Abstract
To obtain information about the transition state for the cationic polymerization of monophenylbutadienes, the ring-substituent and the temperature effects on the copolymerizability were investigated. Judging from the magnitude of the ρ+ values for the copolymerizations of styrene with ring-substituted 1- and 2-phenylbutadienes, it is suggested that the propagation of monophenylbutadiene proceeds through the transition state which involves an cyclic carbonium ion intermediate. The same interpretation could be applied for the attack of a cinnamyl-type cation onto monophenylbutadiene. The reactivity of monomers toward a styryl cation decreased according to the following order: 1-phenylbutadiene>styrene>2-phenylbutadiene. The lower reactivity of 2-phenylbutadiene in comparison with styrene may be ascribed to the enthalpy increase which overweighs the entropy increase in the transition state.
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