Copolymerization of Methyl Methacrylate
with Diacrylate Oligomers¹

G. V. Korolev, A. A. Baturina, M. P. Berezin², and S. V. Kurmaz

Institute of Problems of Chemical Physics, Russian Academy of Sciences,
pr. Semenova 1, Chernogolovka, Moscow oblast, 142432 Russia

Received June 24, 2003;
Revised Manuscript Received November 10, 2003

Abstract—The kinetics of free-radical copolymerization of MMA (M₁) with diacrylates (M₂) was studied by
calorimetry and IR spectroscopy. In the latter case, a fully deuterated MMA was used, which allowed the kinet-
ics of consumption of M₁ and M₂ in copolymerization to be monitored separately. As the content of M₂ in the
starting mixture M₁ + M₂ increased, conversion corresponding to the onset of autoacceleration (the gel effect)
and conversion corresponding to the highest rate of copolymerization decreased. Based on the kinetic data on
the separate consumption of M₁ and M₂ , time evolutions in the current composition of the reaction mixture and
in the copolymer composition (instantaneous and integral) were determined. It was shown that the reactivity
ratios r₁ and r₂ change in the course of copolymerization beginning from conversions close to zero. The exper-
imental results of this work provide evidence that the kinetic data on the separate consumption of M₁ and M₂ ,
rather than the values of r₁ and r₂ available from the reference literature, offer the most reliable basis for the
macromolecular design of copolymers (especially crosslinked copolymers).

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