Chapter 1

Basics of Polymer Chemistry

What do you know about polymers?!

Why do we need to learn polymer

chemistry?!

• The global polymers market size was reached at USD 713.9 billion in
2021.
• It is expected to reach around USD 1078.5 billion by the end of 2030

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Polymers are EVERYWHERE

Look at your shoes

• Almost every shoe is made from some sort of polymer.
Many are made from leather, which is one of many
natural polymers

• The running (sport) shoe has panels made of leather,

and also of nylon. The sole is made out of a rubber
called SBS rubber.
• A lot of the same stuff goes into hiking boots,
including insole padding made from polyurethane
foam.
• Shoe laces are made from stuff like nylon and cotton.
Cotton is a form of another natural polymer called cellulose.

• Socks are made from polymers like cotton, and

synthetic polymers like polyester and nylon
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Polymers are EVERYWHERE

Electronics
• Polymers tend to be good insulators.
All cables should be insulated with polymers like
polyethylene or poly(vinyl chloride) PVC.

• For wires that get really hot we use insulation made

from a fireproof polymer called poly(vinylidene
fluoride).

• The circuit boards are made of epoxy resins.

These piezoelectric tweeters contain poly(vinylidiene
fluoride).
Poly(vinylidene fluoride) is good for use in tweeters
because it will change its shape when you put it in an
electric field. An alternating field makes it vibrate, and the
vibration can be made to produce sound.

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Polymers are EVERYWHERE

Eyeglasses and contact lenses

• In the old days, eyeglasses were made of glass. But for some
people with really bad eyesight, glass lenses would just be too
thick and heavy. Also glass are breakable.
• Nowadays eyeglasses are often made of a special kind of
polycarbonate that is a lot lighter than glass. Also it has a higher
refractive index, so really strong lenses don't have to be nearly
so thick. Lenses can also be made of poly(methyl methacrylate)
(PMMA).
• There are also polymers in contact lenses.
A long time ago people wore hard contact lenses that
were made of poly(methyl methacrylate) (PMMA).
Nowadays much more comfortable soft contact lenses
made from polyacrylamides and other soft and flexible
polymers are available.

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Polymers are EVERYWHERE

Clothes
• The polymers in clothes can come from plant
materials, synthetics, or even proteins like silk and
wool.
• The one thing that most of the polymers in clothes
have in common is that they are fibers.
• Blue jeans and t-shirts are made of cotton, which is mostly cellulose.

• Sweaters like these can be made from wool, which is a

protein called keratin. So is your hair and fingernails, by
the way. Sweaters can also be made out of acrylics, like
polyacrylonitrile or Rayon.

SpandexTM is a special kind of polyurethane that's very stretchy.

SpandexTM is also used in bicycle pants, swimsuits, and other items of
stretchwear. While it is very stretchy, it's also very tough.

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Polymers are EVERYWHERE

Auto parts
• A lot of auto body parts are made out of polymer
like acrylonitrile-butadiene-styrene plastic, called
ABS.
• ABS plastic makes cars: lighter so they use less gas
and pollute less.

• The tread of the tires is made from random

copolymers of styrene and butadiene. The sidewalls
are made of another rubber called polyisoprene.
And the inner liner is made of another kind of rubber
called polyisobutylene.

• The windshield wiper and its blade is made

from a rubber called polyisoprene.
• This air filter is made mostly of heavy paper, which is made
of a natural polymer called cellulose. The black parts are
made of polymers like poly(vinyl chloride).
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Course Outline
• Basics:
- Definition and nomenclature, degree of polymerization, and classification of
polymers
• Polymerization:
- Addition polymerization, step-growth polymerization and copolymerization
- Polymerization in homogeneous and heterogeneous systems
• Molecular weight and molecular weight distribution (polydispersity)
• Natural polymers
• Polymer structure and physical properties
- Microscopic features of bulk polymers, properties of common polymers in bulk
• Degradation and recycling
• Future of polymer science

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Introduction
• Polymers are a large class of materials consisting of many
small molecules (called monomers) that can be linked
together to form long chains.

• Typical polymer may include tens of thousands of

monomers.

• Because of their large size, polymers are classified as

Macromolecules.

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 • Polymers are high molecular mass compounds formed by
polymerization of monomers

ethylene

polyethylene

• The long chain nature sets polymers apart from other

materials and gives rise to their characteristic properties.
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Polymer Classification
• There are a number of methods of classifying polymers. Based on:
Origin of source, Monomer, Structure of the polymer Chain, Polymerization mechanism , Response
to thermal treatment (molecular forces)

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Classification based on chain structure

Skeletal Structure
I. Linear polymers are represented
linear
by a chain with two ends.

