Progress in Polymer Science 34 (2009) 1068–1133

Contents lists available at ScienceDirect

Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

Thermal stability and flame retardancy of polyurethanes

D.K. Chattopadhyay 1 , Dean C. Webster ∗
Department of Coatings & Polymeric Materials, North Dakota State University, Fargo, ND 58105, USA

a r t i c l e i n f o a b s t r a c t

Article history: The thermal stability and flame retardancy of polyurethanes is reviewed. Polyurethanes
Received 31 January 2008 (PUs) are an important class of polymers that have wide application in a number of dif-
Received in revised form 27 May 2009
ferent industrial sectors. More than 70% of the literature that deals with PUs evaluates
Accepted 2 June 2009
their thermal stability or flame retardancy and attempts to provide a structure–property
Available online 24 June 2009
correlation. The importance of studying thermal degradation, understanding the processes
occurring during thermal stress as well as the parameters affecting the thermal stability of
Keywords:
Polyurethane PUs are essential in order to effectively design polyurethanes having tailor-made properties
Thermal stability suitable for the particular environment where they are to be used. A detailed description
Polyurethane-isocyanurate of TGA, TGA-MS and TGA-FTIR methods for studying the decomposition mechanism and
Polyurethane-oxazolidone kinetics is also a part of this review. In general, thermal decomposition of PUs begins with
Polyurethane-imide the hard segment (HS) and a number of parameters govern a polyurethane’s thermal stabil-
Nanocomposite ity. Detailed description of the parameters such as HS, soft segment (SS) and chain extender
POSS (CE) structure and molecular weight, NCO:OH ratio, catalyst nature and crosslink density
Carbon nanotube
that affect the nature of PU degradation is given. Descriptions of approaches to improve the
Fullerenes
Flame retardancy
thermal stability in PUs such as formation of poly(urethane-isocyanurate), poly(urethane-
Functionalization oxazolidone) and poly(urethane-imide) in addition to other methods such as PUs with an
s-triazine ring or increased aromatic ring concentration, azomethane linkages as well as
use of hyperbranched polyols as crosslinking agents is given. A part of the review is also
concentrated on the improvement of thermal stability via hybrid formation such as the
incorporation of appropriate amounts of fillers, e.g., nano-silica; Fe2 O3 ; TiO2 ; silica graft-
ing; nanocomposite formation using organically modified layered silicates; incorporation
of Si–O–Si crosslinked structures via sol–gel processes; and the incorporation of polyhedral
oligomeric silsesquioxane (POSS) structures into the PU backbone or side chain. Incorpo-
ration of carbon nanotubes (CNT) into PUs and the use of functionalized fullerenes in PUs
are also described as these are the newest tools to obtain good thermal stability and flame

Abbreviations: MDI, methylene diphenyl diisocyanate; H12 MDI, hydrogenated MDI; TDI, toluene diisocyanate; IPDI, isophorone diisocyanate;
XDI, xylene diisocyanate; NDI, 1,5-naphthalene diisocyanate; HDI, hexamethylene diisocyanate; DMPA, dimethylol propanoic acid; PEG, polyethylene
glycol; PPG, polypropylene glycol; PTMG, polytetramethylene glycol; BD, 1,4-butanediol; DA, 2,4-hexadiyene-1,6-diol; TMP, trimethylol propane; 1,4-
CHDM, 1,4-cyclohexane dimethanol; BEP, 2-butyl 2-ethyl 1,3 propanediol; DIE, 2,2-dimethyl 1,3 propanediol; MOCA, methylene bisorthochloroaniline;
BAPS, bis[4-(4-aminophenoxy)phenyl]sulfone; THF, tetrahydrofuran; PU, polyurethane; PUD, polyurethane dispersion; TPU, thermoplastic PU; DBTDL,
dibutyltin dilaurate; DETDC, diethyltin dicaprylate; MMT, montmorillonite; TEOS, tetraethoxysilane; POSS, polyhedral oligomeric silsesquioxane; OpePOSS,
octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane; OapPOSS, octaaminophenyl-POSS; CNT, carbon nanotube; SWNT, single-walled carbon
nanotube; MWNT, multi-walled carbon nanotube; EG, expandable graphite; (N = PCl2 )3 , hexachlorocyclotriphosphazene; HS, hard segment; SS, soft seg-
ment; CE, chain extender; SD, soft domains; Tg , glass transition temperature; Tm , melting temperature; TGA, thermogravimetric analysis; TS, transition
state; εr , dielectric constant; +I effect, inductive effect.
∗ Corresponding author. Tel.: +1 701 231 8709; fax: +1 701 231 8439.
E-mail addresses: dipak chattopadhyay@yahoo.co.in (D.K. Chattopadhyay), dean.webster@ndsu.edu (D.C. Webster).
1
Present address: Department of Organic Chemistry, Polymer Chemistry Research Group, Ghent University, Krijgslaan 281 S4 bis, B-9000 Ghent,
Belgium.

0079-6700/$ – see front matter © 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2009.06.002
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133 1069

retardancy. Part of the review also concentrates on the process that occurs during burning of
PUs, flame retardant mechanisms and different additives or reactive type flame retardants
used in the PU industry. The use and working function of expandable graphite and melamine
as additive type flame retardants are shown. Description of the use of different reactive type
organophosphorus compounds, cyclotriphosphazenes, aziridinyl curing agents in aqueous
polyurethane dispersions (PUDs), organoboron compounds and organosilicon compounds
for improving flame retardancy is also given.
© 2009 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1069
1.1. Importance of understanding thermal degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1071
1.2. Processes occurring during thermal stress . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1071
1.3. TGA, pyrolysis–GC/MS, TGA-MS and TGA-FTIR analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1071
1.4. Cone calorimetery, limiting oxygen index (LOI) and UL-94 analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1073
1.5. Thermal degradation mechanisms of PUs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1074
1.6. Thermo-oxidative degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1078
1.7. Kinetic parameters from thermal degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1080
1.8. Polyurethanes from renewable resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1082
2. Parameters affecting thermal stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1083
2.1. Hard segment structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1083
2.2. Soft segment structure and molecular weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084
2.3. Chain extender structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1085
2.4. Effect of NCO:OH ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1086
2.5. Effect of catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1087
2.6. Effect of crosslink density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1088
3. Methods to improve thermal stability of PUs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1088
3.1. Poly(urethane-isocyanurate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1088
3.2. Poly(urethane-oxazolidone) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1089
3.3. Poly(urethane-imide) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
3.4. Other methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1092
4. Inorganic–organic hybrids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1093
4.1. Incorporation of fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1093
4.2. Silica grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1094
4.3. Organically modified layered silicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1094
4.4. PU–silica hybrids via sol–gel process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1096
4.5. Carbon nanotubes (CNTs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1100
4.6. Fullerene-containing PUs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1102
5. Thermal stability vs. flammability of PUs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1103
5.1. Correlation of char yield with fire retardance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1105
5.2. Methods to improve flame retardancy of PUs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1106
5.2.1. Additive type flame retardants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1106
5.2.2. Reactive type flame retardants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1107
5.3. Intumescent and nonintumescent systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1107
5.4. Expandable graphite (EG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1108
5.5. Melamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1109
5.6. Organophosphorus compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1110
5.7. PUs with cyclotriphosphazenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1110
5.8. Phosphorus-containing aziridinyl curing agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1115
5.9. Organoboron compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1116
5.10. Organosilicon compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1123
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1124
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1124

1. Introduction polyurethanes. Due to the wide range of compositions

possible, PUs have found extensive use in numerous com-
Considerable attention in the literature has mercial applications such as coatings, foams, adhesives,
been devoted towards an understanding of the sealants, synthetic leathers, membranes, elastomers as
structure–property relationships of polyurethanes (PUs). well as in many biomedical applications. PUs are one of
The study of structure–property relationships has acquired the most useful commercial classes of polymers which
significance due to the broad range of applications of are widely used in both industry and in everyday life. The
1070 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

Scheme 1. Basic reaction scheme for urethane formation [9].

repeating unit in PUs is the urethane linkage produced
from the reaction of an isocyanate (–N C O) with an
alcohol (–OH). The basic reaction of urethane formation is
shown in Scheme 1.
Although PUs contain repeating urethane groups, other
moieties such as urea, ester, ether and aromatic may
also be present in the structure. The flexibility avail-
able in the selection of raw material components such
as di-/tri-isocyanates, polyols, as well as chain extenders
have made it possible to custom tailor the properties of
PUs to a large extent. The most commonly used poly-
ols are polyethers, polyester polyols or acrylic polyols. On
the other hand, methylene diphenyl diisocyanate (MDI),
hydrogenated MDI (H12 MDI), toluene diisocyanate (TDI),
isophorone diisocyanate (IPDI), xylene diisocyanate (XDI),
and 1,5-naphthalene diisocyanate (NDI) are widely used
diisocyanates in PU formulations. PUs are available as
both thermoplastics and thermosets. Thermoplastic PUs
(TPUs) are linear, segmented copolymers consisting of
alternating hard segments (HSs) and soft segments (SSs).
HSs, comprised of diisocyanate and short chain extender
(CE) molecules such as diols or diamines, are rigid and
highly polar. HSs have high inter-chain interaction due to
hydrogen bonding between the urethane/urea groups. The
hydrogen bonding associations within the HSs in TPUs act
as a reinforcing filler for the soft matrix. On the other hand,
SSs, formed from linear long-chain diols or polyols, are flex-
ible and weakly polar. The polyol component of the PUs
can be a polyfunctional polyether [e.g., polyethylene glycol
(PEG), polypropylene glycol (PPG), polytetramethylene gly-
col (PTMG)], polyester polyol, acrylic polyol, polycarbonate
polyol, castor oil or a mixture of these. Phase separation
occurs in TPUs because of the thermodynamic immisci-
bility or incompatibility between the hard and soft phase
[1–9]. Phase separation results in microdomain structure
formation as first proposed by Cooper and Tobolsky [1].
The early work of Cooper and Tobolsky [1] and Schollen-
berger [2,3] established that segmented PUs consist of high
glass transition temperature (Tg ) or high melting temper-
ature (Tm ) hard domains (HD) microphase-separated from
relatively low Tg soft domains (SD). The degree of phase
separation in PUs depends on the types of diisocyanate
and polyol employed to produce the PU, CE nature, type of
polyfunctional compound used in the crosslinking process,
NCO:OH ratio, sizes of HSs and SSs, method of synthesis,
etc. Fig. 1 shows the HD and SD structures of TPUs at low
and high hard segment content. The domain size may range
from 3 to 20 nm and depends on the reactants used as well
as the polymerization conditions [4].
On the other hand, thermoset PUs are formed by using
either one or a combination of the following:
• using polyols with functionalities greater than 2,
• substitution of a trifunctional hydroxyl compound in
place of the normal glycol CE,
• using isocyanates with functionalities greater than 2,
• using NCO:OH ratios greater than 1, and
• introduction of a crosslinker into the HS, SS or CE.
A detailed description of the different schemes involved
in the synthesis of high performance thermoset PUs can be
found elsewhere [9]; whereas the present article is devoted
towards an understanding of the importance of thermal
degradation studies, processes occurring during thermal

Fig. 1. Hard domains (HD) and soft domains (SD) of TPUs with (a) a low hard segment content where HDs are isolated; and (b) a high hard segment
content where HDs are interconnected. Reproduced from [8] with permission, which was adapted from [6,7] also with permission. Copyright 2005 Elsevier;
Copyright 1991 Elsevier; Copyright 2007 American Chemical Society.
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
stress, factors influencing the thermal stability of PUs and
methods available to improve the thermal stability and
flammability of PUs.
1.1. Importance of understanding thermal degradation
The thermal decomposition of PUs (their degradation
attributed to absorbed thermal energy) constitutes an
important phenomenon from both a fundamental and a
technological perspective [10]; the investigation of degra-
dation processes allows for the determination of optimum
conditions for designing and processing PUs as well as
obtaining high-performance polymers with improved ther-
mal stability [11–15]. Therefore, it is essential to analyze
the decomposition process in such a way that the different
aspects involved are considered in a systematic manner.
Fundamental research has established that the thermal
decomposition of PUs is a complex heterogeneous process
and consists of several partial decomposition reactions [16].
The decomposition of PUs occurs as a result of a multitude
of physical and chemical phenomena and is not dominated
by a single process. The study of the decomposition of PUs is
particularly difficult since they degrade with the formation
of various gaseous products and a number of decompo-
sition steps are typically observed in thermogravimetric
analysis (TGA) experiments. Some authors claim that the
study of the thermo-degradation behavior of PUs at high
temperatures provides a fingerprint of the material that
has to do not only with the characteristics of the original
material, but also with its processing and the final qual-
ity of the end-use products [17]. Furthermore, the study of
thermal stability by means of TGA allows the analysis of the
degradation response of the sample subjected to different
atmospheres (inert or oxidizing) and to draw conclusions
with respect to its useful life and durability [18].
An important characteristic of any material for appli-
cation purposes concerns its thermal stability, especially
when considering the potential end uses in varying fields.
The thermal stability of a material is defined by the spe-
cific temperature or temperature-time limit within which
the material can be used without excessive loss of prop-
erties [19]. With respect to commercial applications, the
investigation of thermal decomposition processes has two
important aspects. The first concerns the stabilization of
a polymer to obtain novel materials with a desired level
of thermal stability/flame resistance that will be able to
fulfill the demands of contemporary materials engineering
[9,20]. The second is to understand material performance
as well as to obtain characteristic thermal decomposition
data for further study. For instance, the usefulness of many
PU materials is largely determined by their thermal, oxida-
tive, and fire resistance. Crucial information in this area
is obtained from kinetic and mechanistic studies of ther-
mal degradation and is a wide application area for thermal
analysis methods, especially thermogravimetric analysis
(TGA). TGA is a valuable tool towards developing a bet-
ter understanding of degradation mechanisms of polymers
and offers methods for the evaluation of kinetic parame-
ters, provided that the basic relationships and assumptions
on which they are based are properly taken into account.
A more complete analysis of the investigated phenomena
1071
is possible if methods for identification of volatile prod-
ucts are applied, such as the techniques of pyrolysis–gas
chromatography/mass spectrometry (Py–GC/MS), TGA-MS
or TGA-FTIR analysis [21].
1.2. Processes occurring during thermal stress
Upon thermal excitation, the covalent bonds in PU
chains undergo complex vibration and rotation within their
local space. With further excitation, these bonds can break
to form a variety of fragment radicals or small molecules,
which may further mutually recombine or undergo further
fragmentation. Ultimately, the resulting fragments may be
vaporized, diffused out, or carbonized. The decomposi-
tion process ends with the loss of all volatile material and
with the formation of char (a complex insoluble material)
that does not change further above the char temperature.
Depending on the structure of the PU, char is composed of
polynuclear aromatic carbon containing compounds with
heteroatoms such as O, N, P, S and consists of crystalline
and amorphous regions. In addition to the carbonaceous
(char) residue, inorganic residue might also be present and
originates from heteroatoms contained in the PU, either
within the structure or as a result of additive incorporation
[22–29]. Therefore, the thermal stability is a direct mea-
sure of molecular rigidity, because chemical reaction and
degradation depends on macromolecular chain excitation
and motion gained from the thermal energy during expo-
sure to a high temperature. The course of decomposition
is affected not only by the nature of the sample but is also
affected by the surrounding environment.
The thermal decomposition of PUs takes place via any of
the following routes or more likely through a combination
of them: (1) random-chain scission, (2) chain-end scis-
sion, i.e., unzipping, and (3) crosslinking. However, random
chain scission and crosslinking are predominant routes for
the decomposition of PUs. For crosslinked PUs, the bond
breaking inside the bulk polymeric matrix requires sub-
stantial heat energy. Therefore, the thermal decomposition
of crosslinked PUs starts preferentially via degradation of
side chains. In general, the thermal degradation of PUs
involves an initial stage where trapped volatile materials
are released. The next step is scission and depolymeriza-
tion, resulting in weight loss and degradation of mechanical
properties (Scheme 2). Finally a complete thermal break-
down of the chains yields a mixture of simple hydrocarbons,
CO, CO2 , HCN, MeOH, acetonitrile, acrylonitrile, propi-
onitrile, pyrrole, pyridine, aniline, benzonitrile, quinoline
and phenylisocyanate) and a complex char [23,30–33].
However, the composition of the decomposition products
depends on the structure of the PU material.
1.3. TGA, pyrolysis–GC/MS, TGA-MS and TGA-FTIR
analysis
Thermogravimetric analysis (TGA) is an analytical tech-
nique that measures the weight of a small PU sample
(typically 10 mg or less) as a function of time or temperature
and hence gives a quantitative description of the thermal
stability of the material and the amount of the correspond-
ing residue. The measurement is normally carried out in
1072 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

Scheme 2. Thermal degradation mechanism of (a and b) the urethane segment [19] and (c) N-substituted PUs [33].

an atmosphere such as N2 /helium/argon or in air, O2 , to
understand the thermal stability of the materials in an inert
atmosphere or to study their thermo-oxidative stability,
respectively. TGA experiments can be carried out as either
isothermal or non-isothermal (i.e., dynamic) weight-loss
measurements. The isothermal method requires almost
instantaneous heating of the polymer sample to the desired
temperature, followed by maintaining that temperature for
a specified time. On the other hand, non-isothermal meth-
ods require a program with a linear increase in sample
temperature with respect to time. TGA instruments usually
consist of a high-precision balance with a pan containing
the sample and the pan is placed in a small electrically
heated furnace containing a thermocouple that accurately
measures the temperature. Since the instrument records
the weight of the sample with respect to time, therefore
the instrument needs to have a high degree of precision in
measurements such as weight (wt), temperature (T), tem-
perature change (T) and time (t). Once the experiment
is over, the data can be presented in terms of percent wt
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
change vs. T or t, which is known as a TGA thermogram.
Curve smoothing and other operations may be done to find
the exact points of inflection. In addition to the TGA thermo-
gram, a derivative weight loss curve known as differential
thermogravimetric analysis (DTG) can be used to under-
stand onset decomposition temperature, the temperature
at which the rate of decomposition is at a maximum, end
decomposition temperature as well as the number of steps
involved in the thermal degradation of the sample. Each
step of weight loss corresponds to a peak in the DTA curve
that could be due to one or a series of degradation processes
occurring in a particular temperature range. Sometimes,
interpretation may require further manipulation and/or
deconvolution of overlapping peaks due to the complex-
ity of the process. In summary, classical TGA experiments
allow researchers to follow the overall change of mass of
a PU sample under precisely controlled temperature–time
relationships. However, researchers need to establish a few
fixed experimental parameters such as heating rate, initial
sample mass, environment, etc. Changes in these param-
eters can have an impact on the thermo-stability of the
polymer. For instance, increasing the heating rate has a
positive influence on the thermal stability because of the
hindered diffusion of decomposition products. Similarly, a
change in the environment from N2 to O2 typically results
in a decrease in thermal stability of the sample [34,35].
Therefore, the experimental parameters used for evalua-
tion should be the same for accurate structure–property
comparisons of different PUs.
In addition to studying the kinetics of the thermal
decomposition steps, researchers also try to under-
stand the nature of the complex decomposition pro-
cess. Pyrolysis–gas chromatography/mass spectrometry
(Py–GC/MS), a simple, rapid, reliable, sensitive and repro-
ducible method, is widely utilized to characterize the
volatiles formed during the thermal decomposition of poly-
mers. Pyrolysis–GC/MS has the capability to evaluate the
relative composition of the volatiles formed during decom-
position in the pyrolyzer. The pyrolyzates provide abundant
information for investigating the structure of polymers.
Identification of degradation products at different temper-
atures, times and heating rates gives information on the
decomposition mechanism [32,36,37].
Coupling a TGA instrument with an evolved gas ana-
lyzer such as an FTIR or a mass spectrometer produces a
powerful analytical technique that gives information from
the thermal balance as well as compositional informa-
tion from the spectrometer simultaneously. Determination
of volatile products evolved during thermal degradation
using TGA-MS or TGA-FTIR analysis gives important infor-
mation regarding the nature and mechanism of thermal
decomposition [38]. Coupling a TGA instrument with an
MS analyzer provides high sensitivity and high resolution
measurements of extremely low concentrations of evolved
gases during the degradation process. The MS analyzer
repeatedly measures the entire mass spectrum and mon-
itors the intensity of characteristic fragment ions (m/z;
the mass to charge ratio). On the other hand, a single
TGA-FTIR analysis can provide extensive information with
regard to the weight loss with respect to time and tempera-
ture, decomposition kinetics, char reactivity and functional
1073
group composition. The TGA-FTIR apparatus consists of a
sample suspended from a balance in a gas stream within a
furnace and once the sample is heated volatile decomposi-
tion products are formed. The TG-FTIR system has a suitable
interface to carry the gaseous decomposition products from
the TGA furnace to the detection system of an FTIR spec-
trometer, i.e., the method consists of carrying the evolving
volatile products out of the furnace directly into the FTIR
gas cell, where the gases are analyzed. The instrument pro-
vides different ways of viewing the TGA-FTIR data and these
include: (1) tabular display of mass loss and gases evolved
in each region; (2) display of individual spectra at different
temperatures during the dynamic or isothermal TGA exper-
iments; (3) display of spectra at different temperatures as
a stacked plot; and (4) display of the IR transmittance for
some peak(s) overlaid on the TGA curve [39].
1.4. Cone calorimetery, limiting oxygen index (LOI) and
UL-94 analysis
The cone calorimeter test is widely used to examine the
performance of fire retardant polymers and it is at present
the one of the most advanced method for assessing the
fire behavior of materials. The test apparatus contains an
electric heater, an ignition source and a gas collection sys-
tem. In cone calorimetery, the thermal response of a sample
depends on the applied radiation intensity. The principle
of cone calorimeter experiments is based on the measure-
ment of the decreasing O2 concentration in the combustion
gases of a sample subjected to a given heat flux. The test
gives a possibility to evaluate: (i) ignition time, (ii) heat
release rate (HRR) and mass loss, (iii) specific extinction
area, (iv) the ignitability; (v) the combustibility; (vi) the
smoke production and (vii) the production of toxic gases.
Typically, the subject material is irradiated with a heat
intensity similar to that experienced in a fire situation
(25–75 kW/m2 ) and the ignition, heat release and smoke
release characteristics of the materials are measured. Gen-
erally, the heat of combustion of any organic material is
directly related to the amount of oxygen required for com-
bustion in which 13.1 MJ of heat is released per kg of oxygen
consumed [40]. The cone calorimeter brings quantitative
analysis to materials flammability research by investigating
parameters such as heat release rate (HRR), time to ignition
(TTI), total heat release (THR) and mass loss rate (MLR). The
HRR measurements can be further interpreted by looking at
average HRR, peak HRR and time to peak HRR. Heat release
rate is the key measurement required to assess the fire haz-
ard of materials and products as it quantifies fire size, rate
of fire growth and consequently the release of associated
smoke and toxic gases. The cone calorimeter, if so config-
ured, can also measure and quantify smoke output as well
as CO/CO2 release rates [41]. Cone calorimeter tests can be
conducted in accordance with national and international
standards including BS 476 (Part 15), ASTM 1356-90, ASTM
E1354 and ASTM E1474, ISO 5660 [40].
The limiting oxygen index (LOI) or oxygen index (OI) is
a method for evaluation of the flammability of materials.
LOI is defined as the minimum concentration of oxygen in
an oxygen–nitrogen mixture, required to sustain burning
of a vertically mounted specimen. Thus, the more oxygen
1074 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
required (higher LOI), the stronger the flame retardancy
effect. The oxygen index was described as follows and oxy-
gen index of the air is 21.
[O2 ]
oxygen index = × 100
[O2 ] + [N2 ]
As air contains 21% O2 , materials with an LOI below 21
are combustible, whereas those with an LOI above 21 are
self-extinguishing.
Hence, higher LOI values represent better flame retar-
dancy and a smaller LOI represents a more flammable
material [42]. Preliminary tests are first carried out in order
to ascertain the approximate O2 /N2 ratio required for the
material under investigation. This is reached when the
materials burns at a uniform slow rate after ignition. The
oxygen content of the O2 /N2 mixture is then lowered until
the test specimen just continues to burn. After the next
lower O2 concentration (a reduction of 0.2% in the oxygen
content) the test specimen must be extinguished. The oxy-
gen index can be determined by the ASTM D 2863, ISO 4589,
DIN 4102-B2, NF T51-071 procedures.
UL-94 horizontal (ASTM D 635, IEC 60695-11-10, IEC
60707, ISO 1210) and vertical (ASTM D635-77, ASTM D3801,
IEC 60695-11-10, IEC 60707, ISO 1210) burning tests are the
standard applied by the American Underwriters Laborato-
ries for testing the flammability and fire safety of plastic
materials used in devices and appliances. Underwriters
Laboratories is a non-profit organization that operates lab-
oratories around the world for examination and testing of
devices, systems and materials. Underwriters Laboratories
identifies material properties and their hazards. UL-94 tests
classify plastics according to the way they burn in vari-
ous orientations and thicknesses [43]. UL-94 contains test
procedures for both horizontally and vertically positioned
test specimens in the form of rods. In the UL-94HB (Hori-
zontal Burning) test, the burning of a horizontal specimen
is tested, and in the most demanding HB, specifications
are: slow burning on a horizontal specimen; burning rate
<76 mm/min for thickness <3 mm. In UL-94VB (Vertical
Burning) tests, the test specimen is vertical and ignited
by a Bunsen burner to be classified according to self-
extinguishing characteristics as V-0, V-1, or V-2. These
tests are more rigorous than the HB test since the vertical
specimens are burned by their lower ends, thus preheat-
ing material above it, and the samples must extinguish
themselves. The top class, i.e. V-0 is achieved if the mean
inter-flame time of five samples after 10 applications of the
flame does not exceed 5 s. The material is placed in class
V-1 if the mean after-flame time is less than 25 s. If flaming
drippings occur, the material is classified in V-2; the igni-
tion of surgical cotton placed below the specimen serves as
a criterion for this phenomenon [40,44].
1.5. Thermal degradation mechanisms of PUs
From the literature, it is obvious that the thermal degra-
dation of PUs occurs in a two- to three-step process
[29,45–49]. The first step is due to degradation of the HS,
which results in the formation of isocyanate and alcohol,
primary or secondary amine and olefin, and carbon diox-
ide. The rate of the first degradation stage decreases when
a higher content of soft segments is used. The second and
third steps correspond to the thermal decomposition of the
SS. After the first decomposition step, i.e., when the weakest
bonds in the PU have been broken up, the second and third
steps are much slower and depend on the SS structure and
its three-dimensional arrangement. The simultaneous use
of IR data suggests that the rupture of the weakest bond,
C–NH, having an activation energy of about 98 kJ/mol, is
the primary degradation step. The temperature of the ini-
tial decomposition of the urethane bond depends on the
structure of the isocyanate and alcohol used. Researchers
have reported that the more easily formed urethanes are
less stable, i.e., they easily dissociate, and the highest degra-
dation temperatures are generally observed for urethanes
that form slowly such as from an alkyl isocyanate and an
alkyl alcohol [27,29,50,51]. As the reactivity in the follow-
ing series increases, the decomposition temperature of the
urethane bond decreases:
alkyl isocyanate-alkyl alcohol (∼250 ◦ C) > aryl
isocyanate-alkyl alcohol (∼200 ◦ C) > alkyl isocyanate-
aryl alcohol (∼180 ◦ C) > aryl isocyanate-aryl alcohol
(∼120 ◦ C) [52].
For instance, urethane groups made from phenols revert
quite readily at moderate temperatures.
The thermal decomposition of urethanes has been the
subject of numerous studies over the past 40 years. Work
pertinent to commercial PUs has been summarized by
Ravey and Pearce [53]. Early studies of model carbamates
by Dyer et al. [54,55] indicated three pathways for the ini-
tial low temperature (180–300 ◦ C) cleavage of the urethane
linkage, whereas Saunders and Frisch [56] and Pielichowski
et al. [57] summarized four types of reactions that take
place in the thermal degradation of urethanes (Scheme 2).
The thermal stability of PUs depends primarily on the
polymerization ⇔ depolymerization equilibria of the func-
tional groups in the polymer molecule [58]. The isocyanate
formed during thermal decomposition may be dimerized
to carbodiimide. Carbodiimide can then react with ure-
thane groups to form a crosslinked structure. Dissociation
to primary amine, CO2 and olefin (Eq. (2); Scheme 2(b))
is reported to proceed via a six-membered ring transition
state (TS), possibly with a carbamic acid (R–NH–COOH)
intermediate [54,55]. On the other hand, formation of a
secondary amine and elimination of CO2 is reported to pro-
ceed via a concerted intramolecular displacement of carbon
dioxide with a four-membered ring TS [54,55; Eq. (3)].
While these reaction mechanisms were initially developed
for simple (nonpolymeric) urethanes, the general reactions
are also believed to be applicable to commercial materi-
als. In a review of the subject, Fabris stated that urethanes
made from primary and secondary alcohols start to decom-
pose (albeit very slowly) in the 150–200 ◦ C temperature
range [19]. The decomposition proceeds at a measurable
rate between 200 and 250 ◦ C. Also the kinetics of the
thermal decomposition depends on the electron-acceptor
(aromatic) or electron-donor (aliphatic) character of the
isocyanate. In the former case the decomposition will fol-
low Eq. (2), while in the latter case it will follow Eq. (1) of
Scheme 2(a) [59].
Grassie investigated the degradation mechanism of
MDI and BD urethane segment and suggested that hard
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
segment degradation is a depolycondensation process
that takes place around 210 ◦ C, followed by a complex
process of degradation [60]. Lattimer et al. studied the
degradation of segmented PUs based on MDI, hydroxyl-
terminated tetramethylene glycol adipate (PMGA) and diol
chain extenders such as BD or 1,4-cyclohexane dimethanol
(1,4–CHDM) [61]. At lower temperatures (<300 ◦ C), the
major products were those of Eq. (1) of Scheme 2(a) to
produce the starting materials. At higher temperatures,
degradation of the polyester to cyclic oligomers became
prominent. Gaboriaud and Vantelon tested the decom-
position mechanism of a PU consisting of MDI, PPG and
trimethylol propane (TMP) units [11]. They found that at
lower temperatures (250–400 ◦ C) the reaction according to
Eq. (1) was dominant while at higher temperatures (over
400 ◦ C) the radical decomposition of the polyol chain was
superimposed on the decomposition according to Eq. (1) of
Scheme 2(a). The formation of methane, ethane, propane,
ethylene, propylene, ethanol, propanol as well as CO2 was
detected as the decomposition products [11,62]. Abu-Zeid
et al. proved by photo-accustic absorption spectroscopy
that PUs based on MDI decomposed to their constituents
on heating. At the same time, formation of amines and
dienes was observed during the decomposition process
[63]. Herrera et al. studied PU degradation using TGA-MS
and TGA-FTIR analysis and found degradation products
such as H2 O (m/z 18), CO2 (m/z 44), HCN (m/z 27) or some
nitriles, BD or oligomers from n-butyl ether (at m/z 41,
57, 71) and degradation products from the poly(butanediol
adipate) and the chain extender (at m/z 31, 39, 42, 54 and
71) [32]. The thermoplastic PU samples were prepared from
MDI, tetrahydrofuran as polyether or butanediol adipate as
polyester and BD as chain extender.
Zhang et al. synthesized PUDs from polycaprolactone
glycol, TDI and dimethylolpropionic acid (DMPA) and stud-
ied the thermal degradation process with Py–GC/MS and
TGA analysis. They have identified more than 20 character-
istic volatile pyrolyzates and classified the pyrolyzates into
three groups shown below [64]:
• Group I. Carbon dioxide (m/z of 44), 1-pentanol
(m/z of 88) 1,3-diisocyanate-2-methyl-benzene (m/z of
174), 2,4-diisocyanate-1-methyl-benzene (m/z of 174),
2-methyl-1,3-benzenediamine (m/z of 122) and 4-
methyl-1,3-benzenediamine (m/z of 122). These products
arise due to the primary scission of the urethane linkage
and the ester bond.
• Group II. 1,3-Cyclopentadiene (m/z of 66), cyclopentene
(m/z of 68), cyclohexanone (m/z of 98), 2-propenoic
acid, 2-propenyl ester (m/z of 112), cyclopentanone
(m/z of 84), 2-methyl-2-propenoic acid (m/z of 86),
1-cyclopropyl-2-propen-1-one (m/z of 96), 2-methyl-2-
cyclopenten-1-one (m/z of 96), 2-cyclohexen-1-one (m/z
of 96), 5-hexenoic acid (m/z of 114), hexanoic acid (m/z
of 116), 2-oxepanone (m/z of 114) and cyclopentanecar-
boxylic acid, heptyl ester (m/z of 212) is generated from
the degradation of the polyester construction of the PU,
followed by dehydration, hydrogen transfer and ester
exchange reactions.
• Group III. Unsaturated (olefinic) end groups such as 1-
pentene (m/z of 70), 1,5-hexadiene (m/z of 82) and
1075
2-methyl-2-propen-1-ol (m/z of 72) produced according
to step 2 of Scheme 2(a) or due to the pyrolysis of the
polyester itself.
In another article, Zhang et al. qualitatively and quan-
titatively investigated the thermal degradation of PU dis-
persions by Py–GC/MS and TGA. The PUDs were prepared
from PPG, IPDI, BD and DMPA [65]. The primary scission of
the urethane linkage and the ester bond in the pyrolyzate
corresponds to BD, IPDI, structural isomer of IPDI, 3-
aminomethyl-3,5,5-trimethyl cyclohexyl isocyanate and
CO2 . The other group of volatiles in the pyrolyzate
corresponds to tetrahydrofuran (THF), oxepane, cyclopen-
tanealdehyde, 2-propenoic acid, 2-methyl-, oxiranylmethyl
ester, cyclopentanol, 2-oxepanone, 1,6-hexanediol, 2-
propenoic acid, 2-methyl-cyclohexylester, cyclopentane
carboxylic acid, undec-10-enyl ester, dodecanoicacid,
5-hexen-1-yl ester and 1,5,12,16-tetraoxa-cyclodocosane-
2,4,13,15-tetraone generates from the thermal degradation
of the polyether-polyol, followed by dehydration, hydrogen
transfer and ester exchange reactions. The generation of
unsaturated (olefinic) end groups containing compounds
such as 2-methyl-2-propen-1-ol and 5-hexen-1-ol could
be due to the urethane dissociation as shown in Eq. (2)
of Scheme 2(a) or could be due to the pyrolysis of the
polyether PPG itself. In an earlier pyrolysis study of a PU
foam, it was proposed that diols formed by Eq. (1) shown
in Scheme 2(a) could dehydrate to produce secondary prod-
ucts with olefinic end groups (Scheme 2(b); [66]).
Beachell and Ngoc Son investigated the decomposi-
tion of a PU synthesized from TDI and ethylene glycol in
N2 atmosphere at 150–215 ◦ C. 2,4-Toluene diamine, ethy-
lene glycol, ethylene oxide, carbon dioxide and water as
well as polyurea residue were found as the decomposition
products. A reaction according to Eq. (1) of Scheme 2(a)
was assumed as the first step of the decomposition and
the amine formation was attributed to secondary reac-
tions [67]. Ingham and Rapp studied the decomposition
of a TDI–PPG based PU and found that low-temperature
degradation (∼200 ◦ C) led to the substantial regeneration
of monomers PPG and TDI [68]. However, they also found
evidence for the formation of unsaturation, aromatic amine
and CO2 , particularly when diffusion of TDI from the poly-
mer is limited. At temperatures above 250 ◦ C, scission of the
polyether bonds takes place. Wooley studied the decom-
position of TDI-based polyester (ethylene adipate) and
polyether (glycerol:propylene oxide:ethylene oxide) ure-
thane foams [69]. In a flowing pyrolysis system (in which
volatile products are removed from the hot zone), there was
a rapid and complete loss of the TDI unit in the heating
range 200–300 ◦ C, leaving a polyol residue. A characteris-
tic yellow smoke was formed under these conditions, but
its identity was not determined. Ravey and Pearce reported
the pyrolysis of PU based on TDI and a complex polyether
(glycerol:propylene oxide:ethylene oxide) [53]. Pyrolyses
conducted in the range 320–360 ◦ C showed near quantita-
tive loss of TDI under flowing conditions; the residue (by
infrared analysis) consisted largely of regenerated polyol.
Under confined conditions, however, diamine (diamino-
toluene) was produced. Ravey and Pearce proposed that the
decomposition followed both Eqs. (1) and (2), but that Eq.
1076 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

