Poly(arylene ether)s containing superacid groups as proton exchange membranes.
Poly(arylene ether)s containing superacid groups as proton exchange membranes.
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DOI：
10.1021/am100224z
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发表时间：
2010-05
影响因子：
9.5
通讯作者：
Takefumi Mikami;K. Miyatake;Masahiro Watanabe
中科院分区：
文献类型：
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作者：
Takefumi Mikami;K. Miyatake;Masahiro Watanabe
合成了一系列荧基上含有侧链超强酸基团的聚芳醚-S，并研究了其在燃料电池中的应用。以2，7-二碘-9，9-二(4-羟基苯基)茂为原料，与十氟联苯、双(4-氟苯基)砜、双(4-氟苯基)酮等二氟化合物在亲核取代条件下进行聚合，合成了含碘的聚芳醚S。通过Ullmann偶联反应将荧基上的碘基转化为全氟磺酸基团。全氟磺化度被控制在92%，相当于离子交换容量(IEC)为1.52meq/g。离聚体通过溶液浇铸获得了柔韧的延展性膜。离聚体膜表现出典型的亲水/疏水相分离，具有小的相互连接的亲水团簇(2-3 nm)，这与基准的全氟化膜(Nafion)相似。与主链结构相似的磺化芳香离聚体相比，含有超强酸基团的芳香离聚体具有更高的质子电导率。同时对超酸性离聚体膜的燃料电池性能进行了测试。
A series of poly(arylene ether)s containing pendant superacid groups on fluorenyl groups were synthesized and their properties were investigated for fuel cell applications. Poly(arylene ether)s containing iodo groups were synthesized by the polymerization of 2,7-diiodo-9,9-bis(4-hydroxyphenyl)fluorene with difluorinated compounds such as decafluorobiphenyl, bis(4-fluorophenyl)sulfone, and bis(4-fluorophenyl)ketone, under nucleophilic substitution conditions. The iodo groups on the fluorenyl groups were converted to perfluorosulfonic acid groups via the Ullmann coupling reaction. The degree of perfluorosulfonation was controlled to be up to 92%, which corresponds to an ion exchange capacity (IEC) of 1.52 meq/g. The ionomers yielded flexible, ductile membranes by solution casting. The ionomer membranes exhibited a characteristic hydrophilic/hydrophobic phase separation, with small interconnected hydrophilic clusters (2-3 nm), which is similar to that of the benchmark perfluorinated membrane (Nafion). The aromatic ionomers containing superacid groups showed much higher proton conductivities than those of the conventional sulfonated aromatic ionomers with similar main chain structures. Fuel cell performance with the superacidic ionomer membranes was also tested.