Asymmetric metallocene catalysts based on dibenzothiophene: A new approach to high molecular weight polypropylene plastomers

Organometallics

Volumn 22, Issue 17, 2003, Pages 3495-3501

  Deisenhofer, Sandra ^a   Feifel, Tanja ^a   Kukral, Jürgen ^a   Klinga, Martti ^b   Leskelä, Markku ^b   Rieger, Bernhard ^a  

^a UNIVERSITY OF ULM   (Germany)

^b UNIVERSITY OF HELSINKI   (Finland)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS; MOLECULAR WEIGHT; POLYMERIZATION; POLYPROPYLENES; SYNTHESIS (CHEMICAL); X RAY ANALYSIS;

METALLOCENES;

ORGANOMETALLICS;

EID: 0041876422     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om030212f     Document Type: Article

References (65)

1. For recent reviews, see: (a) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 107, 1255.
2. (b) Metallocene-Based Polyolefins. Preparation, Properties and Technology; Scheirs, J., Kaminsky, W., Eds.; Wiley: New York, 1999.
3. (c) Resconi, L.; Cavallo, L.; Fait, A.; Piemontesi, F. Chem. Rev. 2000, 100, 1253.
4. (a) Maliin, D. T.; Rausch, M. D.; Lin, Y.; Dong, S.; Chien, J. C. W. J. Am. Chem. Soc. 1990, 112, 2030.
5. (b) Chien, J. C. W.; Llinas, G. H.; Rausch, M. D.; Lin, Y.; Winter, H. H. J. Am. Chem. Soc. 1991, 113, 8569.
6. (c) Llinas, G. H.; Dong, S.-H.; Mallin, D. T.; Rausch, M. D.; Lin, Y.-G. ; Winter, H. H.; Chien, J. C. W. Macromolecules 1992, 25, 1242.
7. (d) Llinas, G. H.; Day, R. O.; Rausch, M. D.; Chien, J. C. W. Organometallics 1993, 12, 1283.
8. (e) Thomas, E. J.; Chien, J. C. W.; Rausch, M. D. Organometallics 1999, 18, 1439.
9. (f) Thomas, E. J.; Rausch, M. D.; Chien, J. C. W. J. Organomet. Chem. 2001, 631, 29.
10. (g) Herzog, M. N.; Chien, J. C. W.; Rausch, M. D. J. Organomet. Chem. 2002, 654, 29.
11. (a) Gauthier, W. J.; Corrigan, J. F.; Nicholas, N. J.; Collins, S. Macromolecules 1995, 28, 3771.
12. (b) Gauthier, W. J.; Collins, S. Macromolecules 1995, 28, 3778.
13. (c) Gauthier, W. J.; Collins, S. Macromol. Symp. 1995, 98, 223.
14. (d) Bravakis, A. M.; Bailey, L. E.; Pigeon, M.; Collins, S. Macromolecules 1998, 31, 1000.
15. (e) For recent kinetic modeling work see: Nele, M.; Mohammed, M.; Xin, S.; Collins, S. Macromolecules 2001, 34, 3830.
16. (a) Herzog, T. A.; Zubris, D. L.; Bercaw, J. E. J. Am. Chem. Soc. 1998, 118, 11988.
17. (b) Veghini, D.; Henling, L. M.; Burkhardt, T. J.; Bercaw, J. E. J. Am. Chem. Soc. 1999, 121, 564.
18. (c) Miller, S. A.; Bercaw, J. E. Organometallics 2002, 21, 934.
19. (a) Dietrich, U.; Hackmann, M.; Rieger, B.; Klinga, M.; Leskelä, M. J. Am. Chem. Soc. 1999, 121, 4348.
20. 2- and Unsymmetric ansa-Zirconocenes - Application in Homogeneous Catalysis for the Production of Isotactic and Thermoplastic Elastic Polypropene. Diss., Ulm, University, 1998.
21. Kukral, J.; Lehmus, P.; Feifel, T.; Troll, C.; Rieger, B. Organometallics 2000, 29, 3767.
22. Kukral, J.; Lehmus, P.; Klinga, M.; Leskelä, M.; Rieger, B. Eur. J. Inorg. Chem. 2002, 1349.
23. (a) Lederc, M. K.; Brintzinger, H. H. J. Am. Chem. Soc. 1995, 117, 1651.
24. (b) Lederc, M. K.; Brintzinger, H. H. J. Am. Chem. Soc. 1996, 118, 9024.
25. (a) Busico, V.; Cipullo, R. J. Am. Chem. Soc. 1994, 116, 9329.
26. (b) Busico, V.; Caporaso, L.; Cipullo, R.; Landriani, L.; Angelini, G.; Margonelli, A,; Segre, A. L. J. Am. Chem. Soc. 1996, 118, 2105.
27. (c) Busico, V.; Brita, D.; Caporaso, L.; Cipullo, R.; Vacatello, M. Macromolecules 1997, 30, 3971.
28. (d) Busico, V.; Cipullo, R.; Caporaso, L.; Angelini, G.; Segre, A. L. J. Mol. Catal. A 1998, 128, 53.
29. Yoder, J. C.; Bercaw, J. E. J. Am. Chem. Soc. 2002, 124, 2548.
30. Rieger, B.; Troll, C.; Preuschen, J. Macromolecules 2002, 35, 5742.
31. In contrast to conventional isotactic polypropylene (95 ≤ [mmmm] ≤ 100) with high stiffness and homopolypropylene elastomers (25 ≤ [mmmm] ≤ 60) showing rubber elastic behavior nonelastic but flexible polymers in the range of 60-95% tacticity are named "plastomers", Compared to highly isotactic thermoplastic materials, plastomers display lower stiffness and show therefore increased flexibility.
32. For further results on heteroatom-containing systems see: (a) Dreier, T. ; Erker, G.; Fröhlich, R.; Wibbeling, B. Organometallics 2000, 29, 4095.
