膜科学与技术

含氟三苯二胺结构强化聚酰亚胺气体渗透性

作者：王汉利¹，²，阮雪华¹，代岩¹，贺高红¹，单体美²，王磊¹，²，孟祥青²，许国锋²

单位： 1.大连理工大学精细化工国家重点实验室，膜科学与技术研发中心，石油与化学工程学院，辽宁省石化行业高效节能分离技术工程实验室，盘锦 124221； 2.山东华夏神舟新材料有限公司,山东东岳集团含氟功能膜国家重点实验室，淄博 255000

关键词：结构设计；含氟聚酰亚胺；气体渗透性；分子模拟

DOI号：

分类号： TQ028.3

出版年,卷(期):页码： 2018,38(6):34-40

摘要：

在玻璃态聚合物中引入立体侧基，能够降低主链堆叠、增加自由体积，提高聚合物的气体渗透性。本文提出利用立体结构的六氟三苯二胺（BABTFMM），同六氟二酐(6FDA)进行缩聚制备具有高气体渗透性的含氟聚酰亚胺，采用巨正则蒙特卡罗(GCMC)和分子动力学(MD)方法预测了其气体渗透分离性能。分子模拟结果表明，二胺单体中的六氟二甲苯侧基，通过空间位阻和主链构型限制，增加了含氟聚酰亚胺的主链间距，降低了堆积密度、增加了自由体积，可以提高含氟聚酰亚胺的气体渗透性。制备了6FDA-BABTFMM和6FDA-ODA两种含氟聚酰亚胺的均质膜进行气体渗透性能测试。结果表明，气体渗透性能测试结果同分子模拟结果一致，6FDA-BABTFMM较6FDA-ODA型聚酰亚胺的渗透性大幅增加，O2、N2、CH4和CO2渗透速率分别为75.2、20.5、17.2、311.3 Barrer。

The incorporation of stereo side groups in the glassy polymer is an effective method to reduce the accumulation of the main chain, increase the free volume, and increase the gas permeability of the polymer. In this paper, the hexafluorotriphenylenediamine(BABTFMM) with tri-dimensional structure was polycondensed with hexafluoro dianhydride (6FDA) to prepare polyimides with high gas permeabilities, and using Grand Canonical Monte Carlo and molecular dynamics methods to predict its gas permeation separation performance. Homogeneous membranes were prepared for experimental test. The results of molecular simulations show that the hexafluoroxylene side groups in the diamine monomer is useful to increase the main chain spacing of the polyimide, reduce the packing density, and increase the free volume by the effect of steric hindrance and main chain configuration restriction, as a result, the gas permeability of 6FDA-BABTFMM polyimides is improved. Homogenous films of 6FDA-BABTFMM and 6FDA-ODA fluorine-containing polyimide were prepared for gas permeability test. The gas permeation performance test results are consistent with those of the molecular simulation. The permeability of 6FDA-BABTFMM is significantly higher than that of 6FDA-ODA polyimide, and the permeation rates of oxygen, nitrogen, methane, and carbon dioxide are 75.2, 20.5, 17.2, 311.3 bar, respectively.

基金项目：

国家自然科学基金青年基金（21606035, 21706023）；中国博士后科学基金资助项目（2018M631167）

作者简介：

第一作者简介：王汉利（1974-），男，山东滨州博兴人，博士研究生，高级工程师，主要研究方向为含氟膜材料制备及气体膜分离，Email：whl7327@126.com；　通讯作者，Email：hgaohong@dlut.edu.cn

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