Photochemical Behavior of Poly(Organophosphazenes). 15. Light-Induced Cross-Linking of [(4-Benzoylphenoxy)x(Methoxyethoxyethoxy)2 − x] Phosphazene Copolymers

The synthesis of a new, highly photosensitive, phosphazene copolymer containing an almost-equimolecular quantity of benzophenone and methoxyethoxyethoxy substituents is reported in this paper, together with the photochemical behavior of this material when irradiated in film both in oxygen and in an argon atmosphere. It has been detected that the photoreactivity of the phosphazene material strongly depends on the light absorption process by the benzophenone moieties, whose selective excitation predominantly brings about an intramolecular hydrogen abstraction reaction from the ethylene oxide units, thus producing highly reactive phosphazene macroradicals. The coupling reactions of these species results in the complete cross-linking of the polyphosphazene substrate and in its total insolubilization. Moreover, the influence of molecular oxygen on the overall photochemical process of the benzophenone/ethyleneoxide-substituted phosphazene copolymer is investigated. The implications of the light-induced reticulation process in the controlled insolubilization of poly[ bis (methoxyethoxyethoxy)phosphazene] are also discussed.