A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composit...A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composition dependence of thermal behavior,morphology and mechanical properties was investigated by differential scanning calorimetry（DSC）,atomic force microscopy（AFM）,and tensile testing.The crystallization temperature（T_c） and melting temperature（T_m） of the PBS block within poly（ether-ester）s decrease steadily at first,but decrease sharply with PTMO content above 50 wt%.Two crystallization peaks were detected for PTMO in PBSPTMO60 sample,suggesting the occurrence of fractionated crystallization.The crystallization enthalpies（△H_c） and melting enthalpies（△H_m） of PBS block decrease at first,then increase as PTMO content increases further.AFM has demonstrated that phase-separated morphology transforms from a phase of continuous hard matrix to one of continuous soft matrix containing isolated hard domain as PTMO content is increased.Finally,the results of tensile testing show that the poly（ether-ester）s present the behavior of plastics when PTMO content is below 40 wt%,and of thermoplastic elastomers with PTMO content above 50 wt%.By varying the composition of copolymer,the aliphatic poly（ether-ester）s plastics,or especially biodegradable aliphatic poly（ether-ester）s thermoplastic elastomers can be obtained.展开更多
A novel poly(ether block amide)(PEBA)based solid-state polymer electrolyte(SPE)was prepared using a casting method,in which 20wt%lithium(Li)bis-(trifluoromethanesulfonyl)imide(LiTFSI)and aluminum oxide(Al_(2)O_(3))nan...A novel poly(ether block amide)(PEBA)based solid-state polymer electrolyte(SPE)was prepared using a casting method,in which 20wt%lithium(Li)bis-(trifluoromethanesulfonyl)imide(LiTFSI)and aluminum oxide(Al_(2)O_(3))nanoparticles were used as the Li salt and solid plasticizer,respectively.In the case of addition of 3wt%Al_(2)O_(3) nanoparticles,ion conductivity of the obtained PEBA 2533-20wt%LiTFSI-3wt%Al_(2)O_(3) SPE was 3.57×10^(−5) S cm^(−1) at 25°C.Furthermore,the Li symmetrical battery assembled with it showed excellent cycling stability(1000 h)at 0.1 mA cm^(−2).While,the assembled all-solid-state Li/PEBA 2533-20%LiTFSI-3wt%Al_(2)O_(3)/LiFePO 4(areal capacity:0.15 mAh cm^(−2))battery maintained 94.9%of the maximal capacity(133.9 mAh g^(−1@0.1) mA cm^(−2))at 60°C even after 650 cycles with a superior average coulombic efficiency(CE)of 99.84%.By using X-ray photoelectron spectroscope(XPS),self-aggregation layer(SAL)of polyamide 12(PA12)of PEBA 2533 was discovered,which should contribute to promoting the robustness of lithium fluoride(LiF)enriched solid-electrolyte interphase(SEI)layer.In addition,it is considered that the state of interface between SPE and cathode should be the cause of voltage polarization of the full cell.展开更多
Because glycidyl(Gly) contains an epoxy and an active hydroxyl group, the Gly unit is difficult to introduce into certain polymeric chains in a controlled manner and usually yields hyperbranched polyglycidyl. Alternat...Because glycidyl(Gly) contains an epoxy and an active hydroxyl group, the Gly unit is difficult to introduce into certain polymeric chains in a controlled manner and usually yields hyperbranched polyglycidyl. Alternatively, the monomer 1-ethoxyethyl glycidyl ether(EEGE), derived from Gly and ethyl vinyl ether, has shown potential for application in polymer chemistry, and homopolymerization of this monomer directly produces linear poly(1-ethoxyethyl glycidyl ether) and further yields linear polyglycidyl. In this review, the initiation system of the EEGE monomer is first discussed in terms of chain transfer to monomers in ring-opening polymerization of epoxides with substituent groups. Then, random copolymerization of EEGE with other epoxides is considered. In addition, because the EEGE units on polymers can be transferred to Gly units and further used to construct copolymers with complicated architectures, the applications of EEGE monomers to block, graft, and hyperbranched copolymers are reviewed. Finally, the synthesis of main chain and terminal functional polyethers by transforming the hydroxyl groups at the polymer end or on the main chain into certain functional groups are also discussed. Chemistry based on EEGE has been proved to be an efficient, versatile route to constructing copolymers containing Gly units and ultimately yielding the target properties and applications.展开更多
