INTRODUCTION TO POLYMERS

The term polymer is made from greek word, ‘poly’ meaning “many” and ‘meros’ meaning parts
of “units”.

Polymers are macromolecules having molecular weights of the order of thousands and are
formed by linking small molecular units together by chemical bonds.

Ex: Polyethylene
nCH2=CH2 [ CH2-CH2 ] n

Monomers: Ethylene Polyethylene

(monomer) (polymer)

Small molecules that combine with each other to form polymer molecules are called monomers
and the molecular unit that repeats itself in a polymer chain is called the repeating unit.

CH2=CH [ CH2-CH ] n

Cl Cl
Vinylchloride Polyvinl chloride Repeating unit
(Monomer)

Functionality:

Functionality means the number of bonding sites in a monomer or the number of reactive sites in
a monomer.
For a molecule to act as a monomer, it should have atleast two reactive sites.

1. Functionality due to presence of double or triple bonds:

In the case of vinyl monomers (CH2=CH), if the double bond is broken, two single bonds
become available for combination.
X

Thus the functionality of ethylene or other vinyl monomers is two i.e., they are bifunctional.

 0 0 0 0
CH2 CH2 CH2 CH2
CH2 CH2



In the case of acetylene (CH≡CH), it has two double bond, so four single bonds are available, it
has a functionality of 4., i.e acetylene is tetrafunctional.
 
 0
0
CH CH CH CH
0 0


2. Functionality due to presence of functional groups: Compounds having reactive functional
groups like –OH, -COOH, -NH2, -SH, -NCO etc also undergo polymerisation and the number of
such groups in the compound is defined as its functionality.

Malonic acid HOOC-CH2-COOH bifunctional

Acetic acid CH3COOH monofunctional

Hexamethylene diamine H2N-(CH2)6-NH2 bifunctional

CH2 CH2

Ethylene glycol OH OH bifunctional

CH2 CH CH2

Glycerol OH OH OH trifunctional

Caproic acid H2N -CH2-COOH bifunctional

Monomers having functionality two or above only can undergo polymerisation. But in the above
examples, hexamethylene diamine cannot undergo self polymerisation. Caproic acid undergoes
self polymerisation.

3. Functionality due to presence of easily replaceable hydrogen atoms: In some compounds,

the presence of easily replaceable hydrogen atoms imparts functionality.
OH

OH H H

Phenol has three replaceable hydrogen and so it is trifunctional.

SIGNIFICANCE OF FUNCTIONALITY:

Functionality is an important factor that decides the structure of a polymer.

1. In the case of a bifunctional monomer, two reactive groups attach side by side to each other
forming a linear or a straight chain molecule and they are held together by strong covalent bond
forces. The different chains are held together by vander Waals forces. This makes the chains slide
each other, such type of polymers have less strength, low heat resistance and soft and flexible.

Vander Waals forces(secondary forces) strong covalent bond(primary forces)

Thus linear chain molecules are formed from bifunctional monomer.

2. When a trifunctional monomer is mixed in small amounts with a bifunctional monomer and
polymerized branched chain polymers are formed. They are also linear but the movement in
branched chain molecules are restricted than that of simple straight chain molecules.

3. In case of polyfunctional groups, all monomer molecules are connected to each other by
covalent bonds resulting in the formation of a three dimensional network. In such polymeric
molecule the movement of individual molecules is prevented by strong crosslinks.

Polymers formed by trifunctional molecules have high strength, hardness, toughness, heat
resistance and insoluble in almost all organic solvents. Thus functionality decides whether the
polymer will be linear, branched or networked.
Examples of some monomers and polymers:
S.NO Monomers Polymers
1. n H2C CH2 CH2 CH2
n
Ethylene
Polyethylene (PE)
n CH2 CH CH2 CH
n
2. CH3
CH3
Polypropylene(PP)
Propylene
n CH2 CH CH2 CH
3.
Cl n
Cl
Vinyl chloride Polyvinylchloride(PVC)
n CH2 CH CH2 CH
4. COOH n
COOH
Acrylic acid
Polyacrylic acid (PAc)
5. n CH2 CH CH2 CH
OH n
Vinyl alcohol OH
Polyvinylalcohol (PVA)
6. n CH2 CH CH2 CH
n
COOCH3 COOCH3
Methyl acrylate Polymethacrylate (PMA)
7. CH3 CH3

