The asymmetric alternating copolymerization of meso-epoxide and cyclic anhydrides provides an efficient access to enantiopure polyesters.Contrary to the extensive investigation of the stereochemistry resulting from ep...The asymmetric alternating copolymerization of meso-epoxide and cyclic anhydrides provides an efficient access to enantiopure polyesters.Contrary to the extensive investigation of the stereochemistry resulting from epoxide building block,the chirality from anhydride and the configurational match with epoxide remain elusive.Herein,we discover that the bimetallic chromium catalysts have led to an obvious enhancement in terms of reactivity and enantioselectivity for the asymmetric copolymerization of meso-epoxide with various non-symmetric chiral anhydrides.Up to 97%ee was obtained during the asymmetric copolymerization of cyclohexene oxide(CHO)with(R)-methylsuccinic anhydride(R-MSA),and three-or four-carbon chiral centers were simultaneously installed in the aliphatic polyester backbone.In particular,the different combinations of stereochemistry in epoxide and anhydride building blocks considerably affect the thermal properties and crystalline behaviors of the resulting polyesters.This study uncovers an interesting method for regulating polymer crystallinity via matching the chirality of different monomers.展开更多
The thermotropic liquid crystal polyester(TLCP)fiber is an increasingly important strategic high-performance fiber.In this paper,the TLCP was prepared by two-step melt polymerization using 4-hydroxybenzoic acid(HBA)an...The thermotropic liquid crystal polyester(TLCP)fiber is an increasingly important strategic high-performance fiber.In this paper,the TLCP was prepared by two-step melt polymerization using 4-hydroxybenzoic acid(HBA)and 6-hydroxy-2-naphthoic acid(HNA)as comonomers at a molar ratio of 7∶3.The structure of TLCP was confirmed by the Fourier transform infrared(FTIR)spectrometer and nuclear magnetic resonance(NMR)spectrometer.The thermal and rheological properties of TLCP before and after heat treatment were analyzed systematically by the differential scanning calorimeter(DSC),dynamic mechanical analyzer(DMA)and high-temperature rotational rheometer.The results revealed that the melting temperature,glass transition temperature and melt viscosity of the TLCP increased significantly after heat treatment.It indicates that the crystallization of the TLCP is perfect,and solid-phase condensation occurs during heat treatment,which increases its molecular mass.In conclusion,heat treatment at a temperature below but close to the melting temperature can effectively regulate the structure and properties of the TLCP,and the results of this study can provide a reference for the high strengthening of TLCP fibers.展开更多
Chemical modification of polymers represents a pivotal method for achieving functionalized polymer materials.However,due to the lack of post-functional handle,the chemical modification of polyester materials remains a...Chemical modification of polymers represents a pivotal method for achieving functionalized polymer materials.However,due to the lack of post-functional handle,the chemical modification of polyester materials remains a significant challenge.Ring-opening copolymerization of cyclic anhydride and epoxides is a powerful approach to synthesize polyesters.In this work,we for the first time demonstrate the functionalizability of polyesters synthesized with brominated anhydride monomers.The post-functionalization is amenable to a wide variety of reactive groups and reactions with high yields.With multiple well-established functionalization pathways of brominated polyester materials and optimized the conditions for the modification reactions,a series of functionalized polyester materials can be obtained with high yields,providing new insights for the research about functionalization of polymers.展开更多
