Abstract

Ring-opening radical polymerization of 1,1-bis(ethoxycarbonyl)-2-vinylcyclopropane (BEVCP) with dimethyl 2,2‘-azobisisobutyrate (MAIB) was investigated kinetically in benzene. The overall activation energy (Ea = 94 ± 4 kJ/mol) was calculated from the polymerization rate (Rp) obtained at 30−60 °C. Rp (40 °C) is given by Rp = k[MAIB]0.6±0.1[BEVCP]1.0±0.1, which is similar to that of conventional radical polymerizations involving bimolecular termination. The present polymerization system involves ESR-observable polymer radicals under the actual polymerization conditions. The total polymer radical concentration ([P•]) was determined at different temperatures by ESR. Using Rp, [P•], and the initiation rate obtained separately, the apparent rate constants of propagation (kp) and termination (kt) were estimated at different temperatures. The kp (71 L/mol·s, 60 °C) and kt (5.8 × l04 L/mol·s, 60 °C) values are much lower than those of typical vinyl monomers such as methyl methacrylate (MMA) and styrene. Owing to t...

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