Tertiary-Amine-Functional Poly(arylene ether)s for Acid-Gas Separations

IF 8.5 Q1 CHEMISTRY, MULTIDISCIPLINARY JACS Au Pub Date : 2024-10-02 DOI:10.1021/jacsau.4c0048910.1021/jacsau.4c00489

Pablo A. Dean, Yifan Wu, Sheng Guo, Timothy M. Swager* and Zachary P. Smith*,

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Abstract

Competitive sorption enables the emergent phenomenon of enhanced CO₂-based selectivities for gas separation membranes when using microporous polymers with primary amines. However, strong secondary forces in these polymers through hydrogen bonding results in low solvent solubility, precluding standard solution processing approaches to form these polymers into membrane films. Herein, we circumvent these manufacturing constraints while maintaining competitive-sorption enhancements by synthesizing eight representative microporous poly(arylene ether)s (PAEs) with tertiary amines. High-pressure H₂S, CO₂, and CH₄ sorption isotherms were collected for these samples to demonstrate enhanced affinity for acid gases relative to the unfunctional control polymer. Although competitive sorption was observed for all samples, improvements were less pronounced than for primary-amine-functional analogs. For H₂S-based separations, the benefits of competitive sorption offset decreases in selectivity due to plasticization. This detailed study helps to elucidate the role of tertiary amines for acid gas separations in solution-processable microporous PAEs.

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用于酸气分离的叔胺官能团聚芳基醚

当使用带有伯胺的微孔聚合物时，竞争性吸附可使气体分离膜的二氧化碳选择性得到增强。然而，这些聚合物中通过氢键产生的强大次生力导致其溶剂溶解度较低，因此无法采用标准溶液加工方法将这些聚合物制成膜。在此，我们通过合成八种具有代表性的微孔聚芳基醚（PAE）与叔胺，在保持有竞争力的吸附增强效果的同时，规避了这些生产限制。收集了这些样品的高压 H2S、CO2 和 CH4 吸附等温线，以证明相对于无功能对照聚合物，它们对酸性气体的亲和力有所增强。虽然在所有样品中都观察到了竞争性吸附，但与伯胺功能类似物相比，其吸附性的改善并不明显。对于基于 H2S 的分离，竞争吸附的优势抵消了塑化导致的选择性下降。这项详细研究有助于阐明叔胺在可溶液加工的微孔聚醚中分离酸性气体的作用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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