n CH2 C CH2 C
n
COOCH 3
COOCH 3
Methylmethacrylate Polymethylmethacrylate (PMMA)
8. n CH2 CH CH2 CH
CN n
CN
Vinyl cyanide/acrylonitrile
Polyacrylonitrile (PAN)
9. n CH2 CH CH2 CH
n
C6H5 C6H5
Styrene Polystyrene (PS)
10. CH2 CH CH2 CH2 CH2 CH CH2 CH2
Butadiene n
Polybutadiene
11. CH3 CH3

CH2 CH CH2 CH C CH2

C CH2
n
Isoprene Polyisoprene
CLASSIFICATION OF POLYMERS

1. Based on nature of main chain: The polymers are broadly classified as organic and
inorganic polymers.
(i) Organic polymers – contain carbon in their main chain.
Example: PE, PP, PS, nylon, polyester etc.,
(ii) Inorganic polymers – contain atoms other than carbon.
Example: silicones

Si O Si O Si

Further these two can be classified as homochain and heterochain polymers.

Homochain polymers:These are polymers containing the same elements throughout the
polymer chain. Example: Polystyrene

CH2 CH CH2 CH CH2 CH

n
C6H5 C6H5
C6H5

The main chain consist of carbon atoms only.

Heterochain polymers: If the main chain is made up of different elements then it is a

heterochain polymer

Example: Nylon 6,6

OC (CH2)4 CO NH (CH2)6 NH OC (CH2)4 CO NH (CH2)6 NH

Here, the main chain is made up of carbon and nitrogen.

2. Based on repeating unit: The polymers are classified as homopolymers and copolymers.
a. Homopolymers: If the polymer chain contains only one repeating unit, it is called as
homopolymer. Example: PE, PVC, Nylon 6,6, polyester etc.,
b. Copolymers : If a polymer contains more than one repeating unit we call it us copolymers.
In copolymerisation two or more monomers or monomer pairs are polymerised
simultaneously and hence, the polymer formed is composed of more than one repeating unit.
 Example: (i) Poly (acrylonitrile-co-vinyl chloride)
n CH2 CH n CH2 CH

Cl + CN

CH2 CH CH2 CH
n
CN Cl

Vinyl chloride acrylonitrile Poly (acrylonitrile-co-vinyl

chloride)

(ii)Styrene butadiene rubber (BuNa-S) , which is a copolymer of butadiene and styrene.

n CH2 CH CH2 CH CH CH2 CH2

C6H5 + CH2 CH CH2 CH2

Styrene butadiene Poly (butadiene-co styrene) rubber

Types of copolymers: Depending on the arrangement of monomer units in the chain, copolymers
are classified into the following types.

(i) Random copolymer: Monomer units are randomly distributed along the polymer chain. This
type of structure occurs in majority of commercially produced copolymers.
A B B A B A A B

(ii) Block copolymers: A block of one repeating unit followed by block of another repeating
unit.

A A A A B B B B
(iii) Graft copolymer: A chain formed by one kind of repeating unit is grafted on to a chain
containing another repeating unit.
A A A A A A A A

B
(iv) Alternate copolymer : The monomeric units are arranged in a regular alternating fashion.

A A B B A A

3. Based on their configuration:-

The arrangement of monomeric units in a polymer molecule is called as tacticity

and this can be in an orderly or disorderly fashion based on the polymers arc classified as atactic
, isotactic and syndiotactic
a) Isotactic:-

If the side groups present in the polymer chain are all arranged on the same side of the
chain, the polymer is said to be isotactic

H H H H H H H H H H H H

C C C C C C C C C C C C

H Cl H Cl H Cl H Cl H Cl H Cl

b) Syndiotatic:-

If the side groups are arranged alternatively above and below the chain, the polymer is
termed as syndiotactic

H H H Cl H H H Cl H H

C C C C C C C C C C

H Cl H H H Cl
H Cl H H

c) Atactic:-

If the side groups are arranged in a random fashion above or below the main chain, the
polymer is termed as atactic.

