磺化聚苯醚酮质子交换膜的制备与表征

doi:10.11944/j.issn.1000-0518.2017.10.170026

摘要/Abstract

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。

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

Abstract:

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 are 80.2% and 37.2%, respectively. At 25 ℃, the methanol permeability of the two membranes is 2.38 and 7.20, 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.

Key words: sulfonated poly(p-phenylene-co-aryl ether ketone)s, proton exchange membranes, microblock, swelling ratio, methanol permeability

毕伟辉, 郑吉富, 张所波. 磺化聚苯醚酮质子交换膜的制备与表征[J]. 应用化学, 2017, 34(10): 1117-1126.

BI Weihui, ZHENG Jifu, ZHANG Suobo. Preparation and Characterization of Sulfonated Poly(p-phenylene-co-aryl ether ketone) for Proton Exchange Membranes[J]. Chinese Journal of Applied Chemistry, 2017, 34(10): 1117-1126.

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