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
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
The demand for energy-efficient and environmental-friendly power grid construction has made the exploitation of bio-based electrical epoxy resins with excellent properties increasingly important.This work developed th...The demand for energy-efficient and environmental-friendly power grid construction has made the exploitation of bio-based electrical epoxy resins with excellent properties increasingly important.This work developed the bio-based electrotechnical epoxy resins based on magnolol.High-performance epoxy resin(DGEMT)with a double crosslinked points and its composites(Al_(2)O_(3)/DGEMT)were obtained taking advantages of the two bifunctional groups(allyl and phenolic hydroxyl groups)of magnolol.Benefitting from the distinctive structure of DGEMT,the Al_(2)O_(3)/DGEMT composites exhibited the advantages of intrinsically high thermal conductivity,high insulation,and low dielectric loss.The AC breakdown strength and thermal conductivity of Al_(2)O_(3)/DGEMT composites were 35.5 kV/mm and 1.19 W·m-1·K-1,respectively,which were 15.6%and 52.6%higher than those of petroleum-based composites(Al_(2)O_(3)/DGEBA).And its dielectric loss tanδ=0.0046 was 20.7%lower than that of Al_(2)O_(3)/DGEBA.Furthermore,the mechanical,thermal and processing properties of Al_(2)O_(3)/DGEMT are fully comparable to those of Al_(2)O_(3)/DGEBA.This work confirms the feasibility of manufacturing environmentally friendly power equipment using bio-based epoxy resins,which has excellent engineering applications.展开更多
By investigating the performance characteristics of the bio-based surfactant 8901A,a composite decontamination and injection system was developed using 8901A as the primary agent,tailored for application in low-permea...By investigating the performance characteristics of the bio-based surfactant 8901A,a composite decontamination and injection system was developed using 8901A as the primary agent,tailored for application in low-permeability and heavy oil reservoirs under varying temperature conditions.The results demonstrate that this system effectively reduces oil–water interfacial tension,achieving an ultra-low interfacial tension state.The static oil washing efficiency of oil sands exceeds 85%,the average pressure reduction rate reaches 21.55%,and the oil recovery rate improves by 13.54%.These enhancements significantly increase the system’s ability to dissolve oilbased blockages,thereby lowering water injection pressure caused by organic fouling,increasing the injection volume of injection wells,and ultimately improving oil recovery efficiency.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
In the context of transitioning toward more sustainable construction materials,this study explores the impact of incorporating millet husks as an alternative to sand on the physical,mechanical,and thermal performance ...In the context of transitioning toward more sustainable construction materials,this study explores the impact of incorporating millet husks as an alternative to sand on the physical,mechanical,and thermal performance of lightweight concrete.Through a mixture design approach,five formulations were selected and thoroughly characterized.The analysis of iso-response curves enabled an in-depth assessment of the cross-effects between formulation parameters and their interactions on the final properties of the material.The results show that integrating millet husks leads to a significant reduction in density,reaching up to 21%,while maintaining notable mechanical performance.A balanced formulation of sand and fibers achieved a maximum compressive strength of 12.11 MPa,demonstrating that,under specific conditions,plant fibers actively contribute to the structural integrity of the composite.In tensile strength,the positive influence of fibers is even more pronounced,with a maximum resistance of 8.62 MPa,highlighting their role in enhancing material cohesion.From a thermal perspective,millet husks reduce both thermal conductivity and effusivity,thereby limiting heat transfer and accumulation within the composite.Iso-response curve analysis reveals that these effects are directly linked to the proportions of the constituents and that achieving an optimal balance between sand,fibers,and cement is key to maximizing performance.These findings demonstrate that the adopted approach allows moving beyond conventional substitution methods by identifying optimal configurations for the design of lightweight bio-based concretes that are both strong and insulating,thereby confirming the potential of millet husks in developing lightweight concretes suitable for sustainable construction applications.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
