STUDIES OF SULFONYL RADICALS .5. ACTIVATION-ENERGIES FOR THE DECOMPOSITION OF ALKANESULFONYL RADICALS

One of the peculiar features of the copolymerization of SO2 and vinyl monomers is that the growing sulfonyl radical may undergo depropagation (process 1) as well as propagation (process 2)2-7 [formula omitted] where M stands for vinyl monomer. The relative rate of the two processes will therefore affect the composition of the resulting copolymer. An understanding of the mechanism of the copolymerization might be assisted by kinetic data on the two processes. In this study, we have taken the reaction of α-chloroethanesulfonyl chloride with styrene in the presence of CuCl2 catalyst as a model reaction. This sulfonyl chloride is related to the copolymerization of SO2 and vinyl chloride, 5-7 in which the structural formula of the growing sulfonyl radical is CH2CH(C1)SO2. The mechanism of the reaction of sulfonyl chloride and styrene has been studied intensively by Orochov et al., 8 who have proposed the following scheme. © 1979, American Chemical Society. All rights reserved.