Macromolecular Research

The Polymer Society of Korea (한국고분자학회)
권호 표지

Titanium Complexes: A Possible Catalyst for Controlled Radical Polymerization

  • Kwark, Young-Je (Department of Textile Engineering, Soongsil University) ;
  • Kim, Jeong-Han (Kolon Industries, Inc.) ;
  • Novak Bruce M. (Department of Chemistry, North Carolina State University)
  • Published : 2007.02.28
Download PDF
⟨ Previous Next ⟩

Abstract

Pentamethylcyclopentadienyltitanium trichloride, bis(cyclopentadienyl)titanium dichloride ($Cp_2TiCl_2$), and bis(pentamethylcyclopentadienyl)titanium dichloride were used in the polymerization of styrene without the aid of Group I-III cocatalysts. The properties of the resulting polymer indicated that polymerization was more controlled than in thermal polymerization. The kinetic studies indicated that a lower level of termination is present and that the polymer chain can be extended by adding an additional monomer. To elucidate the mechanism of polymerization, a series of experiments was performed. All results supported the involvement of a radical mechanism in the polymerization using $Cp_2TiCl_2$. The possibility of atom transfer radical polymerization (ATRP) mechanism was investigated by isolating the intermediate species. We could confirm the activation step from the reaction of 1-PEC1 with $Cp_2TiCl$ by detecting the coupling product of the generated active radicals. However, the reversible deactivation reaction competes with other side reactions, and it detection was difficult with our model system.

Keywords

References

  1. D. F. Herman and W. K. Nelson, J. Am. Chem. Soc., 75, 3877 (1953) https://doi.org/10.1021/ja01100a054
  2. A. N. Nesmeyanov, O. V. Nogina, and R. K. Freidlina, Dokl. Akad. Nauk SSSR, 95, 813 (1954)
  3. S. Inoue, T. Tsuruta, and J. Furukawa, Makromol. Chem., 49, 13 (1961)
  4. J.-S. Wang and K. Matyjaszewski, J. Am. Chem. Soc., 117, 5614 (1995)
  5. D. M. Haddleton, S. G. Jackson, and S. A. F. Bon, J. Am. Chem. Soc., 122, 1542 (2000)
  6. V. Percec, A. D. Asandei, F. Asgarzadeh, T. K. Bera, and B. Barboiu, J. Polym. Sci.; Part A: Polym. Chem., 38, 3839 (2000)
  7. A. S. Brar and S. Kaur, J. Polym. Sci.; Part A: Polym. Chem., 43, 5906 (2005)
  8. M. Kato, M. Kamigaito, M. Sawamoto, and T. Higashimura, Macromolecules, 28, 1721 (1995)
  9. S. C. Hong, K. E. Shin, S. K. Noh, and W. S. Lyoo, Macromol. Res., 13, 391 (2005)
  10. C. W. Bielawski, J. Louie, and R. H. Grubbs, J. Am. Chem. Soc., 122, 12872 (2000)
  11. R. Drozdzak, B. Allaert, N. Ledoux, I. Dragutan, V. Dragutan, and F. Verpoort, Adv. Synth. Cat., 347, 1721 (2005)
  12. T. Ando, M. Kamigaito, and M. Sawamoto, Macromolecules, 30, 4507 (1997)
  13. K. Matyjaszewski, M. Wei, J. Xia, and N. E. McDermott, Macromolecules, 30, 8161 (1997)
  14. J. Louie and R. H. Grubbs, Chem. Commun., 1479 (2000)
  15. R. K. O'Reilly, V. C. Gibson, A. J. P. White, and D. J. Williams, Polyhedron, 23, 2921 (2004)
  16. M. P. Shaver, L. E. N. Allan, H. S. Rzepa, and V. C. Gibson, Angew. Chem. Int. Ed., 45, 1241 (2006)
  17. C. Granel, Ph. Dubois, R. Jérôme, and Ph. Teyssie, Macromolecules, 29, 8576 (1996)
  18. H. Uegaki, Y. Kotani, M. Kamigaito, and M. Sawamoto, Macromolecules, 31, 6756 (1998)
  19. E. Duquesne, J. Habimana, P. Degee, and Ph. Dubois, Macromol. Chem. Phys., 207, 1116 (2006)
  20. Ph. Lecomte, I. Draiper, Ph. Dubois, Ph. Teyssie, and R. Jerome, Macromolecules, 30, 7631 (1997)
  21. M.-S. Weiser and R. Mülhaupt, J. Polym. Sci.; Part A: Polym. Chem., 43, 3804 (2005)
  22. V. Percec, B. Barboiu, A. Neumann, J. C. Ronda, and M. Zhao, Macromolecules, 29, 3665 (1996)
  23. G. Moineau, C. Granel, Ph. Dubois, R. Jerome, and Ph. Teyssie, Macromolecules, 31, 542 (1998)
  24. Y. Kotani, M. Kamigaito, and M. Sawamoto, Macromolecules, 32, 2420 (1999)
  25. S. Komiya, T. Chigira, T. Suzuki, and M. Hirano, Chem. Lett., 347 (1999)
  26. J. A. M. Brandts, P. van de Geijn, E. E. van Faassen, J. Boersma, and G. van Koten, J. Organomet. Chem., 584, 246 (1999)
  27. Unpublished result
  28. D. Landini and F. Rolla, J. Org. Chem., 45, 3527 (1980) https://doi.org/10.1021/jo01294a013
  29. K. Matyjaszewski, B. E. Woodworth, X. Zhang, S. G. Gaynor, and Z. Metzner, Macromolecules, 31, 5955 (1998)
  30. A. B. Pangborn, M. A. Giardello, R. H. Grubbs, R. K. Rosen, and F. J. Timmers, Organometallics, 15, 1518 (1996)
  31. I. Li, B. A. Howell, K. Matyjaszewski, T. Shigemoto, P. B. Smith, and D. B. Priddy, Macromolecules, 28, 6692 (1995)
  32. K. Matyjaszewski, K. Davis, T. Patten, and M. Wei, Tetrahedron, 53, 15321 (1997)