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Polypropylene sold by Aldrich is reported as free of antioxidants. However, in any case, the concentration of antioxidants should not be larger than several ppm. Consequently, taking into account the large amount of peroxides and oxygen applied in the experiments, the antioxidant will play a minor role in the reactivity. In any case, its role will be to reduce the amount of radical species and then to delay the initiation of the degradation as long as it would not have been totally consumed. The results reported in this article show unambiguously that antioxidants play no major role
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Although MeOO{radical dot} is very different from molecular biradical dioxygene, we assume that it is an acceptable model for the reactivity of O2. There is no doubt that on thermokinetic point of view the H-abstraction by O2 is not favoured but under our experimental conditions it occurred unambiguously
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Modelling the H-abstraction reaction by molecular oxygen with hydroperoxyl radical HOO$ might seem more pertinent than with MeOO$. However, only minor changes are expected for thermodynamic parameters, and only the activation entropy is expected to be changed significantly. That is, the approach of HOO$ is expected to be less hampered than that of MeOO$. Consequently, the difference in reactivity between tertiary central and terminal sites should be smaller. As we were not seeking quantitative assessments, it was of no use to perform these calculations
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Modelling the H-abstraction reaction by molecular oxygen with hydroperoxyl radical HOO$ might seem more pertinent than with MeOO$. However, only minor changes are expected for thermodynamic parameters, and only the activation entropy is expected to be changed significantly. That is, the approach of HOO$ is expected to be less hampered than that of MeOO$. Consequently, the difference in reactivity between tertiary central and terminal sites should be smaller. As we were not seeking quantitative assessments, it was of no use to perform these calculations.
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2 was neglected because it leads to 1) to the formation of polymeric peroxyl radical whose the reactivity is accounted either by the model presented in this article or it will react by intra/inter molecular H-transfer to generate a new polymeric radical and will lead to the reactivity described in this article, or 2) to formation of a new dialkyl peroxide which would decompose at the experimental temperatures to afford alkoxyl radicals whose the reactivity is described by the model presented in this article.
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