In-situ block copolymerization of 1,3-butadiene with cyclohexene oxide and trimethylene carbonate via combination of coordinative chain transfer polymerization and ring opening polymerization by neodymium-based catalyst system

Abstract

Incorporating polar segment or polar block to non-polar polybutadiene is eye-catching as they can modify the interfacial energy and adhesion between polybutadiene matrix and polar materials. Herein, we report the in-situ preparation of well-defined polybutadiene-based block copolymers (poly(1,3-butadiene)-b-poly(cyclohexene oxide) and poly(1,3-butadiene)-b-poly(trimethylene carbonate)) using a commercially available neodymium-based catalytic system Nd(vers)3/AliBu2H/Me2SiCl2. First, the polybutadiene block was conveniently and highly efficiently synthesized via Coordinative Chain Transfer Polymerization (CCTP), yielding 5–11 polymer chains per catalyst molecule. This system revealed a high catalytic efficiency and well-controlled fashion, narrowly distributed together with well-regulated molecular weights were also resulted. Then, taking advantage of the living metal-capped polybutadienyl chain that were produced during the CCTP reaction in the first step, in-situ Ring Opening Polymerization of cyclohexene oxide, trimethylene carbonate were assessed. All the products were carefully characterized by combination of GPC, FTIR, 1H NMR, 2D DOSY NMR and DSC analysis, providing advantages and limitations for this method to prepare nonpolar-polar block copolymers.