4.54-3.00
Az =2.3 x 10m3 Mm045
11.0
9.98
11.8
10.9
7.31
0
0
0
0
0
1.48
1.25
1.65
4.92
3.2-1.45
1.55
1.5-1.2
4 8 0 0 0.021
4 4 4 0 0.042
4 2 0 0 0.075
3 7 7 0 0.127
8v; OS 6 1 7
9v; CLS 6 1 7
1 lv; CLS 6 1 7
8% CLS 6 1 7
2v; CLS 2 9 4
2v; CLS 2 9 4
OS 4 4 3
CLS
OS
CLS
1 Iv; CLS
See Ref.
2v; CLS
See Ref.
CLS, micelles 1018
8 1 6
4 4 3
8 1 8
2 9 4
2 9 4
5 0 7
2 9 4
5 0 7
a w = mass fraction of component *.
TABLE 17. (0, C)-HETEROCHAIN POLYMERS (POLY(ETHERS), POLY(ESTERS), POLYKARBONATES))
Polymer Sol vent
T C-3 M ( x 10e3) (g/mol) A2 ( x 104) (mol cm3/g2) Remarks Ref s.
Poly(carbonate) see Poly(oxycarbonyloxy........)
Poly(3,3-dimethyl oxetane) 25
Cyclohexane
Poly(ethylene terephthalate) see Poly(oxyethyleneoxyterephthaloy1)
Poly(formaldehyde) see Poly(oxymethylene)
Poly(oxybutene) Butanone 3 0
18.5 0.159 OS 9 7 6
37.0 0.162
52.0 0.156
55.0 0.154
67.5 0.148
130 0.155
2100-343 2.3-1.8 6v; CLS 598
TABLE 17. contcf
Second Virial Coefficients of (0, C)-Heterochain Polymers VII / 189
Polymer
T (3 M ( x 10 -3) (gimol) AZ ( x 104) (mol cm3/g2) Remarks Ref s.
Poly(oxycarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene)
Chloroform 2 5
Cyclohexanone
Dioxane
Dioxanekyclohexanone
Ethylene chloride
Ethylene dichloride
Methylene chloride
3 0
2 5
2 0
2 5
3 0
Tetrahydrofuran
21
2 0
2 5
Poly(oxyethylene)
2 7
Benzene 2 5
Dimethylformamide
Methanol
25-120
2 5
Methanol 2 5
Water
2 0
2 5
4 0
Water (D20) 2 5
Poly(oxyethylene)/Poly(oxypropylene) copolymer star structure
molar fraction oxyethylene Water 2 5
0.724-0.866
76.9-28.5
10.2-463
88-37.3
76.9-31.6
76.9-28.5
76.9-3 I .6
56.4-97.7
3 5 9
146-401
76.9-28.5
61-122
23-182
8-266
76.9-31.6
59.2-469
23-92
7. 70
3. 79
3. 79
3.5 (approx.)
7. 70
3. 79
0.3 16-6.75
See Ref.
0.062-37.3
1-31
l - 1 0
4 - 2 3
3-48
68.5 5 M, 5 852 AZ=
4 0
7 4
145
5 9 4
1 2 0 0
6. 95
3 5 . 7
1. 59
2. 88
10.9-800
1 0 . 1
6. 95
2 0 . 5
3 5 . 7
177
3 0 0
1 1 9 0
6. 95
2 0 . 5
3 5 . 1
2 0 1 2
18f2
1 9
30.1-36
11.9-14.4
24-8.91
12.5-18.0
8.8-10.1
10.9-12.4
0
10.6-12.7
11 .o-9.0
1. 43
7.83-5.75
12.1-14.4
3.6-2.5
3.9-2.9
4-1.29
11 .o- 13.0
8.7-5.23
2.5- 1.7
2 7 . 4
7 8
3 0
37-47
66.0
56.0
18.0-16.4
170-34.8
1220-46
102.5-39
84.5-47.5
87-46
48-27.5
0.0329 M, *** O6
2 9 . 5
2 8 . 3
2 3 . 9
1 8 . 7
1 7 . 6
0. 465
0. 318
0. 2963
0. 2611
116-30.4
6 2
0.289
0. 243
0.232
12. 17
9. 25
1. 36
0. 267
0.196
0. 195
24f2
16&2
13f2
0.06-0.2 15
6v; OS
14V, CLS; two different
wavelengths M, / M, given
in Ref.
