Skip to main content
Log in

Heterogeneous Ziegler-Natta, metallocene, and post-metallocene catalysis: Successes and challenges in industrial application

  • Ziegler-Natta catalysis: 50 years after the Nobel Prize
  • Published:
MRS Bulletin Aims and scope Submit manuscript

Abstract

The success of polyolefins is governed to a large extent by the development of robust and versatile catalysts offering excellent morphology control. This review highlights the major evolution steps made in the polyolefin catalyst systems in terms of productivity and possibilities to control the molecular architecture of both polypropylene and polyethylene. Starting from the initial TiCl3-types, the continuous improvement of the Ziegler-Natta catalysts in terms of performance and cost is the major factor behind their wide market penetration. On the other hand, metallocene and the other “single-site” catalysts enable an unprecedented fine-tuning of chain microstructure by ligand design. In this article, special emphasis is placed on the influence of catalyst type on polymer structure characteristics such as molecular weight distribution, stereoregularity, and comonomer distribution and, ultimately, on the end-use properties of polyolefins. It is the excellent balance among price, performance, and processability that will further strengthen the position of polyolefins as a dominant class of materials in the polymer industry.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Figure 1
Figure 2

Similar content being viewed by others

References

  1. R. Mühlhaupt, Macromol. Chem. Phys. 204, 289 (2003).

    Google Scholar 

  2. K. Ziegler, H. Breil, E. Holzkamp, H. Martin, DE Patent 973626 (November 18, 1953).

  3. L.L. Böhm, Angew. Chem. Int. Ed. 42, 5010 (2003).

    Google Scholar 

  4. H.C. Welborn, J.A. Ewen, US Patent 5,324,800 to Exxon (August 18, 1991).

  5. J.C. Stevens, Stud. Surf. Sci. Catal. 11, 101 (1996).

    Google Scholar 

  6. D. Stephan, Organometallics 24, 2548 (2005).

    Google Scholar 

  7. G. Natta, G. Mazzanti, G. Boschi, DE Patent 1293453 (December 22, 1956).

  8. P. Galli, G. Veccellio, Prog. Polym. Sci. 26, 1287 (2001).

    Google Scholar 

  9. K. Soga, T. Shiono, Prog. Polym. Sci. 22, 1503 (1997).

    Google Scholar 

  10. M. Bartke, M. Oksman, M. Mustonen, P. Denifl, Macromol. Mater. Eng. 290, 250 (2005).

    Google Scholar 

  11. L. Resconi, L. Cavallo, J. Chadwick, in Comprehensive Organometallic Chemistry, 3rd ed., R.H. Crabtree, D.P. Mingos, Eds. (Elsevier, Oxford, 2006), vol. 4, pp. 1005 – 1166.

    Google Scholar 

  12. J. Severn, J.C. