Determination of propagation rate constants for the copolymerization of methylmethacrylate and styrene using a pulsed laser technique

Recently, T. Fukuda et al. demonstrated that the bulk copolymerization of styrene (STY) and methyl methacrylate (MMA) conformed to the terminal model with respect to composition but entirely failed to conform to it with respect to absolute values of the propagation rate constant k_p. The aim of the present work is to reproduce and confirm the results for MMA-STY copolymerization using a new technique to measure propagation rate constants recently developed by O.F. Olaj and co-workers. The adoption of a pulsed UV laser as an initiating source for free-radicals considerably simplifies the kinetic expressions normally associated with the rotating sector or spatially intermittent polymerization techniques. In summary, the results of Fukuda et al. for the copolymerization of STY with MMA have been duplicated here using a new experimental technique, thus confirming the failure of the Mayo-Lewis model to describe absolute propagation rate constants for this copolymerization.