Synthesis of poly(methyl methacrylate)‐b‐poly(vinyl chloride)‐b‐poly(methyl methacrylate) block copolymers by CuCl/2,2′‐bipyridine‐catalyzed living radical block copolymerization initiated from α,ω‐di(iodo)poly(vinyl chloride) prepared by single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization

Abstract α,ω‐Di(iodo)poly(vinyl chloride)s with number‐average molecular weights (Mn's) of 2100–29,800 and weight‐average molecular weight/number‐average molecular weight (Mw/Mn) ratios of 1.66–2.16 were synthesized by the single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization of vinyl chloride initiated with CHI3 and catalyzed by Na2S2O4. These α,ω‐di(iodo)poly(vinyl chloride)s were used as initiators for the metal‐catalyzed living radical block copolymerization of methyl methacrylate mediated by CuCl/2,2′‐bipyridine. Poly(methyl methacrylate)‐b‐poly(vinyl chloride)‐b‐poly(methyl methacrylate) block copolymers with Mn values of 36,500–95,700 and Mw/Mn values lower than 1.20 were synthesized by this novel and general synthetic method.