(1) of Scheme 2(a) has a much higher rate. When TDI pro-
duced by reversible Eq. (1) is confined to the pyrolysis zone,
an equilibrium is established in which the irreversible Eq.
(2) is favored. Earlier work with a similar PU also indicated
that Eq. (1) dominates, with some contribution by Eq. (2)
as well [56].
Researchers have stated that decomposition to primary
amine and olefin by Eq. (2) of Scheme 2(a) is favored
when the corresponding alcohol is easily dehydrated (e.g.
tertiary alcohols). Voorhees and Lattimer tried to deter-
mine the decomposition mechanism of a PU based on
poly(phenyl isocyanate), PPG and TMP by isotope trac-
ing [70]. The decomposition mechanism according to Eq.
(1) of Scheme 2(a) was assumed as the primary reaction
while the majority of the detected decomposition products
(aliphatic, saturated and unsaturated hydrocarbons, aro-
matic hydrocarbons, alcohols, aldehydes, ketones, amines,
polyol fractions and carbon dioxide) were considered as
products of secondary reactions.
Wang et al. studied the thermal degradation behavior in
N2 environment of different PUs using TGA-FTIR analysis
and identified the pyrolysis gas products such as THF and
CO2 [71]. Other researchers have investigated the thermal
degradation of polyurethanes by means of TGA-MS [72–75]
and TGA-FTIR analysis [71,76].
The mechanism of thermal decomposition also depends
on the type of substituents on the N and O atoms in
the urethane groups. For instance, Balhsteri showed that
N-monosubstituted PUs follow quantitative depolycon-
densation, whereas N-disubstituted PUs did not form
isocyanate and alcohol, but produced a secondary amine,
an olefinic end group and CO2 [12]. Montaudo and co-

Scheme 3. (a) Thermal degradation of BD chain extended PU (PUBD) prepared from MDI as diisocyanate and PTMG as polyol in N2 atmosphere and (b)
hard segment degradation of 2,4-hexadiyene-1,6-diol chain extended PU (PUDA) prepared from MDI as diisocyanate and PTMG as polyol in N2 . The soft
segment decomposition products of PUDA are same as that of PUBD [83].
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
workers demonstrated that N-substituted PUs containing
an aliphatic chain adjacent to the oxygen atom (i.e., made
from an aliphatic di-alcohol) decompose thermally via
an intramolecular hydrogen-transfer reaction producing
olefin, secondary amine and CO2 (Scheme 2(c)). For aro-
matic N-substituted PUs the formation of cyclic oligomers
in the primary thermal fragmentation has been established
[12,77–80]. The same group also synthesized aromatic,
aliphatic and N-substituted PUs and examined their ther-
mal decomposition [79]. It was stated that in addition to the
dominant mechanism characteristic of the decomposition
of aromatic and aliphatic polymers cyclic products are also
formed [79]. Researchers also showed that a recombination
reaction leading to tertiary amines might be operative in
the thermal degradation of N-substituted PUs [33,81]. Liaw
and Lin showed that the thermal stability of N-substituted
PUs depends on the degree of N-substitution [82].
Chuang studied the thermal degradation of diacetylene-
containing PUs consisting of MDI and PTMG and two
different short chain diols, BD and 2,4-hexadiyene-1,6-diol
(DA), by TGA and TGA-FTIR analysis. They identified CO2 ,
THF and ether-containing olefin and carbodiimide as the
main decomposition products; the proposed degradation
mechanism is shown in Scheme 3 [83]. In another study,
Chuang et al. investigated the degradation of poly(siloxane-
urethane) copolymers by TGA and TGA-FTIR analysis and
identified degradation products between 250 and 292 ◦ C
due to THF and CO2 (arising from the degradation of ure-
Scheme 4. Formation of substituted ureas and isocyanurate during thermal decomposition of PUs in N2 environment [87,88].
1077
thane groups consisting of BD and isocyanate), and between
292 and 406 ◦ C due to CO2 generation and degradation
of the siloxane soft segment [84]. Lattimer et al. stud-
ied the low temperature pyrolysis products of segmented
PUs by MALDI-MS analysis and showed that at higher
temperatures (>300 ◦ C) the nitrogen-containing pyrolyzate
oligomers are no longer present in the residue confirm-
ing the complete loss of diisocyanate from the PU before
attaining a temperature >300 ◦ C [85]. They have also
observed the formation and dehydration of linear and cyclic
polyester pyrolyzates at higher temperatures >300 ◦ C. For
both polyester and polyether based PUs the intramolec-
ular exchange to produce cyclic, low molecular weight
urethane-containing oligomers was observed. Additionally,
cyclic polyesters were observed as pyrolyzates from the
polyester-PU but no cyclic polyethers were observed as
pyrolyzates for PEG or PTMG based PUs [86].
Berta et al. showed that PUs degrade and produce alco-
hol and isocyanates in the first step in a N2 atmosphere
[87]. The second step is the dimerisation of isocyanates to
carbodiimides, which react with the alcohol groups to give
relatively stable substituted ureas. Substituted urea then
decomposes in the third step. Trimerisation of isocyanates
may also occur under certain conditions to yield thermally
stable isocyanurate rings (Scheme 4). The final step is the
high temperature degradation of these stabilized structures
to yield volatile products and a small quantity of carbona-
ceous char [89].
1078 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Several other studies have focused on the gaseous prod-
ucts from the combustion of PU [11,66,89–91]. However,
because of the highly crosslinked structure of the char
formed even at low temperatures, detailed chemical anal-
ysis of this residue has proven to be difficult [92].
1.6. Thermo-oxidative degradation
The oxidative stability of PUs is of great concern to mate-
rials scientists from an application point of view, as the
material has to withstand both the deteriorating effect of
O2 (singlet state) as well as thermal stress [19]. During the
autoxidation process, PUs in the presence of heat react with
molecular oxygen, resulting in the loss of physical prop-
erties and discoloration of the material. During oxidative
degradation process, free radicals (R• ) are produced and
react rapidly with molecular oxygen to form peroxy radi-
cals (ROO• ). The peroxy radicals may further react with the
PU chain and form hydroperoxides (ROOH). In the presence
of heat, hydroperoxides decompose and produce more rad-
icals that can reinitiate the decomposition of PUs. However,
researchers reported that the presence of oxygen does not
influence the decomposition rate of PU to diisocyanates
and polyols, although it affects the breakage of the poly-
meric chains [93,94]. Researchers have shown that the SS
is more prone to oxidative degradation than the HS and
this may be the cause of the discoloration of foams typ-
ically known as scorch [95]. Under oxidative conditions,
Gaboriaud et al. found that for polyether-based PUs, the
first step involves the scission of the PU molecule into pri-
Scheme 5. Schematic diagram of the oxidative degradation of a PTMG segment [97].
mary amine, carbon dioxide and propenyl ether species; the
latter leading to propene formation [11]. The mechanism
was reduced to a depolymerization process followed by
radical breakdown of the polyol chain in conjunction with
simple radical formation. The radicals formed can explain
the formation of the various gaseous species formed dur-
ing heating. Researchers have shown that PU elastomers
(whose composition was changed by varying the polyol,
isocyanate and chain extender) were thermo-resistant up
to their melting point. In the molten state they were highly
sensitive to oxidation unless stabilized by the addition of
antioxidants. The oxidation of polyethers, e.g. PEG, PPG or
PTMG, usually starts at the ␣-position of the ether bridge
and proceeds by a radical chain process via hydroperoxide
formation (Scheme 5). Oxidative initiation is thought to be
site-specific at the –CH2 –O– linkage when the hydrogen
atom is abstracted from SS followed by breakage of the C–O
bond and subsequent unzipping of the polyether chains
[29,96]. An auto-catalytic oxidation takes place for PTMG in
between 90 and 120 ◦ C. At the beginning of oxidation, the
rate of O2 consumption was the same as for the formation
of hydroperoxide. However, in the latter stages of degra-
dation, decomposition products also influence the rate and
amount of O2 consumption [98]. The sensitivity of oxidative
degradation is higher for the PPG segment in comparison to
PEG and PTMG segments in PUs. The formed hydroperoxide
decomposes and produces free radicals, which in turn fur-
ther initiate decomposition [56]. This finally leads to chain
scission and a reduction in the molecular weight of the PU
and, as a consequence, the mechanical properties decrease.
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133 1079

Scheme 6. A simplified diagram of the thermo-oxidative degradation mechanism of the ester segment in polyester based PUs [99,100].

Aldehydes, acetates and formates have been identified as
products resulting from oxidation [98].
Polyester-PUs are more resistant to thermo-oxidative
degradation than polyether-PUs. Scheme 6 shows the
thermo-oxidative degradation mechanism of the ester seg-
ment in a polyester based PU and the formation of char at
high temperature [99,100]. The oxidation of aromatic PUs
results in the formation of a quinoid structure and produces
discoloration in the polymer (Scheme 7; [101]). The for-
mation of conjugated products from aromatic PUs at the
beginning of thermo-oxidation might act as an inhibitor
for further thermo-oxidation of the polyether chains in
polyether based PUs [19].
While working with an MDI based polyester-PU, Ser-
vay et al. have shown that the MDI methylene unit was
converted into a benzophenone structure (Scheme 8)
upon oxidation whereas the urethane groups were hardly
affected [98]. Their investigations on thermal aging of TPUs
showed that, in addition to the polyether segments, the MDI
structure in TPUs is also another weak point in the polymer
structure. Therefore, the aging of TPUs can be retarded by
the right choice of raw materials.
1080 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Scheme 7. Mechanism of quinoid formation via hydrogen abstraction
from the N- and C-atoms and electronic rearrangement of the diisocyanate
portion in the PU structure. Reproduced from [101] with permission. Copy-
right 1997 John Wiley and Sons.
1.7. Kinetic parameters from thermal degradation
The derivation of kinetic data in the study of PU decom-
position using TGA has received increasing attention in the
last decade. Kinetic data obtained from TGA is very useful
for understanding the thermal degradation processes and
mechanisms, used as input kinetic parameters through the
course of the degradation and of the relationship of the
data obtained in the process to other interesting proper-
ties. Kinetic studies also help to identify whether or not a
stabilizer, filler or an additive helps to improve the ther-
mal stability of a material. The values for activation energy
and reaction order obtained depend on atmosphere, sam-
ple mass, sample shape, flow rate, heating rate, and the
mathematical treatment used to evaluate the data [102].
Scheme 8. Benzophenone formation during the thermal oxidation of MDI based PU Reproduced from [98] with permission. Copyright 2000 Elsevier.
A reaction rate is defined as the derivative of conversion
with respect to time. The normalized TG curves were used
for the percentage conversion evaluation.
The rate of conversion in a dynamic TGA experiment at
a constant heating rate can be expressed as:
d˛
 d˛ 
=ˇ = k(T )f (˛) (1)
dt dT
where ˇ is the heating rate (ˇ = dT/dt, unit: ◦ C/min), k(T)
is the temperature-dependent rate constant, t is the time,
T is the absolute temperature in K (T = T0 − ˇt), f(˛) is
the differential form of kinetic model and ˛ is the extent
of decomposition defined as the ratio (m0 − m)/(m0 − mf ),
where m0 , m and mf refer to the initial, actual and final
mass of the sample. f(˛) depends on the particular decom-
position mechanism and describes the dependence of the
reaction rate to the extent of decomposition, ˛. The tem-
perature dependence of the rate constant is described by
the Arrhenius equation as shown below:
d˛
 d˛ 
=ˇ = Z e−E/RT f (˛) (2)
dt dT
where Z (pre-exponential factor, assumed to be indepen-
dent of temperature, unit: s−1 ), E (activation energy, unit:
J/mol) are the Arrhenius parameters and R is the universal
gas constant (8.314 J mol−1 K−1 ). E, A and f(˛) are called the
kinetic triplet and can be used to kinetically describe the
time evolution of degradation [103,104].
The preceding rate expression can be transformed into
non-isothermal rate expressions describing reaction rates
as a function of temperature at a constant heating rate, ˇ:
d˛ Z
= e−E/RT f (˛) (3)
dT ˇ
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133 1081

Eqs. (2) and (3) are the basic equations for kinetic calcu- Therefore, the plot of ln Z(1 − ˛)n vs. ln (1 − ˛) is a straight
lations. The simplest and most frequently given model for line with a slope equal to n:
f(˛) in TGA data is
ln Z(1 − ˛)n = ln Z + n ln(1 − ˛) (11)
n
f (˛) = (1 − ˛) (4)
Chang [107,109,110] method is very similar to the Fried-
where (1 − ˛) is the dimensionless amount of reactive man method and is based on Eq. (12).
remaining and n is the reaction order. The combination of  d˛  E
Eqs. (3) and (4) gives the following equation: ln (1 − ˛)n ] = ln Z − (12)
dt RT
d˛ Z Thus a plot of ln [(d˛/dt)/(1 − ˛)n ] (X-axis) against 1/T
= e−E/RT (1 − ˛)n (5)
dT ˇ (Y-axis) will yield a straight line only if the decomposition
reaction order n was correctly selected. The slope of the
The integral form of the rate equation in a dynamic heat-
line and intercept of the straight line to X-axis will provide
ing experiment may be expressed as
the E and ln Z, respectively.
 ZE 
g(˛) = p(x) (6) Kissinger method [111]
ˇR

where p(x) = f˛x [exp(−x)/x2 ] dx, and x = E/RT g(˛) is the Kissinger assumes that the product n(1 − ˛max )n−1 is
integral form of the conversion dependency function. independent of ˇ and obtained the following expression:
To solve the function p(x) several methods have been    ZR 
developed. Flynn–Wall–Ozawa [105], Friedman [106–108], B E
ln = ln + ln[n(1 − ˛max )n−1 ] − (13)
Chang [109,110], Kissinger [111] and other researchers have 2
Tmax E RTmax
solved this function. The equations used herein are as fol-
lows: where Tmax corresponds to the temperature at the inflec-
Flynn–Wall–Ozawa (FWO) method is a linear integral tion point of the TGA curve and ˛max is the conversion
degree at the inflection point. The plot of ln [ˇ/Tmax2 ] vs.
method based on Eq. (7) [105]. This is a relatively sim-
ple method of determining activation energy directly from 1/Tmax can be fitted to a straight line, and the activation
weight loss vs. temperature data obtained at several heat- energy, E, can be calculated from the slope of the line. The
ing rates. FWO method has the advantage that E can be Kissinger method is applicable without any assumptions
calculated without making any assumptions about the about the reaction mechanism and can be easily applied to
reaction model. determine the activation energy of thermal degradation.
The standard Eq. (5) can be given as follows: Other models for calculating kinetic triplets are shown
in Table 1 [24,106,107,112–124]. Thermal decomposition
d˛ Z −E/RT studies using TGA offer a simple and convenient method
= e dT (7)
(1 − ˛)n ˇ for use as an accelerated ageing process for quality con-
trol experiments. The kinetics of decomposition at elevated
which is integrated with the initial condition of ˛ = 0 at
temperature can be extrapolated back to the service tem-
T = T0 to obtain the following expression:
perature for which the lifetime prediction of the material
 ˛  T is required. The parameter of life-time tf of a PU structure
1 Z
F(˛) = d˛ = e−E/RT dT (8) to failure at a constant temperature can be defined as the
0 (1 − ˛)n ˇ T0 period when the sample weight loss reaches 5%. Thus the
where F(˛) is the integral function of conversion. The result mathematical integration of Eq. (3) can be deduced and give
of the integration of Eq. (8) using the Doyle approximation the new expression shown in Eq. (14), and the parameter
can be simplified as of life-time can thus be evaluated [125]:
 ZE    
0.4567E (0.95)1−n − 1
log ˇ = log F(˛) − 2.315 − (9) tf = eE/RT (n =
/ 1) (14)
R RT Z(n − 1)

Eq. (9) can used to determine the activation energy with-
out knowledge of the reaction order. The activation energy
(E) can be obtained from a plot of logarithms of heating rate
(ˇ) as a function of the reciprocal of temperature (1/T) for
a constant F(˛);the slope of the line will be −0.4567E/R.
Friedman method is a linear differential method based
on Eq. (5) [106–108].
 d˛  E
ln = ln Z + n ln(1 − ˛) −
dt RT
The plot of d˛/dt vs. (1/T) is a straight line with a slope
equal to −E/R and an intercept equal to ln [Z(1 − ˛)n ]. The
reaction order can be evaluated by means of Eq. (11). The
left-hand side of Eq. (5) is constant as the intercept of Eq. (5).
The above equations are used extensively for calculat-
ing the activation energies and degradation parameters to
supplement the qualitative thermo-stability data in spite
of the criticism regarding its use in the determination of
rate constants, activation energies, reaction orders, and
pre-exponential factor. The criticism arises from different
assumptions and approaches used to solve the function p(x)
by different researchers. Researchers have justifiably crit-
(10) icized different methods for the evaluation of the kinetic
triplet (E, Z, and n) [126,127]. Vyazovkin and Wight noted
that different equations ignore the fact that the correla-
tion coefficient and other statistical measures are subject
to random fluctuations and changes in one or more model
parameters away from their true value can compensate for
1082 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

Table 1
Different kinetic models to calculate kinetic triplets.

Model name Equation References

Coats-Redfern When n has a value different from 1, the expression is: [112]
log [{1 − (1 − ˛)1−n }/T2 (1 − n)] = log(ZR/ˇE)[l − 2RT/E] − E/2.3RT for n = l, the expression is:
log [−log (1 − ˛)/T2 ] = log (ZR/ˇE)[1 − 2RT/E] − E/2.3RT
Horowitz-Metzger / 1; and ln [ln(1 − ˛)−1 ] = E8/RTm 2 for n = 1
ln [ln(1 − ˛)1−n ] = −E/RTm 2 + ln (1 − n) for n = [113]
Tm = temperature at maximum rate of weight loss,  = (T − Tm )
MacCallum Tanner log [{1 − (1 − ˛)1−n }/(1 − n)] = log (ZE/ˇR) − 0.483E0.435 − [(0.449 + 0.217E) × 103 ]/T [114]
van Krevelen ln [{1 − (1 − ˛)1−n }/(1 − n)] = ln [Z/ˇ(0.368/Tref )E/RTref (E/RTref )−1 ] + (E/RTref + 1)ln T [115,116]
Broido ln ln(1/Y) = E/RT + Constant where, Y = (m0 − mt )/m0 [117]
Flynn ln (t) = ln [(1 − 2˛)/Z] + E/RT [118]
Flynn Wall log ˇ = log [ZE/R] − ln (˛) − 0.4567 E/RT [24,119]
Friedman-Reich-Levi ln [ˇ(d˛/dT)] = ln Z f(˛) − E/RT [106]
Achar ln [{l/f(˛)}d˛/dt = ln (Z/ˇ) − E/RT [120]
Ozawa ln ˇ = ln [0.0048ZE/R g(˛)] − 1.0516 E/RT [120]
Kissinger-Akahira-Sunose ln [ˇ/T2 ] = ln [ZE/Rg(˛)] − E/RT [121]
Phadnis-Deshpande g(˛) = ZRT2 /ˇE [1 − 2RT/E] e−E/RT [122]
Freeman-Carroll  ln [d˛/dt]/ ln(l − ˛) = n − (E/RT)[ (l/T)/ ln(1 − ˛)] [107]
Heide [ ln (d˛/dt) −  ln f(˛)]/ ln(1 − ˛) = (E/R)[ (1/T)/ ln(1 − ˛)] [123]
Vachuska-Voboril [(d2 ˛/dT2 )/(d˛/dT)]T2 = E/R − [{n/(1 − ˛)}(d˛/dT)T2 ] [124]

and hide the underlying deficiencies of a particular model
[127]. Additionally, the energy and pre-exponential factor
are dependent on the heating rate used [128]. However,
some authors claim a physical meaning for these parame-
ters, showing that a TG curve may be correctly described
by several various kinetic models [129–138].
1.8. Polyurethanes from renewable resources
PU materials from natural, renewable substances such
as vegetable oils have attracted a lot of attention in recent
years. The advantages of these starting materials include
their low cost, easy availability, renewability, attractive
properties related to the oil structure and biodegradability
of the resultant PUs after their use [139–143]. A wide variety
of vegetable oils such as corn, safflower, sunflower, peanut,
olive, rapeseed, palm, canola, castor and soybean oils have
been used for the preparation of segmented PUs. Petrovic et
al. studied the thermal stability of different crosslinked PUs
prepared from different vegetable oil based polyols and PPG
[144–147]. Their study showed that the following factors
affect the thermal stability of urethane groups:
(a) type of polyols used—PUs derived from primary
hydroxyls were more stable than those with secondary
hydroxyls,
(b) structure of polyols—PUs derived from castor oil pos-
sessed higher thermal stability in comparison to
soy-based PUs and PPG–PUs were least stable as
observed by isothermal weight losses in TGA experi-
ments. A comparison of thermal stability of soybean oil
polyol based PU foam vs. PPO-based foam in N2 and air
is shown in Fig. 2.
(c) urethane group concentration—a higher urethane
group concentration lowers thermal stability,
(d) crosslink density—higher crosslink density improve
thermal stability.
They have also concluded that vegetable oil based PUs
have considerably better oxidative thermal stability than

