The concentration of acetaldehyde(AA) is the main quality index of poly(ethylene terephthalate)(PET) used in food and drink packaging.A new method for AA removal has been developed by using supercritical carbon dioxid...The concentration of acetaldehyde(AA) is the main quality index of poly(ethylene terephthalate)(PET) used in food and drink packaging.A new method for AA removal has been developed by using supercritical carbon dioxide(sc CO2) during the solid-state polycondensation of PET.The influence factors of AA removal including the temperature,pressure,reaction time and the size of pre-polymer particles are systematically studied in this work.The results indicate that it is a highly efficient way to obtain high molecular weight PET with relative low concentration of AA.Correspondingly,the polymerization degree of PET could increase from 27.9 to 85.6 while the concentration of AA reduces from 0.229 × 10^(-6) to 0.055 × 10^(-6) under the optimal operation conditions of 230 °C,8 MPa and size of 0.30–0.45 mm.Thermodynamic performance tests show the increasing extent of PET crystallinity due to the fact that the plasticization of sc CO_2 is not obvious with extended reaction time,therefore the increasing crystallinity has no significant influence on AA removal.SEM observations reveal that the effects of sc CO_(2-) induced plasticization and swelling on PET increase significantly with the decrease of prepolymer size,and the surface of PET becomes more loose and porous in favor of the AA removal.展开更多
A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation proc...A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation process.The relationship between the anions of the ILs and the catalytic activities was investigated,and the readily‐prepared IL tetraethylammonium imidazolate(TEAI)was found to exhibit the highest catalytic activity.After optimizing the reaction conditions,a PIC with a weight‐average molecular weight(Mw)of25600g/mol was obtained,in conjunction with an isosorbide conversion of92%.As a means of modifying the molecular flexibility and thermal properties of the PIC,poly(aliphatic diol‐co‐isosorbide carbonate)s(PAIC)s were successfully synthesized,again using TEAI,and polymers with Mw values ranging from29000to112000g/mol were obtained.13C NMR analyses determined that the PAIC specimens had random microstructures,while differential scanning calorimetry demonstrated that each of the PAICs were amorphous and had glass transition temperatures ranging from50to115°C.Thermogravimetric analyses found Td‐5%values ranging from316to332°C for these polymers.Based on these data,it is evident that the incorporation of linear or cyclohexane‐based diol repeating units changed the thermal properties of the PIC.展开更多
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
The intense research of lithium-ion batteries has been motivated by their successful applications in mobile devices and electronic vehicles.The emerging of intelligent control in kinds of devices brings new requiremen...The intense research of lithium-ion batteries has been motivated by their successful applications in mobile devices and electronic vehicles.The emerging of intelligent control in kinds of devices brings new requirements for battery systems.The high-energy lithium batteries are expected to respond or react under different environmental conditions.In this work,a tri-salt composite electrolyte is designed with a temperature switch function for intelligently temperature-controlled lithium batteries.Specifically,the halide Li_(3)YBr_(6)together with LiTFSI and LiNO_(3)works as active fillers in a low-melting-point polymer matrix(polyethyleneglycol dimethyl ether(PEGDME)and polyethylene oxide(PEO)),which is further filled into the pre-lithiated alumina fiber skeleton.Above 60°C,the composite electrolyte exists in the liquid state and fully contacts with the working electrodes on the liquid–solid interface,effectively minimizing the interfacial resistance and leading to high discharge capacity in the cell.The electrolyte is changed into a solid state below 30°C so that the ionic conductivity is significantly reduced and the interface resistance is increased dramatically on the solid–solid interface.Therefore,by simply adjusting the temperature,the cell can be turned“ON”or“OFF”intentionally.This novel function of the composite electrolyte has enlightening significance in developing intelligently temperature-controlled lithium batteries.展开更多
Six novel hydrolytically degradable polyesters were synthesized from thiodipropionic acid(TDPA)and five diols by melt polycondensation,and characterized by FT-IR,1H NMR,gel permeation chromatography,differential scann...Six novel hydrolytically degradable polyesters were synthesized from thiodipropionic acid(TDPA)and five diols by melt polycondensation,and characterized by FT-IR,1H NMR,gel permeation chromatography,differential scanning calorimetry and thermogravimetry analysis.The polystyrene-equivalent number-average(Mn)and weight-average molecular weight(Mw)of these polyesters ranged from 4900-11100 Da and 7900-20879 Da,respectively,with PDI values of 1.48-1.98.The melting point varied from 62.3-127.9℃,and the 50%mass-loss temperature ranged between 387-417℃.The degradation of these polyesters was studied in terms of relative weight loss in distilled water at different pH.Weight losses of 14%-26%were obtained at pH 7.0,26%-38%at pH 6.0,and 32%-43%at pH 8.3 over a 20-week period.The ecotoxicity study suggested that safety of the synthesized polyesters for the eisenia foetida.These results indicate that these polyesters have a combination of good thermal and degradability behaviors,which can be tailored through selection of the diol monomers used in the synthesis.展开更多
基金Supported by the National Key Research and Development Program of China(2016YFB0302702)the National Natural Science Foundation of China(21676083)+1 种基金the Shanghai Rising-Star Program(16QB140130)the 111 Project(B08021)
文摘The concentration of acetaldehyde(AA) is the main quality index of poly(ethylene terephthalate)(PET) used in food and drink packaging.A new method for AA removal has been developed by using supercritical carbon dioxide(sc CO2) during the solid-state polycondensation of PET.The influence factors of AA removal including the temperature,pressure,reaction time and the size of pre-polymer particles are systematically studied in this work.The results indicate that it is a highly efficient way to obtain high molecular weight PET with relative low concentration of AA.Correspondingly,the polymerization degree of PET could increase from 27.9 to 85.6 while the concentration of AA reduces from 0.229 × 10^(-6) to 0.055 × 10^(-6) under the optimal operation conditions of 230 °C,8 MPa and size of 0.30–0.45 mm.Thermodynamic performance tests show the increasing extent of PET crystallinity due to the fact that the plasticization of sc CO_2 is not obvious with extended reaction time,therefore the increasing crystallinity has no significant influence on AA removal.SEM observations reveal that the effects of sc CO_(2-) induced plasticization and swelling on PET increase significantly with the decrease of prepolymer size,and the surface of PET becomes more loose and porous in favor of the AA removal.
