Dialkoxy-substituted, C1-symmetric metallocenes: Synthesis and catalytic behavior in the propylene polymerization reaction

Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences

Volumn 59, Issue 2, 2004, Pages 233-240

  Schlögl, Martin ^a   Rieger, Bernhard ^a  

^a UNIVERSITY OF ULM   (Germany)

Author keywords

Dialkoxy Substitution; Metallocene Catalysis; Propylene Polymerization

Indexed keywords

ALUMINUM COMPOUNDS; CATALYSTS; ETHANE; HEPTANE; ORGANOMETALLICS; POLYMERIZATION; POLYPROPYLENES; PROPYLENE; SYNTHESIS (CHEMICAL);

CATALYTIC BEHAVIOR; HEPTANE SOLUTIONS; HYDROCARBON SOLVENTS; METALLOCENE CATALYSIS; METALLOCENE COMPLEXES; PROPYLENE POLYMERIZATION; TRIISOBUTYLALUMINUM; ZIRCONIUM DICHLORIDE;

ZIRCONIUM COMPOUNDS;

HEPTANE DERIVATIVE; HYDROCARBON; PROPYLENE; TOLUENE DERIVATIVE; ZIRCONIUM DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL INTERACTION; CHEMICAL REACTION; COMPLEX FORMATION; MOLECULAR WEIGHT; POLYMERIZATION; SYNTHESIS;

EID: 1642446127     PISSN: 09320776     EISSN: None     Source Type: Journal    
DOI: 10.1515/znb-2004-0217     Document Type: Article

References (27)

