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Russian Chemical Bulletin

, Volume 47, Issue 8, pp 1491–1497 | Cite as

Effect of substituents on the catalytic properties of bis(cyclopentadienyl) zirconocene dichlorides in polymerization of ethene

  • N. M. Bravaya
  • V. V. Strelets
  • Z. M. Dzhabieva
  • O. N. Babkina
  • V. P. Maryin
Physical Chemistry

Abstract

Comparative analysis of catalytic activity of substituted bis(cyclopentadienyl)zirconium dichlorides with the general formula (R n Cp)2ZrCl2 (Cp2ZrCl2, (MeCp)2ZrCl2, (PriCp)2ZrCl2, (Pri 2Cp)2ZrCl2, (BunCp)2ZrCl2, (BuiCp)2ZrCl2, (ButCp)2ZrCl2, Cp* 2ZrCl2 (Cp*=Me5C5), (Me3SiCp)2ZrCl2, (cyclo-C6H11Cp)2ZrCl2, and [(cyclo-C6H11)2Cp]2ZrCl2) in ethene polymerization using polymethylalumoxane as the cocatalyst was performed. The molecular mass characteristics of the polyethylene samples obtained were determined. A linear correlation of the specific activity of the catalysts and the turnover number with the electronic and steric characteristics of substituents at the Cp ring of the complexes was established for the first time. Analysis of the polymerization kinetics and the obtained correlation between the specific activity of the complexes and molecular mass characteristics of the polyethylene samples suggest that alkyl substituents participate in reactions responsible for the restriction of the polymer chain growth and regeneration of the active center. These interactions most likely involve associates of AlMe3 with polymethylalumoxane molecules.

Key words

metallocene complexes bis(cyclopentadienyl)zirconium dichlorides effect of substituents ethene polymerization 

