Kinetic analysis of polydicyclopentadiene oxidation

Type Article
Date 2017-08
Language English
Author(s) Defauchy Virginie1, Le Gac Pierre-YvesORCID2, Guinault Alain1, Verdu Jacques1, Recher Gilles3, Drozdzak Renata3, Richaud Emmanuel1
Affiliation(s) 1 : CNRS, Lab PIMM, Ensam, Cnam, 151 Blvd Hop, F-75013 Paris, France.
2 : IFREMER Ctr Bretagne, Marine Struct Lab, BP70, F-29280 Plouzane, France.
3 : TELENE SAS, 2 Rue Marie Curie, F-59910 Bondues, France.
Source Polymer Degradation And Stability (0141-3910) (Elsevier Sci Ltd), 2017-08 , Vol. 142 , P. 169-177
DOI 10.1016/j.polymdegradstab.2017.06.005
WOS© Times Cited 20
Keyword(s) Polydicyclopentadiene, Thermal oxidation, Segmental mobility, Catalysis, Diffusion limited 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.

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