基金supported by the National Key Projects for Fundamental Research and Development of China(2016YFB0600903)the National Natural Science Foundation of China(91434107,21506226,21476245)the Key Research Program of Frontier Sciences of Chinese Academy of Sciences(QYZDY-SSW-JSC011)~~
文摘A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation process.The relationship between the anions of the ILs and the catalytic activities was investigated,and the readily‐prepared IL tetraethylammonium imidazolate(TEAI)was found to exhibit the highest catalytic activity.After optimizing the reaction conditions,a PIC with a weight‐average molecular weight(Mw)of25600g/mol was obtained,in conjunction with an isosorbide conversion of92%.As a means of modifying the molecular flexibility and thermal properties of the PIC,poly(aliphatic diol‐co‐isosorbide carbonate)s(PAIC)s were successfully synthesized,again using TEAI,and polymers with Mw values ranging from29000to112000g/mol were obtained.13C NMR analyses determined that the PAIC specimens had random microstructures,while differential scanning calorimetry demonstrated that each of the PAICs were amorphous and had glass transition temperatures ranging from50to115°C.Thermogravimetric analyses found Td‐5%values ranging from316to332°C for these polymers.Based on these data,it is evident that the incorporation of linear or cyclohexane‐based diol repeating units changed the thermal properties of the PIC.
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Financial support from the National Natural Science Foundation of China(22279065 and 21935006)is gratefully acknowledged.
文摘The intense research of lithium-ion batteries has been motivated by their successful applications in mobile devices and electronic vehicles.The emerging of intelligent control in kinds of devices brings new requirements for battery systems.The high-energy lithium batteries are expected to respond or react under different environmental conditions.In this work,a tri-salt composite electrolyte is designed with a temperature switch function for intelligently temperature-controlled lithium batteries.Specifically,the halide Li_(3)YBr_(6)together with LiTFSI and LiNO_(3)works as active fillers in a low-melting-point polymer matrix(polyethyleneglycol dimethyl ether(PEGDME)and polyethylene oxide(PEO)),which is further filled into the pre-lithiated alumina fiber skeleton.Above 60°C,the composite electrolyte exists in the liquid state and fully contacts with the working electrodes on the liquid–solid interface,effectively minimizing the interfacial resistance and leading to high discharge capacity in the cell.The electrolyte is changed into a solid state below 30°C so that the ionic conductivity is significantly reduced and the interface resistance is increased dramatically on the solid–solid interface.Therefore,by simply adjusting the temperature,the cell can be turned“ON”or“OFF”intentionally.This novel function of the composite electrolyte has enlightening significance in developing intelligently temperature-controlled lithium batteries.
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 at Wuhan University of Science and Technology (WKDM202005)。
文摘Six novel hydrolytically degradable polyesters were synthesized from thiodipropionic acid(TDPA)and five diols by melt polycondensation,and characterized by FT-IR,1H NMR,gel permeation chromatography,differential scanning calorimetry and thermogravimetry analysis.The polystyrene-equivalent number-average(Mn)and weight-average molecular weight(Mw)of these polyesters ranged from 4900-11100 Da and 7900-20879 Da,respectively,with PDI values of 1.48-1.98.The melting point varied from 62.3-127.9℃,and the 50%mass-loss temperature ranged between 387-417℃.The degradation of these polyesters was studied in terms of relative weight loss in distilled water at different pH.Weight losses of 14%-26%were obtained at pH 7.0,26%-38%at pH 6.0,and 32%-43%at pH 8.3 over a 20-week period.The ecotoxicity study suggested that safety of the synthesized polyesters for the eisenia foetida.These results indicate that these polyesters have a combination of good thermal and degradability behaviors,which can be tailored through selection of the diol monomers used in the synthesis.
