Thermooxidative aging of polydicyclopentadiene in glassy state

Thermal aging of thin films of unstabilized polydicyclopentadiene (pDCPD) at several temperatures ranging from 120 to 30 °C was investigated by means of carbonyl build up by FTIR with ammonia derivatization, double bond titration, mass uptake measurement, hydroperoxides titration by iodometry and DSC coupled with sulfur dioxide treatment. In the temperature range under investigation, pDCPD is in glassy state and it oxidizes faster than common polymers oxidized at rubbery state (e.g. polydienic elastomers). Using the kinetic analysis, these results were ascribed to increased initiation rate due to catalyst residues, some possible intramolecular processes favoring propagation, or a very low termination rate of oxidation radical chains because of the control of termination reactions by macroradical diffusion.