高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (5): 1089-1095.doi: 10.7503/cjcu20180721

• 高分子化学 • 上一篇    下一篇

硅氧烷交联的咪唑基团功能化聚苯醚/聚四氟乙烯耐高温质子交换膜

任小蕊, 刘超, 李欢欢, 杨景帅(), 何荣桓   

  1. 东北大学理学院化学系, 沈阳 110819
  • 收稿日期:2018-10-23 出版日期:2019-03-29 发布日期:2019-03-29
  • 作者简介:

    联系人简介: 杨景帅, 男, 博士, 副教授, 主要从事功能膜材料的制备与性能研究. E-mail: yjs@mail.neu.edu.cn

  • 基金资助:
    国家自然科学基金(批准号: 51603031, 51572044)、 中央高校基本科研业务费研究项目(批准号: N160504006)和辽宁省自然科学基金(批准号: 20180550871)资助.

Siloxane Crosslinked Imidazolium PPO/PTFE Membranes for High Temperature Proton Exchange Membranes

REN Xiaorui, LIU Chao, LI Huanhuan, YANG Jingshuai*(), HE Ronghuan   

  1. Department of Chemistry, College of Sciences, Northeastern University, Shenyang 110819, China
  • Received:2018-10-23 Online:2019-03-29 Published:2019-03-29
  • Contact: YANG Jingshuai E-mail:yjs@mail.neu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.51603031, 51572044), the Fundamental Research Funds for the Central Universities of China(No.N160504006) and the Scientific Research Foundation of Liaoning Province, China(No.20180550871)

摘要:

以聚苯醚(PPO)为基体材料, 通过溴甲基化及咪唑基团功能化, 与聚四氟乙烯(PTFE)复合、 硅氧烷基团水解交联及磷酸掺杂, 制备了兼具高磷酸掺杂含量、 高质子电导率和良好机械性能的高温质子交换膜材料. 以甲基咪唑(MeIm)和咪唑基硅氧烷化合物(SiIm)为功能化试剂(其中咪唑基团提供了磷酸作用位点, 同时SiIm中的硅氧烷基团水解后得到Si—O—Si交联网络结构), 提高了膜材料的机械稳定性. 与PTFE的复合进一步增强了膜材料的机械强度. 结果表明, 复合膜具有较高的电导率和一定的机械强度. 当磷酸掺杂质量分数为242.5%时, PPO-50%SiIm-50%MeIm/PTFE复合膜在160 ℃不加湿条件下的电导率为0.09 S/cm, 室温下的断裂拉伸强度为3.6 MPa.

关键词: 高温质子交换膜, 聚苯醚, 聚四氟乙烯, 咪唑功能化, 硅氧烷交联

Abstract:

Based on poly(2,6-dimethyl-1,4-phenylene oxide)(PPO), novel high temperature proton exchange membranes were prepared with high phosphoric acid content, superior proton conductivity and excellent mechanical properties. Both methylimidazole(MeIm) and triethoxysilylpropyldihydroimidazole(SiIm) were used as functional reagents to graft the imidazolium groups onto the PPO polymer, in which the imidazolium group provided the phosphoric acid interaction sites. Meanwhile crosslinking of the modified PPO was achieved by forming a crosslinked silane network via the hydrolysis reaction of SiIm in an acidmedium. Moreover, porous poly(tetrafluoroethylene)(PTFE) was used as the membrane matrix toenhance the dimensional stabilities and mechanical strength of the fabricated membranes. Physicochemical properties of composite membranes with various crosslinking degrees were investigated accordingly. The results showed that the PPO-SiIm-MeIm/PTFE composite membranes possessed dense structure, superior thermal stability, improved chemical stability, high conductivity and suitable mechanical strength simultaneously. As an example, the PPO-50%SiIm-50%MeIm/PTFE membrane with a phosphoric acid doping content of 242.5% exhibited a conductivity of 0.09 S/cm at 160 ℃ under no humidification conditions, and a tensile strength of 3.6 MPa at room temperature. The results indicate that PPO-x%SiIm-y%MeIm/PTFE membranes have the potential to be used as HT-PEMs.

Key words: High temperature proton exchange membrane, Poly(2, 6-dimethyl-1, 4-phenylene oxide), Porous poly(tetrafluoroethylene), Imidazolium functionalization, Siloxane crosslinking

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