Anhydrous polymeric proton conductors based on imidazole functionalized polysiloxane

Intrinsically proton conducting polymers with imidazole as proton solvent tethered to a polysiloxane backbone via a flexible spacer have been synthesized. Apart from the standard characterization also their thermal properties and transport behavior have been investigated. The materials exhibit proton conductivity as a consequence of self-dissociation of the imidazole moieties and structure diffusion of the resulting defects. In particular, no liquid phase such as water or monomeric imidazole is needed for the observed proton conductivities. To study the influence of the tether structure on the transport properties, cyclic oligomers and open chain polymers with different spacer lengths have been synthesized. The materials are thermally stable up to 200 degrees C and become soft around room temperature. The conductivity exhibits VTF and WLF behavior with maximum conductivities around sigma = 1.5(.)10(-3) S cm(-1) at T = 160 degrees C. The activation volume of the conductivity as derived from pressure dependent measurements is found to be unusually high. The lowest activation volumes and the highest conductivities are observed for the materials with the highest segmental mobilities, i.e. the longest spacers. Proton self-diffusion coefficients as obtained from PFG NMR diffusion measurements are significantly higher than expected from the proton conductivities obtained by dielectric spectroscopy. This corresponds to unusually high Haven ratios which have been interpreted by correlated proton transfers allowing for fast proton diffusion while minimizing the separation of ionic charge carriers.