Reference Book:

Syllabus:
 What is a Polymer?

• A high molar mass material

• (103 - 106 Daltons or more)

• Macromolecules: Formed by the combination of a large number

of smaller units which are called ‘monomers’
 Types of Polymer

Based on composition and polymer structure

 Types of Polymer

Based on polymerization mechanism:

q The terms condensation and step are often used synonymously as are the terms
addition and chain.
q Although most condensation polymers are produced by step polymerizations and
most addition polymers are produced by chain polymerizations, this is not always
the case.
 Polymer Composition and Structure
Condensation Polymers: Formed from polyfunctional monomers by the
various condensation reactions of organic chemistry with the elimination
of some small molecule such as water.

Example: Polyamides formed from diamines and diacids with the

elimination of water

R = (CH2)6 ; Hexamethylene diamine

Rʹ = (CH2)4; Adipic acid

Formed nylon 6/6 or poly(hexamethylene adipamide)

Other Examples of Condensation Polymers

Polyester:

Polycarbonate:

Polyurethanes:
Ø Some naturally occurring polymers such as cellulose, starch, wool,
and silk are classified as condensation polymers

Ø Cellulose can be thought of as the polyether formed by the

dehydration of glucose.

Condensation polymers are those in which the formula of the repeating

unit lacks certain atoms that are present in the monomer(s)
Addition Polymers: the repeating unit of an addition polymer has the
same composition as the monomer.

Example:
Condensation polymers à polymers whose repeating units are
joined together by functional groups of one kind or another such
as the ester, amide, urethane, sulfide, and ether linkages.

Addition polymers à do not contain such functional groups as

part of the polymer chain.
 Polymerization Mechanism
Step Growth Polymerization à polymer grows by any
combination of reactions between monomers, oligomers, and
polymers is possible

Step growth reaction occurs between any of the different-sized

species present in the reaction system.
Chain Growth Polymerization à polymer grows by addition of
only monomer to growing chain

An initiator à produce R* with a reactive center. The reactive

center may be either a free radical, cation, or anion. Polymerization
occurs by the propagation of the reactive center by the successive
additions of large numbers of monomer molecules in a chain
reaction. The
Step Growth
Chain Growth
 The ring-opening polymerizations:

Usually proceed by the chain polymerization

mechanism
 Molecular Weight

• i=1 M i N i
Number average M n= 
i =1 N i

i=1 N i M i
2
• Weight average
M w= 
i=1 N i M i

1+ a 1a
•  N M 

Viscosity average M v = i =1


i i

  N Mi 
i =1 i

Mw
• Polydispersity Index
Mn
 Molecular weight distribution
Mn

Weight
fraction Mv

Mw

Molar Mass M x
The Polymer Parameters
• Chemical Composition
– Homopolymers
– Copolymers
– Terpolymers
• Molecular Weight
• Stereochemistry
– Geometrical isomers
– Configuration - atactic, isotactic, syndiotactic
• Topology
– Chains
– Branches - star, comb, random
– Network
 Topology

Chains

Branches - star, comb, random

Network
 5
Fibre 10

Rigid 4
Plastic 10
Stress
Flexible Plastic
N/cm2
3
10

Elastomer
2
10

0 1 5 6
Strain D L/ L