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Table of Contents
Topic 1 Introduction...................................................................................................................................... 2
1.1 Historical Development (for self-reading) ....................................................................... 2
1.2 Definition and nomenclature ........................................................................................... 3
1.2.1 Basic Terminology ................................................................................................................. 3
1.2.2 Degree of Polymerization (DP).............................................................................................. 4
1.2.3 Nomenclature ....................................................................................................................... 4
1.3 Classification of Polymers ................................................................................................ 6
1.3.1 Natural vs. Synthetic ............................................................................................................. 6
1.3.2 Homopolymer vs. Copolymer ............................................................................................... 6
1.3.3 Vinyl vs. Non-vinyl polymers ................................................................................................. 8
1.3.4 Thermal Behavior: Thermoset vs. Thermoplastic ............................................................... 10
1.3.5 Polymerization Mechanism................................................................................................. 12
1.3.6 Polymer morphology: Amorphous vs. Crystalline............................................................... 13
1.3.7 Polymer Structure: Linear/branch/cross-link...................................................................... 15
1.4 Molecular Weight .......................................................................................................... 16
1.4.1 Average Molecular Weight ................................................................................................. 18
1.4.2 Number-average Molecular Weight ................................................................................... 18
1.4.3 Weight-average Molecular Weight ..................................................................................... 18
1.4.4 Polydispersity Index (PDI) ................................................................................................... 19
1.5 Polymer Stereochemistry............................................................................................... 20
1.5.1 Constitutional Isomerism .................................................................................................... 20
1.5.2 Tacticity ............................................................................................................................... 20
1.5.3 Geometric Isomerism .......................................................................................................... 24
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UEMT 2123 Topic 1: Introduction
Topic 1 Introduction
1.1 Historical Development (for self-reading)
• Polymers have been with us from the beginning of time; they form the basic (building blocks) of
life. Animals, plants – all classes of living organisms – are composed of polymers.
• However, it was not until the middle of the 20th century that we began to understand the true
nature of polymers. This understanding came with the development of plastics, which are true
man-made materials that are the ultimate tribute to man’s creativity and ingenuity.
• Following a better understanding of the nature of polymers, there was a phenomenal growth in
the numbers of polymeric products that achieved commercial success in the period between
1925 and 1950.
• The search for materials to aid in the defense effort during World War II resulted in a profound
impetus for research into new plastics.
• Polyethylene, now one of the most important plastics in the world, was developed because of
the wartime need for better-quality insulating materials for such applications as radar cable.
• 1833: The word polymer was first used by the Swedish chemist Berzelius.
• 1839: Charles Goodyear developed the vulcanization process that transformed the sticky latex
of natural rubber to a useful elastomer for tire use.
• 1847: Christian F. Schöbein commercialized the first man-made thermoplastic, Celluloid.
• 1907: Belgian-born chemist Leo Baekeland produced Bakelite, a thermosetting phenol
formaldehyde resin.
• 1930s: Nylon and TeflonTM had been produced by researchers at DuPoint in US.
• 1938: Dow had produced polystyrene in commercial scale.
• 1939: The first synthetic rubber, polyethylene was made by scientists at ICI in England.
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Oligomer
1.2.3 Nomenclature
• To provide each polymer a unique name.
• Source based: Place the prefix poly before the name of the corresponding monomer.
• For example: Polyethylene, Polytetrafluoroethylene, Polystyrene
• If the monomer name consists of more than a word, or if the name is preceded by a letter or
number, the monomer name is enclosed in parentheses and prefixed with poly.
• For example: Poly(acrylic acid), Poly(α-methylstyrene), Poly(1-pentene).
• IUPAC: The smallest base unit is identified.
• Substituent groups on the backbone are assigned the lowest possible numbers.
• The name is placed in parentheses and prefixed with poly.
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Polystyrene-block-polyisoprene-block-
Block-copoly(styrene/isoprene/styrene)
polystyrene
Polybutadiene-block-(polystyrene-graft- Block-copoly[butandiene/graft-
polyacrylonitrile) co(styrene/acrylonitrile)]
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• Often, it is possible to obtain polymers with new and desirable properties by linking two or three
different monomers or repeating units during polymerization. Polymers with two different
repeating units are defined as copolymers.
• Copolymerization leads to materials with properties quite different from those of either
corresponding homopolymer. Thus it gives a vast amount of flexibility for devising new
materials.
• The exact distribution of repeating units depending on the initial proportions of the two
reactant monomers and their relative reaction.
• The repeating units on the copolymer chain may be arranged in various degrees of order along
the backbone; it is even possible for one type of backbone to have branches of another type.
• Based on the distribution pattern of monomer units in the chain, there are four basic types of
copolymer.
Random Copolymer Alternating Copolymer
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• Block Copolymer: contains a linear arrangement of different blocks of identical repeating units
alternate with each others. Prepared by initiating the polymerization of monomer as if growing
a homopolymer chain and then adding an excess of the second monomer to the still-active
reaction mix.
