Mass spectrometric characterization and thermal decomposition mechanism of some poly(organophosphazenes)

This work is concerned with the mass spectrometric characterization of polyaryloxy‐ and polyaminophosphazenes 1a–e. The mass spectral data show that the pyrolytic breakdown of poly(di‐β‐naphthoxyphosphazene) (1a) leads to the formation of cyclic oligomers. The poly(di‐arylaminophosphazenes) 1b–d decompose at low temperatures by a two‐stage process involving amine evolution. Finally, in the case of poly(dipiperidinophosphazene) (1e) the thermal decomposition leads to the complete destruction of the polymer backbone, with formation of ammonia and elemental phosphorus. The wide range of thermal decomposition pathways observed are peculiar of the phosphazene structure and represent a remarkable difference between this class of inorganic polymers and the organic ones.