Fig. 2. TGA thermograms of soybean oil polyol based PU foam vs. PPO-based foam in (a) N2 and (b) in air. Reproduced from [144] with permission. Copyright
2000 John Wiley and Sons.
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
standard PPG based PUs [145]. Petrovic et al. also syn-
thesized thermally stable polyisocyanurate cast resins and
foams from soybean oil-based polyols [148,149].
Xu et al. synthesized PUs with different soft segment
weight concentration from polyricinoleate diol (synthe-
sized from methyl ricinoleate), MDI and BD and showed
that polyricinoleate segmented PUs are stable enough to
be processed by injection molding and extrusion [150].
In this regard, PUs based on lignin, a renewable mate-
rial containing both aromatic and aliphatic hydroxyl groups
has also showed good promise of better thermal properties.
For instance, Sarkar and Adhikari prepared lignin-hydroxy
terminated polybutadiene (HTPB) copolyurethane and
HTPB–PU and studied the dynamic and isothermal TGA
behavior in air [151]. They showed that the thermal stabil-
ity of lignin-HTPB containing PUs were higher than that of
HTPB–PUs. The lower rate of thermal degradation of lignin-
HTPB copolyurethane was attributed to its higher crosslink
density than that of HTPB–PU.
2. Parameters affecting thermal stability
The thermal degradation and stability of PUs is related
to the HS, SS and CE structures. Hence, it is understandable
that with variations in the type and amount of these three
basic building blocks of PUs, namely, diisocyanate, long-
chain diol or short-chain diol, the thermal stability of the
resultant product can be altered. The degree to which the
HS and SS phase separate into microdomains also plays a
vital role in determining the thermal stability of segmented
PUs. Also, using the same starting materials, the thermal
stability of PUs can be varied simply by changing the ratio
of the HS to SS (i.e., NCO:OH ratio), catalyst concentra-
tion, temperature of the reaction and method of synthesis.
Therefore, a number of parameters including structural
features, as well as the reaction conditions, can have a dra-
matic influence on the thermal stability of the final polymer
Scheme 9. Structures of MDI, DMMDI, TODI, MPDI, TDI, DADI and polymeric MDI [158].
1083
obtained. In this section, we will briefly survey the struc-
tural parameters and their effect on the thermal stability of
PUs.
2.1. Hard segment structure
The thermal decomposition of PUs starts with the
decomposition of the HS; therefore, the chemical composi-
tion, content, length, structure, symmetry and distribution
of the HS plays an important role in PU thermal stabil-
ity [29,152]. The decomposition route is strongly affected
by the pseudo-crosslinking effect which results from HS
aggregation. The HS domain generally exhibits a degree of
order or semicrystalline structure that is able to reinforce
the polyurethane. The presence of an amorphous region
inside the HS domain may constitute a weak part [153].
Matuszak and Frisch compared the thermal degradation
of PUs based on PEG and three diisocyanates: H12 MDI,
TDI, and XDI [154]. At higher temperatures (>300 ◦ C), ther-
mal degradation predominately yielded amine and CO2 .
The aliphatic H12 MDI:PEG PU was more thermally stable
than the aromatic TDI- and XDI-based materials. Song et
al. evaluated the thermal stability of three PUs based on an
aliphatic polyester and three diisocyanates, i.e., MDI, XDI
and TDI [27]. The authors synthesized an aliphatic polyester
using adipic acid, hexanediol and 1,2-propanediol. Their
observations suggested the thermal stability order: XDI-
based PU > MDI-based PU > TDI-based PU. Their results
implied that the alkyl isocyanate nature of XDI produces
more thermo-stability and that the absence of symme-
try in TDI reduces hard segment crystallinity as well as
thermal stability for TDI-based PUs. Zhang and Huang
observed that MDI based PUs are thermally more stable
than the corresponding TDI based PUs [34]. Chattopad-
hyay et al. studied moisture-cured PUs prepared from
PTMG, TMP and IPDI as well as PTMG, TMP and TDI at
an NCO:OH ratio of 1.6:1 [35,155]. The results showed that
1084 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
at lower temperature during the TGA experiments the PU
prepared from the aliphatic diisocyanate (IPDI) was more
stable than the aromatic diisocyanate (TDI) containing PU,
whereas at higher temperature the stability order followed
the reverse trend. Coutinho et al. compared the thermal
stability of aqueous PU dispersions (PUDs) in N2 with dif-
ferent diisocyanates and showed that the flexible –(CH2 )–
chain in hexamethylene diisocyanate (HDI) facilitated ther-
mal degradation, whereas PUs prepared from diisocyanates
with cycloaliphatic structures such as H12 MDI and IPDI
were more thermally resistant [156]. H12 MDI-PU showed
the highest thermal stability in the group because its more
symmetrical nature can enhance intermolecular interac-
tions.
A comparison of the thermal stability of PUDs using
diisocyanates with cycloaliphatic structures (H12 MDI and
IPDI) and aromatic structures (TDI) showed that at low
temperature the aromatic diisocyanate resulted in poly-
mer chains with lower thermal stability. The aromatic rings,
with 2,4- and 2,6-isocyanate groups formed asymmetrical
rigid chains, which makes the HS–HS interactions difficult
and thereby reduces thermal resistance at the beginning
of the process, but at high temperatures TDI based PUDs
showed improved stability. Stanciu et al. have shown that
diisocyanates from HS influence the thermal stability of
PU–polysiloxane elastomers in the order: TDI < MDI < HDI
in air [157]. For polyester-polyurethane, the thermooxida-
tive stability of different diisocyanates follows the order:
NDI > 4, 4 -diphenyl ether diisocyanate > TDI > MDI
> HDI.
Similarly, for PPG-isocyanate system the rate of O2
absorption at 140 ◦ C was found to be lower for NDI and
higher for HDI and the order of O2 absorption follows:
HDI > MDI > TDI > NDI. Thus, the higher aromaticity in these
diisocyanates results an increased resistance against ther-
mal oxidation [19,97].
Singh reacted a series of aromatic diisocyanates shown
in Scheme 9 with polyethylene glycol adipate and produced
NCO-capped prepolymers [158]. The NCO-terminated pre-
polymers were further reacted with TMP to form PU
networks. It was shown that the specific rate constant
for the cleavage of urethane groups based on dimethyl
diphenylmethane diisocyanate (DMMDI) and o-tolidine
diisocyanate (TODI) at any given temperature was about
twice that of MDI based urethane. There are two oppos-
ing factors that affect the stability of DMMDI and TODI
based PUs such as (1) ortho-methyl groups exert +I effect
and stabilize the urethane linkage, and (b) steric or crowd-
ing effect of methyl group at the ortho position of the ring
and in the vicinity of the urethane linkage destabilizes the
urethane group. Singh showed that the steric effect over-
whelms the +I effect and results in decreasing urethane
bond thermal stability for DMMDI and TODI based PUs.
Similarly, a comparison of the specific rate constants for the
thermal cleavage of urethane linkages prepared from 2,6-
TDI and 1,3-phenylene diisocyanate (MPDI) showed that
the ortho-methyl group in TDI increases steric crowding of
the urethane linkage (Scheme 9; [158]).
Polymeric isocyanates (such as polymeric MDI) are
extremely thermally stable and produce thermally sta-
ble PUs. Baumann showed that PUs prepared from a
polyoxypropylene triol, Pluracol TP-440, and four dif-
ferent isocyanates followed the thermal stability order:
HDI < 2,4-TDI < dianisidine diisocyanate (DADI) < polymeric
MDI [159].
Liminana et al. prepared different anionic aqueous
PUDs using the prepolymer mixing process and showed
that decreasing dimethylol propanoic acid (DMPA) con-
tent increased the particle size and thermal stability of the
ionomer due to a decrease in hydrophilicity and the pres-
ence of lower HS content, respectively [160].
Researchers showed the following thermal stability
order for the following isocyanate derivatives formed in the
HS during PU formation:
isocyanurate > urea > urethane > biuret > allophanate.
Isocyanurates degrade above 270 ◦ C and are the more
stable structure obtained from isocyanates [19].
2.2. Soft segment structure and molecular weight
The chemical composition and molecular weight distri-
bution of the incorporated soft block influences the thermal
stability of the resulting material. Additionally, polyols con-
taining aromatic groups show higher thermal stability than
that of aliphatic polyols [151]. Pielichowski et al. studied
the thermal degradation of PUs based on MDI and differ-
ent polyols [75]. They proposed that the higher the oxygen
content in the polyol the higher the weight loss. Ge et al.
used two different polyols namely PTMG (Mn = 1500) and
fluorinated polyether glycol (PTMG-g-HFP, Mn = 1500) and
synthesized fluorinated PUs (FPUs) and hydrogenated PUs
(TPUs), respectively using HDI or TDI as the diisocyanate
and BD as the chain extender [161]. Their thermal decom-
position study in a N2 atmosphere showed that the FPUs
were more thermally stable in comparison to TPUs. Petrovic
et al. investigated the effect of molecular weight and con-
centration of the SSs on the apparent activation energies of
the thermal degradation of PUs [29]. The thermal stability
of PUs prepared from polyols depends on the functionality
and equivalent weight of the polyol, i.e., on the number of
urethane groups per unit volume. Wang and Hsieh investi-
gated the thermal stability of PUs prepared from MDI, three
different polyols (namely PEG, PPG and PTMG) and ethy-
lene diamine chain extender at a 1:2:1 mole ratio [162].
Their observation suggests the stability order of:
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Scheme 10. The conformational arrangements of different diol chain extenders used in PU formulations. For comparison purpose of hydrogen bonding,
the most stable staggered conformation is shown here. Double sided arrow shows the butane–gauche interactions.
in both N2 and air environments. Increasing the soft seg-
ment molecular weight from 1000 to 2000 suggested that
for PPG-PU, thermal stability decreased while thermal
stability for both PEG-PU and PTMG-PU increased with
increasing molecular weight of the SS. Coutinho et al.,
while studying the thermal stability of different aqueous
PUDs, concluded that higher length SSs improved the ther-
mal stability [22]. Grassie et al. showed that the threshold
degradation temperature of polyester PU–urea increases
with increasing SS content [163]. In another work, indi-
rect evidence for the mutual stabilization effect of soft
and hard phases was presented [51]. The authors reported
that at the initial stage of degradation, thermal stabil-
ity increased with increasing soft segment concentration,
while the reverse is true in the later stages of degradation
[51].
Researchers have noticed that polyester-based TPUs
exhibit equally rapid degradation in air and N2 , indicating
that a non-oxidative degradation mechanism is involved
[164,165]. Ester and ether bonds dissociate in N2 at approx-
imately 260 and 350 ◦ C, respectively. On the other hand, the
oxidation of SSs plays a major role in the aging of polyether
based PUs. This finally leads to chain cleavage, i.e. a decrease
of the molecular weight. In polyethers, the CH bond of the
methylene group adjacent to the oxygen (␣-carbon) is sen-
sitive to oxidation, followed by breakage of the C–O bond
and subsequent unzipping of the polyether chains [29,166].
Therefore, in O2 , polyether–urethanes are less thermally
stable than polyester–urethanes because of the oxidative
cleavage of the polyether structure at high temperatures
[58].
2.3. Chain extender structure
A number of systematic investigations have been
made to study the effect of the chemical structures of
CEs on the thermal stability of PUs. The chain length,
1085
molecular volume, functionality of the CE and the con-
formational arrangement can influence hard segment
packing, crystallinity and thus the thermal stability of the
hard domains. Lee and Ko have shown that an increase
in the CE concentration lowered the initial degrada-
tion temperature as revealed from TGA [46]. CEs used
to prepare PUs may be either aliphatic, cycloaliphatic
or aromatic in nature. Among the aliphatic diols used
as chain extenders, BD is widely used as it gives a
high degree of phase separation. The conformational
arrangement of different diol chain extenders is shown in
Scheme 10. Bulky chain extenders, such as 2-butyl 2-ethyl
1,3 propanediol (BEP) or 2,2-dimethyl 1,3 propanediol
(DIE), because of the presence of side branching, leads to
reduced phase separation and produces less thermally
stable PUs [30,63]. The presence of a side functional
group in the CE molecule interferes with the formation
of urethane–urethane hydrogen bonds which makes it
difficult for HSs to agglomerate, i.e. their phase separation
becomes hindered. Blackwell et al. suggested that CEs with
an even number of CH2 groups in its backbone produces
polymers with a more phase separated structure than
those containing an odd number of carbons [167–169].
Chuang prepared MDI and PTMG-1000 containing PUs
with two different chain extenders, 2,4-hexadiyene-1,6-
diol (DA) and 1,4-butylene diol (BYD), and showed that
DA produces more thermally stable PUs in comparison to
BYD chain-extended PUs [83]. In another study, Chuang
et al. prepared PTMG-MDI based PUs using 1,3-bis(4-
hydroxybutyl)-1,1,3,3,-tetramethyldisiloxane (OH-BTMS),
1,3-bis(3-aminopropyl)-1,1,3,3,-tetramethyldisiloxane
(NH2 -BTMS) and BD chain extenders and concluded that
samples with OH-BTMS as a chain-extender were more
thermally stable in the initial step of degradation than
those with NH2 -BTMS or BD as the chain-extenders [170].
However, following the initial step of degradation, NH2 -
BTMS chain extended PU samples had an unexpectedly
1086 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
higher thermal stability than those with OH-BTMS and BD
as the chain-extended PUs.
Diamine chain-extended PUs leads to the formation of
urea bonds whereas urethane bonds are produced by diol
CEs. The urea structure has a higher hydrogen bonding
capability, rigidity and tends to promote more complete
phase separation as compared to the urethane linkage [23].
Therefore, diamine chain extended PUs are more thermally
stable than diol chain extended PUs [35,155]. Coutinho et
al. showed that hydrazine as a CE improved the thermal
stability of PUDs when compared with ethylene diamine
CE PUDs due to the higher polarity of the resultant HS [22].
Liaw compared the thermal stability of tetrabromo
bisphenol-A chain extended PUs to that of unbrominated
bisphenol-A chain extended PUs and showed that substi-
tution of the aromatic rings in aromatic diol containing the
CE structure reduces the thermal stability [25]. In addition,
Liaw gave the thermal stability order for PUs with different
aromatic diol CEs as [25]:
The lower thermal stability of the bisphenol-AF-based
PUs was attributed to the weaker intermolecular forces
between the polymer chains.
A comparison of the thermal stability of different
aromatic diamine chain extended PU–ureas showed the
stability order:
The lower stability of PU-DIS was due to the presence
of weak sulfur–sulfur (S–S) bond or divalent sulfur (SII ).
The larger size of the 3p orbital than that of the 2p orbital
causes poor sp3 hybridization and overlapping, thus pro-
moting a weaker S–S ␴-bond than that of sp3 –sp3 (2p–2p)
overlap as in the C–C bond. On the other hand, the presence
of strong resonant aryl sulfone groups in PU-SUL forms a
strong and thermally stable C–SVI bond due to the higher
electron affinity of SVI , and greater ␴-bonding orbital over-
lap. In addition, the SUL chain extended PU chain has a
highly phase-separated structure and hence a higher ther-
mal stability [35,155,171].
Qin et al. prepared 2,2-bis[4-(4-aminophenoxy)phenyl]
hexafluoropropane (BAPF6 P; a fluorine-containing bisphe-
noxydiamine) and methylene bisorthochloroaniline
(MOCA) chain extended PU–urea, F-PU and M-PU, respec-
tively from the NCO capped prepolymer of TDI and
PTMG-1000 that was prepared at an NCO:OH ratio of
2:1 [172]. Their study showed that F-PU possessed better
thermal stability in comparison to M-PU. In another
work from the same group, they prepared bis[4-(4-
aminophenoxy)phenyl]sulfone (BAPS) and MOCA chain
extended PU–urea from the NCO capped PU prepolymer
used earlier and showed that PU–urea prepared from BAPS
exhibited higher thermal stability due to the presence of
the polar sulfone group [173]. The structures of MOCA,
BAPF6 P and BAPS are shown in Scheme 11.
Lin et al. used diphenyl silanediol and methylphos-
phonic acid as CEs with an NCO-capped PU prepolymer
prepared from PTMG and MDI and showed that Si–PU had
higher thermal stability because of the presence of the ther-
mally stable silicon-containing segment [174]. On the other
hand, P–PU showed less stability since the phosphorus-
containing segment easily degrades during thermal stress.
Subramani et al. prepared silylated PUDs (SPUDs) using
a prepolymer of PTMG, DMPA and IPDI (NCO:OH ratio
of 1.2:1 and 1.4:1). The NCO capped PUD ionomers were
chain extended with 3-aminopropyl trimethoxysilane and
it was shown that the thermal stability of the SPUDs were
higher than that of the pure PUDs without any CE and with
tetraethylene pentamine chain-extended PUDs [175].
2.4. Effect of NCO:OH ratio
The ratio of isocyanate to hydroxyl (NCO:OH) plays
an important role in determining the structure and
thermal properties of PUs. Researchers have shown
that increasing the NCO:OH ratio has an influence on
side product formation and thereby changes the onset
decomposition temperature [24,26,176]. The presence of
excess isocyanate in the reaction system may result
in side reactions that produce allophanate and biuret
(Scheme 12; [9]). Allophanate and biuret crosslinks decom-
pose quite readily on heating whereas conventional
urethane and urea crosslinks decompose at consider-
ably higher temperatures. Additionally, isocyanates may,
under appropriate conditions, react with themselves to
give dimer uretidione or trimer isocyanurates. The iso-
cyanurate linkage possesses an inherently higher thermal
stability than that of the urethane linkage (urethane
dissociates at approx. 200 ◦ C as opposed to 350 ◦ C for
polyisocyanurates) [26,177]. Isocyanate-based polymers
provide thermo-stability in the following order: isocya-
nurate (350 ◦ C) > urea (250 ◦ C) > urethane (200 ◦ C) > biuret
(135–140 ◦ C) > allophanate (106 ◦ C) [19,178]. Bajsic et al.
found that an increase in the HS content by varying the
NCO:OH ratio from 2:1 to 4:1 results in an enhance-
ment of the onset decomposition temperature for both
of the two decomposition steps [179]. Similarly, Asif
and Shi showed that for the synthesized waterborne
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Scheme 11. Structures of MOCA, BAPF6 P and BAPS [173].
hyperbranched PU–acrylate UV cured films, the thermal
degradation temperature and activation energy calculated
from the initial stages of degradation increased with
increasing HS content [180].
2.5. Effect of catalyst
Catalysts play an important role in the reactions of iso-
cyanates. Various catalysts such as tertiary amines and
Scheme 12. Formation of secondary isocyanate reaction products [9].
1087
organometallic compounds accelerate the formation of
urethane as well as urea. Some of the catalysts widely used
are [9]:
Tertiary amines. Triethylamine (TEA), tripropylamine,
dimethyl aniline, N-methyl morpholine, N,N -dimethyl
piperazine, N,N-dimethyl cyclohexylamine, 1,4-
diazabicyclo [2.2.2] octane (DABCO), N,N,N ,N -tetramethyl
methane diamine, etc. Catalytic efficiency of tertiary
amines depends on the chemical activity and the structure
of the catalyst. For instance, increasing the basicity of
tertiary amines by substituents with increased +I effect
increases the catalytic activity [181].
Organometallic compounds. Dibutyltin dilaurate
(DBTDL), diethyltin dicaprylate (DETDC), dibutyltin
di-2-ethylhexoate, stannous octoate, stannous oleate,
THORCAT 535 (organomercury catalyst, phenyl mercury
ester), ferric acetylacetonate (FeAA), tetravalent tin com-
pounds of the type Rn SnX(4−n) with R being a hydrocarbon
group (alkyl, aryl, cycloalkyl, etc.) and X being a halogen
atom or a carboxylate group (acetate, laurate, etc.), etc. [9].
In some cases, a formulator may prefer to use a com-
bination of catalysts consisting of a tertiary amine and
a tin compound. Some of these catalysts can also cat-
alyze the trimerization reactions if an excess of isocyanate
is present. Semsarzadeh and Navarchian examined the
effect of DBTDL concentration on isocyanurate forma-
tion at an NCO:OH ratio of 2 and observed that the
trimer/urethane ratio increased with increasing catalyst
concentration [24]. Their observations on the use of dif-
1088 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
ferent catalysts suggest that PUs synthesized with DBTDL
are generally more thermally stable than those synthesized
with FeAA. Researchers also reported that stannous octoate
and DETDC have a stabilizing effect towards thermo-
oxidation of PUs prepared from PPG and TDI, whereas
DABCO initiates an early oxygen absorption around
170–180 ◦ C [97].
2.6. Effect of crosslink density
In the case of crosslinked PUs, the thermal stability
depends primarily on crosslink concentration rather than
on molecular weight itself. Drastic variations in PUs proper-
ties can be introduced by varying the extent of crosslinking.
PUs having different thermal stability may be formed by the
reaction of excess isocyanate with urea or urethane groups
yielding biuret or allophanate crosslinking, using diiso-
cyanates or polyols with functionality > 2 or by using tri
or poly-functional alcohols or amines as CEs. Additionally,
variations in the cure conditions and crosslinker concen-
trations also influence the properties of PUs by affecting
the extent of crosslinking and, therefore, the structure of
the network. Researchers have shown that PUs with high
crosslink density possess good thermal stability in inert as
well as in oxidative environments [14,154]. This is because
more thermal energy is needed to break the additional
bonds with increasing crosslink density before the break-
down of the total network takes place [19]. Factors that
govern the degree of crosslinking are the functionality of
the reactants, NCO:OH ratio, triol/diol ratio and side prod-
uct formation.
Scheme 13. Formation of heat-resistant isocyanate based polymers [192].
3. Methods to improve thermal stability of PUs
Thermally stable PUs have recently gained considerable
attention because of their potential application in a number
of areas. Many applications of PUs require materials that
can resist a variety of external stresses such as heat and
fire among others. However, pure PUs generally have low
thermal stability at high temperatures and thermal degra-
dation can begin to occur at processing temperatures above
180 ◦ C, depending on the parameters already discussed. It is
well documented in the literature that the chemical mod-
ification of the PU backbone through the introduction of
thermally stable heterocyclic structures such as isocyanu-
rate, oxazolidone, imide, triazine or phosphazene are viable
methods for improving thermal stability. The thermal sta-
bility of these linkages, as measured on model compounds
and model polymers, has been reported by a number of
different investigators [182–192]. Scheme 13 shows the
formation of different heat-resistant isocyanate-based link-
ages.
Kordomenos et al. reported that the thermal stability
of different heat resistant groups in PUs for the studied
model systems decreases in the order: isocyanurates
(380–420 ◦ C) > oxazolidones (330–360 ◦ C) > urethanes
(260–360 ◦ C) [193,194]. The thermal decomposition data
are for model PU systems.
3.1. Poly(urethane-isocyanurate)
The isocyanurate ring is generally produced by iso-
cyanate trimerization using selective catalysts and is both
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133 1089

Scheme 14. Structure of trifunctional isocyanurate monomers.

hydrolytically and thermally very stable, as already dis- isocyanurate or tris[2-(acryloyloxy)ethyl] isocyanurate
cussed. The reaction between the isocyanate groups and (Scheme 14) can be used as crosslinkers in PU formulations.
the formation of poly(urethane-isocyanurate) generally
takes place at high temperatures such as 120–140 ◦ C and
3.2. Poly(urethane-oxazolidone)
in the presence of catalyst [195]. For instance, Sendi-
jarevic et al. used 2,4,6-tris(dimethylaminomethyl)phenol
The chemical reaction between an isocyanate group and
(DMP-30) as a catalyst for the preparation of poly(urethane-
an epoxy group containing compound is the most conve-
isocyanurate) by the trimerization of an NCO-terminated
nient methods used for the synthesis of oxazolidone rings.
urethane prepolymer [192]. The trimerization reaction can
Oxazolidone groups in PUs increase the heat resistance of
also be carried out at room temperature using an epoxy
such polymers and improve the properties for high temper-
compound (ethylene, propylene or butylene oxide) and a
ature applications.
tertiary amine catalyst. For instance, Burkus used a tri-
The substituents on the oxazolidone ring influences
ethylamine and propylene oxide mixture as a trimerization
the thermal stability of PU–oxazolidones. For instance,
catalyst for the preparation of PU–isocyanurate from an
electron-donating substituents on the nitrogen increase
NCO-capped polyester prepolymer [196].
the thermal stability and the presence of electron-
Researchers have demonstrated that solvents with a
withdrawing groups decrease the thermal stability of the
high dielectric constant (εr ) favor the trimerization reac-
oxazolidone ring [193,194].
tion. For instance, dimethyl sulfoxide (εr = 45.0 at 20 ◦ C),
The formation of oxazolidone is a very complex reac-
because of its high polarity, has a high relative reactivity
tion. In addition to oxazolidone formation, side reactions
(12.3) for the trimerization of phenyl isocyanate. On the
such as isocyanurate formation also take place. The selec-
other hand, benzene (εr = 2.28 at 20 ◦ C), a less polar solvent
tivity of oxazolidone formation was found to be affected by
possess relative reactivity of 1.47 for the trimerization of
the type and amount of catalyst, type of reactants, reaction
phenyl isocyanate [181].
media and even the mode of reactant addition [197,198].
In addition, 1,3,5-tris(2-hydroxyethyl) isocyanurate,
In order to obtain the highest yield of 2-oxazolidones, the
tris(2,3-epoxypropyl) isocyanurate, tris(2-propene)
synthesis should be carried out at temperatures over 100 ◦ C

Scheme 15. Synthesis of NCO-terminated oxazolidone adduct from the reaction of diglycidyl ether of bisphenol A and a diisocyanate or NCO-capped PU
prepolymer [192].
1090 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

Scheme 16. Synthetic route used to prepare crosslinked poly(urethane-oxazolidone) [198].

and excess isocyanate with respect to epoxide should be
avoided [199,200]. A schematic diagram of the synthesis
of an NCO-terminated oxazolidone adduct from the reac-
tion of diglycidyl ether of bisphenol A and a diisocyanate or
NCO-capped PU prepolymer is given in Scheme 15.
Iwakura prepared oxazolidone derivatives by the reac-
tion of urethane compounds and epoxides using tertiary
amines and quarternary ammonium salts as catalysts [201].
Frisch reported several different types of oxazolidone-
forming catalysts consisting of metal alkoxides (e.g.
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
methoxides of aluminum, calcium and magnesium), metal
halides, and their complexes with thioethers, phosphines,
phosphine oxides and organometallic compounds such as
dialkyl zinc and trialkyl aluminum [202,203]. Kitayama and
coworkers synthesized polyoxazolidone elastomers using
a MgCl2 –hexamethylphosphoric triamide complex as cat-
alyst [200]. Using the complex catalyst AlCl3 –triphenyl
phosphine oxide (TPPO), it was possible to obtain NCO-
terminated oxazolidone adducts based on 2,4-TDI and
80/20 TDI with low isocyanurate formation, in the tem-
perature range of 60–110 ◦ C. Under the same reaction
conditions, the complex catalyst AlCl3 –TPPO was more
efficient than AlCl3 and AlC13 -hexamethylphosphoric
triamide [204–206]. Sankaran and Chanda reacted NCO-
capped polybutadiene with an aromatic diepoxy com-
pound to prepare an oxazolidone–urethane copoly-
mer [207]. Yeganeh et al. prepared N-methyl aniline
blocked (TDI + TMP) adduct, which was later on reacted
with glycidyl terminated PU to prepare crosslinked
poly(urethane-oxazolidone) (Scheme 16; [198]). Roth et
al. synthesized isocyanurate-oxazolidone systems from
the reaction of an isocyanate-capped PU prepolymer
with diepoxy compounds [208]. Frisch and coworkers
prepared poly(urethane-isocyanurate-oxazolidone)s from
either the reaction of NCO-terminated prepolymers with
triglycidyl isocyanurate or the trimerization of equimo-
lar mixtures of NCO-terminated urethane prepolymers
and an NCO-terminated oxazolidone prepolymer adduct
[209].
3.3. Poly(urethane-imide)
The chemical modification of PU chains by the incorpo-
ration of heterocyclic imides has been another method used
for improving thermal stability. Several synthetic method-
ologies have been followed to introduce imide structures
into PUs [152,210–212]. Some of the widely used methods
include:
• introduction of imide groups via chain extender:
pyromellitic dianhydride (PMDA), mellophanic dian-
hydride, 3,3 ,4,4 -biphenyl dianhydride, 2,3 ,3,4 -biphe-
nyl dianhydride, 2,2 ,3,3 -biphenyl dianhydride, benzo-
phenonetetracarboxylic dianhydride, 4,4 -hexafluoroi-
sopropylidenediphthalic anhydride, 2,2 -pyromellit-
diimidodisuccinic anhydride, 3,3 ,4,4 -benzophenone
tetracarboxylic dianhydride (BTDA), and 3,3 ,4,4 -
Scheme 17. Formation of poly(urethane-imide) from the reaction of NCO-capped PU prepolymer and PMDA.
1091
sulphonyldiphthalic anhydride (DSDA). These are widely
used commercially available acid dianhydrides that can
be reacted with an NCO-capped PU prepolymer. This
method has the benefit of using commercially available
NCO-terminated PU prepolymers and enhancing the
phase separation due to the strong dipole–dipole interac-
tion of the imide groups present in the HS [183,189,212].
Scheme 17 shows the formation of poly(urethane-imide)
from the reaction of an NCO-capped PU prepolymer and
PMDA.
• reaction of NCO-capped PUs with aromatic diamines and
dianhydrides to prepare PU–imides [9].
• reaction of an acid dianhyhydride with aminoethanol to
produce a hydroxyl-terminated imide monomer, which
can then be reacted with an NCO-capped PU prepolymer
[9].
• reaction of an oligoimide with an NCO-terminated PU
prepolymer [213].
• reaction of an NCO-terminated PU prepolymer with
glycols containing an imide functional group as CE
[183–185]. Qin et al. prepared several new glycols con-
taining both imide and sulfone groups with the name
sulfonyl bisimide glycol (SBIG; Scheme 18) from pri-
mary aromatic diamine, trimellitic anhydride (TMA) and
excess low molecular weight glycols [214]. The synthe-
sized SBIGs were used as CEs along with an NCO-capped
PU prepolymer to prepare a series of thermoplastic
poly(urethane-imide)s.
• reaction of diisocyanates containing built-in imide
groups with polyols [215].
• intermolecular Diels–Alder reaction of 4-methyl-1,3-
phenylenebis (2-furanylcarbamate) with bismaleimides
[216,217].
• reaction of polyamic acid [218] and diimide-dinaphthols
[219] with a PU prepolymer to produce a PU–imide.
The presence of free isocyanate groups in NCO-capped
PU prepolymers has a disadvantage because of isocyanate
toxicity and therefore as an improved method glycidol is
used to convert the NCO-terminated PU into an epoxy-
terminated PU. For instance, the crosslinking reaction of
an epoxy-terminated PU with diimide diacid and polyamic
acid are reported by Yeganeh et al. (Scheme 19; [183,220]).
On the other hand, the incorporation of both imide and oxa-
zolidone rings into the PU backbone was reported by Nair
et al. [221].
1092 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

Scheme 18. Synthesis of sulfonyl bisimide glycol. Reproduced from [214] with permission. Copyright 2005 John Wiley and Sons.

