Poly(arylene ether)s Containing Superacid Groups as Proton Exchange Membranes

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)fluore...

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Bibliographic Details
Published in:ACS applied materials & interfaces 2010-06, Vol.2 (6), p.1714-1721
Main Authors: Mikami, Takefumi, Miyatake, Kenji, Watanabe, Masahiro
Format: Article
Language:English
Subjects:
Acids - chemistry
Electric Conductivity
Electrolytes
Ethers - chemistry
Gases
Hot Temperature
Ions
Materials Testing
Membranes, Artificial
Microscopy, Electron, Transmission - methods
Models, Chemical
Permeability
Polymers - chemistry
Protons
Water - chemistry
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Summary: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.
ISSN:1944-8244
1944-8252
DOI:10.1021/am100224z