Synthesis and microstructural characterization of low to high molecular weight poly(vinylphosphonic acid)s: effect of molecular weight and temperature on acidity and polyelectrolyte behavior

Poly(vinylphosphonic acid) (PVPA) was synthesized by free radical polymerization of vinylphosphonic acid (VPA) in different solvents. Bromotrichloromethane as a chain transfer agent (CTA) was used in some experiments to control molecular weight of the PVPA. The effects of solvent type and initiator and CTA concentrations on the microstructure, molecular weight and stereoregularity of the resulting PVPA was extensively investigated by FTIR, 1HNMR, 31PNMR and elemental analysis. Polymers with a number-average molecular weight (Mn) in the range of 1550 to 42,190 gmol−1 were prepared. High molecular weight PVPA with Mn of 42,190 gmol−1 was obtained from aqueous solution polymerization of VPA with initiator/monomer molar ratio of 0.16/100 at 80°C. Molecular weight decreased with increasing the concentration of initiator and CTA. 1HNMR spectra were used to investigate tetrad sequences for the methylene protons of PVPA, from which stereochemical information of the polymer chain was obtained. Tetrad sequences were also calculated by Bernoullian probabilities. Moreover, the percent of head-to-head and tail-to-tail irregularities of the resulting PVPA were obtained to be in the range of 16.6–58% depending on the reaction conditions. The PVPA synthesized in acetic anhydride as a solvent had highest amount of the irregularities due to the high reaction rate, which does not allow controlling the structure. Furthermore, due to the importance of PVPA in the proton exchange membranes (PEMs), the effects of molecular weight and temperature on the acidity and titration behavior of PVPA polyelectrolyte were investigated. It was found that molecular weight has no significant effect on the acidity and dissociation of protons at operational conditions of degree of dissociation lower than 0.5. It was also found that by increasing the temperature, pH values were decreased, meaning that dissociation of protons and consequently the proton conductivity of PVPA membranes can be affected by temperature. Titration behavior of PVPA also showed that the PVPA has a behavior similar to a monoprotic acid.