POLYMERS

Polymers

Polymers are defined as high molecular mass macromolecules which consist of repeating
structural units derived from the appropriate monomers.

Monomer

The unit molecules that combine with each other to to form a polymer is called a monomer.

Polymerisation

The process of formation of polymers from respective monomers is called polymerisation.

For example:

Classification of Polymers

On the basis of source of availability, polymers can be divided into the following types:

 Natural polymers: These are the polymers that exist in nature,i.e., are found in plants and
animals.

For example: Starch, cellulose, rubber, silk.

 Semi-synthetic polymers: These are polymers that are prepared by making some modification
in natural polymers by artificial means, in laboratory.

For example: Rayon, vulcanised rubber, gun cotton.

 Synthetic polymers: These are the man-made polymers,i.e., the polymers that are prepared in
laboratory.

For example: Bakelite, Teflon, PVC, polystyrene, nylon.

On the basis of structure, polymers can be categorized into the following types:

 Linear polymers: These are the polymers in which the monomer units are linked to one
another to form long and straight chains.
These chains are closely packed in space which causes the linear polymers to have high
densities, tensile strength and high melting and boiling points.

For example:  High density polyethene (HDPE), PVC, nylon, polyester.

 Branched chain polymers: These are the linear chain polymers having some branches.

Branching causes these polymers to be loosely packed in space due to which thay have low
densities, low tensile strength as well as low melting and boiling points. For example: Low
density polyethene (LDPE), amylopectin, glycogen.

 Cross-linked or network polymers:  These are the polymers formed of various linear
polymers connected to each other by strong covalent bonds.

These are polymers hard, rigid and brittle.

For example: Bakelite, formaldehyde polymer, glyptal, melamine-formaldehyde polymer.

On the basis of mode of polymerization, polymers are of following two types:

 Addition polymers: These are the polymers formed by the repeated addition of monomer
molecules containing multiple bonds. It is further subdivided into homopolymers and
copolymers.

(i) Homopolymers: These are the polymers derived from the polymerisation of only one kind
of monomers.

For example:

(ii) Copolymers: These are the polymers obtained by the polymerisation of two or more kind
of monomers.
For example:

Condensation polymers: These polymers are formed by the repeated condensation reaction
of different bifunctional or trifunctional monomers, with the elimination of small
molecules like H2O,HCl, CH3OH. 

For example:
 On the basis of the molecular forces, the polymers can be classified as:

Elastomers: These polymers are held together by weak van der Waals, forces and have low
elasticity. For example: Buna-S, buna-N, neoprene.
Fibres: These are the polymer held together by strong hydrogen bonds. They have high
tensile strength and sharp melting point. For example: Nylon, polyster, silk, wool, orlon,
rayon.
Thermoplastics polymers: They are the polymers having intermolecular forces of attraction
intermediate between elastomers and fibers. They can be made soft and remoulded by
heating. For example: Polythene, PVC, polystrene, polypropene.
Thermosetting polymers: These are the hard, rigid, cross-linked polymers. They cannot be
remoulded once set into a desired shape.  For example: Melamine, bakelite.

Types of Polymerisation Reactions

There are two general methods of polymerisation:

(i) Addition polymerisations or chain growth polymerisation

(ii) Condensation polymerization or step growth polymerization

(iii) Copolymerisation

Addition polymerization

Molecules of the same monomer or different monomers simply add together to form a
polymer.

The monomers used are mainly the unsaturated compounds.

Addition polymerization generally follows the free radical mechanism.

 Free radical polymerization: It involves formation of reactive intermediate such as free radical,
a carbocation or a carbanion.

This is a three step process:

(i) Chain initiating step

(ii) Chain propagating step

(iii) Chain terminating step.

For example, the ethene is converted to polythene by free radical polymerization as follows:

o Chain initiating step:

o Chain propagating step

o Chain terminating step

Preparation of some important addition polymers

Polyethene

The polythene is of two types:

(i) Low density polyethene (LDPE): It is obtained by polymerization of ethene at 350 to 750
K and 1000 to 2000 atm pressure.

It is chemically inert and tough but flexible and a poor conductor of electricity.

It is used in the insulation of electricity carrying wires and manufacture of squeeze bottles,
toys and flexible pipes.

(ii) High density polyethene (HDPE): It is obtained by the addition polymerisation of ethene
at 330 to 350 K at atmospheric pressure.

It is tough and hard with high tensile strength.

It is used in the manufacture of plastic containers, house wares, pipes.

Polyacrylonitrile

• It is obtained by the addition polymerisation of acrylonitrile in presence of a peroxide

catalyst.

• It is used in the formation of substitute for wool as orlon or acrilan.

Polytetrafluoroethene (Teflon)

• It is obtained by the free radical polymerisation of tetrafluoroethene at high pressures.

• It is chemically inert and resistant to attack by corrosive reagents.

