| Abstract: | Dense films of poly[(4-ethylphenoxy)(phenoxy)phosphazene] (PEPP), a potentially attractive ion-exchange membrane material, were crosslinked to varying degrees using UV light and a photoinitiator. This polymer contained two kinds of substituents: phenoxy groups to be used for possible functionalization (e.g., sulfonation) and ethylphenoxy side-chains for photocrosslinking, where hydrogens at the benzylic carbons could be abstracted by a photoinitiator-leaving macroradicals that after recombination formed covalent bonds. The polyphosphazene polymer was synthesized, mixed with a photoinitiator, shaped into a thin film by solvent casting, and irradiated with UV light for a specified period of time. Benzophenone (BP), was selected as the photoinitiator because it was miscible with poly-phosphazene, had the highest rate of hydrogen abstraction, and absorbed UV light of 365 nm wavelength. The half-life of benzophenone in 50 μm-thick irradiated films was determined to be 20 min. When the BP–PEPP molar ratio was increased from 0 to 0.5, the glass transition temperature increased after irradiation from −8.8 to 53.5°C. At the same time, the equilibrium swelling in dimethylacetamide, at 25°C, decreased from infinity to 0.31. Tensile strength tests of the crosslinked films revealed a nonlinear dependence on BP–PEPP molar ratio. © 1996 John Wiley & Sons, Inc. |
