Study of the thermal degradation of polychlorotrifluoroethylene, poly(vinylidene fluoride) and copolymers of chlorotrifluoroethylene and vinylidene fluoride

A systematic study of the thermal degradation of a series of homopolymers and copolymers of chlorotrifluoroethylene and vinylidene fluoride was carried out using thermogravimetry and thermal volatilisation analysis (TVA). Volatile products were separated by subambient TVA and characterised by means of infrared spectroscopy and mass spectrometry. On degradation, polychlorotrifluoroethylene gives the monomer as the major product and CO2, C2F2Cl2, C3F5Cl and C2F3Cl3 in traces. Poly(vinylidene fluoride) forms hydrogen fluoride in appreciable quantity along with the monomer and C4H3F3. The copolymers show a similar type of degradation pattern. The structural changes which take place during degradation have also been studied and mechanisms of formation of the various products are disccused.