6V; OS
5v; OS
5v; OS
4V; OS
5v; OS
3V, OS; M, given
CLS
4V, OS; M. given
4v; OS
2v; CLS; (J cm3/g2)
6V; OS; (J cm3/g2)
6v; M,.D; (J cm3/g2)
5v; OS
7v; CLS
6V; OS; (J cm3/g2)
CLS; B; (bar cm6/g2)
OS. B. (bar cm6/g2) 7 3
OS; B; (bar cm6/g2)
4V; OS; B; (bar cm6/gZ)
OS. I+ (bar cm6/g2) 9 ,
OS. B (bar cm 6/g ) 3 ,
3v; OS
3v; CLS
CLS; B; (bar cm6/g2); data
for seven solvents and for
OS; SE given in Ref.
11V CLS. B. (bar cm6/g2) . 0
4V, CLS; B; (bar cm6/gZ)
3V; CLS; B; (bar cm6/g2)
2V CLS. B. (bar cm6/g2) , 13
CLS
CLS; M, / M, = 1. 03
CLS; M, I M, =1. 02
CLS; M, / M, = 1.04
CLS; M, / M, = 1.10
CLS; Me/ M, = 1.12
LALLS; M, / M, = 1.04
LALLS; M, / M, = 1.04
CLS
CLS
5V; B; (bar cm6/g 2,
CLS; B; (bar cm 6/g 2,
LALLS; M, f M, = 1.04
LALLS; M, / M, = 1.03
LALLS; M, / M, = 1.04
CLS; M, / M, = 1.04
CLS; M, / M, = 1.05
CLS; M, I M, = 1.12
LALLS; M, / M, = 1.04
LALLS; M, / M, = 1. 03
LALLS; M, / M, =1. 04
SANS; p=O MPa; M, l
M, < 1.1
SANS; p = 100 MPa;
M, / M, < 1.1
SANS; p = 200 MPa;
M, / M, < 1.1
4v; CLS
4 9 6
8 5 0
4 9 6
4 9 6
4 9 6
496
4 9 6
8 5 0
8 5 0
8 5 0
4 9 6
4 5
4 5
4 5
4 9 6
8 5 0
4 5
4 0 7
4 0 7
4 0 7
1 8 8
4 0 7
4 0 7
5 1 8
4 2 3
4 2 3
1 9 2
193
1 8 4
1 8 5
9 0 7
1 0 0 3
9 7 5
9 6 5
1 8 9
1 8 4
9 7 5
1 0 0 2
9 7 5
1001
9 8 6
References page VII - 198
VII / 190 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 17. contd
Polymer S o l v e n t T(3 M ( x 10e3) (g/mol) AZ ( x 10) (mol cm3/gZ) Remarks Refs.
Poly(oxyethyleneoxyterephthaloy1)
fractionated
unfractionated 2 5 3 9 2 6
fractionated
Poly(oxyhexamethylene-
oxydipoyl)
Poly(oxyhexamethylene-
oxyterephthaloyl)
Poly(oxymethylene)
-; diacetate
unfractionated
fractionated
unfractionate
fractionated
Poly(oxymethylene-co-
oxyethylene)
Poly(oxypentamethyleneoxy-
terephthaloyl)
Poly(oxypropylene)
Poly(oxytetramethylene),
Poly(tetrahydrofuran)
Poly(oxytetramethylene-
oxyadipoyl
Poly(oxytetramethylene-
oxyisophthaloyl)
Poly(oxytetramethylene-
oxyterephthaloyl)
Poly(P-propiolactone)
Poly(terephthalic acid4-
aminobenzohydrazide)
o-Chlorophenol 2 5 107-18.1
o-Chlorophenol/tetra-
chloroethylene 60/40
Hexafluoro isopropanol
Chloroform
o-Chlorophenolketra-
chloroethylene 60/40
Hexafluoroacetone hydrate
Hexafluoroacetone 25
p-Chlorophenol 7 0
lH, IH. SH-Octafluoro-
pentanol- 1
o-Chlorophenolltetra-
chloroethylene 60/40
Acetone
Hexane
Methanol
Iso-octane
Hexane
Ethyl acetate
4 6
2 0
48-85
50-89
4 6
3 0
0.067 - 9 0 CLS
0.125 0 CLS
0.45-3.85 15.2 (approx.) 6V; CLS
783-901 0.46-4.50 5v; CLS
0.535-3.31 (10.75-0.95)X 10-j 6V; A; A 2; (cm/g); see Ref.