II. Cyclic polymers (ring polymers)

have no chain ends and show
cyclic
properties that are quite different
to their linear counterparts.

III. Branched polymers have side chains, or

branches, of significant length which are
bonded to the main chain at branch
points (junction points), and are
characterized in terms of the number and
size of the branches. branched
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Classification based on chain structure
IV. Network polymers (crosslinked) have three dimensional
structures in which each chain is connected to all others
by a sequence of junction points and other chains.

• Crosslinked polymers are characterized by

their crosslink density, or degree of
crosslinking, which is related directly to
the number of junction points per unit
volume. Network
• Branched and network polymers may be
formed by polymerization, or can be
prepared by crosslinking pre- existing
chains.

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Classification based on chain structure

Is the skeletal structure important?

1. Linear polyethylene has a melting point about 20 °C higher than
that of branched polyethylene.

2. Network polymers do not melt upon heating and will not

dissolve.

3. The importance of crosslink density has already been

described in terms of the vulcanization (i.e. sulphur-
crosslinking) of natural rubber. With low crosslink densities
(i.e. low levels of sulphur) the product is a flexible elastomer,
whereas it is a rigid material when the crosslink density is high. 14
Classification based on Monomer

I. Homopolymers
• A Homopolymer is a polymer derived from one
species of monomer
〰 A–A–A–A–A–A–A–A〰

• − A ! − where n is the number of repeat units

linked together to form the macromolecule.

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Classification based on Monomer

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Classification based on Monomer

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Classification based on Monomer

II. Copolymers
• A Copolymer is a polymer derived from more than
one species of monomer.
• Copolymer more commonly is used to describe
polymers whose molecules contain two or more
different types of repeat unit

~A–B–A–A–B–B–A–A 〰

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Classification based on Monomer

Categories of copolymer
1. Random copolymers:
the distribution of repeat units is truly random
〰 B−B−B−A−B−B−A−B−A−A〰

2. Alternating copolymers:
have only two different types of repeat units and these are
arranged alternately along the polymer chain
~A−B−A−B−A−B−A−B−A−B〰

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Classification based on Monomer

3. Block copolymers:

are linear copolymers in which the repeat units exist only in

long sequences, or blocks, of the same type.

A −A−A−A−A−A−A−A−A−A−B−B−B−B−B−B−B−B−B−B
AB di-block copolymer
A−A−A−A−A−A−A−A−B−B−B−B−B−B−B−B−A−A−A−A−A−A−A−A
ABA tri-block copolymers

20
Classification based on Monomer

4. Graft copolymers

are branched polymers in which the branches have a different

chemical structure to that of the main chain.
B−B−B−B−B−B−B−B−B−B
B
A−A−A−A−A−A−A−A−A−A−A−A−A−A−A−A−A−A−A
B
B−B−B−B−B−B−B

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Classification based on Monomer

Nomenclature of Copolymers

a The example is for polyB branches on a polyA main chain

22
Classification based on their response to thermal treatment
(molecular forces)

23
 Thermoplastics

• Polymer chains in a thermoplastic are held together by

relatively weak intermolecular forces so that the material
softens when exposed to heat and then returns to its original
condition when cooled.
• Most linear and slightly branched polymers are
thermoplastic.
• They can be moulded (and remoulded) into any shape
using processing techniques such as injection moulding
and extrusion.

24
• Amorphous polymers (and amorphous phases of semi-
crystalline polymers) are characterized by their glass
transition temperature Tg.

• Tg: the temperature at which they transform abruptly from

the glassy state (hard) to the rubbery state (soft).

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 Elastomers
• Are crosslinked rubbery polymers (i.e. rubbery
networks) that can be stretched easily to high
extensions (e.g. 3× to 10× their original dimensions)
and which rapidly recover their original dimensions
when the applied stress is released.
• This property is a reflection of their molecular
structure in which the network is of low crosslink
density. The rubbery polymer chains become extended
upon deformation but are prevented from permanent
flow by the crosslinks and driven by entropy.
• The word rubber, often used in place of
elastomer. (A) is an unstressed polymer;
(B) is the same polymer under
stress.
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 Thermosets
• Are rigid materials and are network polymers in which chain
motion is greatly restricted by a high degree of crosslinking.
• They cannot be reshaped by heating
• As for elastomers, they are intractable once formed and degrade
rather than become fluid upon the application of heat.
• Their processing into artefacts is often done using processes, such
as compression moulding, that require minimum amounts of
flow.

