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Kinetics and Catalysis

, Volume 46, Issue 2, pp 166–176 | Cite as

Mechanism of olefin polymerization on supported Ziegler-Natta catalysts based on data on the number of active centers and propagation rate constants

  • G. D. Bukatov
  • V. A. Zakharov
  • A. A. Barabanov
Article

Abstract

The number of active centers (Cg) and propagation rate constants (kg) for the polymerization of propylene and ethylene on highly active titanium-magnesium catalysts (TMCs) of different compositions at 70°C were determined using the method of 14CO inhibition of polymerization. In the polymerization of propylene on the TiCl4/D1/MgCl2-AlEt3/D2 system (D1 is dibutyl phthalate or 2,2′-diisobutyl-1,3-dimethoxypropane; D2 is a silane), the effects of D1 and D2 donors on the values of Cg and kg were studied. It was found that the donors decreased the values of kg for nonstereospecific centers, had no effect on the values of kg for stereospecific centers, and increased the fraction of stereospecific centers, as well as the fraction of “sleeping” centers regardless of their stereospecificity. The rate constants of isotactic-chain transfer with C3H6, AlEt3, H2,and ZnEt2 were determined. In the polymerization of ethylene, a number of TMCs exhibited strong diffusion limitations, which manifested themselves in a dramatic decrease in the determined values of kg. It was demonstrated that diffusion limitations can be removed by decreasing the particle size and the concentration of active centers and by performing prepolymerization with propylene. The values of kg in ethylene polymerization were similar for stereospecific and nonstereospecific centers.

Keywords

Propylene Active Center Phthalate C3H6 Diffusion Limitation 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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REFERENCES