901 O-l.58 9v; CLS
783 -0. 25-1. 72 7v; CLS
34.2-4410 3.16-0.523 16v; CLS
34.6-1030 6.14-2.47 1ov; CLS
Chloroform 25 14.7
o-Chlorophenolltetra-
chloroethylene 60/40
o-Chlorophenolltetra-
chloroethylene 60/40
2,2,2-trifluoroethanol
25 12.8
25
3 0
13.4
6.80x IO<
M, 5 861 x 10
Dimethyl sulfoxide 23
5 0 74-26.2 15 (approx.)
25 12.2 19
25 33 39f 1.8 CLS 911
25 17.2 53 O S 5 4 2
25 11.3 35 OS 5 4 2
25
1 1 0
23-170 (5.6-2.0) x 10-j
23-185 56-25
41 3 2
86.5-27 35 av.
35-58 31-28
46-66.5 32-31
34-56 See Ref.
25 10.6 4 7
25
4 0
21
3 0
AZ =(0.025iO.O03) M,"'9*oo' CLS 978
3.78 0.787 CLS 1017
14-25.5
40 (approx.)
5.67 0.529
7.06 0.636
9.16 0.572
9.79 0.406
16.6 0.442
28.5 0.594
47.1 0.559
83.9 0.498
155 0.171
2 6 0 0.327
8V; OS
Different types of osmometers
used; see Ref.
Different types of osmometers
used; see Ref.
4v;os
OS
5V; CLS; see Ref.
5v; CLS
O S
5v; OS
3v;os
2v
OS: (cm3/mol); CLS-
measurements also given in Ref
OS
OS
OS
OS
5 2 6
5 4 2
4 3 0
2 3 6
5 1 0
4 0 2
5 4 2
4 7 5
4 2 8
4 7 0
4 2 8
2 0 7
4 1 3
5 4 2
542
542
Second Virial Coefficients of (N, C)- and (0, N, C)-Heterochain Polymers VII / 191
TABLE 18. (N, C)- AND (0, N, C)-HETEROCHAIN POLYMERS (POLYAMIDES, POLYUREAS, POLYURETHANE9
Polymer Solvent
T (3
M ( x 10 -3) (g/mol) A2 ( x 104) (mol cm3/g2) Remarks Ref s.
1 0 2 8
4 3 3
4 3 3
5 6 5
1 0 2 9
1 0 3 0
5 3 4
5 3 4
8 4 9
4 0 3
2 1 7
2 1 7
2 1 9
219
2 1 9
2 1 8
Poly(allylammonium
hydrochloride)
Poly( 1,4-benaamide)
Poly((n-butylimino)carbonyl)
(Poly(n-butyl isocyanate))
Aq. NaCl
0.05-3.OM
Dimethylacetamide,
3% LiCl
Chloroform
Toluene
31
2 3 1 2
3 5
3 5
2 5
1 5
6 0
2 5
2 5
2 5
2 5
2 5
1 8 0 2.4-33.7
3. 06
61-10000 2 5 . 1
2 3 i 0 . 5 - 53Ozt60
21. 2f 2. 7
2 1 . 3
0. 278
23-523
8 9
Poly(dimethyldiallyl-
ammonium chloride)
Aq. NaCl I.OM
(pH = 5.5)
1 1 4
2 8 1
3 5 2
4 1 8
4 7 3
16.6-5320
366i5 - 100+5
0. 247
0. 15
0. 122
0. 127
0. 222
A*=O,135 /$,p53+002
w
Poly(ethylene imine)
Poly(A-(3-hydroxypropyl)-L-
glutamine)
Aq.. NaCl 1 M
Methanol
CLS; M,IM,= 1.8-2.2
5v; CLS
CLS
9v; CLS
2.40-4.1 f 0.6
3 . 3
0.15-1.11
5 5 1 1
4.1-20.8
22.5-266
1 8
1 8
3 1
3 1
3 1
2-52
Poly(imino- 1,4(2-cyano- Sulfuric acid 96%
phenylene)iminoterephthaloyl)
Poly(imino(2,5-dicarboxy- Dimethylacetamide
terephthaloyl)imino- 1.4-
phenyleneoxy- 1,4-phenylene)
0.1 M LiBr
Poly(iminohexamethyleneiminoadipoy1)
(Nylon 66) w-Cresol
Formic acid (90%)
Formic acid (90%)IKCl
0.2-2.5 M KC1
Formic acid (90%)/KCl
2. 3 M KC1
Formic acid/2 M KC1
82.5-40s Acid
Formic acid
(90%)/ 2 M KC1
Formic acid (75-98s)
0.5 M Sodium formide
(21.1-14.3) x 10m4
1 8 3
8 4 0
59.2 to - 7.0
0
~ 9.4 to 36.5
312-10.1
13v; CLS; A zM; (cm3/g); OS
OS. B. (bar cm6/g2) 3 1
OS; B; (bar cm6/g2)
7v; CLS; B; (bar cm6/g2)
5V CLS, B, ( bar cm6/g2) 3 3%
2OV CLS. B. (bar cm6/gZ) 1 I,
Poly(n-hexyliminocarbonyl)
2,2,3,3-Tetrafluoropropanol 2 5
0.1 M Sodium 2 5
trifluoroacetate/2.2.3.3-
tetrafluoropropanol
Toluene 3 7
Poly(n-hexyl isocyanate) Dichloromethane 2 0
3 2
6 2
1.0-4.0 (approx.)
