WHAT IS A POLYMER?

These are macromolecules (higher molecular weight compounds) formed by the

repeated linkage of large number of small molecules called monomers.

A polymer consists of a large number of simple monomeric structural units which are
repeated over and over again to form a giant molecule called a macromolecule.
The molecular weight of a polymer usually ranges from 5000Da to several million
Dalton.

Example : Polyethylene

Polymerisation
n CH2 CH2 CH2 CH2 polyethylene
n
Ethylene
Monomer

CH2 CH2 CH CH
2 2

Monomeric unit in a
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polymer
 Degree of polymerisation (P)

Degree of polymerisation represents the number of structural units

or monomeric units contained in a polymer

P = M/m; Mass of a polymer M = m x P; m = mass of monomeric unit

Polymerisation
3 CH2 CH2 CH2 CH2
3

Ethylene
polyethylene

Degree of polymerisation (P) = 3

Mass of this polymer M = (28 x 3) = 84Da

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 DEGREE OF
POLYMERIZATION
• The number of repeating units in the chains of which
a polymer is made up is called degree of a
polymerization (n).

• Polymers with high degree of polymerization are

called the “High Polymer”, and those with low
degree of polymerization are called “Oligopolymers”
e. g PU

• High polymers have very high molecular mass

(10000 to 1000000 u) and are called macromolecules
e. g PS
 TYPES OF MACROMOLECULES

• A macromolecule may consist of monomer of

identical or different chemical structure and
accordingly they are called Homopolymers or
copolymers (or Heteropolymers).

A A A A …
Homopolymers

A A B A …
Copolymers
 LINKING OF POLYMERS
• Polymers can be linear, branched or cross-linked.
The monomer may be arranged in the chain at
random or regularly.

(LINEAR POLYMER)
A A A A … … B B B

A A A A A A

A A A A A

A A A

(BRANCHED POLYMER)
 A A

A A A

A A A A A A

A A A

A A A A A A

(CROSS-LINKED POLYMER)
 Tacticity-- Plane representation of polypropylene
Tacticity
polymer

1. Isotactic polymers
H H H H H
CH2 C CH2 C CH2 C CH2 C CH2 C
Functional groups on the
CH3 CH3 CH3 CH3 CH3 same side of the main carbon
skeleton

2. Syndiotactic polymers
H CH3 H CH3 H
Functional groups arranged in
CH2 C CH2 C CH2 C CH2 C CH2 C the alternate fashion of the
main carbon skeleton
CH3 H CH3 H CH3

3.Atactic polymers
H CH3 CH3 H H
Functional groups arranged in
CH2 C CH2 C CH2 C CH2 C CH2 C a random manner around the
main carbon skeleton
CH3 H H CH3 CH3
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 Functionality
The number of reactive sites present in a monomer is called functionality

1.

O
Linear chain polymer is formed if the functionality of the
HO C CH2 NH2
monomer is only two (Bifunctional)

2. Ex. Glycine

O
O
HO C CH2 NH2
OH CH2 CH C OH
NH2

Ex. Serine
O
Cross linked chain polymer is
OH CH2 CH C OH formed if the functionality of the
monomer is more than two
NH2 (multifunctional)
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Glycine
 Classification of Polymers
• Classification based on Source
1. Natural polymers
E.g., Proteins, Cellulose, Starch, Rubber (polymer
of cis isoprene). Gutta Percha is a polymer of
isoprene having trans configuration.

2. Semi-synthetic polymers
E.g., Cellulose derivatives - Cellulose acetate
(Rayon)

3. Synthetic polymers
E.g., Buna-S, Buna-R, Nylon, Polythene, Polyester.
• Classification based on Structure
1. Linear polymers
consist of long and straight chains. E.g., Polyvinyl chloride

2. Branched chain polymers

contain linear chains having some branches, e.g., low density polymer.