3.4. Other methods Karak prepared s-triazine containing hyperbranched

Other methods of improving the thermal resistance of
PUs are:
(a) use of a soft component containing a thermostable
heterocyclic ring, such as an s-triazine ring [222].
Polyetherols of this type are most often obtained in
reactions of isocyanuric acid [223], melamine or their
derivatives with oxiranes [224,225].
(b) incorporation of azomethine (–CH N–) linkages in the
PU structure and making poly(azomethine urethane)s
that result in improved thermal stability [226,227].
(c) use of hyperbranched polyol (HBP) or hyperbranched
polyamine as a crosslinking agent [228]. The thermal
stability improves with increasing generation number
of the HBPs [229,230]. In a recent report, Mahapatra and
polyamines from 4,4 -(1,4-phenylenediisopropylidene)
bis-aniline and cyanuric chloride using the A2 + B3
approach (Scheme 20) in high yield that was then used
as a crosslinking agent to increase the thermal stability
of PUs [231].
(d) use of high aromatic ring concentrations in the HS or SS.
An aromatic ring has a stabilizing effect against ther-
mal degradation [232,233]. Bruk [234] and Winslow et
al. [235] showed that polymers with high concentra-
tions of aromatic rings in their repeating unit degrade to
form relatively small amounts of volatile products and
the main degradation reaction led to fusion of the aro-
matic rings with the formation of char. Researchers also
reported that the formation of nonvolatile char depends
on the concentration of aromatic rings in the polymer
[193,194].
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Scheme 19. Synthesis of poly(urethane-imide) from epoxy capped PU prepolymer using (a) diimide diacid [183] and (b) polyamic acid [220].
4. Inorganic–organic hybrids
Inorganic–organic hybrid PUs possess inherently higher
thermal and oxidative stability because of their unique
interfacial interaction and the synergistic interaction
between these components. The nature of the interface or
the links and interactions between the organic and inor-
ganic components is used to categorize PU hybrids into
Class I and Class II materials [9]. Class I materials are
those where no covalent or iono-covalent bonds are present
between the organic and inorganic phases. The interactions
between the two components in these materials are weak
such as hydrogen bonding, van der Waals, London or elec-
trostatic forces. On the other hand, in Class II materials a
covalent link is established between the soft organic and
hard inorganic components through a chemical reaction
[9]. Below we will discuss the thermal properties of PU
hybrid materials having Class I and Class II inorganic phases.
4.1. Incorporation of fillers
A wide variety of fillers, whiskers and fibers, clays and
wollastonites have been used in PU formulations to rein-
force the matrix. Conventional PU microcomposites are
usually formulated by premixing the inorganic compo-
nent with the polyol and then reacting the mixture with
diisocyanates. In general, the degree of thermal stability
improvement of PUs depends on the size, shape, nature,
amount of filler used, dispersion uniformity, as well as
the degree of interaction between the inorganic filler and
the PU matrix. Therefore, ideal performance is achieved
using inorganic fillers of nano-scale dimensions that are
uniformly dispersed throughout the matrix and interact
strongly with the organic matrix. Benli et al. studied the
1093
effect of a number of fillers (carbon black, silica, aluminum
oxide and zirconium (III) oxide) on the thermal proper-
ties of PU elastomers prepared from hydroxyl-terminated
polybutadiene [236]. In general, both reducing the size
and increasing the aspect ratio of the filler are routes to
enhancing their effectiveness against thermal degradation
[87,237]. Mahfuz et al. reported the enhancement of ther-
mal stability of PU foams through the use of TiO2 and
SiC particles [238]. They showed that thermal stability
increases with increasing TiO2 amount, due to its catalytic
effect on the cross-linking of the PU foams. On the other
hand at highest SiC content (3 wt%) the fillers weaken the
van der Waals interaction between PU chains and decrease
thermal stability [238]. The high surface area of nano-sized
fillers results in increasing the interfacial interaction and
thereby the thermal stability of the binder can be improved.
Different nano-sized fillers widely used to reinforce a PU
matrix are nano-silica, Fe2 O3 , TiO2 or clay particles. Nano-
sized silica particles possess a large interfacial area when
dispersed properly and thereby improve the thermal stabil-
ity as they significantly reduce the heat release rate of the
polymers. Yang et al. used aqueous solutions of colloidal sil-
ica to prepare PUD–silica hybrids and showed that hybrid
films possess good thermal stability in comparison to the
pure PUDs [239]. Kim et al. prepared nanosilica-reinforced
UV-cured PUDs from two different nanosilicas – hydropho-
bic nanosilica and hydrophilic modified nanosilica – and
showed that the decomposition temperatures of the PU,
especially that of the HS, increased with the addition of and
with increasing amount of silica, thus improving the ther-
mal stability of the segmented PUs [240]. The above effect
was more pronounced with the hydrophilic modified sil-
ica indicating a better dispersion of this type of silica in PU
ionomers where the ionic center is hydrophilic in nature.
1094 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Scheme 20. Synthesis of hyperbranched polyamine by Mahapatra and Karak [231].
4.2. Silica grafting
Fumed or ultrafine silica is a widely used inorganic filler
in the composites industry and, accordingly, the improve-
ment of the mechanical behavior of silica composites has
been for years the object of experimental investigations,
many of them involving the chemical modification of the
particle surface and/or polymer grafting [241]. The chemi-
cal modification or functionalization of silica nanoparticles
and attachment of the modified silica to PUs are of great
interest owing to their improved properties and potential
use in several different applications. This system with cova-
lently anchored functional groups on the silica causes its
surface to have specific attributes, such as a stereochemical
configuration and binding sites that enhance compatibil-
ity with organic binders which improves thermal stability.
The modification of silica surfaces via the reaction of sur-
face silanols with different organic molecules is shown in
Scheme 21 [241–245]. Incorporation of increasing amounts
of 3-aminopropyl triethoxysilane (APTS)-modified silica
into PU/silica nanocomposites resulted in increased ther-
mal stability [246].
4.3. Organically modified layered silicates
Talc, mica, montmorillonite (MMT), hectorite, rectorite,
laponite and saponite belong to the 2:1 layered or phyl-
losilicates family. Generally, the naturally occurring clays
are of hydrophilic character and require modification
by intercalating with amino acids, alkyl ammonium or
phosphonium salts or with cationic surfactants to make
them hydrophobic and organically compatible. Otherwise,
phase segregation and filler agglomeration results, which
decreases the overall performance of the PU composite.
Thus, it is desirable to use stable and organically modified
hydrophilic clay particles as fillers. Wang and Pinnavaia
demonstrated maximum benefit from nanolayer disper-
sal and reinforcement using montmorillonites exchanged
with long-chain onium ions (carbon number > 12) [247].
Chang and An studied the thermal stability of PU
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Scheme 21. Surface modification reactions of silica nanoparticles [241–246].
nanocomposites with three different organoclays such
as hexadecylamine–montmorillonite (C16 –MMT), dode-
cyltrimethyl ammonium–montmorillonite (DTA–MMT)
and Cloisite 25A [248]. C16 –MMT and DTA–MMT were
prepared using the same Na+ MMT with different organo-
modifiers, e.g., hexadecylamine and dodecyltrimethyl
ammonium bromide, respectively. Their study showed that
the initial degradation temperature (at a 2% weight loss) of
the PU/organoclay hybrid films increased with the amount
of organoclay, with a maximum increase of 18 ◦ C for 4 wt%
DTA–MMT and 6 wt% Cloisite 25A relative to the PU. Lee
et al. studied waterborne PU/clay nanocomposites and
showed that PUD/clay films containing more clay exhibited
higher thermal resistance [249]. Kuan et al. prepared 1,12-
diaminododecane modified saponite clay and prepared
PUD/clay nanocomposites with improved thermal stability
[250].
The addition of organically modified clay improves the
thermal stability by acting as a thermal insulator and mass
transport barrier (labyrinth effect) to the volatile products
generated during decomposition, i.e., organoclays mini-
mize the permeability of volatile degradation products out
of the PU material. In an oxidative environment, the ther-
mal decomposition behavior is influenced by the hindered
penetration of oxygen through silicate layers that protect
the bulk of the polymer matrix. Therefore, nanoclays delay
the thermal degradation product’s release [251–253]. The
effect of clay as a thermal insulator and mass transport
barrier can be enhanced by improving the dispersibil-
1095
ity of the organoclay [254,255]. For instance, Seo et al.
reported that the thermal stability and fire resistance prop-
erties of PU/clay nanocomposites were enhanced when
a higher degree of dispersion of filler using ultrasound
treatment during montmorillonite modification with iso-
cyanate was achieved [256]. The observed ‘labyrinth effect’
plays an important role in thermal stability improvement of
PU–MMT nanocomposites since composite materials hav-
ing poor dispersion of MMT usually exhibit less thermal
improvement in comparison to well exfoliated or inter-
calated nanocomposites [257,258]. Additionally, the high
aspect ratio characteristic of silicate nanolayers in exfoli-
ated nanocomposites highly reduces the gas permeability
of polymers prepared from such materials [259].
Several routes have been developed to achieve a high
degree of dispersion of the organically modified clay
nanoparticles and these are: (i) in situ polymerization of
monomers which were initially intercalated between sili-
cate layers, (ii) melt intercalation and further exfoliation for
thermoplastic polymers and (iii) combination with a poly-
mer solution [9]. The other factors that affect the dispersion
of clay nanolayers and morphology of the nanocompos-
ites are mixing temperature and time, solvent used, solvent
concentration, size of the monomer or polymer, intercala-
tion agent, ion-exchange yield, etc. [260].
Tien and Wei improved the thermal durability of
PUs by modifying montmorillonite with reactive swelling
agents containing one to three hydroxyl groups (such
as 3-amino 1-propanol, 3-amino 1,2-propanediol and
1096 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Scheme 22. PU/layered silicate nanocomposite formation using a reac-
tive swelling agent containing tri-hydroxyl groups. Reproduced from [261]
with permission. Copyright 2002 John Wiley and Sons.
tris-hydroxymethyl aminomethane) and then using the
swelling agent as a pseudo-chain extender, along with the
regular chain extender BD, in the reaction with the –NCO
of the prepolymer for the PU (Scheme 22; [261]). Their
study showed that a 40 ◦ C increase in degradation temper-
ature and a 14% increase in the activation energy at 20%
mass loss during heating in TGA occurred for a PU con-
taining 1 wt% trihydroxyl swelling agent-modified silicate
compared with the pristine PU. Subramani et al. prepared
water-borne crosslinked silylated PU–urea/clay nanocom-
posites with various amounts of the organically modified
clay by the reaction of TDI or IPDI with PTMG and DMPA
[262]. Free NCO groups of the synthesized PU prepolymer
were end-capped with phenylamino propyl trimethoxysi-
lane and the silane modified PU polymer was later on
self-crosslinked. The thermal stability of the nanocompos-
ites increased with increasing clay loading.
Chen et al. prepared sepiolite/PU nanocomposites with
different amounts of sepiolite [263]. The sepiolite surface
was modified by reacting the Si–OH groups on the sepio-
lite surface with aminopropyl triethoxyl silane. The results
showed that the thermal stability of the composites was
higher than that of the pristine PU, but there was little influ-
ence of the amount of sepiolite. Baral et al. showed that the
thermal stability of mica filled TPU was higher than the
unmodified PU and the incorporation of mica delayed the
thermal degradation process of the PU [264].
4.4. PU–silica hybrids via sol–gel process
The sol–gel method provides a cost-effective way to
incorporate an inorganic silica network into PUs that results
in thermo-oxidatively stable polymers due to the presence
of the stable Si–O–Si network. The high thermal stability of
the Si–O bond is due to its high bond dissociation energy
of 110 kcal/mole as compared with 85.5 kcal/mole for C–O,
82.6 kcal/mole for C–C, and 76 kcal/mole for Si–C bonds. In
addition, the Si–O bond length is 1.64 Å, significantly less
than the value calculated from additivity of atomic radii
(1.17 Å for silicon + 0.66 Å for oxygen = 1.83 Å). This is due
to the existence of p − d back bonding between oxygen
and silicon. In addition to that, the Si–O bond has partial
ionic character due to the electronegativity difference of Si
and O. Therefore, the high strength exhibited by the Si–O
bond accounts for its high thermal and oxidative stability
[265–267].
Metal alkoxides and halides based on silicon, aluminum,
titanium and zirconium are widely used as sol–gel precur-
sors for the inorganic counterpart of the formulation. The
reactivity of tetra-alkoxy metals follows the order: Zr(OR)4 ,
Al(OR)3 > Ti(OR)4 > Sn(OR)4  Si(OR)4 . The alkyl group, sol-
vent, temperature, water to alkoxide molar ratio, presence
of acid or base catalysts, etc., affect the hydrolysis reaction
of the sol–gel precursor and hence leads to polymers having
different properties. For instance, the hydrolysis reaction
of trifunctional silane (R SiX3 where X = Cl, OMe, OEt, etc.)
in acid catalysis produces loose, coil-like polysilsesquiox-
ane (SSQO) structures, whereas basic catalysts promote fast
polycondensation and produce compact cagelike products
[9]. A number of reports in the literature are available which
show that PU–silica hydrids possess improved thermal sta-
bility; the thermal stability improvement depends on the
sol–gel processing parameters in addition to the structure
of the organic matrix. For instance, Chen et al. prepared
silica sol from the hydrolysis of tetraethoxysilane (TEOS),
which was used to prepare a polyester-PU–silica hybrid,
and then the thermal degradation profile was studied [268].
The polyester was a four component system prepared from
phthalic anhydride, adipic acid, neopentyl glycol and BD.
PU–silica hybrids with different silica contents were pre-
pared by two methods: (a) an in situ (IS) method: silica
sol was mixed with the monomers and polycondensation
was carried out, the resultant hydroxylated polyester was
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Scheme 23. Different hydroxyl terminated dendrimeric silicon compounds [272–274].
treated with IPDI trimer at an NCO:OH ratio of 1.1:1; and (b)
a blending (BL) method: silica sol was directly mixed with
the polyester resin at 165 ◦ C by vigorous stirring and later
on treated with IPDI trimer at the same NCO:OH ratio. Their
results showed that the IS method produces much stronger
interactions between the organic and inorganic phases and
the residual mass at 600 ◦ C increases with increasing silica
content. Lai et al. prepared a silica sol of TEOS via hydrol-
ysis using HCl and acetic acid (HOAc) catalysts, and then
incorporated it into a TPU formulation, and showed that,
although the initial temperature of weight loss does not
increase with increasing silica content, at a weight loss
of 50%, the silica tends to increase the thermal resistance
of the hybrid [269]. Jeon et al. prepared PUD-silica hybrid
composites using a sol–gel approach in three steps [270].
An NCO-capped prepolymer was synthesized using PTMG-
1000, DMPA and IPDI in the first step; which was reacted
with 3-aminopropyltriethoxysilane coupling agent in the
second step. The third step consisted of dispersing the
ionomer in water and the addition of nanosilica Aerosol-
200 (nano-sized amorphous silica oxide filler: average
particle size 12 nm, specific surface area 200 m2 /g). Hydrol-
ysis of the ethoxy groups in the PU gives silanol groups
which then subsequently condense with silanol groups on
the nanosilica and form a thermally stable Si–O–Si network.
1097
Kuan et al. prepared PUD/polysilicic acid nanoparticles
(PSN) nanocomposites with improved thermal stability by
a sol–gel approach [271]. They hydrolyzed sodium metasil-
icate in HCl and the –OH groups of the obtained PSN
were coupled with the triethoxy silane group of the silane-
terminated anionic PUDs containing SO3 H as the ionic
water dispersible group.
Functionalized hydroxyl terminated dendrimeric com-
pounds containing peripheral Si–OH groups varying in
number from 3 to 16 have been synthesized and these are
shown in Scheme 23 [272–274]. These compounds can be
reacted with NCO-terminated PU prepolymers, and result
in nanostructured PUs with improved thermal resistance.
Zhang et al. used a polyhedral oligomeric silsesquioxane
(POSS) diol as a partial replacement of diol monomers to
synthesize hybrid polyester resins containing POSS, which
were then cured by an IPDI-trimer to produce hybrid
PUs [275]. Their observation showed that the thermal
stability improved with the addition of POSS-diol. Dif-
ferent POSS-diol and POSS-polyol structures that can be
used to modify PU structures are shown in Scheme 24.
Janowski and Pielichowski studied the thermo-oxidative
stability of PU–POSS nanohybrids and showed that the
thermal stability of the nanohybrids increases as the POSS
contents increase from 0 to 6 wt% [276]. The PU–POSS
1098 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

Scheme 24. POSS-diol and POSS-polyol structures [275,276].

nanohybrids were prepared from different molecular
weight of PTMG; MDI, BD chain extender and 1-(1-(2,3-
dihydroxypropoxy) butyl)-3,5,7,9,11,15-isobutylpentacyclo
[9.5.1.1.(3,9).1(5,5).1(7,13)] octasiloxane (PHIPOSS). Liu et
al. synthesized octa(propylglycidyl ether) polyhedral
oligomeric silsesquioxane (OpePOSS) via the hydrosilyla-
tion reaction of octahydrosilsesquioxane (H8 Si8 O8 ) and
incorporated OpePOSS into PUs to make hybrid nanocom-
posites (Scheme 25; [277]). The authors showed that the
thermal stability increased with increasing POSS content.
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133 1099

Scheme 25. Schematic diagram of the formation of organic–inorganic hybrid networks using OpePOSS. Reproduced from [277] with permission. Copyright
2006 Wiley-VCH.

They attributed this phenomenon to the formation of a
tethered structure of POSS cages in the PU network as
well as the nano-scaled dispersion of the POSS in the PU.
In another study from the same group, Liu et al. syn-
thesized a PU network containing octaaminophenyl-POSS
(OapPOSS) and showed that the thermal stability improved
significantly [278]. Liu et al. used OapPOSS (Scheme 26)
to replace part of the aromatic amine crosslinking agent
and produced a crosslinked PU with POSS cages [278]. The
incorporation of OapPOSS into the PU networks signifi-
cantly improved the thermal stability as well as the char
yield at high temperature. Kim et al. prepared urethane
acrylate (UA) oligomers from PTMG, IPDI and hydrox-
yethyl acrylate (HEA) and the UA oligomers were UV
cured with different amount of octavinyl POSS in the
presence of 2-hydroxy-2-methyl-1-phenyl propane-1-one
(Darocur 1173) photoinitiator [279]. Their study showed
that the presence of the POSS does not significantly
alter the degradation characteristics of the UA matrix
and the degradation temperature is slightly increased
with the addition of POSS. Very recently, Markovic et al.
synthesized PEG derivatives of two different POSS struc-

Scheme 26. PU hybrid network containing POSS structures. Reproduced from [278] with permission. Copyright 2005 Wiley-VCH.
1100 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Scheme 27. Hydrosilylation of Q8 M8 H (CAS No. 125756-69-6) or T8H (CAS No. 281-50-5) with ethylene glycol monoallyl ethers. Reproduced from [280]
with permission. Copyright 2007 American Chemical Society.
tures octa(dimethylsiloxy)silsesquioxane (Q8 M8 H ) and
octa(hydrido)silsesquioxane (T8 H ) (Scheme 27), where the
attached PEGs have varying chain lengths (n = 2–6) [280].
These can be used as a crosslinker for an NCO-capped PU
formulation to improve the thermal resistance.
4.5. Carbon nanotubes (CNTs)
Recent research efforts on introducing a small amount
of CNTs into PU matrices to prepare high performance
PU–carbon nanotube composites has resulted in improved
thermal stability. CNTs have nanometer scale diameters,
high aspect ratios (in the range 100–1000), low density and
are therefore ideal reinforcing fibers for nanocomposites.
Advancements in understanding the chemistry and pro-
duction processes have resulted in obtaining CNTs with
high structural perfection either as single-walled carbon
nanotubes (SWNTs) consisting of a single graphite sheet
seamlessly wrapped into a cylindrical tube with diameters
of 0.4–3 nm, or multi-walled carbon nanotubes (MWNTs)
comprising an array of concentric cylinders with diameters
of 1.4–100 nm [281]. However, strong van der Waals forces
or ␲–␲ interactions between CNTs result in the formation
of aggregates making it difficult to obtain a fine homoge-
neous dispersion in a PU matrix [282]. The agglomeration
of CNTs also results in poor interfacial interaction with the
matrix. Therefore, achieving a homogeneous dispersion of
CNTs in a PU matrix is a key requirement for the realiza-
tion of the desired enhancement in the final properties of
nanocomposites. The degree of dispersion depends on the
size of the dispersed particles, particle wettability by the
dispersing medium as well as the nature of the attractive
forces between them. In order to improve the dispersabil-
ity and compatibility, a number of different physical or
chemical surface treatments have been applied to CNTs.
For instance, Xia et al. used a mechano-chemical milling
process (i.e., a physical treatment) with the aid of a dis-
persing agent to disperse CNTs into a polyol and prepared
PU–CNT composites with good dispersion and showed that,
at 1 wt% loading of SWNT and MWNT, the second step of
PU decomposition is delayed due to: (1) uniformly dis-
persed CNTs providing thermo-oxidative stability to the PU
in the vicinity of the tube surfaces; (2) enhanced thermal
conductivity of the composite facilitating easy heat trans-
port and thus increased thermal stability and (3) uniformly
dispersed CNTs producing stabilized CNT-bonded macro-
radicals [283].
The modification of CNTs via chemical functionaliza-
tion (Scheme 28) and covalent attachment is considered an
effective way to increase compatibility and achieve a homo-
geneous dispersion of CNTs into PU matrices. This method
improves the interfacial bonding between the CNTs and the
polymer matrix due to direct chemical linkages between
the CNT and PU [284–287]. Xia et al. prepared PU-grafted
SWNTs from hydroxy functional SWNTs (SWNT–OH) by
in situ polymerization [288]. The results suggested that
SWNT-g-PU improved the dispersion of SWNT in the matrix
and strengthened the interfacial interaction between the
PU and SWNT. Xiong et al. prepared PPG-grafted SWNTs and
reacted them with TDI to produce PU–SWNT composites
with anisotropic structures and chemical linkages between
the SWNTs and the PU matrix [289]. Chen et al. reported the
preparation of self-aligned SWNT–PU nanocomposites by
a simple solvent casting method using polar THF as solvent
[282].
Sahoo et al. reported the preparation of carboxyl-
functionalized MWNT–COOH/PU composites by solution
mixing as having better dispersion and interfacial adhe-
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133 1101

Scheme 28. Routes to functionalization of MWNT using different reactants [291,292]. The SWNT open-end functionalizations via oxidation route produce
shortened nanotubes with carboxylic acid end groups that can be derivatized by reactions with thionyl chloride and amines or by esterification reaction.

sion between MWNT and PU [284]. Jung et al. reported
MWNT–PU nanocomposites via crosslinking of NCO capped
PU prepolymers with carboxyl functional MWNTs [285].
They prepared a PU–MWNT composite via the in situ poly-
merization of a prepolymer in the presence of modified
MWNTs and evaluated the thermal stability of the raw
MWNT–PU composite and NCO-capped PU prepolymer car-
boxyl functional MWNT crosslinked nanocomposites at
different modified MWNT loadings and showed that the
modified MWNT-PUs possessed better thermal stability
than the raw MWNT–PU composite (Fig. 3). Kuan et al.
synthesized MWNT-waterborne PU nanocomposites with
improved compatibility using (a) covalent attachment (Sys-
tem I) and (b) ionic attachment (System II) of MWNT with
PU chains and showed that the improvement in thermal
stability was greater for System I than System II [290].
Xu et al. prepared aminated MWNTs with triethoxysi-
lane groups as shown in Scheme 28, which were then
introduced into a trimethoxy-silane containing PU–urea
system by chemical linkages using a sol–gel approach
[291]. Xiong et al. modified CNT with methylene-bis-ortho-
chloroanilline (MOCA) and the MOCA-grafted CNTs were
reacted with TDI and PPG [292]. The authors showed
that the thermal stability of the materials increased with
increasing CNT weight fraction in PU matrix. Gao et al.
bonded PU, polyurea and hyperbranched PU–urea with
1102 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Fig. 3. TGA thermograms of (a) pure PU, (b) PU composite with raw MWNT
and PU-modified MWNT nanocomposite with (c) 4 wt% modified MWNT
loading and (d) 6 wt% modified MWNT loading. Reproduced from [285]
with permission. Copyright 2000 Wiley-VCH.
amino-functionalized MWNTs [293]. The in situ polycon-
densation approach to functionalize CNTs and preparing
CNT-polyureas is shown in Scheme 29.
Xia and Song prepared PU–CNT nanocomposites and
showed that the incorporation of MWNT and SWNT did
not improve the first onset decomposition temperature,
but the second decomposition temperature caused by the
soft segment degradation is delayed. This indicates that
CNTs may preferably interact with the soft segment in
the PU structure [283]. The possible cause of thermal
stability improvements are: (1) the uniformly dispersed
CNTs presumably provided thermo-oxidative stability to
the PUs in the vicinity of the tube surfaces; (2) the
enhanced thermal conductivity of the composite can facil-
itate heat transport and thus increase its thermal stability;
(3) like fullerene (C60 ), CNTs possibly can lead to the
Scheme 29. Functionalization of CNT and preparation of MWNT-NH2 and MWNT-polyurea. Reproduced from [293] with permission. Copyright 2005
American Chemical Society.
formation and stabilization of CNT-bonded macroradicals
[283].
4.6. Fullerene-containing PUs
Fullerenes or “buckyballs” are allotropes of carbon with
spheroidally shaped structures that may produce thermally
stable PU composites due to their radical scavenging effi-
ciency [294]. The incorporation of C20 , C60 (a roundish
molecule made of 60 carbon atoms), C70 or C80 into a PU
matrix is an important technological accomplishment as
it allows combining in a single material the very unique
properties of fullerenes such as low density and good
physical strength, with the well-known advantages of PUs.
The low solubility or incompatibility of C60 is a main
drawback for many applications and hence multiple func-
tionalizations to build the desired fullerene derivatives
having appropriate functional groups in defined geome-
try, to achieve covalent attachment to PU is a route to
make a thermally stable networks. The structures of dif-
ferent functional group containing fullerenes are shown
in Scheme 30 [295,296]. Research efforts on fullerene-
crosslinked PUs are still in an infant stage and only a few
reports are available. For instance, Narang et al. prepared
fullerene-functionalized amine-containing polymeric or
polymerizable monomeric materials with improved high
temperature stability [297]. Chiang et al. prepared a
C60 crosslinked PU from PTMG based NCO capped PU
prepolymer and C60 (OH)10–12 shown in Scheme 31(a)
[298]. Chen et al. prepared trihydroxyl-containing C60 ,
which was later reacted with a triisocyanate compound
(Scheme 31(b); [299]). Zhang et al. used a sol–gel approach
to incorporate C60 into PU–urea structure [300]. They have
reacted C60 with APTES at 100 ◦ C and prepared aminated
C60 with trimethoxysilane group (APTES–C60 ) shown in
Scheme 31(c). Then, APTES–C60 was reacted with trimethy-
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Scheme 30. Functional group containing Fullerene (buckyball) structures. Structures reproduced from [295,296] with permission. Copyright 2006
Wiley–VCH; Copyright 1999 Royal Society of Chemistry.
loxysilane groups on the PU–urea via a sol–gel hydrolysis
and condensation reaction.
5. Thermal stability vs. flammability of PUs
Applying increasing temperature to a PU system results
in the thermal excitation of the covalent bonds in PU chains
and once a critical temperature is reached, the PU starts
decomposing and produces small molecules in the gaseous
phase. The decomposed small molecules evaporate, dif-
fuse into the flame zone above the polymer/air interface
and mix with air to form a flammable mixture. When the
concentration of this mixture and the system temperature
crosses the flammability limit, it starts to burn. A part of
the exothermic heat that results from the burning process
is fed back to the condensed phase and accelerates the
degradation of the PU, producing more volatile fragments
and sustaining the combustion cycle. Finally, the combus-
tion process ends with a material of different morphology.
Branca et al. examined the thermal response of PU foam
[Fig. 4(a)] at two radiation intensities 25 and 50 kW/m2 in
1103
a cone calorimeter and showed that the cellular structure
of the foam is completely lost becoming an open network of
lumps consisting of micron-sized particles and/or a smooth
slightly corrugated surface. The charred residue possessed
a homogeneous structure at the surface when lower heat
flux (25 kW/m2 ) was applied [Fig. 4(b)], whereas at higher
heat flux (50 kW/m2 ), the obtained char residue possessed
a compact and fragile structure [Fig. 4(c)] [301].
The flammability of PU materials presents a threat to
both the integrity of the product and to human health.
Therefore, the search for an appropriate fire retardant or
synthesizing an inherently non-flammable PU represents a
major scientific challenge. In this respect, it is essential to
know the structural and energetic features that influence
the thermal stability and flammability of PUs. Flammabil-
ity is associated with the formation of flammable, gaseous
decomposition products during the initial decomposition.
However, the decomposition rate and extent of decom-
position is connected and controlled by the amount of
flame propagation. Therefore, it is understandable that fire-
resistant PUs might be prepared by incorporating thermally
1104 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

Scheme 31. Schematic diagram of Fullerene modification and incorporation into PUs. Reproduced from [298–300] with permission. Copyright 1995
American Chemical Society; Copyright 1995 American Institute of Physics; Copyright 2003 Elsevier.

