POLYMER CHEMISTRY 7

COPOLYMERISATION

Shuang Cui
Imperial College London, UK

Different forms of copolymers

Homopolymer
Alternating copolymer
Periodic copolymer
Random copolymer
Block copolymer
Graft copolymer

Copolymers more than simple mix

Graft copolymer

Graft copolymers are a special type of branched

copolymer where the side chains are structurally
distinct from the main chain
Individual chains of a graft copolymer may be
homopolymers or copolymers

Block copolymer
More than one kind of block can be made, tri or tetra are also common
Comprise of two or more linked homopolymer subunits.

Block copolymers with two or three distinct blocks are called diblock
copolymers and triblock copolymers, respectively.

Copolymerisation
Copolymers are formed by simultaneous

polymerisation of two or more different

monomers.
Copolymers can be produced by both step

copolymerisation and chain copolymerisation.

The simplest step copolymersiation are the

general type ARB + ARB or RA2 + RB2 + RB2.

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Step copolymerisation
ethylene glycol, terephthalicacid, and isophthalicacid

poly(ethylene terephthalate-co-ethyleneisophthalate)

Step copolymerisation
Statistical copolymers

Most step copolymerisation are taken to high extents of

reaction in order to produce copolymers with suitable high
molar masses. A consequence of this is that the overall
compositions of the copolymers obtained correspond to
those of the comonomer mixtures used to prepare them.
However, the sequence distribution of the different repeat
units along the copolymer chains is an important factor
controlling the properties of copolymer and that the
distribution is affected by difference in monomer reactivity.

Step copolymerisation
Block copolymerisation

By using as comonomers, low molar mass prepolymers with

terminal functional groups, step copolymerisation can be
used to prepare alternating block copolymers.
For alternating copolymers prepared by such step
copolymerisation, it is usual to call the block segments and
the copolymer segmented copolymers.

Soft segments

Hard segments

Amorphous rubbery phase

Rigid crystalline phase

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Chain copolymerisation
Reaction
Initiation

R + M1
R + M2

Propagation M + M
1
1
M1 + M2
M2 + M1
M2 + M2
Termination M + M
1
1
M1 + M2
M2 + M2

Rate

ki1
ki2
k11
k12
k21
k22
k t11
k t12
k t22

RM1

Ri1

RM2

Ri2

M1

R11= k11[M1] [M1]

M2

R12= k12[M1] [M2]

M1

R21= k21[M2] [M1]

M2

R22= k22[M2] [M2]

R t11

R t12

R t22

Chain copolymerisation
Rate of consumption of M1and M2
d [M1]
= R11 + R 21 = k 11[M1 ][M1] + k 21[M2][M1]
dt
d [M2]

= R12 + R 22 = k 12[M1][M2] + k 22[M2][M2]

dt

Instant composition of copolymer

k11 [M1 ] [M1] + k21 [M2 ] [M1]
d [M1]
=
d [M2]
k12 [M1 ] [M2] + k22 [M2 ] [M2]

Mayo-Lewis

d [M1]
d [M2]

Steady-state condition to [M1] and [M2

d [M1 ]
d [M2 ]
= 0
= 0
dt
dt

r1 [M1] + [M2]

[M1]
[M2]

[M1] + r2 [M2]

r1 = k11 / k12
r2 = k22 / k21
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Chain copolymerisation
Instantaneous composition of feed and polymer
f1= mole fraction of M1in the feed
f2= mole fraction of M2in the feed
F1= mole fraction of M1in the copolymer
F2= mole fraction of M2in the copolymer

[M1]
f1 =
[M1] + [M2]

[M2]
f2 =
[M1] + [M2]

f1 + f2 = 1

d[M1]
F1 =
d[M1] + d[M2]

d[M2]
F2 =
d[M1] + d[M2]

F1 + F 2 = 1

F1 =

r1 f12 + f1f2
r1 f12 + 2 f1f2 + r2 f22

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Chain copolymerisation

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Chain copolymerisation
r1= r2= 1, random copolymer

F1= f1
No preference for homo-polymerisation or copolymerization
r1= r2= 0, alternating copolymer
F1= 0.5
0 < r1, r2< 1 , azeotropic copolymerization
1 << r1 and r2<< 1, essentially homopolymer
1 << r1 and 1 << r2 , block copolymerisation

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Reactivity ratios

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Example - ABS
Acrylonitrile Butadiene Styrene
Acrylonitrile : 15 ~ 35%
Butadiene : 5 ~ 30%
Styrene : 40 ~ 60%

The nitrile groups from neighbouring chains attract each other and bind the chains together,
making ABS stronger than pure polystyrene. The styrene gives the plastic a shiny, impervious
surface. The butadiene, a rubbery substance, provides resilience even at low temperatures.

Example - SBS
Styrene Butadiene Styrene

styrene

Butadiene

styrene

Polystyrene is a tough hard plastic, and this

gives SBS its durability. Polybutadiene is
rubbery, and this gives SBS its rubber-like
properties. In addition, the polystyrene
chains tend to clump together. This gives
the material the ability to retain its shape
after being stretched.

The Pros and Cons of co-polymer

Advantage
An important process enables to have combined performance
Final material can be designed to cope with specific needs
Using different monomers to compensate individual weaknesses

Disadvantage
The reaction is apparently complex and time consuming
Good chance to have nasty byproducts or even toxins
Mix ratio has to be precise or having phase separation