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References

  1. 1.
    P. C. Möhring and N. J. Coville,J. Organomet. Chem., 1994,479, 1.CrossRefGoogle Scholar
  2. 2.
    J. C. W. Chien and B.-P. Wang,J. Polym. Sci., A, Polym. Chem., 1990,28, 15.CrossRefGoogle Scholar
  3. 3.
    V. P. Maryin, L. A. Nekhaeva, L. I. Vyshinskaya, B. A. Krentsel', and N. I. Ivanova,Metalloorg. Khim., 1990,3, 474 [Organomet. Chem. USSR, 1990,3 (Engl. Transl.)].Google Scholar
  4. 4.
    L. A. Nekhaeva, B. A. Krentsel', V. L. Khodzhaeva, S. V. Rykov, S. D. Artamonova, Yu. M. Antipov, S. I. Ganicheva, and A. A. Boitsov,Vysokomol. Soedin., Ser. A, 1992,34, 84 [Russ. Polym. Sci., A, 1992,34 (Engl. Transl.)].Google Scholar
  5. 5.
    P. C. Möhring and N. J. Coville,J. Mol. Catal., 1992,77, 41.CrossRefGoogle Scholar
  6. 6.
    P. C. Möhring, N. Vlachakis, N. E. Grimmer, and N. J. Coville,J. Organomet. Chem., 1994,483, 159.CrossRefGoogle Scholar
  7. 7.
    N. G. Alameddin, M. F. Ryan, J. R. Eyler, A. R. Siedle, and D. E. Richardson,Organometallics, 1995,14, 5005.CrossRefGoogle Scholar
  8. 8.
    C. Janiak, K. C. H. Lange, U. Versteeg, D. Lentz, and P. H. M. Budzelaar,Chem. Ber., 1996,129, 1517.Google Scholar
  9. 9.
    J. Bliemeister, W. Hagendorf, A. Harder, B. Heitmann, I. Scimmel, E. Schemedt, W. Schnuchel, H. Sinn, L. Tikwe, N. von Thienen, K. Urlass, H. Winter, and O. Zarncke, inZiegler Catalysts, Eds. G. Fink, R. Mülthaupt, and H. H. Brintzinger, Springer, New York-London-Paris, 1995, p. 57.Google Scholar
  10. 10.
    I. Tritto, M. C. Sacchi, P. Locatelli, and S. X. Li,Macromol. Chem. Phys. 1996,197, 1537.CrossRefGoogle Scholar
  11. 11.
    E. A. Fushman, A. D. Margolin, S. S. Lalayan, and V. E. L'vovskii,Vysokomol. Soedin., Ser B, 1995,37, 1589 [Russ. Polym. Sci., B, 1995,37 (Engl. Transl.)].Google Scholar
  12. 12.
    A. D. Margolin, E. A. Fushman, S. S. Lalayan, and V. E. L'vovskii,Vysokomol. Soedin., Ser. A, 1996,38, 1812 [Russ. Polym. Sci., 1996,A,38 (Engl. Transl.)].Google Scholar
  13. 13.
    D. Cam and U. Giannini,Makromol. Chem., 1992,193, S. 1049.CrossRefGoogle Scholar
  14. 14.
    A. K. Zefirova and A. E. Shilov,Dokl. Akad. Nauk SSSR, 1961,136, 599 [Dokl. Chem., 1961,136 (Engl. Transl.)].Google Scholar
  15. 15.
    F. S. Dyachkovskii, A. K. Shilova, and A. E. Shilov,J. Polym. Sci. Part C, 1967,16, 2333.Google Scholar
  16. 16.
    J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe, and F. L. Lee,J. Am. Chem. Soc., 1985,107, 7219.CrossRefGoogle Scholar
  17. 17.
    R. F. Jordan,Adv. Organomet. Chem., 1991,32, 325.CrossRefGoogle Scholar
  18. 18.
    C. Sishta, R. M. Hathom, and T. J. Marks,J. Am. Chem. Soc., 1992,114, 1112.CrossRefGoogle Scholar
  19. 19.
    T. K. Woo, L. Fan, and T. Ziegler,Organometallics, 1994,13, 2252.CrossRefGoogle Scholar
  20. 20.
    M. Brookhart and L. H. Green,J. Organomet. Chem., 1983,250, 395.CrossRefGoogle Scholar
  21. 21.
    H. H. Brintzinger, D. Fischer, R. Mülhaupt, R. Reiger, and R. Waymouth,Angew. Chem., 1995,107, 1255.Google Scholar
  22. 22.
    R. Grubbs and G. W. CoatesAcc. Chem. Rev., 1996,29, 85.CrossRefGoogle Scholar
  23. 23.
    J. A. Støvneng and E. Rytter,J. Organomet. Chem., 1996,519, 277.CrossRefGoogle Scholar
  24. 24.
    L. A. Nekhaeva, B. A. Krentsel', V. P. Maryin, I. M. Khrapova, V. L. Khodzhaeva, A. I. Mikaya, and S. I. Ganicheva,Neftekhimiya, 1991,31, 209 [Petroleum Chem., 1991,31 (Engl. Transl.)].Google Scholar
  25. 25.
    V. P. Maryin, L. I. Vyshinskaya, and O. N. Druzhkov,Metalloorg. Khim., 1991,4, 546 [Organomet. Chem. USSR, 1991,4 (Engl. Transl.)].Google Scholar
  26. 26.
    Yu. A. Andrianov and V. P. Maryin,J. Organomet. Chem., 1992,441, 419.CrossRefGoogle Scholar
  27. 27.
    N. Piccolrovazzi, P. Pino, G. Consiglio, A. Sironi, and M. Moret,Organometallics 1990,9, 3098.CrossRefGoogle Scholar
  28. 28.
    I.-M. Lee, J. Gauthier, J. M. Ball, B. Iyengar, and S. Collins,Organometallics, 1992,11, 2115.CrossRefGoogle Scholar
  29. 29.
    L. A. Nekhaeva, G. N. Bondarenko, S. V. Rykov, A. I. Nekhaev, B. A. Krentsel', V. P. Maryin, L. I. Vyshinskaya, I. M. Khrapova, A. V. Polonskii, and N. N. Korneev,J. Organomet. Chem., 1991,406, 139.CrossRefGoogle Scholar
  30. 30.
    J. A. Ewen,Stud. Surf. Sci. and Catal., 1986,25, 271.CrossRefGoogle Scholar
  31. 31.
    G. P. Belov, H. R. Gyulumyan, I. M. Khrapova, V. P. Maryin, and N. N. Korneev,J. Mol. Catal., A: Chemical, 1997,115, 155.CrossRefGoogle Scholar
  32. 32.
    C. Hansch, A. Leo, and R. W. Taft,Chem. Rev., 1991,91, 165.CrossRefGoogle Scholar
  33. 33.
    V. A. Pal'm,Osnovy kolichestvennoi teorii organicheskikh reaktsii [Fundamentals of the Quantitative Theory of Organic Reactions], Khimiya, Leningrad, 1977, (in Russian).Google Scholar
  34. 34.
    G. L. Soloveichik, A. B. Gavrilov, and V. V. Strelets,Metalloorg. Khim., 1989,2, 431, [Organomet. Chem. USSR, 1989,2 (Engl. Transl.)].Google Scholar
  35. 35.
    T. C. McKenzie, R. D. Sanner, and J. E. Bercaw,J. Organomet. Chem., 1975,102, 457.CrossRefGoogle Scholar
  36. 36.
    M. Bochmann,J. Chem. Soc. Dalton Trans. 1996, 255.Google Scholar
  37. 37.
    N. M. Bravaya, Z. M. Dzhabieva, V. P. Maryin, and V. V. Strelets,Polymers, 1997,42, 591.Google Scholar

Copyright information

© Plenum Publishing Corporation 1998

Authors and Affiliations

  • N. M. Bravaya
    • 1
  • V. V. Strelets
    • 1
  • Z. M. Dzhabieva
    • 1
  • O. N. Babkina
    • 1
  • V. P. Maryin
    • 1
  1. 1.Institute of Chemical Physics in ChernogolovkaRussian Academy of SciencesChernogolovkaRussian Federation

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