5 7 . 1
6v; CLS
CLS, B. (bar cm6/g2) 1 9
4 0 5
220, 221
3V, OS; see Ref. for
measurements in THF
CLS
61-606 20 (approx.) 5 6 5
9 8 3 1 1 1
1 8 0
2 5 3
3 4 2
4 8 1
7 2 4
1 0 6 0
68-200
6.10
6. 24
6. 49
6. 28
6. 46
5. 97
6. 23
20 (approx.) 31; OS; see Ref. for
measurements in THF
CLS; B; (bar cmh/g2)
CLS; B; (bar cm6/g2)
CLS. B. (bar cm6/g2) 1 ,
CLS; B; (bar cm6/g)
6V; CLS; B; (bar cm 6/g )
6V CLS. B, ( bar cm6/g2) 3 3%
4V, CLS; B; (bar cm6/g2)
CLS; B; (bar cm/g*)
Poly(ureyleneheptamethylene) Dichloroacetic acid
Formic acid 98WKCl
9614
2 5
4 5
7 3
9 8
4 5
7 3
25-98
4 5
5 6 5
0
6 . 5
3 8
5 2
32-6.2
82-8.0
O-52
4 0 0
4 0 0
400
4 0 0
183
183
183
2 8 . 5
1 7 . 5
1 7 . 8
1 3 . 2
3.1-17.8
2.6-23.5
17.5 (approx.)
1 8 3 0 . 5 5
References page VII - 198
VII/192 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 18. contd
Polymer Sol vent T(C) M ( x lo-) (g/mol) A 2 ( x 10) (mol cm3/g2) Remarks Ref s.
Poly(ureyleneheptamethylene) Formic acid 98%/KCl 4 5 3-13.9 10459 6v; CLS; B; (bar cm6/g2) 183
9614
Formic acid 73 5.7-12.5 512-30 8V; CLS; B; (bar cm6/gZ) 4 0 0
85.8-99.5%/
KC1 3.0- 10.0%
83 19.5-26.3 83-0.0 6V; CLS; B; (bar cm6/g2) 4 0 0
Formic acid 98%/KCl 4% 25 10.6 - 190 CLS. 3I? 3(bar cm6/gZ) 4 0 0
TABLE 19. OTHER SYNTHETIC POLYMERS
Polymer Sol vent T ("C) M ( x lo-) (g/mol) A2 (x 104) (mol cm3/g2) Remarks Ref s.
Poly(acenaphthylene) Toluene 25 1720-33 0.26-2.42 17v; CLS 4 5 8
1140-23 0.28-2.10 17v; OS
Poly(rert-butyl crotonate) n-Butylchloride 2 5 60.6-351 7.75-5.81 4v; CLS 8 3 8
Ethylacetate 25 60.6-351 2.11-1.46 4v: CLS 8 3 8
Poly(ttimethylene sulfide) Chloroform 25 19.3 0.2047 OS 1027
21.5 0.1808
27.3 0.1750
33.4 0.1634
47.3 0.1651
TABLE 20. INORGANIC POLYMERS
Polymer Sol vent T (3 M ( x 10m3) (g/mol) A2 (x 104) (mol cm3/g2) Remarks Ref s.
