1

STEP POLYMERIZATION
I. Basics
A. Two difunctional monomers undergo a combination (often condensation)
reaction.
1.
Common condensation products are H2O and HCl.
2.

Usually one or both of the monomers are dicarboxylic acid derivatives.

B. Polymer chain grows at both ends.

C. Monomer is consumed quickly; many dimers, trimers, tetramers are formed
initially.
1.
Degree of polymerization increases quickly
D. High molecular weights are difficult to achieve.
1. Increasing viscosity of reaction mixture severely limits diffusion of
reactants to collide with each other.
E. Polydispersity is significant.
F.Examples of classes of polymers formed with step polymerization.
1. Polyesters
2. Polyamides (nylons)
3. Polyurethanes
4. Polyureas
5. Polycarbonates
6. Polysulfides
7. Polysiloxanes (silicones)
II. Quantitative kinetics of step polymerization
A. Degree of polymerization depends on the rate order of the reaction.
B. Degree of polymerization depends on the molar ratio of monomers.
-

ratio needs to be very close to one for high molecular weights

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C. Uncatalysed step polymerizations have third-order kinetics. (That is the
diacid itself acts as a catalyst.)
(Use polyester as example.)

d A
dt

k A D k A
2

1.

Integrated rate law 2kt

2.

Express concentration in terms of extent of reaction.

[A] diacid [D] diol

A 0

A A 0 1 p
# of functional groups reacted
# of initial functional groups
1
1
1
2
2kt

2kt A 0
1
2
2
2
1 p
A A 0
p

- slope yields rate constant.

(Data stolen from P. J. Flory, JACS 61 3334 (1939)

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3.

Carothers equation (number average degree of polymerization)

DP N

A 0
A 0
1

A t A 0 1 p 1 p

a. p needs to be very close to one to make useable polymers

p = 0.9; DP = 10 p = 0.99; DP = 100

D. Catalysed (with acid or base) step polymerizations have second-order

kinetics.

1.

d A
dt

k A D k A

Integrated rate law

kt

1
1

A A 0

2.

Degree of polymerization
1
1
1
1
kt

kt

A A 0
A 0 1 p A 0

A 0 kt

A 0 kt

1
1
1 p

1
1 DP N 1 DP N A 0 kt 1
1 p

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E. Molecular weight averages and degree of polymerization
1. Probability of molecule with n repeating units.
a. Probability of finding AB in polymer = extent of reaction.
Probability of finding n-1 AB units is pn-1.

b.

c. Probability of finding unreacted A or B is 1-p

d.

Probability to find polymer with n repeat units,

N n N 1 p p n 1

e. Recall Carothers equation

N0
1

N 1 p

N N0 1 p

N n N 0 1 p p n 1
2

2.

Weight-average molecular weight distribution

n 1
nN n nN 0 1 p p
2
Wn

n 1 p p n 1
N0
N0
2

3.

Number-average molecular weight

N0

Mn

Mn Nn
n 1
N0

N
n 1

N0

N0

mn N 1 p p
n 1

n 1

N0

m 1 p np n 1
n 1

np

n 1

1 2p 3p 2 4p3 L

n 1

N0

M n m 1 p np n 1
n 1

m 1 p

1 p

or

Mn

mN 0
m

N
1 p

1 p

m
mDPN
1 p

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4.

Weight-average molecular weight

N0

Mw

N0

M W
n

n 1
N0

Wn

N0

mn nN mn nN 1 p p
n

n 1

nN n

n 1

m 1 p n 2 p n 1
n 1
N0

1 p np n 1

n p
2

n 1

m n 2 p n 1

n 1
N0

np

np

n 1

n 1

5.

n 1

n 1

m 1 p

n 1

m n 2 p n 1

1 4p 9p2 16p 3 L

N0

Mw

nN 1 p p
n 1

n 1

n 1
N0

N0

N0

n 1

N0

n 1

n 1

N0

N0

n 1

1 p

1 p

1 p
3
1 p

m 1 p
Mn 1 p
1 p

Polydispersity index
Mw m 1 p 1 p

1 p
Mn
m 1 p
Mw
2
- if p = 1
Mn

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F.Modified Carothers equations
1. Polymerization can be stopped at a specific DP with slight excess of one
reactant.
a. Define monomer ratio r of [A] to [B] as a number always less than one.
r

A 0
A

DP N

A 1
B

n 2

n 1 p 2

n 1 2
r

1 rp
1 p
r

1
1
r 1
1 r
r

1 rp r rp 1 rp
1 r 2rp
1 p

p = 1; r = 0.98

DP N

1 r

1 0.98
1 r 2rp 1 0.98 2 0.98 1

1.98
97
0.02

2. Reaction can be stopped with a specific amount of monofunctional

monomer.
a. Define functionality factor f as the number average of functional
groups per monomer.
A 0
A 0
2
DP N

A A 1 pf 2 pf

0
2

Example: Let a mixture have 0.02 mol of alcohol and 0.98 mol of diol.

0.02 mol 1 0.98 mol 2

1.96
0.02 mol 0.98 mol

If p = 1, DP N

2
2
2

50
2 pf 2 1 1.96 0.04