Introduction

Do you think that daily life would have been easier and colourful without the discovery and varied
applications of polymers? The use of polymers in the manufacture of plastic buckets, cups and saucers,
children’s toys, packaging bags, synthetic clothing materials, automobile tyres, gears and seals, electrical
insulating materials and machine parts has completely revolutionised the daily life as well as the industrial
scenario. Indeed, the polymers are the backbone of four major industries viz. plastics, elastomers, fibres
and paints and varnishes.
The word ‘polymer’ is coined from two Greek words: poly means many and mer means unit or part. The
term polymer is defined as very large molecules having high molecular mass (10 3-107u). These are also
referred to as macromolecules, which are formed by joining of repeating structural units on a large scale.
The repeating structural units are derived from some simple and reactive molecules known as monomers
and are linked to each other by covalent bonds. This process of formation of polymers from respective
monomers is called polymerisation.

Classification of Polymers
There are several ways of classification of polymers based on some special considerations. The following
are some of the common classifications of polymers:

Classification Based on Source

1. Natural polymers
These polymers are found in plants and animals. Examples are proteins, cellulose, starch, some resins and
rubber.
2.Synthetic polymers
A variety of synthetic polymers as plastic (polythene), synthetic fibres (nylon 6,6) and synthetic rubbers
(Buna - S) are examples of manmade polymers extensively used in daily life as well as in industry.

Classification Based on Structure of Polymers

1. Linear polymers
These polymers consist of long and straight chains. The examples are high density polythene, polyvinyl
chloride, etc. These are represented as:

2. Branched chain polymers

These polymers contain linear chains having some branches, e.g., low density polythene. These are
depicted as follows:

3. Cross linked or Network polymers

These are usually formed from bi-functional and tri-functional monomers and contain strong covalent
bonds between various linear polymer chains, e.g. bakelite, melamine, etc. These polymers are depicted as
follows

Classification Based on Mode of Polymerisation

1. Addition polymers
The addition polymers are formed by the repeated addition of monomer molecules possessing double or
triple bonds, e.g., the formation of polythene from ethene and polypropene from propene. However, the
addition polymers formed by the polymerisation of a single monomeric species are known as
homopolymers, e.g., polythene

The polymers made by addition polymerisation from two different monomers are termed as copolymers,
e.g., Buna-S, Buna-N, etc.

2. Condensation polymers
The condensation polymers are formed by repeated condensation reaction between two different bi-
functional or tri-functional monomeric units. In these polymerisation reactions, the elimination of small
molecules such as water, alcohol, hydrogen chloride, etc. take place. The examples are terylene (dacron),
nylon 6, 6, nylon 6, etc. For example, nylon 6, 6 is formed by the condensation of hexamethylene diamine
with adipic acid.

Classification Based on Molecular Forces

1. Elastomers
These are rubber – like solids with elastic properties. In these elastomeric polymers, the polymer chains are
held together by the weakest intermolecular forces. These weak binding forces permit the polymer to be
stretched. A few ‘crosslinks’ are introduced in between the chains, which help the polymer to retract to its
original position after the force is released as in vulcanised rubber. The examples are buna-S, buna-N,
neoprene, etc.

2. Fibres
Fibres are the thread forming solids which possess high tensile
strength and high modulus. These characteristics can be attributed to the strong intermolecular forces like
hydrogen bonding. These strong forces also lead to close packing of chains and thus impart crystalline
nature. The examples are polyamides (nylon 6, 6), polyesters (terylene), etc.

3. Thermoplastic polymers
These are the linear or slightly branched long chain molecules capable of repeatedly softening on heating
and hardening on cooling. These polymers possess intermolecular forces of attraction intermediate
between elastomers and fibres. Some common thermoplastics are polythene, polystyrene, polyvinyls, etc.

4 Thermosetting polymers
These polymers are cross linked or heavily branched molecules, which on heating undergo extensive cross
linking in moulds and again become infusible. These cannot be reused. Some common examples are
bakelite, urea-formaldelyde resins, etc.
Types of Polymerisation Reactions
1. Addition Polymerisation or Chain Growth Polymerisation
In this type of polymerisation, the molecules of the same monomer or
diferent monomers add together on a large scale to form a polymer. The
monomers used are unsaturated compounds, e.g., alkenes, alkadienes
and their derivatives. This mode of polymerisation leading to an increase
in chain length or chain growth can take place through the formation
of either free radicals or ionic species. However, the free radical governed
addition or chain growth polymerisation is the most common mode.
Free radical mechanism
A variety of alkenes or dienes and their derivatives are polymerised in the presence of a free radical
generating initiator (catalyst) like benzoyl peroxide, acetyl peroxide, tert-butyl peroxide, etc. For example,
the polymerisation of ethene to polythene consists of heating or exposing to light a mixture of ethene with
a small amount of benzoyl peroxide initiator. The process starts with the addition of phenyl free radical
formed by the peroxide to the ethene double bond thus generating a new and larger free radical. This step
is called chain initiating step. As this radical reacts with another molecule of ethene, another bigger sized
radical is formed. The repetition of this sequence with new and bigger radicals carries the reaction forward
and the step is termed as chain propagating step. Ultimately, at some stage the product radical thus
formed reacts with another radical to form the polymerised product. This step is called the chain
terminating step. The sequence of steps may be depicted as follows:

Chain initiation steps

Chain propagating step

Chain terminating step

For termination of the long chain, these free radicals can combine in different ways to form polythene. One
mode of termination of chain is shown as under:

Some important addition polymers

1. Polytetrafluoroethene (Teflon)
Teflon is manufactured by heating tetrafluoroethene with a free radical or persulphate catalyst at high
pressures. It is chemically inert and resistant to attack by corrosive reagents. It is used in making oil seals
and gaskets and also used for non – stick surface coated utensils.
 2. Polyacrylonitrile
The addition polymerisation of acrylonitrile in presence of a peroxide catalyst leads to the formation of
polyacrylonitrile. Polyacrylonitrile is used as a substitute for wool in making commercial fibres as orlon or
acrilan.

