Essentials of Polymer Engineering

(Introduction to Polymers)
ChE 197
Copolymerization

What we have covered so far

Introduction basic concepts and definitions; classification of polymers
Polymerization mechanisms chain-reaction; ionic and coordination
polymerization; step-growth and ring-opening polymerization
Chemical bonding and polymer structure primary, secondary, and
tertiary structures
Thermal transition in polymers Tg and Tm
Polymer modification copolymerization; postpolymerization reactions;
functional polymers
Condensation (Step-Reaction) polymerization mechanism; kinetics;
stoichiometry; molecular weight control and distribution
Chain-Reaction (Addition) Polymerization
Copolymerization

Review on types of copolymers

Alternating copolymer

Block copolymer

Graft copolymer

Relevant observations of
copolymerization kinetics
Number of reactions involved in copolymerization of two
or more monomers increases geometrically w/ the
number of monomers (e.g. propagation steps in
copolymerization of two monomers involves four
reactions)
Number of radicals to be considered equals the number
of monomers
Two radicals in the copolymerization of two monomers
Composition and structure of the resulting copolymer
are determined by the relative rates of the different
chain propagation reactions

The copolymer equation

Four propagation steps for

copolymerization of two monomers
- first subscript in the rate constant refers to the reacting radical
- second subscript designates the monomer
- homopropagation or self-propagation (reactions with k11 and k22)
- crosspropagation or crossover reaction

Rate of disappearance of
monomers M1 and M2:

The copolymer equation

M1*
- a steady-state concentration is assumed for
each of the reactive species M1* and M2*
separately.
- for the concentrations of M1* and M2* to
remain constant, their rates of interconversion
must be equal

rates of generation and consumption

of these radicals are equal

Dividing the top and bottom

of the right side by

copolymer equation
Mayo-Lewis equation

The copolymer equation

f1 and f2 are the mole fractions of
monomers M1 and M2 in the feed

Copolymer equation in
terms of mole fractions

F1 and F2 are the mole fractions of

monomers M1 and M2 in the copolymer

Types of copolymerization
behavior: Ideal
two types of propagating species M1* and M2*
show the same preference for adding one or the
other of the two monomers

relative rates of incorporation of the two

monomers into the copolymer are independent
of the identity of the unit at the end of the
propagating species
Copolymer equations
sequence of monomer units in an ideal
copolymer is random

- one of the monomers is more reactive than

the other toward the propagating species
- copolymer will contain a greater
proportion of the more reactive monomer in
the random sequence of monomer units

-growing radicals cannot distinguish

between the two monomers
-composition of the copolymer is the same
as that of the feed
-monomers are arranged randomly along
the chain

Types of copolymerization
behavior: Alternating
-each radical reacts exclusively with the other monomer
-neither radical can regenerate itself
-monomer units are arranged alternately along the chain
irrespective of the feed composition
Copolymer equations

Extreme or perfect
alternation

Moderate alternating
behavior

Types of copolymerization
behavior: Block

each radical would prefer adding its

own monomer
- addition of the same type of monomer would
continue successively until there is a chance
addition of the other type of monomer
- sequence of this monomer is added repeatedly

Extreme case:

Both monomers undergo simultaneous and

independent homopolymerization

Reactivity Ratios of Some

Monomers

There are no established cases where r1r2 > 1

Product r1r2 is almost always less than unity

Example 1
The reactivity ratios for the copolymerization
of methyl methacrylate (1) and vinyl chloride
(2) at 68C are r1 = 10 and r2 = 0.1. To ensure
that the copolymer contains an appreciable
quantity (>40% in this case) of the vinyl
chloride, a chemist decided to carry out the
copolymerization reaction with a feed
composed of 80% vinyl chloride. Will the
chemist achieve his objective?

Example 1 Solution

Copolymer equation

If the difference in the reactivities of the two monomers is large, it is impossible to

increase the proportion of the less-reactive monomer in the copolymer simply by
increasing its composition in the feed.

Polymer Composition Variation

with Feed Composition: Ideal
Variation of instantaneous
composition of copolymer (mole
fraction, F1) with feed composition
(mole fraction f1 for ideal
copolymerization with the values of
r1 = 1/r2 indicated).
range of feed composition that
gives copolymers containing
appreciable amounts of both
monomers is small except the
monomers have very similar
reactivities
Analogy of curves with vapor
liquid equilibria in ideal liquid
mixtures

Polymer Composition Variation

with Feed Composition: Nonideal
Instantaneous composition of
copolymer F1 as a function of
monomer composition f1 for the
values of the reactivity ratios r1/r2
indicated
When r1 and r2 both less than
unity, the F1/f1 plots cross the line
representing F1 = f1
crossover points = the copolymer and
feed compositions are the same and
copolymerization occurs without a
change in the feed composition.
Azeotropic copolymerizations

Polymer Composition Variation

with Feed Composition: Nonideal
Azeotropic copolymerization

Simplification of
copolymer equation

Critical feed
composition

-If both r1 and r2 are greater than unity or if both are less than unity, critical composition lies
within the acceptable range 0 < f1 < 1
-If r1 > 1 and r2 < 1 or vice versa, there will be no critical feed composition

Special nonideal
copolymerization:

both types of propagating species

preferentially add monomer M1
(consecutive homopolymerization)

Polymer Composition Variation

with Conversion
Consider a system initially containing a total of M moles of the two monomers and in
which the copolymer formed is richer in monomer M1 that is the feed (i.e., F1 > f1)

