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The Mechanism of the Decomposition of Peroxides and Hydroperoxides by Mineral Fillers
Authors:D. H. Solomon  Jean D. Swift  G. O'leary  I. G. Treeby
Affiliation:Division of Applied Chemistry C.S.I.R.O. , Melbourne, Australia
Abstract:The interaction of fillers and pigments with free radical initiators has been studied. Clay minerals have a marked influence on both the rate and the mechanism of the decomposition of peroxides and hydroperoxides. Kaolinite is a particularly effective catalyst and causes rapid decomposition even at room temperature. The reaction of cumene hydroperoxide with kaolinite is first-order in peroxide and the rate constant is proportional to the ratio of clay to hydroperoxide. From a study of the products of the reaction and the influence of solvent on the decomposition, a mechanism involving an intramolecular rearrangement or closely associated ion pairs has been proposed. The application of these results to polymer filler composites is discussed.
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