• It is used in the manufacture of oil seals and gasket and non-stick kitchen wares.

Condensation Polymerisation

Such polymerisation involves a repetitive condensation reaction between two bi-functional

monomers.

It occurs in a stepwise manner with elimination of some smaller molecules like H2O, NH3,
HCI, ROH, etc., therefore it is also named as step Growth Polymerisation.

For example: Dacron is obtained by the condensation polymerization of ethylene glycol and
terephthalic acid.

Some important condensation polymers are:

Polyamides
These are the polymers possessing amide linkages and are named as nylons.

Preparation and uses of some important polyamides are given below:

• Nylon 6: It is obtained by heating caprolactum with water at a high temperature.

It is used for the manufacture of tyre cords, fabrics and ropes.

• Nylon 6,6: It is prepared by the condensation polymerisation of hexamethylenediamine with

adipic acid under high pressure and at high temperature.

• It is used in making stocking, socks, ropes, Parachutes, fabrics, bristles of tooth brush.

Melamine – formaldehyde polymer

• It is obtained by the condensation polymerisation of melamine and formaldehyde.

• It is used in the manufacture of unbreakable crockery.

Copolymerisation

It is a type of polymerisation reaction in which a mixture of more than one monomeric

species is allowed to polymerise and form a polymer called copolymer.
Copolymer contains multiple units of each monomer.

For example: 1, 3-Butadiene and styrene can undergo copolymerization to form butadiene –
styrene copolymer ( Buna-S)

Rubber

Rubber is of two types: Natural and synthetic

1. Natural Rubber

It is a natural polymer possessesing elastic properties.

It is a linear 1, 4-polymer of isoprene (2-methyl-1, 3-butadiene).

Drawbacks of Natural Rubber:

•   It becomes soft at high temperature and brittle at low temperatures.

•   It is non-resistant to the attack of oxidizing agents.

Vulcanisation of Rubber: The process of adding sulphur to rubber to improve its physical
properties is called vulcanisation of rubber.
Vulcanisatlon is carried out by adding sulphur (3-5%) and zinc oxide to the rubber, and then
heating the object at about 110°Cfor about 20-30 minutes.

Zinc oxide accelerates the rate of vulcanisation

Sulphur forms cross links at the reactive sites of double bonds and thus the rubber gets
stiffened.

Thus about 5% sulphur is used for making tyre rubber and 30% of it for making battery case
rubber.           

The improved properties of vulcanised rubber are:

(i) High elasticity.

(ii) Low water-absorption tendency

(iii) Resistance to oxidation.

2. Synthetic Rubber

Synthetic rubbers are polymers derived from 1, 3 - butadiene or 1, 3 - butadiene derivatives.

The synthetic rubber is of two types:

•    Neoprene
     o  It is a homopolymers of chloroprene (2-Chloro-1,3-butadiene).

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

•    Buna-N

     o  It is a copolymer of 1,3-Butadiene with acrylonitrile (Buna-N) carried out in the

presence of a peroxide catalyst.
      o  Uses: It is used in making conveyor belts and printing rollers.

Biodegradable Polymers

These are the synthetic polymers that are hydrolysed by enzymes and to some extent degrade
by oxidation.

These polymers contain functional groups similar to the functional groups present in
biopolymers.

Some important examples of biodegradable polymers are given below:

1.  Poly-hydroxybutyrate- co-β-hydroxy valerate (PHBV):

•   Preparation: It is a copolymer of 3-hydroxy butanoic acid and 3-hydroxy pentanoic acid
in which the monomeric units are connected by ester linkages.

•   Uses: It is used in packaging, orthopaedic devices and even in controlled drug release.

2. Suture Polymer:

•  It is a copolymer of glycolic acid and lactic acid.

•  Sutures help the healing process by closing and sealing a wound.

•  Dextron was the first biodegradable suture made from biodegradable polyesters for post-
operation sticher.

3. Nylon-2-Nylon-6:

It is a copolymer of glycine (H2N–CH2–COOH) and amino caproic acid [H2N (CH2)5 COOH]
and is biodegradable.
Polymers of Commercial Importance

Some Commercially Important Polymers, their monomers and uses are given below:

Polymer Monomer Uses

CH2=CHCl Manufacture of rain coats, hand
Polyvinyl chloride (PVC) bags, vinyl flooring, and water
Vinyl Chloride pipes.
CH2=CH2
Manufacture of wire insulators,
Polyethylene
bags, used in packaging.
Ethylene
CH2=CH‒C6H5
As insulator, wrapping material,
Polystyrene manufacture of toys, radio and
Vinylbenzene
television cabinets
(Styrene)
CH2=CH‒OCOCH3
Polyvinyl acetate (PVA) Making latex, paint
Vinylacetate
CH2=CH‒CH=CH2
BUNA rubber Manufacture of tyres and hoses
1,3-Butadiene