An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthrolin...An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthroline/bipyridine,and poly-F substituted phenyl ligands as the mixture linkers.The results of control experiments and theoretical calculations reveal that the–F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr_(6) clusters bridges,which favors the adsorption and activation of the furan ring.Furthermore,the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation,respectively.As a result,the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects.Under the optimized conditions,72.2%FA conversion and 74.8%mono aryl furan(MAF)selectivity are shown in the Heck-type insertion.Meanwhile,85.3%of MAF is converted,affording 74.8%selectivity of final product(AFs)in the subsequent electrophilic palladation reaction.This process efficiency is remarkably higher than that with homogeneous catalysts.In addition,furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F)show significantly better properties than that from conventional Suzuki coupling method.Therefore,the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.展开更多
Considerable progress has been made in recent years to the development of sustainable polymers from bio-based feedstocks.In this study,100%bio-based nylons were prepared via an integrated chemical and biological proce...Considerable progress has been made in recent years to the development of sustainable polymers from bio-based feedstocks.In this study,100%bio-based nylons were prepared via an integrated chemical and biological process from lignocellulose.These novel nylons were obtained by the melt polymerization of 3-propyladipic acid derived from lignin and 1,5-pentenediamine/1,4-butanediamine derived from carbohydrate sugar.Central to the concept is a three-step noble metal free catalytic chemical funnelling sequence(Raney Ni mediated reductive catalytic fractionation-reductive funnelling-oxidative funnelling),which allowed for obtaining a single component 3-propyladipic acid from lignin with high efficiency.The structural and thermodynamic properties of the obtained nylons have been systematically investigated,and thus obtained transparent bio-based nylons exhibited higher Mw(>32,000)and excellent thermal stability(Td5%>265℃).Considering their moderate Tg and good melt strength,these transparent bio-based nylons could serve as promising functional additives or temperature-responsive materials.展开更多
Due to their extraordinary durability and thermal stability,Epoxy Resin Thermosets(ERTs)are essential in various industries.However,their poor recyclability leads to unacceptable environmental pollution.In this study,...Due to their extraordinary durability and thermal stability,Epoxy Resin Thermosets(ERTs)are essential in various industries.However,their poor recyclability leads to unacceptable environmental pollution.In this study,Wu et al.successfully synthesized a completely bio-based ERT using lignocellulose-derived building blocks which exhibit outstanding thermal and mechanical properties.Remarkably,these bio-materials degrade via methanolysis without the need of any catalyst,presenting a smart and cost-effective recycling strategy.Furthermore,this approach could be employed for fabricating reusable composites comprising glass fiber and plant fiber,thereby expanding its applications in sustainable transportation,coatings,paints or biomedical devices.展开更多
Toughening the petroleum-based epoxy resin blends with bio-based modifiers without compromising their modulus,mechanical strength,and other properties is still a big challenge in view of the sustainability.In this stu...Toughening the petroleum-based epoxy resin blends with bio-based modifiers without compromising their modulus,mechanical strength,and other properties is still a big challenge in view of the sustainability.In this study,a bio-based liquid crystal epoxy resin(THMT-E P)with an s-triazine ring structure was utilized to modify a petroleum-based bisphenol A epoxy resin(E51)with 4,4'-diaminodiphenylsulfone(DDS)as a curing agent,and the blended systems were evaluated for their thermal stability,mechanical properties,and flame retardancy.The results showed that the impact strength of the blended system initially increased and then decreased with the increase in THMT-EP content,and it reached the a maximum value of 26.5 kJ/m^(2)when the THMT-EP content was 5%,which was 31.2%higher than that of E51/DDS.Notably,the flexural strength,modulus,and glass transition tem perature of the blended system were all simultaneously improved with the addition of THMT-EP.At the same time,the addition of THMT-EP enhanced the flame retardancy of the system by increasing the char yield at 700℃and decreasing the peak heat release rate and total heat release rate.This work paves the way for a more sustainable improvement in the comprehensive performance of epoxy resin.展开更多
