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Thermo-Oxidative Stability of Polymers

SpecialChem / Oct 16, 2008

Chien and Kiang [1, 2] oxidized polypropylene (PP) at temperatures between 240 and 289° C. The products were separated by gas chromatography (GC) and online identification was by an interfaced GC peak identification system. The major products are CO2, H2O, acetaldehyde, acetone, butanol, formaldehyde, methanol and other ketones and aldehydes. Most of the products can be accounted for by well-known reactions of alkoxy and peroxy radicals; the major products are derived from the secondary alkoxy and peroxy species. Oxygen starvation is manifested in diffusion limited products of olefins and dienes, and the increase of CO2 and H2O formation in pure oxygen atmosphere. The first order rate at 240° C is 2.4 x 10-3 s-1 with an overall activation energy of approximately 16 kcal/mol (67 kJ/mol). If one assumes the oxidative pyrolysis to share the same reaction pathways as auto-oxidation at lower temperatures, then the observed rate constants and activation energy may be calculated from kinetic parameters measured earlier for auto-oxidation of PP from 71 to 140° C.

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