3. Cross-linked or Network polymers

formed from bi-functional and tri-functional monomers and contain
strong covalent bonds e.g. bakelite, melamine,
• Classification based on Molecular Forces
1. Elastomers- elasticity of an
Elastomer is caused by lenghtening
And shortening of their polymeric
Chain springs. Low molar cohesion, poor mechanical properties,
Tensile strength-300-1000 psi.
eg. Buna-S, Buna-N, neoprene
2. Fibers- Strongest. Tensile strength- 20,000-150000 psi. strong
Intermolecular forces, crystalline in nature.
eg. Polyesters, Polyamides.
3. Plastics- much stronger than rubber, tensile strength- 4000-13,000 psi.
a. Thermoplastic polymers- can be softened on heating and hardened on cooling reversibly i.e,
their hardness is a temporary property subject to change with rise or fall of temperature. They
can be processed again and again.
eg. Polythene, Polystyrene, PVC.
b. Thermosetting polymers- during molding gets hardened and once they have solidified they
cannot be softened, they are permanent setting polymers. Such polymers acquire 3D cross
linked structures with strong covalent bonds.
eg. Bakelite, urea-formaldelyde resins
Order of strength :-
Thermosetting > Fibres > Thermoplastics > Elastomers
• Classification based on mode of Polymerization
1. Addition polymers
formed by the repeated addition of monomer molecules
possessing double or triple bonds
n(CH2=CH2) -(CH2 -CH2 )-
Ethylene polyethylene

2. Condensation polymers
formed by repeated condensation reaction between two
different bi-functional or tri-functional monomeric units.
eg. terylene (dacron), nylon 6, 6, nylon 6.

n(H2N(CH2)6 NH2) + n(HOOC(CH2)4COOH)

[-NH(CH2)6NHCO(CH2)4CO-]n + nH2O
(Nylon 6:6)
 POLYMERIZATION
• Polymerization is of two types;

Addition or chain polymerization

Condensation polymer
1. Free radical mechanism:- Alkenes or dienes and their derivatives are
polymerized in the presence of a free radical generating initiator (catalyst)
like benzoyl peroxide, acetyl peroxide, t-bu peroxide, etc.

This process involves in 3 steps –

a) Chain initiation step - addition of phenyl free radical formed by the
peroxide to the ethene double bond ,thereby forming a larger radical.

b) Chain propagation step - repetition of this sequence with new and bigger
radicals.

c) Chain terminating step - the product radical thus formed reacts

with another radical to form the polymerized product.

Some of polymers formed by this process are-

Polytetrafluroethene (Teflon), Polyacrylonitrile, Polyethylene, etc.
 ADDITION OR CHAIN POLYMER

In addition polymers , the polymer is formed from
the monomer, without the loss of any material, and
the product is the exact multiple of the original
monomeric molecule.

CH2=CH2 -CH2-CH2- POLYMERIZATION (-CH2-

CH2-)n
Ethylene monomer Molecular Rearrangement Polyethylene
Addition polymerization proceeds by the initial
formation of some reactive species such as free
radicals or ions and by the addition of the reactive
species to the other molecule, with the regeneration
of the reactive feature.
 CHAIN
POLYMERIZATION
Chain polymerization occur in three steps:-

•Chain initiation step

•Chain propagation step
•Chain termination step
 CHAIN INITIATION STEP
In chain initiation step, a free radical is first generated
as a result of physical or chemical effect, which is
responsible for the further continuation of the chain
polymerization
 CHAIN PROPAGATION STEP
The primary free radical react with the double bond of
an unexcited monomer molecule and adds to it
forming a new radical capable of further interaction
with the initial monomers.
 CHAIN TERMINATION STEP
The most common termination processes are Radical
Combination and Disproportionate.
These reactions are illustrated by the following equations.
 CONDENSATION
POLYMERIZATION
In condensation polymerization, the chain growth is
accompanied by the elimination of small
molecules.
The molecules are in the form of the water molecule
H2O ; methanol molecule CH3OH ,etc.
Step Growth polymerization:- It involves a repetitive condensation
reaction between two bi-functional monomers.
Eg. Formation of Nylon 6,6
nHOOC(CH2)4COOH + nH2N(CH2)6 NH2 553K
High pressure

[-N-(CH2) 6-N-C(CH2)4-
C-]n

H O O
Nylon6,6