MODELING OF THE FREE-RADICAL POLYMERIZATION OF METHYLMETHACRYLATE UP TO HIGH-TEMPERATURE

Many models have been developed to describe the kinetics of the free r adical polymerisation of methyl methacrylate (MMA). However, they are restricted to low temperatures, e.g., below the glass transition tempe rature of the polymer, T-g. In this work, kinetics of bulk and solutio n polymerisation of MMA were determined by differential scanning calor imetry (DSC) for temperatures above T-g, i.e. 130-165 degrees C. On th e basis of our own experimental results (high temperatures) acid those published in the literature (low temperatures), it has been shown tha t with small modifications, the model of Achilias and Kiparissides giv es a good description of kinetics for a temperature range from 20 to 1 65 degrees C. Furthermore, all parameters appearing in the diffusion-l imited part of the kinetic rate constants have a clear physical meanin g and can be evaluated in terms of physical and transport properties o f the reacting species.