含氟磺化双三蝶烯型聚芳醚砜质子交换膜的制备及性能

利用3,3,4,4-四氟二苯砜、十氟联苯、6F-双酚A及6,13-双三蝶烯二酚,通过亲核取代共聚及后磺化方法制备了2个系列不同磺化度的磺化双三蝶烯型聚芳醚砜,并通过氢核磁共振波谱(1H NMR)对其化学结构进行了表征.研究发现,所得磺化聚芳醚砜均表现出了优异的热稳定性.此类膜材料具有优良的机械性能、尺寸稳定性、氧化稳定性及高温低湿度条件下高的质子传导率.透射电子显微镜的结果表明,聚合物主链中大量氟原子的引入显著改善了聚合物的相分离结构,并且随着聚合物主链中氟含量的增加,亲水区域明显增大.这也是含氟磺化双三蝶烯型聚芳醚砜质子交换膜材料在高温低湿度条件下具有高质子传导率的主要原因.

Synthesis and Properties of Fluorinated Poly(arylene ether sulfone)s with Sulfonated Pentiptycene Pendants as Proton Exchange Membranes

Two series of poly(aryl ether sulfone)sSPES-x-PPD(10F) and SPES-x-PPD(4F)] containing sulfonated pentiptycene groups were synthesized through nucleophilic aromatic substitution polycondensation using pentiptycene-6,13-diol, decafluorobiphenyl, 4,4'-(hexafluoroisopropylidene)diphenol, and 3,3',4,4'-tetrafluorodiphenyl sulfone, followed by postsulfonation with chlorosulfonic acid. The structures of polymers were characterized by 1H NMR spectra. These ionomers generally show high thermal stability. The correspon-ding membranes generally show good mechanical properties, excellent dimensional changes, good oxidative stability and high proton conductivity under high temperature and low humidity. Transmission electron microscopic photos reveal that the microphase separated structures of SPES-x-PPD(10F) and SPES-x-PPD(4F) membranes are improved greatly after fluorine atoms introducing. Meanwhile, the hydrophilic domain enlarged when the contents of fluorine atoms in polymer backbone increased. This is just the main reason of high conductivity for these membranes.