磺化聚苯醚酮质子交换膜的制备与表征  

Preparation and Characterization of Sulfonated Poly( p-phenylene-co-aryl ether ketone)for Proton Exchange Membranes

作　　者：毕伟辉[1,2] 郑吉富 张所波[1,3] BI Weihui ZHENG Jifu ZHANG Suobo(Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China University of Chinese Academy of Sciences ,Beijing , 100049, China Jiangsu National Synergetic Innovation Center for Advanced Materials（SICAM） ,Nanjing ,211816, China)

机构地区：[1]中国科学院长春应用化学研究所,生态环境高分子材料重点实验室,长春130022 [2]中国科学院大学,北京100039 [3]江苏国家先进材料协同创新中心,南京211816

出　　处：《应用化学》2017年第10期1117-1126,共10页Chinese Journal of Applied Chemistry

基　　金：国家重大基础研究"973"计划项目(2015CB655302);国家自然科学基金项目(51473163);吉林省科学发展计划基金项目(20160101316JC)资助~~

摘　　要：设计、合成了一种含氰基双氯单体,其结构特点是氰基分布在3个以间位醚键相连的苯环上。以此单体和2,5-二氯-3'-磺酸钠二苯甲酮为原料,利用Ni(0)催化偶联反应制备了微嵌段型质子交换膜材料(中等长度磺化聚苯-三氰基聚苯醚酮共聚物(m-SPP-co-PAEK 3CN x),x代表聚合物的离子交换容量)。结果表明,与相同离子交换容量的磺化聚合物相比,该类聚合物膜表现出较低的吸水、溶胀率和较低的甲醇渗透性能。以离子交换容量2.16为例,80℃下,m-SPP-co-PAEK 3CN 2.16的吸水率、溶胀率分别为29.7%、28.2%,而SPP-co-PAEK MO 2.33的吸水率、溶胀率分别为80.2%、37.2%。25℃下,二者的甲醇渗透系数分别为2.38和7.20。聚合物骨架结构中存在丰富的氰基基团,导致膜具有良好的尺寸稳定性和较低的甲醇渗透性能。基于这些优异的性能,新制备的膜材料在燃料电池领域显示了潜在的应用前景。A novel monomer was designed and synthesized,in which the cyano groups were distributed on three benzene rings linked by meta ether linkages. Then using this monomer and 2,5-dichloro-3＇-sulfobenzophenone as raw materials,a series of novel micro-block copolymer proton exchange membranes（ middle length-sulfonated polyphenylene-co-poly aryl ether ketone 3CN（ m-SPP-co-PAEK 3CN x）, x represents the ion exchange capacity of the polymer） was prepared by nickel（ 0） catalyzed coupling copolymerization. The experimental results show that these membranes exhibit low water uptake and swelling ratio as well as methanol permeability under similar ion exchange capacity. As the ion exchange capacity is equal to 2. 16 and the temperature is 80 ℃,the water uptake and swelling ratio of m-SPP-co-PAEK 3CN 2. 16 are 29. 7% and 28. 2%,respectively,while the water uptake and swelling ratio of SPP-co-PAEK MO 2. 33 are80. 2% and 37. 2%,respectively. At 25 ℃,the methanol permeability of the two membranes is 2. 38 and7. 20,respectively. The good dimensional stability of the as-synthesized membrane can be attributed to the introduction of the polar-CN groups into the skeleton. With these properties,the prepared membranes are promising proton exchange membrane materials in fuel cell applications.

关 键 词：磺化聚苯醚酮 质子交换膜 微嵌段 溶胀率 甲醇渗透率 

分 类 号：O633.1[理学—高分子化学]