Polysulfone ionomers functionalized with benzoyl(difluoromethylenephosphonic acid) side chains for proton‐conducting fuel‐cell membranes

Abstract

AbstractPolysulfones carrying benzoyl(difluoromethylenephosphonic acid) side chains were prepared and investigated for use as proton‐conducting fuel‐cell membranes. In the first step, polysulfones were lithiated and reacted with methyl iodobenzoates to prepare p‐ and o‐iodobenzoyl polysulfones. Next, the phosphonated polysulfones were prepared via CuBr‐mediated cross‐coupling reactions between the iodinated polymer and [(diethoxyphosphinyl)difluoromethyl]zinc bromide. Finally, dealkylation with bromotrimethylsilane afforded highly acidic CF2PO3H2 derivatives. The replacement of the iodine atoms by CF2PO3Et2 units was almost quantitative in the case of o‐iodobenzoyl polysulfone. Membranes based on ionomers having 0.90 mmol of phosphonic acid units/g of dry polymer took up 6 wt % water when immersed at room temperature, and conductivities up to 5 mS cm−1 at 100 °C were recorded. This level of conductivity was comparable to that reached by a membrane based on a sulfonated polysulfone having 0.86 mmol of sulfonic acid/g of dry polymer. Thermogravimetry revealed that the arylCF2PO3H2 arrangement decomposed at approximately 230 °C via cleavage of the CP bond. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 269–283, 2007.