UEMT 2123 Topic 1: Introduction

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

1
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
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.

Milestones of Polymer Science

• 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.

2
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

Nobel Laureates in Chemistry

• 1953: German chemist Hermann Staudinger, who demonstrated the existence of

macromolecules, which he characterized as polymers.
• 1963: German Karl Ziegler and Italian Giulio Natta, who discovered new polymerization reaction
with controlled stereochemistry.
• 1974: Paul Flory, who established a quantitative basis for polymer behavior.

Polymers are everywhere

• Polymers have incalculable impact on our present way of life.

• More than 50% of all chemist & chemical engineers, large number of physicists, mechanical
engineers and material scientists work on polymer.
• Polymer science is interdisciplinary.
– Polymer science cuts across the traditional lines of chemistry, physics, engineering,
biology and nanotechnology.
• Applications: Packaging, Sports, Infrastructure, Automobile, Defense, Semiconductors, Nano- &
Bio-technology.

1.2 Definition and nomenclature

1.2.1 Basic Terminology
• Poly (Greek):
• Mer (Greek):
• Monomer:
• Polymer: Large molecules built up by repetitive bonding together of monomers.
• Repeating unit: the structural unit enclosed by brackets or parentheses.
• Structural unit: the residue from monomer employed in the preparation of a polymer.
• Base unit: the smallest possible repeating unit.
• It is more conventional to define repeating unit in terms of monomer structure.

3
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

• The conversion of the monomer to the polymer involves a rearrangement of electrons.

• End groups: the structural units that terminate polymer chain (or backbone).
• End groups are usually shown outside the bracket.

Oligomer

• Oligomer: low-molecular-weight (< 10 DP) polymer (Greek oligos, “few”)

• For example: dimer, trimer, tetramer, etc.
• Polymer vs. Oligomer: Thermal and Mechanical properties.
• E.g. At room temperature, oligomeric styrene (DP = 7) is a viscous liquid while polystyrene (DP =
1000) is brittle solid that does not soften until it is heated to above approximately 100oC.

1.2.2 Degree of Polymerization (DP)

• Degree of polymerization: the total number of structural units, including end groups.
• Example: CH3CH2-[CH2CH2]98-CH=CH2, DP =
• Average DP is normally referred because polymer chains within a given polymer sample are
almost always of varying lengths.
• DP is related to chain length and molecular weight.
• The molecular weight of a polymer is the product of DP and the molecular weight of repeating
unit. MW (Polymer) = DP × MW (Repeating Unit)
• Example: If average DP = 500, what is the molecular weight of poly(vinyl acetate) or PVA?MW
(PVA) = DP x MW(VA)=

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.

4
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

• IUPAC recommends source-based names for copolymers.

• Two types: Systematic and Concise
• Terpolymer: denote a copolymer prepared from 3 difference monomers.
• Co is used if no distribution of the monomeric repeating unit is specified.
• Ran is used if the distribution is completely random.
• Stat is used of the distribution follows some specified statistical distribution.
• With graft copolymers, the order of monomer names is important.
Systematic Concise
Poly[styrene-co-(methyl methacrylate)] Copoly(styrene/methyl methacrylate)

Poly[styrene-alt-(methyl methacrylate)] Alt-copoly(styrene/methyl methacrylate)

Polystyrene-block-poly(methyl methacrylate) Block-copoly(styrene/methyl methacrylate)

Polystyrene-graft-poly(methyl methacrylate) Graft-copoly(styrene/methyl methacrylate)

Polystyrene-block-polyisoprene-block-
Block-copoly(styrene/isoprene/styrene)
polystyrene

Polybutadiene-block-(polystyrene-graft- Block-copoly[butandiene/graft-
polyacrylonitrile) co(styrene/acrylonitrile)]

5
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

1.3 Classification of Polymers

1.3.1 Natural vs. Synthetic
• Polymers may either be naturally occurring or purely synthetic.
• Enzymes, nucleic acids and proteins are polymers of biological origin. Their structures are
normally very complex.
• Starch, cellulose and natural rubber are examples of plant origin and have relatively simpler
structure than those of enzymes or proteins.
• On the other hand, there are a large number of synthetic (man-made) polymers consisting of
various families: fibers, elastomers, plastics, adhesives, etc.