The pressing demand for sustainable advancements in road infrastructure has catalyzed extensive research into environmentally conscious alternatives for the maintenance and restoration of asphalt concrete pavements.Th...The pressing demand for sustainable advancements in road infrastructure has catalyzed extensive research into environmentally conscious alternatives for the maintenance and restoration of asphalt concrete pavements.This paper offers a comprehensive review and analysis of bio-based rejuvenators as a promising avenue for enhancing the longevity and sustainability of asphalt.Through a multifaceted exploration,it delves into various aspects of this innovative approach.Providing a thorough overview of bio-based rejuvenators,the study highlights their renewable and environmentally friendly characteristics.It conducts an in-depth examination of a wide spectrum of bio-derived materials,including vegetable oils,waste-derived bio-products,and biopolymers,through a comprehensive survey.The paper evaluates how bio-based rejuvenators enhance aged asphalt binders and mixes,effectively mitigating the adverse impacts of aging.Furthermore,it investigates how these rejuvenators address environmental concerns by identifying compatibility issues,assessing long-term performance,and evaluating economic feasibility.Finally,the paper outlines potential advancements and research pathways aimed at optimizing the utilization of bio-based rejuvenators in asphalt concrete,thereby contributing to the sustainable evolution of road infrastructure.展开更多
Aqueous-phase reforming(APR)is an attractive process to produce bio-based hydrogen from waste biomass streams,during which the catalyst stability is often challenged due to the harsh reaction conditions.In this work,t...Aqueous-phase reforming(APR)is an attractive process to produce bio-based hydrogen from waste biomass streams,during which the catalyst stability is often challenged due to the harsh reaction conditions.In this work,three Pt-based catalysts supported on C,AlO(OH),and ZrO_(2)were investigated for the APR of hydroxyacetone solution in afixed bed reactor at 225℃and 35 bar.Among them,the Pt/C catalyst showed the highest turnover frequency for H_(2)production(TOF of 8.9 molH_(2)molPt^(-1)min^(-1))and the longest catalyst stability.Over the AlO(OH)and ZrO_(2)supported Pt catalysts,the side reactions consuming H_(2),formation of coke,and Pt sintering result in a low H_(2)production and the fast catalyst deactivation.The proposed reaction pathways suggest that a promising APR catalyst should reform all oxygenates in the aqueous phase,minimize the hydrogenation of the oxygenates,maximize the WGS reaction,and inhibit the condensation and coking reactions for maximizing the hydrogen yield and a stable catalytic performance.展开更多
L-glutamic acid(LA)is a bio-based,non-toxic,environmentally friendly material derived from biomass.The present study reports the application of Passerini three-component polymerization(P-3CP)for the straightforward pr...L-glutamic acid(LA)is a bio-based,non-toxic,environmentally friendly material derived from biomass.The present study reports the application of Passerini three-component polymerization(P-3CP)for the straightforward preparation of LA-based light-responsive polyesters(PLTDs)under mild conditions.PLTDs with molar masses up to 8500 g/mol and high yields exceeding 90%are obtained.The chemical structures and light-responsive self-immolative behavior of PLTDs are comprehensively characterized by employing ultraviolet-visible(UV-Vis)spectroscopy,size exclusion chromatography(SEC),nuclear magnetic resonance(NMR)spectroscopy,and liquid chromatography mass spectrometry(LC-MS).Meanwhile,monodisperse PLTD-based doxorubicin-loaded nanoparticles(PLTD-DOX-NP)(size=193 nm,PDI=0.018)are formulated by nanoprecipitation method.Upon light-induced depolymerization,the PLTD-DOX-NP undergoes rapid decomposition,resulting in a burst release of 80%cargo within 13 s.Furthermore,according to biological toxicity tests,the PLTD-NP possesses adequate biosafety,both before and after irradiation.Overall,the incorporation of P-3CP with biorenewable LA-based monomer adheres to the principles of green chemistry,significantly simplifying the synthetic pathway of light-responsive polymers.展开更多
Recently, the textile industry has increasingly advocated for natural resource-based healthcare textiles. This research presents a facile and eco-friendly approach to developing durable antibacterial polyester fabrics...Recently, the textile industry has increasingly advocated for natural resource-based healthcare textiles. This research presents a facile and eco-friendly approach to developing durable antibacterial polyester fabrics. Polyester fabric was first subjected to an alkaline hydrolysis to impart hydroxyl groups on the fiber surface. A natural antibacterial agent, betaine, was then covalently bonded to the hydrolyzed polyester fiber surface through esterification. XPS, Raman, SEM, and Wicking measurements were carried out to verify the esterification reaction. Antibacterial tests confirmed that betaine treatment grafted polyester fabrics revealed a remarkable antibacterial effect with inhibition rates > 99.9% against both E. coli and S. aureus and still remained inhibition rates of up to 91.5% against both bacteria after home washing for 20 cycles. Moreover, the modification significantly increased the capillary effect of polyester fabric but did not cause apparent adverse effects on the fabric’s hand or tensile strength. Overall, this grafting strategy for durable, antibacterial polyester fabric represents a significant practicality in the textile industry.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
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.
