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A general kinetic model is proposed to describe the polypropylene thermal oxidation of thin polypropylene films in a wide range of temperatures (from 60 to 200 C) and oxygen partial pressures (from 0.02 to 5 MPa) using a single set of parameters.This model was calibrated with several series of experimental data including analyses of primary (hydroperoxides) and secondary oxidation products (carbonyl species), and subsequent changes in macromolecular properties (average molecular masses). It predicts the experimental data previously published in the literature in terms of induction times and maximal oxidation rates. The variability of the oxygen solubility coefficient allows to explain the scattering of induction times and oxidation rates among the whole iPP family, but also the dependence of this latter quantity with oxygen partial pressure. This variability is presumably due to iPP polymorphism in the temperature range where oxygen permeability is commonly measured. It is concluded that the kinetic model can be used to study the direct effect of iPP morphology on its thermal oxidation kinetics (chemistry of oxidation).

is an open access repository that collects the work of Arts et Métiers ParisTech researchers and makes it freely available over the web where possible. A B S T R A C TA general kinetic model for the photothermal oxidation of polypropylene has been derived from the basic auto-oxidation mechanistic scheme in which the main sources of radicals are the thermolysis and photolysis of the most unstable species, i.e hydroperoxides. Thermolysis is a uni-or bi-molecular reaction whose rate constant obeys an Arrhenius law. In contrast, photolysis is exclusively a unimolecular reaction and its rate constant is independent of temperature. According to the quantum theory, this latter is proportional to the energy absorbed by photosensitive species and thus, accounts for the impact of UVlight intensity and wavelength on the global oxidation kinetics.The validity of this model has been checked on iPP films homogeneously oxidized in air over a wide range of temperatures and UV-light sources. It gives access to the concentration changes of: (i) primary (hydroperoxides) and secondary (carbonyls) oxidation products, (ii) double bonds, (iii) chain scissions and crosslinking nodes, but also to the subsequent changes in molecular masses. These calculations are in full agreement with the photolysis results reported by Carlsson and Wiles in the 70s [1][2][3]. However, the model seems to be only valid for UV-light energies equivalent to about 10 suns as upper boundary, presumably because of multiphotonic excitations or chromophores photosensitization (i.e. termolecular photo-physical reactions), both enhanced at high irradiances.

is an open access repository that collects the work of Arts et Métiers ParisTech researchers and makes it freely available over the web where possible. a b s t r a c tA criterion based on the energy absorbed by photosensitive species was proposed to describe the contribution of UV-light to the initiation of the polypropylene photothermal oxidation whatever the light source. The calculation of this energy was performed using the widely accepted quantum theory. The criterion was then introduced in two different types of analytical models commonly used to describe the combined effects of UV light and temperature on induction time, namely: the reciprocity law and kinetic model. The limitations of both types of analytical models were then investigated: the latter, derived from a realistic mechanistic scheme, was found to be much more relevant than the former, which is presumably valid in a restricted range of light intensities, essentially due to its empirical origin. Ó

International audienceAnalysis of volatile organic compounds (VOCs) during PP thermal oxidation under three oxygen partial pressures (0%, 21% and 100% of atmospheric pressure) at 140 C was performed by proton transfer reaction coupled with Fourier transform ion cyclotron resonance mass spectrometry. Six main VOCs were identified: acetone, acetic acid, 2,4- pentanedione, acetaldehyde, formaldehyde and methyl acrolein. Their formation was shown to obey two main reaction pathways, both involving methyne units as driving oxidation sites: (i) the widely accepted chain scission mechanism of tertiary alkoxy radicals, which generates primary radicals undergoing secondary reactions leading to the oxidation of methylene units; (ii) the chain scission mechanism occurring on tertiary alkyl radical, which is proposed here as a realistic path leading to methyl acrolein. The relative proportions of the six main VOCs depend on the oxygen partial pressure, which mostly impacts the oxidation of methylene units rather than the competition between the two previous paths