stable structural units that either do not decompose eas-
ily but, once they decompose, produce non-combustable
products [302]. For instance, researchers have shown that
aromatic polyol based PUs are significantly more flame-
retardant than aliphatic polyol based PU foams [303,304].
Specifically designed aromatic polyols with high hydrolytic
and thermal stability may be used in fully water-blown
foams that possess good flame-retardant performance. For
example, Terol 708, a highly aromatic polyester polyol
developed by Oxid produces enhanced fire-retardant prop-
erties [305]. Additionally, the flow of fuel gases during
decomposition is also important for the predication of
flame retardancy.
In order to stop, delay or retard the burning process,
a flame retardant may be added to the PU system, which
may or may not be a part of the PU macromolecular chain
[71,306]. The objective of using flame retardants is to lower
the PU’s inherent fire risk by lowering the combustion rate
and flame spreading in the presence of fire. Fig. 5 shows the
typical process that takes place during the combustion of
PU in the presence and absence of a flame retardant.
Song et al. showed that organo-modified clay fillers
reduce the flammability of PU/clay nanocomposites due
to the formation of a multilayered carbonaceous-silicate
structure in the condensed phase. This high-performance
carbonaceous silicate char builds up on the surface of burn-
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Fig. 4. SEM micrographs of the surface of PU foam (a) before exposure (20×), (b) after exposure to a radiative heat flux of 25 kW/m2 in a cone calorimeter
(100×) and (c) after exposure to a radiative heat flux of 50 kW/m2 in a cone calorimeter (250×). Reproduced from [301] with permission. Copyright 2003
Elsevier.
ing PUs thus insulates the underlying material. The process
slows down heat and mass transfer between the gaseous
and condensed phases, and thus retards the thermo-
oxidative degradation [307].
Flame retardant PUs are combustible materials that pre-
vent or delay flashover from the surface of combustibles; a
flame retardant is not designed to prevent the material from
ignition but to keep the flame spread rate to a minimum
and prevent sustained burning. Therefore, flame retardants
tend to keep the flame from spreading by increasing the
resistance of the polymer to ignition [308,309]. Hence, the
flame resistance of a PU depends on the structure of the
components, the isocyanurate index (i.e., the amount of
thermally stable isocyanurate groups present particularly
in PU foams), the density of the material and the addition
of some additive, known as a flame retardant, that delays
flashover.
The flame retardance mechanism – the interference
with the combustion process – can function either in the
condensed phase (solid phase) or in the vapor phase (flame
zone) through a physical mechanism, a chemical mecha-
nism or a combination of these mechanisms. Combustion
is a complex process and different mechanisms may be
involved in the presence of different types of flame retar-
Fig. 5. A typical picture of PU without flame retardant-resulting large
heat release (a) and with flame retardant-resulting low heat release (b),
showing the processes occurring during combustion. A low-density, high-
porosity char produces better flame retardancy.
1105
dants. Therefore, the substitution of one type of flame
retardant with another may result in a change in the flame
retardance mechanism. Flame retardants interfere with
combustion during specific stages of processes such as
heating, decomposition, ignition, or flame spread [310].
For example, the incorporation of inorganic fillers dilute
the polymer, produce a stable organic–inorganic inter-
face, reduce the concentration of decomposition gases and
increase the diffusion path barrier of the volatiles produced
during the degradation process.
Condensed phase. Flame retardants accelerate the break-
down of the polymer and cause a layer of carbon (char) on
the polymer surface. The char layer protects the PU mate-
rial, and its protective property depends on the physical and
chemical structure of the char layer. The char formation at
the surface often produces a foamed matrix in a process
known as intumescence. Intumescent systems containing
phosphorus and nitrogen generally follow the condensed
phase flame retardant mechanism.
Vapor phase. Radical mechanism of the combustion pro-
cess is stopped by a flame retardant in the gas phase. The
exothermic processes that occur in the flame are therefore
stopped and the system cools down due to the reduced
concentration of the formation of flammable gases. The
reactive radicals such as HO• and H• can react in the gas
phase with radicals like X• (halogenated radicals) or others
that result from flame retardant degradation. Halogen-type
flame retardants usually follow the vapor phase flame retar-
dant mechanism.
Therefore an ideal flame retardant might have prop-
erties such that (a) it should be resistant towards flame
and reduce the flammability up to a certain point, (b) it
should be thermally stable at processing temperatures, (c)
it should be compatible with the PU binder, (d) it should at
least maintain or improve the mechanical properties of the
PU, (e) it should be free of health hazards, and, finally, (f) it
should be cost effective [308,309].
5.1. Correlation of char yield with fire retardance
Lyon developed a mechanistic model of fire retardancy
from char-forming polymers using TGA data [311]. The
1106 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
typical char is a carbonaceous material that forms during
thermal degradation or pyrolysis. It is generally accepted
that char yields as determined from TGA experiments are
an indirect way of measuring the fire retardant properties
of polymers. Char formation in a fire limits the amount
of volatile fuel that can be produced by the burning poly-
mer. Char provides a thermally insulating layer or barrier at
the surface of the burning polymer, reduces heat and mass
transmission into the material and provides good insula-
tion to the underlying combustible polymer from the heat
and fire. There are several ways to improve the yield and
integrity of charred layers that contains carbon along with
other elements such as N, O, P, etc. [312].
Char formation is a major factor in flame retardant PUs
[312–314]. van Krevelen studied the relationship between
char yield and flame retardant properties of different
polymers [315]. An ideal char former could be an inor-
ganic material that is not prone to combustion. On the
other hand, an organic component which may serve as
a binder to hold the material together could also act as
a char former by thermal degradation at a temperature
lower than the temperature at which the PU degrades.
In this case, the char formed from the degradation of the
organic component is available to protect the PU when the
degradation of the PU commences. Examples include the
addition of a char-forming additive, such as phosphates,
into nonchar-forming polymers to reduce the flammability
of the polymers [312]. Grassie and Scott studied the thermal
degradation behavior and mechanism of PUs derived from
MDI and BD [316]. With the addition of poly(ammonium
phosphate), the degradation of PU was accelerated due
to the formation of phosphoric acid which further con-
verted the butanediol to THF by dehydration. In addition,
the phosphoric acid could also crosslink with carbodiimide
and form a brown stable solid on the surface. Therefore, the
char yield was increased and the remaining PU was able
to avoid further degradation. By chemical bonding of phos-
phorus onto the polyol, Grassie and Mackerron were able to
synthesize a series of PUs with different amounts of phos-
phorus and study their thermal degradation mechanisms
and products [317–319]. Chang et al., in another way, syn-
thesized PUs with chain extenders containing phosphorus
[320,321,102]. They also found that the thermal degrada-
tion occurred earlier than that of pure PU. In addition, it also
promoted the dehydration reaction and increased the char
yield [71]. In the case of phosphate-containing PUs where
the phosphate is on the hard segment, Grassie and Mack-
erron concluded that the thermal decomposition started
at the hard phosphate-containing urethane segment [318].
On the other hand, when phosphate groups were in the soft
segment, the initial onset decomposition temperature for
the phosphated PUs was lower than the ones without phos-
phate suggesting that the degradation started at the soft
segment [312]. Chang et al. used Flynn and Broido meth-
ods to evaluate the activation energy values of common
PU and phosphorus-containing PUs containing phenyl-
bis(hydroxyethyl)phosphonate for the first 10% and 30%
weight loss [102]. The activation energy values of first 10%
conversion of common PU and phosphorus-containing PU
were 120 and 105 kJ/mol, respectively. At 30% conversion
in air, the activation energy of phosphorus-containing PUs
decreases with increasing phosphorus content, suggest-
ing that char yield increases with increasing phosphorus
content [321]. The higher char yield of the phosphate-
containing PUs can thus be related to their fire retardant
properties.
5.2. Methods to improve flame retardancy of PUs
Nowadays, more and more attention is being paid to
improving the flame retardant properties of PUs as it is
an essential requirement for applications such as in wire
and cables, PU foams in different household stuffs such
as upholstered furniture and mattresses, aircraft interi-
ors, fire-resistant coatings and clothes, etc. The driving
forces for the development of flame retardant PUs include
increasing safety awareness of consumers, environmen-
tal pollution generated during burning, and economic loss
incurred due to burning of materials. The main approaches
taken are to incorporate flame retardants either as addi-
tives or to incorporate reactive flame retardants into the
PU formulation. Additive type flame retardants are incor-
porated into the PU by physical means, which may result
in poor compatibility, leaching, as well as a reduction in
mechanical properties. On the other hand, reactive type
flame retardants are mainly organic compounds having a
flame retarding moiety as well as active functional groups
that can form covalent bonds with PUs. Reactive type flame
retardants have the advantages of (a) increasing compat-
ibility between polymer and the flame retardant, (b) not
degrading the mechanical properties of the PU, (c) possess-
ing better compatibility as the flame retardant group is a
part of the binder and (d) using small amount or low con-
centration for the enhancement of fire-retardancy [310].
5.2.1. Additive type flame retardants
Examples of additive type flame retardants are:
halogenated paraffins, chlorofluorocarbons (CFCs), inor-
ganic oxides and hydroxides (such as antimony oxide,
magnesium di-hydroxide, aluminum tri-hydroxide, mica
[264,322]), inorganic carbonates (such as potassium
carbonate, calcium carbonate, magnesium carbonate, mag-
nesium hydroxycarbonate), boron containing inorganic
compounds (such as boric acid, borax, zinc borate,
ammonium pentaborate), inorganic phosphorus contain-
ing compounds (such as di-ammonium hydrogen phos-
phate, ammonium polyphosphate (Scheme 32), melamine
phosphate [323–325]), triphenylphosphine oxide, red
phosphorus, expandable graphite, melamine, etc. Halo-
genated additives such as chlorofluoro carbons (CFCs)
release corrosive, obscuring, toxic and irritant halogen acids
[326]. CFCs may damage the ozone layer. In addition to the
mentioned additive type flame retardants, different widely
used organic phosphate, phosphonate and bromine con-
taining additive type flame retardants are as follows:
Alkyl phosphate or phosphonate. Trimethyl phosphate,
triethyl phosphate, tributyl phosphate tris(monochloro-
propyl) phosphate, chloroalkyl phosphate such as tris(2-
chloroethyl) phosphate, tris(2,3-dichloropropyl) phos-
phate, tris(␤-chlor-ethyl)-phosphate, tris(␤-chlor-
isopropyl)-phosphate, tris-(␤,␤ -dichlor-isopropyl)-phos-
phate, bis-, tris- and tetrakis(neopentylglycol) phos-
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Scheme 32. Chemical structure of ammonium polyphosphates.
phates [327], triallyl phosphate, triallyl phosphoric tria-
mide, tris(1,3-dichloro-2-propyl) phosphate [328–330],
neopentylglycol bis(diphenyl phosphate), poly(ethylene
glycol ethyl phosphate), tris(2-butoxyethyl) phosphate,
tris(2-ethylhexyl) phosphate, diethyl-N,N-bis-(2-hydroxy-
ethyl) aminomethylphosphonate [74], tetrakis(2-chloro-
ethyl) ethylene diphosphate [322–325], dimethyl
methylphosphonate [331], diethyl ethylphosphonate,
cyclic alkyl phosphate and diphosphonate ester
(Scheme 33; [332]), etc.
Aryl phosphates or phosphonates. Triphenyl phosphate,
diphenyl 2-isopropylphenyl phosphate, phenyl di-(2-
isopropylphenyl) phosphate, diphenyl 4-isopropylphenyl
phosphate, tris-(2-isopropylphenyl) phosphate, tris-(4-
isopropylphenyl) phosphate, tris-(2,4-xylenyl) phosphate,
tris-(2,5-xylenyl) phosphate, tris-(3,5-xylenyl) phosphate,
phenyl di-(4-isopropylphenyl) phosphate, ethylene glycol
bis(diphenyl phosphate), bisphenol A bis(diphenyl phos-
phate), resorcinol bis(diphenyl phosphate) [333], triphenyl
phosphonate etc.
Bromine-containing compounds. Tribromoneopentyl
alcohol, dibromopentyl glycol, hexabromocyclodode-
cane, decabromobiphenyl, decabromodiphenyl oxide
(DBDPO), tetrabromobisphenol A and its derivatives
Scheme 33. Chemical structure of cyclic alkyl phosphate and diphospho-
nate ester [332].
1107
such as brominated bisphenol A diglycidylether, tetra-
bromobisphenol-A-bis(2,3-dibromopropyl ether), tetra-
bromophthalic anhydride (TBPA), N,Nı̌-ethylene
bis(tetrabromophthalimide), pentabromotoluene, penta-
bromodiphenyl ether, hexabromocyclododecane (HBCD),
decabromodiphenyl ether, tetradecabromodiphenoxy
benzene, 1,2-bis(2,4,6-tribromophenoxy) ethane, poly-
brominated biphenyls, tris(2,3-dibromopropyl) phosphate,
tris(2,3-dibromopropyl) isocyanurate, polybrominated
diphenyl ethers such as pentabromodiphenyl ether,
decabromodiphenyl ether, etc.
Sometimes a mixture of additive type flame retardants
possess improved flame retardancy due to the synergistic
mechanism involved in suppressing combustion. Additive
type flame retardants are widely used in PUs; however
they have several limitations such as poor compatibility,
high volatility, loss of mechanical properties of PU, and for-
mation of increased amount of carbon monoxide (CO) and
smoke during combustion [334].
5.2.2. Reactive type flame retardants
Phosphorus-containing compounds containing reac-
tive functional groups that can be reacted with a
suitable functional group in PUs are widely used as
reactive type flame retardants. Phosphorus compounds
act as char-forming agents reducing the generation of
flammable gases. For instance, phosphorus-containing
polyols or hydroxyalkyl phosphonates such as ethyleneg-
lycol bisphosphonates, ethyleneglycol bisphosphate, N,N
bis(hydroxyethyl) aminomethylphosphonate, etc., have
been used [335–337]. Different reactive type organophos-
phorus compounds, cyclotriphosphazenes, phosphorus
containing aziridinyl curing agents for aqueous PUDs,
organoboron compounds and organosilicon compounds
will be discussed in an upcoming section.
5.3. Intumescent and nonintumescent systems
Based on the flame-retardant mechanism, PUs can
be classified into either intumescent or nonintumescent
types. The use of intumescent flame-retardant PUs is one
of the easiest, economical and the most efficient ways to
1108 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

protect materials against fire. Intumescent flame retardants

swell, bubble and char on exposure to a flame and the car-
bonaceous porous foamed mass acts as a barrier to heat,
air/O2 and pyrolysis products. At high temperature, the
formed charred layer on the surface provides resistance
to heat and mass transfer, giving good heat insulation to
the underlying binder. Therefore, an intumescent system
shields the underlying PU from heat and fire. This lowers
the temperature of the PU surface beneath the char and
causes a lag in the surface temperature rise. Additionally,
the char layer hinders the diffusion of oxygen to the PU site,
i.e., the site of combustion.
A char-forming catalyst and a foaming agent are used
in intumescent systems. Traditional intumescent systems
consist of an acid source that acts as a dehydrating agent
(e.g., phosphorus in the form of a substance such as
ammonium polyphosphate), a carbon source that acts
as a carbonific or char former (e.g., polybasic alcohol
such as pentaerythritol and dipentaerythritol) and a gas
source or blowing agent called a spumific (nitrogen-
containing substances such as melamine, guanidine, urea,
etc.) (Scheme 34; [338,339]).
The char formation mechanism of an intumescent
system starts with the acid catalyzed dehydration of a
polyhydric alcohol (Scheme 35). The acid catalyst for the
dehydration reaction is phosphoric acid that is evolved Scheme 34. Different intumescent systems.
from the phosphate containing flame retardants. The
evolved water during the dehydration reaction also acts as mescent systems do not swell and char during exposure to
a blowing agent. flame.
The intumescent fire retardant/PU system has several
advantages such as low smoke, low toxicity, low corrosion, 5.4. Expandable graphite (EG)
long life, and are halogen free. The physical structure of the
char layer plays a very important role in the performance EG is a kind of intumescent flame retardant that can
of the flame retardant [340]. On the other hand, nonintu- effectively improve the flame retardance property of PUs.

Scheme 35. Schematic diagram of phosphoric acid dehydration and char formation in an intumescent system.
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Fig. 6. Structure of expandable graphite intercalated by H2 SO4 [339].
EG is widely used in PU foams. Such flame retarded PU
foams are used as a seat material in aircraft and other vehi-
cles. They are also used for sound and thermal insulation
for cars, but special chemical treatment of this material is
required before use. In the building industry, such flame
retarded PU foams are used as sealing tapes for windows
and doors [341]. EG has a flake-like graphite structure, i.e.,
stacked layers of hexagonal sp2 hybridized carbon struc-
tures, which is treated with sulfuric, nitric acid or acetic
acid which are intercalated into the graphite crystal struc-
ture (Fig. 6; [339,342]). The intercalated graphite particle
under heat expands or exfoliates (expansion along c-axis
of the crystal structure by about 100 times occurs). EG is
halogen-free and works mainly in the condensed phase
thereby strongly reducing the smoke density. In addition,
the expanded carbon layer works as an insulating layer
to reduce the heat transfer. Decomposition of intercalated
compounds (e.g., H2 SO4 decomposes to H2 O and SO2 gas)
as well as oxidation of EG by acid (H2 SO4 oxidise and
produce CO2 and SO2 around 220 ◦ C) in the presence of
heat produces pressure that ultimately increases the dis-
tance between the graphite basal planes [325,342,343].
Therefore, once exposed to heat, EG forms a low den-
sity worm-like thermal insulating layer structure on the
surface of the PU that prevents heat and oxygen transfer
and provides good fire retardant performance. The blow-
ing reaction is shown below:
The flame retardant efficiency of EG is influenced by the
size, density and amount of EG used [338,344]. For instance,
Modesti et al. studied the flame retardant properties of
EG/PU foam with a density of 0.035 g/cm3 , and concluded
that increasing EG content gives a significant improvement
in fire reaction of the materials [338,345–347]. Duquesne
et al. showed that high-density EG (0.46–0.50 g/cm3 ) pro-
1109
vides excellent flame retardant properties [348]. In another
study, Duquesne et al. showed that the addition of EG to PU
enables a decrease the emission of toxic gases such as CO
or HCN [349]. Researchers also showed that lower size EG
particles led to lower volume expansion and hence had less
flame retardant efficiency [338,350–353].
5.5. Melamine
Melamine (thermally stable, crystalline powder, melt-
ing temp. 345 ◦ C) and its derivatives are non-halogenated
flame retardants that are widely used as a fire retardant
additive in different formulations such as flexible PU foams
[354]. Its mode of action as a fire retardant additive is due
to the following [346,355–363]:
• during combustion, the heat energy of the PU matrix is
absorbed by the melamine;
• the generation of non-combustible nitrogen-containing
vapors from the decomposition of melamine dilutes the
gaseous combustible species derived from the decompo-
sition of the PU matrix;
• in addition to melamine sublimation that takes place
above 250 ◦ C, during heating melamine is known to
undergo progressive endothermic condensation with the
elimination of ammonia (a flame diluent) and the for-
mation of polymeric products such as melam, melem,
and melon. These condensation products constitute the
superficial char layer (ca. 7%) and are more thermally
stable than melamine itself (melam ∼350 ◦ C, melem
∼450 ◦ C, and melon ∼600 ◦ C) (Scheme 36). The low-
temperature de-ammonation product of melamine is
melam. Melam is formed upon linking two molecules
of melamine with concomitant release of one mole of
ammonia. At high temperature melem and melon are
formed. Further heating of melon produces graphitic car-
1110 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
Scheme 36. (a) Schematic representation of thermal decomposition of melamine and the formation of melam, melem, melon and graphitic carbon nitride
char; and (b) two tautomeric forms of melam. Reproduced from [364] with permission. Copyright 2007 Wiley–VCH.
bon nitride, g-C3 N4 [364]. The condensation may lead to
(a) fused ring structure of cyameluric triamide-that may
react as a trifunctional monomer to give the final conden-
sate or (b) the condensate results in polymers where the
triazine rings are linked by –NH– bridges [361,365].
5.6. Organophosphorus compounds
Phosphorus is an effective element for imparting good
fire resistance to PUs. Compounds containing phospho-
rus such as phosphines, phosphine oxides, phosphonium
compounds, phosphonates, phosphites and phosphate are
an important group of environmental friendly flame retar-
dants which have several advantages such as low toxicity,
no release of poison gas – e.g., dioxin and halogen acids
– during combustion, as well as producing low smoke
during burning. The fire-retardancy of the PUs depends
on the structures of the phosphorus-containing oligomers.
The increased char yield of phosphorus-containing PUs
is attributed to the fact that phosphorus both promotes
carbonization and inhibits combustion. Table 2 shows dif-
ferent organophosphorus fire-retardant additives in the
form of reactive diols, diamines, diacid, diepoxy and unsat-
urated types that are widely used to improve the flame
retardancy of PUs [88,366–390].
Chao and Wang studied the thermal decomposi-
tion behavior of flame-retardant foams and interpre-
tated the fire-retardant action as a dual gas-phase and
condensed-phase mechanism for phosphorus-containing
flame-retardants [391]. Their thermal analysis results
showed that phosphorus-containing flame-retardant addi-
tives decrease the thermal stability and induce emission
of more volatiles in the temperature range from 200 to
300 ◦ C. Therefore, the initial weight-loss temperatures of
phosphorus-containing PUs are lower than that of the
phosphate-free PUs and the presence of phosphorus-
containing reactive type additive does not improve the
onset decomposition temperature either in an inert atmo-
sphere or under an oxidative environment [391–393]. This
is due to the fact that when exposed to flame or heat,
the phosphorus-containing groups in the PU decompose
more rapidly than the other parts of the polymer matrix.
Additionally, a high yield in char formation was observed
in the temperature range 300–400 ◦ C. From the kinetic
parameters, it was seen that in a lower thermal degrada-
tion temperature range (about 200–300 ◦ C) the activation
energy of thermal degradation of the flexible polyurethane
foam with flame-retardant additives is lower than that
without flame-retardant additives. In a higher thermal
degradation temperature range (about 300–400 ◦ C), how-
ever, the reverse trend in the activation energy of thermal
decomposition was noticed [388]. Therefore, the percent-
ages of char yield for phosphorus containing PUs were
higher than those of phosphorus-free PUs [394]. Increasing
the phosphorus content in PUs results in increasing decom-
position residuals (Fig. 7), which result in increasing the
thermal stability of the PU at high temperature as the char
layer once formed, inhibits further decomposition of the PU
matrix [312]. This is because the thermally insulating char
layer provides resistance to heat and mass transfer, reduces
heat transmission into the material, acts as a diffusion bar-
rier to combustible gasses and provides good insulation to
the underlying combustible polymer. The higher char yield
of the phosphate-containing PUs can thus be related to its
fire retardant properties [393].
5.7. PUs with cyclotriphosphazenes
Recently, researchers have focused on hybrid
inorganic–organic polymers containing cyclophosp-
hazenes as side-groups on the carbon chain as one of the
methods to develop PUs with good thermal resistance
and flame retardancy [395–398]. Cyclotriphosphazenes
are composed of an inorganic ring with three P = N units,
and exhibit unusual thermal properties such as flame
retardancy and self-extinguishability. Several classes of
cyclotriphosphazenes with different properties can be syn-
thesized from hexachlorocyclotriphosphazene (N = PCl2 )3
[395,397,399–402]. The chlorine groups of cyclotriphos-
phazenes are attached to the phosphorus atoms, can be
easily substituted by various nucleophiles to form reactive
cyclotriphosphazenes. (N = PCl2 )3 can be functionalized
with different organic substituents useful for the modi-
fication of PU materials. There are two possible ways to
Table 2
Organophosphorus reactive type fire-retardant additives.

Type Example References Type Example References

[366,367] Diamine type [377]

D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

[378–380]

[368] [380]

[368] [380]

[368] [380]

[369–371] [380]

1111
 1112
Table 2 (Continued )

Type Example References Type Example References

[377]

D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

[369–371] [380]

[379]

[369–371] Diol type [381]

[372] [382,383,394]

[373]
 [374] Diacid type

D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

[375]

[389]

Spyrocyclic phosphorus containing [376]

[88] Diepoxy type [390]

[368]

Unsaturated type [385]

1113
Table 2 (Continued )

1114
Type Example References Type Example References

[377]

D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

[385] [381]

Aldrich catalog

CAS No. 4141-48-4

Aldrich catalog

[386]
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133 1115

Fig. 7. The effect of the amount of phosphate (expressed as elemental P)

on TGA curves of polyurethane coating films. Reproduced from [312] with
permission. Copyright 2002 Elsevier.

obtain cyclotriphosphazene-containing PUs: (1) reaction

of cyclophosphazenes containing polymerizable vinyl,
acrylic, or methacrylic groups linked to phosphorus by P–O
or P–C bonds with acrylate/methacrylate terminated PUs
and (2) polycondensation of suitable substituted bifunc-
tional cyclotriphosphazenes such as hydroxyl terminated
cyclophosphazenes with an NCO capped PU prepolymer
[403]. Hydroxyl functional cyclophosphazenes shown in
Table 3 can be reacted with an NCO-capped PU prepolymer
[387]

[388]

that results in improving the thermal stability and flame

retardancy [9,404]. On the other hand amine terminated
cyclophosphazenes [405,406] can be reacted with epoxy
capped PU prepolymers, which results in the improvement
of thermal stability and flame retardancy. Table 4 shows
carboxyl, epoxy, ene and silane functional reactive type
cyclotriphosphazenes that can react with NCO-terminated
prepolymers or diols (for making polyester-PU), NH2 -
terminated, unsaturated terminated (e.g., acrylated or
methacrylated PU) and alkoxy silane terminated PU
prepolymers, respectively [403,407–417].

5.8. Phosphorus-containing aziridinyl curing agents

Aziridine groups can react with pendent carboxylic acid

groups in anionic PUDs and result in crosslinked network
formation. Therefore, the introduction of phosphorus con-
taining aziridine curing agents in aqueous anionic PUDs
is a very effective way to improve the thermal stability
and impart flame retardancy [9,310,418–420]. A synergis-
tic effect can be observed in the aziridinyl and phosphorus
containing cured PUDs. A series of phosphorus contain-
ing aziridinyl curing agents synthesized by Wang and Chen
[420] and Huang et al. [421] are shown in Scheme 37. Huang
et al. showed that a small dose of aziridinyl phosphazene
(NPAZ), a reactive a flame retardant, into an anionic PUD
is sufficient to improve thermal and mechanical properties
of the PUD considerably [421]. NPAZ was prepared from
the nucleophilic substitution reaction of (N = PCl2 )3 with
aziridine.
1116 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

Table 3
Hydroxyl and amine functional reactive type cyclotriphosphazenes.

Type Example References Type Example References

Hydroxy functional Amine functional [407]

[395,400–403]

[400] [408]

[397]

[9,395,397,400,401]

[404]

[405] [407]

[9]

5.9. Organoboron compounds
The chemical modification of a PU chain with boron-
containing compounds leads to significant improvements
in flame retardancy [9,422]. Different boron-containing
triols shown in Table 5 are obtained from the reac-
tion of boric acid with diols such as 1,2-propanediol
[423], 1,3-Butanediol or with aminoalcohols such as
monoethanol-amine [424,425]. Additionally, unsaturated
functional borates such as triallyl borate or thimethallyl
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133 1117

Table 4
Carboxyl, epoxy, ene and silane functional reactive type cyclotriphosphazenes.

Type Example References Type Example References

Acid functional [409] Silane functional [415–417]

[410]

Epoxy functional [411]

[412]

Ene functional [413]

Ene-ol functional [403]

 1118
Table 5
Organoboron reactive type flame retardant additives.

Type Example References Type Example References

Boron containing triol [423] Armine functional [310,434]

D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

[424] [310,434]

[424] NCO functional [310,434]

[424] [310,435]

Ene functional
Hydroxyl functional carborane Aldrich catalog [310,435]

D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

[429]

[310,435]

Acid functional [430] [310,435]

Ene functional

1119
 1120
Table 6
Organosilicon reactive type flame retardant additives.

