Controlled Random and Alternating Copolymerization of Methyl Acrylate with 1-Alkenes

Controlled random copolymerization of methyl acrylate (MA) with 1-alkenes was achieved through the reversible addition−fragmentation transfer (RAFT) technique using benzyl 1-pyrrolcarbodithioate as the transfer agent. NMR analysis reveals that RAFT agent-capped MA units are the predominant end groups. This allowed chain extension to synthesize the novel block copolymer, (MA- co -1-hexene)- b -PMA, by treating poly(MA- co -1-hexene) with AIBN in the presence of MA. The perfectly alternating copolymer of MA and ethene was obtained by using AlCl 3 as the complexing agent. Additionally, the first controlled alternating copolymerization of MA and ethene was achieved by degenerative transfer polymerization with iodoform as transfer agent.