Biodegradable polymers are a promising sustainable alternative to conventional petroleum-based polymers and have attracted recent extensive research interest due to their potential environmental friendliness and susta...Biodegradable polymers are a promising sustainable alternative to conventional petroleum-based polymers and have attracted recent extensive research interest due to their potential environmental friendliness and sustainability. Among them, aliphatic polyesters and polycarbonates are the most extensively studied ones. The metal-catalyzed ring-opening polymerization(ROP) of cyclic esters and ring-opening copolymerization(ROCOP) of epoxides with anhydrides or CO_(2) are often considered to be the classic and efficient methods to synthesize stereoregular polymers. Moreover, the versatile salen-type metal complexes have been used to prepare almost all types of biodegradable polymers with excellent stereoselectivity control. Hence, this review focuses on stereoselective synthesis of biodegradable polymers by salen-type metal catalysts developed in the last decade.Aliphatic polyesters from ROP of cyclic esters, ROCOP of epoxides with cyclic anhydrides, and carbonylative polymerization of epoxides, as well as aliphatic poly(thio)carbonate from ROCOP of epoxides with CO_(2) or COS are discussed in detail. This review highlights the polymerization mechanisms, catalyst characteristics, and factors controlling the stereoselectivity of each polymerization reaction, aiming to provide general rules for the future design of stereoselective catalysts.展开更多
基金supported by the National Natural Science Foundation of China (52173093)the Peking University Ge Li and Ning Zhao Life Science Research Fund for Young Scientists。
文摘Biodegradable polymers are a promising sustainable alternative to conventional petroleum-based polymers and have attracted recent extensive research interest due to their potential environmental friendliness and sustainability. Among them, aliphatic polyesters and polycarbonates are the most extensively studied ones. The metal-catalyzed ring-opening polymerization(ROP) of cyclic esters and ring-opening copolymerization(ROCOP) of epoxides with anhydrides or CO_(2) are often considered to be the classic and efficient methods to synthesize stereoregular polymers. Moreover, the versatile salen-type metal complexes have been used to prepare almost all types of biodegradable polymers with excellent stereoselectivity control. Hence, this review focuses on stereoselective synthesis of biodegradable polymers by salen-type metal catalysts developed in the last decade.Aliphatic polyesters from ROP of cyclic esters, ROCOP of epoxides with cyclic anhydrides, and carbonylative polymerization of epoxides, as well as aliphatic poly(thio)carbonate from ROCOP of epoxides with CO_(2) or COS are discussed in detail. This review highlights the polymerization mechanisms, catalyst characteristics, and factors controlling the stereoselectivity of each polymerization reaction, aiming to provide general rules for the future design of stereoselective catalysts.
