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Chapter : Polymers

Top concepts

1. Polymers are high molecular mass substance consisting of large number of

repeating structural units. As polymers are single, giant molecules i.e. big size
molecules, they are also called macromolecules

2. Simple molecules which combine to form polymers are called monomers

3. Process of formation of polymers from respective monomers is called

polymerization

4. Classification of Polymers
No. Classification Types Examples
based on
1. Natural polymers: Polymers obtained Cellulose, starch, etc.
from nature,mostly plants and animals

1. Source of 2. Synthetic polymers: Polymers prepared Teflon,

availability in laboratory Nylon 6,6 ,
Synthetic rubber (Buna -
S) etc.
3. Semi synthetic polymers: Polymers Rayon (cellulose
derived from naturally occurring acetate),
polymers by carrying out chemical cellulose nitrate, etc.
modifications
2. Structure of 1. Linear polymers: Polymer consist of High density polythene,
polymer long and straight chains polyvinyl chloride, etc.
2.Branched chain polymers: Polymers
contains linear chains having some Low density polythene
branches
3.Cross linked or network polymers:
Polymers in which monomer units are Bakelite, melamine, etc.
cross linked together to form a 3
dimensional network polymers
3. Mode of 1.Addition polymers 1.Homopolymers:
polymerisation :Polymers are Polymers formed by
formed by the the polymerisation Polythene,
repeated addition of of a single Polystyrene
monomers with monomeric species
double and triple 2.Copolymers:
bonds Polymers formed by
addition Buna-S,
polymerisation of Buna -N
two different

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monomers

Condensation polymers: Polymers formed

by repeated condensation reaction Nylon 6, 6,
between two different bi-functional or tri- Nylon 6
functional monomeric units with
elimination of simple molecules
4. Molecular forces 1. Elastomers: Polymer chains are held Buna – S,
together by weakest intermolecular Buna – N,
forces. Polymers are rubber – like solids Neoprene
with elastic properties
2. Fibre: Polymers have strong Nylon 6, 6,
intermolecular force like hydrogen Polyesters
bonding. Fibres are the thread forming
solids which possess high tensile strength
and high modulus
3. Thermoplastic polymers: Polymers are Polythene,
held by intermolecular forces which are in Polystyrene
between those of elastomers and fibres.
These polymers are capable of repeated
softening on heating and hardening on
cooling
4. Thermosetting polymers: Polymers are Bakelite,
cross linked or heavily branched Urea-formaldelyde resins
molecules, which on heating undergo
extensive cross linking in moulds and
eventually undergoes a permanent

5. Addition Polymerisation or Chain Growth Polymerisation: Most common

mechanism for addition polymerisation reactions is free radical mechanism
Steps involved are:

Step 1: Chain initiating step: Organic peroxides undergo homolytic fission to

form free radicals which acts as initiator. Initiator adds to C-C double bond of
an alkene molecule to form a new free radical

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Step 2: Chain propagating step: Free radicals formed by homolytic cleavage

adds to a double bond of monomer to form a larger free radical. Radical
formed adds to another alkene molecule to form a larger free radical. This
process continues until the radical is destroyed. These steps are called
propagation steps.

Step 3: Chain terminating step: For termination of the long chain, free
radicals combine in different ways to form polythene. One mode of
termination of chain is shown as under:

Addition polymerisation is called chain growth polymerisation because it

takes place through stages leading to increase in chain length and each stage
produces reactive intermediates for use in next stage of the growth of chain

6 .Important Addition Polymers:

No. Name of polymer Polymerisation Reaction & Uses

1 Low density
polythene (LDP)

Uses: It is used in the insulation of electricity carrying

wires and manufacture of squeeze bottles, toys and
flexible pipes
2 High density
polythene(HDP)

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Uses: It is used for manufacturing buckets, dustbins,

bottles, pipes, etc.
3 Polytetrafluoroethene
(Teflon)

Uses: It is used in making oil seals and gaskets and also

used for non – stick surface coated utensils

4 Polyacrylonitrile

Uses: It is used as a substitute for wool in making

commercial fibres as orlon or acrilan

7. Condensation Polymerisation or Step Growth polymerization:

Polymerisation generally involves a repetitive condensation reaction between
two bi-functional monomers. In condensation 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.

