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

作　　者：Xiao-Bing Lu Bai-Hao Ren 

机构地区：[1]State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,China

出　　处：《Chinese Journal of Polymer Science》2022年第11期1331-1348,共18页高分子科学（英文版）

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

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.

关 键 词：EPOXIDE Ring-opening copolymerization Synergistic catalysis CO_(2) Stereochemistry control 

分 类 号：TQ316[化学工程—高聚物工业] TQ426