Type Example References Type Example References

NCO functional [9] Si-epoxy type

D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

Ene functional [438]

[276] [9]
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133 1121
[276]

[276]

[276]
[9]
Aldrich catalog

[276]

[9]

[9]
Amine functional
 1122
Table 6 (Continued )

D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133

Type Example References Type Example References

Si-phosphinate type [88]

[9] [88]

Functionalized silica nanoparticle [246] Si-phosphinate-ene type [88]

 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133 1123

Scheme 37. Phosphorus-containing aziridinyl curing agents [9,418–421].

borate can be used in the UV/thermal cured formulation
to improve the flame retardancy.
Organoborane cluster compounds such as icosahe-
dral carboranes (dicarba-closo-dodecaboranes) possess
remarkable heat and chemical stability and it is possible
to carry out a variety of reactions on substituent groups
attached to carborane while leaving the cage system intact
[426,427]. These qualities have made possible the devel-
opment of extensive derivative and substitution products
containing suitable functional groups that can be reacted
with a PU prepolymer containing complementary func-
tional groups. Therefore, structural variations may produce
pendent carborane groups on the PU backbone or inclusion
of carborane units in PU chains linked either by ester, amide
and other functional groups bonded directly to the carbo-
rane carbon. Different reactive carborane compounds are
also shown in Table 5 [310,428–435].
5.10. Organosilicon compounds
Considerable research has shown that the addition of
relatively small amounts of reactive type silicon com-
pounds can significantly improve both the thermal stability
and flame retardancy of PUs. This is due to the fact that sil-

