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Initiation of radical reactions by thermal decomposition of alkyl tert-butyl monoperoxalates

L. Matisová-Rychlá, J. Rychlý, V. Pastušáková, and M. Schulz

Polymer Institute, Centre for Chemical Research, Slovak Academy of Sciences, CS-842 36 Bratislava

 

Abstract: Polymerization of methyl methacrylate at 30 °C and oxidation of ethylbenzene at 60 °C initiated by alkyl ŕerí-butyl monoperoxalates (alkyl = methyl, isopropyl, tert-butyl, n-pentyl and n-decyl) of known rate constants of monomolecular decomposition have been studied. According to the initial rate, the initiation efficiency of individual peroxalates decreases in the order: tert-butyl, isopropyl, methyl, n-decyl, n-pentyl It was found that the by-products of decomposition — alkyl tert-butyl carbonates — also decompose above 60 °C. The rate of decomposition depends on the bulkiness of the alkyl group in the alkyl ŕerŕ-butyl monoperoxalates.

Full paper in Portable Document Format: 401a61.pdf

 

Chemical Papers 40 (1) 61–69 (1986)

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