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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(Td5)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CO2渗透系数(PCO2)为351Barrer,CO2/CH4渗透选择性为27.9。
Abstract
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 [NTDA-BHPDAF/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,N-dimethykacetamide (DMAc),dimethyl sulfoxide (DMSO) and γ-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 (Td5)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 CO2 permeability coefficient (PCO2) of 351 Barrer and a selectivity of CO2 toward CH4 (PCO2/PCH4) of 27.9 at 35℃ and 202kPa.
关键词
六元环型聚酰亚胺
/
膜
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气体分离
Key words
six-membered ring polyimide
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membrane
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gas separation
基于圈形二胺的六元环聚酰亚胺共聚物膜的制备与气体分离性能研究[J].
化工新型材料, 2023, 51(3): 89-94 DOI:10.19817/j.cnki.issn1006-3536.2023.03.016
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基金资助
国家“973”计划项目(2014CB643600)
