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Use of stable iminoxyl radical to estimate the rate constants and volume effect of activation in Diels-Alder condensation of styrene

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Bulletin of the Academy of Sciences of the USSR, Division of chemical science Aims and scope

Conclusions

  1. 1.

    The stable iminoxyl radical 2,2,6,6-tetramethylpiperidin-1-oxyl (I), which reacts almost completely toward the end of the induction period in styrene at 80° and pressures of 1–2000 kgf/cm2, is partially regenerated on contact with the air or PbO2, which is associated with the oxidation of the hydroxylamine that is formed by the cleavage of an H atom by radical (I) from the intermediate condensation product of styrene that is formed by the Diels-Alder reaction.

  2. 2.

    The rate constants and the volume effect of activation ΔV DA≠ for the formation of the hydroxylamine were calculated from the results of determining the concentration of (I) that is regenerated by oxidation. A high absolute value for ΔV DA≠ characteristic for reactions of the Diels-Alder type, and does not contradict the Mayo scheme for the thermal initiation of styrene polymerization.

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Literature cited

  1. V. M. Zhulin, G. A. Stashina, and É. G. Rozantsev, Izv. Akad. Nauk SSSR, Ser. Khim.,1977, 1511.

  2. G. B. Guarise, Polymer,7, 497 (1966).

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  3. F. R. Mayo, International Symposium on Macromolecular Chemistry [Russian translation], Moscow (1960), p. 11.

  4. F. R. Mayo, J. Am. Chem. Soc.,90, 1289 (1968).

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  5. É. G. Rozantsev, Free Iminoxyl Radicals [in Russian], Khimiya (1970), p. 79.

  6. É. G. Rozantsev, Ibid., p. 57.

  7. B. S. El'yanov and M. G. Gonikberg, Izv. Akad. Nauk SSSR, Otd. Khim. Nauk,1961, 934; Zh. Fiz. Khim.,36, 604 (1962).

  8. B. S. El'yanov and M. G. Gonikberg, Izv. Akad. Nauk SSSR, Ser. Khim.,1967, 1044.

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Authors and Affiliations

  1. N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow

    V. M. Zhulin & G. A. Stashina

Authors
  1. V. M. Zhulin
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  2. G. A. Stashina
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Additional information

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2586–2589, November, 1977.

The authors express their gratitude to É. G. Rozantsev for supplying the 2,2,6,6-tetramethylpiperidin-1-oxyl.

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Zhulin, V.M., Stashina, G.A. Use of stable iminoxyl radical to estimate the rate constants and volume effect of activation in Diels-Alder condensation of styrene. Russ Chem Bull 26, 2396–2398 (1977). https://doi.org/10.1007/BF00958737

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  • DOI: https://doi.org/10.1007/BF00958737

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