基金Funded by the National Natural Science Foundation of China(No.50873071)the Teaching and Research Award Program for Outstanding Young Professors in Higher Education Institute,MOE,China
文摘A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composition dependence of thermal behavior,morphology and mechanical properties was investigated by differential scanning calorimetry（DSC）,atomic force microscopy（AFM）,and tensile testing.The crystallization temperature（T_c） and melting temperature（T_m） of the PBS block within poly（ether-ester）s decrease steadily at first,but decrease sharply with PTMO content above 50 wt%.Two crystallization peaks were detected for PTMO in PBSPTMO60 sample,suggesting the occurrence of fractionated crystallization.The crystallization enthalpies（△H_c） and melting enthalpies（△H_m） of PBS block decrease at first,then increase as PTMO content increases further.AFM has demonstrated that phase-separated morphology transforms from a phase of continuous hard matrix to one of continuous soft matrix containing isolated hard domain as PTMO content is increased.Finally,the results of tensile testing show that the poly（ether-ester）s present the behavior of plastics when PTMO content is below 40 wt%,and of thermoplastic elastomers with PTMO content above 50 wt%.By varying the composition of copolymer,the aliphatic poly（ether-ester）s plastics,or especially biodegradable aliphatic poly（ether-ester）s thermoplastic elastomers can be obtained.
文摘A novel poly(ether block amide)(PEBA)based solid-state polymer electrolyte(SPE)was prepared using a casting method,in which 20wt%lithium(Li)bis-(trifluoromethanesulfonyl)imide(LiTFSI)and aluminum oxide(Al_(2)O_(3))nanoparticles were used as the Li salt and solid plasticizer,respectively.In the case of addition of 3wt%Al_(2)O_(3) nanoparticles,ion conductivity of the obtained PEBA 2533-20wt%LiTFSI-3wt%Al_(2)O_(3) SPE was 3.57×10^(−5) S cm^(−1) at 25°C.Furthermore,the Li symmetrical battery assembled with it showed excellent cycling stability(1000 h)at 0.1 mA cm^(−2).While,the assembled all-solid-state Li/PEBA 2533-20%LiTFSI-3wt%Al_(2)O_(3)/LiFePO 4(areal capacity:0.15 mAh cm^(−2))battery maintained 94.9%of the maximal capacity(133.9 mAh g^(−1@0.1) mA cm^(−2))at 60°C even after 650 cycles with a superior average coulombic efficiency(CE)of 99.84%.By using X-ray photoelectron spectroscope(XPS),self-aggregation layer(SAL)of polyamide 12(PA12)of PEBA 2533 was discovered,which should contribute to promoting the robustness of lithium fluoride(LiF)enriched solid-electrolyte interphase(SEI)layer.In addition,it is considered that the state of interface between SPE and cathode should be the cause of voltage polarization of the full cell.
基金supported by the National Natural Science Foundation of China(21274024,21004011)
文摘Because glycidyl(Gly) contains an epoxy and an active hydroxyl group, the Gly unit is difficult to introduce into certain polymeric chains in a controlled manner and usually yields hyperbranched polyglycidyl. Alternatively, the monomer 1-ethoxyethyl glycidyl ether(EEGE), derived from Gly and ethyl vinyl ether, has shown potential for application in polymer chemistry, and homopolymerization of this monomer directly produces linear poly(1-ethoxyethyl glycidyl ether) and further yields linear polyglycidyl. In this review, the initiation system of the EEGE monomer is first discussed in terms of chain transfer to monomers in ring-opening polymerization of epoxides with substituent groups. Then, random copolymerization of EEGE with other epoxides is considered. In addition, because the EEGE units on polymers can be transferred to Gly units and further used to construct copolymers with complicated architectures, the applications of EEGE monomers to block, graft, and hyperbranched copolymers are reviewed. Finally, the synthesis of main chain and terminal functional polyethers by transforming the hydroxyl groups at the polymer end or on the main chain into certain functional groups are also discussed. Chemistry based on EEGE has been proved to be an efficient, versatile route to constructing copolymers containing Gly units and ultimately yielding the target properties and applications.
