Novel fluorene-based poly(aromatic diacetylene)s have been synthesized by CuCl-catalyzed oxidative coupling of aromatic diynes.New aromatic diynes 2,7-diethynyl-9,9-bis(triphenylamine)fluorene(M_1)is synthesized by mu...Novel fluorene-based poly(aromatic diacetylene)s have been synthesized by CuCl-catalyzed oxidative coupling of aromatic diynes.New aromatic diynes 2,7-diethynyl-9,9-bis(triphenylamine)fluorene(M_1)is synthesized by multistep reactions.The structures and properties of the polymers are characterized and evaluated by IR,NMR,TGA,UV, photoluminescence(PL),and cyclic voltammetry analyses.These polymers possess good thermal stability.All the polymers are completely soluble in coammon solvents such as toluene,THF,c...展开更多
A novel cross-linking process using two high molecular weight aromatic poly（thioether）s, which were synthesized by the reactions of 4,4＇-thiobisbenzenethiol with 4,4＇-difluorobenzophenone and 4,4＇-difluorodipheny...A novel cross-linking process using two high molecular weight aromatic poly（thioether）s, which were synthesized by the reactions of 4,4＇-thiobisbenzenethiol with 4,4＇-difluorobenzophenone and 4,4＇-difluorodiphenylsulfone, respectively, and commercially available lower molecular weight poly（p-phenylene sulfide） was investigated. These reactions were carried out in bulk by the addition of silver tetrafluroborate and α,α＇-dibromo-p-xylene at 190℃ over a period of 45 min. Furthermore, the same procedure could be modified to cross-link compression-molded films of these three polymers. The thermal and solubility behaviors of these polymers before and after cross-linking reactions, are presented.展开更多
A series of hydroxide conductive polymers QTBMs carrying dense aromatic side-chain quaternary ammonium groups has been synthesized by using a new monomer of 3,3＇-di（3＂,5＂-dimethylphenyl）-4,4＇-difluorodiphenyl su...A series of hydroxide conductive polymers QTBMs carrying dense aromatic side-chain quaternary ammonium groups has been synthesized by using a new monomer of 3,3＇-di（3＂,5＂-dimethylphenyl）-4,4＇-difluorodiphenyl sulfone and other commercial monomers via polycondensation reaction, and subsequent bromination, quaternization and alkalization. The chemical structures of the ionomers were confirmed by 1H- and 13C-NMR spectroscopy. Water uptake, swelling ratio, hydroxide conductivity, the number of bonded water per ammonium group （A）, volumetric ion exchange capacity （IECvwet）, mechanical and thermal properties, and chemical stability were systematically evaluated for the series of QTBMs membranes. QTBMs showed IECs ranging from 1.02 meq·g-1 to 2.11 meq·g-1; in particular, QTBM-60 membrane with the highest IEC （2.11 meq·g-1） had very high hydroxide ion conductivity of 131.9 mS·cm-1 at 80 ℃, which was attributed to the well assembled nano-channels with distinct phase separation evidenced by small-angle X-ray scattering （SAXS）. It was found that the hydrated QTBMs membranes were mechanically stable with moderate water uptakes and swelling ratios, high chemical stability under the harsh alkaline conditions. This work provides a facile way to prepare anion exchange membranes （AEMs） with high performances for the application in alkaline fuel cells.展开更多
从4,4＇-二氟三苯二酮（DFTBDK）和酚酞出发,利用＂拟高稀（pseudo high dillution）＂技术,一步法制备酚酞聚芳醚酮酮环状齐聚物（c-PEKK-C）,成环率78%。基质辅助激光解吸电离飞行时间质谱MALDI-TOF MS数据表明,聚合产物系聚合度为n=...从4,4＇-二氟三苯二酮（DFTBDK）和酚酞出发,利用＂拟高稀（pseudo high dillution）＂技术,一步法制备酚酞聚芳醚酮酮环状齐聚物（c-PEKK-C）,成环率78%。基质辅助激光解吸电离飞行时间质谱MALDI-TOF MS数据表明,聚合产物系聚合度为n=2~8的环状低聚物,其中以二、三聚体为主要成分（占环化产物的85%）。运用J-S高分子环化理论证实4,4＇-二氟三苯二酮的单体结构有利于形成环状化合物。以4,4＇-联苯二酚钾盐为催化剂,在300~350℃范围内,N2气保护下,环状齐聚物进行熔融开环聚合反应得到相应的线性高相对分子质量酚酞聚芳醚酮酮（ROP-PEKK-C）,GPC测得其Mw为1.2×10^5。展开更多
基金This project was financially supported by National Natural Science Foundation of China(No.50473034).