• Graft Copolymer: comprises of a backbone homopolymer (e.g. poly A) and a side-chain
homopolymer (e.g. poly B) which are grafted onto one of mers of A.Made by gamma irradiation
of a completed homopolymer chain in the presence of the second monomer generating radical
sites that can initiate polymerization of the added monomer.
Example1: Estimate the molecular weight (MW) of alternating copolymer of A (MWA = 65 g/mol) and B
(MWB = 114 g/mol) with a DP of 130.
Example 2: Determine the mole fractions of vinyl chloride and vinyl acetate in a copolymer having a
molecular weight of 12,520 g/mol and a DP of 180.
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• Polymers derived from monomers containing carbon-carbon double bonds are often referred to
vinylpolymer.
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• For engineering purposes, the most useful classification of polymers is based on their thermal
response, i.e. thermoplastics or thermosets.
• Thermoplastics soften and flow under the action of heat and pressure. Upon cooling, the
polymer hardens and assumes the shape of the mold. Examples: PS, PE, PP, nylon.
• When compounded with appropriate ingredients, thermoplastics can usually withstand several
of these heating and cooling cycles without suffering any structural breakdown. Hence, the
waste thermoplastics can be recovered and refabricated by application of heat and pressure.
• In comparison, thermosets can be shaped into desired forms by the application of heat and
pressure, but are incapable of undergoing repeated cycles of softening and hardening. They
usually exist initially as liquids called prepolymers. Examples: epoxy and phenol-formaldehyde
resins.
• The basic structural difference between them is that thermoplastics are composed of mainly of
linear and branched molecules, whereas thermosets are made up of cross-linked systems.
Linear/Branched Cross-Linked
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• The individual chains of linear and branched polymers are not chemically tied together; hence,
they can slide past one another.
• For cross-linked systems, however, chains are linked chemically by covalent bonds;
consequently, chains will not flow freely even under the application of heat and pressure.
• Therefore, these cross-linked networks resist heat softening, creep and solvent attack. Such
properties make thermosets suitable for composites, coating and adhesive applications.
• Typically, thermoplastics are ductile while thermosets are brittle and hard.
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• Condensation polymers are obtained by the random reaction of two molecules (monomers,
dimers, trimers, oligomers, etc.), where each having complementary functional groups, such as
carboxylic acid or hydroxyl groups. Typically, the process occurs by the liberation of a small
molecule in the form of a gas, water or salt. Example: the synthesis of nylon-6,6 by condensation
of adipic acid and hexamethylenediamine.
• In the recent years, in view of the new polymerization processes have been developed, there
are far too many exceptions for this traditional classification to be useful.
• Hence, another classification scheme based on polymerization kinetics has been adopted,
namely, step growth or chain growth polymerization, which will be discussed in detail in Chapter
2.
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Crystallinity
PMMA PVC PS
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• Polymers with a degree of crystallinity approaching zero or one will tend to be transparent,
while polymers with intermediate degrees of crystallinity will tend to be opaque due to light
scattering by crystalline or glassy regions.
• Thus for many polymers, reduced crystallinity may also be associated with increased
transparency.
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• The functionality of a molecule is simply its interlinking capacity or the number of sites it has
available for bonding with other molecules under the specific polymerization conditions.
• A molecule may be classified as monofunctional, difunctional, trifunctional, tetrafunctional or
polyfunctional monomer depending on it has one, two, three, four or more sites available for
linking with other molecules.
• For example, the olefinic monomers which contain a single C=C double bond have a
functionality of two because each C=C double bond gives rise to two chain links. The monomers
with a functionality of two are linear polymers.
• If a monomer has a functionality of greater than two, then this will lead to formation of
branches and possibly to the formation of a network polymer, depending on the particular
polymerization and reactant stoichiometry.
Linear Polymerization
Branching Polymerization
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(i)
(ii)
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• There is a minimum polymer MW (Point X), usually a thousand or more, to create any significant
mechanical strength.
• Above point X, the mechanical strength increases rapidly with MW until a critical point, Y.
• The mechanical strength increases slowly above Y and eventually saturates at a limiting point Z.
• The critical point Y (in the range of 5,000 – 10,000) commonly corresponds to the minimum MW
for a polymer to exhibit sufficient strength to be useful.
• Most practical applications of polymers require higher MW to obtain higher strengths.
• Polymer chains with stronger intermolecular forces, (e.g. polyamides & polyesters) develop
sufficient strength to be useful at lower MW than polymer having weaker intermolecular forces
(e.g. polyethlene).
• The plot of dependence of mechanical strength on MW generally shifts to right as the
intermolecular force decrease.
Dependence of Tg on Polymer MW
Other Dependences
• Some polymer processing properties, such as melt viscosity and solution viscosity, increase
monotonically with MW.