H H H Cl H H H H H H

C C C C C C C C C C

H Cl H Cl H Cl
H Cl H H

4. Based on thermal response:-

Based on the way they behave on heating, polymers are classified into two types namely,
thermoplastics and thermosetting plastics.

a) Thermoplastics:- Polymers which can be softened on heating and harden on cooling

reversibly. Repeated heating and cooling do not alter their chemical nature. Heating produces only
physical changes. On cooling they regain their original rigidity and hardness. Ex: PE, PP, PVC.,etc.
They can be recycled, reused, reclaimed from waste.

b) Thermosetting plastics:- Polymers which when heated get hardened and once they have
solidified, cannot be softened are called thermosetting resins or plastics. Such resins undergo cross-
linking during heating forming covalent bond. They are usually harder, stronger and more brittle
than the thermoplastics. They are infusible mass, so cannot be recycled, reused and reclaimed from
waste. Ex: urea-formaldehyde resins, phenol-formaldehyde resins, epoxy resins etc.,

Degree of polymerisation (Dp):

The number of repeating units found in a polymer chain is called the degree of polymerisation.

Molecular weight of the polymer

Dp=
Molecular weight of the repeating units

MOLECULAR WEIGHT OF POLYMERS

All the molecules of the polymer sample do not have identical molecular weight, hence polymers
are polydisperse. As there is spread in the molecular weight of the product, hence the molecular
weights are average.

Number average molecular weight 𝑀𝑛: It is defined as the total weight (W) of all molecules in a
polymer sample divided by the total number of moles present.
W Z𝑁𝑖𝑀𝑖
𝑀𝑛 = = Where Ni is the number of molecules of molecular weight Mi.
ZNi Z𝑁𝑖

Z𝑁𝑖𝑀𝑖2
Weight average molecular weight 𝑀w: It is defined by 𝑀𝑤 = , where Ni is the
Z𝑁𝑖𝑀𝑖
number of molecules of molecular weight Mi.
Molecular weight distribution: Index of polydispersity or polydispersity index (PDI) is used as
Mw
a measure of molecular weight distribution = .
Mn
In the case of monodisperse systems, PDI = 1, 𝑀w =𝑀𝑛 Ex: natural polymers and synthetic
polymers made by anionic polymerisation.
In the case of polydisperse systems PDI>1, 𝑀w > 𝑀𝑛 . this is for all synthetic polymers.

The dispersity with respect to the lowest to the highest molecular weight homologues is expressed
by a simple molecular weight distribution curve. Such a curve for a polymer sample is computed
by plotting the number fraction(ni) of molecules having a particular molecular weight (M i) against
the corresponding molecular weight.

ni

Mi
Mechanism of polymerisation

Polymerisation

Addition polymerisation Condensation polymerisation

Mechanism

Cationic
Free radical Ionic Coordination
Anionic

Mechanism of addition polymerisation: Addition polymerisation reaction involves three major

steps namely (i) Initiation (ii) Propogation (iii) Termination. Depending on the intiators used, the
mechanism can be free radical, ionic or coordination.

Free radical polymerisation:

Free radical initiators used; Compounds that undergo homolytic decomposition to give free
radicals when heated or exposed to light.
Ex 1.Peroxides Hydrogen peroxides ∆/
HO OH hʋ 2 HO°

Benzoyl peroxide C6H5 CO O O CO C6H5 ∆ 2 C6H5COO°

-CO2
2C6H5°

2. Azocompounds

Azobisisobutyronitrile

CN CN CN

CH3 C N N C CH3 2 CH3 C0 + N2

CH3 CH3 CH3

General mechaism of free radical polymerisation:

I Initiation:
(i) Decompostion of initiator;
R R
0
2R (highly reactive free radical)

(ii) Attack on monomer

R0 CH2 CH 0 0 0
+ R + 0
R CH2 CH
CH2 CH
X
X X

Free radical vinyl monomer First

monomer free radical

The free radical attacks the monomer and the free radical site is transferred on to the monomer.

