华南理工大学学报(自然科学版) ›› 2014, Vol. 42 ›› Issue (6): 79-87.doi: 10.3969/j.issn.1000-565X.2014.06.013

• 材料科学与技术 • 上一篇    下一篇

大尺寸亲水结构序列嵌段离聚物的结构及性能

李秀华 林永华   

  1. 华南理工大学 化学与化工学院∥广东省燃料电池技术重点实验室,广东 广州 510640
  • 收稿日期:2013-12-12 修回日期:2014-04-08 出版日期:2014-06-25 发布日期:2014-05-01
  • 通信作者: 李秀华(1970-),女,副教授,主要从事燃料电池关键膜材料研究. E-mail:lixiuhua@scut.edu.cn
  • 作者简介:李秀华(1970-),女,副教授,主要从事燃料电池关键膜材料研究.
  • 基金资助:

    国家自然科学基金资助项目(51173045);广东省燃料电池技术重点实验室开放基金资助项目(201104)

Structure and Properties of Sequenced Block Ionomers Containing Hydrophilic Macrosegments

Li Xiu- hua Lin Yong- hua   

  1. School of Chemistry and Chemical Engineering∥Key Laboratory of Fuel Cell Technology of Guangdong Province,South China University of Technology,Guangzhou 510640,Guangdong,China
  • Received:2013-12-12 Revised:2014-04-08 Online:2014-06-25 Published:2014-05-01
  • Contact: 李秀华(1970-),女,副教授,主要从事燃料电池关键膜材料研究. E-mail:lixiuhua@scut.edu.cn
  • About author:李秀华(1970-),女,副教授,主要从事燃料电池关键膜材料研究.
  • Supported by:

    国家自然科学基金资助项目(51173045);广东省燃料电池技术重点实验室开放基金资助项目(201104)

摘要: 以双酚芴、4,4’-二氯二苯砜、联苯双酚型二氮杂萘酮、二氟二苯酮磺酸钠为原料,采用“二锅二步”法制备了一系列具有不同尺寸亲水结构的芴-联苯双酚型氮杂萘酮-两亲序列嵌段聚芳醚砜酮离聚物质子交换膜材料.对合成的质子交换膜材料结构和性能的研究表明:该系列新型离聚物的结构可控;离聚物膜具有明显的微相分离结构,憎水相以小的分离的连续相包裹在亲水连续相中,且随着亲水链段尺寸的增大,其亲水区域的尺寸增大,呈现明显的吸水溶胀状态,形成了大的质子交换通道;该系列膜具有良好的热稳定性,合适的吸水率和溶胀率, 良好的质子传导率、力学性能以及高温水解稳定性;随着大尺寸亲水链段尺寸的增加,膜的吸醇率增加,抗氧化性能降低;该系列膜的质子传导率随着温度的升高而增大,5c,5d 在20℃下的质子传导率接近或高于Nafion 117 的30℃质子传导率,5d 的质子传导率在80℃下达到了15.63mS/cm.

关键词: 序列嵌段离聚物, 磺化聚芳醚砜酮, 联苯双酚, 氮杂萘酮, 质子交换膜燃料电池

Abstract:

A series of hydrophile- lipophile sequenced block ionomers with hydrophobic macrosegments and size- var-ying hydrophilic macrosegments was synthesized via a two- pot two- step nucleophilic polycondensation of bis(4- chlo-rophenyl) sulfone,9,9- bis(4- hydroxyphenyl) fluorene (BHF),bisphthalazinone containing biphenyl moiety andsulfonated 4,4- difluorobenzophenone (SDFBP),and was used as the material of proton exchange membrane.Then,the structure and properties of the ionomers were investigated.The results show that (1) the structure of theionomers is in good accordance with the designed backbone structure; (2) wet ionomers membranes exhibit a clearmicrophase separation structure with continuous hydrophilic and small- size isolated hydrophobic regions; (3) thesize of hydrophilic regions increases with the size of hydrophilic segments to hydrophobic segments,which benefitsthe swelling of hydrophilic regions and the formation of large- size proton conductive channels; (4) the synthesizedpolymers membranes possess good thermal stability,appropriate water absorption and swelling ratio,high protonconductivity,excellent mechanical properties as well as good high- temperature hydrolytic stability; (5) with thesize increase of large- size hydrophilic chains,the methanol penetration resistance of the membranes improves andthe oxidation resistance degrades; and (6) the proton conductivity of the membranes increases with temperature.Inparticular,the proton conductivity of ionomers 5c and 5d at 20℃ is close to or even higher than that of Nafion 117at 30℃,and the proton conductivity of ionomer 5d reaches 15.63 mS/cm at 80℃.

Key words: sequenced block ionomer, sulfonated block poly(aryl ether sulfone ketone), biphenol, phthalazi-none, proton exchange membrane fuel cell

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