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Updated: Oct 2, 2026

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
Reactions of methyl radicals with propene at temperatures between 750 and 1000 K
E Goos1, H Hippler, K Hoyermann
1Institut für Physikalische Chemie, Universität Karlsruhe, Fritz-Haber-Weg 4, D-76128 Karlsruhe, Germany.
Abstract:
The pyrolysis of propene, initiated by methyl radicals, has been studied in the temperature range 750-1000 K and at a pressure of 0.13 bar in a quasi-wall-free reactor using laser heating by fast vibrational-translational (V-T) energy transfer. This is a convenient method to study homogeneous high-temperature kinetics since the reactor walls remain cold. The radial temperature distribution in the reactor has been investigated by four different methods: a stationary heat balance, optical absorption, pressure rise, and the temperature dependence of the rate of an isomerization reaction. Methyl radicals were produced via the fast thermal dissociation of di-tert-butyl-peroxide and the products were analysed using GC-MS. The main products of the overall reaction of the model system propene and methyl (C3H6 + CH3) were isopentane (iso-C5H12) and but-1-ene (1-C4H8), whereas allene (C3H4), trans-but-2-ene (trans-2-C4H8) and cis-but-2-ene (cis-2-C4H8) were minor components, all showing a strong dependence on temperature. The product distribution and the temperature dependence were analysed by a kinetic model of 61 species and 166 reactions developed for the high-temperature oxidation of butane and the low-temperature oxidation of n-pentane and isopentane. It was necessary to include a few missing reactions and to adjust some rate constants to make the modeling agree with the experimental investigations. This extended mechanism has to be evaluated further in forthcoming experiments.
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