Polymers

Polymer is a macromolecule formed by repeating unit of several simple

molecules called monomer.The process of linking of monomers (repeating unit) is
called as polymerization.
Monomer is a simple molecule which undergo self addition to form long chain
called polymer.Monomers are building blocks of polymers.A molecule is said to be
monomer ,if it has at least two bonding sites in the form of double bond or triple
bond or should contain groups like OH , COOH ,NCO, NH 2 etc.

Polymerisation: the process of conversion of substance of low molecular

mass(monmers) into substance of high molecular mass with or without elimination
of by products like HCl ,H2O, NH3 etc.Polmerisation reaction usually takes place in
presence of initator.
Degree of polymerization:The number of repeating unit present in a polymer is
called degree of polymerization.Here n is the degree of polymerization .When the
value of n is very large (in range of 100 or 1000)the polymers are said to be high
polymers.When the value of n is less than 10 , the polymers are called as
oligopolymers.
Functionality :The total number of bonding sites or functional groups present in
the monomer is called as functionality of monomer.
For Ex: Ethylene , methylmethaacrylate,adipic acid ,are bi functional. Phenol and
glycerol are trifunctional.
TYPES OF POLYMERISATION
There are two types of polymerization.
1)Addition Polymerisation
2)Condensation Polymerisation
1)Addition Polymerisation:The process of addition of monomer to each other by
covalent bonds without elimination of by products is called addition polymerization
and the polymer is called addition polymer.For ex:
Polyethylene,Polyvinylchloride(PVC), Polymethylmethaacrylate(PMMA) ,Teflon,
Polypropylene

a)it is also called chain polymerization.

b)Only alkene or vinyl compounds undergo addition polymerization.
c)Polymer initiates by an initiator like free radical
d) The composition of the polymer is same as monomer.
e)Addition polymerization occurs rapidly
f)No eleimination of byproducts.
2)Condensation polymerization: The process of condensation of two or more
monomersv(similar or different) with elimination of by products lke water , HCl ,NH3.
Alcohol ,etc is called condensation polymerisaton and the polymer is called
condensation polymer.
For ex: Nylon 6,6 , Expoxy resin , Polyesters.

1)It is called as step-growth polymer

2)Elimination of by products occurs
c) Reaction catalysed by acid or base
d)The polymer chain built up is slow and stepwise.
e)The composition of polymer is different from monomer.
f) Polymerization proceeds through inter molecular condensation.

Mechanism of polymerization of Vinyl Chloride by Free radical method

(6MARKS)
Polymerisation of vinyl chloride is an example of addition polymerization and takes
place by free radical mechanism.It involves four steps.
1)Generation of free radical
2)Chain Initiation Step
3)Chain Propogation step
4)Chain Termination step.

1)Generation of free radical In this step homolytic dissociation of dibenzoyl

chloride (initator) takes place.This results in generation of pair of free radical. Free
radicals are highly active species with unpaired (odd) electron.

2)Chain initiTION STEP: It involves addition of free radical to monomer, which

leads to formation of chain initiating species(radical).

3)Chain propogation step: The radical formed in above step ,attacks another
monomer to give new radical. This process continiuos and growth of polymer chain
occurs
.

4)Chain termination: The propgating chain stops growing and

terminates.Termination occurs by two methods a) Coupling b)Disproportionation.
a)Coupling: Combination of two long chain radical ocuurs .

b)Disproportionation. Here transfer of hydrogen atom of one polymer chain to

another chain ocuurs. It leads to formation of two dead polymer chains ,out of which
one is saturated and other is unsaturated

Molecular weight of polymers

Polymer chains contain chains of different length , so it is not possible assign
specific molecular mass. Hence average molecular mass is taken . The average
molecular mass is expressed in two ways
a) Number average molecular mass: it is given by Mn
b) Weight average molecular mass

Number average molecular mass:It is represented by Mn, If a sample is having

N1 molecules with molecular mass M1
N2 molecules wit molecular mass M2
Ni molecules with molecular mass Mi
The number average molecular mass , Mn =
. .

n1M1+n2M2++niMi
n 1+n2++ni

N represents number of each species

M represents molecular mass of each species

Number average molecular mass:It is represented by Mw, If a sample is having

w1 weight of molecules with molecular mass M1

w2 weight molecules with molecular mass M2

wi weight molecules with molecular mass Mi

The weight average molecular mass , Mw

. .

w1M1+w2M2++wiMi
w 1+ w2++wi

We know that , W=n M

Mw
2

+niMi
n1M1+n2M2++niMi

n 1M12+ n2M22 +

=
.

N represents number of each species

M represents molecular mass of each species
The ratio of Mw/Mn is either equal to or greater than 1. { Mw/Mn 1} .The ratio is
called poldispersity index , if the ratio is equal to one the polymer is said to be
mono dispersed . If the ratio is greater than one the polymer is said to be
polydispersed. Polydispersity is the measure of distribution of molecules of different
sizes.

ELASTOMERS
Are the polymers which elongates on stretching and regain their original shape on
leaving.
Ex :Rubber is an example of elastomer
A linear polymer can be converted into rubber if it meets following characteristics
1)It should posses glass transition temperature less than working temperature of
rubber.
2)Possibility of cross linking should be there to get required rigidity.
3)Long chains should be geometrically irregular , so that coiling can takes place on
thermal agitation.

Synthesis , properties and applications of silicon rubber

Silicon rubber is an example of inorganic polymer
It is chain of alternating silicon and oxygen atoms.Each silicon atom carries two
methyl groups.
Synthesis: Silicon rubber is synthesized by condensation polymerization of dimthyl
silanol.The dimethyl silanol is prepared by hydrolysis of dimethyl dichlorosilane.
Dimethyl silanol is unstable and immediately undergoes intermolecular
condensation to give silicone