Scheme 38. Structure of organosilanes that can be blended with a reactive type alkoxysilane to improve thermal stability and flame retardancy.
1124 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
icon compounds reduce the amount of more combustible
organic components and produce silicaceous residue bar-
rier layers that inhibit heat and mass transfer across it.
Silicon containing flame retardants are environmentally
friendly as they release low and non-corrosive smoke dur-
ing combustion [186,436–438]. Different types of silicon
containing reactive type flame retardants are listed in
Table 6 [9,88,438]:
1. Organo hydroxyl and organo amine terminated silox-
anes, which react with NCO capped PU prepolymers.
Amino-terminated siloxanes can also be reacted with
epoxy capped PU prepolymers. Hydroxyl terminated
polyorganosiloxane; in particular, polydimethylsiloxane
(PDMS) is also an effective flame retardant.
2. Epoxy-terminated siloxanes: amino terminated PU pre-
polymers can be reacted with epoxy capped siloxanes.
3. Siloxanes with unsaturation: unsaturated (vinyl, acrylate)
functional siloxanes can be polymerized with acrylate
or methacrylate terminated PU prepolymers either in
the presence of heat using initiators such as benzoyl
peroxide, tert-butyl hydroperoxide, 2,2 -azobis(2,4-
dimethylpentanenitrile), 2,2 -azobis-(2-methylbutyro-
nitrile) (AMBN) 2,2 -azobis-(2-isobutyronitrile) (AIBN),
dimethylazodiisobutyrate (WAKO 601), 2,2 -azobis-
2,4-dimethylvaleronitrile (VAZO 52), 2,2 -azobis-iso-
butyronitrile (VAZO 64), 2,2 -azobis-(2-methylbutyro-
nitrile) (VAZO 67), 1,1 -azobis-cyclohexanecarbonitrile
(VAZO 88), etc. or UV cured in the presence of photoini-
tiators such as benzophenone, Irgacure 184, Irgacure 651,
Irgacure 2959, Darocur 1173, Darocure 4265, etc.
4. Silsesquioxanes and bridged siloxanes [9].
5. Sol–gel precursors such as alkoxides that form Si–O–Si
networks during cure [9].
6. Some other alkoxysilanes that may be blended with
a reactive type silicon compounds are shown in
Scheme 38.
6. Conclusions
PUs are one of the most versatile classes of materials
today and their demand as a high performance indus-
trial material continues to grow. The wide application of
PUs necessitates understanding the chemistry and struc-
tural elements that improve the thermal stability and flame
retardancy as these are important prerequisites to obtain
tailor-made products for high performance applications
such as in aggressive environments. Selecting proper PU
raw materials for a specific application requires an evalua-
tion of the environment in which it is anticipated to operate
and the performance required. Success is dictated by select-
ing a PU having good thermal stability and flame retardancy
that meets the environmental requirement for which the
application is intended. The material performance should
be consistent with the desired level of performance for a
sufficiently long time. The primary reason to go through
a knowledge-based understanding is to utilize proper raw
materials and develop suitable products for the application
under consideration. It is therefore essential to understand
the basic chemistry and tools involved for designing PU
material with improved thermal stability and flame retar-
dancy.
With the aim to summarize the recent literature avail-
able on the PU chemistry, the present review emphasized
the different processes taking place during the thermal
decomposition of PUs and the parameters affecting their
thermal stability. A number of parameters related to the
structural features of PUs such as SS, HS and CE struc-
ture, NCO:OH ratio, catalyst concentration, etc., in addition
to the formation of side products, affect the degrada-
tion characteristics of PUs. In this review, we have also
described different methods for modifying the structure
as well as incorporating thermo-stable functional moi-
eties into the backbone and forming PU–isocyanurate,
PU–oxazolidone and PU–imide. Additionally, methods to
improve the thermal stability of PUs using nano-composite
formation, Si–O–Si crosslinked structure via sol–gel pro-
cess, incorporation of POSS structure into PU backbone, use
of CNT and functionalized fullerenes as the latest tools for
structural engineering of PUs is shown to improve thermal
stability.
The information included in this review on the flame-
retardant mechanism and widely used materials shows
that much progress has been made over the years on
flame-retardant PUs. A major effort has been devoted
towards developing phosphorus and halogenated flame
retardants but due to environmental restrictions, and cus-
tomer needs to improve the flame-retardancy without
sacrificing mechanical properties, recent research efforts
have resulted in different reactive-type flame retardants
that can bond with suitable functional groups in PUs. In
this respect, we found the need to summarize the different
reactive-type flame retardants in tabular form so that the
future development and understanding the fundamental
principles of fire retardation will be easier for the reader.
Hopefully this review has given ample information to
the reader regarding structure–property relationships in
relation to the thermo-stability and flame-retardancy of
PUs and to understand the useful structural elements that
may be incorporated in order to improve these properties.
References
[1] Cooper SL, Tobolsky AV. Properties of linear elastomeric
polyurethanes. J Appl Polym Sci 1966;10:1837–44.
[2] Schollenberger CS, Scott H, Moore GR, Polyurethan VC. A virtually
cross-linked elastomer. Rubber World 1958;137:549–55.
[3] Schollenberger CS. Polyurethane elastomers. US Patent 2,871,218
(1959).
[4] Koutsky JA, Hien NV, Cooper SL. Electron microscopic investigations
of polyether-urethane and polyester-urethane block copolymers. J
Polym Sci, Polym Lett Ed 1970;8:353–9.
[5] Chen-Tsai CHY, Thomas EL, MacKnight WJ, Schneider NS. Struc-
ture and morphology of segmented polyurethanes. 3. Electron
microscopy and small angle X-ray scattering studies of amorphous
random segmented polyurethanes. Polymer 1986;27:659–66.
[6] Petrovic ZS, Ferguson J. Polyurethane elastomers. Prog Polym Sci
1991;16:695–836.
[7] Estes GM, Seymour RW, Cooper SL. Infrared studies of segmented
polyurethane elastomers. II. Infrared dichroism. Macromolecules
1971;4:452–7.
[8] Qi HJ, Boyce MC. Stress–strain behavior of thermoplastic
polyurethanes. Mech Mater 2005;37:817–39.
[9] Chattopadhyay DK, Raju KVSN. Structural engineering of
polyurethane coatings for high performance applications. Prog
Polym Sci 2007;32:352–418.
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
[10] Pielichowski K, Słotwinska D, Dziwinski E. Segmented MDI/HMDI-
based polyurethanes with lowered flammability. J Appl Polym Sci
2004;91:3214–24.
[11] Gaboriaud F, Vantelon JP. Mechanism of thermal degradation of
polyurethane based on MDI and propoxylated trimethylol propane.
J Polym Sci Polym Chem Ed 1982;20:2063–71.
[12] Ballistreri A, Foti S, Maravigna P, Montaudo G, Scamporrino E. Mech-
anism of thermal degradation of polyurethanes investigated by
direct pyrolysis in the mass spectrometer. J Polym Sci Polym Chem
Ed 1980;18:1923–31.
[13] Barendregt RB, Berg PJVD. The degradation of polyurethane. Ther-
mochim Acta 1980;38:181–95.
[14] Gupta T, Adhikari B. Thermal degradation and stability of HTPB-
based polyurethane and polyurethaneureas. Thermochim Acta
2003;402:169–81.
[15] Barikani M, Hepburn C. Isocyanurate crosslinking as a means of
producing thermally stable polyurethane elastomers. Cell Polym
1986;5:169–85.
[16] Scaiano JC. In: Jellinek HHG, editor. Laser photolysis in polymer
chemistry. Degradation and stabilization of polymers, vol. 2. Ams-
terdam: Elsevier; 1989. p. 1–43.
[17] Prime RB, Burns JM, Karmin ML, Moy CH, Tu HB. Applications of
DMA and TGA to quality and process control in the manufacture of
magnetic coatings. J Coat Technol 1988;60:55–60.
[18] Neag M, Floyd L, Manzuk S. The application of thermogravime-
try to the service life prediction of coatings. Polym Mater Sci Eng
1993;68:331–3.
[19] Fabris HJ. Thermal and oxidative stability of urethanes. In: Frisch
C, Reegen SL, Klempner D, editors. Advances in urethane science
and technology, vol. 4. Westport: Technomic Publication; 1976. p.
89–111.
[20] Pielichowski K. Thermal behavior and flammability of
polyurethanes based on diphenylmethane-4,4 -diisocyanate
and incorporating 3-chloro-1,2-propanediol in the main chain.
Polym J 1997;29:848–53.
[21] Blazso M. Recent trends in analytical and applied pyrolysis of poly-
mers. J Anal Appl Pyrolysis 1997;39:1–25.
[22] Coutinho FMB, Delpech MC. Degradation profile of films cast
from aqueous polyurethane dispersions. Polym Degrad Stabil
2000;70:49–57.
[23] Oprea S. Effect of structure on the thermal stability of cur-
able polyester urethane urea acrylates. Polym Degrad Stabil
2002;75:9–15.
[24] Semsarzadeh MA, Navarchian AH. Effects of NCO/OH ratio
and catalyst concentration on structure, thermal stability, and
crosslink density of poly(urethane-isocyanurate). J Appl Polym Sci
2003;90:963–72.
[25] Liaw DJ. The relative physical and thermal properties of
polyurethane elastomers: effect of chain extenders of bisphe-
nols, diisocyanate, and polyol structures. J Appl Polym Sci
1997;66:1251–65.
[26] Zhang Y, Shang S, Zhang X, Wang D, Hourston DJ. Influence of the
composition of rosin-based rigid polyurethane foams on their ther-
mal stability. J Appl Polym Sci 1996;59:1167–71.
[27] Song YM, Chen WC, Yu TL, Linliu K, Tseng YH. Effect of isocyanates
on the crystallinity and thermal stability of polyurethanes. J Appl
Polym Sci 1996;62:827–34.
[28] Steinlein C, Hernandez L, Eisenbach CD. Synthesis and ther-
mal stability of oligourethanes based on the cycloaliphatic
diisocyanate trans,trans-4,4 -methylenebis(cyclohexylisocyanate).
Macromol Chem Phys 1996;197:3365–82.
[29] Petrovic ZS, Zavargo Z, Flynn JH, Macknight WJ. Thermal
degradation of segmented polyurethanes. J Appl Polym Sci
1994;51:1087–95.
[30] Zulfiqar S, Zulfiqar M, Kausar T, McNeill IC. Thermal degradation
of phenyl methacrylate-methyl methacrylate copolymers. Polym
Degrad Stabil 1987;17:327–39.
[31] Wlodarczak D. Studies of temperature and atmosphere composi-
tion influence on thermal degradation products of polyurethane
foam. J Appl Polym Sci 1988;36:377–86.
[32] Herrera M, Matuschek G, Kettrup A. Thermal degradation of ther-
moplastic polyurethane elastomers (TPU) based on MDI. Polym
Degrad Stabil 2002;78:323–31.
[33] Montaudo G, Puglisi C, Scamporrino E, Vitalini D. Mechanism
of thermal degradation of polyurethanes. Effect of ammonium
polyphosphate. Macromolecules 1984;17:1605–14.
[34] Zhang L, Huang J. Effects of hard-segment compositions on
properties of polyurethane–nitrolignin films. J Appl Polym Sci
2001;81:3251–9.
1125
[35] Chattopadhyay DK, Sreedhar B, Raju KVSN. Thermal stability of
chemically crosslinked moisture-cured polyurethane coatings. J
Appl Polym Sci 2005;95:1509–18.
[36] Kulesza K, Pielichowski K, German K. Thermal decomposition
of bisphenol A-based polyetherurethanes blown with pentane
Part I–Thermal and pyrolytical studies. J Anal Appl Pyrolysis
2006;76:243–8.
[37] Font R, Fullana A, Caballero JA, Candela J, Garcıa A. Pyrolysis study
of polyurethane. J Anal Appl Pyrolysis 2001;58–59:63–77.
[38] Jang BN, Wilkie CA. A TGA/FTIR and mass spectral study on the
thermal degradation of bisphenol A polycarbonate. Polym Degrad
Stabil 2004;86:419–30.
[39] Wilkie CA. TGA/FTIR: an extremely useful technique for studying
polymer degradation. Polym Degrad Stabil 1999;66:301–6.
[40] Hamdani S, Longuet C, Perrin D, Lopez-cuesta JM, Ganachaud F.
Flame retardancy of silicone-based materials. Polym Degrad Stabil
2009;94:465–95.
[41] Morgan AB, Bundy M. Cone calorimeter analysis of UL-94 V-rated
plastics. Fire Mater 2007;31:257–83.
[42] Troitzsch J. International plastics flammability handbook. Princi-
ples, regulations, testing and approval. 2nd edition Munich: Carl
Hanser Verlag Publishers; 1990.
[43] Bonsignore PV, Levendusky TL. Alumina trihydrate as a flame
retardant and smoke suppressive filler in rigid high density
polyurethane foams. J Fire Flammability 1977;8:95–114.
[44] Laoutid F, Bonnaud L, Alexandre M, Lopez-Cuesta JM, Dubois P. New
prospects in flame retardant polymer materials: from fundamentals
to nanocomposites. Mater Sci Eng R 2009;63:100–25.
[45] Lage LG, Kawano Y. Thermal degradation of biomedi-
cal polyurethanes—a kinetic study using high-resolution
thermogravimetry. J Appl Polym Sci 2001;79:910–9.
[46] Lee HK, Ko SW. Structure and thermal properties of polyether
polyurethaneurea elastomers. J Appl Polym Sci 1993;50:1269–
80.
[47] Grassie N, Mendoza GAP. Thermal degradation of polyether-
urethanes: 5, Polyether-urethanes prepared from methylene
bis(4-phenylisocyanate) and high molecular weight poly(ethylene
glycols) and the effect of ammonium polyphosphate. Polym Degrad
Stabil 1985;11:359–79.
[48] Day M, Cooney JD, MacKinnon M. Degradation of contaminated
plastics: a kinetic study. Polym Degrad Stabil 1995;48:341–9.
[49] Zhang Y, Shang S, Zhang X, Wang D, Hourston DJ. Influence
of structure of hydroxyl-terminated maleopimaric acid ester on
thermal stability of rigid polyurethane foams. J Appl Polym Sci
1995;58:1803–9.
[50] Vieweg R, Hoechtlen A. Plastics Handbook, vol. VII, Polyurethanes.
Munich: Carl Hanser Publishers; 1966.
[51] Ferguson J, Petrovic Z. Thermal stability of segmented
polyurethanes. Eur Polym J 1976;12:177–81.
[52] Dombrow BA. Chemistry. In: Simonds HR, editor. Polyurethanes.
second edition New York: Reinhold Publishing Corp; 1965. p. 12–
33.
[53] Ravey M, Pearce EM. Flexible polyurethane foam. I. Thermal decom-
position of a polyether-based, water-blown commercial type of
flexible polyurethane foam. J Appl Polym Sci 1997;63:47–74.
[54] Dyer E, Wright GC. Thermal degradation of alkyl N-
phenylcarbamates. J Am Chem Soc 1959;81:2138–43.
[55] Dyer E, Read RE. New catalysts for the conversion of isocyanates to
carbodiimides. J Org Chem 1961;26:4677–8.
[56] Saunders JH, Frisch KC. Polyurethanes: chemistry and technology.
High polymers, Vol. XVI Part 1. New York: Wiley–Interscience; 1962.
p. 106–121.
[57] Pielichowski K, Kulesza K, Pearce EM. Thermal degradation studies
on rigid polyurethane foams blown with pentane. J Appl Polym Sci
2003;88:2319–30.
[58] Deanin RD. In: Szycher M, editor. Structure–property relations in
polyurethanes. High performance biomaterials. Boca Raton, FL: CRC
Press, Taylor & Francis Group; 1991. p. 51–69.
[59] Simon J, Barla F, Haller AK, Farkas F, Kraxner M. Thermal stability of
polyurethanes. Chromatographia 1988;25:99–106.
[60] Grassie N, Zulfiqar M. Thermal degradation of the polyurethane
from 1,4-butanediol and methylene bis(4-phenyl isocyanate). J
Polym Sci Polym Chem Ed 1978;16:1563–74.
[61] Lattimer RP, Muenster H, Budzikiewicz H. Pyrolysis tandem mass
spectrometry (Py-MS/MS) of a segmented polyurethane. J Anal Appl
Pyrolysis 1990;17:237–49.
[62] Rotival C, Renacco E, Arfi C, Pauli AM, Pastor J. Gases emitted during
thermal decomposition of a polypropylene film and a polyurethane
adhesive. J Therm Analysis Calorim 1994;41:1519–27.
1126 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
[63] Abu-Zeid ME, Nofel EE, AbduI-Rasoul FA, Marafi MA, Mahmoud
GS, Ledwith A. Photoacoustic study of thermal degradation of
polyurethane. J Appl Polym Sci 1983;28:2317–24.
[64] Zhang Y, Xia Z, Huang H, Chen H. A degradation study of waterborne
polyurethane based on TDI. Polymer Testing 2009;28:264–9.
[65] Zhang Y, Xia Z, Huang H, Chen H. Thermal degradation of
polyurethane based on IPDI. J Anal Appl Pyrolysis 2009;84:89–94.
[66] Hileman FD, Voorhees KJ, Wojcik LH, Birky MM, Ryan PW, Einhorn
IN. Pyrolysis of a flexible urethane foam. J Polym Sci Polym Chem
Ed 1975;13:571–84.
[67] Beachell HC, Ngoc Son CP. Color formation in polyurethanes. J Appl
Polym Sci 1963;7:2217–37.
[68] Ingham JD, Rapp NS. Polymer degradation. II. Mechanism of thermal
degradation of polyoxypropylene glycol-toluene 2,4-diisocyanate
polymer (POPG-TDI) and a block polyether glycol-TDI polymer. J
Polym Sci Polym Chem Ed 1964;2:4941–64.
[69] Wooley WD. Nitrogen-containing products from the thermal
decomposition of flexible polyurethane foams. British Polym J
1972;4:27–43.
[70] Voorhees KJ, Lattimer RP. Mechanisms of pyrolysis for a specif-
ically labeled deuterated urethane. J Polym Sci Polym Chem Ed
1982;20:1457–67.
[71] Wang PS, Chiu WY, Chen LW, Denq BL, Don TM, Chiu YS. Ther-
mal degradation behavior and flammability of polyurethanes
blended with poly(bispropoxyphosphazene). Polym Degrad Stabil
1999;66:307–15.
[72] Ohrbach KH, Kettrup A. The thermal degradation of a polyurethane
foam containing the flame-retardant tetrakis(2-chloroethyl)
ethylenediphosphate using simultaneous thermal analysis-mass
spectrometry. Polym Degrad Stabil 1985;13:99–104.
[73] Lorinci G, Matuschek G, Fekete J, Gebefugi I, Kettrup A. Investigation
of thermal degradation of some adhesives used in the automo-
bile industry by thermal analysis/mass spectrometry and GC–MS.
Thermochim Acta 1995;263:73–86.
[74] Matuschek G. Thermal degradation of different fire retardant
polyurethane foams. Thermochim Acta 1995;263:59–71.
[75] Pielichowski K, Pielichowski J, Altenburg H, Balloff HJ. Thermal
degradation of polyurethanes based on MDI: characteristic rela-
tionships between the decomposition parameters. Thermochim
Acta 1996;284:419–28.
[76] Nakamura K, Nishimura Y, Zetterlund P, Hatakeyama T, Hatakeyama
H. TG-FTIR studies on biodegradable polyurethanes contain-
ing mono- and disaccharide components. Thermochim Acta
1996;282/283:433–41.
[77] Ballistreri A, Foti S, Maravigna P, Montaudo G, Scamporrino E. Ther-
mal degradation of polyurethanes investigated by direct pyrolysis
in the mass spectrometer. Die Makromol Chem 1980;181:2161–73.
[78] Foti S, Maravigna P, Montaudo G. Mechanisms of thermal decom-
position in totally aromatic polyurethanes. J Polym Sci Polym Chem
Ed 1981;19:1679–87.
[79] Foti S, Giuffrida M, Maravigna P, Montaudo G. Direct mass spectrom-
etry of polymers, VIII. Primary thermal fragmentation processes in
polyurethanes. J Polym Sci Polym Chem Ed 1983;21:1583–98.
[80] Foti S, Maravigna P, Montaudo G. Effects of N-methyl substitution on
the thermal stability of polyurethanes and polyureas. Polym Degrad
Stabil 1982;4:287–92.
[81] Dyer E, Hammond RJ. Thermal degradation of N-substituted poly-
carbamates. J Polym Sci Polym Chem Ed 1964;2:1–14.
[82] Liaw DJ, Lin SP. Phosphorus-containing polyurethanes based
on bisphenol-S, prepared by N-alkylation. Eur Polym J
1996;32:1377–80.
[83] Chuang FS. Analysis of thermal degradation of diacetylene-
containing polyurethane copolymers. Polym Degrad Stabil
2007;92:1393–407.
[84] Chuang FS, Tsi HY, Chow JD, Tsen WC, Shu YC, Jang SC. Thermal
degradation of poly(siloxane-urethane) copolymers. Polym Degrad
Stabil 2008;93:1753–61.
[85] Lattimer RP, Polce MJ, Wesdemiotis C. MALDI-MS analysis of pyrol-
ysis products from a segmented polyurethane. J Anal Appl Pyrolysis
1998;48:1–15.
[86] Lattimer RP, Williams RC. Low-temperature pyrolysis products from
a polyether-based urethane. J Anal Appl Pyrolysis 2002;63:85–104.
[87] Berta M, Lindsay C, Pans G, Camino G. Effect of chemical struc-
ture on combustion and thermal behaviour of polyurethane
elastomer layered silicate nanocomposites. Polym Degrad Stabil
2006;91:1179–91.
[88] Chen X, Hu Y, Jiao C, Song L. Preparation and thermal prop-
erties of a novel flame-retardant coating. Polym Degrad Stabil
2007;92:1141–50.
[89] Napier DH, Wong TW. Toxic products from the combustion and
pyrolysis of polyurethane foams. Br Polym J 1972;4:45–52.
[90] Jellinek HHG, Takada K. Toxic gas evolution from polymers: evo-
lution of hydrogen cyanide from linear polyurethane. J Polym Sci
Polym Chem Ed 1975;13:2709–23.
[91] Paabo M, Levin BC. A review of the literature on the gaseous prod-
ucts and toxicity generated from the pyrolysis and combustion of
rigid polyurethane foams. Fire Mater 1987;11:1–29.
[92] Tang Z, Maroto-Valer MM, Andresen JM, Miller JW, Listemann
ML, McDaniel PL, et al. Thermal degradation behavior of rigid
polyurethane foams prepared with different fire retardant concen-
trations and blowing agents. Polymer 2002;43:6471–9.
[93] Bilbao R, Mastral JF, Ceamanos J, Aldea ME. Kinetics of the thermal
decomposition of polyurethane foams in nitrogen and air atmo-
spheres. J Anal Appl Pyrolysis 1996;37:69–82.
[94] Benbow AW, Cullis CF. Combustion of flexible polyurethane foams,
mechanisms and evaluation of flame retardance. Combustion Flame
1975;24:217–30.
[95] Gray RL, Lee RE. Scorch inhibitors for flexible polyurethanes. In:
Plastic Additives: An A–Z Reference. Edited by Pritchard M, Chap-
man & Hall, London, 1998, p. 567–75.
[96] Takahara A, Coury AJ, Hergenrother RW, Cooper SL. Effect of soft
segment chemistry on the biostability of segmented polyurethanes.
I. In vitro oxidation. J Biomed Mater Res 1991;25:341–56.
[97] Mathur G, Kresta JE, Frisch KC. In: Frisch KC, Reegen SL, editors.
Stabilization of polyether-urethanes and polyether (urethane-urea)
block copolymers. Advances in urethane science and technology,
vol. 6. Westport: Technomic Publication; 1978. p. 103–72.
[98] Servay T, Voelkel R, Schmiedberger H, Lehmann S. Thermal oxi-
dation of the methylene diphenylene unit in MDI-TPU. Polymer
2000;41:5247–56.
[99] Bellucci F, Camino G, Frache A, Sarra A. Catalytic charring-
volatilization competition in organoclay nanocomposites. Polym
Degrad Stabil 2007;92:425–36.
[100] Wang Z, Han E, Ke W. Effect of acrylic polymer and nanocom-
posite with nano-SiO2 on thermal degradation and fire resistance
of APP-DPER-MEL coating. Polym Degrad Stabil 2006;91:1937–
47.
[101] Khatua S, Hsieh YL. Chlorine degradation of polyether-based
polyurethane. J Polym Sci Polym Chem Ed 1997;35:3263–73.
[102] Chang TC, Shen WS, Chiu YS, Ho SY. Thermo-oxidative degrada-
tion of phosphorus-containing polyurethane. Polym Degrad Stabil
1995;49:353–60.
[103] Vyazovkin S. Staying free of multiplying entities without necessity.
J Thermal Anal Calorim 2006;83:45–51.
[104] Pielichowski K, Njuguna J, editors. Thermal Degradation of Poly-
meric Materials. Shawbury, Shropshire, UK: Rapra Technology
Limited; 2005.
[105] Ozawa T. A new method of analyzing thermogravimetric data. Bull
Chem Soc Jpn 1965;38:1881–6.
[106] Friedman HL. Kinetics of thermal degradation of char-forming
plastics from thermogravimetry—application to a phenolic resin.
J Polym Sci Part C Polym Symposia 1964;6:183–95.
[107] Wang XS, Li XG, Yan D. Thermal decomposition kinetics
of poly(trimethylene terephthalate). Polym Degrad Stabil
2000;69:361–72.
[108] Sreedhar B, Chattopadhyay DK, Hari Karunakar MS, Sastry ARK.
Thermal and surface characterization of plasticized starch polyvinyl
alcohol blends crosslinked with epichlorohydrin. J Appl Polym Sci
2006;101:25–34.
[109] Chang WL. Decomposition behavior of polyurethanes via mathe-
matical simulation. J Appl Polym Sci 1994;53:1759–69.
[110] Narayan R, Chattopadhyay DK, Sreedhar B, Raju KVSN, Mallikarjuna
NN, Aminabhavi TM. Degradation profiles of polyester-urethane
(HP-MDI) and polyester-melamine (HP-HMMM) coatings: A ther-
mal study. J Appl Polym Sci 2005;97:518–26.
[111] Kissinger HE. Reaction kinetics in differential thermal analysis. Anal
Chem 1957;29:1702–6.
[112] Coats AW, Redfern JP. Kinetic parameters from thermogravimetric
data. Nature 1964;201:68–9.
[113] Horowitz HH, Metzger G. A new analysis of thermogravimetric
traces. Anal Chem 1963;35:1464–8.
[114] MacCallum JR, Tanner J. Derivation of rate equations used in ther-
mogravimetry. Nature 1970;225:1127–8.
[115] van Krevelen DW, van Heerden C, Huntjens FJ. Physicochemical
aspects of the pyrolysis of coal and related organic compounds. Fuel
1951;30:253–8.
[116] Lua AC, Su J. Isothermal and non-isothermal pyrolysis kinetics of
Kapton® polyimide. Polym Degrad Stabil 2006;91:144–53.
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
[117] Broido A. A simple, sensitive graphical method of treating thermo-
gravimetric analysis data. J Polym Sci Polym Phys 1969;7:1761–73.
[118] Saikrasun S, Wongkalasin O. Thermal decomposition kinet-
ics of thermotropic liquid crystalline p-hydroxy benzoic
acid/poly(ethylene terephthalate) copolyester. Polym Degrad
Stabil 2005;88:300–8.
[119] Flynn JH, Wall LA. A quick, direct method for the determination of
activation energy from thermogravimetric data. J Polym Sci Part B
Polym Lett 1966;4:323–8.
[120] Li L, Guan C, Zhang A, Chen D, Qing Z. Thermal stabilities and the
thermal degradation kinetics of polyimides. Polym Degrad Stabil
2004;84:369–73.
[121] Erceg M, Kovacic T, Perinovic S. Kinetic analysis of the non-
isothermal degradation of poly(3-hydroxybutyrate) nanocompos-
ites. Thermochim Acta 2008;476:44–50.
[122] Liu BY, Zhao XJ, Wang XH, Wang FS. Thermal degradation kinetics
of poly(propylene carbonate) obtained from the copolymeriza-
tion of carbon dioxide and propylene oxide. J Appl Polym Sci
2003;90:947–53.
[123] Heide K, Holand W, Golker H, Seyfarth K, Muller B, Sauer R. Die
bestimmung kinetischer parameter endothermer zersetzungsreak-
tionen unter nicht-isothermen bedingungen. Thermochim Acta
1975;13:365–78.
[124] Vachuska I, Voboril M. Kinetic data computation from non-
isothermal thermogravimetric curves of non-uniform heating rate.
Thermochim Acta 1971;2:379–92.
[125] Li F, Xu X, Li Q, Li Y, Zhang H, Yu J, et al. Thermal degradation
and their kinetics of biodegradable poly(butylene succinate-co-
butylene terephthate)s under nitrogen and air atmospheres. Polym
Degrad Stabil 2006;91:1685–93.
[126] Galwey AK. Is the science of thermal analysis kinetics based
on solid foundations? A literature appraisal. Thermochim Acta
2004;413:139–83.
[127] Vyazovkin S, Wight CA. Model-free and model-fitting approaches to
kinetic analysis of isothermal and nonisothermal data. Thermochim
Acta 1999;340/341:53–68.
[128] Conesa JA, Marcilla A, Caballero JA, Font R. Comments on the validity
and utility of the different methods for kinetic analysis of thermo-
gravimetric data. J Anal Appl Pyrolysis 2001;58–59:617–33.
[129] Criado JM, Morales J. Thermal decomposition reactions of solids
controlled by diffusion and phase-boundary processes: possible
misinterpretation of the mechanism from thermogravimetric data.
Thermochim Acta 1977;19:305–17.
[130] Criado JM, Gonzalez M, Ortega A, Real C. Some considerations
regarding the determination of the activation energy of solid-
state reactions from a series of isothermal data. J Therm Anal
1984;29:243–50.
[131] Criado JM, Morales J, Rives V. Computer kinetic analysis of simulta-
neously obtained TG and DTG curves. J Therm Anal 1978;14:221–8.
[132] Budrugeac P, Segal E. On the compensation effect at the form
of the differential conversion function. J Therm Anal Calorim
1998;53:269–83.
[133] Adonyi Z. Quantitative method for comparing thermogravimetric
data under various measuring circumstances. Thermochim Acta
1982;55:269–85.
[134] Koga N, Tanaka H. A kinetic compensation effect established for
the thermal decomposition of a solid. J Therm Anal 1991;37:347–
63.
[135] Campisi LR, Bourbigot S, Le Bras M, Delobel R. Thermal behaviour
of cotton-modacrylic fibre blends: kinetic study using the invariant
kinetic parameters method. Thermochim Acta 1996;275:37–49.
[136] Rose N, Le Bras M, Bourbigot S, Delobel R. Thermal oxidative degra-
dation of epoxy resins: evaluation of their heat resistance using
invariant kinetic parameters. Polym Degrad Stabil 1994;45:387–97.
[137] Park JW, Oh SC, Lee HP, Kim HT, Yoo KO. A kinetic analysis of thermal
degradation of polymers using a dynamic method. Polym Degrad
Stabil 2000;67:535–40.
[138] Sreedhar B, Sairam M, Chattopadhyay DK, Rathnam PAS, Rao
DVM. Thermal, mechanical, and surface characterization of starch-
poly(vinyl alcohol) blends and borax-crosslinked films. J Appl
Polym Sci 2005;96:1313–22.
[139] Sharma V, Kundu PP. Condensation polymers from natural oils. Prog
Polym Sci 2008;33:1199–215.
[140] Lu Y, Larock RC. Soybean-oil-based waterborne polyurethane dis-
persions: effects of polyol functionality and hard segment content
on properties. Biomacromolecules 2008;9:3332–40.
[141] Lligadas G, Ronda JC, Galià M, Cádiz V. Poly(ether urethane)
networks from renewable resources as candidate biomaterials: syn-
thesis and characterization. Biomacromolecules 2007;8:686–92.
1127
[142] Liu D, Tian H, Zhang L, Chang PR. Structure and properties of
blend films prepared from castor oil-based polyurethane/soy pro-
tein derivative. Ind Eng Chem Res 2008;47:9330–6.
[143] Hablot E, Zheng D, Bouquey M, Aveı̌rous L. Polyurethanes based on
castor oil: kinetics, chemical. Mechanical and thermal properties.
Macromol Mater Eng 2008;293:922–9.
[144] Guo A, Javni I, Petrovic Z. Rigid polyurethane foams based on soy-
bean oil. J Appl Polym Sci 2000;77:467–73.
[145] Javni I, Petrovic ZS, Guo A, Fuller R. Thermal stability of
polyurethanes based on vegetable oils. J Appl Polym Sci
2000;77:1723–34.
[146] Petrovic ZS. Polyurethanes from vegetable oils. Polym Rev
2008;48:109–55.
[147] Husic S, Javni I, Petrovic ZS. Thermal and mechanical properties of
glass reinforced soy-based polyurethane composites. Compos Sci
Technol 2005;65:19–25.
[148] Javni I, Zhang W, Petrovic ZS. Soybean oil based polyisocyanurate
cast resins. J Appl Polym Sci 2003;90:3333–7.
[149] Javni I, Zhang W, Petrovic ZS. Soybean oil based polyisocyanurate
rigid foams. J Polym Environ 2004;12:123–9.
[150] Xu Y, Petrovic Z, Das S, Wilkes GL. Morphology and properties of
thermoplastic polyurethanes with dangling chains in ricinoleate-
based soft segments. Polymer 2008;49:4248–58.
[151] Sarkar S, Adhikari B. Thermal stability of lignin–hydroxy-
terminated polybutadiene copolyurethanes. Polym Degrad Stabil
2001;73:169–75.
[152] Liu J, Ma D. Study on synthesis and thermal properties of
polyurethane–imide copolymers with multiple hard segments. J
Appl Polym Sci 2002;84:2206–15.
[153] Li Y, Gao T, Linliu K, Desper CR, Chu B. Multiphase structure of
a segmented polyurethane: effects of temperature and annealing.
Macromolecules 1992;25:7365–72.
[154] Matuszak ML, Frisch KC. Thermal degradation of linear
polyurethanes and model biscarbamates. J Polym Sci Polym
Chem Ed 1973;11:637–48.
[155] Chattopadhyay DK, Sreedhar B, Raju KVSN. Influence of vary-
ing hard segments on the properties of chemically crosslinked
moisture-cured polyurethane–urea. J Polym Sci Part B Polym Phys
2005;44:102–18.
[156] Coutinho FMB, Delpech MC, Alves TL, Ferreira AA. Degradation pro-
files of cast films of polyurethane and poly(urethane-urea) aqueous
dispersions based on hydroxyterminated polybutadiene and differ-
ent diisocyanates. Polym Degrad Stabil 2003;81:19–27.
[157] Stanciu A, Bulacovschi V, Condratov V, Fadei C, Stoleriu A,
Balint S. Thermal stability and the tensile properties of some
segmented poly(ester-siloxane)urethanes. Polym Degrad Stabil
1999;64:259–65.
[158] Singh A. In: Frisch KC, Reegen SL, editors. Effect of chemical struc-
ture on the thermal stability of crosslinked urethane elastomers.
Advances in urethane science and technology, vol. 1. Technomic
Publication; 1971. p. 95–109.
[159] Baumann GF. In: Bruins PF, editor. Polymeric polyisocyanates in
urethane foams. Polyurethane technology. New York: Wiley Inter-
science Publishers; 1969. p. 95–116.
[160] Liminana MAP, Ais FA, Palau AMT, Barcelo ACO, Martinez JMM.
Characterization of waterborne polyurethane adhesives contain-
ing different amounts of ionic groups. Int J Adhesion Adhesives
2005;25:507–17.
[161] Ge Z, Zhang X, Dai J, Li W, Luo Y. Synthesis, characterization
and properties of a novel fluorinated polyurethane. Eur Polym J
2009;45:530–6.
[162] Wang TL, Hsieh TH. Effect of polyol structure and molecular weight
on the thermal stability of segmented poly(urethaneureas). Polym
Degrad Stabil 1997;55:95–102.
[163] Grassie N, Zulfiqar M, Guy MI. Thermal degradation of a
series of polyester polyurethanes. J Polym Sci Polym Chem Ed
1980;18:265–74.
[164] Wilhelm C, Gardette JL. Infrared analysis of the photochemical
behaviour of segmented polyurethanes: aliphatic poly(ether-
urethane)s. Polymer 1998;39:5973–80.
[165] Mathur GN, Kresta JE. Thermooxidation and stabilization of ure-
thane and urethane-urea block copolymers. Polym Sci Technol
1984;26:135–53.
[166] Xiao HX, Yang S, Kresta JE, Frisch KC, Higley DP. Thermostability
of urethane elastomers based on p-phenylene diisocyanate. J Elast
Plast 1994;26:237–51.
[167] Blackwell J, Nagarajan MR, Haitink TB. Structure of polyurethane
elastomers: effect of chain extender length on the structure of
MDI/diol hard segments. Polymer 1982;23:950–6.
1128 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
[168] Blackwell J, Nagarajan MR. Conformational analysis of poly(MDI-
butanediol) hard segment in polyurethane elastomers. Polymer
1981;22:202–8.
[169] Blackwell J, Quay JR, Nagarajan MR, Born L, Hespe H. Molecular
parameters for the prediction of polyurethane structures. J Polym
Sci Polym Phys Ed 1984;22:1247–59.
[170] Chuang FS, Tsen WC, Shu YC. The effect of different siloxane chain-
extenders on the thermal degradation and stability of segmented
polyurethanes. Polym Degrad Stabil 2004;84:69–77.
[171] Kendagannaswamy BK, Siddaramaiah. Chain-extended
polyurethanes–synthesis and characterization. J Appl Polym
Sci 2002;84:359–69.
[172] Qin XM, Fang F, Yang XH, Wang XL, Zheng Z. Synthesis and char-
acterization of polyurethane urea based on fluorine-containing
bisphenoxydiamine. J Appl Polym Sci 2006;102:1863–9.
[173] Qin XM, Xiong JW, Yang XH, Wang XL, Zheng Z. Preparation, mor-
phology, and properties of polyurethane–urea elastomers derived
from sulphone-containing aromatic diamine. J Appl Polym Sci
2007;104:3554–61.
[174] Lin MF, Tsen WC, Shu YC, Chuang FS. Effect of silicon and phos-
phorus on the degradation of polyurethanes. J Appl Polym Sci
2001;79:881–99.
[175] Subramani S, Lee JM, Cheong IW, Kim JH. Synthesis and char-
acterization of water-borne crosslinked silylated polyurethane
dispersions. J Appl Polym Sci 2005;98:620–31.
[176] Modesti M, Lorenzetti A. An experimental method for evaluating
isocyanate conversion and trimer formation in polyisocyanate-
polyurethane foams. Eur Polym J 2001;37:949–54.
[177] Ashida K, Saiki K, Goto J, Sasaki K. Polyisocyanurate foams modified
by thermally stable linkages. ACS Symp Series 1997;669:81–100.
[178] Szycher M. Basic concepts in polyurethane chemistry and tech-
nology. Szycher’s handbook of polyurethanes. Boca Raton, FL: CRC
Press, Taylor & Francis; 1999. p. 2–8.
[179] Bajsic EG, Rek V. Thermal stability of polyurethane elastomers
before and after UV irradiation. J Appl Polym Sci 2001;79:864–73.
[180] Asif A, Shi W. UV curable waterborne polyurethane acrylate dis-
persions based on hyperbranched aliphatic polyester: effect of
molecular structure on physical and thermal properties. Polym Adv
Technol 2004;15:669–75.
[181] Reegen SL, Frisch KC. Catalysis in isocyanate reactions. In: Frisch KC,
Reegen SL, editors. Advances in urethane science and technology,
vol. 1. Westport: Technomic Publication; 1971. p. 1–31.
[182] Sarwade BD, Wadgaonkar PP, Mahajan SS. Synthesis and properties
of polyurethanes containing s-triazine rings in the main chain. J
Polym Sci Polym Chem Ed 1989;27:3263–9.
[183] Yeganeh H, Atai M, Talemi PH, Jamshidi S. Synthesis, characteri-
zation and properties of novel poly(urethane-imide) networks as
electrical insulators with improved thermal stability. Macromol
Mater Eng 2006;291:883–94.
[184] Yeganeh H, Shamekhi MA. Poly(urethane-imide-imide), a new gen-
eration of thermoplastic polyurethane elastomers with enhanced
thermal stability. Polymer 2004;45:359–65.
[185] Yeganeh H, Barikani M, Khodabadi FN. Synthesis and proper-
ties of novel thermoplastic poly(urethane-imide)s. Eur Polym J
2000;36:2207–11.
[186] Levchik SV, Weil ED. Thermal decomposition, combustion and fire-
retardancy of polyurethanes—a review of the recent literature.
Polym Int 2004;53:1585–610.
[187] Wang CL, Klemper D, Frisch KC. Morphology of
polyurethane–isocyanurate elastomers. J Appl Polym Sci
1985;30:4337–44.
[188] Sehovic H, Sendijarevic A, Sendijarevic V, Frisch KC, Wong SW. Poly-
2-oxazolidone-urethane coatings. J Coat Technol 1987;59:29–35.
[189] Deligoz H, Yalcinyuva T, Ozgumus S. A novel type of Si-containing
poly(urethane-imide)s: synthesis, characterization and electrical
properties. Eur Polym J 2005;41:771–81.
[190] Kordomenos PI, Frisch KC, Kresta JE. Oxazolidone coatings, Part
II. Structure–properties relationships and thermal stability. J Coat
Technol 1983;55:59–61.
[191] Farrissey Jr W, Rose JS, Carleton PS. Preparation of a polyimide foam.
J Appl Polym Sci 1970;14:1093–101.
[192] Sendijarevic A, Sendijarevic V, Frisch KC, Vlajic M. Novel heat-
resistant isocyanate-based polymers. J Elast Plast 1991;23:192–217.
[193] Kordomenos PI, Kresta JE. Thermal stability of isocyanate-
based polymers. 1. Kinetics of the thermal dissociation of
urethane, oxazolidone, and isocyanurate groups. Macromolecules
1981;14:1434–7.
[194] Kordomenos PI, Kresta JE, Frisch KC. Thermal stability of isocyanate-
based polymers. 2. Kinetics of the thermal dissociation of model
urethane, oxazolidone, and isocyanurate block copolymers. Macro-
molecules 1987;20:2077–83.
[195] Luchkina LV, Askadskii AA, Bychko KA. Composite polymeric mate-
rials based on polyisocyanurates and polyurethanes. Russ J Appl
Chem 2005;78:1337–42.
[196] Burkus J. Process of trimerizing isocyanates. US Patent 2,979,485
(1961).
[197] Pankratov VA, Frenkel TsM, Fainleib AM. 2-Oxazolidinones. Russ
Chem Rev 1983;52:576–93.
[198] Yeganeh H, Jamshidi S, Talemi PH. Synthesis, characterization and
properties of novel thermally stable poly(urethane-oxazolidone)
elastomers. Eur Polym J 2006;42:1743–54.
[199] Kinjo N, Numata SI, Koyama T, Narahara T. Synthesis and viscoelastic
properties of new thermosetting resins having isocyanurate and
oxazolidone rings in their molecular structures. J Appl Polym Sci
1983;28:1729–41.
[200] Kitayama M, Iseda Y, Odako F, Anzai S, Irako K. Synthesis and
properties of polyoxazolidone elastomers from diepoxides and
diisocyanates. Rubber Chem Technol 1980;53:1–13.
[201] Iwakura Y, Izawa S. Glycidyl ether reactions with urethanes and
ureas, A new synthetic method for 2-oxazolidones. J Org Chem
1964;29:379–82.
[202] Kaneyoshi A, Frisch KC. Polyoxazolidone catalyst. US Patent
3,817,938 (1974).
[203] Ashida K, Frisch KC. Modified isocyanurate foams, II. Preparation
and properties of epoxy-isocyanurate foams by means of a two-step
process. Adv Urethane Sci Technol 1973;2:255–68.
[204] Sendijarevic A, Sendijarevic V, Frisch KC. Studies in the formation of
poly(oxazolidones) I, Kinetics and mechanism of the model oxazoli-
done formation from phenyl isocyanate and phenylglycidyl ether.
Selectivity of catalysts. J Polym Sci Polym Chem Ed 1987;25:151–70.
[205] Zilic M, Sendijarevic A, Sendijarevic V, Frisch KC. Studies in the for-
mation of poly(oxazolidone)s, III. Catalysis and kinetics of the model
oxazolidone formation from cyclohexyl isocyanate and phenylgly-
cidyl ether. J Polym Sci Polym Chem Ed 1989;27:1843–51.
[206] Sehovic H, Sendijarevic A, Sendijarevic V, Frisch KC. Studies in
the formation of poly(oxazolidones), II. Selectivity of catalysts and
kinetics in the synthesis of 2-oxazolidone from butyl isocyanate and
