SRI KRISHNA COLLEGE OF ENGINEERING AND TECHNOLOGY

(AN AUTONOMOUS INSTITUTION, AFFILIATED TO ANNA UNIVERSITY, ACCREDITED BY NAAC WITH ‘A’ GRADE)
ACCREDITED BY NBA (CSE, IT, ECE, EEE, MECH, MCT & CIVIL)

SKCET CLASS LECTURE

SUBJECT : 23AS101 - APPLIED SCIENCE

(Common to B.E. CSD, CSE, CSE (CYBER SECURITY),
ECE, EEE, MCT & B.Tech. AI&DS, IT)

MODULE : POLYMERS

TOPIC : POLYMERS & ITS CLASSIFICATION

FACULTY : Dr. M. JEYARAJ

www.skcet.ac.in
 Polymer Chemistry

Introduction

Classification of Polymers

Degree of Polymerization (Simple Problems)

Mechanism of Addition polymerization

 Introduction to polymers

• Polymers are “macromolecules” (molecules of high molecular

weight) made up by linking together of large number of small
molecules called “Monomers”.
Example
• Polythene is a polymer formed by linking together of a large
number of ethene molecules.

2CH2=CH2 -(CH2-CH2)-(CH2-CH2)-
Ethylene Poly ethylene
(Monomer) (Polymer)
 Introduction to polymers

• Monomers are “micromolecule”(small molecule) which

combines with each other to form a polymer.

• Examples

H H H H

C C C C

H H CH3 H

Ethylene Propylene
 Representation
of Polymerization
 NOMENCLATURE OF POLYMER

1. Homo polymer

2. Hetero polymer (or) co polymer

3. Homo chain polymer

4. Hetero chain polymer

5. Tacticity or Sterio specific Polymers

 NOMENCLATURE OF POLYMER

Homo polymer
A polymer containing same type of monomers is
known as homo polymer.
Example : polyethylene, polypropylene
- M - M - M - M- M - M - M - M - M - M -
 NOMENCLATURE OF POLYMER

Homo chain polymer

If the main chain of a polymer is made up same
species of atoms, it is called homochain polymer.
Example : polyethylene, polypropylene
- C - C - C - C - C - C - C - C - C-
Hetero chain polymer
If the main chain of a polymer is made up different
species of atoms, it is called hetero chain polymer.

Example: Nylon-6, Nylon-6,6

Structure: - C - C - O - C - C - O - C - C - O - C - C –
 NOMENCLATURE OF
POLYMER
The orientation of monomeric units or functional
groups in a polymer molecule can takes place in an
orderly or disorderly manner with respect to the main
chain is known as tacticity.
Types of Tacticity (IAS)
1. Isotactic polymer
2. Atactic polymer
3. Syndiotactic polymer

specific Polymers
Tacticity of Polymer
 FUNCTIONALITY OF A
POLYMER
The number of bonding sites or reactive
sites or functional groups present in a
monomer/polymer is known as its functionality

EXAMPLE FUNCTIONALITY
2 (two bonding sites are due
CH2=CH2 to the presence of one
(Ethylene) double bond in a
monomer)
NH2-(CH2)6-NH2 -2(this monomer contains
Hexamethylene two functional groups ,hence
diamine it is a bi functional
monomer)
 Degree of Polymerization

The number of repeating units (n) or monomer

present in the polymer chain is called the degree of
polymerization.

DP = average number of repeat units per chain

Mn - molecular weight of the polymeric network
m- molecular weight of the repeating unit
Example: 2CH2=CH2 -(CH2-CH2)- (CH2-CH2)-
In this example two repeating units are present in
the polymer chain aSo the degree of polymerization is
2.
 Types of Degree
of Polymerization
1. Oligo Ploymers
Polymers with low degree of polymerization are known
as oligo polymer, their molecular weight ranges from
500-5000.
2. High Ploymers
Polymers with high degree of polymerization are known
as high polymer, their molecular weight ranges from
10,000-2,00,000.
 Problems

1.Calcuate the degree of polymerisation of PVC.

DP= Mn/m
m= 2 X 12.01+ 3 X 1.01+ 1 X 35.45 = 62.50 g/mol
Mn = 21150 g/mol

DP= 21150 g/mol /62.5 g/mol =338.4.

