Preparation and evaluation of crosslinked sulfonated polyphosphazene with poly(aryloxy cyclotriphosphazene) for proton exchange membrane

Several crosslinked proton exchange membranes with high proton conductivities and low methanol permeability coefficients were prepared, based on the sulfonated poly[(4-fluorophenoxy)(phenoxy)] phosphazene(SPFPP) and newly synthesized water soluble sulfonated poly(cyclophosphazene)(SPCP) containing clustered flexible pendant sulfonic acids. The structure of SPCP was characterized by fourier transform infrared spectroscopy(FTIR) and ~1H NMR spectra. The membranes showed moderate proton conductivities and much lower methanol permeability coefficients when compared to Nafion 117. Transmission electron microscopy(TEM) results indicated the well-defined phase separation between the locally and densely sulfonated units and hydrophobic units, which induced efficient proton conduction. In comparison with SPFPP membrane, the proton conductivities, oxidative stabilities and mechanical properties of crosslinked membranes remarkably were improved. The selectivity values of all the crosslinked membranes were also much higher than that of Nafion 117(0.74×10~5S· s/cm~3). These results suggested that the c SPFPP/SPCP membranes were promising candidate materials for proton exchange membrane in direct methanol fuel cells.

Composite Polyphosphazene Membranes Doped with Phosphotungstic Acid and Silica

Poly（bis（phenoxy）phosphazene） （SPBPP）/phosphotungstic acid （PWA）/silica composite membranes for fuel cells were prepared. The composite membranes were characterized by using FTIR, TGA and SEM techniquies. Incorporation of PWA particles and silica particles into the SPBPP polymer matrix and a specific interaction between them were confirmed by FTIR spectra. TGA results showed that the composite membranes had high thermal stability. Homogeneous distribution of PWA and silica particles within the SPBPP matrix was verified by SEM micrographs. The doped membranes showed increased water uptake and proton conductivity.

Synthesis and Characterization of Sulfonated Polyphosphazene-graft-Polystyrene Copolymers for Proton Exchange Membranes

A novel series of polyphosphazene-grafl-polystyrene （PP-g-PS） copolymers were successfully prepared by atom transfer radical polymerization （ATRP） of styrene monomers and brominated poly（bis（4-methylphenoxy）phosphazene） macroinitiator. The graft density and the graft length could be regulated by changing the bromination degree of the macroinitiator and the ATRP reaction time, respectively. The PP-g-PS copolymers readily underwent a regioselective sulfonation reaction, which occurred preferentially at the polystyrene sites, producing the sulfonated PP-g-PS copolymers with a range of ion exchange capacities. The resulting sulfonated PP-g-PS membranes prepared by solution casting showed high water uptake, low water swelling and considerable proton conductivity. They also exhibited good oxidative stability and high resistance to methanol crossover. Morphological studies of the membranes by transmission electron microscopy showed clear nanophase-separated structures resulted from hydrophobic polyphosphazene backbone and hydrophilic polystyrene sulfonic acid segments, indicating the formation of proton transferring tunnels. Therefore, these sulfonated copolymers may be candidate materials for proton exchange membranes in direct methanol fuel cell （DMFC） applications.