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第 36 卷第 1 期 精 细 化 工 Vol.36, No.1
201 9 年 1 月 FINE CHEMICALS Jan. 2019

有机电化学与工业
纳米 TiO 增强阴离子导电膜中碱性离子液体稳定性
2

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韩 旭，王吉林 ，王璐璐，封瑞江，赵崇峰
（辽宁石油化工大学 化学化工与环境学部 石油化工学院，辽宁 抚顺 113001）

摘要：以 N-甲基吡咯为原料，通过两步法合成碱性甲基吡咯烷离子液体（[DMPy]OH）。通过物理掺杂方式在聚
乙烯醇（PVA）膜基质中引入碱性离子液体[DMPy]OH 和纳米二氧化钛（Nano-TiO 2 ），然后引入戊二醛（GA）
交联 PVA，制得 PVA-[DMPy][OH]-TiO 2 复合膜。借助 X 射线衍射（XRD）和 Mapping（元素分析）测试证实了
Nano-TiO 2 和[DMPy]OH 间自组装作用的存在。对复合膜的机械性能、热稳定性能、电导率、耐碱性等指标进行
了测试。结果表明，该系列复合膜形貌平整、均一；当离子液体质量分数为 25%、Nano-TiO 2 质量分数为 1%、
80 ℃时，PVA-[DMPy][OH]-TiO 2 复合膜的电导率(σ)为 2.78×10 3 S/cm，室温下水中浸渍 12 h 后，离子液体流
失率为 23.2%；与未添加 Nano-TiO 2 的 PVA-[DMPy][OH]膜相比，80 ℃时电导率提高了 19.3%，室温下离子液
体流失率降幅约 34.3%；室温下，3 mol/L KOH 水溶液中耐碱性测试 120 h 后，电导率和初始值相比并无明显变
化，具有优异的耐碱稳定性。热稳定性测试结果表明，该膜分解温度高于 200 ℃，具有良好的热稳定性。
关键词：膜；聚乙烯醇；离子液体；纳米二氧化钛；电导率；有机电化学与工业
中图分类号：TQ517.4 文献标识码：A 文章编号：1003-5214 (2019) 01-0129-07

Stabilization of Alkaline Ionic Liquids in Anion-Conducting
Membranes Reinforced by Nano-TiO 2

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HAN Xu, WANG Ji-lin , WANG Lu-lu, FENG Rui-jiang, ZHAO Chong-feng
（School of Petroleum and Chemical Technology, College of Chemistry, Chemical Engineering and Environmental
Engineering, Liaoning Shihua University, Fushun 113001, Liaoning, China）

Abstract: A new pyrrolidonium ionic liquid ([DMPy]OH) was synthesized with 1-methylpyrrolidine as a
raw material via two-step method. Subsequently, [DMPy]OH and nano titanium dioxide (Nano-TiO 2) were
introduced into polyvinyl alcohol (PVA) as matrix by physical doping, and then glutaraldehyde (GA) was
used to cross-link PVA to obtain PVA-[DMPy] [OH]-TiO 2 composite membrane. The existence of self-
assembly between Nano-TiO 2 and [DMPy]OH was confirmed by X-ray diffraction (XRD) and Mapping.
The mechanical properties, thermal stability, conductivity, alkali resistance, and other properties of the
composite membrane were also tested. The result indicated that the morphology of PVA-[DMPy]OH]-TiO 2
composite membrane was uniform. When the mass fraction of [DMPy]OH and Nano-TiO 2 was 25% and 1%,
respectively, the prepared PVA-[DMPy][OH]-TiO 2 composite membrane had a conductivity of 2.78×
3
10 S/cm at 80 ℃. After the PVA-[DMPy][OH]-TiO 2 composite membrane was immersed in water for 12 h
at room temperature, its ionic liquid loss rate was 23.2%. Compared with the PVA-[DMPy][OH] composite
membrane without Nano-TiO 2 addition, the conductivity of PVA-[DMPy][OH]-TiO 2 composite membrane
increased by 19.3% at 80 ℃, and the loss rate of ionic liquid decreased by 34.3% at room temperature. No
obvious variety in conductivity was observed for the composite membrane after immersing in 3 mol/L KOH
aqueous solution at room temperature, showing that the composite membrane had excellent alkali stability.
TGA analysis revealed that this composite membrane exhibited good thermal stability, its initial
decomposition temperature was higher than 200 ℃.

收稿日期：2018-01-30; 定用日期：2018-08-07; DOI: 10.13550/j.jxhg.20180088
基金项目：辽宁省科技厅博士启动项目（20141126）；辽宁省教育厅科学研究一般项目（L2013153）；抚顺市科学技术发展资金计划项
目（20141115）；辽宁石油化工大学博士启动基金（2013XJJ-006）；辽宁石油化工大学国家级科研项目培育项目
作者简介：韩 旭（1990—），男，硕士生。联系人：王吉林（1978—），男，副教授，E-mail：wangjilin1978@163.com。