Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation...Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation reaction.The structures of PIKs are characterized by means of elemental analysis,FT-IR,~1H-NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structure.The general properties of PIKs are studied by DSC,TG and wide-angle X-ray diffraction,the solubility behavior is...展开更多
Poly（Imino Ketone） （PIK） is a group of novel high performance polymer material with excellent thermal properties and dissolubility. Aiming at the requirements of inertial confined fusion （ICF） studies on low den...Poly（Imino Ketone） （PIK） is a group of novel high performance polymer material with excellent thermal properties and dissolubility. Aiming at the requirements of inertial confined fusion （ICF） studies on low density polymer foams, we firstly synthesized poly（imino imino ketone） （PIIK） by palladium catalyzed C-N cross-coupling reaction, and successfully prepared the PIIK foam material with a density of 80-300 mg/cm3 by using PIIK as the raw material with thermal-induced phase separation and lyophilization technique. Mercury injection method was used to determine the structure of PIIK foams, and the results indicated that the mean pore diameter was lower than 5 ~tm and it had relatively high voidage and specific surface area.展开更多
A series of Poly（arly ether sulfone ether ketone）s containing pendant methyl groups were synthesized by the reaction of 4,4＇-[sulfonylbis （1,4-phenylene）dioxy] dibenzoyl chloride （SODBC） with 4,4＇- diphenoxy d...A series of Poly（arly ether sulfone ether ketone）s containing pendant methyl groups were synthesized by the reaction of 4,4＇-[sulfonylbis （1,4-phenylene）dioxy] dibenzoyl chloride （SODBC） with 4,4＇- diphenoxy diphenylsulfone （DPODPS）, 4,4＇- di（2-methylphenoxy） diphenylsulfone （o-Me-DPODPS）, 4,4＇- di（3-methylphenoxy） diphenylsulfone （m-Me-DPODPS）, 4,4＇- di （2,6-bimethylphenoxy） biphenylsulfone（o-Me2-DPODPS） respectively, in a mixture of 1,2-dichloroethane （DCE） and N-methylpyrrolidone （NMP）. These reactions were catalyzed by anhydrous aluminum chloride （AlCl）. The characteristic of copolymers were studied by means of advanced analytical techniques such as FT-IR,1H-NMR, DSC, TGA and WAXD. The results show glass transition temperature （Tg） in the range of 193-206℃, thermally stable in excess of 434℃ and excellent solubility in polar solvents. Methyl-substituted Poly（aryl ether sulfone ketone）s had higher glass transition temperatures, lower initial decomposition temperatures than the unsubstituted ones.展开更多
In this paper, the synthesis and crystallization behavior of poly(ether ether ketone ether ketone) (PEEKEK) are reported. PEEKEK was prepared from 4,4'-bis(p-fluorobenzoyl) diphenyl ether (4,4'-FBDE) and hydro...In this paper, the synthesis and crystallization behavior of poly(ether ether ketone ether ketone) (PEEKEK) are reported. PEEKEK was prepared from 4,4'-bis(p-fluorobenzoyl) diphenyl ether (4,4'-FBDE) and hydroquinone along the nucleophilic substitution route. The thermal properties were investigated by using DSC and TGA. The crystallization behavior of PEEKEK under several conditions, i.e., crystallization from the molten state (melt crystallization), crystallization from a quenched sample (cold crystallization) and crystallization induced by exposing glassy sample to methylene chloride (solvent-induced crystallization) has also been investigated. The results show that crystallization of PEEKEK could be induced by the above methods, and no polymorphism was found. The differences in the crystallization of PEEKEK induced by the above methods are seen in their degree of crystallinity.展开更多
A novel type of aromatic poly（ ether ether ketone） s with carboxyl groups were prepared by polycondensation of 4,4-bis（4-hydroxyphenyl）pentanoic acid with difluoro-monomers. Their mo- lecular structures were deter...A novel type of aromatic poly（ ether ether ketone） s with carboxyl groups were prepared by polycondensation of 4,4-bis（4-hydroxyphenyl）pentanoic acid with difluoro-monomers. Their mo- lecular structures were determined by ^1H-NMR and IR, respectively. Their molecular weights were measured by gel permeation chromatography （ GPC ）, which showed that all the polymers had high molecule weights （ 〉 42 000）. Due to the long side chains of polymers, all the polymers had good solubility （soluble in NMP, DMAc, THF, etc. ）. The differential scanning calorimeter （DSC） detected their excellent glass transition temperatures （ Tg ） up to 195 ℃. The Tg increased with the content of carboxylic units in the polymer chains, because the interactions of H bonds increased with increasing content of carboxylic. The polymers could form transparent and flexible films, which make them a candidate for membrane materials.展开更多
