Polymers Notes

Live Sahab20
Polymers
By Singh Sahab
Introduction
Polymer = Poly + Mer
(Many) (Unit/Part)
Polymer - very large molecules having high molecular mass (10 3-107u).
These are also referred to as macromolecules

• Polymers are formed by joining of repeating structural units on a
large scale.
• The repeating structural units are called monomers
• These monomers are linked to each other by covalent bonds.
• Polymerisation - Process of formation of polymers from monomers.

Ethene to polythene
Formation of Nylon 6, 6
Classification of Polymers
Based on Source
1. Natural polymers - polymers which are found in plants and

animals.
Examples - proteins, cellulose, starch, resins and rubber.
2. Semi-synthetic polymers - Cellulose derivatives as cellulose

acetate (rayon) and cellulose nitrate, etc.
3. Synthetic polymers -
-manmade polymers
Examples- plastic (polythene), synthetic fibres (nylon 6,6) and

synthetic rubbers (Buna - S).
Based on Structure of Polymers
1. Linear polymers
These polymers consist of long and straight chains.

Examples - high density polythene, polyvinyl chloride, etc.
2. Branched chain polymers –
These polymers contain linear chains having some branches.

e.g., low density polythene
3. Cross linked or Network polymers –
Formed from bi-functional and tri-functional monomers

Contains strong covalent bonds between various linear polymer chains,
e.g. bakelite, melamine, etc.
Based on Mode of Polymerisation
1. Addition polymers-
Formed by the repeated addition of monomer molecules possessing double

or triple bonds
e.g., polythene from ethene &
polypropene from propene.
Homopolymers
The addition polymers formed by the polymerisation of a single

monomeric species
e.g., polythene.
Copolymers –
The polymers made by addition polymerisation from two different

monomers,
e.g., Buna-S, Buna-N, etc.
2. Condensation polymers
Formed by repeated condensation reaction between two different bi-functional

or tri-functional monomeric units.
Elimination of small molecules such as water, alcohol, hydrogen chloride, etc.

takes place.
Formation of nylon 6, 6
Based on Molecular Forces
Polymer’s mechanical properties depends upon intermolecular forces

like
• van der Waals forces
• Hydrogen bonds
These forces also bind the polymer chains.

1. Elastomers
• Rubber – like solids with elastic properties.

• Polymer chains held together by the weakest intermolecular forces
which allows 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.
Examples - buna-S, buna-N, neoprene, etc.
2. Fibres
Thread forming solids which possess high tensile strength and high modulus.
Reason- Hydrogen bonding.

This lead to close packing of chains and thus impart crystalline nature.
Examples - polyamides (nylon 6, 6),

polyesters (terylene), etc.
3. Thermoplastic polymers –
• Linear or slightly branched long chain molecules capable of repeatedly

softening on heating and hardening on cooling.
• Intermolecular forces of attraction intermediate between elastomers and fibres.
Examples- polythene, polystyrene, polyvinyls, etc.

4. Thermosetting polymers
Cross linked or heavily branched molecules, which on heating undergo

extensive cross linking in moulds and again become infusible.
These cannot be reused.
Examples - bakelite, urea-formaldelyde resins, etc.
Types of Polymerisation Reactions
Addition Polymerisation or
Chain Growth Polymerisation
In this, molecules of the same monomer or different monomers add together

on a large scale to form a polymer.
Here, monomers used are unsaturated compounds.
This polymerisation leads to increase in chain length or chain growth

Two Types-
1. Free radical mechanism
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.
Chain initiation steps
Chain propagating steps
Chain Termination steps
For termination of the long chain, these free radicals can combine in
different ways to form polythene. One mode can be-
Preparation of some important addition
polymers
(a) Polythene
(i) Low density polythene
Obtained by the polymerisation of ethene under high pressure of 1000 to

