Copolymerization

Step Copolymerization

Simultaneous polymerization of two or more different monomers

e.g., ARB + ARB’ or R2A + R’B2 + R’’B2

Statistical Copolymers

• Functional group with same reactivities

→ Random copolymers with the most probable distribution of
molecular weight
• Functional group with different reactivities
→ “Blocky” copolymers
E.g.,
HO2CRCO2H + H2NR'NH2 + HOR"OH
more less
reactive reactive

O O O O
HO CRCNHR'NH m CRCOR"O nH
poly(ester-co-amide)

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Block Copolymers
O O
H3COC COCH3 + H O(CH2)4 nOH + HOCH2CH2OH
low molar mass
prepolymer

Segmented copolymer

Soft segment: amorphous rubbery phase

Hard segment: rigid crystalline phase

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Preparation of polyurethane elastomer

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Chain Copolymerization

For copolymerization of monomer A with monomer B

Two types of active center

~~~A* and ~~~B*

Four possible propagation reactions

kAA
~~~A* + A ~~~AA* homopropagation
~~~A* + B kAB ~~~AB* crosspropagation
~~~B* + B kBB ~~~BB* homopropagation
~~~B* + A kBA ~~~BA* crosspropagation

Rates of consumptions of monomers A and B

-d[A]/dt = kAA[A*][A] + kBA[B*][A]

-d[B]/dt = kBB[B*][B] + kAB[A*][B]

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The ratio of the amount of monomer A to monomer B incorporated
into the copolymer chains
d [ A] [ A]  k AA[ A*] /[ B*] + k BA 
=  
d [ B ] [ B ]  k BB + k AB [ A*] /[ B*] 

Under steady-state condition

d [ A*]
= k BA[ B*][ A] − k AB [ A*][ B] = 0
dt
d [ B*]
= k AB [ A*][ B] − k BA[ B*][ A] = 0
dt
[ A*] k BA[ A]
=
[ B*] k AB [ B]

Copolymer composition equation

d [ A] [ A]  rA[ A] + [ B] 
=  
d [ B] [ B]  [ A] + rB [ B] 

where rA and rB are monomer reactivity ratios

rA = kAA/kAB and rB = kBB/kBA

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Mole fraction fi of monomer i in comonomer mixture
[ A] [ B]
fA = and fB = = 1− fA
[ A] + [ B] [ A] + [ B]
Mole fraction Fi of i-type repeat units in copolymer
d[ A] d[ B]
FA = and FB = = 1 − FA
d[ A] + d [ B ] d[ A] + d [ B ]
Copolymer composition equations
rA f A + f A f B
2
FA =
rA f A + 2 f A f B + rB f B
2 2

rB f B + f A f B
2
FB =
rA f A + 2 f A f B + rB f B
2 2

Monomer Reactivity ratios and Copolymer Composition/Structure

rA > 1 ~~A* prefers to add monomer A (homopolymerization)
rA < 1 ~~A* prefers to add monomer B (copolymerization)
rA = rB = 1 Random copolymers with FA = fA

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 rA > 1, rB < 1 
r r = 1 ideal copolymerization
(or rA < 1, rB > 1 A B
1 k AA k BA
rA = , i.e. =
rB k AB k BB
Relative rates at which two monomers are incorporated into the
copolymer chains are the same for both types of active center
→ Random copolymers
rA f A
FA =
rA f A + f B
rA > 1, rB < 1 
rA rB ≠ 1 (usually rArB < 1)
(or rA < 1, rB > 1
FA vs fA curves are skewed towards copolymer composition richer in
the repeat units derived from the more reactive monomer

rA/rB (rA > 1, rB < 1)↑ continuous sequences of A-type repeat units ↑
continuous sequences of B-type repeat units ↓

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Azeotropic copolymerization

rA < 1, rB < 1 (or rA > 1, rB.> 1)

FA vs fA curves are characterized by their intersection of FA = fA line at
one pint which corresponds to the azeotropic composition (fA)azeo

Since d[A]/d[B] = [A]/[B],

rA [ A]azeo + [ B]azeo
=1
[ A]azeo + rB [ B]azeo
rA [f A ]azeo + [f B ]azeo
=1
[f A ]azeo + rB [f B ]azeo
1 − rB
( f A ) azeo =
2 − rA − rB

rArB ↓ tendency towards alternating addition ↑

rA = rB = 0, perfect alternating copolymer (no homopropagation)

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