Synthesis of degradable poly(ϵ-caprolactone)-based graft copolymers via a "grafting-from" approach

The controlled ring-opening polymerisation (ROP) of α-bromo-ε-caprolactone (αBrCL), a derivative of ε-caprolactone (εCL), and its copolymerisation with εCL is reported. Functional and monodisperse poly(α-bromo-ε-caprolactone) homopolymers and P(αBrCL-co-εCL) copolymers that contain pendant bromine initiators were obtained with targeted molecular weights using diphenyl phosphate (DPP) as the catalyst at room temperature. Using Cu(0)-mediated Controlled Radical Polymerisation (CRP), methyl acrylate (MA) was successfully “grafted from” P(αBrCL-co-εCL) macroinitiators under mild conditions, resulting in polymers with low dispersity, produced with fast reaction times and minimal termination side reactions.