In situ melt polycondensation was proposed to prepare biodegradable aliphatic-aromatic copolyesters/nano-SiO2 hybrids based on terephthalic acid （TPA）, poly（L-lactic acid） oligomer （OLLA）, 1,4-butanediol （BDO）...In situ melt polycondensation was proposed to prepare biodegradable aliphatic-aromatic copolyesters/nano-SiO2 hybrids based on terephthalic acid （TPA）, poly（L-lactic acid） oligomer （OLLA）, 1,4-butanediol （BDO） and nano-SiO2. TEM and FT-IR characterizations confirmed that TPA, OLLA and BDO copolymerized to obtain biodegradable copolyesters, poly（butylene terepbthalate-co-lactate） （PBTL）, and the abundant hydroxyl groups on the surface of nano-SiO2 provided potential sites for in situ grafting with the simultaneous resulted PBTL. The nano-SiO2 particles were chemically wrapped with PBTL to form PBTL/nano- SiO2 hybrids. Due to the good dispersion and interfacial adhesion of nano-SiO2 particles with the copolyester matrix, the tensile strength and the Young＇s modulus increased from 5.4 and 5.6 MPa for neat PBTL to 16 and 390 MPa for PBTL/nano-SiO2 hybrids with 5 wt.% nano-SiO2, respectively. The mechanical properties of PBTL/nano-SiO2 hybrids were substantially improved.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
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
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
A series of biodegradable aliphatic-aromatic copolyesters, poly(butylene terephthalate-co-butylene adipate-co- ethylene terephthalate-co-ethylene adipate) (PBATE), were synthesized from terephthalic acid (PTA), adipic...A series of biodegradable aliphatic-aromatic copolyesters, poly(butylene terephthalate-co-butylene adipate-co- ethylene terephthalate-co-ethylene adipate) (PBATE), were synthesized from terephthalic acid (PTA), adipic acid (AA), 1,4-butanediol (BG) and ethylene glycol (EG) through direct esterification and polycondensation. The sequence structure and crystallinity of the copolyester were investigated by 1H NMR spectroscopy and the wide-angle X-ray diffractometry (WAXD). The analytical results showed that the PBATE copolyester was a random copolymer and the composition of PBATE copolyester was almost consistent with the feed molar ratios. The crystal structure of PBATE copolyester belonged to the triclinic crystalline system; The variation in melting point of the synthesized PBATE copolyester agreed well with the estimation obtained by the Flory equation and was applicable to the random copolymer.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
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
Six new thermally stable polyesters （4a-f） were synthesized through the solution polycondensation reaction of 2,5-pyridine dicarbonyldichloride （2） with six aromatic diols in N,N＇-dimethyl acetamide （DMAc） solu...Six new thermally stable polyesters （4a-f） were synthesized through the solution polycondensation reaction of 2,5-pyridine dicarbonyldichloride （2） with six aromatic diols in N,N＇-dimethyl acetamide （DMAc） solution and in the presence of pyridine as a base. The polycondensation reactions produce a series of new polyesters （4a-f） in high yields, and inherent viscosity between 0.30 and 0.55 dL/g. The resulting polyesters were characterized by elemental analysis, viscosity measurements, thermal gravimetric analysis （TGA and DTG）, solubility test, Fourier transform infrared （FT-IR） spectroscopy and gel permeation chromatography （GPC）. C 2009 Khalil Faghihi. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
Copolyesters having secondary and tertiary amine salt groups in the main and side chains are prepared by chemoselective polymerization. These copolyesters are soluble in a 10% aqueous solution of poly(vinyl alcohol) ...Copolyesters having secondary and tertiary amine salt groups in the main and side chains are prepared by chemoselective polymerization. These copolyesters are soluble in a 10% aqueous solution of poly(vinyl alcohol) (PVA) at 90 degree C and act as plasticizer in the blend films cast from the solution. Only a glass transition temperature is observed for all these blends indicating the formation of compatible blends from these polyesters with PVA. These blends exhibit manifold characteristics such as ionic conductivity, complex formation with metal ions, absorption of moisture and color changes. The electric conductivity of the copolyesters and blends is in the range of 10** minus **6 Scm** minus **1. The blends with PVA forms complexes with Cu**2** plus and Co**2** plus . The coordination structure with two chelate rings is suggested for these polymer blend/metal complexes. (Author abstract) 10 Refs.展开更多
