The thermal oxidation of an unvulcanized, unstabilized polyisoprene rubber (IR) has been studied in the 40–140 °C temperature range. Ageing was monitored by FTIR determination of double bonds and carbonyl groups, mass uptake measurement, and weight average molar mass determination. A mechanistic scheme based on the standard scheme for radical chain oxidation, but taking into account the diversity of initiation processes and the existence of inter and intramolecular radical additions to double bonds, was built. The kinetic model derived from this scheme is composed of seven differential equations to be solved in discretized thickness layers to take into account the kinetic control by oxygen diffusion. This system was numerically solved using a Matlab program dedicated to stiff systems of differential equations. The elementary rate constants and other kinetic parameters were then determined from experimental data, using an inverse approach. A set of physically reasonable parameter values was obtained, allowing thus to envisage lifetime predictions at low temperature (long term). The results lead to observations difficult to make from classical analytical studies, for instance the predominance of bimolecular hydroperoxide decomposition among other initiation modes or the competition between intermolecular hydrogen abstraction and intramolecular addition of peroxy radicals to double bonds.

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