文摘Novel fluorene-based poly(aromatic diacetylene)s have been synthesized by CuCl-catalyzed oxidative coupling of aromatic diynes.New aromatic diynes 2,7-diethynyl-9,9-bis(triphenylamine)fluorene(M_1)is synthesized by multistep reactions.The structures and properties of the polymers are characterized and evaluated by IR,NMR,TGA,UV, photoluminescence(PL),and cyclic voltammetry analyses.These polymers possess good thermal stability.All the polymers are completely soluble in coammon solvents such as toluene,THF,c...
文摘A novel cross-linking process using two high molecular weight aromatic poly（thioether）s, which were synthesized by the reactions of 4,4＇-thiobisbenzenethiol with 4,4＇-difluorobenzophenone and 4,4＇-difluorodiphenylsulfone, respectively, and commercially available lower molecular weight poly（p-phenylene sulfide） was investigated. These reactions were carried out in bulk by the addition of silver tetrafluroborate and α,α＇-dibromo-p-xylene at 190℃ over a period of 45 min. Furthermore, the same procedure could be modified to cross-link compression-molded films of these three polymers. The thermal and solubility behaviors of these polymers before and after cross-linking reactions, are presented.
基金supported by the National Natural Science Foundation of China(No.51173045)Student Research Program(SRP) Funds of South China University of Technology(Nos.105612015S165 and 105612016S198)
文摘A series of hydroxide conductive polymers QTBMs carrying dense aromatic side-chain quaternary ammonium groups has been synthesized by using a new monomer of 3,3＇-di（3＂,5＂-dimethylphenyl）-4,4＇-difluorodiphenyl sulfone and other commercial monomers via polycondensation reaction, and subsequent bromination, quaternization and alkalization. The chemical structures of the ionomers were confirmed by 1H- and 13C-NMR spectroscopy. Water uptake, swelling ratio, hydroxide conductivity, the number of bonded water per ammonium group （A）, volumetric ion exchange capacity （IECvwet）, mechanical and thermal properties, and chemical stability were systematically evaluated for the series of QTBMs membranes. QTBMs showed IECs ranging from 1.02 meq·g-1 to 2.11 meq·g-1; in particular, QTBM-60 membrane with the highest IEC （2.11 meq·g-1） had very high hydroxide ion conductivity of 131.9 mS·cm-1 at 80 ℃, which was attributed to the well assembled nano-channels with distinct phase separation evidenced by small-angle X-ray scattering （SAXS）. It was found that the hydrated QTBMs membranes were mechanically stable with moderate water uptakes and swelling ratios, high chemical stability under the harsh alkaline conditions. This work provides a facile way to prepare anion exchange membranes （AEMs） with high performances for the application in alkaline fuel cells.
文摘从4,4＇-二氟三苯二酮（DFTBDK）和酚酞出发,利用＂拟高稀（pseudo high dillution）＂技术,一步法制备酚酞聚芳醚酮酮环状齐聚物（c-PEKK-C）,成环率78%。基质辅助激光解吸电离飞行时间质谱MALDI-TOF MS数据表明,聚合产物系聚合度为n=2~8的环状低聚物,其中以二、三聚体为主要成分（占环化产物的85%）。运用J-S高分子环化理论证实4,4＇-二氟三苯二酮的单体结构有利于形成环状化合物。以4,4＇-联苯二酚钾盐为催化剂,在300~350℃范围内,N2气保护下,环状齐聚物进行熔融开环聚合反应得到相应的线性高相对分子质量酚酞聚芳醚酮酮（ROP-PEKK-C）,GPC测得其Mw为1.2×10^5。