II Propogation

Further addition of monomers

0
R CH2 CH + CH2 CH
0
R CH2 CH CH2 CH

X X X X

0
0
R CH2 CH CH2 R CH2 CH CH2 CH CH2 CH
CH + CH2 CH

X X X X X
X

0
R CH2 CH CH 2 CH
m
X X
The chain growth continues to give a polymer chain

III Termination: The growth of the polymer chain can be arrested or terminated by the
following ways that occur spontaneously.
a) By coupling: When two growing chains come close to each other, the polymer growth
can be arrested by coupling of the two chains.
 0 0
2 CH CH2 CH 2 CH2 R
CH + CH CH
R CH
m m
X
X X X

R CH2 CH CH2 CH CH CH2 CH CH2 R

m
X m
X X X
b) By disproportionation:

When two growing chains collide with each other one of the chain can abstract a hydrogen atom
from the other growing chain. The chain growth is arrested by the formation of two polymer chains
of shorter chain length

0 0
R CH2 CH CH2 CH CH CH CH CH2 R
+
m
X X X X

R CH2 CH CH2 CH2 + CH CH CH CH2 R

m
X X X
X

c) By chain transfer:
In this case a transfer reaction takes place by the abstraction of a hydrogen atom or some other
atom from the initiator, monomer or polymer or from any other species present in the system,
including the solvent or any impurity.
0 0
R CH2 CH CH 2 CH + R H R CH2 CH CH 2 CH2 + R
m m
X X X
X

However, in this case the growth of one polymer chain is arrested; there is a simultaneous
generation of a new free radical capable of initiating a fresh polymer chain growth.
 MORPHOLOGY OF POLYMERS – CRYSTALLINE AND AMORPHOUS STATES

The morphology of most polymers is semi-crystalline. That is, they form mixtures of small
crystals and amorphous material and melt over a range of temperature instead of at a single melting
point. There is now definite boundary between amorphous and crystalline regions of a polymer.
In the crystalline regions, the polymer chains fold and make lamellar structure arranged in
the regular manner and in amorphous regions, the chains are in the irregular randomly coiled
manner. The lamellae are embedded in the amorphous part. The density of crystalline component
is higher than that of amorphous component.
Polymers may be completely amorphous or partially crystalline with varying degree of
crystallinity.

Actual crystallinity depends on processing conditions like rate of cooling polymer melt,
residence time, temperature of molten polymer and heat dissipation under which
crystallisation takes place. In slow cooling, sufficient time is available for crystallization to
take place.

The polymers having structural regularity can achieve good crystallinity under favourable
conditions.

Structural features that influence the tendency of polymers to crystallise are:

 Structural regularity
a) Stereoregular polymers ie isotactic and syndiotactic are found to crystallise
whereas atactic ones are unable to do so.
b) Linear polymers pack closely and have ability to crystallise Branched polymers do
not crystallise as linear ones.
c) Random copolymers do not generally crystallise. Homopolymers have tendency to
crystallise. Eg: linear polyethylene is highly crystalline whereas copolymer of
ethylene and propylene is non-crystalline.
 Strong intermolecular forces (Hydrogen bonding, dipole-dipole interaction) favour
crystallisation
 Presence of small side groups or pendant groups favour crystallization (bulky side groups
hinder the close packing of polymer chains and hence reduce their tendency to crystallise).
For eg., polystyrene with a phenyl side group is mostly amorphous.
Effect of crystallinity on the properties of polymers:
High degree of crystallinity in polymers,
 Increases density and hardness
 Increases the tensile strength
 Decreases the permeability of the polymer to liquids and gases. Liquids and gases
can easily penetrate through the amorphous regions than the crystalline regions.
 Increases the modulus or the stiffness of the polymer.
 Decreases the impact resistance. Very high crystallinity makes the polymer brittle.
Amorphous regions in a polymer are more rapidly attacked by oxygen than crystalline regions and
hence are more susceptible to oxidative degradation.

