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POLYMERS
RS
POLYMERS:
Polymers are the compounds of high molecular mass formed by the combination of
large no. of simple molecule called monomer.
The process by which monomers are converted into polymer is called
polymerization.

Structural unit:
It is the part of a monomer that form a polymer. It is consider as building block of a
polymer chain.

Structural unit of polyethylene.

Repeating unit:
It is the smallest monomeric unit of a polymer that repeat itself to form a polymer
chain.

Ex: It is the repeating unit of

polyethylene.
Some polymers, their monomers and repeating unit cells:
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Classification based on source:

Polymer

Natural Polymer Synthetic Polymer Semisynthetic Polymer

Polymers that are obtained These are manmade polymer Polymers which are obtain
from nature (plants and prepared in laboratory. by chemical reaction with
animals) are called natural Ex: Teflon, PVC, PAN natural polymer by
polymer. artificially.
Ex: Natural rubber, starch, Ex: Cellulose nitrate,
cellulose, protein cellulose acetate.

Classification based on structure:

Polymer

Linear Polymer Branched Polymer Cross-linked Polymer

These polymer consist of These polymer contain linear These polymers are usually
long and straight chain. chain having some branches. formed from bifunctional and
Ex: Nylon, Polyster Ex: Low density polyethylene trifunctional monomers and
strong covalent bond between
linear polymer
chain.ex:Bakene

Classification based on method of polymerization:

Chain polymerization(Addition Condensation polymerisation

polymerization)
The polymer which is produced by successive The polymer formed by the repeated
addition of monomer molecule through condensation reaction between bi
chain reaction without formation of any by functional or trifunctional monomer unit
product is called chain polymerization. usually with elimination of small molecule
Ex: PVC, Polyethene such as water, alcohol, ammonia etc.
e.g, nylon 6,6
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Classification based on on Molecular forces

Elastomer Fibre Thermoplastic Thermosetting

Polymer Polymer
Elastomer:
These are the polymer having the weakest inter molecular force of attraction
between the polymer chain. The weak forces permit the polymer to be stretched. A few
cross links are introduced in between the chains, which held to polymer to retract its
original position after the force is replaced as in Vulcanised rubber.
Elastomer does posses an elastic character.
e.g: Buna – S, Buna – N
**Fibres:
These are the polymer which have strongest intermolecular forces such as hydrogen
bond or dipole – dipole interaction. These polymers can be used for making fibre as their
molecules are long and thread like.
e.g., Nylon 6,6, Terylene and the some common fibre.
** Thermoplastic polymer:
This polymer posses inter molecular force of attraction intermediate between
elastomer and fibres. These are linear or slightly branch chain polymer, capable of
repeatedly softening on heating and hardening on cooling.
e.g; Polythene, polypropylene, PVC etc.

**Thermosetting polymer:
This polymer are cross linked or heavily branch molecules which on heating undergo
extensively cross linking in moulds and again become infusible. These can be reshaped.
e.g; Bacalite, urea formaldehyde rejin etc.

Type of the polymerization

Addition or chain growth polymerisation Condensation or step growth

polymerisation
This type of Polymerisation involve It occurs through a series of Independent
successive addition of monomer unit to the reaction or step. Each step involves the
growing chain carrying a reacting condensation between two bifunctional
intermediate such as free radical. monomer unit with elimination of water
e.g; ethelene alcohol ammonia and lead to the formation
i) Free Radicle Polymerisation of polymer. As it is carried out stepwise. It
ii) Cationic Polymerisation called step growth polymerization.
iii) Anionic Polymerisation

Free Radicle polymerization:

The polymerization of ethane to polyethene consist of heating or exposing to light. A
mixture of ethane and small amount of Benzoyl peroxide initiator. The reaction takes place
in following step.
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Step – I :Chain initiation step:

Benzoyl peroxide undergo hemolytic fission to form free radical.

Step – II :Chain propasation step:

Phenyl free radical in chain propagation step at two ethane molecule to form a new
free radical.

The free radical forms attack another ethane molecule and the process continue
building a long chain.

Step – III :Chain termination step:

The chain reaction stop when two free radical, chain combine.

Addition polymer:

i) Low density polyethelene: When n molecules of ethylene undergo

Polymerisation with traces of O2 at 350 – 5700c or 1000 – 2000 atm pressure it
forms L.D.P.

It is used in the insulation of electricity carrying wire and manufacture of bottles

and toys.

ii) High density Polyethelene:

It is the mixture of triethyl alliminium and Titenium tetra chloride.

