Thermal Degradation of Polystyrene

The thermal degradation of polystyrene in the absence of oxygen is examined, at temperatures above or below 300°C. The decrease in degree of polymerisation occurring either with negligible volatilisation at lower temperatures, or with evolution of low molecular weight products at higher temperatures, is simulated by Monte-Carlo procedures. The results suggest that below 300°C, scission of the polymer chains is random, and involves also a minor fraction of some abnormal, as yet unidentified, structures. Above 300°C, an extensive intermolecular transfer process seems to be the main cause of the decrease in degree of polymerisation, whereas an overall depolymerisation of 100 structural units at each chain scission is the source of volatilisation.