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 China Postdoctoral Science Foundation(No.2023M743622)Natural Science Foundation of Ningbo City(No.2024J109)+2 种基金National Natural Science Foundation of China(Nos.E52307038 and U23A20589)Ningbo 2025 Key Scientific Research Programs(Nos.2022Z111,2022Z160 and 2022Z198)the Leading Innovativeand Entrepreneur Team Introduction Program of Zhejiang(No.2021R01005).
文摘The demand for energy-efficient and environmental-friendly power grid construction has made the exploitation of bio-based electrical epoxy resins with excellent properties increasingly important.This work developed the bio-based electrotechnical epoxy resins based on magnolol.High-performance epoxy resin(DGEMT)with a double crosslinked points and its composites(Al_(2)O_(3)/DGEMT)were obtained taking advantages of the two bifunctional groups(allyl and phenolic hydroxyl groups)of magnolol.Benefitting from the distinctive structure of DGEMT,the Al_(2)O_(3)/DGEMT composites exhibited the advantages of intrinsically high thermal conductivity,high insulation,and low dielectric loss.The AC breakdown strength and thermal conductivity of Al_(2)O_(3)/DGEMT composites were 35.5 kV/mm and 1.19 W·m-1·K-1,respectively,which were 15.6%and 52.6%higher than those of petroleum-based composites(Al_(2)O_(3)/DGEBA).And its dielectric loss tanδ=0.0046 was 20.7%lower than that of Al_(2)O_(3)/DGEBA.Furthermore,the mechanical,thermal and processing properties of Al_(2)O_(3)/DGEMT are fully comparable to those of Al_(2)O_(3)/DGEBA.This work confirms the feasibility of manufacturing environmentally friendly power equipment using bio-based epoxy resins,which has excellent engineering applications.
文摘By investigating the performance characteristics of the bio-based surfactant 8901A,a composite decontamination and injection system was developed using 8901A as the primary agent,tailored for application in low-permeability and heavy oil reservoirs under varying temperature conditions.The results demonstrate that this system effectively reduces oil–water interfacial tension,achieving an ultra-low interfacial tension state.The static oil washing efficiency of oil sands exceeds 85%,the average pressure reduction rate reaches 21.55%,and the oil recovery rate improves by 13.54%.These enhancements significantly increase the system’s ability to dissolve oilbased blockages,thereby lowering water injection pressure caused by organic fouling,increasing the injection volume of injection wells,and ultimately improving oil recovery efficiency.
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).
文摘In the context of transitioning toward more sustainable construction materials,this study explores the impact of incorporating millet husks as an alternative to sand on the physical,mechanical,and thermal performance of lightweight concrete.Through a mixture design approach,five formulations were selected and thoroughly characterized.The analysis of iso-response curves enabled an in-depth assessment of the cross-effects between formulation parameters and their interactions on the final properties of the material.The results show that integrating millet husks leads to a significant reduction in density,reaching up to 21%,while maintaining notable mechanical performance.A balanced formulation of sand and fibers achieved a maximum compressive strength of 12.11 MPa,demonstrating that,under specific conditions,plant fibers actively contribute to the structural integrity of the composite.In tensile strength,the positive influence of fibers is even more pronounced,with a maximum resistance of 8.62 MPa,highlighting their role in enhancing material cohesion.From a thermal perspective,millet husks reduce both thermal conductivity and effusivity,thereby limiting heat transfer and accumulation within the composite.Iso-response curve analysis reveals that these effects are directly linked to the proportions of the constituents and that achieving an optimal balance between sand,fibers,and cement is key to maximizing performance.These findings demonstrate that the adopted approach allows moving beyond conventional substitution methods by identifying optimal configurations for the design of lightweight bio-based concretes that are both strong and insulating,thereby confirming the potential of millet husks in developing lightweight concretes suitable for sustainable construction applications.
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.
文摘An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthroline/bipyridine,and poly-F substituted phenyl ligands as the mixture linkers.The results of control experiments and theoretical calculations reveal that the–F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr_(6) clusters bridges,which favors the adsorption and activation of the furan ring.Furthermore,the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation,respectively.As a result,the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects.Under the optimized conditions,72.2%FA conversion and 74.8%mono aryl furan(MAF)selectivity are shown in the Heck-type insertion.Meanwhile,85.3%of MAF is converted,affording 74.8%selectivity of final product(AFs)in the subsequent electrophilic palladation reaction.This process efficiency is remarkably higher than that with homogeneous catalysts.In addition,furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F)show significantly better properties than that from conventional Suzuki coupling method.Therefore,the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.