Poly(dihexoxyphosphaene) Tetrahydrofuran
Poly(di-N-hexylsilane)
Poly(ferrocenylsilane)
symmetrically substituted
Poly(oxydimethylsilylene)
(Poly(dimethy1 siloxane))
Hexane
Tetrahydrofuran
Tetrahydrofuran
Toluene
linear
cyclic
linear
Toluene
-
-
-
25
Bromocyclohexane 28
Bromobenzene
Bromocyclohexane
18
25
32
2 0
2 0
59.1-110.8
70-108.3
73.7-111.1
16.7-60.2
18.2-60.2
29.2-60.2
24.1-90.3
25.5-60.2
2 3 4 0 0.758
26.3 3.98
245 1.67
9 1 7 1.27
2 2 8 0 0.655
2 2 6 0 0.576
6 2 0 0 0.76
loo-lOGO AZ = 0.0019 M-,t9
w
2 2 9 1.3
CLS 9 8 2
CLS; M,fM, given 9 5 3
CLS 9 5 5
CLS 9 5 4
3.6 10.3 CLS; MJM, given 9 5 6
7.2 8.6
25.5 6.3
79.2 4.4
2 8 2 3.6
6 2 5 3.0
1.89-30.1 13.6-8.04
1.98-21.8 13.0-6.76
0.93 8.42
3.03 2.62
10.6-32.6 0
8 0 - 2.025 to 1.750
3 4 0 - 0.587 to 0.890
1060 - 0.272 to 0.772
33 - 1.3 to 2.260
85 - 0.782 to 2.012
3 4 0 -0.136 to 1.329
7 8 0 - 0.257 to 1.985
1060 -0.190 to 0.985
15400 3 2
14OOil 37
5 8 0 0 3 6
8V; CLS 8 3 6
9v; CLS 8 3 6
6v: CLS 8 3 6
9V; CLS
8v; CLS
7v; CLS
8v; CLS
SV; CLS
8v; CLS
1OV; CLS
6V: CLS
2 1 6
2 1 6
4 3 7
4 3 7
437
TABLE 20. contd
Second Virial Coefficients Inorganic Polymers VII / 193
Polymer Solvent
T P-3
M ( x 10m3) (g/mol) A2 (x 104) (mol cm3/g2) Remarks Refs.
Bromocyclohexane/ 2 3 . 9 - 8 8 . 8
p h e n e t o l (6/7) 2 6 . 8 - 9 3 . 9
31.8-90
Chlorobenzene 20
n - D o d e c a n e ( D O D ) / 2 0
butanone p M)D = O.OO- 1 .OO
n- He xa de c a ne ( HED) / 20
butanone p HER = O.oO- I .oO
n - U n d e c a n e (UND)/ 2 0
butanone p UM) = O.OO- 1 .OO
Poly(oxydimethylsilylene)
linear
(Poly(dimethy1 siloxane))
n-Hexane (HEX)/
butanone = 0- 1 (o ~sx
2 0
n-Heptane (HEP)/ 20
butanone HEP = 0- 1 (o
n-Nonane (NON)/ 20
butanone = 0- 1 plop
n-Decane (DEC)/ 20
butanone DEC = 0- 1 +G
Phenetol 80.8-122.8
81.7-123.1
79.5- 122. 8
90- 112. 8
Styrene 14
2 8
3 5
6 0
2 5
2 8
3 0
3 3
3 5
4 0
5 0
2 5
3 0
3 5 (Q)
4 0
5 0
Toluene 20
2 5
Poly(oxymethy1 Acetone 25
phenylsilylene)
(Poly(methylphenylsiloxane))
Cyclohexane
5 4 0 0 4 3
4400 3 8
4 3 0 0 5 0
8 0 - 1.23 to 2.14
3 4 0 - 0.536 to 1.490
1 0 6 0 - 0.239 to 1.280
1 0 7 1. 88
2 3 2 1. 70
6 8 0.08-4.32
8 0 . 5 0.92-4.29
1 2 5 0.09-3.47
1 5 0 0.10-3.08
8 0 . 5 0.01-2.49
1 2 5 0.00-2.14
1 5 0 0.00-2.09
3 1 . 5 o.O-6.08
8 0 . 5 0.12-5.00
125 0.093-4.65
1 5 0 0.096-4.50
