Photoinitiated bulk polymerization of furfuryl methacrylate. Experimental and kinetic modelling results obtained at different temperatures

A kinetic model has been proposed for the photopolymerization of furfuryl methacrylate taking into account degradative transfer by the furan ring. Solution of the ordinary differential equation system obtained through the proposed kinetic scheme and the Arrhenius correlation have allowed one set of kinetic constants to be chosen from several estimated sets at different temperatures. The Arrhenius parameter values calculated for each individual proposed step in the model were found to be in good agreement with experimental values for methyl methacrylate and furan compounds. The apparent calculated activation energy gave the value 3.1 kcal mol(-1) which was close to the experimental value (3.4 kcal mol(-1)) determined photocalorimetrically. In all steps where allylic radicals were involved, the activation energy values were found to be higher in comparison to those steps in which less-stabilized species operate. Statistical analysis of the adequacy of the model has shown excellent agreement between the experimental data and those determined theoretically at different temperatures using the best set of kinetic constants "estimated" by simulation. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.