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.
A series of hydrophile-lipophile sequenced block ionomers with hydrophobic macrosegments and size-varying hydrophilic macrosegments was synthesized via a two-pot two-step nueleophilic polycondensation of bis （4-chlorophenyl） sulfone, 9,9-bis （4-hydroxyphenyl） fluorene （ BHF）, bisphthalazinone containing biphenyl moiety and sulfonated 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 the ionomers is in good accordance with the designed backbone structure; （2） wet ionomers membranes exhibit a clear microphase separation structure with continuous hydrophilie and small-size isolated hydrophobic regions; （3） the size of hydrophilic regions increases with the size of hydrophilie segments to hydrophobic segments, which benefits the swelling of hydrophilie regions and the formation of large-size proton conductive channels; （4） the synthesized polymers membranes possess good thermal stability, appropriate water absorption and swelling ratio, high proton conductivity, excellent mechanical properties as well as good high-temperature hydrolytic stability; （5） with the size increase of large-size hydrophilic chains, the methanol penetration resistance of the membranes improves and the oxidation resistance degrades ; and （6） the proton conductivity of the membranes increases with temperature. In particular, the proton conductivity of ionomers 5 c and 5 d at 20 ℃is close to or even higher than that of Nafion 117 at 30℃ , and the proton conductivity of ionomer 5d reaches 15.63 mS/era at 80 ℃.
出处
《华南理工大学学报（自然科学版）》
EI
CAS
CSCD
北大核心
2014年第6期79-87,共9页
Journal of South China University of Technology(Natural Science Edition)
基金
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)
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
sequenced block ionomer
sulfonated block poly （ aryl ether sulfone ketone ）
biphenol
phthalazi-none
proton exchange membrane fuel cell
