自具微孔聚合物PIM-1膜在气体分离领域的研究进展

doi:10.16085/j.issn.1000-6613.2020-2061

摘要/Abstract

摘要：

PIM-1由自身扭曲且刚性的单体组成，具有比表面积高、热稳定性好和结构简单等优点，是最具代表性的一种自具微孔聚合物。与传统有机聚合物膜相比，PIM-1膜可表现出极高的气体渗透性，在气体分离领域展现出巨大的研究价值与应用潜力。因此概括并总结PIM-1膜在气体分离领域的研究进展，同时梳理制约PIM-1膜的发展的关键问题及解决策略十分有必要。本文首先概述了气体分离膜的性能指标及气体在膜内的传递模型，重点总结了近二十年来PIM-1膜在气体分离中的主要研究进展，包括纯PIM-1膜、改性PIM-1膜和PIM-1混合基质膜的设计制备及气体分离性能，并分析了不同改性方法和制膜策略对膜气体分离性能的影响以及膜内结构与性能之间的关系。最后，文章对PIM-1膜在实现工业应用前亟待解决的问题以及未来的研究重点进行了总结和展望，如继续致力于PIM-1膜对气体的渗透选择性提高，同时加强膜稳定性与超薄化的研究。

关键词: 自具微孔聚合物, PIM-1, 膜, 气体分离

Abstract:

PIM-1(polymers of intrinsic micro-porosity) constructed by rigid and contorted component monomers has the characteristics of high surface area, good thermal stability and solvent treatability and is one of the most studied polymers of intrinsic micro-porosity. When compared with traditional polymer membrane, PIM-1 has extremely high gas permeability for molecules, making PIM-1 membrane a promising research value and application prospect in the field of gas separation. Therefore, it is necessary to summarize the current research progress and discuss the key problems restricting the development of PIM-1 membrane and their solutions. In this review, the performance index of gas separation membrane and the gas transfer model in the membrane were summarized firstly, and the main research progress of PIM-1 membrane of gas separation in the past two decades was summarized emphatically, including the progress in pure PIM-1 membrane and modified PIM-1 membranes and PIM-1 mixed matrix membranes. Simultaneously, the influence of diverse modification techniques on PIM-1 and the structure-property relationship was analyzed. Finally, the future research focus of PIM-1 membrane and the problems that needed to be solved before realizing industrial application was intensively discussed, such as to study on improving the permselectivity of PIM-1 membranes and strengthening the membrane stability and thinness.

Key words: polymers of intrinsic micro-porosity, PIM-1, membranes, gas separation

中图分类号:

TQ028.8

郭海燕, 彭东来, 冯孝权, 金业豪, 田志红, 王景, 张亚涛. 自具微孔聚合物PIM-1膜在气体分离领域的研究进展[J]. 化工进展, 2021, 40(10): 5577-5589.

GUO Haiyan, PENG Donglai, FENG Xiaoquan, JIN Yehao, TIAN Zhihong, WANG Jing, ZHANG Yatao. Progress in the membranes of polymers of intrinsic micro-porosity PIM-1 for gas separation[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5577-5589.

图/表 12

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膜类型	渗透性（P_i）/cm³（STP）·cm^-3·（cmHg）^-1							选择性（ɑ_i/j=P_i/P_j）
膜类型	H₂	CO₂	O₂	CH₄	N₂	C₃H₆	C₃H₈	H₂/N₂	O₂/N₂	CO₂/CH₄	CO₂/N₂	C₃H₆/C₃H₈
纤维素-2.45^{［36， 40］}	12	4.8	0.82	0.15	0.15	15.2	5.8	80	5.5	32	32	2.6
聚砜^{［36， 40］}	14	5.6	1.4	0.25	0.25	25.0	17.8	56	5.6	22.4	22.4	1.4
聚苯醚^［41-42］	—	90	16.7	5.4	3.7	9	2.1	—	4.5	16.7	24.3	4.3
聚酰亚胺^［43-44］	480	653	131	25.3	39.1	30	2.7	12.3	3.4	25.8	16.7	11
聚醚酰胺-1657^［45］	—	55.8	4.7	3.1	1.4	—	—	—	3.4	18	39.8	—
自聚微孔聚合物-1^{［8， 32］}	1300	2300	370	125	92	1575	205	14.1	4.0	18.4	25	7.7

膜类型	渗透性（P_i）/cm³（STP）·cm^-3·（cmHg）^-1							选择性（ɑ_i/j=P_i/P_j）
膜类型	H₂	CO₂	O₂	CH₄	N₂	C₃H₆	C₃H₈	H₂/N₂	O₂/N₂	CO₂/CH₄	CO₂/N₂	C₃H₆/C₃H₈
纤维素-2.45^{［36， 40］}	12	4.8	0.82	0.15	0.15	15.2	5.8	80	5.5	32	32	2.6
聚砜^{［36， 40］}	14	5.6	1.4	0.25	0.25	25.0	17.8	56	5.6	22.4	22.4	1.4
聚苯醚^［41-42］	—	90	16.7	5.4	3.7	9	2.1	—	4.5	16.7	24.3	4.3
聚酰亚胺^［43-44］	480	653	131	25.3	39.1	30	2.7	12.3	3.4	25.8	16.7	11
聚醚酰胺-1657^［45］	—	55.8	4.7	3.1	1.4	—	—	—	3.4	18	39.8	—
自聚微孔聚合物-1^{［8， 32］}	1300	2300	370	125	92	1575	205	14.1	4.0	18.4	25	7.7

分子量（M_w） /g·mol^-1	溶剂	后处理方式	测试条件	气体渗透系数（P）/cm³（STP）·cm^-3·（cmHg）^-1				参考文献
分子量（M_w） /g·mol^-1	溶剂	后处理方式	测试条件	O₂	N₂	CH₄	CO₂	参考文献
—	四氢呋喃	—	30℃	370	92	125	2300	［8］
100000	二氯甲烷	—	35℃，4atm	786	238	360	3496	［49］
66674	二氯甲烷	120℃真空	35℃，3.5atm	712	166	204	3375	［50］
—	氯仿	80℃真空	25℃，1atm	969	252	320	5303	［32］
370000	氯仿	室温真空	25℃，1atm	580	180	310	4390	［9］
370000	氯仿	与水接触后室温真空	25℃，1atm	150	45	114	1550	［9］
370000	氯仿	甲醇浸泡后室温真空	25℃，1atm	1610	500	740	12600	［9］

分子量（M_w） /g·mol^-1	溶剂	后处理方式	测试条件	气体渗透系数（P）/cm³（STP）·cm^-3·（cmHg）^-1				参考文献
分子量（M_w） /g·mol^-1	溶剂	后处理方式	测试条件	O₂	N₂	CH₄	CO₂	参考文献
—	四氢呋喃	—	30℃	370	92	125	2300	［8］
100000	二氯甲烷	—	35℃，4atm	786	238	360	3496	［49］
66674	二氯甲烷	120℃真空	35℃，3.5atm	712	166	204	3375	［50］
—	氯仿	80℃真空	25℃，1atm	969	252	320	5303	［32］
370000	氯仿	室温真空	25℃，1atm	580	180	310	4390	［9］
370000	氯仿	与水接触后室温真空	25℃，1atm	150	45	114	1550	［9］
370000	氯仿	甲醇浸泡后室温真空	25℃，1atm	1610	500	740	12600	［9］

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