Aliphatic polyesters and polycarbonates are among the promising sustainable polymers,which exhibit unique degradability and chain-chain interactions owing to their heterofunctionality.However,monocomponent aliphatic p...Aliphatic polyesters and polycarbonates are among the promising sustainable polymers,which exhibit unique degradability and chain-chain interactions owing to their heterofunctionality.However,monocomponent aliphatic polyesters and polycarbonates usually suffer from inferior properties and functionalities.By contrast,precisely modulated block copolymers composed of polyesters and polycarbonates give rise to sustainable materials with tailored performance.An efficient approach to synthesize the block copolymers is the ring-opening(co)polymerization of the heterocycle monomers.Herein,this review presents the heterocycle monomer ring-opening(co)polymerization for the formation of sequence-controlled block polyesters and polycarbonates.Available synthetic strategies,different monomers,monomer combinations and the catalyst systems for the formation of different block polyesters and polycarbonates are summarized.展开更多
To enhance the properties of bio-based polyesters,enabling them to more closely mimic the characteristics of terephthalate-based materials,a series of aliphatic-aromatic copolyesters(P_(1)–P_(4))were synthesized via ...To enhance the properties of bio-based polyesters,enabling them to more closely mimic the characteristics of terephthalate-based materials,a series of aliphatic-aromatic copolyesters(P_(1)–P_(4))were synthesized via melt polycondensation.Diester monomers M and N were synthesized via the Williamson reaction,using lignin-derived 2-methoxyhydroquinone,methyl 4-chloromethylbenzoate,and methyl chloroacetate as starting materials.Hydroquinone bis(2-hydroxyethyl)ether(HQEE)and 1,4-cyclohexanedimethanol(CHDM)were employed as cyclic segments,while 1,4-butanediol(BDO)and 1,6-hexanediol(HDO)served as alkyl segments within the copolymer structures.The novel copolyesters exhibited molecular weights(Mw)in the range of 5.25×10^(4)–5.87×10^(4) g/mol,with polydispersity indices spanning from 2.50–2.66.Evaluation of the structural and thermomechanical properties indicated that the inclusion of alkyl segments induced a reduction in both crystallinity and molecular weight,while significantly improving the flexibility,whereas cyclic segments enhanced the processability of the copolyesters.Copolyesters P_(1) and P_(2),due to the presence of rigid segments(HQEE and CHDM),displayed relatively high glass transition temperatures(Tg>80℃)and melting temperatures(Tm>170℃).Notably,P_(2),incorporating CHDM,exhibited superior elongation properties(272%),attributed to the enhanced chain mobility resulting from its trans-conformation,while P_(1) was found to be likely brittle owing to excessive chain stiffness.Biodegradability assessment using earthworms as bioindicators revealed that the copolyesters demonstrated moderate degradation profiles,with P_(2) exhibiting a degradation rate of 4.82%,followed by P_(4) at 4.07%,P_(3) at 3.65%,and P_(1) at 3.17%.The higher degradation rate of P_(2) was attributed to its relatively larger d-spacing and lower toxicity,which facilitated enzymatic hydrolytic attack by microorganisms.These findings highlight the significance of optimizing the structural chain segments within aliphatic-aromatic copolyesters.By doing so,it is possible to significantly enhance their properties and performance,offering viable bio-based alternatives to petroleum-based polyesters such as polyethylene terephthalate(PET).展开更多
Renewable 2,5-furandicarboxylic acid-based polyesters are one of the most promising materials for achieving plastic replacement in the age of energy and environmental crisis.However,their properties still cannot compe...Renewable 2,5-furandicarboxylic acid-based polyesters are one of the most promising materials for achieving plastic replacement in the age of energy and environmental crisis.However,their properties still cannot compete with those of petrochemical-based plastics,owing to insufficient molecular and/or microstructure designs.Herein,we utilize the Ti_(3)C_(2)T_(x)-based MXene nanosheets for decorating carbon nanotube(CNT)and obtaining the structurally stable and highly dispersed dendritic heterostructured MXene@CNT,that can act as multi-roles,i.e.,polycondensation catalyst,crystal nucleator,and interface enhancer of polyester.The biobased MXene@CNT/polybutylene furandicarboxylate(PBF)(denoted as MCP)nanocomposites are synthesized by the strategy of“in situ catalytic polymerization and hot-pressing”.Benefiting from the multi-scale interactions(i.e.,covalent bonds,hydrogen bonds,and physical interlocks)in hybrid structure,the MCP presents exceptional mechanical strength(≈101 MPa),stiffness(≈3.1 GPa),toughness(≈130 MJ m^(-3)),and barrier