• The goal of polymer synthesis is not to make the largest possible MW, but to create a polymer
large enough to get onto the plateau region.
• Increasing MW beyond this point will not improve physical properties much but worsen the
processing condition.
• Few properties are dictated by repeating units, and therefore not changed much by MW. E.g.
color, dielectric constant and refractive index.
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•
• Since most polymers are mixtures of many large molecules (except for some biological
polymers, such as proteins, which have a single and well-defined molecular weight), it is
necessary to define an average molecular weight to describe polymer MW.
• Two common ways to calculate/measure an average MW
i. Number-average MW
ii. Weight-average MW
• The molecular weight values obtained depend on the method of measurement.
• Where Ni is the number of molecules or the number of moles of those molecules having
molecular weight Mi.
• Where Wi = NiMi.
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UEMT 2123 Topic 1: Introduction
Example
1) Given a polymer sample consisting of 9 moles of 30,000 g/mol and 5 moles of 50,000 g/mol
polymers. Calculate number-average and weight-average molecular weight.
2) Given a polymer sample consisting of 9 grams of 30,000 g/mol and 5 grams of 50,000 g/mol.
Calculate number-average and weight-average molecular weight.
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1.5.2 Tacticity
• Stereoisomers have the same connectivity, but differ in their configurations.
• Configuration is the relative orientation in space of the atoms of a stereoisomer, independent of
spatial changes that occur by rotations about single bonds.
• The regularity in the configurations of successive stereocenters determines the overall order
(tacticity) of the polymer chain.
• The polymerization of a monosubstituted ethylene, CH2=CHR, leads to polymers in which every
alternate carbon atom in the polymer chain is a stereocenter (or chiral center or stereogenic
center).
• A stereocenter is an atom bearing substituents of such identity that a hypothetical exchange of
the positions of any two substituents would convert one stereoisomer into another
stereoisomer.
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Monosubstituted Ethylene
• If the R groups on successive stereocenters are randomly distributed on the two sides of the
planar zigzag polymer chain, the polymer does not have order and is termed as atactic or
heterotactic.
• Two types of ordered/tactic structures or placements can happen: Isotactic and Syndiotactic.
• An isotactic structure occurs when the stereocenter in each repeating unit in the polymer chain
has the same configuration.
• All the R groups are located on one side of the plane of the carbon-carbon polymer chain, either
all above or below the plane of the chain.
• A syndiotactic structure happens when the configurations of the stereocenters alternate from
one repeating unit to the next with the R groups located alternately on the opposite sides of the
plane of the polymer chain.
Atactic
Isotactic
Syndiotactic
• The term isotactic and syndiotactic are placed the name of a polymer indicate the respective
tactic structures, such as isotactic polypropene and syndiotacticpolypropene
• Alternatively, the prefixesit- and st- have been used. E.g. it-[CH2CH(CH3)]n and st-[CH2CH(CH3)]n.
• The absence of these two terms denotes the atactic structure. E.g. Polypropene means
atacticpolypropene.
• In general, tactic polymer (i.e. isotactic or syndiotactic) are partially crystalline, while atactic
polymers are amorphous indicating the absence of all crystalline order.
• In addition, other polymer properties, such as thermal and mechanical behavior, can be
significantly affected by the tacticity of the polymer.
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Di-substituted Ethylenes
1,1-Disubstituted Ethylenes
• When R and R’ are different (e.g. –CH3 and –COOCH3 in methyl methacrylate), stereoisomerism
occurs exactly as in the case of a monosubstituted ethylene.
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• In the polymerization of 1,2-disubstituted ethylene, CHR=CHR’, when both R and R’ groups are
the same, stereoisomerism occurs almost similar as in the case of a monosubstituted ethylene.
• In this case, tacticity refers to every backbone carbon, not alternate carbons in monosubstituted
ethylene.
• When R and R’ are different (e.g. –CH3 and –C2H5 in 2-pentene), there are two
differentstereocenter in each repeating unit.
• Several possibilities of ditacticity exist that involve different combinations of tacticity for the
two stereocenters.
• Diisotactic structures occur when placement at each of the two stereocenters is isotactic.
• Disyndiotactic structures occur when placement at each of the two different stereocenters is
syndiotactic.
• Two diisotactic or disyndiotactic are possible.
• These are differentiate with prefixes, thero- and erythro-, which refer to similar groups being on
the opposite side or on the same side, respectively.
thero-Diisotactic erythro-Diisotactic
thero-Disyndiotactic erythro-Disyndiotactic
Stereoselective Polymerization
• Polymerizations that yield tactic structure (either isotactic or syndiotactic) are termed as
stereoselective polymerization.
• A reaction is termed as stereoselective if it results the preferential formation of one
stereoisomer over another.
• Isoselective and syndioselective polymerization are stereoselective polymerization yielding
isotactic and syndiotactic, respectively.
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Monomer: 1,3-butadiene (X = H)
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