8 .Important Condensation Polymers:

1. Polyamides: Polymers possess amide linkage (-CONH-) in chain. These
polymers are popularly known as nylons.
Examples:
(a) Nylon 6, 6: It is prepared by the condensation polymerisation of
hexamethylenediamine with adipic acid under high pressure and at
high temperature.

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Uses: Nylon 6, 6 is used in making sheets, bristles for brushes and in textile
industry

(b) Nylon 6: It is obtained by heating caprolactum with water at a high

temperature

Uses: Nylon 6 is used for the manufacture of tyre cords, fabrics and ropes

(2) Polyesters: These are the polycondensation products of dicarboxylic acids

and diols
Example: Terylene or Dacron

Terylene or Dacron: It is manufactured by heating a mixture of ethylene

glycol and terephthalic acid at 420 to 460 K in the presence of zinc acetate-
antimony trioxide catalyst

Uses: Dacron fibre (terylene) is crease resistant and is used in blending with
cotton and wool fibres and also as glass reinforcing materials in safety
helmets, etc.

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

Bakelite: These are obtained by the condensation reaction of phenol with

formaldehyde in the presence of either an acid or a base catalyst. The initial
product could be a linear product – Novolac used in paints.

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Novolac on heating with formaldehyde forms Bakelite

Uses: 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

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Uses: It is used in the manufacture of unbreakable crockery

9. Rubber
(i) Natural rubber: Natural rubber is a linear polymer of isoprene (2-methyl-
1, 3-butadiene) and is also called as cis - 1, 4 - polyisoprene.

Vulcanisation of rubber: Process of heating a mixture of raw rubber with

sulphur and an appropriate additive in a temperature range between 373 K
to 415 K to improve upon physical properties like elasticity, strength etc.

(ii) Synthetic rubber: Synthetic rubbers are either homopolymers of 1, 3 -

butadiene derivatives or copolymers of 1, 3 - butadiene or its derivatives
with another unsaturated monomer

Examples of synthetic rubber:

No. Name of Polymerisation Reaction and uses
polymer
1 Neoprene or
polychloropre
ne

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Uses: It is used for manufacturing conveyor belts, gaskets and

hoses

2 Buna – N

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Uses: It is used in making oil seals, tank lining, etc. because it is

resistant to the action of petrol, lubricating oil and organic solvents

3 Buna – S

10. Biodegradable Polymers: Polymers which are degraded by

microorganisms within a suitable period so that biodegradable polymers and
their degraded products do not cause any serious affects on environment

Examples of biodegradable polymer:

1. Poly -  -hydroxybutyrate – co-  -hydroxy valerate (PHBV): It is obtained
by the copolymerisation of 3-hydroxybutanoic acid and 3 - hydroxypentanoic
acid

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Uses: PHBV is used in speciality packaging, orthopaedic devices and in

controlled release of drugs

2. Nylon 2–nylon 6: It is an alternating polyamide copolymer of glycine

(H2N–CH2–COOH) and amino caproic acid (H2N (CH2)5 COOH)

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11. Some commercially important polymers along with their structures and
uses
Name of Monomer Structure Uses
Polymer
Polypropene Propene Manufacture of
ropes, toys, pipes,
fibres, etc.

Polystyrene Styrene As insulator,

wrapping
material,
manufacture
of toys, radio and
television cabinets
Polyvinyl Vinyl chloride Manufacture of rain
chloride coats, hand bags,
(PVC) vinyl flooring, water
pipes
Glyptal (a) Ethylene Manufacture of
glycol paints and lacquers
Manufacture
of
(b) Phthalic
acid

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