properties(e.g.,O_(2)0.0187 barrer,CO_(2)0.0264 barrer,and H2O 1.57×10^(-14) g cm cm^(-2) s Pa)that are higher than most reported bio-based materials and engineering plastics.Moreover,it also displays satisfactory multifunctionality with high reprocessability(90%strength retention after 5 recycling),UV resistance(blocking 85%UVA rays),and solvent-resistant properties.As a state-of-art high-performance and multifunctional material,the novel bio-based MCP nanocomposite offers a more sustainable alternative to petrochemical-based plastics in packaging and engineering material fields.More importantly,our catalysis-interfacial strengthening integration strategy opens a door for designing and constructing high-performance bio-based polyester materials in future.展开更多
The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/M...The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/MS). PGC was applied to study the F t curve of the multiblock copolymer and PGC/MS was used to separate and identify the pyrolyzates. DTA experiment was used to study the decomposition temperature. The results show that the beginning point of elastomer’s decomposition was about 300?℃ and the decomposition temperature of most of the sample was 550?℃. Many pyrolyzates were produced because of the breaking of weak bonds in the sample. The possible microstructure was verified and the pyrolysis pathway of the copolymer was investigated.展开更多
A series of novel thermotropic liquid crystalline polyesters bearing nonlinear optical azobenzene side group were synthesized by high temperature solution polycondensation and their structures,thermal stability, phas...A series of novel thermotropic liquid crystalline polyesters bearing nonlinear optical azobenzene side group were synthesized by high temperature solution polycondensation and their structures,thermal stability, phase transition behavior and crystallinity were characterized by IR,elemental analysis, TG-DTA, polarizing optical microscope (POM) equipped with a hot stage and X-ray diffraction techniques. The results demonstrate that all the synthesized polyesters exhibit nematic liquid crystalline phases and show relatively high glass transition temperatures and good thermal stability.展开更多
The crystalline morphology of a thermotropic aromatic polyester has been studied by microscopy techniques. Spherulites with ringed structure under polarizing micioscope were observed for solution cast specimens, They ...The crystalline morphology of a thermotropic aromatic polyester has been studied by microscopy techniques. Spherulites with ringed structure under polarizing micioscope were observed for solution cast specimens, They were composed of radially growing crystalline lamellae of thickness around 100. It was found that the molecules were packed in the thickness direction. Banded texture was observed in randomly packed domains for melt cast specimens. The bands have the same width and internal structure as those usually observed in oriented specimens of these polymers obtained by shearing their mesomorphic melt.展开更多
Terpolymer of 1, 8-octanediol, adipic acid, and L-malic acid was synthesized via a lipase-catalyzed direct polycondensation. The products were characterized by GPC and 1H NMR. The results indicated that the molecular ...Terpolymer of 1, 8-octanediol, adipic acid, and L-malic acid was synthesized via a lipase-catalyzed direct polycondensation. The products were characterized by GPC and 1H NMR. The results indicated that the molecular weight of the prepared polymers decreased with increasing L-malic acid content in the monomer feed ratio, and that change in the L-malic acid content from 0 to 20 mol % did not remarkably influenced on the molecular weight distribution Mw /Ma of the prepared samples. The 1H NMR spectra of the obtained copolymer samples showed that hydroxyl groups of L-malic acid did not take part in the polymerization reaction.展开更多
