聚酰亚胺气体分离膜的物理老化现象浅析

doi:10.16085/j.issn.1000-6613.2023-1010

摘要/Abstract

摘要：

气体分离膜技术是一项广受关注的新兴技术，芳香族聚酰亚胺是最具应用前景的气体分离膜材料之一。目前，学术界已对多种结构的聚酰亚胺进行了实验室规模的开发和研究，但在实际工业应用情境下，膜材料长期服役过程中的物理老化现象极大影响着气体分离性能的准确评估和工艺参数的合理设计。本文综述了当前针对聚酰亚胺类薄膜和非对称膜物理老化行为的研究现状，总结了前人提出的老化机理模型，分析了影响老化进程的主要因素，提出了物理老化的预防和改善方法。提出不易老化的气体分离膜用聚酰亚胺应具备的特质包括较强的分子链刚性、受限的链空间构型和合适的链间相互作用。未来相关研究的重点方向可能为聚酰亚胺新结构探索、交联剂开发、制备工艺优化等方面。

关键词: 聚酰亚胺, 气体, 分离, 膜, 物理老化, 自由体积, 模型

Abstract:

As an emerging technology, membrane-based gas separation has received widespread attention. Aromatic polyimide is one of the most promising materials for gas separation membranes. Currently, polyimide with various structures has been developed and researched on laboratory scales. However, in situations of industrial application, the physical aging phenomenon of membrane materials during long-term operation significantly affects the accurate evaluation of gas separation performance and the reasonable design of process parameters. The current research status of the physical aging behavior of polyimide thin films and asymmetric membranes was reviewed, the aging mechanism and models proposed by predecessors were summarized, the main factors affecting the aging process were analyzed and the prevention methods of physical aging were proposed. The characteristics of polyimide used for gas separation membranes that were not prone to aging included high molecular chain rigidity, limited chain space configuration, and appropriate inter-chain interactions. Future research was expected to focus on not only developing new structures of polyimides as well as crosslinking agents, but also preparation process optimization.

Key words: polyimide, gas, separation, membranes, physical aging, free volume, model

中图分类号:

TQ317.6

唐安琪, 魏昕, 丁黎明, 王玉杰, 徐一潇, 刘轶群. 聚酰亚胺气体分离膜的物理老化现象浅析[J]. 化工进展, 2024, 43(7): 3923-3933.

TANG Anqi, WEI Xin, DING Liming, WANG Yujie, XU Yixiao, LIU Yiqun. Discussing physical aging phenomenon of polyimide gas separation membranes[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3923-3933.

图/表 9

图1 聚酰亚胺结构通式

图2 玻璃态聚合物的焓/自由体积随温度变化[7]

图3 自由体积扩散和晶格收缩机理模型[17]

图4 6FDA-DAM和6FDA-mPDA的化学结构[24]

图5 蝶烯类单体的化学结构和内部自由体积（IFV）示意图[32]

图6 伪Tröger碱型聚酰亚胺分子结构[33]

图7 使用含氟单体6FpDA与不含氟单体DAM所合成两种聚酰亚胺的化学结构[14]

图8 聚酰亚胺结构中的电子供体和电子受体[39]

图9 使用对二甲苯二胺对聚酰亚胺交联改性的反应机理[46]

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