Thermal degradation of phosphonated polystyrenes. Part 2: The volatilisation step

On heating at volatilisation temperatures, polystyrene (PS) and telechelic chloromethoxyphosphonated polystyrene (TPPS) behave differently in the very early stage of the process. The initial rate of volatilisation of PS is zero and increases with conversion whereas TPPS polymers volatilise at an initial high rate which decreases with conversion. However, in the main stage of volatilisation (from 10–20 to 70% weight loss) both polymers liberate the same volatile products through the same basic mechanism of depolymerisation. Nevertheless, the overall rate of volatilisation of TPPS polymers in this stage is much lower than that of PS. This is attributed to the creation in degrading TPPS polymers of less reactive chain carriers of the depolymerisation process which are stabilised by the phosphoryl group