一类低溶胀率磺化聚芳醚砜质子交换膜材料的制备及性能  

Preparation and Properties of Sulfonated Poly(aryl sulfone)s with Low Swelling Ratio for Proton Exchange Membrane

作　　者：周远鹏 汪称意 陶正旺 邢毅 余彬 李坚 任强 Yuanpeng Zhou;Chenyi Wang;Zhengwang Tao;Yi Xing;Bin Yu;Jian Li;Qiang Ren(School of Materials Science and Engineering,Changzhou University,Changzhou 213164,China)

机构地区：[1]常州大学材料科学与工程学院

出　　处：《高分子材料科学与工程》2019年第12期22-29,共8页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(21404016);江苏省重点研究计划(BE2017645);江苏省研究生实践创新计划(KYCX17-2088);江苏省“青蓝工程”优秀青年骨干教师资助计划

摘　　要：通过两步有机反应,设计合成了一种含3,5-二苯基苯侧基结构的活性二氟砜单体--3,3’-二(3,5-二苯基苯)-4,4’-二氟二苯砜。以此单体、4,4’-二氟二苯砜和4,4’-二羟基二苯甲酮为起始原料,经过芳香亲核取代缩聚和温和的后磺化反应,制备了一系列磺化聚芳砜质子交换膜(TS-PAS-xx)。分别利用红外光谱和核磁共振氢谱对所制聚合物的结构进行了表征分析。结果表明,所制质子交换膜表现出适中的吸水率和较低的溶胀率,在80℃时,膜的溶胀率均不超过15.7%。原子力显微镜测试表明这些质子交换膜形成了明显的"亲水-疏水"相分离结构,该结构有利于质子传导率的提高,80℃时TS-PAS-34膜的质子传导率达到了182 mS/cm,与Nafion112相当,优于其它已报道的一些具有相同离子交换容量(IEC)的聚芳砜质子交换膜的传导率。该膜还具有良好的热性能、力学性能和优异的耐化学氧化稳定性。A novel monomer 3,3′-bis(3,5-diphenylbenzene)-bis(4-fluorophenyl)sulfone was designed and synthesized through free-radical substitution and Suzuki coupling reactions.A series of sulfonated poly(aryl sulfone)s were prepared by the aromatic nucleophilic substitution polycondensation and post-sulfonation reaction using this monomer,bis(4-fluorophenyl)sulfone and 4,4′-dihydroxybenzophenone as starting material.The results of FT-IR and^1H-NMR spectra show that the structures of polymers are in good agreement with the proposed structures.All obtained membranes own low water uptake and swelling ratio and their swelling ratios are not more than 15.7%.AFM test shows that these membranes form an obvious"hydrophilic-hydrophobic"phase separation structure,which is beneficial to the increase of proton conductivity.At 80℃,the proton conductivity of the TS-PAS-34 membrane with an IEC of 1.96 mmol/g reaches 182 mS/cm,which is comparable to that of Nafion112.It is superior to other reported proton exchange membranes with a similar ion exchange capacity(IEC).Moreover,TS-PAS-xx also exhibits good thermal properties,mechanical properties and chemical oxidative stability.

关 键 词：质子交换膜 磺化聚芳砜 吸水率 溶胀率 耐化学氧化稳定性 

分 类 号：TQ326.55[化学工程—合成树脂塑料工业]