  1. 1.
    Barbe, P.C., Cecchin, G., and Noristi, L., Adv. Polym. Sci., 1987, vol. 81, p. 1.Google Scholar
  2. 2.
    Albizzati, E., Giannini, U., Collina, G., Noristi, L., and Resconi, L., Polypropylene Handbook, Moore, E.P., Jr., Ed., Vienna: Hanser, 1996, vol. 2.Google Scholar
  3. 3.
    Albizzati, E., Giannini, U., Morini, G., Smith, C.A., and Ziegler, R.C., Ziegler Catalysts, Fink, G., Mulhaupt, R., and Brintzinger, H.H., Eds., Berlin: Springer, 1995, p. 413.Google Scholar
  4. 4.
    Albizzati, E., Giannini, U., Morini, G., Galimberti, M., Barino, L., and Scordamaglia, R., Makromol. Chem., Macromol. Symp., 1995, vol. 89, p. 73.Google Scholar
  5. 5.
    Soga, K., Shiono, T., and Doi, Y., Makromol. Chem., 1988, vol. 189, p. 1531.Google Scholar
  6. 6.
    Barbe, P.C., Noristi, L., and Baruzzi, G., Makromol. Chem., 1992, vol. 193, p. 229.Google Scholar
  7. 7.
    Kashiwa, N. and Kojoh, S., Makromol. Chem., Macromol. Symp., 1995, vol. 89, p. 27.Google Scholar
  8. 8.
    Sacchi, M.C., Forlini, F., Tritto, I., and Locatelli, P., Makromol. Chem., Macromol. Symp., 1995, vol. 89, p. 91.Google Scholar
  9. 9.
    Chadwick, J.C., Ziegler Catalysts, Fink, G., Mulhaupt, R., and Brintzinger, H.H., Eds., Berlin: Springer, 1995, p. 428.Google Scholar
  10. 10.
    Morini, G., Albizzati, E., Balbontin, G., Mindozzi, I., Sacchi, M.C., Forlini, F., and Tritto, I., Macromolecules, 1996, vol. 29, p. 5770.Google Scholar
  11. 11.
    Chadwick, J.C., Morini, G., Balbontin, G., Camurati, I., Heere, J.J.R., Mindozzi, I., and Testoni, F., Macromol. Chem. Phys., 2001, vol. 202, p. 1995.Google Scholar
  12. 12.
    Chadwick, J.C., Makromol. Chem., Macromol. Symp., 2001, vol. 173, p. 21.Google Scholar
  13. 13.
    Matsuoka, H., Liu, B., Nakatani, H., and Terano, M., Macromol. Rapid Commun., 2001, vol. 22, p. 326.Google Scholar
  14. 14.
    Liu., B., Nitta, T., Nakatani, H., and Terano, M., Macromol. Chem. Phys., 2003, vol. 204, p. 395.Google Scholar
  15. 15.
    Bukatov, G.D., Goncharov, V.S., and Zakharov, V.A., Macromol. Chem. Phys., 1995, vol. 196, p. 1751.Google Scholar
  16. 16.
    Tait, P.J., Zohuri, G.H., Kells, A.M., and McKenzie, I.D., Ziegler Catalysts, Fink, G., Mulhaupt, R., and Brintzinger, H.H., Eds., Berlin: Springer, 1995, p. 343.Google Scholar
  17. 17.
    Mori, H., Iguchi, H., Hasebe, K., and Terano, M., Macromol. Chem. Phys., 1997, vol. 198, p. 1249.Google Scholar
  18. 18.
    Bukatov, G.D. and Zakharov, V.A., Macromol. Chem. Phys., 2001, vol. 202, p. 2003.Google Scholar
  19. 19.
    Busico, V., Cipullo, R., and Corradini, P., Makromol. Chem., Rapid Commun., 1992, vol. 13, p. 15.Google Scholar
  20. 20.
    RF Patent 2064836, 1996.Google Scholar
  21. 21.
    UK Patent 2111066.Google Scholar
  22. 22.
    RF Patent 2152404, 2000.Google Scholar
  23. 23.
    USSR Inventor’s Certificate no. 726702, Byull. Izobret., 1981, no. 29.Google Scholar
  24. 24.
    Busico, V., Corradini, P., de Martino, L., Graziano, F., and Iadicicco, A., Makromol. Chem., 1991, vol. 192, p. 49.Google Scholar
  25. 25.
    Sergeev, S.A., Bukatov, G.D., Zakharov, V.A., and Moroz, E.M., Makromol. Chem., 1983, vol. 184, p. 2421.Google Scholar
  26. 26.
    Busico, V., Corradini, P., de Martino, L., Proto, A., and Savino, V., Makromol. Chem., 1985, vol. 186, p. 1279.Google Scholar
  27. 27.
    Keii, T., Suzuki, E., Tamura, M., Murata, M., and Doi, Y., Makromol. Chem., 1982, vol. 183, p. 2285.Google Scholar
  28. 28.
    Noristi, L., Barbe, P.C., and Baruzzi, G., Makromol. Chem., 1991, vol. 192, p. 1115.Google Scholar
  29. 29.
    Yuan, H.G., Taylor, T.W., Choi, K.Y., and Ray, W.H., J. Appl. Polym. Sci., 1982, vol. 27, p. 1691.Google Scholar
  30. 30.
    Floyd, S., Choi, K.Y., Taylor, T.W., and Ray, W.H., J. Appl. Polym. Sci., 1986, vol. 32, p. 2231.Google Scholar
  31. 31.
    Yoon, Y.S. and Ray, W.H., Ind. Eng. Chem. Res., 1987, vol. 26, p. 415.Google Scholar
  32. 32.
    Hutchinson, R.A., Chen, C.M., and Ray, W.H., J. Appl. Polym. Sci., 1992, vol. 44, p. 1389.Google Scholar

Copyright information

© MAIK “Nauka/Interperiodica” 2005

Authors and Affiliations

  • G. D. Bukatov
    • 1
  • V. A. Zakharov
    • 1
  • A. A. Barabanov
    • 1
  1. 1.Boreskov Institute of Catalysis, Siberian DivisionRussian Academy of SciencesNovosibirskRussia

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