In this study, we explore the use of two kinds of inorganic molecular sieves, microporous MFI zeolite and mesoporous MCM-41 silica, as fillers to enhance the gas transport characteristics of thermally rearranged (TR) poly(hydroxyimides) (HPI). To the best of our knowledge, this is the first report on the use of these fillers to modify properties of TR HPIs, except for our previous research on MCM-41 filled HPIs based on BPADA dianhydride. In this work, 6FDA-HAB and BPADA-HAB varying in gas permeability and properties were selected as matrices for preparation of mixed matrix membranes (MMM) with the aim of studying the effect of both the kind of filler and a matrix on thermal rearrangement and properties of the resultant TR-MMMs. In addition to pure gas permeability measurements, HPIs and MMMs were examined by WAXD, SEM, TGA, DMA, and tensile tests before and after thermal rearrangement. For all MMM precursors, the permeability increased in proportion to the filler loading (e.g. by 1.2 to 4.4 times for O₂) while selectivity remained virtually the same. The same effect of improved permeability and maintained selectivity was observed for the series of TR-MMMs; for example, TR-MMM based on 6FDA and filled with 7 wt.% of MCM-41 exhibited 6.7 fold higher O₂ permeability over its filled precursor. The permeation properties of the filled membranes showed a strong dependence on both the kind of matrix and filler. The addition of MCM-41 particles to BPADA-HAB increased permeability more than the incorporation of the similar amount of MFI ones, while the contrary was true for 6FDA-HAB. The best result, comprising the position on the upper bound for He/N₂, has been achieved for 6FDA-HAB filled with 25 wt% of MFI, whereas its TR analogue showed the highest 20.4 fold permeability improvement.

在这项研究中，我们探索了使用两种无机分子筛（微孔MFI沸石和中孔MCM-41二氧化硅）作为填料来增强热重排（TR）聚（羟基酰亚胺）（HPI）的气体传输特性。据我们所知，这是关于使用这些填料来改性TR HPIs的第一份报告，除了我们以前对基于BPADA二酐的MCM-41填充HPIs的研究以外。在这项工作中，选择透气性和特性均不同的6FDA-HAB和BPADA-HAB作为制备混合基质膜（MMM）的基质，目的是研究填料和基质的种类对热重排和TR-MMM的特性。除了进行纯气体渗透率测量外，还通过WAXD，SEM，TGA，DMA，热重组前后的拉伸试验。对于所有MMM前体，磁导率与填料填充量成正比（例如，O的渗透率增加1.2至4.4倍₂），而选择性几乎保持不变。对于一系列TR-MMM，观察到了相同的提高渗透性和保持选择性的效果。例如，基于6FDA的TR-MMM填充了7 wt。％的MCM-41 ，其O ₂渗透性比填充的前体高6.7倍。填充膜的渗透性能显示出对基质和填料种类的强烈依赖性。向BPADA-HAB中添加MCM-41颗粒比掺入相似量的MFI颗粒增加通透性，而6FDA-HAB则相反。最佳结果，包括He / N ₂上限的位置对于填充有25 wt％MFI的6FDA-HAB，已经实现了，，而其TR类似物显示出最高的20.4倍通透性改善。