It is a challenge to develop a biodegradable toughener to toughen polylactic acid(PLA)with both high strength and high toughness,since toughness and strength are mutually exclusive.Here,a series of supertough polyeste...It is a challenge to develop a biodegradable toughener to toughen polylactic acid(PLA)with both high strength and high toughness,since toughness and strength are mutually exclusive.Here,a series of supertough polyester thermoplastic elastomers(TPEs),poly(L/D-lactide)-b-poly(ε-caprolactone-co-δ-valerolactone)-b-poly(L/D-lactide)s(PLLA-PCVL-PLLA,L-TPEs or PDLA-PCVL-PDLA,D-TPEs),were prepared and blended with a PLLA matrix to toughen PLLA.The mechanical properties of PLLA could be regulated in a wide range by changing blending ratios and TPE structures.For PLLA blends toughened by L-TPEs,the highest elongation at break is up to 425%with the tensile strength of 33.1 MPa and the toughness of 104 MJ/m3.By the stereocomplex crystallization of PLA(sc-PLA),the tensile strength of the PLLA/D-TPE blends further increased to 41.8 MPa with a similar elongation at break(418%)and the toughness up to 128 MJ/m3.The detailed characterizations revealed a toughening mechanism:(I)the added soft segments increased the ductility of the PLLA matrix,(II)the PLLA segments of L-TPEs increased the compatibility between TPEs and PLLA matrix,and(III)the formation of sc-PLA between the PDLA segments in D-TPE and PLLA provided higher tensile strength by enhancing the strength of the crystal skeleton.The toughened PLA using TPEs can maintain original non-toxic and degradable properties,and be applied potentially in surgical sutures,and 3D-printed scaffolds.展开更多
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This work was supported by the National Key Research and Development Program of China(No.2022YFB3704900)the National Natural Science Foundation of China(Nos.22225104,22071077,21871107,21975102)the China Postdoctoral Science Foundation(Nos.2022TQ0115,2022M711297).
文摘It is a challenge to develop a biodegradable toughener to toughen polylactic acid(PLA)with both high strength and high toughness,since toughness and strength are mutually exclusive.Here,a series of supertough polyester thermoplastic elastomers(TPEs),poly(L/D-lactide)-b-poly(ε-caprolactone-co-δ-valerolactone)-b-poly(L/D-lactide)s(PLLA-PCVL-PLLA,L-TPEs or PDLA-PCVL-PDLA,D-TPEs),were prepared and blended with a PLLA matrix to toughen PLLA.The mechanical properties of PLLA could be regulated in a wide range by changing blending ratios and TPE structures.For PLLA blends toughened by L-TPEs,the highest elongation at break is up to 425%with the tensile strength of 33.1 MPa and the toughness of 104 MJ/m3.By the stereocomplex crystallization of PLA(sc-PLA),the tensile strength of the PLLA/D-TPE blends further increased to 41.8 MPa with a similar elongation at break(418%)and the toughness up to 128 MJ/m3.The detailed characterizations revealed a toughening mechanism:(I)the added soft segments increased the ductility of the PLLA matrix,(II)the PLLA segments of L-TPEs increased the compatibility between TPEs and PLLA matrix,and(III)the formation of sc-PLA between the PDLA segments in D-TPE and PLLA provided higher tensile strength by enhancing the strength of the crystal skeleton.The toughened PLA using TPEs can maintain original non-toxic and degradable properties,and be applied potentially in surgical sutures,and 3D-printed scaffolds.
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.
