Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Theoretical Models of Ethylene Polymerization

  • Published : 1999.11.20
Download PDF
⟨ Previous Next ⟩

Abstract

Metallocenes, whether using a cocatalyst or not, act as catalysts in ethylene polymerization. The positive charge on the transition metal of a metallocene might have an important role in polymerization as an active site in our model approach. Using semiempirical calculations in the absence of cocatalyst, we show one of the possibilities that the positive charge on a metallocene might be more easily transferred through the Cp ring of a ligand to the ethylene than to transfer directly from the transition metal to the ethylene. In these calculations, the charge on titanium in an eight C2H4 system is transferred and a polymer chain is produced. This reaction takes place only when ethylenes are arranged in a particular direction with respect to the ring, but does not take place for ethylenes near Ti or Cl atoms. The same mechanism is shown for a metallocene ligand which is sterically hindered or where the Cp ring is replaced by fluorenyl. These results suggest an entirely new polymerization mechanism in the absence of a cocatalyst in which the Cp ring is the active site.

Keywords

References

  1. J. Am. chem. Soc. v.97 Petersen, J. L.;Lichtenberger, D. L.;Fenske, R. F.;Dahl, L. F.
  2. J. Am. Chem. Soc. v.108 Erker, G.;Dorf, U.;Atwood,J. L.;Hunter, W. E.
  3. J. Am. Chem. Soc. v.109 Lin, Z.;Le Marechal, J.;Sabat, M.;Marks, T. J.
  4. J. Am. Chem. Soc. v.110 Ewen, J. A.;Jones, R. L.;Razavi, A.
  5. J. Am. Chem. Soc. v.112 Christ, C. S. Jr.;Eyler, R.;Richardson, D. E.
  6. Prog. Polym. Sic. v.21 Po, R.;Cardi, N.
  7. Angew. Chem. v.64 Ziegler, K.
  8. Belg. Pat. 533362; German priority Ziegler, K.
  9. J. Am. Chem. Soc. v.82 Long, W. P.;Breslow, D. S.
  10. J. Am. Chem. Soc. v.81 Breslow, D. S.;Newburg, N. R.
  11. J. Am. Chem. Soc. v.110 Ewen, J. A.;Jones, R. L.;Razavi, A.;Ferrara, J. D.
  12. Macromolecules v.22 Zambelli, A.;Longo, P.;Grassi, A.
  13. Catalytic Olefin Polymerization Ewen, J. A.;Elder, M. J.;Jones, R. L.;Curtis, S.;Cheng, H. N.;Keii,T.(Ed.);Soga, K.(Ed.)
  14. Organometallics v.9 Jordan, R. F.;LaPointe, R. E.;Baenziger, N.;Hinch, G. D.
  15. Macromolecues v.26 Chien, J. C. W.;Song, W.;Rausch, M. D.
  16. Organometallics v.12 Bochmann, M.;Lancaster, S. J.
  17. Organometallics v.11 Eshuis, J. J. W.;Tan, Y. Y.;Meetsman, A.;Teuben, J. H.;Renkema, J.;Evans, G. G.
  18. J. Catal. v.3 Cossee, P. J.
  19. J. Catal. v.3 Arlman, E. J.
  20. J. Catal. v.3 Arlman, E. J.;Cossee, P. J.
  21. J. Chem. Soc., Chem. Commun. Ivin, K. J.;Rooney, J. J.;Stewart, C. D.;Green, M. L. H.;Mahtab, R.
  22. Pure. Appl. Chem. v.50 Green, N. L. H.
  23. J. Am. Chem. Soc. v.101 Evitt, E. R.;Bergman, R. G.
  24. J. Am. Chem. Soc. v.104 Turner, H. W.;Schrock, R. R.
  25. J. Am. Chem. Soc. v.105 Turner, H. W.;Schrock, R. R.;Fellmann, J. D.;Holmes, S. J.
  26. J. Am. Chem. Soc. v.107 Doherty, N. M.;Bercaw, J. E.
  27. Theor. Chim. Acta v.32 Ridley, J. E.;Zerner, M. C.
  28. Theor. Chim. Acta v.42 Ridley, J. E.;Zerner, M. C.
  29. Theor. Chim. Acta v.53 Ridley, J. E.;Zerner, M. C.
  30. J. Am. Chem. Soc. v.108 Edward, W. D.;Weiner, B.;Zerner, M. C.
  31. Bull. Korean Chem. Soc. v.14 Chang, M. C.
  32. Proc. 1st Acad. Conf. Vni. Sci. Tech. Beijing Chang, M. C.
  33. Theor. Chim. Acta v.72 Edward, W. D.;Zerner, M. C.
  34. Gottiger Nachr. v.3 Rumer, G.;Teller, E.;Weyl, H.
  35. Spin Eigenfunctions Pauncz, R.
  36. Zh. Strukt. Khim. v.7 Alekseev, N. V.;Ronova, I. A.
  37. Inorg. Chim. Acta v.7 Epstein, E. F.;Bernal, I.
  38. J. Organomet. Chem. v.30 Davis, B. R.;Bernal, I.
  39. J. Struct. Chem. (Russ.) v.13 Tkachev, V. V.;Atovmyan, L. O.
  40. Can. J. Chem. v.53 Clearfield, A.;Warner, D. K.;Saldarriaga-Molina, C. H.;Ropal, R.;Bernal, I.
  41. Structure Reports v.28 Pearson, W. B.
  42. Polyhedron v.8 Hursthouee, M. B.;Notevalli, M.
  43. J. Polym. Sci., Polym. Lett. v.8 Giannini, V.;Zucchini, V.;Albizzati, E.
  44. Makromol. Chem., Rapid. Commun. v.12 Pellecchia, C.;Proto, A.;Longo, P.;Zambelli, A.
  45. New J. Chem. v.16 Hortmann, K.;Brintzinger, H.
  46. Angew. Chem. v.102 Roll, W.;Brintzinger, H. H.;Rieger, B.;Zolk, R.
  47. New J. Chem. v.14 Spaleck, W.;Antberg, M.;Dolle, V.;Klein, R.;Rohrmann, J.;Winter, A.
  48. Angew. Chem. v.102 Herrmann, W. A.;Rohrmann, J.;Herdtweck, E.;Spaleck, W.;Winter, A.
  49. Polymer v.31 Ventitto, V.;Guerra, G.;Corradini, P.;Fusco, R.
  50. J. Am. Chem. Soc. v.113 Yang, X.;Stern, C. L.;Marks, T. J.
  51. J. Am. Chem. Soc. v.114 Sishta, C.;Hathorn, R. M.;Marks, T. J.
  52. J. Organomet. Chem. v.347 Taube, R.;Krukowka, L.
  53. J. Polym. Sci. A, Polym. Chem. v.32 Fierro, R.;Yu, Z.;Rausch, M. D.;Dong, S.;Alvares, D.;Chien, J. C. W.