ABA block copolymers containing poly(methyl acrylate) (PMA) as the A segment and poly(vinyl chloride) (PVC) as the B segment (PMA-b-PVC-b-PMA) were synthesized by the Cu(O)/tris(2-dimethylaminoethyl)amine (Me-6-TREN)-catalyzed living radical block copolymerization of methyl acrylate (MA) initiated with alpha,omega-di(iodo)poly(vinyl chloride) [alpha,omega-di(iodo)PVC] in dimethyl sulfoxide (DMSO) at 90, 50, and 25 degrees C. 1,1-Chloroiodoethane, a model compound for the chain ends of the alpha,omega-di(iodo)PVC macroinitiator, was used as an initiator for the Cu(O)/Me-6-TREN-catalyzed living radical polymerization of MA in DMSO at 70, 50, and 25 degrees C. Ultrafast block copolymerization and living radical polymerization methods for MA and other acrylates were discovered. These ultrafast methods provided access to the synthesis of PAM-b-PVA-b-PMA in reaction times, which depended on the temperature range, of 3-20 min. (c) 2005 Wiley Periodicals, Inc.