phenylglycidyl ether. J Polym Sci Polym Chem Ed 1987;25:2729–36.
[207] Sankaran S, Chanda M. Chemical toughening of epoxies, I.
Structural modification of epoxy resins by reaction with hydroxy-
terminated poly(butadiene-co-acrylonitrile). J Appl Polym Sci
1990;39:1459–66.
[208] Roth W, Hanella K, Stainbach V, Frosch P. Development of
thermostable reaction resins. Internationales Wissenschaftliches
Kolloquium - Technische Hochschule Ilmenau 1983;28(2):167–70.
[209] Frisch KC, Sendijarevic V, Sendijarevic A, Vlajic M. Novel heat-
resistant isocyanate-based polymers. In: Proceedings of the SPI
Annual Technical/Marketing Conference, 33. 1990. p. 515–26.
[210] Liu J, Li Z, Luo X, Ma D. Synthesis, structure, and properties of
polyimide and polyurethane–urea–imide copolymers. J Polym Sci
Polym Phys 2004;42:216–25.
[211] Mishra AK, Chattopadhyay DK, Sreedhar B, Raju KVSN. Thermal and
dynamic mechanical characterization of polyurethane–urea–imide
coatings. J Appl Polym Sci 2006;102:3158–67.
[212] Ding M. Isomeric polyimides. Prog Polym Sci 2007;32:623–68.
[213] Takeichi T, Ujiie K, Inoue K. High performance poly(urethane-imide)
prepared by introducing imide blocks into the polyurethane back-
bone. Polymer 2005;46:11225–31.
[214] Qin X, Yang X, Wang X, Wang M. Synthesis and characterization
of poly(imide-urethane) based on novel chain-extender containing
both imide and sulphone functions. J Polym Sci Polym Chem Ed
2005;43:4469–77.
[215] Avadhani CV, Wadgaonkar PP, Khisti RS, Gunjikar VG, Vernekar SP.
Synthesis and characterization of imide containing diisocyanates
and poly(imide-urethane)s therefrom. Polym Bull 1990;23:163–9.
[216] Patel HS, Vyas HS. Poly(urethane-imide)s–1. Eur Polym J
1991;27:93–6.
[217] Patel HS, Shah VJ, Vyas HS. Synthesis, characterization and glass
reinforcement of poly(urethane-imide)s–III. High Performance
Polym 1992;4:247–58.
[218] Zuo M, Takeichi T. Novel method for the preparation of
poly(urethane-imide)s and their properties. J Polym Sci Polym
Chem Ed 1997;35:3745–53.
[219] Ataei SM, Keshavarz S. Synthesis and characterization of novel
diimide-dinaphthols and resulting poly(urethane-imide)s. Polym
Int 2003;52:1487–92.
[220] Yeganeh H, Talemi PH, Jamshidi S. Novel method for preparation
of polyurethane elastomers with improved thermal stability and
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
electrical insulating properties. J Appl Polym Sci 2007;103:1776–
85.
[221] Nair PR, Nair CPR, Francis DJ. Effect of imide-oxazolidinone
modification on the thermal and mechanical properties of HTPB-
polyurethanes. J Appl Polym Sci 1999;71:1731–8.
[222] Cicirko IC, Lubczak J. Polyurethane foams of improved thermal sta-
bility. Macromol Mater Eng 2002;287:665–70.
[223] Kucharski M, Lubczak J. Porous polyurethane resins prepared
from reaction products of ethylene oxide (oxirane) with 1,3,5-
tris(hydroxymethyl)isocyanurate. Polimery 1985;30:354–61.
[224] Lubczak J. N,N -diacetylmelamine as a basic material to synthesize
polyetherols. Acta Polymerica 1990;41:464–8.
[225] Lubczak J. Synthesis of s-triazine polyetherols from
bis(methoxymethyl)melamine and oxiranes. J Appl Polym
Sci 1997;66:423–33.
[226] Issam AM, Ismail J. Improvement of thermal stability of new
heteroaromatic poly(azomethine urethane)s. J Appl Polym Sci
2006;100:1198–204.
[227] Buruiana EC, Olaru M, Simionescu BC. Synthesis and prop-
erties of some new polyazomethine-urethanes. Eur Polym J
2002;38:1079–86.
[228] Cao Q, Liu P. Structure and mechanical properties of shape mem-
ory polyurethane based on hyperbranched polyesters. Polym Bull
2006;57:889–99.
[229] Asif A, Shi W, Shen X, Nie K. Physical and thermal properties
of UV curable waterborne polyurethane dispersions incorporating
hyperbranched aliphatic polyester of varying generation number.
Polymer 2005;46:11066–78.
[230] Jena KK, Chattopadhyay DK, Raju KVSN. Synthesis and characteri-
zation of hyperbranched polyurethane–urea coatings. Eur Polym J
2007;43:1825–37.
[231] Mahapatra SS, Karak N. s-Triazine containing flame retardant hyper-
branched polyamines: synthesis, characterization and properties
evaluation. Polym Degrad Stabil 2007;92:947–55.
[232] Koscielecka A. Thermal degradation of polyurethanes, Part VI.
Influence of segment structure of polyurethanes on their thermal
stability. Electronic Design 1985;33:187–91.
[233] Saiani A, Daunch WA, Verbeke H, Leenslag JW, Higgins JS. Ori-
gin of multiple melting endotherms in a high hard block content
polyurethane, 1. Thermodynamic investigation. Macromolecules
2001;34:9059–68.
[234] Bruck SD. Thermally stable polymeric materials. J Chem Educ
1965;42(1):18–24.
[235] Winslow FH, Matreyek W. Pyrolysis of crosslinked styrene poly-
mers. J Appl Polym Sci 1956;22:315–24.
[236] Benli S, Yilmazer Ü, Pekel F, Özkar S. Effect of fillers on thermal and
mechanical properties of polyurethane elastomer. J Appl Polym Sci
1998;68:1057–65.
[237] Zeng Q, Yu A, Lu G(Max). Interfacial interactions and struc-
ture of polyurethane intercalated nanocomposite. Nanotechnology
2005;16:2757–63.
[238] Mahfuz H, Rangari VK, Islam MS, Jeelani S. Fabrication, syn-
thesis and mechanical characterization of nanoparticles infused
polyurethane foams. Composites A 2004;35:453–60.
[239] Yang CH, Liu FJ, Liu YP, Liao WT. Hybrids of colloidal silica and
waterborne polyurethane. J Colloid Int Sci 2006;302:123–32.
[240] Kim BS, Park SH, Kim BK. Nanosilica-reinforced UV-cured
polyurethane dispersion. Colloid Polym Sci 2006;284:1067–
72.
[241] Li Y, Yu J, Guo ZX. The influence of silane treatment on Nylon
6/nano-SiO2 in situ polymerization. J Appl Polym Sci 2002;84:827–
34.
[242] Dubois C, Rajabian M, Rodrigue D. Polymerization compound-
ing of polyurethane-fumed silica composites. Polym Eng Sci
2006;46:360–71.
[243] Yan S, Yin J, Yang Y, Dai Z, Ma J, Chen X. Surface-grafted sil-
ica linked with L-lactic acid oligomer: a novel nanofiller to
improve the performance of biodegradable poly(L-lactide). Poly-
mer 2007;48:1688–94.
[244] Shu CH, Chiang HC, Tsiang RCC, Liu TJ, Wu JJ. Synthesis of
organic–inorganic hybrid polymeric nanocomposites for the hard
coat application. J Appl Polym Sci 2007;103:3985–93.
[245] Garrett TM, Gruzins I. Modified polyurethane including silica and
method of manufacture thereof. US Patent 5,484,832 (1996).
[246] Chen S, Sui J, Chen L. Positional assembly of hybrid polyurethane
nanocomposites via incorporation of inorganic building blocks into
organic polymer. Colloid Polym Sci 2004;283:66–73.
[247] Wang Z, Pinnavaia TJ. Nanolayer reinforcement of elastomeric
polyurethane. Chem Mater 1998;10:3769–71.
1129
[248] Chang JH, An YU. Nanocomposites of polyurethane with various
organoclays: thermomechanical properties, morphology, and gas
permeability. J Polym Sci Polym Phys 2002;40:670–7.
[249] Lee HT, Lin LH. Waterborne polyurethane/clay nanocomposites:
novel effects of the clay and its interlayer ions on the mor-
phology and physical and electrical properties. Macromolecules
2006;39:6133–41.
[250] Kuan HC, Chuang WP, Ma CCM, Chiang CL, Wu HL. Synthesis and
characterization of a clay/waterborne polyurethane nanocompos-
ite. J Mater Sci 2005;40:179–85.
[251] Chattopadhyay DK, Mishra AK, Sreedhar B, Raju KVSN. Thermal and
viscoelastic properties of polyurethane-imide/clay hybrid coatings.
Polym Degrad Stabl 2006;91:1837–49.
[252] Sreedhar B, Chattopadhyay DK, Swapna V. Thermal and surface
characterization of polyurethane–urea clay nanocomposite coat-
ings. J Appl Polym Sci 2006;100:2393–401.
[253] Xiong J, Zheng Z, Jiang H, Ye S, Wang X. Reinforcement of
polyurethane composites with an organically modified montmo-
rillonite. Composites A 2007;38:132–7.
[254] Choi WJ, Kim SH, Kim YJ, Kim SC. Synthesis of chain-extended
organifier and properties of polyurethane/clay nanocomposites.
Polymer 2004;45:6045–57.
[255] Noh MH, Jang LW, Lee DC. Intercalation of styrene-acrylonitrile
copolymer in layered silicate by emulsion polymerization. J Appl
Polym Sci 1999;74:179–88.
[256] Seo WJ, Sung YT, Kim SB, Lee YB, Choe KH, Choe SH, et al. Effects
of ultrasound on the synthesis and properties of polyurethane
foam/clay nanocomposites. J Appl Polym Sci 2006;102:3764–73.
[257] Leszczynska A, Njuguna J, Pielichowski K, Banerjee JR. Poly-
mer/montmorillonite nanocomposites with improved thermal
properties: Part I, Factors influencing thermal stability and mech-
anisms of thermal stability improvement. Thermochim Acta
2007;453:75–96.
[258] Leszczynska A, Njuguna J, Pielichowski K, Banerjee JR. Poly-
mer/montmorillonite nanocomposites with improved thermal
properties: Part II, Thermal stability of montmorillonite nanocom-
posites based on different polymeric matrixes. Thermochim Acta
2007;454:1–22.
[259] Alexandre M, Dubois P. Polymer-layered silicate nanocomposites:
preparation, properties and uses of a new class of materials. Mater
Sci Eng R 2000;28:1–63.
[260] Takeichi T, Zeidam R, Agag T. Polybenzoxazine/clay hybrid
nanocomposites: influence of preparation method on the cur-
ing behavior and properties of polybenzoxazines. Polymer
2002;43:45–53.
[261] Tien YI, Wei KH. The effect of nano-sized silicate layers from mont-
morillonite on glass transition, dynamic mechanical and thermal
degradation properties of segmented polyurethane. J Appl Polym
Sci 2002;86:1741–8.
[262] Subramani S, Lee JY, Kim JH, Cheong IW. Crosslinked aqueous dis-
persion of silylated poly (urethane–urea)/clay Nanocomposites.
Compos Sci Technol 2007;67:1561–73.
[263] Chen H, Zheng M, Sun H, Jia Q. Characterization and proper-
ties of sepiolite/polyurethane nanocomposites. Mater Sci Eng A
2007;445–446:725–30.
[264] Baral D, De PP, Nando GB. Thermal characterization of mica-
filled thermoplastic polyurethane composites. Polym Degrad Stabil
1999;65:47–51.
[265] Mecham J, Synthesis and characterization of cycloaliphatic and aro-
matic polyester/poly(dimethylsiloxane) segmented copolymers.
Thesis submitted to Virginia Polytechnic Institute and State Uni-
versity; 1997.
[266] Yilgor I, McGrath JE. Polysiloxane-containing copolymers: a survey
of recent developments. Adv Polym Sci 1988;86:1–86.
[267] Voronkov MG, Mileshkevich VP, Yuzhelevskii YA. The Siloxane
Bond. Physical Properties and chemical transformations. New York:
Consultant Bureau; 1978.
[268] Chen YC, Zhou SX, Yang HH, Wu LM. Interaction and microstructure
of polyurethane/silica hybrid films prepared by sol–gel process. J
Sol-Gel Sci Technol 2006;37:39–47.
[269] Lai SM, Wang CK, Shen HF. Properties and preparation of ther-
moplastic polyurethane/silica hybrid using sol–gel process. J Appl
Polym Sci 2005;97:1316–25.
[270] Jeon HT, Jang MK, Kim BK, Kim KH. Synthesis and characterizations
of waterborne polyurethane–silica hybrids using sol–gel process.
Colloid Surf A 2007;302:559–67.
[271] Kuan HC, Su HY, Ma CCM. Synthesis and characterization of polysili-
cic acid nanoparticles/waterborne polyurethane nanocomposite. J
Mater Sci 2005;40:6063–70.
1130 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
[272] Coupar PI, Jaffres PA, Morris RE. Synthesis and characterization
of silanol-functionalized dendrimers. J Chem Soc, Dalton Trans
1999:2183–8.
[273] Jaffres PA, Morris RE. Synthesis of highly functionalized dendrimers
based on polyhedral silsesquioxane cores. J Chem Soc, Dalton Trans
1998:2767–70.
[274] Chandrasekhar V, Boomishankar R, Nagendran S. Recent develop-
ments in the synthesis and structure of organosilanols. Chem Rev
2004;104:5847–910.
[275] Zhang S, Zou Q, Wu L. Preparation and characterization of
polyurethane hybrids from reactive polyhedral oligomeric
silsesquioxanes. Macromol Mater Eng 2006;291:895–
901.
[276] Janowski B, Pielichowski K. Thermo(oxidative) stability of novel
polyurethane/POSS nanohybrid elastomers. Thermochim Acta
2008;478:51–3.
[277] Liu Y, Ni Y, Zheng S. Polyurethane networks modified with
octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane.
Macromol Chem Phys 2006;207:1842–51.
[278] Liu Y, Zheng S. Polyurethane networks nanoreinforced by poly-
hedral oligomeric silsesquioxane. Macromol Rapid Commun
2005;26:196–200.
[279] Kim EH, Myoung SW, Jung YG, Paik U. Polyhedral oligomeric
silsesquioxane-reinforced polyurethane acrylate. Prog Org Coat
2009;64:205–9.
[280] Markovic E, Markovic MG, Clarke S, Matisons J, Hussain M, Simon
GP. Poly(ethylene glycol)-octafunctionalized polyhedral oligomeric
silsesquioxane: synthesis and thermal analysis. Macromolecules
2007;40:2694–701.
[281] Tagmatarchis N, Prato M. Carbon-based materials: from fullerene
nanostructures to functionalized carbon nanotubes. Pure Appl
Chem 2005;77:1675–84.
[282] Chen W, Tao X. Self-organizing alignment of carbon nan-
otubes in thermoplastic polyurethane. Macromol Rapid Commun
2005;26:1763–7.
[283] Xia H, Song M. Preparation and characterization of
polyurethane–carbon nanotube composites. Soft Matter
2005;1:386–94.
[284] Sahoo NG, Jung YC, Yoo HJ, Cho JW. Effect of functionalized carbon
nanotubes on molecular interaction and properties of polyurethane
composites. Macromol Chem Phys 2006;207:1773–80.
[285] Jung YC, Sahoo NG, Cho JW. Polymeric nanocomposites of
polyurethane block copolymers and functionalized multi-walled
carbon nanotubes as crosslinkers. Macromol Rapid Commun
2006;27:126–31.
[286] Gojny FH, Nastalczyk J, Roslaniec Z, Schelte K. Surface modified
multi-walled carbon nanotubes in CNT/epoxy-composites. Chem
Phys Lett 2003;370:820–4.
[287] Potschke P, Bhattacharyya AR, Janke A. Melt mixing of polycarbon-
ate with multiwalled carbon nanotubes: microscopic studies on the
state of dispersion. Eur Polym J 2004;40:137–48.
[288] Xia H, Song M. Preparation and characterisation of PU grafted
single-walled carbon nanotubes and derived polyurethane
nanocomposites. J Mater Chem 2006;16:1843–51.
[289] Xiong J, Zhou D, Zheng Z, Yang X, Wang X. Fabrication and
distribution characteristics of polyurethane/single-walled car-
bon nanotube composite with anisotropic structure. Polymer
2006;47:1763–6.
[290] Kuan HC, Ma CHM, Chang WP, Yuen SM, Wu HH, Lee TM. Synthesis,
thermal, mechanical and rheological properties of multiwall car-
bon nanotube/waterborne polyurethane nanocomposite. Compos
Sci Technol 2005;65:1703–10.
[291] Xu M, Zhang T, Gu B, Wu J, Chen Q. Synthesis and properties of
novel polyurethane–urea/multiwalled carbon nanotube compos-
ites. Macromolecules 2006;39:3540–5.
[292] Xiong J, Zheng Z, Song W, Zhou D, Wang X. Microstruc-
ture and properties of polyurethane nanocomposites reinforced
with methylene-bis-orthochloroanilline-grafted multi-walled car-
bon nanotubes. Composites A 2008;39:904–10.
[293] Gao C, Jin YZ, Kong H, Whitby RLD, Acquah SFA, Chen GY, et
al. Polyurea-functionalized multiwalled carbon nanotubes: syn-
thesis, morphology, and Raman spectroscopy. J Phys Chem B
2005;109:11925–32.
[294] Kronholm DL, Hummelen JC, Sieval AB., Preparation of high effi-
ciency fullerene - based radical scavengers. PCT Int Appl WO
2005058002 A2 (2005).
[295] Wahl F, Weiler A, Landenberger P, Sackers E, Voss T, Haas A, et
al. Towards perfunctionalized dodecahedranes–en route to C20
fullerene. Chem Eur J 2006;12:6255–67.
[296] Da Ros T, Prato M. Medicinal chemistry with fullerenes and fullerene
derivatives. Chem Commun 1999:663–9.
[297] Narang SC, Ventura SC, Ganapathiappan S, Bhardwaj TR, Nigam
A. Amine-containing polymerizable monomers and polymers
functionalized with fullerenes to provide polymers with high tem-
perature stability. US Patent 5,367,051 (1994).
[298] Chiang LY, Wang LY, Kuo CS. Polyhydroxylated C60 cross-linked
polyurethanes. Macromolecules 1995;28:7574–6.
[299] Chen Q, Kuang L, Sargent EH, Wang ZY. Ultrafast nonreso-
nant third-order optical nonlinearity of fullerene containing
polyurethane films at telecommunication wavelengths. Appl Phys
Lett 2003;83:2115–7.
[300] Zhang T, Xi K, Yu X, Gu M, Guo S, Gu B, et al. Synthesis, properties
of fullerene-containing polyurethane–urea and its optical limiting
absorption. Polymer 2003;44:2647–54.
[301] Branca C, Blasi CD, Casu A, Morone V, Costa C. Reaction kinetics
and morphological changes of a rigid polyurethane foam during
combustion. Thermochim Acta 2003;399:127–37.
[302] Papa AJ. Reactive flame retardants for polyurethane foams. Ind Eng
Chem Prod Res Devel 1970;9:478–96.
[303] Buszard DL, Dellar RJ. The performance of flame retardants in rigid
polyurethane foam formulations. Cell Polym 1985;4:431–43.
[304] Honkomp DJ, Casagrande G. All-MDI fully water blown molded
flexible foam systems for the North American (“Technical Bulletin
117”) furniture market. In: Polyurethanes Conference, Conference
Proceedings. 2002. p. 393–408.
[305] Shieh D, Marshall D. Novel polyester polyol to enhance the physical
properties of R245fa foams. In: Polyurethanes Conference, Confer-
ence Proceedings. 2002. p. 49–54.
[306] Çelebi F, Aras L, Gündüz G, Akhmedov IM. Synthesis and character-
ization of waterborne and phosphorus-containing flame retardant
polyurethane coatings. J Coat Technol 2003;75:65–71.
[307] Song L, Hu Y, Tang Y, Zhang R, Chen Z, Fan W. Study on the properties
of flame retardant polyurethane/organoclay nanocomposite. Polym
Degrad Stabil 2005;87:111–6.
[308] Green J. Mechanism of flame retardancy and smoke suppression-a
review. J Fire Sci 1996;14:426–42.
[309] Green J. 25 Years of flame retarding plastics. J Fire Sci 1997;15:52–67.
[310] Lu SY, Hamerton I. Recent developments in the chemistry
of halogen-free flame retardant polymers. Prog Polym Sci
2002;27:1661–712.
[311] Lyon RE. Pyrolysis kinetics of char forming polymers. Polym Degrad
Stabil 1998;61:201–10.
[312] Mequanint K, Sanderson R, Pasch H. Thermogravimetric study
of phosphated polyurethane ionomers. Polym Degrad Stabil
2002;77:121–8.
[313] Thirumal M, Khastgir D, Singha NK, Manjunath BS, Naik YP. Effect
of expandable graphite on the properties of intumescent flame-
retardant polyurethane foam. J Appl Polym Sci 2008;110:2586–
94.
[314] Lyon RE, Speitel L, Walters RN, Crowley S. Fire-resistant elastomers.
Fire Mater 2003;27:195–208.
[315] van Krevelen DW. Some basic aspects of flame resistance of poly-
meric materials. Polymer 1975;16:615–20.
[316] Grassie N, Scott G. Polymer degradation and stabilisation. Cam-
bridge, UK: Cambridge University Press; 1985.
[317] Grassie N, Mackerron DH. Synthesis of a series of polyurethanes
containing phosphorus. Eur Polym J 1980;16:113–6.
[318] Grassie N, Mackerron DH. Synthesis and degradation of
polyurethanes containing phosphorus-Part II: Thermal degra-
dation of poly(butylene phenylphosphonate) and poly(butylene
phenylphosphonate) bis(phenylcarbamate). Polym Degrad Stabil
1983;5:43–53.
[319] Grassie N, Mackerron DH. Synthesis and degradation of
polyurethanes containing phosphorus-Part III: Thermal
degradation of a series of polyurethanes incorporating buty-
lene phenylphosphonate structures. Polym Degrad Stabil
1983;5:89–103.
[320] Chang TC, Shen WY, Chiu YS, Chen HB, Ho SY. Synthesis and char-
acterization of phosphorus-containing polyurethanes. J Polym Res
1994;1:353–9.
[321] Chang TC, Chiu YS, Chen HB, Ho SY. Degradation of phosphorus-
containing polyurethanes. Polym Degrad Stabil 1995;47:375–81.
[322] Pinto UA, Visconte LLY, Gallo J, Nunes RCR. Flame retardancy in ther-
moplastic polyurethane elastomers (TPU) with mica and aluminum
trihydrate (ATH). Polym Degrad Stabil 2000;69:257–60.
[323] Batt AM, Appleyard P. The mechanism and performance of com-
bustion modified flexible foams in small scale fire tests. J Fire Sci
1989;7:338–63.
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
[324] Duquesne S, Le Bras M, Bourbigot S, Delobel R, Camino G, Eling B, et
al. Mechanism of fire retardancy of polyurethanes using ammonium
polyphosphate. J Appl Polym Sci 2001;82:3262–74.
[325] Duquesne S, Delobel R, Bras ML, Camino G. A comparative
study of the mechanism of action of ammonium polyphosphate
and expandable graphite in polyurethane. Polym Degrad Stabil
2002;77:333–44.
[326] Peters EN, Braidwood CL. Flame retardant composition and method.
US Patent Appl 20070080330 (2007).
[327] Mauric C, Wolf R. Flameproofed organic materials. US Patent
4,458,045 (1984).
[328] Ravey M, Weil ED, Keidar I, Pearce EM. Flexible polyurethane foam.
II. Fire retardation by tris(1,3-dichloro-2-propyl) phosphate. Part
A. Examination of the vapor phase (the flame). J Appl Polym Sci
1998;68:217–29.
[329] Ravey M, Weil ED, Keidar I, Pearce EM. Flexible polyurethane foam.
II. Fire retardation by tris(1,3-dichloro-2-propyl) phosphate. Part B.
Examination of the condensed phase (the pyrolysis zone). J Appl
Polym Sci 1998;68:231–54.
[330] Smiecinski TM, Wujcik SE, Mente DC. Flame retardant polyurethane
foams. US Patent 5,830,926 (1998).
[331] Klein R, Balbach G. Preparation of phosphonate esters as fireproof-
ing agents for epoxy resins. German Patent 3803030 (1989).
[332] Hoang DQ, Kim J, Jang BN. Synthesis and performance of cyclic
phosphorus-containing flame retardants. Polym Degrad Stabil
2008;93:2042–7.
[333] Blundell C, Wuestenenk JA. Fog reduction in polyurethane foam
using phosphate esters. US Patent 5,958,993 (1999).
[334] Dubois AB. Hazards associated with fires. Fire and Smoke: under-
standing the Hazards, Chapter 4. Washington, DC: National
Academy Press; 1986. p. 62–77.
[335] Park HS, Keun J, Lee K. Syntheses and physical properties
of two-component polyurethane flame-retardant coatings using
chlorine-containing modified polyesters. J Polym Sci Polym Chem
Ed 1996;34:1455–64.
[336] Park HS, Hahm HS, Park EK. Preparation and characteristics
of two-component polyurethane flame retardant coatings using
2,3-dibromo modified polyesters. J Appl Polym Sci 1996;61:
421–9.
[337] Gilman AL, Simpson SS, Svobada P. Flame retardant polyurethane
composition and method of manufacture thereof. PCT Int Appl. WO
2003091308 A1 20031106 (2003).
[338] Bian XC, Tang JH, Li ZM, Lu ZY, Lu A. Dependence of flame-
retardant properties on density of expandable graphite filled rigid
polyurethane foam. J Appl Polym Sci 2007;104:3347–55.
[339] Wang Z, Han E, Ke W. Influence of expandable graphite on fire resis-
tance and water resistance of flame-retardant coatings. Corrosion
Sci 2007;49:2237–53.
[340] Gu JW, Zhang GC, Dong SL, Zhang QY, Kong J. Study on preparation
and fire-retardant mechanism analysis of intumescent flame-
retardant coatings. Surf Coat Technol 2007;201:7835–41.
[341] Zatorski W, Brzozowski ZK, Kolbrecki A. New developments in
chemical modification of fire-safe rigid polyurethane foams. Polym
Degrad Stabil 2008;93:2071–6.
[342] Duquesne S, Bras ML, Bourbigot S, Delobel R, Vezin H, Camino G, et
al. Expandable graphite: a fire retardant additive for polyurethane
coatings. Fire Mater 2003;27:103–17.
[343] Bhagat VJ. Behaviour Of Expandable Graphite As A Flame
Retardant In Flexible Polyurethane Foam. Online presentation:
http://www.metachem.in/Presenation.pdf.
[344] Modesti M, Lorenzetti A, Simioni F, Camino G. Expandable
graphite as an intumescent flame retardant in polyisocyanurate-
polyurethane foams. Polym Degrad Stabil 2002;77:195–202.
[345] Modesti M, Lorenzetti A. Improvement on fire behaviour of water
blown PIR-PUR foams: use of an halogen-free flame retardant. Eur
Polym J 2003;39:263–8.
[346] Modesti M, Lorenzetti A. Flame retardancy of
polyisocyanurate–polyurethane foams: use of different charring
agents. Polym Degrad Stabil 2002;78:341–7.
[347] Modesti M, Lorenzetti A. Halogen-free flame retardants for poly-
meric foams. Polym Degrad Stabil 2002;78:167–73.
[348] Duquesne S, Le BM, Bourbigot S, Delobel R, Camino G,
Eling B, et al. Thermal degradation of polyurethane and
polyurethane/expandable graphite coatings. Polym Degrad Stabil
2001;74:493–9.
[349] Duquesne S, Le Bras M, Bourbigot S, Delobel R, Poutch F, Camino
G, et al. Analysis of fire gases released from polyurethane
and fire-retarded polyurethane coatings. J Fire Sci 2000;18:456–
82.
1131
[350] Shi L, Li ZM, Xie BH, Wang JH, Tian CR, Yang MB. Flame retardancy of
different-sized expandable graphite particles for high-density rigid
polyurethane foams. Polym Int 2006;55:862–71.
[351] Shi L, Li ZM, Yang W, Yang MB, Zhou QM, Huang R. Properties and
microstructure of expandable graphite particles pulverized with an
ultra-high-speed mixer. Powder Technol 2006;170:178–84.
[352] Shi L, Li ZM, Yang MB, Yin B, Zhou QM, Tian CR, et al. Expand-
able graphite for halogen-free flame-retardant of high-density
rigid polyurethane foams. Polym Plast Technol Eng 2005;44:1323–
37.
[353] Wood K, Bell RWH. Flame-retardant latex foams. US Patent 4722945
(1988).
[354] Horrocks AR, Price D, Edwards NLC. The burning behaviour of com-
bustion modified high resilience polyurethane foams. J Fire Sci
1992;10:28–39.
[355] Dufton PW. Fire: Additives and Materials. Shrewsbury, UK: Rapra
Technology; 1995.
[356] Dufton PW. Functional additives for the plastics industry. The
effect of polymer usage on their supply and demand. Addcon
World’98: Additives for the New Millennium, Official Book of
Papers, International Plastics Additives and Modifiers Conference,
London, November 9–10, 1998;Paper 12/1-Paper 12/9.
[357] Barker M, Hannaby MP, Lockwood FJ. Combustion-modified
molded polyurethane flexible foam for the furniture industry.
In: Polyurethanes World Congress Proceedings SPI/SOPA. 1991. p.
628–33.
[358] Knaub PH, Mispreuve H. Combustion modified flexible
polyurethane slabstock foams. In: Proceedings of the SPI
Annual Technical/Marketing Conference, 32nd . 1989. p. 501–9.
[359] Costa L, Camino G, Luda di Cortemiglia MP. Mechanism of ther-
mal degradation of fire-retardant melamine salts. ACS Symp Ser
1990;425:211–38.
[360] Horacek H, Grabner W. Nitrogen based flame retardants for
nitrogen containing polymers. Makromol Chem, Macromol Symp
1993;74:271–6.
[361] Denecker C, Liggat JJ, Snape CE. Relationship between the ther-
mal degradation chemistry and flammability of commercial flexible
polyurethane foams. J Appl Polym Sci 2006;100:3024–33.
[362] Costa L, Camino G. Thermal behaviour of melamine. J Therm Anal
1988;34:423–9.
[363] Feng D, Zhou Z, Bo M. Investigation of the thermal degradation of
melamine phosphonite by XPS and thermal analysis techniques.
Polym Degrad Stabil 1995;50:65–70.
[364] Lotsch BV, Schnick W. New light on an old story: formation of
melam during thermal condensation of melamine. Chem Eur J
2007;13:4956–68.
[365] Dick CM, Denecker C, Liggat JJ, Mohammed MH, Snape CE, Seeley
G, et al. Solid state 13 C and in situ 1 H NMR study on the effect of
melamine on the thermal degradation of a flexible polyurethane
foam. Polym Int 2000;49:1177–82.
[366] Lee FT, Nicholson P, Green J. New reactive phosphorus flame retar-
dant for rigid polyurethane application, Part I. J Fire Retardant Chem
1982;9:194–205.
[367] Lee FT, Green J, Gibilisco RD. Recent developments using
phosphorus-containing diol as a reactive combustion modifier for
rigid polyurethane foams - part III. J Fire Sci 1984;2:439–53.
[368] Sivriev C, Zabski L. Flame retarded rigid polyurethane foams by
chemical modification with phosphorus- and nitrogen-containing
polyols. Eur Polym J 1994;30:509–14.
[369] Witte A, Krieger W. Halogen-free, water-blown, flame-retardant
rigid polyurethane foam and a process for its production. US Patent
6518325 (2003).
[370] Witte A, Krieger W. Halogen-free, pentane-blown, flame-retardant
rigid polyurethane foam and a process for its production. US Patent
6,593,385 (2003).
[371] Witte A, Krieger W. Halogen-free, flame-retardant rigid
polyurethane foam and a process for its production. US Patent
6,472,448 (2002).
[372] Eilbracht C, Sicken M. Process for producing flame-retardant flexi-
ble polyurethane foams. US Patent 6,380,273 (2002).
[373] Sicken M, Staendeke H. Flame-resistant polyurethanes. US Patent
5,985,965 (1999).
[374] Wu W, Yang CQ. Comparison of different reactive organophos-
phorus flame retardant agents for cotton, Part II: Fabric flame
resistant performance and physical properties. Polym Degrad Stabil
2007;92:363–9.
[375] Wilson BN, Gordon I, Hindersinn RR. Phosphoramidates as reac-
tive fire-retardant polymer modifiers. Ind Eng Chem Prod Res Devel
1974;13:85–9.
1132 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
[376] Liu W, Chen DQ, Wang YZ, Wang DY, Qu MH. Char-forming mecha-
nism of a novel polymeric flame retardant with char agent. Polym
Degrad Stabil 2007;92:1046–52.
[377] Jain P, Choudhary V, Varma IK. Flame retarding epoxies with phos-
phorus. J Macromol Sci Polym Rev 2002;42:139–83.
[378] Liu YL, Hsiue GH, Lee RH, Chiu YS. Phosphorus-containing epoxy
for flame retardant, 3. Using phosphorylated diamines as curing
agents. J Appl Polym Sci 1997;63:895–901.
[379] Wang CS, Lin CH. Properties and curing kinetics of diglycidyl ether
of bisphenol A cured with a phosphorus-containing diamine. J Appl
Polym Sci 1999;74:1635–45.
[380] Braun U, Balabanovich AI, Schartel B, Knoll U, Artner J, Ciesielski
M, et al. Influence of the oxidation state of phosphorus on the
decomposition and fire behaviour of flame-retarded epoxy resin
composites. Polymer 2006;47:8495–508.
[381] Ren H, Sun J, Wu B, Zhou Q. Synthesis and properties of a
phosphorus-containing flame retardant epoxy resin based on bis-
phenoxy (3-hydroxy) phenyl phosphine oxide. Polym Degrad Stabil
2007;92:956–61.
[382] Ma ZL, Zhao WG, Liu YF, Shi JR. Intumescent polyurethane coatings
with reduced flammability based on spirocyclic phosphate-
containing polyols. J Appl Polym Sci 1997;66:471–5.
[383] Wang CS, Shieh JY. Synthesis and properties of epoxy resins
containing bis(3-hydroxyphenyl) phenyl phosphate. Eur Polym J
2000;36:443–52.
[384] Petreus O, Bubulac TV, Hamciuc C. Synthesis and characterization
of new polyesters with enhanced phosphorus content. Eur Polym J
2005;41:2663–70.
[385] Price D, Cunliffe LK, Bullett KJ, Hull TR, Milnes GJ, Ebdon JR, et
al. Thermal behaviour of covalently bonded phosphate and phos-
phonate flame retardant polystyrene systems. Polym Degrad Stabil
2007;92:1101–14.
[386] Huang Z, Shi W. Thermal behavior and degradation mecha-
nism of poly(bisphenyl acryloxyethyl phosphate) as a UV curable
flame-retardant oligomers. Polym Degrad Stabil 2006;91:1674–
84.
[387] Wang TL, Cho YL, Kuo PL. Flame-retarding materials, II. Syn-
thesis and flame-retarding properties of phosphorus-on-pendent
and phosphorus-on-skeleton polyols and the corresponding
polyurethanes. J Appl Polym Sci 2001;82:343–57.
[388] Zhu S, Shi W. Synthesis, characterization and flame retar-
dancy of methacrylated phosphate/diphosphate. Polym Int
2004;53:266–71.
[389] Wang LS, Kang HB, Wang SB, Liu Y, Wang R. Solubilities, ther-
mostabilities and flame retardance behaviour of phosphorus
containing flame retardants and copolymers. Fluid Phase Equil
2007;258:99–107.
[390] Liu YL, Hsiue GH, Lan CW, Chiu YS. Phosphorus-containing epoxy
for flame retardance: IV, Kinetics and mechanism of thermal degra-
dation. Polym Degrad Stabil 2007;56:291–9.
[391] Chao CYH, Wang JH. Comparison of the thermal decomposi-
tion behavior of a non-fire retarded and a fire retarded flexible
polyurethane foam with phosphorus and brominated additives. J
Fire Sci 2001;19:137–56.
[392] Troev K, Tsevl R, Bourova T, Kobayashi S, Uayama H, Roundhill DM.
Synthesis of phosphorus-containing polyurethanes without use of
isocyanates. J Polym Sci Polym Chem Ed 1996;34:621–31.
[393] Capek I. Nature and properties of ionomer assemblies, II. Advan Coll
Interf Sci 2005;118:73–112.
[394] Harashina H, Yamada S. Flame-retardant resin composition. US
Patent 7,411,013 (2008).
[395] Dez I, Henry N, Jaeger RD. New heat-resistant polyurethanes
prepared from hydroxylated cyclotriphosphazenes. Polym Degrad
Stabil 1999;64:433–7.
[396] Dez I, De Jaeger R. Organic-inorganic polymers: synthesis and
characterization of cyclophosphazene-substituted polyurethanes.
J Inorg Organomet Polym 1996;6:111–21.
[397] Modesti M, Zanella L, Lorenzetti A, Bertani R, Gleria M. Ther-
mally stable hybrid foams based on cyclophosphazenes and
polyurethanes. Polym Degrad Stabil 2005;87:287–92.
[398] Yuan CY, Chen SY, Tsai CH, Chiu YS, Yang YWC. Thermally stable
and flame-retardant aromatic phosphate and cyclotriphosphazene-
containing polyurethanes: synthesis and properties. Polym Adv
Technol 2005;16:393–9.
[399] Jaeger RD, Gleria M. Poly(organophosphazene)s and related com-
pounds: synthesis, properties and applications. Prog Polym Sci
1998;23:179–276.
[400] Gleria M, De Jaeger R. Aspects of phosphazene research. J Inorg
Organomet Polym 2001;11:1–45.
[401] Taniguchi M, Tada Y, Nishioka Y. Flame-retardant epoxy resin com-
position, molded article thereof, and electronic part. US Patent
6,797,750 (2004).
[402] Nakacho Y, Yabuhara T, Tada Y, Nishioka Y. Crosslinked phe-
noxyphosphazene compounds, flame retardants, flame-retardant
resin compositions, and moldings of flame-retardant resins. US
Patent 6,596,893 (2003).
[403] Dez I, Jaeger RD. Synthesis of polyurethane/polyethylene grafted
polymers using cyclotriphosphazene as a coupling agent. J Appl
Polym Sci 2003;89:1925–34.
[404] Stewart FF, Harrup MK. Phosphazene monomers from the
regiospecific reaction of tert-butylhydroquinone with hexachloro-
cyclotriphosphazene: a new composite material precursor. J Appl
Polym Sci 1999;72:1085–90.
[405] Dez I, Mitjaville JL, Grützmacher H, Gramlich V, Jaeger RD. Syn-
theses of chiral cyclotriphosphazenes and their use in cyclolinear
polymers. Eur J Inorg Chem 1999;10:1673–84.
[406] Mathew D, Nair CPR, Ninan KN. Phosphazene-triazine cyclomatrix
network polymers: some aspects of synthesis, thermal- and flame-
retardant characteristics. Polym Int 2000;49:48–56.
[407] Yuan W, Zhu L, Huang X, Zheng S, Tang X. Synthesis and properties
of pentaarmed poly(l-lactide)s on N-dichlorophosphoryl-
P-trichlorophosphazene derivative core. Eur Polym J
2005;41:1867–73.
[408] Kumar D, Guptat AD. Aromatic cyclolinear phosphazene poly-
imides based on a novel bis-spiro-substituted cyclotriphosphazene
diamine. Macromolecules 1995;28:6323–9.
[409] Tunca U, Hizal G. Synthesis and characterization of aromatic
poly(ether ketone)s containing cyclotriphosphazene units. J Polym
Sci Polym Chem Ed 1998;36:1227–32.
[410] Reed CS, Taylor JP, Guigley KS, Coleman MM, Allcock HR.
Polyurethane/poly[bis(carboxylatophenoxy)phosphazene] blends
and their potential as flame-retardant materials. Polym Eng Sci
2000;40:465–72.
[411] Liu R, Wang X. Synthesis, characterization, thermal properties and
flame retardancy of a novel nonflammable phosphazene-based
epoxy resin. Polym Degrad Stabil 2009;94:617–24.
[412] Scaffaro R, Mistretta MC, Mantia FPL, Gleria M, Bertani R, Samperi
F, et al. On the preparation and characterization of polyethy-
lene/polyamide blends by melt processing in the presence of an
ethylene/acrylic acid copolymer and of new phosphazene com-
pounds. Macromol Chem Phys 2006;207:1986–97.
[413] Huang WK, Chen KJ, Yeh JT, Chen KN. Curing and combustion prop-
erties of a PU-coating system with UV-reactive phosphazene. J Appl
Polym Sci 2002;85:1980–91.
[414] Chen-Yang YW, Chuang JR, Yang YC, Li CY, Chiu YS. New UV-curable
cyclotriphosphazenes as fire-retardant coating materials for wood.
J Appl Polym Sci 1998;69:115–22.
[415] Schneider A, Kairies S, Rose K. Synthesis of alkoxysilyl substituted
cyclophosphazenes and their properties in the sol-gel process.
Monatshefte fur Chemie 1999;130:89–98.
[416] Van De Grampel JC. Phosphazenes. In: Allen DW, Tebby JC, edi-
tors. Organophosphorus Chemistry, vol. 29. Cambridge, UK: Royal
Society of Chemistry; 1999. p. 269–99.
[417] Van De Grampel JC. In: Gleria M, De Jaeger R, editors. Hybrid
inorganic-organic phosphazene polymers. Phosphazenes: a world-
wide insight. Hauppauge, NY: Nova Science; 2002. p. 143–70.
[418] Shao CH, Huang JJ, Chen GN, Yeh JT, Chen KN. Thermal and com-
bustion behaviors of aqueous-based polyurethane system with
phosphorus and nitrogen containing curing agent. Polym Degrad
Stabil 1999;65:359–71.
[419] Shao CH, Wang TZ, Chen GN, Chen KJ, Yeh JT, Chen KN. Aqueous-
based polyurethane with dual-functional curing agent. J Polym Res
2000;7:41–9.
[420] Wang TZ, Chen KN. Introduction of covalently bonded phosphorus
into aqueous-based polyurethane system via postcuring reaction. J
Appl Polym Sci 1999;74:2499–509.
[421] Huang WK, Yeh JT, Chen KJ, Chen KN. Flame retardation improve-
ment of aqueous-based polyurethane with aziridinyl phosphazene
curing system. J Appl Polym Sci 2001;79:662–73.
[422] Armitage P, Ebdon JR, Hunt BJ, Jones MS, Thorpe FG. Chemical mod-
ification of polymers to improve flame retardance–I, The influence
of boron-containing groups. Polym Degrad Stabil 1996;54:387–93.
[423] Czuprynski B, Paciorek J. The effect of tri(2-hydroxypropyl) borate
on the properties of rigid polyurethane—polyisocyanurate foams.
Polimery 1999;44:552–4.
[424] Czuprynski B, Paciorek-Sadowska J, Liszkowska J. Effect of selected
boranes on properties of rigid polyurethane–polyisocyanurate
foams. J Polym Eng 2002;22:59–74.
 D.K. Chattopadhyay, D.C. Webster / Progress in Polymer Science 34 (2009) 1068–1133
[425] Czuprynski B, Paciorek-Sadowska J, Liszkowska J. The effect of tri(1-
chloro-3-ethoxy-propane-2-ol) borate on the properties of rigid
polyurethane–polyisocyanurate foams. Polimery 2002;47:727–9.
[426] Ohta K, Goto T, Endo Y. New synthetic method of 1,2-diaryl-
1,2-dicarba-closo-dodecaboranes employing aromatic nucleophilic
substitution (SNAr) reaction. Tetrahedron Lett 2005;46:483–5.
[427] Petrova AP. Polyurethane adhesives based on carborane-containing
compounds. Polymer Sci: Ser C 2007;49:251–4.
[428] Kaszynski P. Four decades of organic chemistry of closo-boranes: a
synthetic toolbox for constructing liquid crystal materials. A review.
Collect Czech Chem Commun 1999;64:895–926.
[429] Cheung MS, Chan HS, Xie Z. Synthesis and structural characteriza-
tion of hydroxyethyl- and alkoxyethyl-o-carboranes and their alkali
and rare earth metal complexes. Organometallics 2004;23:517–26.
[430] Fox MA, Wade K. Model compounds and monomers for phenylene
ether carboranylene ketone (PECK) polymer synthesis: preparation
and characterization of boron-arylated ortho-carboranes bearing
carboxyphenyl, phenoxyphenyl or benzoylphenyl substituents. J
Mater Chem 2002;12:1301–6.
[431] Packirisamy S. Decaborane (14)-based polymers. Prog Polym Sci
1996;21:707–73.
1133
[432] Delman AD, Kelly JJ, Simms BB. Thermal stability of structurally
related polymers containing carborane and phthalocyanine groups.
J Polym Sci Polym Chem Ed 1970;8:111–23.
[433] Parrott MC, Marchington EB, Valliant JF, Adronov A. Preparation
of synthons for carborane containing macromolecules. Macromol
Symp 2003;196:201–11.
[434] Bekasova NI, Komarova LG, Komarova NG, Ivanova NS, Chizhova EA.
Reactivity of m-carborane-containing diamines in acylation by ben-
zoyl chloride and in polymer synthesis. Zhurnal Obshchei Khimii
1991;61:2224–7.
[435] Pankratov VA, Vinogradova SV, Korshak VV. The synthesis of
polycyanates by the polycyclotrimerisation of aromatic and orga-
noelement cyanate esters. Russ Chem Rev 1977;46:278–95.
[436] Levchik SV, Weil ED. Thermal decomposition, combustion and
flame-retardancy of epoxy resins—a review of the recent literature.
Polym Int 2004;53:1901–29.
[437] Zhang S, Horrocks AR. A review of flame retardant polypropylene
fibres. Prog Polym Sci 2003;28:1517–38.
[438] Mercado LA, Galia M, Reina JA. Silicon-containing flame retardant
epoxy resins: synthesis, characterization and properties. Polym
Degrad Stabil 2006;91:2588–94.