具有交联结构的热重排聚合物膜的制备及气体分离性能  

Preparation and Gas Separation Properties of Thermally Rearranged Polymer Membranes with Crosslinking Structure

作　　者：贺磊 鲁云华[1] 张兼华 侯蒙杰 肖国勇[1] 胡知之[1] 王同华[2] Lei He;Yunhua Lu;Jianhua Zhang;Mengjie Hou;Guoyong Xiao;Zhizhi Hu;Tonghua Wang(School of Chemical Engineering,University of Science and Technology Liaoning,Anshan 114051,China;School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China)

机构地区：[1]辽宁科技大学化学工程学院,辽宁鞍山114051 [2]大连理工大学化工学院,辽宁大连116024

出　　处：《高分子材料科学与工程》2022年第5期1-8,共8页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(21878033);辽宁科技大学青年骨干项目(601011507-17)。

摘　　要：采用不同摩尔比的9,9’-双[4-(4-硝基-3-羟基苯氧基)苯基]芴(BAHPPF)、3,5-二氨基苯甲酸(DABA)与六氟二酐(6FDA)进行共聚,再经热处理后得到一系列聚酰亚胺(PI)膜和具有交联结构的热重排(TR)聚合物膜。结果表明,随着热处理温度升高,热重排和交联反应同时发生,显著提高了层间距和膜材料对5种气体的渗透性。此外,随着DABA摩尔比增加,PI膜的玻璃化转变温度(T_(g))和热分解温度稍有提升;同时,TR膜材料对H_(2),CO_(2),N_(2),O_(2)和CH_(4)的渗透性和理想选择性也获得了提高。其中,TR-7:3膜表现出了最高的气体渗透性,对H_(2),CO_(2),O_(2),N_(2)和CH_(4)的渗透性分别达到了320.9 Barrers,369.7 Barrers,54.3 Barrers,15.0 Barrers和11 Barrers;同时,TR-7:3和TR-6:4膜对CO_(2)/CH_(4)的理想选择性为33.6和40.6,接近2008年的Robeson上限;而TR-9:1和TR-8:2膜对O_(2)/N_(2)的分离性能则超过了2008年的上限。9,9’-bis[4-(4-nitro-3-hydroxyphenoxy)phenyl]fluorine(BAHPPF)and 3,5-diaminobenzoic acid(DABA)with different mole ratios were copolymerized with hexafluorodicarboxylic anhydride(6FDA).After heat treatment,a series of polyimide(PI)and thermal rearrangement(TR)polymer membranes with cross-linked structure were obtained.The experimental results show that with the increase of thermal treatment temperature,the tensile strength and elongation at break of polymer membranes gradually decrease,but the gas permeabilities greatly increases.In addition,the glass transition temperature(T_(g))and thermal decomposition temperature of PI membranes are enhanced slightly with the increase of DABA mole ratio.At the same time,the permeabilities of TR membrane materials to H_(2),CO_(2),N_(2),O_(2)and CH_(4)are also improved.Among them,the TR-7:3 membrane shows the highest gas permeabilities including H_(2)of 320.9 Barrer,CO_(2)of 369.7 Barrer,O_(2)of 54.3 Barrer,N_(2)of 15.0 Barrer and CH_(4) of 11 barrer,respectively.At the same time,the CO_(2)/CH_(4)selectivities of TR-7:3 and TR-6:4 are 33.6 and 40.6,close to the 2008 Robeson upper bound.Moreover,the O_(2)/N_(2)separation properties of TR-9:1 and TR-8:2 exceed the 2008 Limit bound.

关 键 词：热重排聚合物 气体分离 交联 渗透性 选择性 

分 类 号：TQ051.893[化学工程]