Radiation induced oxidative degradation of poly[bis(p-tolylamino)] phosphazene in chlorinated hydrocarbons

Degradation induced by ionizing radiations on polyphosphazenes, dissolved in chlorinated methanes, is the subject of this investigation. Both steady gamma and pulse radiolysis techniques have been employed. The labile sites for radical attack in poly[bis(p-tolylamino)] phosphazene were identified as the aniline N-H and benzyl C-H bonds of the pendant groups. All the primary radicals, by themselves or after peroxidation, can give rise to macroradicals by hydrogen abstraction from the polymer molecules. Appreciable crosslinking appeared only in the presence of quite a high concentration of oxygen, whereas, in its absence or after it had been consumed, practically no M-bar sub(w) changes were detected. Optical spectra of intermediates formed after pulse radiolysis are reported and attributed to radical-polymer charge transfer complexes, anilinium ions and toluidine radicals. p-Toluidine is formed as an end-product by hydrogen abstraction from polymer molecules. In solvents where hydrogen chloride can be formed, the amino functional group is affected. (author)