Advertisement

Polymer Science Series B

, Volume 58, Issue 6, pp 665–674 | Cite as

Photochemical synthesis and formation mechanisms of polyvinyl acetate–CoIII(salen) “dormant” chains during “living” radical polymerization

  • E. A. SvidchenkoEmail author
  • N. M. Surin
  • A. L. Sigan
  • A. A. Safonov
Synthesis
  • 32 Downloads

Abstract

The formation of “dormant” chains due to the acceptance of the photodissociation products of vinyl acetate by stable CoII(salen) radicals was studied. The rate of formation of “dormant” chains was found experimentally to be considerably higher than that of initiating radicals upon the initiator-free photopolymerization of vinyl acetate. A high rate of formation of “dormant” chains is caused by supression of the cell effect in the presence of a strong inhibitor. A kinetic scheme was proposed which allowed drawing up a mechanism of formation of “dormant” chains as a mathematical model suitable for the quantitative description of the process. The comparison between the absorption spectra of the reaction system at different reaction steps and the quantum chemically calculated spectra of forming “dormant” chains showed the polymer chain initiation to afford the acyl radical. The constants for the growing radicals–CoII(salen) interaction, the quantum yield of the Co–C bond dissociation in “dormant” chains, and the quantum yield of the initiator-free vinyl acetate photopolymerization were determined.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    G. V. Korolev and A. P. Marchenko, Russ. Chem. Rev. 69 (5), 409 (2000).CrossRefGoogle Scholar
  2. 2.
    K. Matyjaszewski and T. P. Davis, Handbook of Radical Polymerization (Wiley, New York, 2004).Google Scholar
  3. 3.
    Z. Lu, M. Fryd, and B. Wayland, Macromolecules 37 (8), 2686 (2004).CrossRefGoogle Scholar
  4. 4.
    A. Debuigne, Y. Champouret, R. Jérôme, R. Poli, and C. Detrembleur, Chem.-Eur. J. 14 (13), 4046 (2008).CrossRefGoogle Scholar
  5. 5.
    U. Baisch and R. Poli, Polyhedron 27 (9–10), 2175 (2008).CrossRefGoogle Scholar
  6. 6.
    C. Detrembleur, D.-L. Versace, Y. Piette, M. Hurtgen, C. Jérôme, J. Lalevee, and A. Debuigne, Polym. Chem. 3, 1856 (2012).CrossRefGoogle Scholar
  7. 7.
    H. Kaneyoshi and K. Matyjaszewski, Macromolecules 38 (20), 8163 (2005).CrossRefGoogle Scholar
  8. 8.
    E. A. Svidchenko, A. L. Sigan, and A. A. Kuznetsov, Dokl. Chem. 454, 32 (2014).CrossRefGoogle Scholar
  9. 9.
    C. Floriani, M. Pupis, and F. Calderazzo, J. Organomet. Chem. 12 (1), 209 (1968).CrossRefGoogle Scholar
  10. 10.
    L. V. Levshin and A. M. Saletskii, Optical Investigation Methods of Molecular Systems (MGU, Moscow, 1994), Chap. 1 [in Russian].Google Scholar
  11. 11.
    R. Houwink and A. Staverman, Chemistry and Technology of Polymers (Akad. Verl.-Ges., Leipzig, 1962) [in German].Google Scholar
  12. 12.
    Kh. S. Bagdasar’yan, Theory of Radical Polymeization (Nauka, Moscow, 1966) [in Russian].Google Scholar
  13. 13.
    G. Oster and N. Yang, Chem. Rev. 68 (2), 125 (1968).CrossRefGoogle Scholar
  14. 14.
    G. Odian, Principles of Polymerization (Wiley, New York, 2004).CrossRefGoogle Scholar
  15. 15.
    T. Scherzer, W. Knolle, S. Naumov, and L. Prager, Macromol. Symp. 230 (1), 173 (2005).CrossRefGoogle Scholar
  16. 16.
    T. Lee, T. Ropera, and E. Jonsson, Polymer 44 (10), 2859 (2003).CrossRefGoogle Scholar
  17. 17.
    J. D. Coyle, Introduction to Organic Rhotochemistry (Wiley, New York, 1989).Google Scholar
  18. 18.
    G. O. Bekker, Einfuhrung in die Photochemie. Von Einem Autorenkollektiv (VEB Deutscher Verlag der Wissenschaften, Berlin, 1976).Google Scholar
  19. 19.
    N. Turro, Molecular Photochemistry (W.A. Benjamin, San Francisco, 1967).Google Scholar
  20. 20.
    S. Beuermann and M. Buback, Prog. Polym. Sci. 27 (2), 191 (2002).CrossRefGoogle Scholar
  21. 21.
    A. V. Kizel’, Practical Molecular Spectroscopy: Text Book for HEIs (Izd-vo MFTI, Moscow, 1998) [in Russian].Google Scholar
  22. 22.
    L. A. Gribov, V. I. Baranov, and M. E. Elyashberg, Standardless Molecular Spectral Analysis. Theoretical Foundations (Editorial URSS, Moscow, 2002) [in Russian].Google Scholar
  23. 23.
    A. Debuigne, R. Poli, C. Jérôme, R. Jérôme, and C. Detrembleur, Prog. Polym. Sci. 34 (3), 211 (2009).CrossRefGoogle Scholar
  24. 24.
    H. Fischer, Chem. Rev. 101 (12), 3581 (2001).CrossRefGoogle Scholar
  25. 25.
    M. Calligaris, D. Minichelli, G. Nardin, and L. Randaccio, J. Chem. Soc. A 1971, 2720 (1971).CrossRefGoogle Scholar

Copyright information

© Pleiades Publishing, Ltd. 2016

Authors and Affiliations

  • E. A. Svidchenko
    • 1
    Email author
  • N. M. Surin
    • 1
  • A. L. Sigan
    • 2
  • A. A. Safonov
    • 3
  1. 1.Enikolopov Institute of Synthetic Polymer MaterialsRussian Academy of SciencesMoscowRussia
  2. 2.Nesmayanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussia
  3. 3.Photochemistry CenterRussian Academy of SciencesMoscowRussia

Personalised recommendations