A wide variety of different types of microorganisms are known to produce intracellular energy and carbon storage products, which have been generally described as being poly (β-hydroxybutyrate), PHB, but which are, mo...A wide variety of different types of microorganisms are known to produce intracellular energy and carbon storage products, which have been generally described as being poly (β-hydroxybutyrate), PHB, but which are, more often than not, copolymers containing different alkyl groups at the β-position. Hence, PHB belongs to the family ofpoly (β-hydroxyalkanoastes), PHA, all of which are usually formed as intracellular inclusions in bacteria under unbalanced growth conditions. Recently, it became of industrial interest to evaluate these PHA polyesters as natural biodegradable and biocompatible plastics for a wide range of possible applications, such as surgical sutures or packaging containers. For industrial applications, the controlled incorporation of repeating units with different chain lengths into a series of copolymers is desirable in order to produce polyesters with a range of material properties because physical and chemical characteristics depend strongly on the polymer composition. Such 'tailor-made' copolymers can be produced under controlled growth conditions in that, if a defined mixture of substrates for a certain type of microorganisms is supplied, a well defined and reproducible copolymer is formed.展开更多
Due to the poor solubility of aromatic polyesters in comm on orga nic solve nts,trifluoroacetic acid is usually used as a co-solve nt to increase their solubility for characterizations.However,only few studies have re...Due to the poor solubility of aromatic polyesters in comm on orga nic solve nts,trifluoroacetic acid is usually used as a co-solve nt to increase their solubility for characterizations.However,only few studies have reported the side reactions induced by it.We present here the application of in situ 1H-NMR techniques to explore its effect on the hydroxyl end-groups,which are usually used for the molecular weight determination of polyesters by end-group estimation method.Using bis(2-hydroxyethyl)terephthalate(BHET)as model compound,quantitative NMR results show the peak integration of hydroxyethyl end-groups decreased with time via a pseudo-first-order kinetics in d-trifluoroacetic acid/d-chloroform mixture solvent(1:10,V:V).This is due to the esterification of hydroxyethyl groups with trifluoroacetic acid,revealed by the H-^(13)C gradient-enhanced heteronuclear multiple bond correlation(gHMBC)spectrum.The mixtures of dimethyl terephthalate and BHET with different molar ratios were used to represent poly(ethylene terephthalate)(PET)with different degrees of polymerization,and the effect of trifluoroacetic acid on the estimation of hydroxyethyl groups and subsequent molecular weight determination of polyesters was studied.Our results show that if a relative error of 5%is allowed,the NMR measurements must be finished within 1.3 h of solution preparation at 25℃ in the mixture solve nt.The results were confirmed in PET sample,while in poly(ethyle ne adipate),the obtained esterifaction con stant is faster that those in aromatic system.The results can be applied to other polymer systems with alcohol functionalized groups,and used as a guideline for the characterization of polyesters and polyethers by end-group estimation method.展开更多
Polyesters with cyclic structures in the main chain typically possess superior mechanical and thermal properties together with chemical recyclability.Ring-opening polymerization(ROP)of bridged or fused bicyclic lacton...Polyesters with cyclic structures in the main chain typically possess superior mechanical and thermal properties together with chemical recyclability.Ring-opening polymerization(ROP)of bridged or fused bicyclic lactones is a simple,and in most cases controlled method to synthesize polyesters with alicyclic moieties in the polymer backbone.The stereochemistry of the alicyclic structures has a great effect on the polymer properties,which can be regulated by varying the polymerization conditions.Here,we report a systematic investigation on the ROP of 2-oxabicyclo[2.2.2]octan-3-one([2.2.2]VL)under different conditions.When initiated byn-butyl lithium(n-BuLi)or catalyzed by trifluoromethanesulfonic acid(TfOH)in the presence of benzyl alcohol,P[2.2.2]VLs containing all cis^(-1),4 disubstituted cyclohexane ring were obtained.However,P[2.2.2]VLs initiated by sodium methoxide(MeONa)or catalyzed by organic superbase contained both cis and trans isomeric structural units.The cis to trans transformation mechanism under these conditions was manifested,and the effect of stereochemical variations on the properties ofP[2.2.2]VLwas revealed.The stereoregularP[2.2.2]VLs,bothcisandtrans,exhibited higher crystallinity and melting temperatures(Tm)than those of the stereoirregular isomers.Finally,the degradation of P[2.2.2]VL with acid at high temperature could recover 3-cyclohexenecarboxylic acid.展开更多
