CuI and CuII salts of group VIA elements as catalysts for living radical polymerization initiated with sulfonyl chlorides

The living radical polymerization of methyl methacrylate initiated from sulfonyl chlorides and catalyzed by the new catalytic systems Cu₂Y/Bpy and CuY/Bpy, where Y is O, S, Se, or Te and Bpy is 2,2′‐bipyridine, is described. An induction time was observed in all polymerization experiments. The values of the experimental rate constants of polymerization (k_p ^exp) increased whereas the corresponding induction times decreased in the order Y = O < S < Se < Te. For the entire series of catalysts, k_p ^exp for CuY was less than k_p ^exp for Cu₂Y. A mechanistic interpretation that involves the in situ generation of the CuCl/CuCl₂ pair, starting from Cu₂Y or CuY, is provided. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3839–3843, 2000