一种杂环磺化聚芳醚腈酮质子交换膜材料的合成及表征

用含二氮杂萘酮结构类双酚DHPZ,3,3′-二磺酸钠基-4,4′-二氟二苯酮,2,6-二氯苯腈以及4,4′-二氟二苯酮,通过缩合共聚合反应合成了一系列不同磺化度、高分子量的磺化聚芳醚腈酮.聚合物特性粘数为0·58~2·0dL/g.用红外光谱(FT-IR),核磁共振谱(1H-NMR)表征了聚合物结构.用差示扫描量热仪(DSC)和热重分析仪(TGA)研究了聚合物的耐热性能,研究表明其玻璃化温度(Tg)可达352℃,5%热失重温度大于500℃.以N-甲基吡咯烷酮为溶剂,溶液浇铸法制备了聚合物膜,并测定了膜的溶胀率以及质子交换能力.结果表明,与Nafion膜相比,磺化聚芳醚腈酮膜在相同的质子交换能力条件下,溶胀率显著降低.

SYNTHESIS AND CHARACTERIZATION OF SULFONATED POLY(PHTHALAZINONE ETHER NITRILE KETONE)S FOR PROTON EXCHANGE MEMBRANE

Sulfonated poly(phthalazinone ether nitrile ketone)s (SPPENK) with pendent sulfonate groups were synthesized by direct polycondensation from 4-(4-hydroxyphenyl)-1(2H)-phthalazinone (DHPZ),disodium 3,3′-disulfonate-4,4′-difluorobenzophenone (SDFB),4,4′-difluorobenzophenone (DFB) and 2,6-dicholobenzene (DCBN).The intrinsic viscosity of SPPENK was in the range of 0.58～2.0 dL/g.FT-IR, ~1H-NMR and wide-X-ray scattering were used to characterize the structures of the copolymers.The thermo-stability of the copolymers was detected by DSC and TGA.Tough films were cast successfully from N-methylpyrrolidone solutions.The ion exchange capacity (IEC) values were 0.91～2.06 meq\5g~-1 . The swelling ratios of resulted membranes were 9%～21%,which is much lower than those of Nafion1135 and other reported sulfonated poly(aryl ether ketone)s and poly(aryl ether sulfone)s membranes with the same ion exchange capacity.