A series of degradable polyesters was synthesized via melt polymerization of 3,6-dioxaoctane-1,8-dioic acid and five different diols,catalyzed by antimony trioxide(Sb_(2)O_(3)).The polymers were characterized by FT-IR...A series of degradable polyesters was synthesized via melt polymerization of 3,6-dioxaoctane-1,8-dioic acid and five different diols,catalyzed by antimony trioxide(Sb_(2)O_(3)).The polymers were characterized by FT-IR and ^(1)H NMR spectroscopy,gel permeation chromatography(GPC)and differential scanning calorimetry(DSC)analysis.The polydispersity index(PDI=M_(w)/M_(n))of the polyesters ranged from 1.55 to 1.99,the weight-average molecular weight(M_(w))from 1.8×10^(4) to 3.2×10^(4) Da,the melting point from 63 to 123℃,and the highest decomposition temperature observed was 363℃.The influence of the structure of the polymer chain on hydrolytic degradability was investigated with tests performed at three different values of pH.The findings obtained provide useful insight for the molecular design and the synthesis of degradable polyesters.展开更多
A new class of unsaturated polyesters based on diethylketone have been prepared by interfacial polymerization of 2,4-bis（4-hydroxybenzylidene）-3-pentanone（I） and 2,4-bis（4-hydroxy-3-methoxybenzylidene）-3-pentan...A new class of unsaturated polyesters based on diethylketone have been prepared by interfacial polymerization of 2,4-bis（4-hydroxybenzylidene）-3-pentanone（I） and 2,4-bis（4-hydroxy-3-methoxybenzylidene）-3-pentanone（II） with 4,4’-azodibenzoyl chloride and 3,3’-azodibenzoyl chloride at ambient temperature. The model compounds were synthesized by reaction of（I） and（II） with benzoyl chloride. The new monomers, model compounds and polyesters have been characterized by different spectral analyses. The polyesters have inherent viscosity of 0.55-0.80 d L/g and moderate number average molecular weight（Mn） in the range of 6150-7400 g/mol. Most of the compounds exhibited their solubility in aprotic solvents while partial solubility in various halogenated organic solvents was observed. The temperatures of 10% weight loss were high（225-330 °C） in nitrogen, indicating that these polyesters have excellent thermal stability. Doping with iodine dramatically raised the conductivity and produced brown colored semiconductive polymers with a maximum conductivity of 2.7 × 10-6 --1cm-1. Moreover, the morphological properties of selected example of polyesters were detected by SEM.展开更多
Aliphatic polyesters were synthesized via the ring opening polymerization of the corresponding lactones initiated with dibutylmagnesium both in bulk and in solution. The resulting polymers were characterized by 1H, 13...Aliphatic polyesters were synthesized via the ring opening polymerization of the corresponding lactones initiated with dibutylmagnesium both in bulk and in solution. The resulting polymers were characterized by 1H, 13C NMR, GPC and XRD. The results indicated that dibutylmagnesium is an effective initiator for the ring opening polymerization of lactones.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
The conformation of polymers at the solid-liquid interface has been the subject of considerable interest in the fundamental theory and applied practice. In paints and printing inks, dispersions of pigment or filler po...The conformation of polymers at the solid-liquid interface has been the subject of considerable interest in the fundamental theory and applied practice. In paints and printing inks, dispersions of pigment or filler powders in polymeric binder solutions have to be maintained in the colloidal state. One of the stabilizing mechanisms for paint is the steric stabilization. On the other hand, in the formation reaction of polymer at the solid-liquid interface took place between monomer solutions and solid展开更多
