Abstract
Evaluation of activation energy for the reactions of radical additions to vinyl compounds was studied as an extension of the theory employing two Morse functions for the initial and the final systems. The π-bond dissociation energies of vinyl compounds in the initial system were estimated by using the localization energy method. The difference between the a′Δr* values of the Morse functions of the initial and the final systems in the transition state was empirically determined as a function, af′Δrf*−aπ′Δrπ*=ωΔH, of the reaction heat ΔH. Based on the above finding, an empirical equation for evaluation of the activation energies of the radical addition reactions was derived, and its propriety was checked in comparison with the observed values. An approximate formula of the empirical equation was introduced in order to facilitate calculations of the activation energies. The Evans–Polanyi and Semenov rules, the Hammett-type rule and the Q–e scheme in the radical copolymerizations were derived by using this approximate formula and are discussed in detail.
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Kagiya, T., Sumida, Y. Evaluation of Activation Energy for Addition Reactions of Radicals to Vinyl Compounds. Polym J 1, 137–146 (1970). https://doi.org/10.1295/polymj.1.137
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DOI: https://doi.org/10.1295/polymj.1.137