Condensation Polymerisation or Step Growth polymerisation

This type of polymerisation generally involves a repetitive condensation reaction between two bi-
functional monomers. These polycondensation reactions may result in the loss of some simple molecules
as water, alcohol, etc., and lead to the formation of high molecular mass condensation polymers. In these
reactions, the product of each step is again a bi-functional species and the sequence of condensation goes
on. Since, each step produces a distinct functionalised species and is independent of each other, this
process is also called as step growth polymerisation.

Some important condensation polymers

(i)Nylon 6,6: It is prepared by the condensation polymerisation of hexamethylenediamine with adipic acid
under high pressure and at high temperature. Nylon 6, 6 is used in making sheets, bristles for brushes and
in textile industry.

(ii) Nylon 6: It is obtained by heating caprolactum with water at a high temperature. Nylon 6 is used for
the manufacture of tyre cords, fabrics and ropes.

3. Phenol - formaldehyde polymer (Bakelite and related polymers)

Phenol - formaldehyde polymers are the oldest synthetic polymers. These are obtained by the condensation
reaction of phenol with formaldehyde in the presence of either an acid or a base catalyst. The reaction
starts with the initial formation of o-and/or p-hydroxymethylphenol derivatives, which further react with
phenol to form compounds having rings joined to each other through –CH2 groups. The initial product
could be a linear product – Novolac used in paints.

Novolac on heating with formaldehyde undergoes cross linking to form an infusible solid mass called
bakelite. It is used for making combs, phonograph records, electrical switches and handles of various
utensils.
4. Melamine – formaldehyde polymer
Melamine formaldehyde polymer is formed by the condensation polymerisation of melamine and
formaldehyde. It is used in the manufacture of unbreakable crockery.

Copolymerisation
Copolymerisation is a polymerisation reaction in which a mixture of more than one monomeric species is
allowed to polymerise and form a copolymer. The copolymer can be made not only by chain growth
polymerisation but by step growth polymerisation also. If the various repeating units occur randomly along
the chain structure, the polymer is said to be a random copolymer. When repeating units occurs in blocks
the copolymer is said to be a block copolymer. Graft copolymers are formed when chains of one kind are
attached to the backbone of a different polymer.

Conducting Polymers
A polymer which can conduct electricity is called as Conducting polymer. Conducting polymers can be
classified as:

Conducting
Polymers

Intrinsically Extrinsically
Conducting Conducting
Polymers Polymers

Conjugated Doped Blended

Element Filled
Conducting Conducting Conducting
Polymers
Polymers Polymers Polymers

Intrinsically Conducting Polymers

These polymers have extensive conjugation in their backbone which is responsible for conductance. These
are further of two types:
1. Conjugated conducting polymers
The presence of conjugated π- electrons across the backbone increases their conductivity to the
large extent. This cause the formation of the conduction and the valence bands which extends over
the entire polymer molecule. But this conductivity isn’t sufficient for their use in different
applications. Typical examples are polypyrrole, polyaniline, trans-polyacetylene.
 2. Doped conducting polymers
When conjugated conducting polymers are oxidised or reduced, this creates positive or negative
charge on polymer backbone thus increasing their conductivities. This is termed as doping and is
of two types:
1. p-doping: It is done by the oxidation process. Conjugated conducting polymer is treated with
Lewis acid or with iodine vapour or iodine in CCl4 causing partial oxidation which causes the
formation of delocalised radical ion called polaron. A second oxidation of this polaron,
followed by radical recombination yields two positive mobile charge carriers which are
carried for current conduction.

2. n-doping: It is done by the reduction process. Conjugated conducting polymer is treated with
Lewis base like sodium napthalide causing partial reduction which causes the formation of
delocalised radical ion called polaron and bipolaron yielding two negative mobile charge
carriers which are carried for current conduction.

Interesting range of properties offered by Intrinsically Conducting

Polymers

1. Conductivity
2. Ability to store a charge
3. Ability to ion exchange
4. Absorption of visible light to give coloured products
 5. Transparency to x rays.
Limitations of Intrinsically Conducting Polymers
1.Conductivity is inferior to metals
2.Poor mechanical strength
3.Poor storage stability leading to loss in conductivity
4.Poor durability
Extrinsically Conducting Polymers
These polymers owe their conductivity due to the presence of externally added ingredients in them. They
are of following types:
1. Conductive element filled polymers
In this the polymer acts as a binder to hold the conducting element together in a solid entity. The
minimum concentration of the conductive filler which should be added so that the polymer starts
conducting is called percolation threshold because at this concentration of the filler a conducting
path is formed in the polymer. Generally special conducting grade c carbon is used as a filler.
These polymers possess good bulk conductivity, less in weight, mechanically durable and strong.
2. Blended conducting polymers
These polymers are formed by blending a conventional polymer with a conducting polymer. Such
polymers possess better physical, chemical, electrical and mechanical properties and they can be
easily processed. Such compounds are of interest in electromagnetic shielding.

Applications of Conducting Polymers

1. In rechargeable batteries
2. For making ion exchangers
3. In photovoltaic devices
4. Smart glass windows
5. Bending screens in smartphones
6. In analytical sensors