The photopolymerization of two kinds of prepolyesters containing conjugated diacetylene (PDA-6 and PDA-12) was investigated using DSC. By measuring the endothermic enthalpy of the prepolymers after different UV-irradi...The photopolymerization of two kinds of prepolyesters containing conjugated diacetylene (PDA-6 and PDA-12) was investigated using DSC. By measuring the endothermic enthalpy of the prepolymers after different UV-irradiation times, the polymerizations were found to follow the first-order rate law which agreed with the results of other investigators using a different method. The endothermic enthalpy measurements of PDA-6 and PDA-12 before UV-irradiation precluded the possibility that the decrease of endothermic enthalpy was caused by thermal polymerization.展开更多
基金support from the Natural Science Foundation of Ningbo(No.2007A610030)Science and Technology Department of Zhejiang Province(No.2008C11092-2)
文摘In situ melt polycondensation was proposed to prepare biodegradable aliphatic-aromatic copolyesters/nano-SiO2 hybrids based on terephthalic acid （TPA）, poly（L-lactic acid） oligomer （OLLA）, 1,4-butanediol （BDO） and nano-SiO2. TEM and FT-IR characterizations confirmed that TPA, OLLA and BDO copolymerized to obtain biodegradable copolyesters, poly（butylene terepbthalate-co-lactate） （PBTL）, and the abundant hydroxyl groups on the surface of nano-SiO2 provided potential sites for in situ grafting with the simultaneous resulted PBTL. The nano-SiO2 particles were chemically wrapped with PBTL to form PBTL/nano- SiO2 hybrids. Due to the good dispersion and interfacial adhesion of nano-SiO2 particles with the copolyester matrix, the tensile strength and the Young＇s modulus increased from 5.4 and 5.6 MPa for neat PBTL to 16 and 390 MPa for PBTL/nano-SiO2 hybrids with 5 wt.% nano-SiO2, respectively. The mechanical properties of PBTL/nano-SiO2 hybrids were substantially improved.
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.
文摘A series of biodegradable aliphatic-aromatic copolyesters, poly(butylene terephthalate-co-butylene adipate-co- ethylene terephthalate-co-ethylene adipate) (PBATE), were synthesized from terephthalic acid (PTA), adipic acid (AA), 1,4-butanediol (BG) and ethylene glycol (EG) through direct esterification and polycondensation. The sequence structure and crystallinity of the copolyester were investigated by 1H NMR spectroscopy and the wide-angle X-ray diffractometry (WAXD). The analytical results showed that the PBATE copolyester was a random copolymer and the composition of PBATE copolyester was almost consistent with the feed molar ratios. The crystal structure of PBATE copolyester belonged to the triclinic crystalline system; The variation in melting point of the synthesized PBATE copolyester agreed well with the estimation obtained by the Flory equation and was applicable to the random copolymer.
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.
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.
文摘Six new thermally stable polyesters （4a-f） were synthesized through the solution polycondensation reaction of 2,5-pyridine dicarbonyldichloride （2） with six aromatic diols in N,N＇-dimethyl acetamide （DMAc） solution and in the presence of pyridine as a base. The polycondensation reactions produce a series of new polyesters （4a-f） in high yields, and inherent viscosity between 0.30 and 0.55 dL/g. The resulting polyesters were characterized by elemental analysis, viscosity measurements, thermal gravimetric analysis （TGA and DTG）, solubility test, Fourier transform infrared （FT-IR） spectroscopy and gel permeation chromatography （GPC）. C 2009 Khalil Faghihi. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
文摘Copolyesters having secondary and tertiary amine salt groups in the main and side chains are prepared by chemoselective polymerization. These copolyesters are soluble in a 10% aqueous solution of poly(vinyl alcohol) (PVA) at 90 degree C and act as plasticizer in the blend films cast from the solution. Only a glass transition temperature is observed for all these blends indicating the formation of compatible blends from these polyesters with PVA. These blends exhibit manifold characteristics such as ionic conductivity, complex formation with metal ions, absorption of moisture and color changes. The electric conductivity of the copolyesters and blends is in the range of 10** minus **6 Scm** minus **1. The blends with PVA forms complexes with Cu**2** plus and Co**2** plus . The coordination structure with two chelate rings is suggested for these polymer blend/metal complexes. (Author abstract) 10 Refs.