Vanadium flow batteries(VFBs)have drawn considerable attention as an emerging technology for largescale energy storage systems(ESSs).One of the pivotal challenges is the availability of eligible ion exchange membranes...Vanadium flow batteries(VFBs)have drawn considerable attention as an emerging technology for largescale energy storage systems(ESSs).One of the pivotal challenges is the availability of eligible ion exchange membranes(ICMs)that provide high ion selectivity,proton conductivity,and stability under rigorous condition.Herein,a‘side-chain-type’strategy has been employed to fabricate highly stable phenolphthalein-based cardo poly(arylene ether ketone)s(PAEKs)membrane with low area resistance(0.058Ωcm^(2)),in which flexible alkyl spacers effectively alleviated inductive withdrawing effect from terminal ion exchange groups thus enabling a stable backbone.The assembled VFBs based on PAEKs bearing pendent alkyl chain terminated with quaternary ammonium(Q-PPhEK)demonstrated an energy efficiency above 80%over 700 cycles at 160 mA/cm^(2).Such a remarkable results revealed that the side-chain-type strategy contributed to enhancing the ICMs stability in strong oxidizing environment,meanwhile,more interesting backbones would be woken with this design engaging in stable ICMs for VFBs.展开更多
Poly(aryl ether ketone)s (PAEKs) were successfully synthesized via nucleophilic aromatic substitution (SNAR) mechanism, using ionic liquids as green reaction media. The influence of various reaction parameters includi...Poly(aryl ether ketone)s (PAEKs) were successfully synthesized via nucleophilic aromatic substitution (SNAR) mechanism, using ionic liquids as green reaction media. The influence of various reaction parameters including monomer concentration, dehydration time, polymerization temperature and duration, IL's cations and anions nature, upon PAEKs molecular weight was investigated. In addition, the peculiarities of hydrogen-bonding ability of ILs were investigated. The interaction of 2,2-bis(4-hydroxyphenyl) propane (bisphenol A) with ILs has a strong influence on PAEKs synthesis. Various moderate molecular weight PAEKs have been obtained in high yields with molecular weights ranging from 10000 to 18000g mol-1.展开更多
(1,4-Bis-（4-bromobenzoyl）benzene) as the monomer has been synthesized and characterized by Friedel-Crafts benzoylation reaction.Novel poly（imino ketone）s（PIKs） as high performance polymers have been obtained by ...(1,4-Bis-（4-bromobenzoyl）benzene) as the monomer has been synthesized and characterized by Friedel-Crafts benzoylation reaction.Novel poly（imino ketone）s（PIKs） as high performance polymers have been obtained by the condensation polymerization of（1,4-bis-（4-bromobenzoyl）benzene） and aromatic diamines via palladium-catalyzed aryl amination reaction.The strcture of PIKs is characterized by means of FT-IR and（）1H-NMR spectroscopy,and the results show an agreement with the proposed structure.DSC and TG measurements show that PIKs possess high glass transition temperature（Tg>230℃） and good thermal stability with high decomposition temperatures（TD>500℃）.PIKs also exhibit the excellent solubility,PIK-3 can be dissolved in common organic solvent CHCl3 at room temperature（20℃）.展开更多
A kind of highly fluorinated bisphenol monomer was synthesized. It was characterized by FTIR, 1H NMR and MS. 6F PEEK and 6F PEEKK were prepared via aromatic nucleophilic substitution, based on [3,5 di(trifluoromethyl)...A kind of highly fluorinated bisphenol monomer was synthesized. It was characterized by FTIR, 1H NMR and MS. 6F PEEK and 6F PEEKK were prepared via aromatic nucleophilic substitution, based on [3,5 di(trifluoromethyl)] phenylhydroquinone and difluoro monomers. The T gs of 6F PEEK and 6F PEEKK are 423 and 436 K, respectively. The 6F polymers exhibit a high thermal stability and good solubility. The flexible, creasable and transparent thin films were easily obtained by compression moulding and solution casting.展开更多
Two novel poly(aryl ether ketone)s based on (3 methyl)phenylhydroquinone were synthesized via aromatic nucleophilic substitution reaction. The high molecular polymers were easily obtained because of the high reaction ...Two novel poly(aryl ether ketone)s based on (3 methyl)phenylhydroquinone were synthesized via aromatic nucleophilic substitution reaction. The high molecular polymers were easily obtained because of the high reaction activity of bisphenol monomer. The traces of DSC showed that the T gs of m TPEEK and m TPEEKK were 421 and 432 K, respectively. The two polymers exhibit a high thermal stability and good solubility. The transparent and flexible films were readily prepared with chloroform solution. The film of m TPEEK had a low dielectric constant( ε =2 7).展开更多
基金This work was financially supported by the National Natural Science Foundation of China(No.15076017).
