Co-polymerization

5/11/2014
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.



5/11/2014
Types of Copolymer
1. Random copolymer

the 2 different units are randomly
dispersed along the chain

MMMMMMMMMMMMMMMMMMMMM
5/11/2014
Types of Copolymer
2. Alternating copolymer

the 2 different units alternate chain
position

MMMMMMMMMMMMMMMM
5/11/2014
Types of Copolymer
3. Block copolymer

One in which identical mers are clusterd
in blocks along the chain

MMMMMMMMMMMMMMMMMMMM
5/11/2014
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

5/11/2014
Composition of Copolymer
Cannot be determined simply from the knowledge
of the homopolymerization rates of the two
monomers

5/11/2014
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.

5/11/2014
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 :
M
1
M
1
-M
1
*
M
1
*
M
2
M
1
-M
2
*
5/11/2014
4 possible propagation reactions:
M
1
*
+ M
1
M
1
*


M
1
*
+ M
2
M
2
*


M
2
*
+ M
1
M
1
*


M
2
*
+ M
2
M
2
*



Cross
propagation /
Crossover
reaction
Homo polymerization / self
propagation
K
11
K
12
K
21
K
22
K
xy
= rate constant for a propagating chain ending in M
1
(x) adding to monomer M
1
(y)
5/11/2014
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;
r
1
= k
11
/k
12
and r
2
= k
22
/k
21
5/11/2014
Co-polymerization can be classified into 3 types based on
whether the product of the two monomer reactivity rations:

r
1
r
2
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
5/11/2014
Sample case:
5/11/2014
case 1 Alternating copolymerization
r
1
r
2
r
1
r
2
Preference
Type of co-
polymer
= 0 = 0

= 0

Each monomer prefers to react
with the other
Perfect

=0 0 =0

Each monomer prefers to react
with the other


Not perfect
0 =0 =0
0 0 0
r
1
=

r
2
0
Neither monomer
homopolymerizes very well
Almost
perfect
5/11/2014
case 2 Block copolymerization
r
1
r
2
r
1
r
2
Preference
Type of co-
polymer
r
1
>1 and r
2
>1
Each monomer prefers to
react with others of its
own kind
Block
This type of behavior is rarely encountered
5/11/2014
case 3 Ideal polymerization
r
1
r
2
r
1
r
2
Preference
Type of co-
polymer
= 1 = 1 = 1 There is no preference Ideal random
> 1 <1 One of the monomers is more
reactive than the other
Random
M
1
> M
2

<1 >1 Random
M
2
> M
1
r
1


r
2
Random
M
1
M
2
5/11/2014