文摘A wide variety of different types of microorganisms are known to produce intracellular energy and carbon storage products, which have been generally described as being poly (β-hydroxybutyrate), PHB, but which are, more often than not, copolymers containing different alkyl groups at the β-position. Hence, PHB belongs to the family ofpoly (β-hydroxyalkanoastes), PHA, all of which are usually formed as intracellular inclusions in bacteria under unbalanced growth conditions. Recently, it became of industrial interest to evaluate these PHA polyesters as natural biodegradable and biocompatible plastics for a wide range of possible applications, such as surgical sutures or packaging containers. For industrial applications, the controlled incorporation of repeating units with different chain lengths into a series of copolymers is desirable in order to produce polyesters with a range of material properties because physical and chemical characteristics depend strongly on the polymer composition. Such 'tailor-made' copolymers can be produced under controlled growth conditions in that, if a defined mixture of substrates for a certain type of microorganisms is supplied, a well defined and reproducible copolymer is formed.
基金by the National Natural Science Foundation of China(No.21774090)National Key R&D Program of China(No.2018YFB1105700)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Due to the poor solubility of aromatic polyesters in comm on orga nic solve nts,trifluoroacetic acid is usually used as a co-solve nt to increase their solubility for characterizations.However,only few studies have reported the side reactions induced by it.We present here the application of in situ 1H-NMR techniques to explore its effect on the hydroxyl end-groups,which are usually used for the molecular weight determination of polyesters by end-group estimation method.Using bis(2-hydroxyethyl)terephthalate(BHET)as model compound,quantitative NMR results show the peak integration of hydroxyethyl end-groups decreased with time via a pseudo-first-order kinetics in d-trifluoroacetic acid/d-chloroform mixture solvent(1:10,V:V).This is due to the esterification of hydroxyethyl groups with trifluoroacetic acid,revealed by the H-^(13)C gradient-enhanced heteronuclear multiple bond correlation(gHMBC)spectrum.The mixtures of dimethyl terephthalate and BHET with different molar ratios were used to represent poly(ethylene terephthalate)(PET)with different degrees of polymerization,and the effect of trifluoroacetic acid on the estimation of hydroxyethyl groups and subsequent molecular weight determination of polyesters was studied.Our results show that if a relative error of 5%is allowed,the NMR measurements must be finished within 1.3 h of solution preparation at 25℃ in the mixture solve nt.The results were confirmed in PET sample,while in poly(ethyle ne adipate),the obtained esterifaction con stant is faster that those in aromatic system.The results can be applied to other polymer systems with alcohol functionalized groups,and used as a guideline for the characterization of polyesters and polyethers by end-group estimation method.
基金financially supported by the National Natural Science Foundation of China(Nos.21871014 and 21971005)。
文摘Polyesters with cyclic structures in the main chain typically possess superior mechanical and thermal properties together with chemical recyclability.Ring-opening polymerization(ROP)of bridged or fused bicyclic lactones is a simple,and in most cases controlled method to synthesize polyesters with alicyclic moieties in the polymer backbone.The stereochemistry of the alicyclic structures has a great effect on the polymer properties,which can be regulated by varying the polymerization conditions.Here,we report a systematic investigation on the ROP of 2-oxabicyclo[2.2.2]octan-3-one([2.2.2]VL)under different conditions.When initiated byn-butyl lithium(n-BuLi)or catalyzed by trifluoromethanesulfonic acid(TfOH)in the presence of benzyl alcohol,P[2.2.2]VLs containing all cis^(-1),4 disubstituted cyclohexane ring were obtained.However,P[2.2.2]VLs initiated by sodium methoxide(MeONa)or catalyzed by organic superbase contained both cis and trans isomeric structural units.The cis to trans transformation mechanism under these conditions was manifested,and the effect of stereochemical variations on the properties ofP[2.2.2]VLwas revealed.The stereoregularP[2.2.2]VLs,bothcisandtrans,exhibited higher crystallinity and melting temperatures(Tm)than those of the stereoirregular isomers.Finally,the degradation of P[2.2.2]VL with acid at high temperature could recover 3-cyclohexenecarboxylic acid.
