Microporous Pentiptycene-Based Polymers with Heterocyclic Rings for High-Performance Gas Separation Membranes
Microporous Pentiptycene-Based Polymers with Heterocyclic Rings for High-Performance Gas Separation Membranes
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用于高性能气体分离膜的杂环微孔戊烯基聚合物
DOI：
10.1021/acs.chemmater.1c04212
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发表时间：
2022
影响因子：
8.6
通讯作者：
Guo, Ruilan
中科院分区：
文献类型：
--
作者：
Huang, Zihan;Yin, Claire;Corrado, Tanner;Li, Si;Zhang, Qinnan;Guo, Ruilan
微孔聚合物，如固有微孔聚合物（PIMs）和热重排聚合物（TR），在提高聚合物气体分离膜的性能以克服渗透性和选择性之间的权衡方面显示出了希望。在这项工作中，采用精心设计的热方案，以一种新的戊代烯基聚邻羟基亚胺（PPHI）前驱体为原料，制备了一系列热重排的戊代烯基聚苯并恶唑（PPBO）聚合物。通过综合考察中间处理温度和加热速率对膜微孔隙度、性能和气体分离性能的影响，建立了系列中基本的结构-性能关系。在本研究中，将大体积的pentitycene单元加入到TR PPBO结构中，以及优化的TR热方案，为PPBO的精细调整和最终最大化分离性能提供了一条途径，一些膜远远超过了2015年H2/ ch4和O2/N2的上限。在CO2/CH4混合气体渗透试验中，PPBO膜在高达6.6 atm的CO2分压下表现出优异的抗塑化性能，远远超过2008年CO2/CH4混合气体的上限。5个月老化PPBO膜的分离性能高于2008年O2/ n2上限和2015年H2/ ch4上限，表明PPBO具有优异的耐老化性能。
Microporous polymers, such as polymers of intrinsic microporosity (PIMs) and thermally rearranged (TR) polymers, have shown promise in advancing the performance of polymer gas separation membranes to overcome the permeability–selectivity trade-off. In this work, a series of thermally rearranged pentiptycene-based polybenzoxazole (PPBO) polymers were prepared from a new pentiptycene-based poly(o-hydroxyl imide) (PPHI) precursor using carefully designed thermal protocols. Fundamental structure–property relationships within the series were established by comprehensively examining the effects of intermediate treatment temperature and the heating rate on the membrane microporosity, properties, and gas separation performance. The incorporation of bulky pentiptycene units into TR PPBO structures, along with optimized TR thermal protocols in this study, provided a route to finely tune and eventually maximize the separation performance of PPBOs, with several films far exceeding the 2015 upper bound for H2/CH4and O2/N2. In CO2/CH4mixed-gas permeation tests, PPBO membranes showed excellent resistance to plasticization under CO2partial pressure as high as 6.6 atm, far surpassing the 2008 mixed-gas upper bound for CO2/CH4. Moreover, a 5 month aged PPBO film maintained its superior separation performance above the 2008 O2/N2upper bound and 2015 H2/CH4upper bound, indicating the excellent aging resistance of PPBOs.