化学学报 ›› 2009, Vol. 67 ›› Issue (9): 1013-1018. 上一篇    下一篇

研究论文

新型磺化聚酰亚胺膜的合成与表征

赵 亮 黄玉东* 朴艳梅 孟祥丽 宋元军 龙 军

  

  1. (哈尔滨工业大学应用化学系 哈尔滨 150001)

  • 收稿日期:2008-07-26 修回日期:2008-11-18 出版日期:2009-05-14 发布日期:2009-05-14
  • 通讯作者: 黄玉东

Synthesis and Characterization of Novel Sulfonated Polyimide Membranes

Zhao, Liang Huang, Yudong* Piao, Yanmei Meng, Xiangli
Song, Yuanjun Long, Jun
  

  1. (Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001)
  • Received:2008-07-26 Revised:2008-11-18 Online:2009-05-14 Published:2009-05-14
  • Contact: Huang, Yudong

合成了4,4’-二(间氨基苯氧基)联苯-3,3’-二磺酸(mBAPBDS)单体, 采用红外光谱和核磁共振等方法对其结构进行了表征. 使用mBAPBDS, 2-(对胺基苯基)苯并噁唑-5-胺(APBA)和1,4,5,8-萘四甲酸二酐(NTDA)共聚合成了含有噁唑结构的新型磺化聚酰亚胺(NTDA-mBAPBDS/APBA), 通过控制磺化二胺与非磺化二胺的比例来控制磺化程度. NTDA-mBAPBDS/APBA共聚物表现出较好的溶解性、成膜性能和良好的热稳定性, 其磺酸基团分解温度高于300 ℃. 采用溶液浇铸法制备了磺化聚酰亚胺(SPIs)膜, 对膜的吸水率、溶胀度和质子电导率等性能进行了初步的研究. 结果表明, SPIs膜具有适当的吸水率和良好的尺寸稳定性, 其室温电导率在4.72×10-3和9.60×10-3 S/cm之间, 接近于相同条件下Nafion®117的电导率(9.80×10-3 S/cm).

关键词: 燃料电池, 磺化聚酰亚胺, 质子交换膜

The sulfonated diamine, 4,4’-bis(3-aminophenoxy)biphenyl-3,3’-disulfonic acid (mBAPBDS), was successfully synthesized and characterized by FT-IR and 1H NMR spectra. A series of new sulfonated polyimides (NTDA-mBAPBDS/APBA) containing a benzoxazole structure were synthesized from mBAPBDS, [5-amine-2-(4-aminophenyl)benzo[d](1,3)oxazol] (APBA) and 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) using a one-step high temperature polymerization method. The sulfonation degree of NTDA-mBAPBDS/APBA copolymers was controlled through varying the molar ratio of mBAPBDS to APBA. The results showed that the NTDA-mBAPBDS/APBA copolymers possessed good solubility and film processing property. TG analysis indicated that the SPI copolymers displayed good thermal stability with the decomposition temperature above 300 ℃. The SPI membranes were prepared by casting from the polymer solution, and their water uptake, swelling ratio and proton conductivity were also investigated, which displayed adequate water uptake and good dimensional stability. The proton conductivities of the SPI membranes were between 4.72×10-3~9.60×10-3 S/cm at room temperature, which was close to that of Nafion®117 membrane measured under the same condition (9.8×10-3 S/cm).

Key words: fuel cell, sulfonated polyimide, proton exchange membrane