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醇响应型智能膜的制备及其甲醇检测性能

作者：邓锡彬，谢锐，刘壮，汪伟，巨晓洁，褚良银

单位：四川大学化学工程学院，成都 610065

关键词：醇响应型智能膜；聚偏氟乙烯；甲醇检测；微球；亲水性

DOI号：

分类号： TQ028.8

出版年,卷(期):页码： 2024,44(2):8-18

摘要：

采用沉淀聚合法制备了不同亲水性的聚N-正丙基丙烯酰胺（PNN）、聚N-异丙基丙烯酰胺（PNI）和聚N-甲基异丙基丙烯酰胺（PNM）微球，通过物理共混和液体诱导相分离（LIPS）结合的方法将它们引入聚偏氟乙烯（PVDF）膜基材，成功制备了可在常温下检测甲醇体积分数的醇响应型智能膜。系统探究了微球的温度响应性和醇响应性，以及微球亲水特性对膜微观结构、表面化学成分的影响，并考察了膜在甲醇、乙醇及甲醇-乙醇混合溶液中的响应性能。结果表明，微球亲水性越强，醇响应型智能膜的厚度、孔径和孔隙率也显著增大。添加最亲水PNM微球的智能膜（PVDF/PNM）的膜厚、孔径、孔隙率达到最大值，分别为空白膜的2.4倍、4.7倍和5.9倍。膜的最大渗透率（Pmax）和醇临界响应体积分数受操作温度、醇溶液类型和微球亲水性的影响。PVDF/PNM膜的甲醇和乙醇响应性差异最大，在40 ºC下的临界甲醇响应体积分数（CM）和临界乙醇响应体积分数（CE）差值达到6.5%。常温25 ºC下，随着总醇体积分数为40 %的混合溶液中甲醇比例增大，膜渗透率与甲醇体积分数呈现良好的线性关系，可通过渗透率计算得到混合醇溶液中甲醇体积分数。上述研究结果为甲醇体积分数的便捷检测提供了一种新思路。

Poly(N-n-propylacrylamide) (PNN), poly(N-isopropylacrylamide) (PNI) and poly(N-isopropylmethacrylamide) (PNM) microspheres with different hydrophilicity were fabricated by precipitation polymerization. The alcohol-responsive membranes for methanol detection at room temperature were successfully prepared by physically blending such microspheres into polyvinylidene fluoride (PVDF) membrane materials followed by liquid induced phase separation (LIPS). The thermo-responsive and alcohol-responsive characteristics of microspheres, effect of hydrophilic properties of microspheres on the microstructure, surface chemical composition as well as the responsive properties of membranes in methanol, ethanol and methanol-ethanol mixed solutions were systematically investigated. The results show that the thickness, pore size and porosity of alcohol-responsive membranes increased significantly with the increase of hydrophilicity of microspheres. The thickness, pore size and porosity of the PVDF/PNM membranes blended with the most hydrophilic PNM microspheres reached to the maximum, were 2.4 times, 4.7 times and 5.9 times of those of the blank membranes, respectively. The maximal permeability (Pmax) and critical alcohol response volume fraction of membranes affected by the operation temperature, types of alcohol aqueous solution and the hydrophilicity of microspheres. The PVDF/PNM membranes show the largest variance in the responsivity of ethanol and methanol, and the difference in the critical methanol response volume fraction (CM) and critical ethanol response volume fraction (CE) at 40 ºC reached 6.5%. With the increase of the proportion of methanol in the mixed solution with total volume fraction of 40 % at 25 ºC, the membrane permeability showed a good linear relationship with the methanol volume fraction, and the methanol volume fraction in the mixed solution could be calculated by the permeability. These results provide a new idea for the facile detection of methanol volume fraction.

基金项目：

国家自然科学基金项目（21622604），四川省杰出青年科技人才项目（2019JDJQ0026）

作者简介：

邓锡彬（1998-），女，云南昭通人，硕士研究生，膜材料与膜过程，E-mail: dengxibin@stu.scu.edu.cn

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