高性能氢化星型聚(苯乙烯-b-丁二烯-b-苯乙烯)嵌段共聚物阴离子交换膜的制备、结构与性能

doi:10.11944/j.issn.1000-0518.2019.10.190068

摘要/Abstract

摘要：

利用常压催化加氢法合成氢化星型聚(苯乙烯-b-丁二烯-b-苯乙烯)嵌段共聚物(HSBS),依次通过氯甲基化、季铵化和碱化反应,制备两种综合性能良好的碱性阴离子交换膜(AEMs),HSBS4303-OH和HSBS4402-OH(二者制备原料中苯乙烯质量分数分别为30%和40%)。采用傅里叶变换红外光谱(FTIR)对AEMs的结构和制备过程进行表征,并对膜的离子电导率、吸水率、溶胀度、机械性能、微相结构和耐碱稳定性等进行系统地研究。结果表明,HSBS在90 ℃左右出现了对应于结晶结构的特征熔融峰,相较于SBS,其机械性能及尺寸稳定性显著提高。两种AEMs中,HSBS4402-OH的性能最佳,该膜的离子交换容量为1.99 mmol/g,30 ℃时的吸水率和溶胀度分别为27.65%和5.12%,80 ℃下的离子电导率高达86.8 mS/cm。在60 ℃下,采用2 mol/L NaOH溶液浸泡432 h后,该膜的离子电导率损失仅为8.3%。显而易见,本文方法能为碱性阴离子交换膜燃料电池提供很有前途的AEMs。

关键词: 阴离子交换膜, 聚(苯乙烯-b-丁二烯-b-苯乙烯)共聚物, 结晶结构, 微相分离

Abstract:

Hydrogenated star-shaped poly(styrene-b-butadiene-b-styrene) copolymer(HSBS) was synthesized by catalytic hydrogenation at atmospheric pressure. The product was treated by sequential chloromethylation, quaternization and alkalization to fabricate two kinds of alkaline anion exchange membranes(AEMs) with good comprehensive properties. And they were HSBS4303-OH and HSBS4402-OH(the mass fraction of styrene in the raw materials were 30% and 40%, respectively). The structures and preparation process of AEMs were characterized by Fourier transform infrared(FTIR) spectroscopy. The ionic conductivity, water absorption, swelling, mechanical properties, microphase structure and alkaline resistance of the membranes were systematically studied. The results show that the characteristic melting peak corresponding to the crystalline structure of the HSBS occured at about 90 ℃ and its mechanical properties and size stability were significantly improved compared with parent SBS. In particular, HSBS4402-OH has superior performance. Its ion exchange capacity(IEC), water absorption and swelling degree at 30 ℃ were 1.99 mmol/g, 27.65% and 5.12%, respectively. Its ionic conductivity achieved 86.8 mS/cm at 80 ℃. And the loss of its ionic conductivity was only 8.3% even as the membrane was immersed in 2 mol/L NaOH solution for 432 h at 60 ℃. Apparently, this method can produce promising AEMs for anion exchange membrane fuel cells.

Key words: anion-exchange membrane, poly(styrene-b-butadiene-b-styrene) copolymer, crystalline structures, microphase separation

孟繁志, 赵忠夫, 刘伟, 张春庆, 陈平, 白振民, 师悦. 高性能氢化星型聚(苯乙烯-b-丁二烯-b-苯乙烯)嵌段共聚物阴离子交换膜的制备、结构与性能[J]. 应用化学, 2019, 36(10): 1135-1146.

MENG Fanzhi, ZHAO Zhongfu, LIU Wei, ZHANG Chunqing, CHEN Ping, BAI Zhenmin, SHI Yue. Preparation, Structures and Properties of High-Performance Hydrogenated Star-Shaped Poly(styrene-b-butadiene-b-styrene) Copolymer-Based Anion Exchange Membrane[J]. Chinese Journal of Applied Chemistry, 2019, 36(10): 1135-1146.

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