含异构化萘环结构的热重排膜材料的制备及其气体分离性能  

Preparation and Gas Separation Performance of Thermally Rearranged Membranes Containing Isomerized Naphthalene Ring Structures

作　　者：魏鲁鹏 鲁云华[1] 姜宗岭 肖国勇[1] 李琳[2] 王同华[2] LupengWei;Yunhua Lu;Zongling Jiang;Guoyong Xiao;Lin Li;TonghuaWang(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]大连理工大学化学工程学院,辽宁大连116024

出　　处：《高分子材料科学与工程》2024年第7期136-144,共9页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(22278051,21878033);辽宁省教育厅项目(LJKMZ20220659)。

摘　　要：首先,合成了2种新型含萘环结构的异构化二胺单体1,5-双(4-氨基-5-羟基苯氧基)萘(NDBAP)和1,6-双(4-氨基-5-羟基苯氧基)萘(NDBPA),然后分别与3种二酐单体进行溶液聚合,经热酰亚胺化及450℃热处理制备出6种聚酰亚胺(PI)膜和相应的热重排(TR)膜。研究表明,6种PI膜的热性能优异,玻璃化转变温度在350℃附近。经过热重排处理后,TR膜的气体分离性能显著提高。其中,TR(NDBAP-6FDA)对H_(2),CO_(2),O_(2)和N_(2)的渗透系数分别为268.4Barrer,249.3 Barrer,56.78 Barrer和7.87 Barrer,CO_(2)/N_(2),O_(2)/N_(2)和H_(2)/N_(2)的理想选择性分别为31.67,7.21和34.1,O_(2)/N_(2)超过2008年Robeson上限。而TR(NDBPA-6FDA)对H_(2),CO_(2),O_(2)和N_(2)的渗透系数分别为220.4 Barrer,210.32 Barrer,32.34 Barrer和5.62 Barrer,CO_(2)/N_(2),O_(2)/N_(2)和H_(2)/N_(2)的选择性分别为37.42,5.75和39.22,O_(2)/N_(2)接近2008年Robeson上限。因此,1,5取代的NDBAP比1,6取代的NDBPA可以更加有效地提高TR膜的气体分离性能。Two kinds of novel diamine monomers containing naphthalene rings,1,5-bis(4-amino-5-hydroxyphenoxy)naphthalene(NDBAP)and 1,6-bis(4-amino-5-hydroxyphenoxy)naphthalene(NDBPA)were firstly synthesized.Then,six kinds of polyimide(PI)membranes and the corresponding thermally rearranged(TR)membranes were separately prepared by the solution polymerization of the two diamines and three kinds of dianhydrides,followed by thermal imidization and further thermal treatment at 450℃.The testing results show that the obtained six kinds of PI membranes exhibit excellent thermal properties,with higher glass transition temperatures around 350℃.After further thermal treatment,the gas separation performance of the TR membranes is significantly improved compared to the original PI membrane.The gas permeability coefficients of the TR(NDBAP-6FDA)for H_(2),CO_(2),O_(2),and N_(2) are 268.4 Barrer,249.32 Barrer,56.7 Barrer and 7.87 Barrer,respectively.The ideal selectivities of CO_(2)/N_(2),O_(2)/N_(2) and H_(2)/N_(2) are 31.67,7.21 and 34.1 respectively,beyond 2008 Robeson upper limit of O_(2)/N_(2).However,the H_(2),CO_(2),O_(2) and N_(2) permeabilities of the TR(NDBPA-6FDA)are 220.4 Barrer,210.32 Barrer,32.34 Barrer and 5.62 Barrer.The selectivities of CO_(2)/N_(2),O_(2)/N_(2) and H_(2)/N_(2) reach 37.42,5.75 and 39.22 respectively,close to 2008 Robeson upper limit of O_(2)/N_(2).Therefore,1,5-substituted NDBAP can increase the gas permeabilities of the TR membranes more effectively than 1,6-substituted NDBPA.

关 键 词：萘环 聚酰亚胺 热重排膜 气体分离 异构化 

分 类 号：TQ051.893[化学工程]