Manufacture of toys, ropes, pipes etc.
iii) Polystyrene:

Uses: An insulator, wrapping material, manufacturing of toys, radio, television

cabinet.
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iv) Tetra fluro ethane:

Uses: Making of oil seals Gasket, coating utensil to make them none ticking.
v) Poly vinyl chloride(PVC):

Uses: Manufacturing of Raincoat, water pipe, electrical insulation, hand bag etc.
vi) Poly propylene:

Uses: manufacture of toys,ropes,pipes,carpet fibres etc

vii) Poly Acrylo Nitrile (PAN)/ (orlone):

Uses: It is used as artificial wool for making clothes, carpet or blanket.

viii) Polymethyl meth Acrylate: (PMMA)

Uses: Manufacture of transparent object like aircraft windows plastic jwellery,

lenes etc.
Condensation Polymer:
Polyamide: polymers possessing amide linkage are called polyamide.
(i) Nylon -6,6:

uses: in making sheets, bristles for brushes and in the textile industry.
(ii) Nylon 6
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Uses :Manufacture of tyre cords fabrics and ropes.

Polyesters:polymers possessing ether linkage are called polyester and are prepared by the
condensation polymerization of diacid with diols.
(i) dacron or Terylene.

Uses manufacture of wash and wear fabric ,tyre cords, sails and seat belts.

(ii) Glyptal.

Uses: Manufacture of paint, lacquer, and building material.

Rubber:
Natural Rubber: Natural rubber may be considered as a linear polymer of isoprene( methyl
-1, 3-butadiene) and is also called as cos -1,4-polyisoprene .The cis -poly isoprene consists of
various chains held together by weak van dor waal interaction and has a coiled structure
.Thus it can be stretched like a spring and exhibit elastic property.

Natural rubber is polyisoprene while trans polyisoprene is known as Gutta percha which is
also obtained from Natural sources.

It is used in the preparation of golf ball cable of submarine furniture.

Disadvantages of using pure rubber.
(i) pure rubber is soft at high temperature and brittle at low temperature.
(ii) it has poor tensile strength and abrasion resistance.
(iii) it is soft and sticky with a high water absorption capacity.
(iv) pure rubber is easily attacked by O2 and ozone thereby decreasing its stability.
Vulcanisation: vulcanisation is the heating of natural rubber with Sulphur and an
appropriate additive to improve its physical property .on vulcanisation sulphur forms cross-
linked at the reactive site of the double bond and thus rubber gets stiffened..
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Properties of rubber that change on its vulcanisation.

(i) vulcanisation increases the hardness and tensile strength of rubber.

(ii) vulcanisation remarkably increases the elasticity of rubber.
(iii) it remains affected by Ozone or oxygen.
(iv) vulcanised rubber is abrasion resistance and thermally stable.
The strength of vulcanised rubber depends on the quantity of sulphur present in it. 1-2%
sulphur give soft and elastic rubber and 5 to 10% give hard and solid rubber but 30% sulphur
present in rubber gives extremely hard rubber.

Synthetic rubber: synthetic rubbers are either polymer of 1 3 butadiene derivatives Or

copolymer of 1 3 butadiene or its derivative with another unsaturated monomer.
Neoprene:

It is used to make gaskets ,soles and heels, pipe hoses, insulations.

Buna -N ( nitrile butadiene rubber) :

It is used to make gaskets ,conveyor belts, synthetic leather ,and printer rollers.

Buna-S ( styrene butadiene rubber, SBR)

Bu stands for butadiene in Na stands for Sodium and S stands for styrene.

Uses: Buna S primarily used to make automobile Tyres .It is widely used to make shoes,
heels and soles ,hoses ,doormat ,floor mat etc.

Biodegradable Polymers :Polymers which are decomposed by environmental

microorganisms to form natural by-products such as gases(CO2, N2) , water biomass etc are
known as biodegradable polymers.
Example : poly Acetic Acid (PLA),Polyl-β-hydroxybutyrate(PHB),
polybutylene succinate(PBS)
Non Biodegradable Polymers: Polymers which are not degraded by environmental
microorganism and hence cannot be converted into simple molecules are called Non
Biodegradable polymers.
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Example: Plastic like polyethylene, polyvinyl chloride ,polystyrene etc

Natural biodegradable polymer
example starch cellulose protein etc
Synthetic biodegradable Polymers :
Example polybutylene succinate ,polybutylene adipate,
Biodegradable polymer obtained from natural polymer:
Example: cellulose acetate ,methyl cellulose
Synthetic biodegradable polymer
Example :poly acetic acid, poly(glycolic acid )poly (lactic acid),polycaprolactone, nylon2-
nylon-6.

Phenol formaldehyde polymer (bakelite and related polymer) :These are obtained by
condensation reaction of phenol with formaldehyde in presence of either an acid or base
catalyst the initial product could be a linear product novolac.

Novolac on heating with formaldehyde undergoes cross-linking to form bakelite.

Bakelite is used for making comcomb, electrical switches and handling of various utensils.

Differences between Thermoplastic and Thermosetting:

Thermoplastic Thermosetting
i) These softened and melt on i) These do not softened on heating
heating. but rather become hard. On
prolong heating. This starts
burning.
ii) These can be remoalded, recast ii) These cannot be removlded and
and reshape. reshaped.
iii) These are less brittle and soluble iii) These are more brittle and
in organic solvent. insoluble in organic solvent.
iv) These are formed by addition iv) These are formed by
polymerization. condensation polymerization.
v) Ex: polyethylene, PVC, Teflon. v) Bakelite, Terylene
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