Partners in Epoxide Copolymerization Catalysis:Approach to High Activity and Selectivity

作     者：Xiao-Bing Lu Bai-Hao Ren Xiao-Bing Lu;Bai-Hao Ren

作者机构：State Key Laboratory of Fine ChemicalsDalian University of TechnologyDalian 116024China 

出 版 物：《Chinese Journal of Polymer Science》 (高分子科学（英文版）)

年 卷 期：2022年第40卷第11期

页      面：1331-1348页

核心收录：

学科分类：08[工学] 0805[工学-材料科学与工程（可授工学、理学学位）] 080502[工学-材料学] 0703[理学-化学] 0702[理学-物理学] 

基　　金：financially supported by the National Natural Science Foundation of China(No.21920102006)。 

主　　题：Epoxide Ring-opening copolymerization Synergistic catalysis CO_(2) Stereochemistry control 

摘      要：The ring-opening alternating copolymerization processes of epoxides with small-molecule monomers,such as carbon dioxide(CO_(2)),carbonyl sulfide(COS)and cyclic anhydrides,are powerful strategies for preparing polymeric materials with degradable carbonate/ester/thiocarbonate main-chain backbone units.The catalysts selected for copolymerization processes play crucial roles in determining their reaction rates and productivities,as well as the selectivity,regio-and stereochemistry,compositions,and the molecular weights of their resultant copolymers.These processes often generate undesirable byproducts such as polyether or ether linkages dispersed randomly within the copolymer s chain,and/or more thermodynamically stable cyclic products.In this account,we outline our efforts of over a dozen years on developing highly active well-defined metal catalysts based on inter-and intra-molecular synergistic strategies to selectively produce completely alternating copolymers from epoxides and various small-molecule monomers.Much attention was paid to the enantioselective resolution copolymerization processes of racemic epoxides via regioselective ring-openings,and the asymmetric copolymerization processes of meso-epoxides with CO_(2),COS,or cyclic anhydrides via dissymmetrical ring-openings using multichiral catalytic systems,and affording isotactic copolymers with main-chain chirality.In addition,this account provides a thorough mechanistic understanding of the high reactivities,excellent selectivity,and unprecedented stereochemical controls of these copolymerization systems,mediated by interand intramolecular synergistic catalysis.