A widely accepted view of the thermal degradation of polymers such as PMMA is that an initiation reaction produces radical fragments that undergo rapid depropagation and are also converted back to molecules by a termination reaction. This mechanism is applied to a population of linear molecules and radicals and the evolution of the population is modelled by appropriate discrete sets of ordinary differential equations. In particular, end-chain and random initiation reactions with first-order termination are analysed and compared with experimental data. We find on comparison with TG data for PMMA that the initiation reaction is important in dictating the qualitative behaviour of the overall rate of thermal degradation. Furthermore, the behaviour of degradation rate with initial degree of polymerisation is also investigated and interpreted within the framework of the model. (c) 2007 Elsevier Ltd. All rights reserved.