Europe is grappling with a colossal textile waste problem.Over 125 million tonnes of raw materials are devoured by the global industry each year,yet a mere fraction-less than 1%-of these fibres originate from recycled...Europe is grappling with a colossal textile waste problem.Over 125 million tonnes of raw materials are devoured by the global industry each year,yet a mere fraction-less than 1%-of these fibres originate from recycled textiles.The majority faces an unsustainable fate in landfills,incinerators,or is exported.A pivotal new report by Systemiq,"The Textile Recycling Breakthrough,"offers both a stark assessment and a strategic roadmap:Europe has the potential to amplify polyester textile recycling nearly tenfold by 2035,but this hinges on immediate,decisive action from policymakers and the industry.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22071016 and 21920102006)。
文摘The asymmetric alternating copolymerization of meso-epoxide and cyclic anhydrides provides an efficient access to enantiopure polyesters.Contrary to the extensive investigation of the stereochemistry resulting from epoxide building block,the chirality from anhydride and the configurational match with epoxide remain elusive.Herein,we discover that the bimetallic chromium catalysts have led to an obvious enhancement in terms of reactivity and enantioselectivity for the asymmetric copolymerization of meso-epoxide with various non-symmetric chiral anhydrides.Up to 97%ee was obtained during the asymmetric copolymerization of cyclohexene oxide(CHO)with(R)-methylsuccinic anhydride(R-MSA),and three-or four-carbon chiral centers were simultaneously installed in the aliphatic polyester backbone.In particular,the different combinations of stereochemistry in epoxide and anhydride building blocks considerably affect the thermal properties and crystalline behaviors of the resulting polyesters.This study uncovers an interesting method for regulating polymer crystallinity via matching the chirality of different monomers.
基金National Key Research and Development Program of China (No.2021YFB3700105)。
文摘The thermotropic liquid crystal polyester(TLCP)fiber is an increasingly important strategic high-performance fiber.In this paper,the TLCP was prepared by two-step melt polymerization using 4-hydroxybenzoic acid(HBA)and 6-hydroxy-2-naphthoic acid(HNA)as comonomers at a molar ratio of 7∶3.The structure of TLCP was confirmed by the Fourier transform infrared(FTIR)spectrometer and nuclear magnetic resonance(NMR)spectrometer.The thermal and rheological properties of TLCP before and after heat treatment were analyzed systematically by the differential scanning calorimeter(DSC),dynamic mechanical analyzer(DMA)and high-temperature rotational rheometer.The results revealed that the melting temperature,glass transition temperature and melt viscosity of the TLCP increased significantly after heat treatment.It indicates that the crystallization of the TLCP is perfect,and solid-phase condensation occurs during heat treatment,which increases its molecular mass.In conclusion,heat treatment at a temperature below but close to the melting temperature can effectively regulate the structure and properties of the TLCP,and the results of this study can provide a reference for the high strengthening of TLCP fibers.
基金financially supported by the National Key R&D Program of China(No.2021YFA1501700)the Science and Technology Development Plan of Jilin Province(Nos.20230101042JC and 20210201059GX)+1 种基金the National Natural Science Foundation of China,Basic Science Center Program(No.51988102)the National Natural Science Foundation of China(Nos.52203017 and 52073272)。
文摘Chemical modification of polymers represents a pivotal method for achieving functionalized polymer materials.However,due to the lack of post-functional handle,the chemical modification of polyester materials remains a significant challenge.Ring-opening copolymerization of cyclic anhydride and epoxides is a powerful approach to synthesize polyesters.In this work,we for the first time demonstrate the functionalizability of polyesters synthesized with brominated anhydride monomers.The post-functionalization is amenable to a wide variety of reactive groups and reactions with high yields.With multiple well-established functionalization pathways of brominated polyester materials and optimized the conditions for the modification reactions,a series of functionalized polyester materials can be obtained with high yields,providing new insights for the research about functionalization of polymers.
基金supported by the National Natural Science Foundation of China,Fund for Distinguished Young Scholars(No.52325301)CAS Project for Young Scientists in Basic Research(YSBR-094)the National Natural Science Foundation of China,Basic Science Center Program(No.51988102).