基金support by National Key Research and Development Program of China(Grant No.:2023YFA0913604)Program of National Natural Science Foundation of China(Grant No.:22178170,22378195)+2 种基金Six talent peaks project in Jiangsu Province(SWYY-045)Program of National Natural Science Foundation of China(Grant No.22208155)Jiangsu Province Natural Science Foundation for Young Scholars(Grant No.BK20210552).
文摘Considerable progress has been made in recent years to the development of sustainable polymers from bio-based feedstocks.In this study,100%bio-based nylons were prepared via an integrated chemical and biological process from lignocellulose.These novel nylons were obtained by the melt polymerization of 3-propyladipic acid derived from lignin and 1,5-pentenediamine/1,4-butanediamine derived from carbohydrate sugar.Central to the concept is a three-step noble metal free catalytic chemical funnelling sequence(Raney Ni mediated reductive catalytic fractionation-reductive funnelling-oxidative funnelling),which allowed for obtaining a single component 3-propyladipic acid from lignin with high efficiency.The structural and thermodynamic properties of the obtained nylons have been systematically investigated,and thus obtained transparent bio-based nylons exhibited higher Mw(>32,000)and excellent thermal stability(Td5%>265℃).Considering their moderate Tg and good melt strength,these transparent bio-based nylons could serve as promising functional additives or temperature-responsive materials.
基金the foundational support by the Fundamental Research Funds for the Central Universities(BLX202132)the foundational support by the Beijing Youth Talent Funding Program-Visiting program for young foreign scholars(Q2023043)IIT(BHU)Varanasi.
文摘Due to their extraordinary durability and thermal stability,Epoxy Resin Thermosets(ERTs)are essential in various industries.However,their poor recyclability leads to unacceptable environmental pollution.In this study,Wu et al.successfully synthesized a completely bio-based ERT using lignocellulose-derived building blocks which exhibit outstanding thermal and mechanical properties.Remarkably,these bio-materials degrade via methanolysis without the need of any catalyst,presenting a smart and cost-effective recycling strategy.Furthermore,this approach could be employed for fabricating reusable composites comprising glass fiber and plant fiber,thereby expanding its applications in sustainable transportation,coatings,paints or biomedical devices.
基金financially supported by the National Natural Science Foundation of China(Nos.52073038 and 51873027)the Fundamental Research Funds for the Central Universities(No.DUT22LAB605)。
文摘Toughening the petroleum-based epoxy resin blends with bio-based modifiers without compromising their modulus,mechanical strength,and other properties is still a big challenge in view of the sustainability.In this study,a bio-based liquid crystal epoxy resin(THMT-E P)with an s-triazine ring structure was utilized to modify a petroleum-based bisphenol A epoxy resin(E51)with 4,4'-diaminodiphenylsulfone(DDS)as a curing agent,and the blended systems were evaluated for their thermal stability,mechanical properties,and flame retardancy.The results showed that the impact strength of the blended system initially increased and then decreased with the increase in THMT-EP content,and it reached the a maximum value of 26.5 kJ/m^(2)when the THMT-EP content was 5%,which was 31.2%higher than that of E51/DDS.Notably,the flexural strength,modulus,and glass transition tem perature of the blended system were all simultaneously improved with the addition of THMT-EP.At the same time,the addition of THMT-EP enhanced the flame retardancy of the system by increasing the char yield at 700℃and decreasing the peak heat release rate and total heat release rate.This work paves the way for a more sustainable improvement in the comprehensive performance of epoxy resin.
基金the Swedish Research Council for Sustainable Development FORMAS(grant 2021-00527)Wangjie Wu acknowledges the scholarship funding of the CSC-KTH program.
