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磺化侧苯基杂萘联苯聚芳醚腈酮膜材料的研究

作者：谭相坤，张守海，刘乾，王昭琪，蹇锡高

单位：大连理工大学化工学院，辽宁省高性能树脂工程技术研究中心，辽宁省高分子科学与工程重点实验室，大连市膜材料与膜过程重点实验室，大连 116024

关键词：二氮杂萘酮；聚芳醚腈酮；侧苯基；磺化；质子交换膜

DOI号：

分类号： TQ326.6

出版年,卷(期):页码： 2021,41(5):17-25

摘要：

以4-（4-羟基苯基）-2,3-二氮杂萘-1-酮、4-（3-苯基-4-羟基苯基）-2,3-二氮杂萘-1-酮、2,6-二氯苯腈、4,4´-二氟二苯酮为原料，通过溶液缩聚反应，合成了侧苯基杂萘联苯聚芳醚腈酮（PPENK-P），并对PPENK-P进行磺化改性，制备含有苯磺酸侧基的杂萘联苯聚芳醚腈酮（SPPENK-P）。采用溶液浇铸法制备了SPPENK-P质子交换膜，并对其吸水率、溶胀率、机械性能、耐氧化稳定性、质子传导性等进行测试。结果表明，SPPENK-P可溶解于二甲基乙酰胺、二甲基亚砜等溶剂，5 ％的热失重温度在330 ℃以上；随着SPPENK-P中DHPZ-P单元比例的增加，SPPENK-P膜的吸水率、溶胀率、质子传导率增加，而耐氧化性降低；SPPENK-P膜在25 ℃下的吸水率均在8 ％以上，95 ℃下的质子传导率可达9.59×10-2 S/cm。

Poly(phthalazinone ether nitrile ketone) containing pendant phenyl group (PPENK-P) were synthesized via high temperature polycondensation from 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one(DHPZ), 4-(3-phenyl-4-hydroxyphenyl)-2,3-phthalazin-1-one (DHPZ-P), 2,6-dichlorobenzonitrile, and 4,4´-difluorobenzophenone. A series of sulfonated poly(phthalazinone ether nitrile ketone) containing pendant phenyl group (SPPENK-P) were prepared from the sulfonation of PPENK-P with concentrated sulfuric acid as sulfonating agent. SPPENK-P membranes were prepared through solution casting method. The membrane performance including water uptake, swelling ratio, mechanical property, oxidative stability, and proton conductivity were investigated. The results show that SPPENK-P can be dissolve in solvents such as dimethylacetamide and dimethyl sulfoxide at 25 ℃, and the 5% thermal weight loss temperature is above 330 ℃. As the proportion of DHPZ-P moiety in SPPENK-P increase, the IEC value, water uptake, swelling ratio, and proton conductivity of the membranes increase, while the oxidation resistance decrease. The water uptake of SPPENK-P membranes at 25 ℃ is above 8 %, and the proton conductivity at 95 ℃ can reach 9.59×10-2 S/cm.

基金项目：

国家重点研发计划项目(2017YFB0307600)，国家自然科学基金委创新研究群体项目（22021005），辽宁省‘兴辽英才计划’项目(XLYC1802073)，大连市高层次人才创新支持计划（2019RD08）

作者简介：

谭相坤（1995-），男，黑龙江省大庆市人，硕士生，主要从事磺化聚芳醚膜材料研究，E-mail：18246951021@163.com

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