THERMAL PROPERTIES:
At low temperatures molecular motion in the amorphous regions is restricted to molecular
vibration, but chains cannot rotate or move in space. This form is the glassy state of the amorphous
region. It can be thought of us being a super cooled liquid where the molecular motions have been
frozen. This state is hard, rigid and brittle like a crystalline solid, but retains the molecular disorder
of a liquid.

When the material is heated the polymer will reach a temperature at which segments (20- 50atoms
long) of the entangled chains can move. At this temperature, called the glass transition temperature,
the amorphous region of the polymer becomes rubbery. In this state the polymer will be soft and
flexible. Thus, the temperature at which polymer undergo transition from glassy solid state
to rubbery state is known as “glass transition temperature” (Tg).

On heating further, the polymer is converted into molten state at a particular temperature called
the melting point (Tm) this is transition is the characteristic of the crystalline region of the polymer.
Polymers do not have a sharp melting point. Whether the given polymer behaves like a glass or
rubber depends on whether its Tg is above or below the room temperature, respectively.

FACTOR AFFECTING GLASS TRANSITION TEMPERATURE (Tg):

The Tg of a polymer depends on the mobility of the polymer chain – the more mobile the chain,
the lower the value of Tg. Any factor that tends to restrict rotational motion within the chain will
increase the Tg.
(i) Topology:
The shape of the chain making up the backbone of the molecule is called the topology, the
topology of polymers can be linear, branched or cross-linked branches in the backbone chain
restrict segmental motion and thus increase the Tg. A highly cross-linked polymer has very high
Tg because of prevention of segmental motion.

(ii) Intermolecular forces:

Generally, strong intermolecular forces increase the Tg of a polymer. The forces acting are.

(A) Hydrogen bonding:

Hydrogen bonding can take place when the polymer molecules contain –OH or –NH
groups. Hydrogen bonding is the strongest of the intermolecular forces. Polymers such
as polyvinylalcohol and polyamides are hydrogen bonded and hence have higher Tg.
O

C CH2 CH2 CH2 N

CH2 C CH2 CH2
N CH2 CH2
CH2
CH2 CH2
H O

O H

C CH2 CH2 CH2 N CH2

N CH2 C CH2
CH2 CH2
CH2
CH2 CH2
O

(B) Dipole- Dipole forces: Dipole – dipole forces result from the attraction between
polar groups like those in polyesters and vinyl polymers with chlorine etc. these polymers
have higher Tg.

For eg: PVC has high Tg than polypropylene

CH2 CH CH2 CH CH2 CH

CH2 CH n

CH3 CH3
Cl Cl

PVC (Tg = 81°C) PP (Tg = -20°C)

(C) Dispersion forces: These forces are due to instantaneous dipoles that form in the
polymer molecules. They are the weakest of the intermolecular forces. They depend on the
polarizability of a molecule. Larger molecules are more polarisable. Polymers with high
molecular weights have significant dispersion force. But this does not have affect
(D) on the glass transition of polymers.
(iii) Chain flexibility :

The flexibility of a polymer chain depends on the groups present in the polymer
backbone . Groups such as the following are called stiffing groups because they decrease the
flexibility of the chain.

O O

C N S O
N
H O C H

p-phenylene amide sulphone carbonyl pyrrole

As the chain flexibility decreases the Tg increases. For eg. Polyethylene terephthalate (PET) has a
higher Tg than polyethylene adipate (PEA) because of the presence of the aromatic ring in the
backbone chain.

CH2 CH2 O C C O CH2 CH2 O C CH2 CH2 CH2 CH2 C O

O O O O

PET(Tg = +69°C) PEA (Tg = -70°C)

(iv) Pendant groups : A group attached to the polymer backbone and present in the repeating
unit is called a pendant group.

Bulky pendant groups like benzene ring restrict rotational freedom, this increases Tg.

For example:

CH2 CH CH2 CH CH2 CH CH2 CH

n
n
CH3 CH3 C6H5 C6H 5

PP (Tg = - 20°C) PS (Tg = 100°C)

Flexible pendant groups like methyl, ethyl, butyl groups decreases the Tg. As the length of the
side chain increases, their freedom of flexibility increases, they tend to push the neighbouring main
chains further apart, increasing the free volume, hence the chain mobility.

