Radiochemical ageing of EPDM elastomers. 3. Mechanism of radiooxidation

On the basis of the analysis of the oxidation products formed in EPDM and EPR, and taking into account their relative concentrations, the mechanisms accounting for the EPDM γ-degradation under oxygen atmosphere are proposed in the present paper. Two main processes are involved in the EPDM radiooxidation. The random γ-radiolysis of the polymer provides a constant source of macroalkyl radicals mainly formed on ethylene units. The secondary radicals so formed are likely to initiate a selective oxidation of the polymer through free-radicals reactions involving the abstraction of labile hydrogen atoms. In particular, the hydroperoxides decomposition and the consumption of the ENB moieties, this latter being the most oxidisable site and the source of crosslinking, may result from hydrogen abstraction by radical species.