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过程工程学报 ›› 2021, Vol. 21 ›› Issue (1): 100-107.DOI: 10.12034/j.issn.1009-606X.220054

• 材料工程 • 上一篇    下一篇

高离子电导率及CO2渗透性聚三唑盐薄膜的制备及性能

付 超1, 王秀云2, 万里强1*, 韩心悦1, 王琳晓1, 方建维1, 黄发荣1   

  1. 1. 特种功能高分子材料及相关技术教育部重点实验室,华东理工大学材料科学与工程学院,上海 200237 2. 西安航天复合材料研究所,陕西 西安 710025
  • 收稿日期:2020-02-20 修回日期:2020-03-29 出版日期:2021-01-22 发布日期:2021-01-21
  • 通讯作者: 万里强

Preparation and performance of the 1,2,3-triazolium-based membranes with high ionic conductivity and CO2 permeability

Chao FU1, Xiuyun WANG2, Liqiang WAN1*, Xinyue HAN1, Linxiao WANG1, Jianwei FANG1, Farong HUANG1   

  1. 1. Key Laboratory of Specially Functional Polymeric Materials and Related Technology (Ministry of Education), School of Material Science and Engineering, East China University of Science and Technology, Shanghai 200237, China 2. Xi?an Aerospace Composite Materials Institute, Xi?an, Shaanxi 710025, China
  • Received:2020-02-20 Revised:2020-03-29 Online:2021-01-22 Published:2021-01-21

摘要: 通过叠氮化合物和炔基化合物之间的Huisgen反应,结合烷基化和离子置换反应,制备了具有高离子电导率及高CO2渗透性能的新型交联型聚三唑盐薄膜。首先合成了端炔基聚四氢呋喃(DPPTMEG),利用其与双酚A二炔丙基醚(BADPE)及联苯二苄叠氮(DAMDB)间的Huisgen反应及后续的烷基化和阴离子置换反应制得新型交联型聚三唑盐薄膜。通过核磁共振磁波谱(NMR)、宽频介电阻抗仪(BDS)、动态热机械分析(DMA)、气体渗透装置、热失重分析(TGA)、拉力机对制得的交联型聚三唑盐薄膜的结构、热性能、力学性能、离子导电性和CO2/N2的渗透性进行研究。结果表明,此交联型聚三唑盐薄膜有着优异的离子导电性能,在30℃的直流电导率最高可达2.94×105 S/cm;同时,CO2渗透系数最高可达到550.4 barrer;不同配比的聚三唑盐薄膜的Td10变化不明显,而玻璃化转变温度Tg随双酚A二炔丙基醚含量的增加逐步上升。

关键词: DPPTMEG, 阴离子置换反应, 交联型聚三唑盐薄膜, 离子导电, CO2渗透

Abstract: The 1,2,3-triazole ring can be transformed into a 1,2,3-triazolium through the alkylation or protonation reaction. The research on the application of this novel poly(ionic liquid)s has only been valued recently even though 1,2,3-triazolium have been found long ago. 1,2,3-triazolium can be used in various fields. Compared with the linear triazolium cross-linked triazolium have rarely been reported. The special cross-linked structure makes the mechanical properties of cross-linked triazolium, better than linear triazolium. A series of novel cross-linked 1,2,3-triazolium-based membranes were prepared via 1,3-dipolar cycloaddition reaction between azides and alkynes along with N-alkylation and anion substitution reaction. Firstly, an alkynyl-terminated polytetramethylene ether glycol (DPPTMEG) was synthesized, and reacting with biphenyl dibenzyl azide (DAMDB) and bisphenol A dipropargyl ether (BADPE) along with alkylation and anion substitution reaction, the new kind of membranes were prepared. The structure of the cross-linked polytriazolium membranes were characterized by nuclear magnetic resonance (NMR). The thermal properties and mechanical properties of the cross-linked polytriazolium membranes were studied by dynamic mechanical thermal analysis (DMA), thermogravimetric analysis (TGA), and electronic universal testing machine. While the ionic conductivity and CO2/N2 permeability of the cross-linked polytriazolium membranes were measured by broadband dielectric spectroscopy (BDS) and isochoric gas permeation system. The results showed that the membranes had excellent ionic conductivity, the direct current conductivity at 30℃ up to 2.94×105 S/cm and CO2 permeability of up to 550.4 barrer. The Td10 of the 1,2,3-triazolium-based membranes with different formulations did not change significantly while the glass transition temperature (Tg) increased with the increase of the proportion of bisphenol A dipropargyl ether. The membranes showed great mechanical properties, the tensile strength would reach to 1.70 MPa and the elongation at break up to 136.8%.

Key words: DPPTMEG, anion substitution reaction, cross-linked 1,2,3-triazolium-based membranes, ionic conductivity, CO2 permeability