Abstract
The radical polymerization of allyl alkanoates was studied in the temperature range between +60°C and +80°C. The following activation energies were obtained by the Arrhenius plots: allyl acetate, Ea=24.3 kcal mol−1; allyl propinoate, Ea=25.5 kcal mol−1; allyl butyrate, Ea=26.0 kcal mol−1; allyl isobutyrate, Ea=26.2 kcal mol−1; allyl trimethylacetate, Ea=26.8 kcal mol−1. The frontier molecular orbitals (FMO) of the allyl ester were calculated by the AM-1 method. The activation energy for polymerization of the allyl ester has been found to be nicely correlated with parameters such as Taft’s σ* constants of the alkyl group, 13C NMR chemical shift values of the γ carbon, and further, values of frontier electron density (frR) of the γ carbon in the allyl moiety.
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Shigetomi, Y., Ono, N., Kato, H. et al. Allylic Polymers III. Electronic Effects of Acyloxy Group in Allyl Alkanoates on Polymerization Parameters. Polym J 24, 99–105 (1992). https://doi.org/10.1295/polymj.24.99
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DOI: https://doi.org/10.1295/polymj.24.99