Synthesis of poly(vinyl chloride)‐b‐poly(2‐ethylhexyl acrylate)‐b‐poly(vinyl chloride) by the competitive single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization of vinyl chloride initiated from α,ω‐di(iodo)poly(2‐ethylhexyl acrylate) and catalyzed with sodium dithionite in water

Abstract α,ω‐Di(iodo)poly(2‐ethylhexyl acrylate)s [α,ω‐di(iodo)P2EHAs] with number‐average molecular weights of 13,700 and 20,400 were synthesized by the single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization (SET–DTLRP) of 2‐ethylhexyl acrylate initiated with iodoform and catalyzed by sodium dithionite in water at 23 and 30 °C. These α,ω‐di(iodo)P2EHAs were used as macroinitiators for the SET–DTLRP of vinyl chloride, which was carried out under similar reaction conditions to synthesize ABA block copolymers containing poly(vinyl chloride) in the A blocks and poly(2‐ethylhexyl acrylate) in the B block. Poly(vinyl chloride)‐b‐poly(2‐ethylhexyl acrylate)‐b‐poly(vinyl chloride) was synthesized with 100% initiator efficiency. This synthetic method provides for the first time access to a diversity of block copolymers and other complex architectures based on combinations of thermoplastic poly(vinyl chloride)and elastomeric polyacrylates.