33. (b) Dreier, T.; Fröhlich, R.; Erker, G. J. Organomet. Chem. 2001, 621, 197.
34. (c) Dreier, T.; Unger, G.; Erker, G.; Wibbeling, B.; Fröhlich, R. J. Organomet. Chem. 2001, 622, 143.
35. (d) Ewen, J. A.; Jones, R. L.; Elder, M. J.; Rheingold, A. L.; Liable-Sands, L. M. J. Am. Chem. Soc. 1998, 120, 10786.
36. (e) Ewen, J. A.; Elder, M. J.; Jones, R. L.; Rheingold, A. L.; Liable-Sands, L. M.; Sommer, R. D. J. Am. Chem. Soc. 2001, 123, 4763.
37. (f) Ryabov, A. N.; Gribkov, D. V.; Izmer, V. V.; Voskoboynikov, A. Z. Organometallics 2002, 21, 2842.
38. Meille, V.; Schulz, E.; Lemaire, M.; Faure, R.; Vrinat, M. Tetrahedron 1996, 52, 11, 3953.
39. BuLi as a strong base deprotonates the Cp ring as well as the aromatic proton in α-position to the sulfur atom. By use of the weaker base p-anisyllithium only the desired deprotonation of the Cp ring could be achieved.
40. Ogawa, Y.; Iwasaki, S.; Okuda, S. Tetrahedron Lett. 1981, 22, 37, 3637.
41. Fawzi, R.; Steimann, M.; Jany, G.; Rieger, B. Organometallics 1994, 13, 647. Trials to prepare 5a,b by reaction with 1-(9-fluorenyl)-2-bromoethane remained unsuccessful due to the low nucleophilicity of the Li-MBIT fragment.
42. The corresponding "forward-isomer" of the hafnocene complexes was formed in a 1:1 mixture with 7b. However, it was not separated due to the poor polymerization performance of the isostructural Zr analogue.
43. 3, and Z = 4. The results show clearly the general connectivity and the "front-orientation" of the MBIT unit as suggested in Scheme 1. However, due to poor quality of data and statistical indicators, the results are not suitable for publication.
44. Definitions of the ansa-metallocene angles: β= deviation from perpendicularity of the Zr-centroid vector. γ = distortion of the bridge atom from the Cp plane, δ = angle formed by the metal center and the ring centroid vectors. ø = bite angle between the least-squares planes of the two Cp ligands.
45. Ethylene(bisindenyl)zirconium dichloride.
46. Dang, V. A.; Yu, L.-C.; Balboni, D.; Dall'Occo, T.; Resconi, L.; Mercandelli, P.; Moret, M.; Sironi, A. Organometallics 1999, 18, 3781.
47. Ethylene(bisfluorenyl)zirconium dichloride.
48. (a) Alt, H.; Milius, W.; Palackal, S. J. Organomet. Chem. 1994, 472, 113.
49. (b) Resconi, L.; Jones, R. L.; Rheingold, A. L.; Yap, G. P. A. Organometallics 1996, 15, 998.
50. (a) Hortmann, K.; Brintzinger, H. H. New J. Chem. 1992, 16, 51.
51. (b) Burger, P.; Hortmann, K.; Brintzinger, H. H. Macromol. Chem. Macromol. Symp. 1993, 66, 127.
52. For other fluorenyl complexes with similar coordination properties see: ref 22b. Razavi, A.; Vereecke, D.; Peters, L.; Den Dauw, K.; Nafpliotis, L.; Atwood, J. L. In Ziegler Catalysts; Fink, G., Mülhaupt, R., Brintzinger, H.-H., Eds.; Springer-Verlag: Berlin, 1995; p 111, and references therein.
53. Allred, A. L. J. Inorg. Nucl. Chem. 1961, 17, 215.
54. For the role of cocatalysts see: (a) Chen, E. Y.; Marks, T. J. Chem. Rev. 2000, 100, 1391.
55. (b) Pédeutour, J.-N.; Radhakrishnan, K.; Cramail, H.; Deffieux, A. Macromol. Rapid Commun. 2001, 22, 1095, and references therein.
56. The broad molecular weight distribution results mostly from the insolubility of the ultrahigh molecular weight products in liquid propylene at lower temperatures.
57. (a) Thomas, E. J.; Chien, J. C. W.; Rausch, M. D. Macromolecules 2000, 33, 1546.
58. (b) Thomas, E. J.; Rausch, M. D.; Chien, J. C. W. Organometallics 2000, 19, 4077.
59. Chien, J. C. W.; Tsai, W.-M.; Rausch, M. D. J. Am. Chem. Soc. 1991, 113, 8570.
60. (a) Busico, V.; Cipullo, R.; Monaco, G.; Vacatello, M.; Segre, A. L. Macromolecules 1997, 30, 6251.
61. (b) Busico, V.; Cipullo, R. Prog. Polym. Sci. 2001, 26, 443.
62. TEXAN, Single-Crystal Structure Analysis Software, Version 1.6; MSC, Molecular Structure Corporation: 3200 Research Forest Dr., The Woodlands, TX 77381, 1993.
63. North, A. C. T.; Phillips, D. C.; Mathews, F. S. Acta Crystallogr. 1968, A24, 351.
64. (a) Sheldrick, G. M. SHELX-97, Program for the Solution and Refinement of Crystal Structures; University of Göttingen: Germany, 1997.
65. (b) Farrugia, L. J. ORTEP3 for Windows. J. Appl. Crystallogr. 1997, 30, 565.