羧基化改性对PAN热交联膜孔结构及性能的影响  

Effect of carboxylation modification on pore structure and properties of PAN thermal crosslinking membrane

作　　者：陈放 王磊[2] 李琳[1] 张效露 荣跃飞 孙皓靖 张勇跃 王同华[1] CHEN Fang;WANG Lei;LI Lin;ZHANG Xiaolu;RONG Yuefei;SUN Haojing;ZHANG Yongyue;WANG Tonghua(State Key Laboratory of Fine Chemicals,Dalian Key Laboratory of Membrane Materials and Membrane Process,Group of Carbon Membranes and Porous Materials in Carbon Research Laboratory,School of Chemical Engineering,Dalian University of Technology,Dalian Liaoning 116024,China;School of Kinesiology and Health Promotion,Dalian University of Technology,Dalian Liaoning 116024,China)

机构地区：[1]大连理工大学化工学院,精细化工国家重点实验室,大连市膜材料与膜过程重点实验室,炭膜及多孔炭材料研究室,辽宁大连116024 [2]大连理工大学体育与健康学院,辽宁大连116024

出　　处：《化学工业与工程》2023年第3期48-54,共7页Chemical Industry and Engineering

基　　金：国家重点研发计划(2021YFB3801200);国家自然科学基金(21878033,21978034,22178044);中国博士后科学基金(2021M690516);中央高校基本科研业务费(DUT2021TD03);辽宁省兴辽英才计划(XLYC1908033);大连重点领域创新团队支持计划(2019RT10)资助。

摘　　要：作为热塑性材料,聚丙烯腈不对称膜在热交联的过程中会发生热熔融,导致孔融并。以非溶剂相转化(NIPS)法制备了聚丙烯腈基不对称(PAN)膜,采用NaOH碱性水解工艺,经过羧基化改性和热交联制得具有丰富海绵状孔及指状孔结构的羧基化PAN基热交联(H-TPAN)膜,研究了NaOH浓度对PAN及后处理膜结构与性能的影响。结果表明,羧基化对PAN膜进行改性处理,能够在热交联阶段促进氰基团环化和氧化反应,提高H-TPAN膜的交联程度,避免膜孔在高温下的热融并,保持PAN热交联膜通量。PAN膜在热交联过程中性能最优的羧基化条件为:NaOH浓度0.4 mol·L^(-1)、羧基化时间1 h、羧基化温度60℃。同时,羧基化改性膜表现出优异的热稳定性和良好的耐溶解性。As a thermoplastic material,polyacrylonitrile asymmetric membrane will undergo thermal melting in the process of thermal cross-linking,resulting in pore melting.In this paper,polyacrylonitrilebased asymmetric(PAN)membranes were prepared by non-solvent phase transformation(NIPS)method.Carboxylated PAN-based thermally crosslinked(H-TPAN)membranes with rich sponge and finger pores were prepared by NaOH alkaline hydrolysis process.The effects of NaOH concentration on the structure and properties of PAN and post-treated membranes were studied.The results show that the modification of PAN membrane by carboxylation can promote cyclization and oxidation of cyanide groups in the thermal crosslinking stage,improve the cross-linking degree of H-TPAN membrane,avoid the thermal fusion of membrane pores at high temperature,and maintain the flux of PAN thermal crosslinking membrane.The best carboxylation conditions of PAN membrane in the process of thermal crosslinking are as follows:NaOH concentration 0.4 mol·L^(-1),carboxylation time 1 h,carboxylation temperature 60℃.At the same time,the carboxylated modified membrane showed excellent thermal stability and good solubility resistance.

关 键 词：聚丙烯腈 热交联 孔结构 羧基化 

分 类 号：TQ028.8[化学工程]