基金Funded by the Program(BG20190227001)of High-end Foreign Experts of the State Administration of Foreign Experts Affairs(SAFEA)the Coal Conversion and New Carbon Materials Hubei Key Laboratory in Wuhan University of Science and Technology(WKDM201909)。
文摘A series of degradable polyesters was synthesized via melt polymerization of 3,6-dioxaoctane-1,8-dioic acid and five different diols,catalyzed by antimony trioxide(Sb_(2)O_(3)).The polymers were characterized by FT-IR and ^(1)H NMR spectroscopy,gel permeation chromatography(GPC)and differential scanning calorimetry(DSC)analysis.The polydispersity index(PDI=M_(w)/M_(n))of the polyesters ranged from 1.55 to 1.99,the weight-average molecular weight(M_(w))from 1.8×10^(4) to 3.2×10^(4) Da,the melting point from 63 to 123℃,and the highest decomposition temperature observed was 363℃.The influence of the structure of the polymer chain on hydrolytic degradability was investigated with tests performed at three different values of pH.The findings obtained provide useful insight for the molecular design and the synthesis of degradable polyesters.
文摘A new class of unsaturated polyesters based on diethylketone have been prepared by interfacial polymerization of 2,4-bis（4-hydroxybenzylidene）-3-pentanone（I） and 2,4-bis（4-hydroxy-3-methoxybenzylidene）-3-pentanone（II） with 4,4’-azodibenzoyl chloride and 3,3’-azodibenzoyl chloride at ambient temperature. The model compounds were synthesized by reaction of（I） and（II） with benzoyl chloride. The new monomers, model compounds and polyesters have been characterized by different spectral analyses. The polyesters have inherent viscosity of 0.55-0.80 d L/g and moderate number average molecular weight（Mn） in the range of 6150-7400 g/mol. Most of the compounds exhibited their solubility in aprotic solvents while partial solubility in various halogenated organic solvents was observed. The temperatures of 10% weight loss were high（225-330 °C） in nitrogen, indicating that these polyesters have excellent thermal stability. Doping with iodine dramatically raised the conductivity and produced brown colored semiconductive polymers with a maximum conductivity of 2.7 × 10-6 --1cm-1. Moreover, the morphological properties of selected example of polyesters were detected by SEM.
文摘Aliphatic polyesters were synthesized via the ring opening polymerization of the corresponding lactones initiated with dibutylmagnesium both in bulk and in solution. The resulting polymers were characterized by 1H, 13C NMR, GPC and XRD. The results indicated that dibutylmagnesium is an effective initiator for the ring opening polymerization of lactones.
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The conformation of polymers at the solid-liquid interface has been the subject of considerable interest in the fundamental theory and applied practice. In paints and printing inks, dispersions of pigment or filler powders in polymeric binder solutions have to be maintained in the colloidal state. One of the stabilizing mechanisms for paint is the steric stabilization. On the other hand, in the formation reaction of polymer at the solid-liquid interface took place between monomer solutions and solid
文摘The photopolymerization of two kinds of prepolyesters containing conjugated diacetylene (PDA-6 and PDA-12) was investigated using DSC. By measuring the endothermic enthalpy of the prepolymers after different UV-irradiation times, the polymerizations were found to follow the first-order rate law which agreed with the results of other investigators using a different method. The endothermic enthalpy measurements of PDA-6 and PDA-12 before UV-irradiation precluded the possibility that the decrease of endothermic enthalpy was caused by thermal polymerization.