2000 atmospheres at a temperature of 350 K to 570 K in the presence of
traces of dioxygen or a peroxide initiator (catalyst).
The low density polythene (LDP) obtained through the free radical addition
Low density polythene is
• chemically inert
• Tough
• Flexible
• a poor conductor of electricity
Uses-
insulation of electricity carrying wires, manufacture of squeeze bottles, toys
and flexible pipes.
(ii) High density polythene
Formed by addition polymerisation of ethene in a hydrocarbon solvent in

the presence of a catalyst such as triethylaluminium and titanium
tetrachloride (Ziegler-Natta catalyst) at a temperature of 333 K to 343 K
and under a pressure of 6-7 atmospheres.
High density polythene (HDP) –
• consists of linear molecules
• has a high density due to close packing.
• Is chemically inert
• Is more tougher and harder.
Used in manufacturing buckets, dustbins, bottles, pipes, etc.

(b) Polytetrafluoroethene (Teflon)-
Obtained by heating tetrafluoroethene with a free radical or persulphate

catalyst at high pressures.
It is
• chemically inert
• resistant to attack by corrosive reagents.
(c) Polyacrylonitrile-
The addition polymerisation of acrylonitrile in presence of a peroxide

catalyst leads to the formation of polyacrylonitrile.
Used as a substitute for wool in making commercial fibres as orlon or

acrilan.
Condensation Polymerisation or Step Growth
polymerisation
It involves a repetitive condensation reaction between two bi-functional

monomers.
It may result in the loss of some simple molecules as water, alcohol, etc., and
lead to the formation of high molecular mass condensation polymers.
The formation of terylene or dacron
Some important condensation
polymerisation reactions
1. Polyamides
Also termed as nylons.
General method of preparation –

Condensation polymerisation of diamines with dicarboxylic acids and also of
amino acids and their lactams.
Preparation of nylons
(i) Nylon 6,6
Used in making sheets, bristles for brushes and in textile industry.

(ii) Nylon 6:
Used for the manufacture of tyre cords, fabrics and ropes.

2. Polyesters
It is polycondensation products of dicarboxylic acids and diols.
Dacron fibre (terylene) is used in blending with cotton and wool fibres
3. Phenol - formaldehyde polymer
Condensation reaction of phenol with formaldehyde in the presence of

either an acid or a base catalyst.
Paint → Nerolac
Novolac on heating with formaldehyde undergoes cross linking to form an
infusible solid mass called bakelite.
Uses- making combs, phonograph records, electrical switches and handles

of various utensils.
4. Melamine – formaldehyde polymer
Uses- manufacture of unbreakable crockery.
Copolymerisation
Polymerisation reaction in which a mixture of more than one monomeric
species polymerises to form copolymer.
The copolymer can be made by both-
• chain growth polymerisation

• step growth polymerisation also.
Properties-
• quite tough
• good substitute for natural rubber.
Uses- autotyres, floortiles, footwear components, cable insulation, etc.

Rubber
1. Natural rubber –
Rubber is a natural polymer and possesses elastic properties.
It is also termed as elastomer
cis-polyisoprene
Vulcanisation of rubber
Natural rubber is soft and sticky.
Drawbacks :
1) Large water absorption capacity
2) Low tensile strength
3) Non-resistant
Therefore “Vulcanization” process is done.
Method- heating raw rubber with 3 – 5 % sulphur at 100°C – 150°C.

On vulcanisation, sulphur forms cross links at the reactive sites of double
bonds and thus the rubber gets stiffened.
Example- In the manufacture of tyre rubber, 5% of sulphur is used as a

crosslinking agent.
2. Synthetic rubbers
It is any vulcanisable rubber like polymer, which is capable of getting

stretched to twice its length.
Synthetic rubbers are either

• homopolymers of 1, 3 - butadiene derivatives
• or copolymers of 1, 3 - butadiene
• or its derivatives with another unsaturated monomer.
Neoprene-
Formed by the free radical polymerisation of chloroprene.
Uses- conveyor belts, gaskets and hoses.

Buna – N
Obtained by the copolymerisation of 1, 3 – butadiene and acrylonitrile

in the presence of a peroxide catalyst.
Uses- making oil seals, tank lining, etc.

