On the kinetics and mechanism of thermal degradation of polystyrene

The thermal degradation of polydisperse polystyrene samples with mol. wts. (M?_n) between 60000 and 22000 has been investigated at different temperatures under oxygen free conditions. Product analysis has been carried out by GPC. The experimental degradation could be simulated by a model consisting of scission and depolymerization. The dynamical behaviour of this model is expressed in a matrix from. The ratio of scission and depolymerization is constant for all polymers and different temperatures during degradation. Therefore, a master curve could be evaluated, which gives a general relation between the decrease of mol. wt. and the mass of volatiles. Finally a radical chain mechanism has been proposed in a lumped form which is consistent with the kinetic model and the experimental results.