 Problems
2.You have a Nylon 6,6 with an average molecular
weight of 250,000 g/mol. Calcuate the degree of
polymerisation for this polymer.
DP= Mn/m
Chemical formula: (C12H22N2O2)n
C = 12 X 12.01g/mol, O = 2 X 15.999 g/mol
N = 2 X 14.066 g/mol, H = 22 X 1.01 g/mol
m= 226.3 g/mol Mn = 250000 g/mol
DP = 250000 / 226.3 = 1104
 Polymerisation

Polymerization is a process in which large number of

smaller molecules combine to form a big molecules with
or without elimination of small molecules like water, HCl.
Types of polymerisation
1. Addition or chain growth polymerisation
2. Condensation or step wise polymerisation
3. Co-polymerisation
 Types of polymerisation

1. Addition or chain growth polymerisation

It is the reaction that yields a polymer, which is an
exact multiple of the original monomeric molecule.
The original monomeric molecule, usually contains
one or more double bond
There is no by-product.
Example:
nCH2=CH2 -(CH2-CH2)- (CH2-CH2)n-
Ethylene Poly ethylene
 Types of polymerisation
2. Condensation or step wise polymerisation
It is a reaction between simple polar groups
containing monomers with the foemation of polymer and
elimination of small molecules like water ,HCl.
Example:
 Types of polymerisation
Nylon 6 (Self Polymerization)
In some case condensation polymerisation takes
place without elimination of small molecules like HCl,
H2O but by just the opening of cyclic compounds.
Example:
 Types of polymerisation
3. Co polymerization (Joint Polymerization)
Butadiene and styrene co polymerize to give GR-S
rubber.
nCH2=CH-CH=CH2 + n CH2=CH-C6H5
butadiene styrene

-(CH2-CH=CH-CH2-CH2-CH-C6H5)n
Styrene butadiene rubber - SBR
 Difference between…

Addition polymerization Condensationpolymerization

• The monomer must have • The monomer must have at
least two identical (or)
at least one multiple
different functional groups.
bond.
• Example :
Example : glycol CH2-OH

Ethylene CH2=CH2 CH2-OH

6-amino hexanoic acid
Acetylene CH≡CH H2N-(CH2)6-COOH
 Difference between…
• Monomers add on to give • Monomers condese to give
a polymer and no other by a polymer and by product
product is formed. such as H2O, CH3OH are
• Number of monomeric formed.
units decreases steadily
• Monomers disappear at
throughout the reaction.
the early stage of
• Homo chain polymer is
reaction.
obtained.
• Heterochain polymer is
obtained.
 Difference between…

• Molecular weight of the • Molecular weight of the

polymer is an integral polymer need not be an
multiple of molecular integral multiple of
weight of monomer. monomer.
• Thermoplastics are • Thermosetting plastics
produced are produced.
• High molecular weight • Molecular weight of the
polymer is formed at polymer rises steadily
once. throughout the reaction.
 Mechanism of
Addition Polymerization

The mechanism of addition polymerization

canbe explained by any one of the following
three types.
• Free Radical mechanism
• Ionic mechanism
• Co ordination mechanism
 Free radical mechanism

Free radical mechanism occurs in three major steps

namely,
(i) Initiation -Initiators are compounds which produce
free radicals by the homolytic dissociation . These
free radicals initiate the polymer chain growth .
(ii) Propagation
(iii) Termination
 Free radical mechanism

(i) Initiation
It involves two reactions
(a) First reaction involves production of free radicals
by homolytic dissociation of an initiator (or)
catalyst to yield a pair of free radicals (R)◦
R 2R◦
initiator free radical
 Free radical mechanism

Example-Thermal Initiators
Themal initiator is a substance used to produce free
radicals by homolytic dissociation at high
temperature.
 Free radical mechanism

(b) Second reaction involves addition of this

free radical to the first momoner to produce
chain initiating species.

Free radical First monomer chain initiating species

 Free radical mechanism

(ii) Propagation
It involves the growth of chain iniating species by
successive addition of large number of monomers.

Growing chain or living polymer

The growing chain of the polymer is known as living
polymer.
 Free radical mechanism

(iii) Termination
Termination of the growing chain of the polymer may
occur either by coupling reaction or
disproportionation
a) Coupling or combination

b) Disproportionation
 Free radical mechanism

(a) Coupling or combination

It involves coupling of free radical of one chain end to
another free radical forming a macroliving polymer
molecule.

Macromolecule (dead polymer)

 Free radical mechanism

(b) Disproportionation
It involves transfer of a hydrogen atom of one radical centre
to aother radical centre, forming two macromolcules, one
is saturated and another one is unsaturated.

saturated molecule unsaturated molecule

(Dead polymers)