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Polymer classes and recycling

28
Polymer Nomenclature
1. Common Names
• Names are derived from the place of origin of the material, after their
discoverer or special names and systems of nomenclature were
invented.
• Examples:
ü Hevea brasiliensis—literally “rubber from Brazil”—for natural
rubber.
ü Bakelite, the three-dimensional polymer produced by condensation of
phenol and formaldehyde, which was commercialized by Leo Baekeland
in 1905.
ü Nylons were named according to the number of carbons in the diamine
and carboxylic acid reactants (monomers) used in their syntheses.

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 2. Source-based Names

Based on the common name of the reactant monomer, preceded by

the prefix “poly”

Monomer: 1-phenylethene,
which has the common
name styrene

Most polymers based on the vinyl group (CH2=CHX) or the vinylidene

(CH2=CX2) as the repeat unit are known by their source-based names.

Examples:
o polyethylene is derived from the monomer ethylene
o poly(vinyl chloride) from the monomer vinyl chloride
o poly(methyl methacrylate) from methyl methacrylate
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Many condensation polymers are also named in this manner.
Example: poly(ethylene terephthalate)

Source-based names are conveniently used to describe copolymers

by using an appropriate term between the names of the
monomers.
Example:
An unspecified copolymer of styrene and methyl methacrylate
would be called poly(styrene-co-methyl methacrylate).

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3. Structure-based Names
• The IUPAC system names the components of the repeat unit,
arranged in a prescribed order.

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33
4. Linkage-based Names
• Many polymer “families” are referred to by the name of the
particular linkage that connects the polymers.

34
Trade Names, Brand Names, and abbreviations

They may be used to identify the product of a manufacturer, processor or

fabricator and may be associated with a particular product or with a material
or modified material

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Average Molar mass and Degree of
Polymerization

• Many properties of polymers show a strong

dependence upon the size of the polymer chains, so
it is essential to characterize their dimensions.

• The molar mass M of a polymer which is simply the

mass of 1 mol of the polymer and usually is quoted in
units of g mol−1 or kg mol−1.

36
Degree of Polymerization
• The degree of polymerization (DP or n) in a polymer
molecule is the number, n, of (repeat) repeating
units in the polymer chain.
− A!−
• The relation between (DP or n) and molar mass:
" = #"$
• where "$ is the molar mass of the repeat unit

37
 • For copolymers,
• For copolymers, but ! " needs to be replaced
but 𝑀𝑜 needs to be replaced by by
#"$
, which is the mean repeat unit molar mass of
𝑀0 !0, which
𝑐𝑜𝑝
is the mean repeat unit molar mass of
the copolymer taking into account its composition.
the copolymer taking into account its composition.

𝑐𝑜𝑝
𝑀0 = ෍ 𝑋𝑖 𝑀𝑜𝑖
Where
Where
and &
% & 𝑖 ! " are the mole fraction and molar mass of
𝑋𝑖 and 𝑀𝑜 are the mole fraction and molar mass of
of repeating unit of type & in the copolymer.
of repeating unit of type 𝑖 in the copolymer.

38
38
• Example: a particular polyethylene molecule with
DP=1000 will have a molecular weight of 28,000.

• Polymeric materials do not consist of strictly identical

molecules, but instead are a mixture of many species
having different values of DP, the DP of the material
only is an average value, !".

39
Average Molar Mass
• The molar mass of polymers are much larger than
the small molecules usually encountered in organic
chemistry.

• Most chain reaction and step reaction

polymerizations produce chains with many
different lengths, so polymers also differ from small
molecules in that the polymer molar masses are
average values.

40
• Unless they have been purified, synthetic
polymers have a distribution of molar mass.

• Two of the most important are the number-

average and the weight-average molar masses.

41
Typical weight-fraction molar mass distribution curve
42
Number-Average Molar
Number-Average Molar
Molar Mass
Mass Mass
Number-Average
• The number-average molar mass !":
•• The
Thenumber-average
number-averagemolar
molarmass
mass𝑀 𝑀𝑛𝑛::
is defined as the sum of the products of the molar mass
isisdefined
defined
of eachasas thesum
sum
fraction
the ofthe
theproducts
products
multiplied
of ofthe
by its mole
of the molarmass
fraction
molar mass
ofofeach
eachfraction
fractionmultiplied
multipliedby
byits
itsmole
molefraction
fraction
𝑀𝑛𝑛 ==෍
𝑀 ෍𝑋𝑋𝑖𝑖𝑀
𝑀𝑖𝑖

Where
Where
Where 𝑋𝑋𝑖 𝑖is#
istheis the
$the mole
mole mole fraction
fraction
fraction of molecules
ofmolecules
of molecules of
ofmolar
of molar
molar
mass
mass
mass 𝑀 !
𝑀𝑖 𝑖and
and $ and is given
isisgiven
given by
thethe
bythe
by ratio
ratio
ratio of𝑁of
of %
𝑁𝑖𝑖 to to
thethe
to$ the total
total
total
number
number
number of molecules.
ofmolecules.
of molecules.