1ov; CLS
1OV; CLS
8v; CLS
O S
OS
1 lv; CLS
1ov; CLS
1 lv; CLS
11V; CLS
9v; CLS 9 5 8
9v; CLS; LALLS 958, 963
9v; CLS; LALLS 958, 963
3 1 . 5
8 0 . 5
1 2 5
1 5 0
3 1 . 5
8 0 . 5
125
1 5 0
3 1 . 5
8 0 . 5
1 2 5
1 5 0
6 8
8 0 . 5
125
1 5 0
4 5
8 0
3 4 0
1 0 6 0
2 3 . 5
1Ov; LALLS
1OV; LALLS
1Ov; LALLS
1OV; LALLS
1 lv: LALLS
1 lv; LALLS
11 V, LALLS
11V; LALLS
1OV; LALLS
1Ov; LALLS
1OV; LALLS
1OV; LALLS
1 lv: LALLS
1 lv; LALLS
1 lv; LALLS
1 lv; LALLS
8v; CLS
7 v
7 v
6V
CLS; A 3 given
8 6 0
0.04-9.55
0.12-7.60
0.093-6.78
0.096-6.47
0.04-8.95
0.12-7.00
0.093-6.36
0.096-6.03
0.04-7.92
0.12-6.38
0.093-5.78
0.096-5.43
0.08-5.35
0.12-5.20
0.09-4.74
0.10-4.64
- 2.15 to 3.823
- 0.93 to 3.23
- 0.54 to 1.796
0.015-1.466
- 2. 19
- 0.96
0
1. 37
- 0.77
- 0.42
- 0.36
- 0.22
- 0.04
0.26
0. 59
- 1.06
- 0.86
0
0. 17
0. 68
3. 53
3. 18
25.0-4.05
- 2.66 to 10.6
1 . 6
CLS; A 3 given
1 3 0 CLS 9 6 1
1 0 0
2 3 5
0.66-2.015
2 5 7
OS 5 0 1
OS 5 0 1
3V; OS 5 1 8
3v; CLS 5 1 9
CLS; M,fM, = 1.65 9 5 9
2 7 0 1 . 2 CLS; M,IM, = 1.65
4 3 7
4 3 7
4 3 7
2 1 6
5 0 1
5 0 1
9 5 7
9 6 3
9 6 3
9 6 3
9 6 3
2 1 6
9 6 2
References page VII - 198
VII / 194 SEDIMENTATION COEFFICIENTS, DIFFUSION COEFFICIENTS, PARTIAL SPECIFIC VOLUMES, FRICTIONAL RATIOS
TABLE 20. contd
Polymer
Poly(pheny1 silsesquioxane)
Poly(tetramethyl-p-
silphenylene-siloxane)
Solvent
T0lllellc
TOlUene
T (C) M ( x 10 -3) (ghnol) A2 (x 104) (mol cm3/g) Remarks Refs.
I
3 7 48X.5-26.4 1.123-2.434 15% OS 4 5 9
2 5 3 8 2 0.1 18 OS 9 6 0
4 0 0. 118
5 5 0. 118
2 5 3 6 0 0. 112 OS 9 6 0
3 2 . 5 0. 113
TABLE 21. POLY(SACCHARIDES)
Polymer S o l v e n t T (Cl M ( x 10 -3) (g/mol) A* (x 10") (mol cm3/g2) Remarks Refs. ,
Amylose acetate
Cel1ulose
hydrolized linters
sulfite pulp
regenerated
Cellulose acetate
Cellulose acetate phthalate
acetyl content: 19.5%
phthalyl content: 21.4%
Cellulose diacetate
Cellulose diacetate
Nitromethane
-
Cadmium ethylenediamine 25
Aq. NaOH, 8 wt.% 3 . 5
10
2 6
3 5
4 1
4s
Aq. LiOH, 6 wt.% 2 5
Acetone RT
0.5 N NaHCO 3 3 0
Acetone 1 2 . 1
2 5 . 4
3 7 . 7
4 5 . 0
so.3
Butanone 3 0
4 0
Cellulose carbanilate Dioxane 2 0
Cellulose nitrate
(13.9% N)
(12.9% N)
(ca. 13.55% N)
from row cotton
(ca. 13.66% N)
from cotton
from viscose rayon
from chemical cotton
(12.4% N)
Acetone
