Ocean-degradable polyesters incorporating hydrophilic and rapidly degradable glycolide(GL)units into the polymer chain are the most promising for addressing marine plastic pollution,however,it is challenging to obtain...Ocean-degradable polyesters incorporating hydrophilic and rapidly degradable glycolide(GL)units into the polymer chain are the most promising for addressing marine plastic pollution,however,it is challenging to obtain high-molecular-weight copolymers with narrow molecular weight distributions.Herein,we prepared a novel biodegradable material,poly(butylene succinate-co-glycolide)(PBSGL),through ring-opening copolymerization using glycolide,succinic anhydride,and 1,4-butanediol as raw materials,providing a new solution strategy for marine pollution.GL could be polymerized according to the pre-designed composition by 1H-nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)results,indicating controlled polymerization with the synthesized PBSGLs having a weight-average molecular weight of up to 12.30×10^(4) g/mol and a narrow molecular weight distribution(1.33–1.65).Differential scanning calorimeter(DSC)and thermogravimetric analysis(TGA)results showed that T_(g) of PBSGLs increased from−32.5°C to−26.5°C with the increase of GL content from 0%to 40%,while T_(m)(>76°C)was much lower than T_(d,5%)(>314°C),which indicated that PBSGLs had good thermal stability and expanded the processing window and application range of the original poly(butylene succinate)(PBS)materials.Under simulated difficult conditions,PBSGL copolyesters could degrade faster with increasing GL content,where PBSGL40 degraded by 22.6%in 12 days,showing good biodegradability.Currently,most biodegradable polyesters with good performance slowly degrade in seawater.In a 30-day artificial seawater degradation test,the amorphous PBSGL40 copolyester showed a about 15-fold(2.33%weight loss)improvement in degradation ability compared to pure PBS,demonstrating rapid seawater degradation capability.展开更多
This study proposes to use the unconfined compressive strength(UCS)and the bender element(BE)tests for determining the strength and the initial small-strain shear modulus of Bangkok soft marine clay improved by cement...This study proposes to use the unconfined compressive strength(UCS)and the bender element(BE)tests for determining the strength and the initial small-strain shear modulus of Bangkok soft marine clay improved by cement and polyester fibers.This study varies the content of admixed cement(1%–20%)and polyester fibers(0–20%),including the curing time(3–28 d)for preparing 360 samples.Moreover,this study uses the Michaelis-Menten kinetics concept to model cement hydration saturation.From the study,it is concluded as follows.The modelled results reveals that at least 10%cement and 1%polyester fiber are recommended to attain the 28-d UCS standards(294 kPa)for highway subgrade materials in Thailand.This also fulfils sustainable construction due to reducing normal-use cement from 20%to 10%.Unfortunately,the addition of polyester fibers into the Bangkok clay with at least 5%cement reduces shear modulus by 1.12–1.32 times.The Abram's relationship between shear modulus and the mixing-water-to-cement ratio is found time-dependent.From the composite theory,the BE detects the polyester fiber zone as a defect in the Bangkok clay(matrix)with 5%–20%cement.So,the 28-d shear modulus in the polyester fiber zone is negative(up to0.034 MPa for 20%fiber),similar to softening phenomenon in concrete cracking(negative stiffness).For the 28-d shear modulus of fiber zone,the optimum cement content is around 2%for the positive influences of polyester fibers.Experimentally,the timedependent normalized UCS for 10%and 20%cement is compatible with other studies,and its development rate increases with the cement content as 0.3017,0.3172 and 0.3204 for 5%,10%and 20%cement,respectively.The 28-d relationship between shear modulus and UCS shows that low-cement soft clay requires high polyester fiber content(5%–20%)to activate UCS improvement.However,the soft clay with enough cement(20%)causes the uniformly distributed UCS improvement.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
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
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
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
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
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 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