文摘Aliphatic polyesters and polycarbonates are among the promising sustainable polymers,which exhibit unique degradability and chain-chain interactions owing to their heterofunctionality.However,monocomponent aliphatic polyesters and polycarbonates usually suffer from inferior properties and functionalities.By contrast,precisely modulated block copolymers composed of polyesters and polycarbonates give rise to sustainable materials with tailored performance.An efficient approach to synthesize the block copolymers is the ring-opening(co)polymerization of the heterocycle monomers.Herein,this review presents the heterocycle monomer ring-opening(co)polymerization for the formation of sequence-controlled block polyesters and polycarbonates.Available synthetic strategies,different monomers,monomer combinations and the catalyst systems for the formation of different block polyesters and polycarbonates are summarized.
基金financially supported by State Administration of Foreign Experts Affairs(SAFEA)through the High-End Foreign Expert Program(No.BG2021227001)postdoctoral funding from Wuhan University of Science and Technology(No.105008701)。
文摘To enhance the properties of bio-based polyesters,enabling them to more closely mimic the characteristics of terephthalate-based materials,a series of aliphatic-aromatic copolyesters(P_(1)–P_(4))were synthesized via melt polycondensation.Diester monomers M and N were synthesized via the Williamson reaction,using lignin-derived 2-methoxyhydroquinone,methyl 4-chloromethylbenzoate,and methyl chloroacetate as starting materials.Hydroquinone bis(2-hydroxyethyl)ether(HQEE)and 1,4-cyclohexanedimethanol(CHDM)were employed as cyclic segments,while 1,4-butanediol(BDO)and 1,6-hexanediol(HDO)served as alkyl segments within the copolymer structures.The novel copolyesters exhibited molecular weights(Mw)in the range of 5.25×10^(4)–5.87×10^(4) g/mol,with polydispersity indices spanning from 2.50–2.66.Evaluation of the structural and thermomechanical properties indicated that the inclusion of alkyl segments induced a reduction in both crystallinity and molecular weight,while significantly improving the flexibility,whereas cyclic segments enhanced the processability of the copolyesters.Copolyesters P_(1) and P_(2),due to the presence of rigid segments(HQEE and CHDM),displayed relatively high glass transition temperatures(Tg>80℃)and melting temperatures(Tm>170℃).Notably,P_(2),incorporating CHDM,exhibited superior elongation properties(272%),attributed to the enhanced chain mobility resulting from its trans-conformation,while P_(1) was found to be likely brittle owing to excessive chain stiffness.Biodegradability assessment using earthworms as bioindicators revealed that the copolyesters demonstrated moderate degradation profiles,with P_(2) exhibiting a degradation rate of 4.82%,followed by P_(4) at 4.07%,P_(3) at 3.65%,and P_(1) at 3.17%.The higher degradation rate of P_(2) was attributed to its relatively larger d-spacing and lower toxicity,which facilitated enzymatic hydrolytic attack by microorganisms.These findings highlight the significance of optimizing the structural chain segments within aliphatic-aromatic copolyesters.By doing so,it is possible to significantly enhance their properties and performance,offering viable bio-based alternatives to petroleum-based polyesters such as polyethylene terephthalate(PET).
基金financial supports from the National Natural Science Foundation of China(Grant No.NSFC52473104)National Key R&D Program of China(Grant No.2022YFC2104500)+3 种基金Zhejiang Provincial Natural Science Foundation of China(Grant No.Y24B040002)Ningbo 2025 Key Scientific Research Programs(Grant No.2022Z160)the China Postdoctoral Science Foundation(Grant No.2023M733601)the Ningbo Natural Science Foundation(Grant No.2023I333&2023J409).
