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 Preparation of diblock copolymers of poly(ω‐pentadecalactone) (PPDL) via a combination of enzymatic ring‐opening polymerization (eROP) and reversible addition‐fragmentation chain‐transfer (RAFT) polymerization techniques is reported herein. The synthesis of PPDL via eROP is described using Novozyme 435 as a catalyst and a bifunctional initiator/CTA appropriate for the eROP of ω‐pentadecalactone (PDL) and RAFT polymerization of acrylic and styrenic monomers. RAFT‐functional PPDL was synthesized and chain growth of the macro‐CTA was utilized to prepare acrylic and styrenic diblock copolymers of PPDL, demonstrating a facile, metal‐free, and “greener” alternative to preparing acrylic diblock copolymers of polyethylene (PE).