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Unusual thermal decomposition kinetics of a dihydroperoxide polymerization initiator. Experimental results and theoretical calculations

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Baysal, Bahattin
Onurhan, Erdal

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Peroxides and azo compounds are the most important initiator systems for free-radical vinyl polymerization. Studies on the thermal decomposition kinetics of dihydroperoxides are limited. The thermal decomposition of 2,5-dimethyl-2,5-dihydroperoxyhexane in toluene at 80-100 °C showed a two-step reaction. This was due to the formation of intramolecular hydrogen bonding in this system. The first step consisted of a first-order reaction with a very low activation energy due to the decomposition of H-bonded hydroperoxide groups. The second step consisted of a higher activation energy due to the decomposition of the remaining peroxide groups.

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American Chemical Society (ACS)

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Chemistry

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American Chemical Society, Polymer Preprints, Division of Polymer Chemistry

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