1.3.2 Homopolymer vs. Copolymer

• Polymers may be either homopolymers or copolymers depending on the composition.
• Polymers composed of only one repeating unit in the polymer molecules are known as
homopolymers.

• 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

Block Copolymer Graft Copolymer

6
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

• Random Copolymer: the repeating units are distributed randomly.

• Alternating Copolymer: the repeating units are distributed in alternating fashion, i.e. the ratio of
each repeating unit is 1:1.

• 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.

7
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

1.3.3 Vinyl vs. Non-vinyl polymers

Vinyl Polymer

• Polymers derived from monomers containing carbon-carbon double bonds are often referred to
vinylpolymer.

8
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

Non-Vinyl Polymer (for self-reading)

• Nomenclature of nonvinyl polymers is much more complicated due to the great variety of
possible repeating units.
• Three common commercial polymer types.
o Polyethers: oxy denotes oxygen (–CO– ) atom.
o Polyesters: oxo denotes the carbonyl oxygen group.
o Polyamides: imino denotes the –NH– group.

9
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

1.3.4 Thermal Behavior: Thermoset vs. Thermoplastic

• 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

10
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

• 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.

Thermoplastic Examples (for self-reading)

Thermosets Examples (For self-reading)

11
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

1.3.5 Polymerization Mechanism

• Traditionally, Wallace Carothers first proposed to classify polymer into two main groups
according to the mechanism of polymerization, i.e. condensation and addition polymers.
• Addition polymers are produced by reactions in which monomers are added one after another
to a rapidly growing chain. Monomers generally employed in addition polymerization are
unsaturated (usually with carbon-carbon double bonds). Examples: PS, PP, PMMA and PVC.

• Ring-opening polymerization is traditionally recognized as belonging to addition class, which

involves a sterically strained cyclic monomer. Example: caprolactam to yield nylon 6, an
important textile fiber used for carpets.

• 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.

12
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

1.3.6 Polymer morphology: Amorphous vs. Crystalline

• In general, two morphologies: amorphous and crystalline.
• Amorphous: completely lack of order among the molecules.
• Crystalline: molecules are orientated, or aligned, in a regular array.
• As no polymer achieve 100% crystallinity, semicrystalline is used to refer to polymers that are
partially crystalline.

Crystallinity

• The degree of crystallinity (%) is referred to % of the material that is crystalline,

• Annealing process leads the growth of crystalline regions, i.e. % crystallinity increases.
• The crystallization process depends on (a) easiness of polymer to packing into the crystalline
state; (b) secondary attractive force of the polymer chain.
• Packing is facilitated for polymer chains that have structural regularity (e.g. linear structure),
compactness and some degree of flexibility.
• The stronger the secondary attractive force, the greater the driving force for the ordering and
crystallization of polymer chains.
• For example, polyethylene (PE) has essentially the flexibility structure in terms of its ability to
pack into the crystalline state.
• It’s very simple and perfectly regular structure allows chains to pack tightly.
• The flexibility of PE chains is also conducive to crystallization in that the conformations required
for packing can be easily achieved.
• Despite of its small secondary attractive forces, PE crystallizes easily to a high degree of
crystallization.
• Polymers such PMMA, PVC and PS show very poor crystallization tendencies.
• Loss of structural simplicity compared to PE means a lower degree of crystallization.

PMMA PVC PS

• Nevertheless, fluorocarbon polymers (such as poly(vinyl fluoride), poly(vinylidene fluoride), and

polytetrafluoroethylene) show considerable crystallinity because the small size of fluorine does
not preclude packing into a crystal lattice.
• Besides, the crystallization is also aided by the high secondary attractive forces.

13
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

Effects of Crystallinity on Polymer Properties

• Rigid, tightly packed and large secondary bonds.

• Higher degree of crystallinity leads to stiffer, harder, stronger but lesser impact resistance.

• For example: HDPE versus LDPE

High Density PE Low Density PE

• Linear polymer, containing few short
chain branches.
• Regular arrangement.
• Have tighter packing of the chains in 3D.
• Higher degree of crystallinity.
• Contains significant number of short chain
branches.
• Random locations and varying lengths of
the branches prevent regular packing
• Lower degree of crystallinity.