文摘Renewable 2,5-furandicarboxylic acid-based polyesters are one of the most promising materials for achieving plastic replacement in the age of energy and environmental crisis.However,their properties still cannot compete with those of petrochemical-based plastics,owing to insufficient molecular and/or microstructure designs.Herein,we utilize the Ti_(3)C_(2)T_(x)-based MXene nanosheets for decorating carbon nanotube(CNT)and obtaining the structurally stable and highly dispersed dendritic heterostructured MXene@CNT,that can act as multi-roles,i.e.,polycondensation catalyst,crystal nucleator,and interface enhancer of polyester.The biobased MXene@CNT/polybutylene furandicarboxylate(PBF)(denoted as MCP)nanocomposites are synthesized by the strategy of“in situ catalytic polymerization and hot-pressing”.Benefiting from the multi-scale interactions(i.e.,covalent bonds,hydrogen bonds,and physical interlocks)in hybrid structure,the MCP presents exceptional mechanical strength(≈101 MPa),stiffness(≈3.1 GPa),toughness(≈130 MJ m^(-3)),and barrier properties(e.g.,O_(2)0.0187 barrer,CO_(2)0.0264 barrer,and H2O 1.57×10^(-14) g cm cm^(-2) s Pa)that are higher than most reported bio-based materials and engineering plastics.Moreover,it also displays satisfactory multifunctionality with high reprocessability(90%strength retention after 5 recycling),UV resistance(blocking 85%UVA rays),and solvent-resistant properties.As a state-of-art high-performance and multifunctional material,the novel bio-based MCP nanocomposite offers a more sustainable alternative to petrochemical-based plastics in packaging and engineering material fields.More importantly,our catalysis-interfacial strengthening integration strategy opens a door for designing and constructing high-performance bio-based polyester materials in future.
文摘The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/MS). PGC was applied to study the F t curve of the multiblock copolymer and PGC/MS was used to separate and identify the pyrolyzates. DTA experiment was used to study the decomposition temperature. The results show that the beginning point of elastomer’s decomposition was about 300?℃ and the decomposition temperature of most of the sample was 550?℃. Many pyrolyzates were produced because of the breaking of weak bonds in the sample. The possible microstructure was verified and the pyrolysis pathway of the copolymer was investigated.
文摘A series of novel thermotropic liquid crystalline polyesters bearing nonlinear optical azobenzene side group were synthesized by high temperature solution polycondensation and their structures,thermal stability, phase transition behavior and crystallinity were characterized by IR,elemental analysis, TG-DTA, polarizing optical microscope (POM) equipped with a hot stage and X-ray diffraction techniques. The results demonstrate that all the synthesized polyesters exhibit nematic liquid crystalline phases and show relatively high glass transition temperatures and good thermal stability.
文摘The crystalline morphology of a thermotropic aromatic polyester has been studied by microscopy techniques. Spherulites with ringed structure under polarizing micioscope were observed for solution cast specimens, They were composed of radially growing crystalline lamellae of thickness around 100. It was found that the molecules were packed in the thickness direction. Banded texture was observed in randomly packed domains for melt cast specimens. The bands have the same width and internal structure as those usually observed in oriented specimens of these polymers obtained by shearing their mesomorphic melt.
文摘Terpolymer of 1, 8-octanediol, adipic acid, and L-malic acid was synthesized via a lipase-catalyzed direct polycondensation. The products were characterized by GPC and 1H NMR. The results indicated that the molecular weight of the prepared polymers decreased with increasing L-malic acid content in the monomer feed ratio, and that change in the L-malic acid content from 0 to 20 mol % did not remarkably influenced on the molecular weight distribution Mw /Ma of the prepared samples. The 1H NMR spectra of the obtained copolymer samples showed that hydroxyl groups of L-malic acid did not take part in the polymerization reaction.
文摘Europe is grappling with a colossal textile waste problem.Over 125 million tonnes of raw materials are devoured by the global industry each year,yet a mere fraction-less than 1%-of these fibres originate from recycled textiles.The majority faces an unsustainable fate in landfills,incinerators,or is exported.A pivotal new report by Systemiq,"The Textile Recycling Breakthrough,"offers both a stark assessment and a strategic roadmap:Europe has the potential to amplify polyester textile recycling nearly tenfold by 2035,but this hinges on immediate,decisive action from policymakers and the industry.
