The reactivity of aromatic amines toward free radicals

Yates, Wesley Ross
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Initially this investigation was based upon the hypothesis that an accurate compilation of rate constants for the termination step in aromatic amine-retarded vinyl polymerization could provide information on the detailed mechanism of the reaction, currently a subject of controversy in the literature. In addition, the compilation of precise reactivity data for a large number of aromatic amines was viewed as an important contribution in supplementing the small amount of experimental data now available for theoretical work on such molecules. Failure to realize this goal due to experimental difficulties associated with purifying the materials led to the completion of the survey of amine-reactivity through use of an autoxidation system and a scheme of analysis devised earlier in this laboratory (R. Go Caldwell, Ph. Do Thesis, University of Hawaii, 1960). Absolute values for the rate constants of the termination step were less meaningful than had been expected for the retarded polymerization, but led nevertheless to a satisfactory correlation of relative reactivities with changes in π-electronic energy for the scission of N - -H bonds in the amines, calculated by the Huckel molecular orbital method. This correlation was expected on the basis of both current theories of the inhibition process, but provided no strong support for either. The kinetic analysis and the subsequent successful correlation of the reactivities substantiated the supposition that the antioxidant action of phenols and of aromatic amines are of a similar nature, and that the termination step generally involves the destruction of two kinetic chains for each terminator molecule consumed. The experimental technique used in the reactivity survey was shown to have an upper limit of antioxidant reactivity, above which the terminator is attacked directly by molecular oxygen, so that its behavior is not described by the kinetic analysis of this thesis. Accordingly, about half of the 28 amines tested were productive of significant quantitative data.
Thesis (Ph. D.)--University of Hawaii, 1964.
Bibliography: leaves [104]-109.
vi, 109 l illus., tables
Amines, Radicals (Chemistry), Polymers
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Theses for the degree of Doctor of Philosophy (University of Hawaii (Honolulu)). Chemistry; no. 60
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