膜科学与技术

磺化自聚微孔聚酰亚胺的制备及磺化度对其气体分离性能的影响

作者：刘清潭，储家琛，李建新，马小华

单位：天津工业大学材料科学与工程学院省部共建分离膜与膜过程国家重点实验室，天津300387

关键词：磺酸化；气体分离膜；聚酰亚胺；CO2/CH4分离

出版年,卷(期):页码： 2023,43(3):1-7

摘要：

研究了-SO3H基团的引入和不同磺化度对微孔聚酰亚胺气体分离膜的影响。区别于后磺化法，采用一步法使磺化单体2, 4, 6-三甲基二氨基苯磺酸（TrMSA）和非磺化单体2, 4, 6-三甲基-间苯二胺（DAM）与六氟二酐（6FDA）直接缩聚得到磺化聚酰亚胺（SPI），通过控制TrMSA和DAM的比例得到磺化度分别为25%，50%，75%与100%的聚合物。使用FT-IR、XRD、TGA、BET和气体渗透仪等手段研究不同磺化聚酰亚胺薄膜的化学结构、链段堆积结构、热性能、比表面和气体分离性能。结果显示，引入的-SO3H通过增强链间相互作用力，使得聚合物比表面积减小，以及链间距逐渐降低为0.57、0.52、0.47和0.42 nm，，所有气体的渗透性均随磺化度的升高而下降，然而CO2/CH4选择性在扩散系数的主导下则逐渐上升。当磺化度为75%时，磺化聚酰亚胺CO2 的透过率达到了 107 Barrer，CO2/CH4选择性为47.8，在压力高达2 MPa时仍保持在45，具有良好的抗塑化和气体分离性能。

In this study, a series of novel sulfonated polyimides is prepared by one-pot high temperature polymerization method. Different from the post-sulfonation method, the degree of sulfonation (DS) can be precisely regulated by varying the ratio of 2, 4, 6-trimethyl- diaminobenzenesulfonic acid (TrMSA) and 2, 4, 6-trimethyl-m-phenylenediamine (DAM). The sulfonation degree is controlled to be 25%, 50%, 75% and 100%. And the effect of DS on the gas separation performance was deeply investigated. The physical properties such as chemical structure, chain packing and thermal properties are systematically studied using FT-IR, XRD, TGA, BET, respectively. The results show that as the increment of -SO3H groups, the chain spacing decreases from 0.57, 0.52, 0.47 to 0.42 nm, due to the strong hydrogen bonding interaction of SO3H group. Consequently, the permeability of gases decreases with the increase of DS, while the selectivity of CO2/CH4 gradually increases from 30.8 to 75.4. Particularly, the sulfonated polyimide with DS of 75% displayed a high CO2/CH4 selectivity of 47.8 and remained barely unchanged when the pressure increased from 2 to 20 bar. In a word, our work provides a deep insight for preparation of novel sulfonated polyimides with high gas separation performance.

刘清潭（1997-），女，陕西西安人，硕士研究生，E-mail：liuqt1221@163.com

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