Ex:
CH3 CH3

CH2 C CH2 C
n n

COOCH 3 COOCH 2CH2CH2CH3

PMMA (Tg =105°C) PBMA (Tg =20°C)
The glass transition temperature is an important parameter of a polymeric material. It is used as a
measure for evaluating the flexible of a polymer molecule and the type of response the polymeric
material would exhibit to mechanical stress. The Tg value along with the Tm value gives an
indication of the temperature region at which a polymeric material transforms from a rigid solid to
a soft viscous state. This helps in choosing the right processing temperature i.e., the temperature
region in which the polymers can be converted into finished products through different processing
techniques.

MECHANICAL PROPERTIES OF POLYMERS:

It is of great importance to be familiar with some basic mechanical properties of the material before
its application in any field, such as how much it can be stretched, how much it can be bent, how
hard or soft it is, how it behaves on the application of repeated load and so on.
The mechanical properties that are measured are tensile strength, flexural, tear strength,
fatigue, impact resistance and hardness. The mechanical behaviour of plastics can be best defined
by using their stress-strain diagram.

Stress-strain behaviour of polymers: This experiment is done by measuring continuously the

force developed as the polymer sample is subjected to a deformation.

Stress ( σ ) is defined as the force per unit area.

Stress ( σ ) = Force / Area

There are three basic types of stress measurement namely

(i) Tensile stress which is the resistance of a material to stretching force.
(ii) Compressive stress which is the resistance of a material to ‘squashing’ forces.
(iii) Shear stress is the resistance of a material to ‘push – pull’ forces.

Strain (ϵ) is the amount of deformation per unit length of the material due to the applied load.
ϵ = l –l0 / l0 Where l is the instantaneous length and l0 is the original length of the
polymer sample.

The tensile test is one of the most widely used testing standards for measuring the mechanical
properties of a polymeric material; this test determines the stress-strain curve in tension. This is
done by continuously measuring the force that develops as the test specimen is elongated at a
constant rate of extension. From this test a stress-strain curve is obtained.
Properties of polymer that can be determined from their stress-strain behaviour:

1. Tensile Strength: The strength is the stress required to break the sample when the
sample is stretched. Generally crosslinked polymers have greater strength.

Factors Affecting the Strength of Polymers

(a) Molecular Weight: The tensile strength of the polymer rises with increase in
molecular weight and reaches the saturation level at some value of the molecular
weight. At lower molecular weight, the polymer chains are loosely bonded by weak
vander Waals forces and the chains can move easily, responsible for low strength,
although crystallinity is present. In case of large molecular weight polymer, the chains
become large and hence are entangled, giving strength to the polymer.

(b) Cross-linking: The cross-linking restricts the motion of the chains and increases the
strength of the polymer.

(c) Crystallinity: The crystallinity in a polymer increases the strength, because in the
crystalline phase, the intermolecular bonding is more significant.

2. Percent Elongation to Break (Ultimate Elongation): It is the strain in the material on its
breakage. It measures the percentage change in the length of the material before fracture.
 It is a measure of ductility. Thermoplastics show greater elongation than thermosets
(<5%) at break.

3. Young’s Modulus (Modulus of Elasticity or Tensile Modulus): In the linear region of

the curve, stress is proportional to strain.

Stress (𝜎) = E (strain)

Where E is the proportionality constant called Young’s Modulus. It is the ratio of stress to
the strain in the linear elastic region. Elastic modulus is a measure of the stiffness of the
material.

E = Tensile Stress(𝜎)
Tensile Strain(𝜀)
As crystallinity increases, modulus increases.

4. Toughness: The toughness of a material is given by the area under a stress – strain curve.
The toughness measures the energy absorbed by the material before it breaks.
A flexible plastic material exhibits toughness and hence high impact resistance.
5. Yield stress: The stress at which the polymer yields and undergoes plastic (irreversible)
deformation.
The tensile stress- strain graphs for different classes of materials is given below:

Example for Hard and brittle (polystyrene), Hard and strong (PVC), Hard and tough (cellulose
acetate, nylon), Soft and weak (polymer gels) and soft and tough (rubber and plasticized PVC).