Thermo-oxidative degradation free-radical chain mechanism

The dissociation process is described by a free radical chain mechanism. The thermo-oxidative dissociation is initiated by the oxidation of the aliphatic moieties by a subsequent cleavage of the hydroperoxides formed. With increasing time of oxidation the temperature of the onset of degradation is lower as compared with that for a purely thermal degradation. 

The study of degradation processes of polymers and organic materials is a fundamental topic both from academic and industrial point of view and it can be expected that thermal and thermo-oxidative decomposition mechanisms are reasonably well established. [20,3 8] These complex reactions proceed via a typical free-radical chain as outlined in scheme 2. 

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