摘要
以2,7-二硝基-9-芴酮和苯酚作为原料,通过两步反应合成了一种含羟基的圈形二胺单体2,7-二氨基-9,9-双(4-羟苯基)芴(BHPDAF)。将其与9,9-双(4-氨基苯基)芴(BAPF)和1,4,5,8-萘四甲酸二酐(NTDA)在间甲酚中进行无规共聚,通过控制两种二胺单体之间的摩尔比(BHPDAF/BAPF=1/2,1/1,2/1)合成了三种具有不同羟基含量的新型六元环聚酰亚胺共聚物[NTDA-BHPDAF/BAPF(1/2,1/1,2/1)]。这些聚酰亚胺共聚物在间甲酚、1-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)、二甲亚砜(DMSO)和γ-丁内酯(GBL)等有机溶剂中具有良好的溶解性。用溶液浇铸法制得了具有良好力学性能的薄膜,其拉伸强度为59.6M~70.2MPa,断裂伸长率为16.8%~26.6%。热重分析结果表明,这些聚酰亚胺共聚物膜的5%热失重温度(T_(d5))均超过480℃。气体分离性能测试结果表明,共聚物膜均具有良好的气体分离性能。例如:NTDA-BHPDAF/BAPF(2/1)薄膜在35℃和202kPa(膜两侧压差)条件下的CO_(2)渗透系数(P_(CO_(2)))为351Barrer,CO_(2)/CH4渗透选择性为27.9。
A cardo-type diamine monomer with hydroxyl groups,2,7-diamino-9,9-bis(4-hydroxyphenyl)fluorene(BHPDAF),was synthesized from 2,7-dinitro-9-fluorenone and phenol via two-step reaction.The prepared BHPDAF was randomly copolymerized with 9,9-bis(4-aminophenyl)fluorene(BAPF)and 1,4,5,8-naphthalenetetracarboxylic dianhydride(NTDA)in m-cresol.By controlling the molar ratio between the two diamine monomers(BHPDAF/BAPF=1/2,1/1,2/1),three novel six-membered ring polyimide copolymers[NTDABHPDAF/BAPF(1/2,1/1,2/1)]with different hydroxyl group content were synthesized.These polyimide copolymers showed good solubility in some organic solvents such as m-cresol,1-methyl-2-pyrrolidone(NMP),N,Ndimethykacetamide(DMAc),dimethyl sulfoxide(DMSO)andγ-butyrolactone(GBL).Polyimide membranes with good mechanical properties were obtained by solution cast method.Their tensile strength ranged from 59.6MPa to 70.2MPa,and the elongation at break ranged from 16.8%to 26.6%.Thermogravimetric analysis results exhibited that the 5%thermal weight loss temperatures(T_(d5))of these polyimide copolymer membranes all exceeded 480℃.Gas separation performance test results revealed that these polyimide copolymer membranes all had good gas separation performance.NTDA-BHPDAF/BAPF(2/1),for example,presented a CO_(2) permeability coefficient(P_(CO_(2)))of 351 Barrer and a selectivity of CO_(2)toward CH4(PCO_(2)/PCH 4)of 27.9at 35℃and 202kPa.
作者
余静秋
吴小军
束长朋
王沁
余李歆玥
房建华
郭晓霞
Yu Jingqiu;Wu Xiaojun;Shu Changpeng;Wang Qin;Yu Lixinyue;Fang Jianhua;Guo Xiaoxia(School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240;Shanghai Institute of Aerospace System Engineering,Shanghai 201109;Shanghai Aerospace Equipment Manufacturing General Factory Co.,Ltd.,Shanghai 200245)
出处
《化工新型材料》
CAS
CSCD
北大核心
2023年第3期89-94,共6页
New Chemical Materials
基金
国家“973”计划项目(2014CB643600)。
关键词
六元环型聚酰亚胺
膜
气体分离
six-membered ring polyimide
membrane
gas separation