An epoxy-terminated hyperbranched aromatic polyester (P3) was synthesized from a hyperbranched aromatic polyester containing carboxylic acid end groups (P1), which was derived from the condensation polymerization of t...An epoxy-terminated hyperbranched aromatic polyester (P3) was synthesized from a hyperbranched aromatic polyester containing carboxylic acid end groups (P1), which was derived from the condensation polymerization of the AB(2) monomer, 5-acetoxyisophthalic acid. Polymer P1 was converted into the polymeric acid chloride by reaction with thionyl chloride. The acid chloride was reacted with ethanol and glycidol to form a poly(ethyl ester) (P2) and an epoxy terminated material (P3), respectively. The reaction conditions in each step of these processes had to be controlled very carefully to avoid unwanted cross-linking reactions. The characterization of products and intermediates, including molecular weight distributions and thermal properties, are reported.展开更多
Unsaturated polyester（UPR）/thermoplastic polyurethane（TPU）/organoclay nanocomposites were prepared by melt compounding of thermoplastic polyurethane and unsaturated polyester prepolymer,and then mixing with the hy...Unsaturated polyester（UPR）/thermoplastic polyurethane（TPU）/organoclay nanocomposites were prepared by melt compounding of thermoplastic polyurethane and unsaturated polyester prepolymer,and then mixing with the hybrids of styrene monomers and organoclay at ambient temperature.The crosslinking reaction eventually occurred through the unsaturated polyester prepolymer and styrene monomer.The morphology of the composites was investigated by scanning electron microscopy（SEM） and transmission electron microscopy（TEM）.The results show that the impact strength of UPR/TPU/organoclay nanocomposites increases obviously;the cure shrinkage decreases markedly,the glass transition temperature is enhanced and an elastic response to the deformation is prominent at the temperature above 10℃.展开更多
Amphiphilic hydroxyl functioned polyester（HFP） can be used as compatibilizers for blends of starch and resins.We developed a synthetic method for effective preparation of HFPs.Water was removed by high flow rate N_2...Amphiphilic hydroxyl functioned polyester（HFP） can be used as compatibilizers for blends of starch and resins.We developed a synthetic method for effective preparation of HFPs.Water was removed by high flow rate N_2 rather than high vacuum during polycondensation of sebacic acid with xylitol,sorbitol,or mannitol in the presence of dehydrative condensation catalyst and the product is with[η]of 27.2 mL/g,M_n of 1903,M_w of 167,693,T_g of -30.5℃,T_m of 44.0℃.Weight loss is 1.73%under 200℃. The integral distributions of molecular weight are 43.6 wt%and 63.8 wt%over 10,000 and 3000,respectively.The results indicated that higher molecular weight HFP was economically synthesized.展开更多
A novel polyester containing ferrocenyl was prepared by low-temperature interface polycondensation of 1,1'-ferrocenedicarboxylic acid chloride with 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one(DHPZ),which is a twisted...A novel polyester containing ferrocenyl was prepared by low-temperature interface polycondensation of 1,1'-ferrocenedicarboxylic acid chloride with 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one(DHPZ),which is a twisted non-coplanar heterocyclic bisphenol-like monomer.The newly generated polymer was evaluated based on characterization of its solubility,viscosity measurements,elemental analysis,FTIR spectroscopy,differential scanning calorimetric and thermogravimetric studies.展开更多
The plastification modification of poly （vinyl chloride） （PVC） with the long-chain linear polyester （LP） synthesized by linear dodecanedioic acid （DC12） or tetradecanedioic acid （DC14） with different diols i...The plastification modification of poly （vinyl chloride） （PVC） with the long-chain linear polyester （LP） synthesized by linear dodecanedioic acid （DC12） or tetradecanedioic acid （DC14） with different diols is investigated. The processing characteristics, mechanical properties and extraction property of the PVC/LP blends in different solvents （xylene, cyclohexane, ethanol） were also studied in detail. All results were compared with that of the PVC plasticized with dioctyl phthalate （DOP）. The results show that the molecular weight, molecular structure and loading of LP greatly influence the mechanical properties of the PVC/LP blends. The processability and the mechanical properties of PVC plasticized by LP are comparable to those of the corresponding PVC/DOP blends. However, the PVC/LP blends posses much better migration resistance property than the corresponding PVC/DOP blends, which makes the long-chain linear polyester become a very good plasticizer candidate for PVC industry.展开更多
