A novel polyimide(PI) containing pendent biphenyl ester groups was synthesized from 3,5-diaminobenzoic-4′-biphenyl ester (DABBE)and 3,3′,4,4′-oxydiphthalic dianhydride(ODPA) by a one-step high-temperature polyconde...A novel polyimide(PI) containing pendent biphenyl ester groups was synthesized from 3,5-diaminobenzoic-4′-biphenyl ester (DABBE)and 3,3′,4,4′-oxydiphthalic dianhydride(ODPA) by a one-step high-temperature polycondensation in m-cresol.This PI is a semicrystalline polymer.Lots of short fine fibric crystals with length and diameter about 20、μm and 1、μm respectively disperse randomly in the PI film. The optical textures and the X-ray diffraction patterns of the PI solution and film show that the PI main chains are in the extended conformation and pack parallel to each other, and the pendent biphenyl ester groups occupy the space between the main chain layers,more or less perpendicular to the main chains.At the same time, mechanical and thermally stable properties of the PI film were investigated. The excellent mechanical properties of general polyimide films are reasonably maintained, the polyimide film with pendent groups showes higher tensile strength and modulus and lower T g. TGA study showes a typical two-step weight loss behavior corresponding to the pyrolysis of pendent groups and main chains of the PI,respectively.展开更多
The synthesis of a new azobenzene(azo)-containing main-chain crystalline polymer with reactive secondary amino groups in its backbone and photodeformation behaviors of its supramolecular hydrogen-bonded fibers are des...The synthesis of a new azobenzene(azo)-containing main-chain crystalline polymer with reactive secondary amino groups in its backbone and photodeformation behaviors of its supramolecular hydrogen-bonded fibers are described. This main-chain azo polymer(namely Azo-MP6) was prepared via first the synthesis of a diacrylate-type azo monomer and its subsequent Michael addition copolymerization with trans-1,4-cyclohexanediamine under a mild reaction condition. Azo-MP6 was found to have a linear main-chain chemical structure instead of a branched one, as verified by comparing its ~1H-NMR spectrum with that of the azo polymer prepared via the polymer analogous reaction of AzoMP6 with acetic anhydride. The thermal stability, phase transition behavior, and photoresponsivity of Azo-MP6 were characterized with TGA,DSC, POM, XRD, and UV-Vis spectroscopy. The experimental results revealed that it had good thermal stability, low glass transition temperature,broad crystalline phase temperature range, and highly reversible photoresponsivity. Physically crosslinked supramolecular hydrogen-bonded fibers with good mechanical properties and a high alignment order of azo mesogens were readily fabricated from Azo-MP6 by using the simple melt spinning method, and they could show "reversible" photoinduced bending under the same UV light irradiation and good anti-fatigue properties.展开更多
Thermosets based on direct curing of multifunctional monomers offer processing flexibility that thermoplastics cannot provide.However,this type of thermoset is typically amorphous since it is difficult to meet the str...Thermosets based on direct curing of multifunctional monomers offer processing flexibility that thermoplastics cannot provide.However,this type of thermoset is typically amorphous since it is difficult to meet the stringent requirement of long-range molecular regularity for crystallization.However,we report here a crystallizable poly(thiourethane)thermoset synthesized directly from the curing of low-viscosity liquid precursors that does not employ any solvent.Its crystalline nature results in superior toughness,comparable to commercial high-density polyethylene,in sharp contrast to the brittleness of the typical,rigid,glassy thermoset materials.Beyond that,the network polymer exhibits shape-memory behavior in which the crystalline transition is utilized for temporary shape fixing/recovery whereas the dynamic thiourethane bonds can be activated for bond exchange as a mechanism for complex shape manipulation.Materials with these combined features represent attractive options for demanding engineering applications due to their high performance and multifunctinality.展开更多
Combining the stability of chemical crosslinking and the processability of physical crosslinking is a well-established strategy to design new materials with desirable stimuli–responsive properties. Herein, a series o...Combining the stability of chemical crosslinking and the processability of physical crosslinking is a well-established strategy to design new materials with desirable stimuli–responsive properties. Herein, a series of azobenzenebased thermotropic liquid crystalline polyesters were synthesized by introducing mesogenic dial named 4,4＇-bis（6-hydroxyhexyloxy）azobenzene（BHHAB）, 2-phenylsuccinic acid（PSA）, and different contents of 1,2,3-propanetricarboxylic acid（PTA） as the chemical crosslinker. All these polyesters showed good thermal stability and smectic liquid crystalline phase. Wide-angel X-ray diffraction（WAXD） and the fluorescence emission spectra confirmed the existence of π–πstacking interactions as the physical crosslinking in the polymer chains, particularly at the lower content of PTA. However, when the PTA content increased, the chemical crosslinking changed the chain conformation, and thus the intensity of physical crosslinking slackened gradually. Combining the physical and chemical crosslinking, these polyesters showed the thermoplastic processability, thermal shape memory, heat-assisted healing and photoresponsive behaviors. Taking advantages of these features, these multiple stimuli–responsive polymers can bring more chances for smart materials such as soft actuator.展开更多
