Abstract
The hydrogen abstraction ability of dialkyl peroxides was determined in the presence of 2.0 M 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer, MSD) in cyclohexane at 140°C. Cyclohexyl radicals produced through hydrogen abstraction by peroxide-derived radicals are efficiently trapped by MSD. Trapping yields were greatly dependent on individual peroxides, decreasing in the following order: di-t-butyl peroxide (72%)>dicumyl peroxide (54%)>di-t-amyl peroxide (22%)>di-t-hexyl peroxide (14%). In this case, the main hydrogen abstracting radicals were alkoxy radicals produced from the peroxides. The hydrogen abstraction ability of dialkyl peroxides was also tested in neat cyclohexane. The dehydrodimer yields of cyclohexane were almost the same (40–50%) and close to theoretical values. This clearly demonstrates that alkyl as well as alkoxy radicals act as effective hydrogen abstractors in the absence of MSD. MSD trapping is useful for providing information on hydrogen abstraction ability of organic peroxides in the presence of styrenic monomers.
Similar content being viewed by others
Article PDF
References
J. D. Van Drumpt and H. H. J. Oosterwijk, J. Polym. Sci., Polym. Chem. Ed., 14, 1495 (1976).
Y. Watanabe, H. Ishigaki, H. Okada, and S. Suyama, Polym. J., 29, 366 (1997).
Y. Watanabe, H. Ishigaki, H. Okada, and S. Suyama, Chem. Lett., 1089 (1993).
S. Suyama, H. Ishigaki, Y. Watanabe, and T. Nakamura, Polym. J., 27, 371 (1995).
S. Suyama, H. Ishigaki, Y. Watanabe, and T. Nakamura, Polym. J., 27, 503 (1995).
F. Carrock and M. Szwarc, J. Am. Chem. Soc., 81, 4138 (1959).
J. Chateauneuf, J. Lusztyk, and K. U. Ingold, J. Am. Chem. Soc., 110, 2877 (1988).
J. A. Howard and J. C. Scaiano, in “Landolt-Börnstein. New Series. Radical Reaction Rates in Liquids,” Vol. 13d, H. Fischer, Ed., Springer-Verlag, Berlin, 1984, p 19.
W. A. Cramer, J. Phys. Chem., 71, 1171 (1967).
K. U. Ingold, in “Free Radicals,” Vol. I, J. K. Kochi, Ed., John Wiley & Sons, New York, N.Y., 1973, p 51.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Watanabe, Y., Ishigaki, H., Okada, H. et al. New Method for Determination of Hydrogen Abstraction Ability of Organic Peroxides. Polym J 29, 940–943 (1997). https://doi.org/10.1295/polymj.29.940
Issue Date:
DOI: https://doi.org/10.1295/polymj.29.940
Keywords
This article is cited by
-
Melt Strength and Rheological Properties of Biodegradable Poly(Lactic Aacid) Modified via Alkyl Radical-Based Reactive Extrusion Processes
Journal of Polymers and the Environment (2012)
-
Molecular characterization and crystallization behavior of peroxide-induced slightly crosslinked poly(L-lactide) during extrusion
Polymer Journal (2010)