Composition Drift

Composition drift occurs during the process of free radical copolymerization causing
variation in the instantaneous mole fraction of a monomer added to copolymer, therefore
altering the chemical composition of the copolymer over the period of conversion.

Schematic representation of how two different monomers can be incorporated at different rates
into the copolymer and the effect that could have on the polymer composition.

The degree of composition drift is directly affected by the reactivity ratios of each monomer
in the copolymer system. Both the Mayo-Lewis equation (copolymer equation) and plot of the
equation make evident that as monomer conversion increases, the copolymer composition
will drift as the preferences for monomers change due to the interaction between reactivity
ratios and the instantaneous concentration of each monomer.

Composition drift in some degree will occur unless the reactivity ratios for both monomers
are equal to 1. In this case, each monomer prefers reaction with itself and the other
monomer equally. This causes equal rates of consumption for copolymer formation and
leads to random copolymerization.

Mole fractions

F1 = the mole fraction of monomer added instantaneously to copolymer that is a monomer 1.

f1 = the instantaneous mole fraction of monomer mix that is monomer 1.

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Azeotropic Compositions

Azeotropic point and corresponding composition drift associated with this unstable critical
point.

Binary copolymerization resembles distillation of a bicomponent liquid mixture with

reactivity ratios corresponding to the ratio of vapor pressures of the pure components in
the latter case. Distillation terminology is also borrowed for the case of azeotropic compositions
in copolymer systems. Azeotropic points occur where F1 is equal to f1. At these points,
composition drift will not occur. The equation for the azeotropic concentration is shown below
at the given reactivity ratios for each monomer species:

1−𝑟𝐵
(f1)azeo = [Eqn. 1]
2−𝑟𝐴−𝑟𝐵

The azeotropic concentrations are unstable operation points, as any small change in
temperature will cause a shift in molar concentration through reactivity ratio effects and
cause subsequent composition drift. Azeotropic points occur when the feed monomers have
reactivity ratios that are both less than 1 or both greater than 1.

Control or Elimination of Composition Drift

The goal of engineering for free radical copolymerization is to have F1 = f1 over a broad
range of conversion. For commercial applications, copolymer composition must be consistent
across the aggregate. Batch reactors have no control over composition drift and require the
implementation of engineering solutions to limit drift. Some possible reactor engineering
solutions include:

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 1. Semibatch reactor or fed-batch reactor: by adding the monomer that is
preferentially consumed at the reaction rate, f1 can be held constant and maintained.
2. Continuous stirred tank reactor (CSTR): at steady state the reactor composition (f1)
is constant and will not allow for composition drift. It is important to note that these
reactors can have the issue of multiple steady states if the reaction within the CSTR is
an exothermic process.

Azeotropic Copolymerization, continued

Recall, in azeotropic copolymerization, rA and rB are both less than 1, or, rA and rB are both
greater than one (this case is more rare). Two examples are highlighted below. Notice that these
curves cross the line fA = FA at a point called the azeotropic composition (f1)azeo. These points
have been noted with green dots in the color version of the Figure. Multiple curves are also
shown in the Figure for different values of rA and rB. As mentioned above, the name
“azeotropic” comes from the analogy with phase diagrams of liquid-liquid mixtures, where
an azeotropic mixture is characterized by having a vapor phase upon boiling with the same
ratio of components as the liquid mixture. Similarly for copolymerization, at the azeotropic
composition, (fA)azeo, we find fA = FA indicating that monomer A is being incorporated into
the polymer in the same proportion in which A exists in the monomer solution. Substituting
the fact that fA = FA into our copolymer equation we can simplify to get an expression for the
azeotropic composition [Eqn. 1]:

Highlighted curves are example conditions for azeotropic copolymerizations, and the green
dots indicate the azeotropic composition.

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PROBLEM
A special case of azeotropic copolymerization is where both rA and rB = 0. What would be the
structure of this polymer?

1. Poly(A)-block-poly(B)
2. Poly(A)-rand-poly(B)
3. Poly(A)-graft-poly(B)
4. Poly(A)-alt-poly(B)

ANSWER

4. Poly(A)-alt-poly(B)
Because both reactivity ratios are 0
𝑘𝐴𝐴 𝑘𝐵𝐵
𝑘𝐴𝐵
=
𝑘𝐵𝐴
=0

This means that both kAA and kBB must be zero. Since homopropagations cannot occur, the
sequence MUST alternate.

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PROBLEM
If rA > 1 and rB < 1 then fA…

1. Increases with higher extents of reaction.

2. Decreases with higher extents of reaction.
3. Does not change as a function of extent of reaction.

ANSWER
B. Decreases with higher extents of reaction
Because A is preferentially consumed (which we know, because of the reactivity ratios, and in
turn fA < FA), A will be used up more quickly than B, and so will become depleted in the
commoner mixture at higher extents of reaction.

Given below are some example values of reactivity ratios for pairs of monomers for free
radical polymerization. Notice that you need to consider the monomers together, and not
individually; the reactivity ratio is not inherent to the monomer, but rather is a function of what
you are trying to copolymerize and the conditions of the reaction.

Some Typical Values of Reactivity Ratios for Free-Radical Copolymerization at 60°C

Monomer A Monomer B rA rB rArB

Styrene Butadiene 0.78 1.39 1.08

Styrene Methyl methacrylate 0.52 0.46 0.24

Styrene Methyl acrylate 0.75 0.18 0.14

Styrene Acrylonitrile 0.40 0.04 0.02

Styrene Maleic anhydride 0.02 0 0

Styrene Vinyl chloride 17 0.02 0.34

Vinyl acetate Vinyl chloride 0.23 1.68 0.39

Vinyl acetate Acrylonitrile 0.06 4.05 0.24

Vinyl acetate Styrene 0.01 55 0.55

Methyl methacrylate Methyl acrylate 1.69 0.34 0.57

Methyl methacrylate n-Butyl acrylate 1.8 0.37 0.67

Methyl methacrylate Acrylonitrile 1.20 0.15 0.18

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Some Typical Values of Reactivity Ratios for Free-Radical Copolymerization at 60°C

Monomer A Monomer B rA rB rArB

Methyl methacrylate Vinyl acetate 20 0.0015 0.30

trans-Stilbene Maleic anhydride 0.03 0.03 0.001

The exact reactivity ratios are often hard to predict and therefore are mostly determined
experimentally. Resonance enhances radical stability; if we polymerize a monomer that
stabilizes a radical well via resonance with one that doesn’t (such as, styrene with vinyl chloride)
we find that the more stabilizing monomer (styrene) is preferentially incorporated
(rstyrene>> 1, rvinyl chloride << 1). More alkyl substituents also help to stabilize radicals
(i.e., a radical on a tertiary carbon is more stable than a secondary carbon), so let’s compare
methyl methacrylate versus methyl acrylate. The methyl methacrylate should stabilize the
radical better on a tertiary carbon, and thus we find that the methyl methacrylate is more
readily incorporated into the polymer, as predicted.

methyl methacrylate methyl acrylate

PROBLEM
Consider the cationic polymerization of nitroethane (monomer A) and chloroprene (monomer B)
with rA = 33 and rB = 0.15. How could you describe the structure of the polymer formed based on
these reactivity ratios?

1. Random structure is promoted.

2. Alternating structure is promoted.
3. “blocky” structure is promoted.

ANSWER
3. “blocky” structure is promoted
Monomer A is much more reactive than the monomer B, rArB > 1. This favors
homopolymerization and would lead to formation of blocks.

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