POLYMER SCIENCE AND TECHNOLOGY

Shiv Govind Prasad

Assistant Professor, UPTTI, Kanpur

INTRODUCTION:

The term polymer derived from the Greek words (Poly+mer). Poly means- many and mer
means– parts or unit. Thus polymer is large molecule, formed by repeating linking of thousands
of small molecular units by chemical bonds. Monomer is a small molecule which may react
chemically to link together with other molecules of the same type to form a large molecule called
polymer.

History of polymers starts with the formation of earth when basic elements such as C, H, O, N in
the way of forming complex molecules, have formed polymers. From basic molecules to
formation of human body is actually the story of formation of polymers. In the path of man
living in the jungles to today’s man living in modern worlds is the way of development from
natural polymers (starch, cellulose, cotton etc) to man-made polymer known as synthetic
polymer.

Discovery and use of synthetic polymers starts when we start using decorative article, textiles,
building materials, packaging material and finally use of plastics in our day to day life that we
cannot imagine our life without plastic.

Use of polymer like plastic, fibre and rubber came into human life in such a big way because of
high strength, light weight, good flexibility, special electrical properties, resistant to chemicals
etc.

The first modified natural polymers cellulose nitrate and casein-formaldehyde was commercially
produced in the year 1860. The first fully synthetic polymer is phenol-formaldehyde resin called
Bakelite was made by Leo Backeland in the year 1907. Cellophane was invented in the year
1908 by Jocques Brandenberger. The major development of polymer science and technology has
taken place since about in the year 1920.

In 1922 Hermann Staudinger was the first to propose that polymers consist of long chains of
atoms held together by covalent bonds. He also proposed to name this compound
macromolecule. Before that, scientists believed that polymer were clusters of small molecules
(called colloids) without definite molecular weight, held together by an unknown force.
Staudinger received the Noble Prize in chemistry in the year 1953. Wallace Carothers invented
the first synthetic rubber called neoprene in 1931 and invented nylon a true silk replacement in
the year 1935. Stephanie Kwolck developed and aramid, or aromatic nylon named Kevlar.
There are now a large number of commercial polymers, including composite material such as
carbon fiber-epoxy, polystyrene-poly-butadiene (HIPS), Acrylonitrile-butadiene-styrene (ABS)
and other such material which have best properties of their various components including
polymer designed to work at high temperature in automobile.

MONOMER:

It is a simple molecule with two or more binding sites through which it forms covalent
linkages with other monomer molecule to form polymer. Monomers are thus building block of
polymers. All simple molecules cannot behave as monomers but only those with two or more
building site can act as monomer.

POLYMER:

A polymer is a large molecule built by the repetition of small simple molecule called
monomer. The repeating chemical units are covalently linked to each other in a macromolecule.
The properties of a polymer are entirely different from those of the monomers from which it is
formed. The molar masses of polymer vary from 103 to m107.

n CH2=CH2 (Addition polymerization)  -[CH2-CH2]n-

(monomer) (polymer)
 Due to large size of polymer they are also some times called macromolecule.
 The chemical process leading to the formation of polymer is known as polymerization.
 The number of monomeric units contained in the polymer is known as Degree of
Polymerization (DP)
Molecular weight of polymer (M)= DP x Molecular weight of monomer (m)

CHARACTERSTICS OF POLYMERS:
1. Polymeric molecules are very big molecule. Their average molecular weight of the order
of 105 or more. That’s why they also known as Macromolecule.
2. Polymers are semi-crystalline material. It contains both the properties of amorphous as
well as crystalline. Crystalline region provides strength and hardness and the amorphous
region provide flexibility to polymeric material.
3. Inter molecular forces in polymers can be Wander Waals Forces, dipole-dipole attractions
or hydrogen bonding.
4. The chemical, electrical, optical, mechanical and thermal properties of polymers depends
mainly on (i) Size and shape of polymers and
(ii) The presence or absence of characteristics intermolecular forces
5. Polymer are combustible materials, have low densities and show excellent resistance to
corrosion.
6. Polymer are thermal and electrical insulator and easily mouldable even into complex
shapes.
CLASSIFICATION OF POLYMER:

There are several ways to classify polymers. The classification is based on several
considerations. The source or origin, type of polymerization, nature, type of chain, solid state
behavior etc. are shown in below figure.

