Kinetic analysis of polydicyclopentadiene oxidation

The in situ thermal oxidation of thin unstabilized polydicyclopentadiene was studied by TGA to monitor mass gain, and DSC to characterize hydroperoxides concentration. Results were discussed using kinetic analysis, which allowed the estimation of activation energies for key reactions of the oxidation process. Activation energy for termination was shown to be higher than in hydrocarbon liquids, which was discussed from the theory of diffusion controlled reactions, and a possible link with local motions associated with sub-glassy transition. Activation energy of thermal decomposition of hydroperoxides was found lower than for model hydroperoxides, suggesting an accelerating effect of organometallic catalysts. Despite those two results that indicate a poor thermal stability of thin pDCPD films, measurements of oxygen diffusivity at several temperatures show that oxidation remains confined in a relatively thin surface layer which would allow the pDCPD properties to be preserved.