AbstractThe thermal degradation of polydisperse polystyrene samples with mol. wts. (M̄n) 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