文摘Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation reaction.The structures of PIKs are characterized by means of elemental analysis,FT-IR,~1H-NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structure.The general properties of PIKs are studied by DSC,TG and wide-angle X-ray diffraction,the solubility behavior is...
基金Funded by the National Natural Science Foundation of China(No.11447215)Scientific Research Project of Mianyang Normal University(No.2013A02)Research Fund of Education Department of Sichuan Province(No.13ZB0118)
文摘Poly（Imino Ketone） （PIK） is a group of novel high performance polymer material with excellent thermal properties and dissolubility. Aiming at the requirements of inertial confined fusion （ICF） studies on low density polymer foams, we firstly synthesized poly（imino imino ketone） （PIIK） by palladium catalyzed C-N cross-coupling reaction, and successfully prepared the PIIK foam material with a density of 80-300 mg/cm3 by using PIIK as the raw material with thermal-induced phase separation and lyophilization technique. Mercury injection method was used to determine the structure of PIIK foams, and the results indicated that the mean pore diameter was lower than 5 ~tm and it had relatively high voidage and specific surface area.
基金This work was supported by National Science Foundation of China （No. 20264001 ）, National Science Foundation of Jiangxi Province, Innovation Fund for Technology Based Firms of China （No. 06C26213601342）.
文摘A series of Poly（arly ether sulfone ether ketone）s containing pendant methyl groups were synthesized by the reaction of 4,4＇-[sulfonylbis （1,4-phenylene）dioxy] dibenzoyl chloride （SODBC） with 4,4＇- diphenoxy diphenylsulfone （DPODPS）, 4,4＇- di（2-methylphenoxy） diphenylsulfone （o-Me-DPODPS）, 4,4＇- di（3-methylphenoxy） diphenylsulfone （m-Me-DPODPS）, 4,4＇- di （2,6-bimethylphenoxy） biphenylsulfone（o-Me2-DPODPS） respectively, in a mixture of 1,2-dichloroethane （DCE） and N-methylpyrrolidone （NMP）. These reactions were catalyzed by anhydrous aluminum chloride （AlCl）. The characteristic of copolymers were studied by means of advanced analytical techniques such as FT-IR,1H-NMR, DSC, TGA and WAXD. The results show glass transition temperature （Tg） in the range of 193-206℃, thermally stable in excess of 434℃ and excellent solubility in polar solvents. Methyl-substituted Poly（aryl ether sulfone ketone）s had higher glass transition temperatures, lower initial decomposition temperatures than the unsubstituted ones.
基金This project was financial supported by National Natural Science Foundation of China and the Chinese "863" High Technology Funds.
文摘In this paper, the synthesis and crystallization behavior of poly(ether ether ketone ether ketone) (PEEKEK) are reported. PEEKEK was prepared from 4,4'-bis(p-fluorobenzoyl) diphenyl ether (4,4'-FBDE) and hydroquinone along the nucleophilic substitution route. The thermal properties were investigated by using DSC and TGA. The crystallization behavior of PEEKEK under several conditions, i.e., crystallization from the molten state (melt crystallization), crystallization from a quenched sample (cold crystallization) and crystallization induced by exposing glassy sample to methylene chloride (solvent-induced crystallization) has also been investigated. The results show that crystallization of PEEKEK could be induced by the above methods, and no polymorphism was found. The differences in the crystallization of PEEKEK induced by the above methods are seen in their degree of crystallinity.
基金Supported by Open Project of State Key Laboratory of Supramolecular Structure and Materials(SKLSSM201114)the National Natural Science Foundation of China(51103010)
文摘A novel type of aromatic poly（ ether ether ketone） s with carboxyl groups were prepared by polycondensation of 4,4-bis（4-hydroxyphenyl）pentanoic acid with difluoro-monomers. Their mo- lecular structures were determined by ^1H-NMR and IR, respectively. Their molecular weights were measured by gel permeation chromatography （ GPC ）, which showed that all the polymers had high molecule weights （ 〉 42 000）. Due to the long side chains of polymers, all the polymers had good solubility （soluble in NMP, DMAc, THF, etc. ）. The differential scanning calorimeter （DSC） detected their excellent glass transition temperatures （ Tg ） up to 195 ℃. The Tg increased with the content of carboxylic units in the polymer chains, because the interactions of H bonds increased with increasing content of carboxylic. The polymers could form transparent and flexible films, which make them a candidate for membrane materials.
