Accelerated synthesis of poly(methyl methacrylate)-b-poly(vinyl chloride)-b-poly(methyl methacrylate) block copolymers by the CuCl/tris(2-dimethylaminoethyl)amine-catalyzed living radical block copolymerization of methyl methacrylate initiated with ?,?-di(iodo)poly(vinyl chloride) in dimethyl sulfoxide at 90 �C

Abstract

α,ω-Di(iodo)poly(vinyl chloride)s [α,ω-di(iodo)PVCs] with number-average molecular weights ranging from 2100 to 20,000 and weight-average molecular weight/number-average molecular weight ratios ranging from 1.72 to 2.16 were synthesized through the single-electron-transfer/degenerative-chain-transfer mediated living radical polymerization of vinyl chloride initiated with iodoform and catalyzed by sodium dithionite in water at 25–35 °C. These α,ω-di(iodo)PVCs were used as macroinitiators for the metal-catalyzed living radical block copolymerization of methyl methacrylate to produce poly(methyl methacrylate)-b-poly(vinyl chloride)-b-poly(methyl methacrylate) block copolymers. By searching various copper derivatives, ligands, and solvents, it has been found that CuCl/tris(2-dimethylaminoethyl)amine in dimethyl sulfoxide at 90 °C provides an accelerated method for the synthesis of block copolymers. Poly(methyl methacrylate)-b-poly(vinyl chloride)-b-poly(methyl methacrylate) block copolymers with number-average molecular weights of 41,000–106,700 were produced by this method in 30–80 min. These reaction times were within the range of induction times exhibited when the same block copolymers were synthesized with CuCl/2,2′-bipyridine in diphenyl ether at 90 °C. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1649–1659, 2005