Molecular Mass of Polymers
• Polymer properties are closely related to their molecular mass, size and
structure.
• The growth of the polymer chain during their synthesis is dependent

upon the availability of the monomers in the reaction mixture.
• Thus, the polymer sample contains chains of varying lengths and hence
its molecular mass is always expressed as an average.
• The molecular mass of polymers can be determined by chemical and

physical methods.
Biodegradable Polymers
Aliphatic polyesters are one of the important classes of
biodegradable polymers.
1. Poly β-hydroxybutyrate – co-β-hydroxy valerate

(PHBV)
Uses- packaging, orthopedic devices and in controlled release of drugs.

PHBV undergoes bacterial degradation in the environment.
Uses-
• Packaging
• orthopedic devices
• in controlled release of drugs
PHBV undergoes bacterial degradation in the environment.

2. Nylon 2–nylon 6
It is an alternating polyamide copolymer of glycine (H 2N–CH2–COOH)

and amino caproic acid [H2N - (CH2)5 - COOH] and is biodegradable.
Commercially Important Polymers

Polymers Notes

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Live Sahab20

These are also referred to as macromolecules

• The repeating structural units are called monomers

• These monomers are linked to each other by covalent bonds.

• Polymerisation - Process of formation of polymers from monomers.

1. Natural polymers - polymers which are found in plants and

2. Semi-synthetic polymers - Cellulose derivatives as cellulose

Examples- plastic (polythene), synthetic fibres (nylon 6,6) and

These polymers consist of long and straight chains.

These polymers contain linear chains having some branches.

Formed from bi-functional and tri-functional monomers

Formed by the repeated addition of monomer molecules possessing double

The addition polymers formed by the polymerisation of a single

The polymers made by addition polymerisation from two different

Formed by repeated condensation reaction between two different bi-functional

Elimination of small molecules such as water, alcohol, hydrogen chloride, etc.

Polymer’s mechanical properties depends upon intermolecular forces

These forces also bind the polymer chains.

• Rubber – like solids with elastic properties.

Reason- Hydrogen bonding.

Examples - polyamides (nylon 6, 6),

• Linear or slightly branched long chain molecules capable of repeatedly

Examples- polythene, polystyrene, polyvinyls, etc.

Cross linked or heavily branched molecules, which on heating undergo

In this, molecules of the same monomer or different monomers add together

Here, monomers used are unsaturated compounds.

This polymerisation leads to increase in chain length or chain growth

1. Free radical mechanism

Alkenes or dienes and their derivatives are polymerised in the presence of

(i) Low density polythene

Obtained by the polymerisation of ethene under high pressure of 1000 to

Low density polythene is

Formed by addition polymerisation of ethene in a hydrocarbon solvent in

• consists of linear molecules

• has a high density due to close packing.

• Is more tougher and harder.

Used in manufacturing buckets, dustbins, bottles, pipes, etc.

Obtained by heating tetrafluoroethene with a free radical or persulphate

The addition polymerisation of acrylonitrile in presence of a peroxide

Used as a substitute for wool in making commercial fibres as orlon or

It involves a repetitive condensation reaction between two bi-functional

Also termed as nylons.

General method of preparation –

(i) Nylon 6,6

Used in making sheets, bristles for brushes and in textile industry.

Used for the manufacture of tyre cords, fabrics and ropes.

It is polycondensation products of dicarboxylic acids and diols.

Condensation reaction of phenol with formaldehyde in the presence of

Uses- making combs, phonograph records, electrical switches and handles

The copolymer can be made by both-

• chain growth polymerisation

Uses- autotyres, floortiles, footwear components, cable insulation, etc.

Rubber is a natural polymer and possesses elastic properties.

It is also termed as elastomer

Natural rubber is soft and sticky.

Therefore “Vulcanization” process is done.

Method- heating raw rubber with 3 – 5 % sulphur at 100°C – 150°C.

Example- In the manufacture of tyre rubber, 5% of sulphur is used as a

It is any vulcanisable rubber like polymer, which is capable of getting

Synthetic rubbers are either

Formed by the free radical polymerisation of chloroprene.

Uses- conveyor belts, gaskets and hoses.

Obtained by the copolymerisation of 1, 3 – butadiene and acrylonitrile