The reaction of salicylic chloride and salicylic amide at 170 ℃ gave benzoxazine and a new macrocyclic polyester 3, whose crystal structure has been determined by single-crystal X-ray diffraction analysis. Compound 3...The reaction of salicylic chloride and salicylic amide at 170 ℃ gave benzoxazine and a new macrocyclic polyester 3, whose crystal structure has been determined by single-crystal X-ray diffraction analysis. Compound 3: C28H16O8, Mr = 480.41, monoclinic, space group P21/n, a = 15.353(3), b = 14.196(3), c = 21.147(4) ? b = 103.32(3), V = 4485(2) ?, Z = 8, F(000) = 1984, Dc = 1.423 g/cm3 and m = 0.106 mm-1. The final R = 0.0535 and wR = 0.1275 for 7903 observed reflections (I ≥ 2(I)). In the asymmetric unit of the compound there exist two independent molecules which are connected by weak aromatic CH…O hydrogen bonding between C(47)?H(47) and atom O(7) of the carbonyl group.展开更多
The treatment of polyester wastewater using Up flow activated sludge bed anaerobic filer(UASB AF), demonstrated that UASB AF reactors has a high efficiency, its volume loading is 10～12 kgCOD/(m 3·d),HRT is 22～2...The treatment of polyester wastewater using Up flow activated sludge bed anaerobic filer(UASB AF), demonstrated that UASB AF reactors has a high efficiency, its volume loading is 10～12 kgCOD/(m 3·d),HRT is 22～24 h, and the removal of COD is about 80%. The reactor has advantage of fast starting and enduring pulse loading.展开更多
This paper investigates the effect of recycled polyester fiber, produced from polyethylene （PET） bottles, in combination with nano-SiO2 as a new stabilizer to improve the mechanical properties of soils. We intend to...This paper investigates the effect of recycled polyester fiber, produced from polyethylene （PET） bottles, in combination with nano-SiO2 as a new stabilizer to improve the mechanical properties of soils. We intend to study the effect of adding nano-SiO2 and recycled polyester fiber on soil engineering properties, especially the shear strength and unconfined compressive strength （UCS）, using clayey soil with low liquid limit. Three different combinations of fiber-soil ratios ranging between 0.1% and 0.5% as well as three different combinations of nano-soil ratios ranging between 0.5% and 1% are used. The shear strength and UCS of treated specimens are obtained from direct shear test and unconfined compression test, respectively. Results of this study show that the addition of recycled polyester fiber and nano-SiO2 increases the strength of soil specimens. Both the shear strength and UCS are improved by increasing the contents of recycled polyester fiber and nano-SiO2 in the soil mixture. The increase in the nano-SiO2 content leads to a reduction in failure strain, but the increase in the content of recycled polyester fiber leads to an increase in failure strain. The increase in the contents of recycled polyester fiber and nano-SiO2 leads to an increase in elastic modulus of soils. Based on the test results, the addition of recycled polyester fiber improves the mechanical properties of soils stabilized with nano-SiO2 as well as the recycled polyester fiber has a positive effect on soil behaviors.展开更多
基金financially supported by the National Natural Science Foundation of China (No. 52203012)Shanghai Rising-Star Program (No. 23QC1400900).
文摘Ocean-degradable polyesters incorporating hydrophilic and rapidly degradable glycolide(GL)units into the polymer chain are the most promising for addressing marine plastic pollution,however,it is challenging to obtain high-molecular-weight copolymers with narrow molecular weight distributions.Herein,we prepared a novel biodegradable material,poly(butylene succinate-co-glycolide)(PBSGL),through ring-opening copolymerization using glycolide,succinic anhydride,and 1,4-butanediol as raw materials,providing a new solution strategy for marine pollution.GL could be polymerized according to the pre-designed composition by 1H-nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)results,indicating controlled polymerization with the synthesized PBSGLs having a weight-average molecular weight of up to 12.30×10^(4) g/mol and a narrow molecular weight distribution(1.33–1.65).Differential scanning calorimeter(DSC)and thermogravimetric analysis(TGA)results showed that T_(g) of PBSGLs increased from−32.5°C to−26.5°C with the increase of GL content from 0%to 40%,while T_(m)(>76°C)was much lower than T_(d,5%)(>314°C),which indicated that PBSGLs had good thermal stability and expanded the processing window and application range of the original poly(butylene succinate)(PBS)materials.Under simulated difficult conditions,PBSGL copolyesters could degrade faster with increasing GL content,where PBSGL40 degraded by 22.6%in 12 days,showing good biodegradability.Currently,most biodegradable polyesters with good performance slowly degrade in seawater.In a 30-day artificial seawater degradation test,the amorphous PBSGL40 copolyester showed a about 15-fold(2.33%weight loss)improvement in degradation ability compared to pure PBS,demonstrating rapid seawater degradation capability.
