Metal-free ATRP and ROP for graft copolymers: an orthogonal strategy for sequential and concurrent polymerizations at room temperature

Abstract

Well-defined poly[(methyl acrylate)-co-(hydroxyethyl acrylate)]-graft-) copolymers were synthesized using a completely metal-free strategy by combining atom transfer radical polymerization (ATRP) and ring-opening polymerization (ROP) at ambient temperature. These two orthogonal, metal-free, controlled/living processes, tested in both simultaneous and sequential approaches, were employed to fine-tune grafting density and efficiency by systematically varying monomer concentration and polymerization time. Spectroscopic and chromatographic characterizations confirmed that both ATRP and ROP proceeded in a controlled fashion, yielding graft copolymers with narrowly distributed molecular weights.