• Journal of Hydrogen and New Energy
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• v.28 no.1
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• pp.24-29
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• 2017

A fluorinated polybenzimidazole (FPBI) was synthesized from 3,3-diaminobenzidine (DAB) of tetraamine, 2,2-bis(4-carboxyphenyl)hexafluoropropane of aromatic biscarboxylic acid, and 4,4-sulfonyldibenzoic acid of aromatic biscarboxylic acid in polyphosphoric acid (PPA). A FPBI was easily cast and made into clear films. The structure of condensation polymers and corresponding membranes were analyzed using GPC (gel permeation chromatography), $^1H$-NMR ($^1H$ nuclear magnetic resonance) and FT-IR (fourier transform infrared). TGA (thermogravimetric analysis) analysis showed that the prepared membranes were thermally stable, so that elevated temperature fuel cell operation would be possible. The proton conductivity of the FPBI membranes increased with increasing temperatures in the polymer. A FPBI membrane has a maximum ion conductivity of 45 mS/cm at $90^{\circ}C$ and 100% relative humidity.

• Korean Membrane Journal
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• v.9 no.1
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• pp.43-51
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• 2007

This paper describes the preparation and characterization of two kinds of fluorinated polybenzimidazole (PBI)s which can be potentially used for phosphoric acid-doped, high-temperature polymer electrolyte membrane fuel cells. Two kinds of perfluorocyclobutane (PFCB)-containing monomers were prepared via following synthetic steps; after fluoroalkylation of methyl 3-(hydroxy) benzoate and methyl 4-(hydroxy) benzoate with 1,2-dibromotetrafluoroethane and subsequent Zn-mediated dehalogenation, these compounds were cyclodimerized at $200^{\circ}C$ affording the ester-terminated monomers containing PFCB ether groups. The synthesized intermediates and monomers were characterized using FT-IR, $^1H-NMR,\;^{19}F-NMR$, and mass spectroscopy. The fluorinated PBIs were then successfully prepared through the solution polycondensation of the monomers and 3,3'-diaminobenzidine in polyphosphoric acid. Compared with traditional PBI, the glass transition temperatures of the fluorinated PBIs were obtained at $262^{\circ}C\;and\;269^{\circ}C$ which are lower than that of PBI and their initial degradation temperatures were still high over $400^{\circ}C$ under nitrogen. The fluorinated PBIs showed higher d-spacing values and improved solubility in several organic solvents as well as phosphoric acid, which confirmed they could be good candidates for the high temperature fuel cell membranes.