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. (5th April 2021) - Zhang, Mingming
Graphical abstract: Highlights: An industrialized Nd-system that enables in-situ block copolymerization by CCTP. Incorporating polar blocks to polybutadiene by CCTP method. Functionalized polybutadiene as well as high precatalyst atom economy. 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 /Al i Bu2 H/Me2 SiCl2 . 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, 1 H NMR, 2D DOSY NMR and DSC analysis, providing advantages and limitations for this method to prepare nonpolar-polar block copolymers.