RAFT polymerization of 1-ethoxyethyl acrylate: A novel route toward near-monodisperse poly(acrylic acid) and derived block copolymer structures

The reversible addition fragmentation chain transfer (RAFT) polymerization of 1-ethoxyethyl acrylate (EEA) was demonstrated. Temperature optimization revealed an optimum polymerization temperature of 70 degrees C. Deprotection of the P(EEA) could be performed by a simple heating step, under mild conditions leading to well-defined poly(acrylic acid) (p(AA)) and under more severe conditions resulting in cross-linked networks of p(AA). In addition, block copolymers with a poly(methyl acrylate), a poly(n-butyl acrylate), a poly(methyl methacrylate), or a poly(N,N-(dimethylamino)ethyl methacrylate) first block and a P(EEA) second block were successfully synthesized by RAFT polymerization in toluene as was demonstrated by GPC and H-1 NMR characterization. For all these experiments, a high-throughput workflow procedure was used. Deprotection of the p(EEA) containing block copolymers was also performed, resulting in well-defined P(AA) containing materials as evidenced by both GPC and H-1 NMR spectroscopy.