Synthesis of poly(ω-pentadecalactone)-b-poly(acrylate) diblock copolymers via a combination of enzymatic ring-opening and RAFT polymerization techniques

Abstract

Herein the first reported preparation of diblock copolymers of the polyethylene-like polyester poly(ω-pentadecalactone) (PPDL) via a combination of enzymatic ring-opening polymerization (eROP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization techniques is described. PPDL was synthesized via eROP using Novozyme 435 as a catalyst and a bifunctional initiator/chain transfer agent (CTA) appropriate for the eROP of ω-pentadecalactone (PDL) and RAFT polymerization of acrylic and styrenic monomers. Chain growth of the PPDL macro-CTA was performed to prepare acrylic and styrenic diblock copolymers of PPDL, and demonstrates a facile, metal-free, and “greener” alternative to preparing acrylic diblock copolymers of polyethylene (PE). Diblock copolymer architecture was substantiated via analysis of 1H NMR spectroscopic, UV-GPC chromatographic, DSC onset crystallization (Tc), and MALDI-ToF mass spectrometric data. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3326–3335