花状聚酰亚胺/聚酰亚胺及其热重排混合基质膜的制备及其性能  

Preparation and properties of flower-like polyimide/polyimide and thermally rearranged mixed matrix membranes

作　　者：蔺家弘 肖国勇[1] 鲁云华[1] 侯蒙杰 李琳[2] 王同华[2] LIN Jiahong;XIAO Guoyong;LU Yunhua;HOU Mengjie;LI Lin;WANG Tonghua(College of Chemical Engineering,University of Science and Technology Liaoning,Anshan 114051,China;School of Chemical Engineering,Dalian University of Technology,Dalian 114024,China)

机构地区：[1]辽宁科技大学化学工程学院,鞍山114051 [2]大连理工大学化工学院,大连114024

出　　处：《复合材料学报》2025年第3期1313-1322,共10页Acta Materiae Compositae Sinica

基　　金：国家自然科学基金(22278051,21878033)。

摘　　要：混合基质膜(MMMs)由于制备方法简单,综合性能优异,在气体分离领域具有较强的竞争力。为提高填料与聚合物基体间的相容性,本文采用溶剂热法制备的花状聚酰亚胺(PI)为填料,以含羟基聚酰亚胺为基体,采用原位聚合法,经热酰亚胺化和热重排反应制备出了一系列花状聚酰亚胺/聚酰亚胺及其热重排(TR)混合基质膜。化学结构相似的聚酰亚胺填料和基体间形成了良好的界面相容性,赋予混合基质膜较为优异的气体分离性能。当花状PI的掺杂量为3wt%时,混合基质膜TR-3wt%的晶面间距达到0.64 nm,对H_(2)、CO_(2)、O_(2)、CH_(4)和N_(2)的气体渗透率相对于TR膜分别提高了61.36%、67.90%、81.58%、37.88%和51.72%,且O_(2)/N_(2)的选择性为5.49,接近2015年上限;CO_(2)/CH_(4)的选择性为22.36,超过2008年Robeson上限。因此,该策略将为高性能MMMs的界面设计工程提供一定参考。Mixed matrix membranes(MMMs)show strong competitiveness in the field of gas separation due to their simple preparation method and excellent comprehensive performance.In order to improve the compatibility between fillers and polymer matrix,a series of flower-like polyimide(PI)/polyimide and their thermally rearranged(TR)mixed matrix membranes were prepared by in situ polymerization method,using the flower-like polyimide synthesized from solvothermal method as fillers and the hydroxyl-containing polyimide as matrix,followed by thermal imidization and thermal rearrangement treatment.The polyimide filler and matrix can form better compatibility because of their similar chemical structures,and the mixed matrix membranes showed superior gas separation performance.When the doping content of the flower-like PI particles was 3wt%,the mixed matrix membrane TR-3wt%exhibited a d-spacing value of 0.64 nm,and the gas permeabilities of H_(2),CO_(2),O_(2),CH_(4) and N_(2) were respectively increased by 61.36%,67.90%,81.58%,37.88%,and 51.72%compared to the TR membrane.Moreover,the ideal selectivity of O_(2)/N_(2) was 5.49,close to the 2015 Upper Limit.The selectivity of CO_(2)/CH_(4) reached 22.36,exceeding the 2008 Robeson Upper Limit.Therefore,this design strategy will provide a certain reference for the interface design of MMMs.

关 键 词：混合基质膜 花状聚酰亚胺 热重排 气体分离 界面 

分 类 号：TQ323.7[化学工程—合成树脂塑料工业] TB332[一般工业技术—材料科学与工程]