Effects of Crystallinity on Polymer Transparency

• 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.

14
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

1.3.7 Polymer Structure: Linear/branch/cross-link

• Linear: a chain that is made up of identical units (except for the end groups) arranged in a linear
sequence.
• Branched: graft copolymers are examples of branched polymer.
• Network (Crosslinked): crosslink density related to “hardness”.

Linear Branched Crosslinked

• 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

15
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

Examples: Is the resulting polymer linear or branched/cross-linked?

(i)

(ii)

1.4 Molecular Weight

• Polymer MW is important because it determines many physical properties. Examples: Glass
transition temperature, mechanical properties such as stiffness, strength, viscoelasticity,
toughness and viscosity.
• If MW is too low, the Tg and mechanical properties are generally too low for the polymer
material to have any useful commercial applications.
• If MW is too high, the process condition will be difficult due to high viscosity of polymer.

Dependence of Mechanical Strength on Polymer MW

16
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

• 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

• Tg follows a peculiar pattern with increasing MW.

• Tgof small MW is low, and then increases sharply as the chains grow to intermediate size
(oligomers) until a saturated value when the chains are long enough to be polymers.

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.

17
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

1.4.1 Average Molecular Weight

• A typical synthetic polymer sample contains chains with a wide distribution of chain length. This
means that a distribution of molecular weight exists for synthetic polymers.

•
• 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.

1.4.2 Number-average Molecular Weight

• Number-average MW of a polymer is determined by measurement methods that depend on
end-group analysis or colligative properties (e.g. freezing-point depression, boiling-point
elevation, and ostomic pressure) because the numbers of molecules of each weight in the
sample are counted.
• This is defined by:

• Where Ni is the number of molecules or the number of moles of those molecules having
molecular weight Mi.

1.4.3 Weight-average Molecular Weight

• Weight-average MW is determined by the measurement methods that depend on the mass or
polarizability of the sample (e.g. ultracentrifugation and light scattering).
• The greater the mass, the greater is the contribution to the measurement.
• It is expressed mathematically as

• Where Wi = NiMi.

18
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
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.

1.4.4 Polydispersity Index (PDI)

• Note that the weight-average MW is always larger than the number-average MW.
• The ratio of the weight-average MW to the number-average MW is known as polydispersity
index (PDI).
• PDI provides a rough indication of the breath of the distribution. PDI ≥ 1.
• If PDI = 1, all polymer molecules present have the same MW (e.g. protein) and the system is
called as monodisperse.
• The weight-average is probably the most useful because it fairly accounts for the contributions
of different sized chains to the overall behavior of the polymer and correlates best with most of
the physical properties of interest.

19
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

1.5 Polymer Stereochemistry

1.5.1 Constitutional Isomerism
• Constitutional isomerism is encountered when polymers have the same overall chemical
composition (i.e. same molecular formula) but differ in connectivity(i.e. the order in which the
atoms are connected to each other).
• Examples: Polyacetaldehyde, poly(ethylene oxide) and poly(vinyl alcohol) are constitutional
isomers.

• Example: Poly(methyl methacrylate) and poly(ethyl acrylate) are constitutional isomeric

polymers formed from isomeric monomers.

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.

20
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

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.

21
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

• Commercial polypropylene is an important example of an isotactic polymer. Its regular structure

is crystalline (~65%) and give rise to the good mechanical properties. In contrast, atactic PP is
unable to crystallize because of its irregular structure and is a soft, wax-like amorphous material
which has no useful mechanical properties.

Di-substituted Ethylenes

1,1-Disubstituted Ethylenes 1,2-Disubstitued Ethylenes

1,1-Disubstituted Ethylenes

• In the polymerization of 1,1-disubstituted ethylenes, CH2=CRR’, stereoisomerism does not exist

if the R and R’ groups are the same (e.g. Isobutylene and vinylidene chloride)

• 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.

22
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

1,2-Disubstituted Ethylene (for self-reading)

• 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.

