Polymer Materials

Polymers are high molecular mass compounds whose structure is composed of a large number of
simple repeating units.
The repeating units are usually obtained from low molecular mass compounds called monomers.
Polymers have very vast spectrum of properties and this is why they are so important for
different applications.
The polymer materials are so important in our daily life that survival of human life depends on
these polymers.

What is polymer?

In modern civilization, almost every part of life involves polymers. Polymers are chief products of plastics,
elastomers , fibres and paint & varnish industries. The use of polymers in furniture, automobile parts,
tyres, gear and seals are very much common in our daily life.Polymer is a combination of two Greek word;
Poly means many and mer means unit or parts. Polymer defined as giant molecules with very high
molecular mass and consists of a large number of repeating units, which are known as monomers.

The process of formation of polymer from various monomer units is known as polymerisation. It involves
the conversion of small molecular mass units (monomers) to high molecular mass unit called as polymer.
The term polymer and macromolecules are often used as for same type, but there are some very
important differences between both of them. Polymers are made up of hundred to thousand monomer
units, but it not necessary for macromolecules also. For example; protein, carbohydrates are example of
macromolecule but polythene is an example of polymer. Hence all polymers are macromolecules but all
macromolecules are not polymers.
The branch of science which deals with the structure, properties, reactivity and applications of polymers in
called as polymer science.

Polymerization

The process of formation of polymer from monomer units is known as polymerisation. Depending on the
mode and mechanism of polymerisation reaction, polymerisation can be two types;
1. Addition polymerisation
2. Condensation polymerisation

1. Addition polymer
a. Polymers formed when the individual units are joined together
without the gain or loss of any atoms.
 2. Condensation polymer
a. Polymers formed when the individual units are joined together
with the splitting off of a small molecule by-product.

Copolymer

Polymers formed from two or more different monomers.

Monomers

Small, individual subunits which join together to form polymers.

Polyamide

A polymer, such as nylon, in which the monomers are joined together

by amide linkages.

Addition Polymerisation:

When monomer units added to grow a polymer chain caring a reactive intermediate like free radical,
carbocation or carbanion is known as addition polymerisation.
Since it form a long polymer chain; it also known as chain growth polymerisation.
For example; ethene (H2C=CH2) polymerised and for polythene.

On the basis of the presence of intermediate, addition polymerisation can be three types;

Free radical addition polymerisation:

When polymerization is initiated by peroxides, free radical formed as intermediate.
A verity of unsaturated compounds like alkenes, alkadiens readily undergoes polymerisation in the
presence of peroxide like benzoyl peroxide, acetyl peroxide in the presence of high temperature and high
pressure.
For example; the polymerisation of ethene to form polythene followed free radical polymerisation.
Reaction takes place at high temperature (350-570 k) and high pressure (1000-2000 atm) in the presence
of benzoyl peroxide as an initiator for reaction.
Peroxide generates free radical which reacts with ethene to form another radical, which involve in
propagation step to polymer chain.
The combination of polymeric chain through radical site terminates the reaction to form polymer chain.

Cationic addition polymerisation:

Cationic polymerisation initiated by an acid, which adds on the double bond to form a cation.
This cation involve in chain propagation steo to form polymer chain.
The polymersation of isobutylene to form butyl ruber is an example of cationinc addition polymersation.
Common acids used are phosphoric acid sulphuric acid, are used as initiators.

Anionic addition polymerisation:

Just like free radical and cationic addition polymerisation, an anion can be an initiating reagent in
polymerisation reaction.
Such type of polymerisation reaction is called as anionic addition polymerisation.
Generally vinyl compounds show this type of polymerisation as their positive charge get stabilised by
anion through delocalisation.
Styrene, dienes, methacrylate, vinyl pyridine, aldehydes, epoxide, cyclic siloxane, and lactones show this
type of polymerisation as there is a possibiliy of delocalisation charge in the presence of some anion.
The common initiators for anionic addition polymerisation are covalent or ionic metal amides, alkoxides,
hydroxides, cyanides, phosphines, amines and some organometallic compounds.
For example; formation of polystyrene initiated by anion and form polystyrene.

Condensation polymerisation:

When both reactant of a chemical reaction are bifunctional , they undergoes a series of condensation
reactions and form a polymer chain.
The condensation process takes place in a stepwise manner with the loss of simple molecules like water,
carbon dioxide, alcohol, etc. Condensation polymerisation starts form the condensation reaction of two
reactant molecules and form dimer.
This dimer again reacts with another molecule to forms trimer and so on.
Since the product of condensation reaction is also bifunctional, therefore the sequence of condensation
goes on and the polymer chain keeps on growing step by step.
For example; condensation polymerization of terephthoyl chloride and ethylene glycol forms a polyester
known as poly(ethyleneterephthalate) by the elimination of hydrochloric acid.

Instead of tersphthoyl chloride benzene-1,4-dicarboxylic acid can be used for the formation of PET or
decron.

Another example of condensation polymerisation is Polyurethanes , which is made from a dialcohol and
diisocyanate monomers.

Classification of polymers

Polymers can be classified in a number of ways;

1. Based upon the sources or origin.
2. Based upon the structure of polymer.
3. Based upon the molecular forces.
4. Based upon the nature of monomer units.

