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