23
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

1.5.3 Geometric Isomerism

• Geometric isomerism (also known as cis-trans isomerism) is a form of stereoisomerism.
• trans: from latin meaning "across".
• cis: from latin meaning "on this side".
• Cis-trans isomers arise from different configurations of substituents on a double bond
(polydiene) or on a cyclic structure.
• Polydienes are synthesized from conjugated diene: CH2=CX-CH=CH2.
• If X = H, CH3, or Cl, we have butadiene, isoprene and chloroprene, respectively.
• Natural rubber is a particular geometric isomer of poly(isoprene), i.e.cis-1,4-poly(isoprene).

Monomer: 1,3-butadiene (X = H)

• The carbon atoms of monomer are labeled.

• One of the double bonds are broken and the carbon atoms attached by a single bond with
“unshared” electron. Same for the other double bond.
• The two “unshared” electrons in the middle form a new double bond, leaving “unshared”
electrons hang out on carbon atoms 1 and 4.
• Two such unit can attached via the carbon atoms 1 and 4.
• The chain can be formed continuously by “breaking” double bonds (1-2 or 3-4) and incorporating
new unit into the chain.
• Conjugated dienes 1,3-butadiene undergo both 1,2- and 1,4-addition.
• 1,2-addition gives polymer with pendant vinyl groups.
• 1,4-addition gives polymer with unsaturation in the chain. Both cis and trans configurations are
possible.

Poly(1,2-butadiene) Poly(cis-1,4-butadiene) Poly(trans-1,4-butadiene)

24
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

Monomer: Isoprene (X = CH3)

Effects of Geometric Isomerism: Polymerization (Free-radical)

Polymer Structure (%)

Monomer T (oC)
Cis 1,4 Trans 1,4 1,2 3,4
-20 6 77 17
1,3- 20 22 58 20
Butadiene 100 28 51 21
233 43 39 18
-20 1 90 5 4
10 11 79 5 5
Isoprene
100 23 66 5 6
203 19 69 3 9
-40 1 97 1 1
Chloroprene 20 3 93 2 2
90 8 85 3 4
• For 1,3-butadiene, both 1,2- and 3,4- polymerization yield the same polymer for the symmetric
1,3-butadiene.
• 1,4-polymerization is more preferable to 1,2- or 3,4- polymerization.
• The predominance of 1,4-propagation over 1,2-propagation is primarily a result of the lower steric
hindrance at carbon atom 4 relative to carbon atom 2 for bonding to an incoming monomer
molecule.
• The difference becomes more significant in the polymerization of substituted such as isoprene
and chloroprene.
• Besides, 1,4 polymer (1,2-disubstituted alkene) is generally more stable than the 1,2 polymer (a
monosubstituted alkene).
• Furthermore, trans-1,4-polymerization occurs in preference to cis-1,4-polymerization.
• In general, the trans-1,4-polymer is more stable than cis-1,4-polymer.
• The configuration of the last monomer unit in the propagating chain is determined (with
transfavored over cis) when the next monomer unit adds.
• As the polymerization temperature increases, the amount of cis-1,4 increases proportionately,
but the yield of 1,2-/3,4- remains about the same.

25
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela
UEMT 2123 Topic 1: Introduction

Effects of Geometric Isomerism

Polymer Isomer Tg (oC) Tm (oC)

Cis -95 6
1,4-Polybutadiene
Trans -83 145
Cis -73 28
1,4-Polyisoprene
Trans -58 74
• Stereoisomerism in 1,4-poly-1,3-dienes results in significant difference in the properties of the cis
and trans polymers.
• Thetrans isomer crystalline to a greater extent and thus higher molecular symmetry and higher Tg
and Tm.
• The difference in the cis and trans polymers leads to major difference in their applications.
• Since cis-1,4-polyisoprene has very low crystallinity, low Tg and Tm, it is an excellent elastomer
over a considerable temperature range.
• About 2 billion pounds per year of cis-1,4-polyisoprene are used in U.S. for tires, footwear, gloves,
molded object, adhesives, rubber bands and other typical elastomer applications.
• Since trans-1,4-polyisoprene is a much harder and much less rubbery polymer, it has good
resistance to abrasion and is used in golf-ball covers and orthopedic devices.

26
“Education is the most powerful weapon which you can use to change the world.” – Nelson Mandela