Butyl acetate
Ethyl acetate
1 5
2 0
2 0
2 5
2 9 . 7
Butanone 2 5
5 0
6 0
4 0
5 0
2 5
2 5
RT
2 5
148-3110 2. 43 CLS
225-945 16.1 (approx.) sv; CLS
2 1 5 1 2 . 1 CLS
8 0 4.79 CLS
3. 75
3. 33
2. 15
- 0.58
- 3.06
1 2 1 1 1 . 0
60-173 9.4-5.8
AZ ~2.34 x 10m3 ML
CLS
4v; CLS
CLS; 1.68<M,< 13.44
( x 106)
9 4 4 . 1
3 . 8
3.6
3 . 5
3 . 4
7 1 - 0.5
~ 0.25
9 2
141
2580-80.8
42.0- 1.35
8 I -3850 10.8-8.2 6v; CLS
141-1700 13.3-12.5 4V; CLS
61.6-2482 0.24 (approx.) l4V; OS; B; (bar L2/g2)
77-2640 6.10 (approx.) 1 IV; CLS
7 8 0 1 1 . 2 CLS
22.8-417 0.24 (approx.) 8V; OS; B; (bar L*/g)
31-661 0.28 (approx.) 1 Iv; OS; B; (bar L2/g2)
150-400 1.0-0.5 CLS; B; (bar cm 6/g )
30-360 3.5-0.3 OS; B; (bar cm 6/g )
7 1 . 5 4 4 . 1 OS; A zM; (cm j/g)
295-450 28.5-25.7 2V, OS; A zM, (cm /g)
1 3 0 1 0 . 8 OS
CLS 8 2 5
0
0. 25
- 0.25
0
- 2. 1
2.45- 11 .S 7 v
7.5-20.0 6V
CLS 8 2 6
(d4 z/dTJ = 0.25 x 10 -
[cm Kg WI
846 /
I
9 7
I
941 i
68 :
68
4 7 7
6 1
22 ~
8 2 4
195
1 9 4
2 3 9
2 3 9
9 1
9 1
TABLE 21. contd
Second Virial Coefficients of Poly(saccharides) VII / 195
Polymer Sol vent T (Cl M ( x 10-3) (g/mol) A2 (x 104) (mol cm3/g2) Remarks Ref s.
Cellulose tricarbanilate Tetrahydrofuran 2 5
Dextran 0.05 g/100 ml sodium azide 2 0
Water 2 0
2 5
(2-(Diethylamino)ethyl)
dextran
Aq. sodium nitrate 0.8 M 2 0
Pul l ul an 2 5
hydrophobized 2 5
Tetramethylammonium gellan gum
Tetramethylammonium chloride
C = 0.0200 mol/dm 3 2 8
C = 0.0500 mol/dm 3
C = 0. 0750 mol/dm 3
105
2 0 0
2 9 4
3 8 5
5 0 8
5 7 8
7 8 7
1 0 5 0
1 3 3 0
1 8 2 0
3 7 0 0
8 6
128
1 8 5
2 2 5
2 6 7
4 0 0
5 1 3
8 8 5
I720
7 . 5
1 4 . 5
41.6
120. 7
3 7 4
1 2 7 0
36. 96
67. 94
113. 07
530. 61
4 8 5
4 8 5
9 . 9
3 9 . 7
65.0
4 8 1
2 2 7 0
3 2 5 0
1. 58
1 1 . 3
2 1 . 0
4 5 . 7
1 3 1
4 0 5
429
4 9 5
6 4 0
1 4 7 4
107
188
3 8 4
5 7 2
8 1 1
1 0 5 0
1 4 9 0
2 1 0 0
2 3 6 0
7 6 0
9 7
9 8
9 5
7.0 CLS; M,/M, given 9 4 0
7 . 2
5 . 7
5 . 0
5 . 6
4.2
4.2
4 . 3
4.2
4.0
3 . 8
5 . 5 CLS; M,/M, given 9 4 0
4 . 5
8 . 0
6 . 7
3 . 7
4.8
4.8
4 . 5
3 . 3
9. 80 CLS 1 0 1 5
I .oo
7. 26
5. 87
2. 30
1. 05
0.0616 CLS 9 6 5
0 . 0 4 2 I
0. 0352
0. 0302
4.6 M,fM, = 1.95 9 8 5
4.6 CLS; M,fM, = 1.95 9 4 2
13.8 CLS 9 9 9
9 . 2
7 7
3 . 9
0.9
0 . 7
I .34 CLS 1 0 1 5
1 1 . 6
9 . 5
4.6

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