基金allocated by National Science,Research and Innovation Fund(NSRF)King Mongkut's University of Technology North Bangkok(project no.KMUTNB-FF-67-B-44 and KMUTNB-FF-67-B-45)supported by the NSRF through the Program Management Unit for Human Resources&Institutional Development,Research and Innovation(grant no.B40G660036).
文摘This study proposes to use the unconfined compressive strength(UCS)and the bender element(BE)tests for determining the strength and the initial small-strain shear modulus of Bangkok soft marine clay improved by cement and polyester fibers.This study varies the content of admixed cement(1%–20%)and polyester fibers(0–20%),including the curing time(3–28 d)for preparing 360 samples.Moreover,this study uses the Michaelis-Menten kinetics concept to model cement hydration saturation.From the study,it is concluded as follows.The modelled results reveals that at least 10%cement and 1%polyester fiber are recommended to attain the 28-d UCS standards(294 kPa)for highway subgrade materials in Thailand.This also fulfils sustainable construction due to reducing normal-use cement from 20%to 10%.Unfortunately,the addition of polyester fibers into the Bangkok clay with at least 5%cement reduces shear modulus by 1.12–1.32 times.The Abram's relationship between shear modulus and the mixing-water-to-cement ratio is found time-dependent.From the composite theory,the BE detects the polyester fiber zone as a defect in the Bangkok clay(matrix)with 5%–20%cement.So,the 28-d shear modulus in the polyester fiber zone is negative(up to0.034 MPa for 20%fiber),similar to softening phenomenon in concrete cracking(negative stiffness).For the 28-d shear modulus of fiber zone,the optimum cement content is around 2%for the positive influences of polyester fibers.Experimentally,the timedependent normalized UCS for 10%and 20%cement is compatible with other studies,and its development rate increases with the cement content as 0.3017,0.3172 and 0.3204 for 5%,10%and 20%cement,respectively.The 28-d relationship between shear modulus and UCS shows that low-cement soft clay requires high polyester fiber content(5%–20%)to activate UCS improvement.However,the soft clay with enough cement(20%)causes the uniformly distributed UCS improvement.
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 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.
基金The project is supported by the EPSRC and the Youth Science Foundation of Shanghai Higher Education.
文摘An epoxy-terminated hyperbranched aromatic polyester (P3) was synthesized from a hyperbranched aromatic polyester containing carboxylic acid end groups (P1), which was derived from the condensation polymerization of the AB(2) monomer, 5-acetoxyisophthalic acid. Polymer P1 was converted into the polymeric acid chloride by reaction with thionyl chloride. The acid chloride was reacted with ethanol and glycidol to form a poly(ethyl ester) (P2) and an epoxy terminated material (P3), respectively. The reaction conditions in each step of these processes had to be controlled very carefully to avoid unwanted cross-linking reactions. The characterization of products and intermediates, including molecular weight distributions and thermal properties, are reported.
基金supported by the Natural Science Foundation of Guangdong Province(No.39172)
文摘Unsaturated polyester（UPR）/thermoplastic polyurethane（TPU）/organoclay nanocomposites were prepared by melt compounding of thermoplastic polyurethane and unsaturated polyester prepolymer,and then mixing with the hybrids of styrene monomers and organoclay at ambient temperature.The crosslinking reaction eventually occurred through the unsaturated polyester prepolymer and styrene monomer.The morphology of the composites was investigated by scanning electron microscopy（SEM） and transmission electron microscopy（TEM）.The results show that the impact strength of UPR/TPU/organoclay nanocomposites increases obviously;the cure shrinkage decreases markedly,the glass transition temperature is enhanced and an elastic response to the deformation is prominent at the temperature above 10℃.
基金the financial support of National Key Technology R&D Program(No.2006BAD07A06)National"863"Program Project of China(No.2006AA100216)
文摘Amphiphilic hydroxyl functioned polyester（HFP） can be used as compatibilizers for blends of starch and resins.We developed a synthetic method for effective preparation of HFPs.Water was removed by high flow rate N_2 rather than high vacuum during polycondensation of sebacic acid with xylitol,sorbitol,or mannitol in the presence of dehydrative condensation catalyst and the product is with[η]of 27.2 mL/g,M_n of 1903,M_w of 167,693,T_g of -30.5℃,T_m of 44.0℃.Weight loss is 1.73%under 200℃. The integral distributions of molecular weight are 43.6 wt%and 63.8 wt%over 10,000 and 3000,respectively.The results indicated that higher molecular weight HFP was economically synthesized.
