The ring-opening alternating copolymerization processes of epoxides with small-molecule monomers,such as carbon dioxide(CO2),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 CO2,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 inter-and intramolecular synergistic catalysis.

Xiao-Bing Lu;Bai-Hao Ren

State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,China

高分子科学（英文版）

[1]Xiao-Bing Lu;Bai-Hao Ren-.Partners in Epoxide Copolymerization Catalysis:Approach to High Activity and Selectivity)[J].高分子科学（英文版）,2022(11):1331-1348

Epoxide,thiocarbonate,stereochemistry,dissymmetrical,multichiral,stereochemical

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