Synthesis of polyether ether ketone membrane with pendent phosphonic acid group and determination of proton conductivity and thermal stability

Abstract

Incorporation of phosphonic acid groups in the polymer backbone by direct phosphonation or by polymerization of prefunctionalized monomers requires harsh reaction conditions. The present research work reported an easy synthesis strategy of phosphonic acid-containing diphosphonated polyether ether ketone (P-PEEK) by polycondensation of difluoro benzophenone and phosphonated bisphenol A (BPA). Phosphonation of BPA was carried out by monophosphoazylation followed by rearrangement in the presence of organolithium compound at −78°C. Nuclear magnetic resonance (NMR) imaging, Fourier transform infrared, and electrospray ionization mass spectrometry were performed to acquire complete structural information about the synthesized monomer and polymer. Degree of phosphonation of the synthesized polymer calculated from proton NMR spectra was as high as 70%. Thermal properties of the P-PEEK were checked using a differential scanning calorimeter (DSC) and a thermogravimetric analyzer. Moderate increase in melting point and glass transition temperature (Tg) were observed from the DSC analysis. Solubility of the polymer was improved significantly in the common organic solvents that permitted the polymer to be solution casted. Solid electrolyte membrane exhibited through plane proton conductivity of 7.5 × 10−5 S cm−1 at 25°C under fully hydrated conditions.