Active organic optical waveguide materials(OOWMs)incorporating room temperature phosphorescence(RTP)hold significant promise for diverse applications in photonic and optoelectronic devices.Despite this potential,reali...Active organic optical waveguide materials(OOWMs)incorporating room temperature phosphorescence(RTP)hold significant promise for diverse applications in photonic and optoelectronic devices.Despite this potential,realizing active RTP optical waveguides with large-sized ordered structures and minimal light loss remains a formidable challenge.To address this issue,we present a groundbreaking thermoplastic active OOWM with low light loss,leveraging room temperature phosphorescent liquid crystalline polymer(LCP).This innovative material can be easily synthesized through the copolymerization of phosphorescent and liquid crystalline monomers.The resulting RTP copolymer exhibits a nematic liquid crystal phase with a phosphorescence lifetime of approximately 0.15 ms and an afterglow duration of around 1 second.Leveraging the excellent processability of LCP,we successfully produce meter-scale fibers via melt spinning.These RTP LCP fibers,characterized by a high orientation of mesogens along the fiber axis,demonstrate superior light confinement and efficient light conduction compared to unoriented samples,resulting in a low optical loss coefficient of 0.13 dB/mm.Furthermore,the thermal responsiveness of the RTP LCP optical waveguide enables its use as a photo switch.This pioneering work paves the way for the design of new OOWMs tailored for advanced photonics and optoelectronics devices.展开更多
Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility wit...Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility with electrodes.Herein,a novel all-solid polymer electrolyte(PPLCE)was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol)dimethacrylate(PEGDMA)acts as a structural frame,combined with poly(ethylene glycol)diglycidyl ether short chain interspersed serving as mobile ion transport entities.The preparaed PPLCEs exhibit excellent mechanical property and out-standing electrochemical performances,which is attributed to their unique three-dimensional cocontinuous structure,characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase,resulting in a distinctive nanostructure with short-range order and long-range disorder.Remarkably,the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs,which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte.When used in a lithiumion symmetrical battery configuration,the 6 wt%-PPLCE exhibites super stability,sustaining operation for over 2000 h at 30 C,with minimal and consistent overpotential of 50 mV.The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g^(-1)at current densities of 0.2 and 1 C,respectively.Even after more than 300 cycles at a current density of 0.2 C,it retaines an impressive 73.5%capacity.Moreover,it displayes stable cycling for over 180 cycles at a high current density of 0.5C.The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.展开更多
文摘A novel polyimide(PI) containing pendent biphenyl ester groups was synthesized from 3,5-diaminobenzoic-4′-biphenyl ester (DABBE)and 3,3′,4,4′-oxydiphthalic dianhydride(ODPA) by a one-step high-temperature polycondensation in m-cresol.This PI is a semicrystalline polymer.Lots of short fine fibric crystals with length and diameter about 20、μm and 1、μm respectively disperse randomly in the PI film. The optical textures and the X-ray diffraction patterns of the PI solution and film show that the PI main chains are in the extended conformation and pack parallel to each other, and the pendent biphenyl ester groups occupy the space between the main chain layers,more or less perpendicular to the main chains.At the same time, mechanical and thermally stable properties of the PI film were investigated. The excellent mechanical properties of general polyimide films are reasonably maintained, the polyimide film with pendent groups showes higher tensile strength and modulus and lower T g. TGA study showes a typical two-step weight loss behavior corresponding to the pyrolysis of pendent groups and main chains of the PI,respectively.
基金financially supported by the National Natural Science Foundation of China (Nos. 21574070 and 21774063)Natural Science Foundation of Tianjin (No. 16JCZDJC36800)
文摘The synthesis of a new azobenzene(azo)-containing main-chain crystalline polymer with reactive secondary amino groups in its backbone and photodeformation behaviors of its supramolecular hydrogen-bonded fibers are described. This main-chain azo polymer(namely Azo-MP6) was prepared via first the synthesis of a diacrylate-type azo monomer and its subsequent Michael addition copolymerization with trans-1,4-cyclohexanediamine under a mild reaction condition. Azo-MP6 was found to have a linear main-chain chemical structure instead of a branched one, as verified by comparing its ~1H-NMR spectrum with that of the azo polymer prepared via the polymer analogous reaction of AzoMP6 with acetic anhydride. The thermal stability, phase transition behavior, and photoresponsivity of Azo-MP6 were characterized with TGA,DSC, POM, XRD, and UV-Vis spectroscopy. The experimental results revealed that it had good thermal stability, low glass transition temperature,broad crystalline phase temperature range, and highly reversible photoresponsivity. Physically crosslinked supramolecular hydrogen-bonded fibers with good mechanical properties and a high alignment order of azo mesogens were readily fabricated from Azo-MP6 by using the simple melt spinning method, and they could show "reversible" photoinduced bending under the same UV light irradiation and good anti-fatigue properties.
基金supported by the National Natural Science Foundation of China(grant nos.52322307,52033009,22275162,and 52003232).
