S. V. Kurmaz2, M. L. Bubnova, E. O. Perepelitsina, and V. P. Roshchupkin
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
Chernogolovka, Moscow oblast, 142432 Russia
Received July 25, 2002;
Revised Manuscript Received October 17, 2002
Abstract—A cobalt porphyrin complex was shown to be an efficient regulator in the crosslinking free-radical
polymerization of ethylene glycol dimethacrylate and its copolymerization with styrene due to the occurrence
of reactions of catalytic chain transfer, catalytic inhibition, and reversible cleavage of a Co–C bond. In the pres-
ence of cobalt porphyrin, the rate of the process decreases, the gel effect shifts to higher conversions, and the
structure of the resulting polymer network changes. The structural–kinetic effect of cobalt porphyrin is
accounted for by the formation of low-molecular-mass polymers carrying a great number of pendant meth-
acrylic groups. As a result, the contribution of the intermolecular crosslinking reaction increases as compared
to the intramolecular cyclization reaction; as a consequence, the structure of the produced network is more uni-
form than that in the case of conventional crosslinking polymerization.
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