Synthesis of well-defined glycidyl methacrylate based block copolymers with self-activation and self-initiation behaviors via ambient temperature atom transfer radical polymerization

Well-defined glycidyl methacrylate (GMA) based di- and triblock copolymers, with self-activation and self-initiation behaviors by incorporation of 2-(diethylamino) ethyl methacrylate (DEA) blocks, were synthesized via ambient temperature atom transfer radical polymerization (ATRP). The stability of the GMA pendant oxirane rings in tertiary amine environments at ambient temperature was investigated. More importantly, both self-activation behavior in oxirane ring opening addition reaction and self-initiation behavior in post-cure oxirane ring opening crosslinking of these block copolymers were evidenced by H-1 NMR studies. The results demonstrated that the reactivity of pendent oxirane rings was strongly dependant on the nucleophilicity and steric hindrance of tertiary amine moieties and temperature. This facilitated the synthesis of well-defined block copolymers of GMA and DEA via sequential monomer addition ATRP, particularly for polymerization of GMA monomer at ambient temperature. Moreover, these one-component GMA based block polymers have novel self-activation and self-initiation properties, rendering some potential applications in both enzyme immobilization and GMA-based thermosetting materials. (c) 2007 Wiley Periodicals, Inc.