文摘Thermosets based on direct curing of multifunctional monomers offer processing flexibility that thermoplastics cannot provide.However,this type of thermoset is typically amorphous since it is difficult to meet the stringent requirement of long-range molecular regularity for crystallization.However,we report here a crystallizable poly(thiourethane)thermoset synthesized directly from the curing of low-viscosity liquid precursors that does not employ any solvent.Its crystalline nature results in superior toughness,comparable to commercial high-density polyethylene,in sharp contrast to the brittleness of the typical,rigid,glassy thermoset materials.Beyond that,the network polymer exhibits shape-memory behavior in which the crystalline transition is utilized for temporary shape fixing/recovery whereas the dynamic thiourethane bonds can be activated for bond exchange as a mechanism for complex shape manipulation.Materials with these combined features represent attractive options for demanding engineering applications due to their high performance and multifunctinality.
基金supported by the National Natural Science Foundation of China (51721091)the Sichuan Province Youth Science and Technology Innovation Team (2017TD0006)
文摘Combining the stability of chemical crosslinking and the processability of physical crosslinking is a well-established strategy to design new materials with desirable stimuli–responsive properties. Herein, a series of azobenzenebased thermotropic liquid crystalline polyesters were synthesized by introducing mesogenic dial named 4,4＇-bis（6-hydroxyhexyloxy）azobenzene（BHHAB）, 2-phenylsuccinic acid（PSA）, and different contents of 1,2,3-propanetricarboxylic acid（PTA） as the chemical crosslinker. All these polyesters showed good thermal stability and smectic liquid crystalline phase. Wide-angel X-ray diffraction（WAXD） and the fluorescence emission spectra confirmed the existence of π–πstacking interactions as the physical crosslinking in the polymer chains, particularly at the lower content of PTA. However, when the PTA content increased, the chemical crosslinking changed the chain conformation, and thus the intensity of physical crosslinking slackened gradually. Combining the physical and chemical crosslinking, these polyesters showed the thermoplastic processability, thermal shape memory, heat-assisted healing and photoresponsive behaviors. Taking advantages of these features, these multiple stimuli–responsive polymers can bring more chances for smart materials such as soft actuator.
基金financially supported by the National Natural Science Foundation of China(22275158,21975215 and 51921002)the Key Research and Development Program of Hunan Province of China(2023GK2031)+2 种基金the Funding Project of Furong Scholars Award ProgramXiangtan University-Zhuzhou Feilu High-tech Material Technology Co.,Ltd.the Joint Training Base of Industry-Education Integration of Graduate Students。
文摘Active organic optical waveguide materials(OOWMs)incorporating room temperature phosphorescence(RTP)hold significant promise for diverse applications in photonic and optoelectronic devices.Despite this potential,realizing active RTP optical waveguides with large-sized ordered structures and minimal light loss remains a formidable challenge.To address this issue,we present a groundbreaking thermoplastic active OOWM with low light loss,leveraging room temperature phosphorescent liquid crystalline polymer(LCP).This innovative material can be easily synthesized through the copolymerization of phosphorescent and liquid crystalline monomers.The resulting RTP copolymer exhibits a nematic liquid crystal phase with a phosphorescence lifetime of approximately 0.15 ms and an afterglow duration of around 1 second.Leveraging the excellent processability of LCP,we successfully produce meter-scale fibers via melt spinning.These RTP LCP fibers,characterized by a high orientation of mesogens along the fiber axis,demonstrate superior light confinement and efficient light conduction compared to unoriented samples,resulting in a low optical loss coefficient of 0.13 dB/mm.Furthermore,the thermal responsiveness of the RTP LCP optical waveguide enables its use as a photo switch.This pioneering work paves the way for the design of new OOWMs tailored for advanced photonics and optoelectronics devices.
基金supported by the National Natural Science Foundation of China(52003293,51927806,52272258)the Fundamental Research Funds for the Central Universities(2023ZKPYJD07)the Beijing Nova Program(20220484214).
文摘Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility with electrodes.Herein,a novel all-solid polymer electrolyte(PPLCE)was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol)dimethacrylate(PEGDMA)acts as a structural frame,combined with poly(ethylene glycol)diglycidyl ether short chain interspersed serving as mobile ion transport entities.The preparaed PPLCEs exhibit excellent mechanical property and out-standing electrochemical performances,which is attributed to their unique three-dimensional cocontinuous structure,characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase,resulting in a distinctive nanostructure with short-range order and long-range disorder.Remarkably,the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs,which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte.When used in a lithiumion symmetrical battery configuration,the 6 wt%-PPLCE exhibites super stability,sustaining operation for over 2000 h at 30 C,with minimal and consistent overpotential of 50 mV.The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g^(-1)at current densities of 0.2 and 1 C,respectively.Even after more than 300 cycles at a current density of 0.2 C,it retaines an impressive 73.5%capacity.Moreover,it displayes stable cycling for over 180 cycles at a high current density of 0.5C.The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.
