Cationic Copolymerization of 2-Chloroethyl Vinyl Ether with Styrene Derivatives. II. Temperature Dependence of Monomer Reactivity Ratios

Abstract

Temperature dependence of monomer reactivity ratios, r1 and r2, and their product r1×r2 were studied in the cationic copolymerization of 2-chloroethyl vinyl ether (M1) with styrene derivatives (M2) (p-methoxystyrene, p-methylstyrene and α-methylstyrene). Methylene chloride, toluene and benzene were used as solvents, and SnCl4 CCI3CO2H and BF3O(C2H5)2 were used as catalysts, r1 increased and r2 decreased with increasing polymerization temperature in the copolymerization of M1 with M2 except that of Mi with p-methoxystyrene. On the other hand, r1 and r2 hardly depended on polymerization temperature in the copolymerization between vinyl ethers or styrene derivatives. On the basis of these results, the difference in the transition state of the propagation reaction of vinyl ether and styrene derivatives was discussed. Temperature dependence of the products, r1×r2, was investigated and the propagating end effect was discussed in cationic copolymerization.