1. For recent reviews see: a) H. H. Brintzinger, D. Fischer, R. Mülhaupt, B. Rieger, R. M. Waymouth, Angew. Chem. Int. Ed. 34, 1143 (1995) ; b) L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 100, 1253 (2000).
2. For recent reviews see: a) H. H. Brintzinger, D. Fischer, R. Mülhaupt, B. Rieger, R. M. Waymouth, Angew. Chem. Int. Ed. 34, 1143 (1995) ; b) L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 100, 1253 (2000).
3. a) Y.-X. E. Chen, T. J. Marks, Chem. Rev. 100, 1391 (2000);
4. b) J. N. Pedeutour, K. Radhakrishan, H. Cramail, A. Deffieux, Macromol. Rapid Commun. 22, 1095 (2001);
5. c) Y.-X. E. Chen, M. V. Metz, L. Li, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 120, 6287 (1998).
6. E. g.: H. G. Alt, A. Köppl, Chem. Rev. 100, 1205 (2000) and references therein.
7. a) U. Dietrich, M. Hackmann, B. Rieger, M. Klinga, M. Leskelä, J. Am. Chem. Soc. 121, 4348 (1999);
8. b) K. Kukral, P. Lehmus, M. Klinga, M. Leskelä, B. Rieger, Eur. J. Inorg. Chem. 1349 (2002);
9. c) B. Rieger, C. Troll, J. Preuschen, Macromolecules 35(15), 5742 (2002).
10. Aromatic solvents are difficult to separate from the polymer product due to their relatively high boiling points. Therefore, lower boiling (and less toxic) aliphatic hydrocarbons are predominantly used in industrial processes. Here, the insufficient solubility of metallocene catalyst compounds is considered to be a problem, which hinders a broader application. See: M. K. Gosh, S. J. Maiti, Polym. Mater. 16, 113 (1999).
11. Examples for heptane as a polymerization solvent: a) Y. X. Chen, M. D. Rausch, J. C. W. Chien, J. Polym. Sci. A 33, 2093 (1995); b) A. R. Siedle, W. M. Lamanna, R. A. Newmark, J. Stevens, D. E. Richardson, M. Ryan, Makromol. Chem. Macromol. Symp. 66, 215 (1993).
12. Examples for heptane as a polymerization solvent: a) Y. X. Chen, M. D. Rausch, J. C. W. Chien, J. Polym. Sci. A 33, 2093 (1995); b) A. R. Siedle, W. M. Lamanna, R. A. Newmark, J. Stevens, D. E. Richardson, M. Ryan, Makromol. Chem. Macromol. Symp. 66, 215 (1993).
13. For other oxygen substituted metallocene catalysts see: a) N. Piccolrovazzi, P. Pino, G. Consiglio, A. Sironi, M. Moret, Organometallics 9, 3098 (1990); b) I. K. Lee, W. J. Gauthier, J. A. M. Ball, B. Iyengar, S. Collins, Organometallics 11, 2115 (1992); c) P. Lehmus, E. Kokko, O. Härkki, R. Leino, H. J. G. Luttikhedde, J. H. Näsman, J. Seppälä, Macromolecules 32, 3547 (1999); d) E. Kokko, P. Lehmus, R. Leino, H. J. G. Luttikhedde, P. Ekholm, J. H. Näsman, J. Seppälä, Macromolecules 33, 9200 (2000).
14. For other oxygen substituted metallocene catalysts see: a) N. Piccolrovazzi, P. Pino, G. Consiglio, A. Sironi, M. Moret, Organometallics 9, 3098 (1990); b) I. K. Lee, W. J. Gauthier, J. A. M. Ball, B. Iyengar, S. Collins, Organometallics 11, 2115 (1992); c) P. Lehmus, E. Kokko, O. Härkki, R. Leino, H. J. G. Luttikhedde, J. H. Näsman, J. Seppälä, Macromolecules 32, 3547 (1999); d) E. Kokko, P. Lehmus, R. Leino, H. J. G. Luttikhedde, P. Ekholm, J. H. Näsman, J. Seppälä, Macromolecules 33, 9200 (2000).
15. For other oxygen substituted metallocene catalysts see: a) N. Piccolrovazzi, P. Pino, G. Consiglio, A. Sironi, M. Moret, Organometallics 9, 3098 (1990); b) I. K. Lee, W. J. Gauthier, J. A. M. Ball, B. Iyengar, S. Collins, Organometallics 11, 2115 (1992); c) P. Lehmus, E. Kokko, O. Härkki, R. Leino, H. J. G. Luttikhedde, J. H. Näsman, J. Seppälä, Macromolecules 32, 3547 (1999); d) E. Kokko, P. Lehmus, R. Leino, H. J. G. Luttikhedde, P. Ekholm, J. H. Näsman, J. Seppälä, Macromolecules 33, 9200 (2000).
16. For other oxygen substituted metallocene catalysts see: a) N. Piccolrovazzi, P. Pino, G. Consiglio, A. Sironi, M. Moret, Organometallics 9, 3098 (1990); b) I. K. Lee, W. J. Gauthier, J. A. M. Ball, B. Iyengar, S. Collins, Organometallics 11, 2115 (1992); c) P. Lehmus, E. Kokko, O. Härkki, R. Leino, H. J. G. Luttikhedde, J. H. Näsman, J. Seppälä, Macromolecules 32, 3547 (1999); d) E. Kokko, P. Lehmus, R. Leino, H. J. G. Luttikhedde, P. Ekholm, J. H. Näsman, J. Seppälä, Macromolecules 33, 9200 (2000).
17. 2-symmetric analogues: There is no material-and time-consuming separation of rac-and meso-species, which might be especially difficult or even impossible for alkyl-substituted rac-derivatives.
18. Purification of corresponding complexes with shorter alkoxy substituents at 5,6-position (e.g.: ALK = ethyl) failed due to insufficient solubility in apolar solvents.
19. Activity values and molecular weight averages: ±15%; isotacticities: ±5%.
20. A second hypothesis might be seen in a change of the polymerization mechanism by this 5,6-dialkoxy substitution. The long, flexible n-alkyl substituents might cause an increased interaction with the growing polymer chain. However, this assumption cannot explain the reduced isotacticity values with 8a-d as well as the lack of influence of the polymerization temperature and the length of the n-alkyl substituents on the polymer properties.
21. For analogue examples of reversible chain transfer reactions, see: a) S. Lieber, H. H. Brintzinger, Macromolecules 33, 9192 (2000); b) J. C. W. Chien, Y. Iwamoto, M. D. Rausch, W. Wedler, H. H. Winter, Macromolecules 30, 3447 (1997) ; c) J. C. W. Chien, Y. Iwamoto, M. D. Rausch, J. Polym. Sci. A. 37, 2436 (1999); d) C. Przybyla, G. Fink, Acta Polym. 50, 77 (1999).
22. For analogue examples of reversible chain transfer reactions, see: a) S. Lieber, H. H. Brintzinger, Macromolecules 33, 9192 (2000); b) J. C. W. Chien, Y. Iwamoto, M. D. Rausch, W. Wedler, H. H. Winter, Macromolecules 30, 3447 (1997) ; c) J. C. W. Chien, Y. Iwamoto, M. D. Rausch, J. Polym. Sci. A. 37, 2436 (1999); d) C. Przybyla, G. Fink, Acta Polym. 50, 77 (1999).
23. For analogue examples of reversible chain transfer reactions, see: a) S. Lieber, H. H. Brintzinger, Macromolecules 33, 9192 (2000); b) J. C. W. Chien, Y. Iwamoto, M. D. Rausch, W. Wedler, H. H. Winter, Macromolecules 30, 3447 (1997) ; c) J. C. W. Chien, Y. Iwamoto, M. D. Rausch, J. Polym. Sci. A. 37, 2436 (1999); d) C. Przybyla, G. Fink, Acta Polym. 50, 77 (1999).
24. For analogue examples of reversible chain transfer reactions, see: a) S. Lieber, H. H. Brintzinger, Macromolecules 33, 9192 (2000); b) J. C. W. Chien, Y. Iwamoto, M. D. Rausch, W. Wedler, H. H. Winter, Macromolecules 30, 3447 (1997) ; c) J. C. W. Chien, Y. Iwamoto, M. D. Rausch, J. Polym. Sci. A. 37, 2436 (1999); d) C. Przybyla, G. Fink, Acta Polym. 50, 77 (1999).
25. J. C. W. Chien, W. M. Tsai, M. D. Rausch, J. Am. Chem. Soc. 113, 8570 (1991).
26. B. Peifer, W. Milius, H. G. Alt, J. Organomet. Chem. 553, 205 (1998).
27. D. F. Page, R. O. Clinton, J. Org. Chem. 27, 218 (1962).