基金supported by Education Office of Liaoning Province(No.2008567)
文摘A novel polyester containing ferrocenyl was prepared by low-temperature interface polycondensation of 1,1'-ferrocenedicarboxylic acid chloride with 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one(DHPZ),which is a twisted non-coplanar heterocyclic bisphenol-like monomer.The newly generated polymer was evaluated based on characterization of its solubility,viscosity measurements,elemental analysis,FTIR spectroscopy,differential scanning calorimetric and thermogravimetric studies.
基金the Engineering Developing Foundation of Tongji University
文摘The plastification modification of poly （vinyl chloride） （PVC） with the long-chain linear polyester （LP） synthesized by linear dodecanedioic acid （DC12） or tetradecanedioic acid （DC14） with different diols is investigated. The processing characteristics, mechanical properties and extraction property of the PVC/LP blends in different solvents （xylene, cyclohexane, ethanol） were also studied in detail. All results were compared with that of the PVC plasticized with dioctyl phthalate （DOP）. The results show that the molecular weight, molecular structure and loading of LP greatly influence the mechanical properties of the PVC/LP blends. The processability and the mechanical properties of PVC plasticized by LP are comparable to those of the corresponding PVC/DOP blends. However, the PVC/LP blends posses much better migration resistance property than the corresponding PVC/DOP blends, which makes the long-chain linear polyester become a very good plasticizer candidate for PVC industry.
基金the National Natural Science Foundation of China (Grant No. 29872023)
文摘The reaction of salicylic chloride and salicylic amide at 170 ℃ gave benzoxazine and a new macrocyclic polyester 3, whose crystal structure has been determined by single-crystal X-ray diffraction analysis. Compound 3: C28H16O8, Mr = 480.41, monoclinic, space group P21/n, a = 15.353(3), b = 14.196(3), c = 21.147(4) ? b = 103.32(3), V = 4485(2) ?, Z = 8, F(000) = 1984, Dc = 1.423 g/cm3 and m = 0.106 mm-1. The final R = 0.0535 and wR = 0.1275 for 7903 observed reflections (I ≥ 2(I)). In the asymmetric unit of the compound there exist two independent molecules which are connected by weak aromatic CH…O hydrogen bonding between C(47)?H(47) and atom O(7) of the carbonyl group.
文摘The treatment of polyester wastewater using Up flow activated sludge bed anaerobic filer(UASB AF), demonstrated that UASB AF reactors has a high efficiency, its volume loading is 10～12 kgCOD/(m 3·d),HRT is 22～24 h, and the removal of COD is about 80%. The reactor has advantage of fast starting and enduring pulse loading.
文摘This paper investigates the effect of recycled polyester fiber, produced from polyethylene （PET） bottles, in combination with nano-SiO2 as a new stabilizer to improve the mechanical properties of soils. We intend to study the effect of adding nano-SiO2 and recycled polyester fiber on soil engineering properties, especially the shear strength and unconfined compressive strength （UCS）, using clayey soil with low liquid limit. Three different combinations of fiber-soil ratios ranging between 0.1% and 0.5% as well as three different combinations of nano-soil ratios ranging between 0.5% and 1% are used. The shear strength and UCS of treated specimens are obtained from direct shear test and unconfined compression test, respectively. Results of this study show that the addition of recycled polyester fiber and nano-SiO2 increases the strength of soil specimens. Both the shear strength and UCS are improved by increasing the contents of recycled polyester fiber and nano-SiO2 in the soil mixture. The increase in the nano-SiO2 content leads to a reduction in failure strain, but the increase in the content of recycled polyester fiber leads to an increase in failure strain. The increase in the contents of recycled polyester fiber and nano-SiO2 leads to an increase in elastic modulus of soils. Based on the test results, the addition of recycled polyester fiber improves the mechanical properties of soils stabilized with nano-SiO2 as well as the recycled polyester fiber has a positive effect on soil behaviors.