基金the financial support of the National Natural Science Foundation of China(Nos.22075276,U19A2016,U22B6012)CAS Strategic Leading Science&Technology Program(A)(No.XDA21070000)+2 种基金Dalian High Level Talent Innovation Support Program(No.2020RD05)the Development of Scientic and Technological Project of the Jilin Province(No.20210101126JC)International Partnership Program of Chinese Academy of Sciences(No.121421KYSB20210028)。
文摘Vanadium flow batteries(VFBs)have drawn considerable attention as an emerging technology for largescale energy storage systems(ESSs).One of the pivotal challenges is the availability of eligible ion exchange membranes(ICMs)that provide high ion selectivity,proton conductivity,and stability under rigorous condition.Herein,a‘side-chain-type’strategy has been employed to fabricate highly stable phenolphthalein-based cardo poly(arylene ether ketone)s(PAEKs)membrane with low area resistance(0.058Ωcm^(2)),in which flexible alkyl spacers effectively alleviated inductive withdrawing effect from terminal ion exchange groups thus enabling a stable backbone.The assembled VFBs based on PAEKs bearing pendent alkyl chain terminated with quaternary ammonium(Q-PPhEK)demonstrated an energy efficiency above 80%over 700 cycles at 160 mA/cm^(2).Such a remarkable results revealed that the side-chain-type strategy contributed to enhancing the ICMs stability in strong oxidizing environment,meanwhile,more interesting backbones would be woken with this design engaging in stable ICMs for VFBs.
基金supported by the National Natural Science Foundation of China (21274014)Beijing Municipal Commission of Education+1 种基金the Fundamental Research Funds for the Central UniversitiesMeasuring Fund of Large Apparatus of Beijing Normal University
文摘Poly(aryl ether ketone)s (PAEKs) were successfully synthesized via nucleophilic aromatic substitution (SNAR) mechanism, using ionic liquids as green reaction media. The influence of various reaction parameters including monomer concentration, dehydration time, polymerization temperature and duration, IL's cations and anions nature, upon PAEKs molecular weight was investigated. In addition, the peculiarities of hydrogen-bonding ability of ILs were investigated. The interaction of 2,2-bis(4-hydroxyphenyl) propane (bisphenol A) with ILs has a strong influence on PAEKs synthesis. Various moderate molecular weight PAEKs have been obtained in high yields with molecular weights ranging from 10000 to 18000g mol-1.
文摘(1,4-Bis-（4-bromobenzoyl）benzene) as the monomer has been synthesized and characterized by Friedel-Crafts benzoylation reaction.Novel poly（imino ketone）s（PIKs） as high performance polymers have been obtained by the condensation polymerization of（1,4-bis-（4-bromobenzoyl）benzene） and aromatic diamines via palladium-catalyzed aryl amination reaction.The strcture of PIKs is characterized by means of FT-IR and（）1H-NMR spectroscopy,and the results show an agreement with the proposed structure.DSC and TG measurements show that PIKs possess high glass transition temperature（Tg>230℃） and good thermal stability with high decomposition temperatures（TD>500℃）.PIKs also exhibit the excellent solubility,PIK-3 can be dissolved in common organic solvent CHCl3 at room temperature（20℃）.
文摘A kind of highly fluorinated bisphenol monomer was synthesized. It was characterized by FTIR, 1H NMR and MS. 6F PEEK and 6F PEEKK were prepared via aromatic nucleophilic substitution, based on [3,5 di(trifluoromethyl)] phenylhydroquinone and difluoro monomers. The T gs of 6F PEEK and 6F PEEKK are 423 and 436 K, respectively. The 6F polymers exhibit a high thermal stability and good solubility. The flexible, creasable and transparent thin films were easily obtained by compression moulding and solution casting.
文摘Two novel poly(aryl ether ketone)s based on (3 methyl)phenylhydroquinone were synthesized via aromatic nucleophilic substitution reaction. The high molecular polymers were easily obtained because of the high reaction activity of bisphenol monomer. The traces of DSC showed that the T gs of m TPEEK and m TPEEKK were 421 and 432 K, respectively. The two polymers exhibit a high thermal stability and good solubility. The transparent and flexible films were readily prepared with chloroform solution. The film of m TPEEK had a low dielectric constant( ε =2 7).