文摘The pressing demand for sustainable advancements in road infrastructure has catalyzed extensive research into environmentally conscious alternatives for the maintenance and restoration of asphalt concrete pavements.This paper offers a comprehensive review and analysis of bio-based rejuvenators as a promising avenue for enhancing the longevity and sustainability of asphalt.Through a multifaceted exploration,it delves into various aspects of this innovative approach.Providing a thorough overview of bio-based rejuvenators,the study highlights their renewable and environmentally friendly characteristics.It conducts an in-depth examination of a wide spectrum of bio-derived materials,including vegetable oils,waste-derived bio-products,and biopolymers,through a comprehensive survey.The paper evaluates how bio-based rejuvenators enhance aged asphalt binders and mixes,effectively mitigating the adverse impacts of aging.Furthermore,it investigates how these rejuvenators address environmental concerns by identifying compatibility issues,assessing long-term performance,and evaluating economic feasibility.Finally,the paper outlines potential advancements and research pathways aimed at optimizing the utilization of bio-based rejuvenators in asphalt concrete,thereby contributing to the sustainable evolution of road infrastructure.
基金support from European Union Seventh Frame-work Programme(FP7/2007-2013 project SusFuelCat,grant No.310490)is acknowledged.
文摘Aqueous-phase reforming(APR)is an attractive process to produce bio-based hydrogen from waste biomass streams,during which the catalyst stability is often challenged due to the harsh reaction conditions.In this work,three Pt-based catalysts supported on C,AlO(OH),and ZrO_(2)were investigated for the APR of hydroxyacetone solution in afixed bed reactor at 225℃and 35 bar.Among them,the Pt/C catalyst showed the highest turnover frequency for H_(2)production(TOF of 8.9 molH_(2)molPt^(-1)min^(-1))and the longest catalyst stability.Over the AlO(OH)and ZrO_(2)supported Pt catalysts,the side reactions consuming H_(2),formation of coke,and Pt sintering result in a low H_(2)production and the fast catalyst deactivation.The proposed reaction pathways suggest that a promising APR catalyst should reform all oxygenates in the aqueous phase,minimize the hydrogenation of the oxygenates,maximize the WGS reaction,and inhibit the condensation and coking reactions for maximizing the hydrogen yield and a stable catalytic performance.
基金This work was financially supported by the International Science and Technology Assistance Program of the Ministry of Science and Technology(No.KY202001016)Shandong Provincial Natural Science Foundation Magnitude Fundamental Research,China(No.ZR2022ZD11)Qingdao New Energy Shandong Laboratory Open Project(No.QNESL OP202312).
文摘L-glutamic acid(LA)is a bio-based,non-toxic,environmentally friendly material derived from biomass.The present study reports the application of Passerini three-component polymerization(P-3CP)for the straightforward preparation of LA-based light-responsive polyesters(PLTDs)under mild conditions.PLTDs with molar masses up to 8500 g/mol and high yields exceeding 90%are obtained.The chemical structures and light-responsive self-immolative behavior of PLTDs are comprehensively characterized by employing ultraviolet-visible(UV-Vis)spectroscopy,size exclusion chromatography(SEC),nuclear magnetic resonance(NMR)spectroscopy,and liquid chromatography mass spectrometry(LC-MS).Meanwhile,monodisperse PLTD-based doxorubicin-loaded nanoparticles(PLTD-DOX-NP)(size=193 nm,PDI=0.018)are formulated by nanoprecipitation method.Upon light-induced depolymerization,the PLTD-DOX-NP undergoes rapid decomposition,resulting in a burst release of 80%cargo within 13 s.Furthermore,according to biological toxicity tests,the PLTD-NP possesses adequate biosafety,both before and after irradiation.Overall,the incorporation of P-3CP with biorenewable LA-based monomer adheres to the principles of green chemistry,significantly simplifying the synthetic pathway of light-responsive polymers.
文摘Recently, the textile industry has increasingly advocated for natural resource-based healthcare textiles. This research presents a facile and eco-friendly approach to developing durable antibacterial polyester fabrics. Polyester fabric was first subjected to an alkaline hydrolysis to impart hydroxyl groups on the fiber surface. A natural antibacterial agent, betaine, was then covalently bonded to the hydrolyzed polyester fiber surface through esterification. XPS, Raman, SEM, and Wicking measurements were carried out to verify the esterification reaction. Antibacterial tests confirmed that betaine treatment grafted polyester fabrics revealed a remarkable antibacterial effect with inhibition rates > 99.9% against both E. coli and S. aureus and still remained inhibition rates of up to 91.5% against both bacteria after home washing for 20 cycles. Moreover, the modification significantly increased the capillary effect of polyester fabric but did not cause apparent adverse effects on the fabric’s hand or tensile strength. Overall, this grafting strategy for durable, antibacterial polyester fabric represents a significant practicality in the textile industry.
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.