Figure: Classification of polymers

CLASSIFICATION OF ON THE BASIS OF POLYMERIZATION: On the basis of
chemistry of polymerization, polymerizations are classified as two types:

1. Addition Polymerization or Chain growth polymerization.

2. Condensation Polymerization or Step growth polymerization

ADDITION POLYMERIZATION OR CHAIN GROWTH POLYMERIZATION:

The process of polymerization in which monomers directly combine to form polymer

without elimination of any small molecule is called addition polymerization and the polymer
formed by this process is called as addition polymer. e.g. Teflon, Orlon, polystyrene, PVC, etc..

n CH2=CH2 (Addition polymerization)  -[CH2-CH2]n-

(monomer) (polymer)

SAILIENT FEATURE OF ADDITION POLYMER:

 For addition polymerization monomer must contain double or multiple bonds.
 The empirical formula of polymer is same as the empirical formula of monomer i.e. the
molecular weight of the polymer is an integral multiple of the molecular weight of the
monomer.
 In addition polymerization the type of mechanism involves is chain reaction therefore it
is also called Chain growth polymerization.
 Addition polymer is obtained by successive addition of monomer to growing polymer
chain.
 For addition polymerization some chain initiator is required like free radical or
carbocation or cabanion.
 In addition polymerization or chain growth polymerization, monomers do not combine to
each other, but they combine with the growing chain at active centre created by initiator.

Addition Polymerization:

Addition Polymerization
n CH2=CH CH2-CH Where X= Cl, CN, OCOCH3, C6H5
n
X X
Viny Monomer Vinyl Polymer

MECHANISM: Chain growth addition polymerization involves mainly following three steps.
a) Chain Initiation- Creation of active center after linking of two monomeric units is
known as active centre.
 b) Chain Propagation- Growth of polymer chain having active center is called
propagation steps.
c) Chain Termination- removal of active centre by coupling or by Disproportionation or
by chain transfer is called chain termination step.

TYPES OF ADDITION POLYMERIZATION: Depending upon the nature of active centre or

the chain carrier, the polymerization is classified as follows:
(A) Free Radical Addition Polymerization
(B) Ionic Addition Polymerization

RADICAL OR FREE RADICAL CHAIN GROWTH ADDITION POLYMERIZATION:

In this polymerization process initiation of chain is brought about by either light radiation or by
heat or by organic peroxides. e.g. Polymerization of vinyl compound in presence of benzoyl
peroxide.

C6H5-CO-O-O-CO-C6H5
n CH2=CH CH2-CH Where X= Cl, CN, OCOCH3, C6H5
Benzoyl peroxide
n
X X
Viny Monomer Vinyl Polymer

MECHANISM:
Chain initiation
C6H5-CO-O-O-CO-C6H5 C6H5-CO-Oo + oO-CO-C H
2 C6H5o + 2 CO2
6 5

Active Centre
C6H5o + CH2=CH C6H5-CH2-CHo

X X
Chain propagation

C6H5-CH2-CHo + CH2=CH C6H5-CH2-CH-CH2-CHo

X X X X

Chain Termination: removal of active centre is called chain termination.

IONIC POLYMERIZATION: In ionic polymerization is of two types:

(i) Cationic Polymerization
(ii) Anionic Polymerization
  Anionic and Cationic polymerization are complex and more versatile than free radical
chain polymerization.
 The initiation reaction of ionic polymerization requires only small amount of activation
energy. Therefore, these types of reaction occur at very low temperature.
 Similar to radical polymerization, ionic polymerization has also the mechanism of chain
reaction.

CATIONIC OR CATIONIC CHAIN GROWTH POLYMERIZATION:

 Cationic polymerization takes place in presence of acidic species e.g. HF, H 2SO4, H2O or
by Lewis Acid AlCl3, BF3, SnCl4.
 For cationic polymerization monomer should have electron releasing groups (+I Effect).
 For cationic polymerization carrier of chain is positively charge carbocation i.e. Active
centre of carbocation.

n CH2=C(CH3) H

MECHANISM:
(i) Chain Initiation: Chain initiation is also brought about by Lewis acid e.g. AlCl 3, BF3,
but these halides are active only in presence of water.
BF3 + H2O → H+[BF3-OH]Ɵ
(ii) Carbonium ion salt are also used to initiate the chain e.g. (C 6H5)C+ SbCl6Ɵ (Trityl
hexachloro antimonate)
(iii) Chain Propagation:
(iv) Chain Termination: