A new type of aromatic tetraarnine containing biphenyl moiety in the side chain was synthesized via a modified Chichibabin＇s reaction. 3-Nitro-4-acetamidoacetophenone was reacted with 4-phenyl benzaldehyde in the pre...A new type of aromatic tetraarnine containing biphenyl moiety in the side chain was synthesized via a modified Chichibabin＇s reaction. 3-Nitro-4-acetamidoacetophenone was reacted with 4-phenyl benzaldehyde in the presence of ammonium acetate to obtain 2,6-bis（3＇,4＇-diaminophenyl）-4-biphenyl pyridine （DPPA）. A series of polypyrrolones （PPys） were prepared using tetraamine and various aromatic dianhydrides via a two-step cyclization procedure. All the PPys show excellent high temperature stabilities with the initial decomposition temperatures of 530-549℃ and residual weight ratio of 49%-80% at 750℃ in nitrogen. The polymers exhibit no apparent glass transition temperatures （Tgs） except PPy-1 （Tg= 327℃）, which is derived from tetraamine DPPA and 2,2-bis[4-（3＇,4＇-dicarboxyphenoxy）-phenyl]propane dianhydride （BPADA）. In addition, the polymers have acceptable mechanical properties with the tensile strength of 65-94 MPa. The PPy films show excellent hydrolysis-resistance in alkaline aqueous medium and could maintain most of the properties even after boiling in 10% aqueous sodium hydroxide solution for a week.展开更多
Dispersion-corrected DFT calculations have been performed to study the crystal structure, initial decomposition mechanism, polymerization mechanism, electronic structure and absorption properties of the most powerful ...Dispersion-corrected DFT calculations have been performed to study the crystal structure, initial decomposition mechanism, polymerization mechanism, electronic structure and absorption properties of the most powerful CHNO energetic compound octanitrocubane（ONC） under hydrostatic pressure of 0~200 GPa. Our results show that the lattice parameter c is sensitive to van der Waals interactions and the structure is the stiffest in the a direction. ONC decomposes by the breaking of N–O bond in nitro group at 195 GPa. At 200 GPa, ONC decomposes through the breaking of N–O bond in nitro group and polymerizes through the forming of a new C–O covalent bond between a carbon atom in the cage skeleton and one oxygen atom of nitro group in another ONC molecule. ONC becomes more and more sensitive under high pressure and transforms into a metallic phase in the pressure range of 175~200 GPa. ONC also has higher optical activity and wider absorption range under compression.展开更多
Engineering failure of membrane electrode assembly caused by increasingly fuel poisoning in the high temperature polymer electrolyte membrane fuel cells fed with humidified reformate gases is firstly demonstrated here...Engineering failure of membrane electrode assembly caused by increasingly fuel poisoning in the high temperature polymer electrolyte membrane fuel cells fed with humidified reformate gases is firstly demonstrated herein this work. Based on the results of the in-situ environmental scanning electron microscope, electrochemical analyses, and limiting current method, a water-induced phosphoric acid invasion model is constructed in the porous electrode to elucidate the failure causations of the hindered hydrogen mass transport and the enhanced carbon monoxide poisoning. To optimize the phosphoric acid distribution under the inevitably humidified circumstance, a facile and effective strategy of constructing acid-proofed electrode is proposed and demonstrates outstanding stability with highly humidified reformate gases as anode fuel. This work discusses a potential defect that was rarely studied previously under practical working circumstance for high temperature polymer electrolyte membrane fuel cells, providing an alternative opinion of electrode design based on the fundamental aspects towards the engineering problems.展开更多
Stable high-solids-content acrylate emulsion were obtained with a nonionic polymerizable emulsifier allyloxy nonylphenoxy poly （ethyleneoxy） （10） ether （ANPEO10）, and a conventional emulsifier OP-10 as a referen...Stable high-solids-content acrylate emulsion were obtained with a nonionic polymerizable emulsifier allyloxy nonylphenoxy poly （ethyleneoxy） （10） ether （ANPEO10）, and a conventional emulsifier OP-10 as a reference sample. 1H NMR proves that the polymerizable emulsifier ANPEO10 has been incorporated into the resulted acrylate polymers. TEM demonstrates that there are some differences in the particle morphologies. AFM proves that the polymerizable emulsifier ANPEO10 migrating to the surface of the emulsion film was much less than the conventional emulsifier OP-10. The polymerizable emulsifier ANPEO10 can enhance the adhesion with glass plate compared to the conventional emulsifier. Furthermore, with increasing amount of emulsifier, the surface free energy of the films first decreased and then increased, and the adhesion with glass plate is initially enhanced and then attenuated. The water-resistance and solvent-resistance of the films prepared by the polymerizable emulsifier ANPEO10 are superior to those prepared by the conventional emulsifier OP-10.展开更多
Polymer field-effect transistors operated in the n-channel model with a top-gate/bottom-contact are processed using a solution method. The transistor performance depends on the gate dielectric layer. A high performanc...Polymer field-effect transistors operated in the n-channel model with a top-gate/bottom-contact are processed using a solution method. The transistor performance depends on the gate dielectric layer. A high performance polymer transistor is achieved, with the saturated electron mobility of about 0.46cm2/Vs, threshold voltage nearly 0 V and subthreshold sway of about 0.9 V/decade, employing a polystyrene （PS） dielectric layer. The transistor performances are further improved with increasing current and lower operation voltages by utilizing a bi-layer gate dielectric, comprising a thin PS dielectric layer adjacent to the semiconductor to minimize the density of the interface traps for obtaining a small VT, a large μ and a poly（methyl methacrylate） （PMMA） dielectric layer with a relatively high-k adjacent to the gate electrode for enlarging the capacitance, processed from the orthogonal solvents.展开更多
A polymeric nanopore membrane with selective ionic transport has been proposed as a potential device to convert the chemical potential energy in salinity gradients to electrical power. However, its energy conversion e...A polymeric nanopore membrane with selective ionic transport has been proposed as a potential device to convert the chemical potential energy in salinity gradients to electrical power. However, its energy conversion efficiency and power density are often limited due to the challenge in reliably controlling the size of the nanopores with the conventional chemical etching method. Here we report that without chemical etching, polyimide （PI） membranes irradiated with GeV heavy ions have negatively charged nanopores, showing nearly perfect selectivity for cations over anions, and they can generate electrical power from salinity gradients. We further demonstrate that the power generation efficiency of the PI membrane approaches the theoretical limit, and the maximum power density reaches 130m W/m2 with a modified etching method, outperforming the previous energy conversion device that was made of polymeric nanopore membranes.展开更多
Lithium–sulfur(Li–S)batteries are being explored as promising advanced energy storage systems due to their ultra-high energy density.However,fast capacity fading and low coulombic efficiency,resulting from the disso...Lithium–sulfur(Li–S)batteries are being explored as promising advanced energy storage systems due to their ultra-high energy density.However,fast capacity fading and low coulombic efficiency,resulting from the dissolution of polysulfides,remain a serious challenge.Compared to weak physical adsorptions or barriers,chemical confinement based on strong chemical interaction is a more effective approach to address the shuttle issue.Herein,we devise a novel polymeric sulfur/carbon nanotube composite for Li–S battery,for which 2,5-dithiobiurea is chosen as the stabilizer of long-chain sulfur.This offers chemical bonds which bridge the polymeric sulfur and carbon nanotubes.The obtained composite can deliver an ultra-high reversible capacity of 1076.2 m Ahg^-1(based on the entire composite)at the rate of 0.1 C with an exceptional initial Coulombic efficiency of 96.2%,as well as remarkable cycle performance.This performance is mainly attributed to the reaction reversibility of the obtained polymeric sulfur-based composite during the discharge/charge process.This was confirmed by density functional theory calculations for the first time.展开更多
The seeded semicontinuous emulsion multi-copolymerization of butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), 2-hydroxyl propyl acrylate (HOPA) and acrylic acid (AA) was used to prepare th...The seeded semicontinuous emulsion multi-copolymerization of butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), 2-hydroxyl propyl acrylate (HOPA) and acrylic acid (AA) was used to prepare the acrylic latexes with high-solid content. The effects of monomer emulsion feed rates (R(a)) and (R/E)(E) values, the ratio of emulsifier amount between the initial charge (R) and the addition monomer emulsion (E), on the polymerization reaction features, the viscosities, surface tensions,particle sizes and particle sizes distributions of latexes, T-g and the insoluble fractions of films, the 180 degrees peel strength, tack and holding power of pressure-sensitive adhesive (PSA) tapes, prepared from the latexes, were studied. Experimental study shows that the grafting and crosslinking fraction in the PSA tapes must be controlled within a suitable range to keep the balance of the 180 degrees peel strength, tack and holding power.展开更多
基金This project was supported by the National Natural Science Foundation of China(No.50403025).
文摘A new type of aromatic tetraarnine containing biphenyl moiety in the side chain was synthesized via a modified Chichibabin＇s reaction. 3-Nitro-4-acetamidoacetophenone was reacted with 4-phenyl benzaldehyde in the presence of ammonium acetate to obtain 2,6-bis（3＇,4＇-diaminophenyl）-4-biphenyl pyridine （DPPA）. A series of polypyrrolones （PPys） were prepared using tetraamine and various aromatic dianhydrides via a two-step cyclization procedure. All the PPys show excellent high temperature stabilities with the initial decomposition temperatures of 530-549℃ and residual weight ratio of 49%-80% at 750℃ in nitrogen. The polymers exhibit no apparent glass transition temperatures （Tgs） except PPy-1 （Tg= 327℃）, which is derived from tetraamine DPPA and 2,2-bis[4-（3＇,4＇-dicarboxyphenoxy）-phenyl]propane dianhydride （BPADA）. In addition, the polymers have acceptable mechanical properties with the tensile strength of 65-94 MPa. The PPy films show excellent hydrolysis-resistance in alkaline aqueous medium and could maintain most of the properties even after boiling in 10% aqueous sodium hydroxide solution for a week.
基金Supported by the Science Foundation of Nanjing Institute of Technology(YKJ201507,CKJA201603,ZKJ201402)the Natural Science Foundation of Jiangsu Higher Education Institutions of China(14KJD430002)+1 种基金the Jiangsu Key Laboratory Opening Project of Advanced Structural Materials and Application Technology(ASMA201408)the Youth Natural Science Foundation of Jiangsu Province(BK20130747)
文摘Dispersion-corrected DFT calculations have been performed to study the crystal structure, initial decomposition mechanism, polymerization mechanism, electronic structure and absorption properties of the most powerful CHNO energetic compound octanitrocubane（ONC） under hydrostatic pressure of 0~200 GPa. Our results show that the lattice parameter c is sensitive to van der Waals interactions and the structure is the stiffest in the a direction. ONC decomposes by the breaking of N–O bond in nitro group at 195 GPa. At 200 GPa, ONC decomposes through the breaking of N–O bond in nitro group and polymerizes through the forming of a new C–O covalent bond between a carbon atom in the cage skeleton and one oxygen atom of nitro group in another ONC molecule. ONC becomes more and more sensitive under high pressure and transforms into a metallic phase in the pressure range of 175~200 GPa. ONC also has higher optical activity and wider absorption range under compression.
基金financially supported by the National Science Foundation of China, China (22179130, 91834301)the Foundation of the Key Laboratory of Chinese Academy of Sciences (CXJJ21S024)Dalian Institute of Chemical Physics, China (DICPI202023)。
文摘Engineering failure of membrane electrode assembly caused by increasingly fuel poisoning in the high temperature polymer electrolyte membrane fuel cells fed with humidified reformate gases is firstly demonstrated herein this work. Based on the results of the in-situ environmental scanning electron microscope, electrochemical analyses, and limiting current method, a water-induced phosphoric acid invasion model is constructed in the porous electrode to elucidate the failure causations of the hindered hydrogen mass transport and the enhanced carbon monoxide poisoning. To optimize the phosphoric acid distribution under the inevitably humidified circumstance, a facile and effective strategy of constructing acid-proofed electrode is proposed and demonstrates outstanding stability with highly humidified reformate gases as anode fuel. This work discusses a potential defect that was rarely studied previously under practical working circumstance for high temperature polymer electrolyte membrane fuel cells, providing an alternative opinion of electrode design based on the fundamental aspects towards the engineering problems.
基金Funded by Ministry of Education (No.2006-KL-008),and Qingxin Hanerchem Chemical Technology Co,Ltd.
文摘Stable high-solids-content acrylate emulsion were obtained with a nonionic polymerizable emulsifier allyloxy nonylphenoxy poly （ethyleneoxy） （10） ether （ANPEO10）, and a conventional emulsifier OP-10 as a reference sample. 1H NMR proves that the polymerizable emulsifier ANPEO10 has been incorporated into the resulted acrylate polymers. TEM demonstrates that there are some differences in the particle morphologies. AFM proves that the polymerizable emulsifier ANPEO10 migrating to the surface of the emulsion film was much less than the conventional emulsifier OP-10. The polymerizable emulsifier ANPEO10 can enhance the adhesion with glass plate compared to the conventional emulsifier. Furthermore, with increasing amount of emulsifier, the surface free energy of the films first decreased and then increased, and the adhesion with glass plate is initially enhanced and then attenuated. The water-resistance and solvent-resistance of the films prepared by the polymerizable emulsifier ANPEO10 are superior to those prepared by the conventional emulsifier OP-10.
基金Supported by the National Natural Science Foundation of China under Grant No 61177028
文摘Polymer field-effect transistors operated in the n-channel model with a top-gate/bottom-contact are processed using a solution method. The transistor performance depends on the gate dielectric layer. A high performance polymer transistor is achieved, with the saturated electron mobility of about 0.46cm2/Vs, threshold voltage nearly 0 V and subthreshold sway of about 0.9 V/decade, employing a polystyrene （PS） dielectric layer. The transistor performances are further improved with increasing current and lower operation voltages by utilizing a bi-layer gate dielectric, comprising a thin PS dielectric layer adjacent to the semiconductor to minimize the density of the interface traps for obtaining a small VT, a large μ and a poly（methyl methacrylate） （PMMA） dielectric layer with a relatively high-k adjacent to the gate electrode for enlarging the capacitance, processed from the orthogonal solvents.
基金Supported by the National Natural Science Foundation of China under Grant No 11335003
文摘A polymeric nanopore membrane with selective ionic transport has been proposed as a potential device to convert the chemical potential energy in salinity gradients to electrical power. However, its energy conversion efficiency and power density are often limited due to the challenge in reliably controlling the size of the nanopores with the conventional chemical etching method. Here we report that without chemical etching, polyimide （PI） membranes irradiated with GeV heavy ions have negatively charged nanopores, showing nearly perfect selectivity for cations over anions, and they can generate electrical power from salinity gradients. We further demonstrate that the power generation efficiency of the PI membrane approaches the theoretical limit, and the maximum power density reaches 130m W/m2 with a modified etching method, outperforming the previous energy conversion device that was made of polymeric nanopore membranes.
基金financially supported by the National Natural Science Foundation of China(No.51572116 and 51871113)Key Research and Development Program of Xuzhou(KC17004).
文摘Lithium–sulfur(Li–S)batteries are being explored as promising advanced energy storage systems due to their ultra-high energy density.However,fast capacity fading and low coulombic efficiency,resulting from the dissolution of polysulfides,remain a serious challenge.Compared to weak physical adsorptions or barriers,chemical confinement based on strong chemical interaction is a more effective approach to address the shuttle issue.Herein,we devise a novel polymeric sulfur/carbon nanotube composite for Li–S battery,for which 2,5-dithiobiurea is chosen as the stabilizer of long-chain sulfur.This offers chemical bonds which bridge the polymeric sulfur and carbon nanotubes.The obtained composite can deliver an ultra-high reversible capacity of 1076.2 m Ahg^-1(based on the entire composite)at the rate of 0.1 C with an exceptional initial Coulombic efficiency of 96.2%,as well as remarkable cycle performance.This performance is mainly attributed to the reaction reversibility of the obtained polymeric sulfur-based composite during the discharge/charge process.This was confirmed by density functional theory calculations for the first time.
基金This work was supported by the National Natural Science Foundation of China
文摘The seeded semicontinuous emulsion multi-copolymerization of butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), 2-hydroxyl propyl acrylate (HOPA) and acrylic acid (AA) was used to prepare the acrylic latexes with high-solid content. The effects of monomer emulsion feed rates (R(a)) and (R/E)(E) values, the ratio of emulsifier amount between the initial charge (R) and the addition monomer emulsion (E), on the polymerization reaction features, the viscosities, surface tensions,particle sizes and particle sizes distributions of latexes, T-g and the insoluble fractions of films, the 180 degrees peel strength, tack and holding power of pressure-sensitive adhesive (PSA) tapes, prepared from the latexes, were studied. Experimental study shows that the grafting and crosslinking fraction in the PSA tapes must be controlled within a suitable range to keep the balance of the 180 degrees peel strength, tack and holding power.
