Free radical addition to olefins. Part 20.—A reinvestigation of the addition of methyl radicals to fluoroethylenes.

Abstract

The addition of methyl radicals to fluoroethylenes has been reinvestigated using both azomethane and di-t-butylperoxide as initiators. As in the previous work, excess methyl iodide was added to promote a chain reaction. Unlike the previous study, telomeric products of low volatility were identified and quantitatively estimated. Correction of the monomeric product ratios by addition of the appropriate telomers had a significant effect on the relative Arrhenius parameters in some cases. New values of the activation parameters for the addition of methyl radicals to vinyl fluoride, 1, 1-difluoroethylene, trifluoroethylene and tetrafluoroethylene relative to ethylene, are presented.