Based upon the polymer sources or origin: On the basis of origin or polymer sources, they can be
classified in three types;
(a) Natural polymer: Such type of polymer found in nature like in animal and plants. For example;
protein, cellulose, rubber are natural polymer.

(b) Semi-synthetic polymer: The derivatives of natural polymers included in this class. For example;
cellulose acetate is a derivative of cellulose, which form due to acetylation of cellulose and used for
making threads, films and glasses.

(c) Synthetic polymer: They are man-made polymers made synthetically and extensively in daily life,
like; fibres, plastics, rubbers.

Based upon the structure of polymer:

On the basis of structure of polymers, they can be classified in three types;

(a) Linear polymer: When monomer units are joined together in the form of long straight chain and these
polymeric chains are stacked over one another to give a well packed structure, than such arrangement of
monomer unit is known as linear polymer. For example; polythene, polyvinylchloride, etc. Linear polymer
shows high melting point, high tensile strength and density value.
(b) Branched polymer: when the polymeric linear chains get branches of different length along the main
chain, called as branched polymers. Du to branching along the main chain, these polymers shows low
melting point, densities as well as tensile strength. For example;
glycogen.
(c) Crossed linked or three dimensional network polymer:
In such type of polymers, the linear polymer chains are joined together to form a three dimensional
network.
Due to cross, linking between linear chains, this polymer also termed as cross-linked polymer.
They are hard, rigid and brittle in nature like Bakelite, urea-formaldehyde resin etc.

Based upon the molecular forces:

The mechanical and chemical properties of polymers depend on the intermolecular forces of
attraction like van der wall
forces, hydrogen bonds and dipole-dipole interaction between polymeric chains.
Since the magnitude of these forces depend upon the molecular size and the number of functional group
present in polymers.
On the basis of these intermolecular forces, polymers can be classified in four categories;
(a) Elastomers:
They have weakest attraction force in between polymeric chains. Hence they are amorphous with high
degree of elasticity. They have ability to starch out over ten times than the original length and back to
original position after removing the force. For example; Buna-S , Buna-N , Neoprene.
(b) Fibre: these types of polymers have strongest intermolecular force of attraction between polymeric
chains.
Due to strong force of attraction, they have high tensile strength, and least elasticity. Here either
hydrogen bond or dipole-dipole interaction involve between chains.
Since the molecules of theses polymers are thread like and easily packed, they are termed as fibres.

(c)Thermoplastic (Polymer plastic): they have intermediate intermolecular force of attraction between
molecules.
In such type of polymers, hard linear and branched chain become soft after heating but again get
rigidness after cooling.
The process of heat softening and cooling can be repeated as many times as desired without changing
the chemical composition of polymers. Polythene, polyvinyl chloride, Teflon, polystyrene is some of the
example of thermoplastics.

(d) Thermosetting polymers(Polymer plastic) : They are low molecular mass substance which can be
mould on heating.
But unlike to thermoplastics, the chemical composition gets changed for them after heating to give a hard,
infusible and insoluble mass.
The Harding on heating is due to the cross linking of polymeric chains to give a three dimensional
network polymer and hence they can be heated only once. For example; Bakelite, urea-formaldehyde
resin etc.

Based upon the nature of monomer units: On the basis of nature of repeating units in polymers, they
can classified as ;

(a) Homopolymers: Those polymers which are made up of same type of monomer units are known as
homopolymers.
For example ; Polyvinylchloride is an addition polymer which contains same type of monomer unit that is
vinyl chloride.
nCH2=CH-Cl -----------> -[-CH2-CH-Cl-]-n
Vinyl chloride Polyvinylchloride

(b) Copolymer: When two or more types of monomer units associated in polymerisation reaction to form
polymer, than such type are called as copolymers.
For example; Nylon-6,6 formed by the condensation polymerisation of edipic acid and
hexamethylenediamine.
While Nylon-6 firmed by the polymerisation of Caprolactum only, hence its an example of homopolymers.

Polymer uses

The light duty tyres, belting, hoses and rubber sole are made from the synthetic
rubber or from Buna-S a polymer from styrene and butadiene.Fabric and magnetic
recording tapes are made of Dacron or terylene, a polymer obtained from the
monomers of ethylene glycol and dimethyleterepthallic acid.The glyptol a polymer of
pthallic acid and ethylene glycol is used for the manufacture of paints and
liquors.Nylon-66 is polymer of hexamethylene diamine and adipic acid, it is used to
prepare fabrics, tyre cords, ropes, carpets etc..

Images showing polymer materials

Lot of electric goods , phonograph, records, fountain pen barrels, combs etc.., are
made from a polymer of formaldehyde and phenol called Bakelite.Melamine-
formaldehyde resin or melamine is used in the manufacture of plastic
crockery.Polyurethane a polymer of ethylene glycol and ethylene di-isocynate is used
in the manufacture of paints and heat insulators.Polythene is used to prepare pipes,
toys bags, wire insulators, bottles etc..,The polyvinyl chloride is used to
prepare sheet, water pipes, hand bags etc .Radio and television cabinetare
prepared from the polystyrene a polymer of styrene.Insulators and gaskets are
prepared from the polymer material Teflon or poly fluoroethene.Latex paint is prepared
from polymer material polyvinyl acetate.Now a days polymers are being used in
nanaotechnology and a lot of research is under progress to find the use and the
properties of the polymers for use as semiconductors.Polyacrylonitrile is used to
prepare Orlon fiber and acrilon films.