σσ𝑁𝑁𝑖𝑖𝑀
𝑀𝑖𝑖
𝑀𝑛𝑛 ==
𝑀
σσ𝑁𝑁𝑖𝑖
43
43
43
Weight-Average
Weight-Average Molar Mass Mass
Molar
Weight-Average Molar Mass
• The weight fraction ! " is defined as
• The weight fraction 𝑤𝑖 is defined as the mass of the mass of
molecules
• molecules
The of molar
weightoffraction 𝑤
molar massmass
is #
defined" divided
as theby
𝑖 𝑀𝑖 divided by the total
the
mass total
of
mass of
molecules all
of the molecules
molar mass 𝑀
mass of all the molecules present. present.
𝑖 divided by the total
mass of all the molecules𝑁present.
𝑖 𝑀𝑖
𝑤𝑖 = 𝑁𝑖 𝑀𝑖
𝑤𝑖 = σ 𝑁𝑖 𝑀𝑖
σ 𝑁𝑖 𝑀𝑖
• The
• Theweight-average
weight-average molar
molar massmass𝑀#𝑤!is isdefined
definedasas
• the
Thesum
weight-average
of the molar
products of mass
the 𝑀𝑤 ismass
molar defined
of as
each
the sum of the products of the molar mass of each
the summultiplied
fraction of the products
by its of the molar
weight mass of each
fraction
fraction multiplied by its weight fraction
fraction multiplied by its weight fraction
𝑀𝑤 = ෍ 𝑤𝑖 𝑀𝑖
𝑀𝑤 = ෍ 𝑤𝑖 𝑀𝑖
44
44
44
 Theweight-average
••The weight-averagemolar
molarmass
massformula
formulaisisgiven
givenby:
by:

σ 𝑁𝑖 𝑀𝑖2
𝑀𝑤 =
σ 𝑁𝑖 𝑀𝑖

4545
 Polydispersity
Polydispersity IndexIndex
𝑀𝑤
𝑃𝐷𝐼 =
𝑀𝑛

• polydispersity
• polydispersity or heterogeneity
or heterogeneity index
index (often
(often referred
referred
to as toPDI).
as PDI).
Its value
• Its• value often
often is used
is used as aasmeasure
a measure of the
of the breadth
breadth of of
the the molar
molar mass mass distribution.
distribution.
• Typically
• Typically 𝑃𝐷𝐼!"#is inisthe
in range
the range 1.5−2.0,
1.5−2.0, though
though there are
many there are which
polymers many
havepolymers which
smaller or veryhave
muchsmaller
larger or
valuesveryofmuch larger
polydispersity values of polydispersity index.
index.
A perfectly
• A •perfectly monodisperse
monodisperse polymer
polymer would
would have
have 𝑃𝐷𝐼!"#= =
1.00. 1.00.

46 46
Degree
Degreeofofpolymerization averages
polymerization averages
• Degree
• Degreeofof
polymerization averages
polymerization averages areare
of of
more
moreimportance
importance
than molar
than molarmass
massaverages in in
averages thethe
theoretical
theoreticaltreatment
treatment of of
polymers
polymersand polymerization.
and polymerization.
• For homopolymers
• For homopolymers they may
they may bebe
obtained
obtainedsimply
simplybyby
dividing
dividing
the corresponding
the correspondingmolar mass
molar mass average
average byby
!"𝑀: 𝑜:

𝑀𝑛 𝑀𝑤
𝑥𝑛 = , 𝑥𝑤 =
𝑀𝑜 𝑀𝑜

The
Thesame
sameequations
equationscan bebe
can applied toto
applied calculate #$𝑥and
calculate #%𝑥for
𝑛 and 𝑤 for
&"'
copolymers
copolymersbybyreplacing
replacing!𝑀" 𝑜with
with!
0𝑀0
𝑐𝑜𝑝

47
47
Question

48