When dM moles of monomers have been copolymerized, the polymer will contain F1dM
moles of monomer 1 and the feed will contain (M - dM)(f1 df1) moles of monomer 1

material balance for monomer 1 requires that the moles of M1 copolymerized

equal the difference in the moles of M1 in the feed before and after reaction

Assume df1dM to
be very small:
Degree of
conversion

Use copolymer equation to solve

F1 as function of f1, r1, and r2
Numerical or graphical
integration to solve conversion

Polymer Composition Variation with

Conversion (Analytical Solution)

Analytical solution to obtain the conversion

Variations in feed and copolymer

compositions with conversion for
styrene (M1)-methyl
methacrylate (M2) with (f1)0 = 0.80,
(f2)0 = 0.20, r1 = 0.53, r2 = 0.56

Dependence of Polymer Composition with

Feed Composition and Conversion

Dependence of the
instantaneous copolymer
composition F1 on the initial
comonomer feed composition
f1 and the percent conversion
for styrene (M1)2vinylthiophene (M2) with r1 =
0:35 and r2 = 3:10.

Example 2
What is the composition of the copolymer formed by the
polymerization of an equimolar mixture of butadiene (1) and
styrene (2) at 66C? Which will contain more styrene the
polymer formed first or that formed later in the reaction?

- rate of consumption of butadiene by either

radical is greater than the rate of addition of
styrene.
- the polymer formed first will be richer in
butadiene while the polymer formed at the later
stages of the reaction will be richer in styrene

Example 3
Estimate the feed and copolymer compositions for the
azeotropic copolymerization of acrylonitrile and styrene at 60C.

Critical feed
composition

Example 4
Plot graphs showing the variation of the instantaneous
copolymer composition F1 with monomer composition
for the following systems
I. Vinyl acetate (1), maleic anhydride (2), 75C, r1 = 0.055, r2 = 0.003.
II. Styrene (1), vinyl acetate (2), 60C, r1 = 55, r2 = 0.01.
III. Vinyl chloride (1), methyl methacrylate (2) 68C, r1 = 0.1, r2 = 10

Example 4 Solution
-Range of feed composition
that gives copolymers with
appreciable quantities of both
monomers is small for Cases
II and III where the differences
in reactivity ratios are large
-Case I where
the reactivity ratios are
comparable, copolymers with
comparable quantities of both
monomers are obtainable.

Effect of Reaction Conditions:

Monomer Reactivity
inverse of the reactivity ratio is the ratio of the
rate of reaction of the given radical w/ another
monomer to its rate of reaction with its own
monomer
If k11 = 1, k12 values give the
relative reactivities of monomers with respect to
the reference radical

Effect of Reaction Conditions:

Monomer Reactivity
Effect of substituents in enhancing monomer reactivity

The effect of a second 1-substituent is generally additive

order of monomer reactivities corresponds to the order of increased resonance

stabilization of the resulting radical by the particular substituent
substituents with unsaturation = most effective in conferring resonance stabilization on
radicals
substituents that have only nonbonding electrons for interaction with the radical = weak

Effect of Reaction Conditions:

Radical Reactivity

Order of enhancement of radical reactivity due to substituents is

the reverse of that for the monomers

Effect of Reaction Conditions:

Steric Effects

Vinyldene
chloride

Vinyl
chloride

Cis-1,2dichloroethylene

- addition of a second substituent to the 1- or -position increases monomer reactivity

- same substituent is in the 2- or -position (i.e., 1,2- disubstitution), the reactivity of the
monomer decreases 2- to 20-fold

Example 5
Arrange the following monomers in the possible order
of decreasing reactivity with an acrylonitrile radical.

Methyl methacrylate > Methacrylate > Vinyl acetate > Vinyl methylether
- Increasing stabilization of resulting radical
- Second substituent in 1-position increases monomer reactivity

Effect of Reaction Conditions:

Alternation-Polar Effects
Monomer reactivity is a function of radical reactivity and vice versa

As the quantity r1r2 deviates from unity (ideal behavior) and approaches zero, the
tendency for alternation increases
Alternation tendency increases if the substituents on both monomers exhibit different electrondonating or electron-attracting characteristics
Alternation tendency is enhanced by an increased difference in the polarity of monomer pairs

Example 6
Which of the following pairs of monomers will most
probably form an alternating copolymer?
a. Butadiene (1), Styrene (2), 60C, r1 = 1.89, r2 = 0.78
b. Vinyl acetate (1), styrene (2), 60C, r1 = 0.01, r2 = 55
c. Maleic anhydride (1), isopropenyl acetate (2), 60C,
r1 = 0.002, r2 = 0.032.
Monomer pair (c) has
the highest
alternating tendency.

The Q-e scheme

The Q-e scheme is an attempt to express free radical copolymerization data on a
quantitative basis by separating reactivity ratio data for monomer pairs into parameters
characteristic of each monomer

P1 - reactivity of radical M1*; Q2 - reactivity of monomer M2

e1 and e2 - degrees of polarity of the radical and monomer, respectively
Monomer and its radical have the same e value

Negative values of e indicate electron-rich monomers

Positive e values indicate electron-poor monomers

The Q-e scheme

Criticisms on the Q-e scheme

1. No justification for assuming the same e
values for the monomer and the radical
derived from it
2. Q and e values for a particular
monomer are not unique; they vary with the
monomer to which the monomer is paired