Thermal degradation of chlorinated polystyrenes

p-Chlorostyrene was polymerized using a radical initiator, ?,??-azobis(isobutyronitrile). Polystyrene was chlorinated in the liquid phase using an SbCl3, catalyst combined with 10-trifluoroacetylphenothiazine. The chlorinated polymers were characterized spectroscopically and molecular weight measurements were carried out. The polymers were pyrolysed at 600°C, the pyrolysis products identified by means of gas chromatography/mass spectrometry and their relative percentages calculated. The differences in the products distributions gave helpful indications about the structure and the mechanism of degradation of the chlorinated polymers.