PST 213 1.

0 Kinetics of Polymerization
Tutorial

1. Consider the free-radical polymerization of methyl methacrylate in toluene at 77 °C,

initiated by AIBN. When the initial monomer concentration was 2.07 M and the initial
AIBN concentration was 2 × 10–4 M, the initial rate of polymerization was determined to
be 2.49 × 10–3 M min–1. Determine the initial rate of initiation, Ri, and kp/(kt)1/2 by
considering that the rate constant for the decomposition of AIBN at 77°C is ki = 5.7× 10–3
min–1, and that virtually all radicals are capable of initiating chains.

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2. Effect of chain transfer to solvent on the average degree of polymerization (𝐷𝑃
o
polystyrene at 100 C is given by Figure 1. Estimate the chain transfer constants for
styrene to isopropylbenzene, ethylbenzene, toluene, and benzene and comment on the
relative magnitude of these constants in terms of the structure of the solvent molecules.

3. The second-order rate constant for the catalyzed polyesterification of 12-

hydroxystearic acid at 133.5°C is 9.23 × 10–5 mol–1 L sec–1. Using an initial concentration
of acid groups equal to 3.5 mol L–1, determine the time required for the extent of the
reaction to reach values of
a. 0.5
b. 0.7
c. 0.9

4. The reactivity ratios for the copolymerization of methyl methacrylate (1) and vinyl
chloride (2) at 68°C 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?
5. Plot graphs showing the variation of the instantaneous copolymer composition with
monomer composition for the following systems:
(i) Vinyl acetate (1), maleic anhydride (2), 75°C, r1 = 0.055, r2 = 0.003.
(ii) Styrene (1), vinyl acetate (2), 60°C, r1 = 55, r2 = 0.01.
(iii) Vinyl chloride (1), methyl methacrylate (2) 68°C, r1 = 0.1, r2 = 10

6. i. Mayo et al. (1948) have reported reactivity ratios for the copolymerization of vinyl
acetate (reactivity ratio = r2) with eight representative monomers (corresponding
reactivity ratio = r1) and can be found in Figure 1.

Figure 1
a. Calculate the composition of the copolymer that would be formed from equimolar
mixtures of vinyl acetate and methyl acrylate.

b. State which system is closest to an ideal copolymerization?

ii. Q and e values of few monomers are listed in Figure 2. Calculate the r1 and r2 values
for the monomer pair styrene (M1)-acrylonitrile (M2).

Figure 2