Co-polymerization

Definition
„ Process of using more than one monomer
„ Polymer that contain more than one kind of
monomer repeating unit
ADVANTAGE:
„ Improved properties or better property
combinations than are offered by the
homopolymers.
Types of Copolymer
1. Random copolymer

„ the 2 different units are randomly

dispersed along the chain

MMMMMMMMMMMMMMMMMMMMM
Types of Copolymer
2. Alternating copolymer

„ the 2 different units alternate chain

position

MMMMMMMMMMMMMMMM
Types of Copolymer
3. Block copolymer

„ One in which identical mers are clusterd

in blocks along the chain

MMMMMMMMMMMMMMMMMMMM
Types of Copolymer
4. Graft copolymer

„ Homopolymer side branches of the type

may be grafted to homopolymer main
chain that are composed of different mer
M M
M M
MMMMMMMMMMMMMMMMMMMMM
M
M
Composition of Copolymer
„ Cannot be determined simply from the knowledge
of the homopolymerization rates of the two
monomers
Chain End Model (Terminal Model)
ASSUMTION
„ Dependent only on the identity of the monomer
unit at the growing chain end
„ Independent of the chain composition
preceeding the last monomer unit
„ All propagation reactions are irreversible.
Chain End Model
„ How does a monomer repeat unit at the
growing chain end tend to react?
MORE OF ITS KIND?
WITH THE OTHER MONOMER(S) ?
IN GENERAL :
M1 M1-M1*
M1*
M2 M1-M2*
 4 possible propagation reactions:
K11
M1* + M1→ M1*
K12
M1* + M2→ M2*
Cross
propagation / Homo polymerization / self
Crossover K21 propagation
reaction M2* + M1→ M1*

K22
M2* + M2→ M2*

Kxy = rate constant for a propagating chain ending in M1 (x) adding to monomer M1 (y)
Adopting monomer reactivity ratio to predict
copolymer composition.
„ Monomer reactivity ration (r) is the tendency of
the two monomers to copolymerized i.e the
ration of rate constant for a reactive propagating
species adding its own kind to the rate constant
for its addition of the other monomer. Where;
r1= k11/k12 and r2= k22/k21
„ Co-polymerization can be classified into 3 types based on
whether the product of the two monomer reactivity rations:

r1 r2 Preference Type of co-

polymer
= 0 Prefers to react with the other Alternating

= 1 No preference Random

> 1 Preferentially adds its own kind Block

<1 Preferentially adds the other Alternating

Sample case:
case 1 – Alternating copolymerization
r1 r2 r1 r2 Preference Type of co-
polymer
=0 =0 =0 Each monomer prefers to react Perfect
with the other
=0 ≈0 =0
Not perfect
≈0 =0 =0 Each monomer prefers to react
with the other
≈0 ≈0 ≈0

r1 = r2 ≈ 0 Neither monomer Almost

homopolymerizes very well perfect
case 2 – Block copolymerization

r1 r2 r1 r2 Preference Type of co-

polymer
r1 >1 and r2 >1 Each monomer prefers to Block
react with others of its
own kind

This type of behavior is rarely encountered

case 3 – Ideal polymerization
r1 r2 r1 r2 Preference Type of co-
polymer
=1 =1 =1 There is no preference Ideal random

>1 <1 One of the monomers is more Random

reactive than the other M1 > M2
<1 >1 Random
M2 > M1
r1 ≈ r2 Random
M1 ≈ M2
Exercise :
M1 r1 M2 r2

Styrene 0.80 Isoprene 1.68

Styrene 0.52 Methyl methacrylate 0.46

Styrene 55 Vinyl acetate 0.01

Styrene 0.04 Acrylonitrile 0.4

Styrene 0.04 Maleic anhydride 0.015

Example 2:
r1= 0.81 ; r2= 0.86
R1= 0.046 r2= 0.36
R1= 50 r2 = 3