Living Radical Network Polymerization:
Alkoxyamine-Mediated Copolymerization
of Dimethacrylates with Styrene¹

G. V. Korolev², I. S. Kochneva, G. M. Bakova, and M. P. Berezin

Institute of Problems of Chemical Physics, Russian Academy of Sciences,
Chernogolovka, Moscow oblast, 142432 Russia

Received July 5, 2000;
Revised Manuscript Received September 28, 2000

Abstract—The kinetics of network copolymerization of styrene with dimethacrylates in the presence of
alkoxyamines as initiators of “living” radical polymerization (iniferters) was studied. Conclusive evidence that
the copolymerization proceeds in the “living” chain mode was obtained with the techniques of precision iso-
thermal calorimetry, ESR, and rheokinetics. This conclusion is based on the dramatic shift of the conversion
corresponding to the formation of a continuous polymer network to the region of high degrees of polymeriza-
tion (>10%) as compared to the conventional network polymerization (<1%), as well as on the high concentra-
tions of a nitroxide radical, the inhibitor, during the polymerization process at simultaneously retained fairly
high reaction rates.

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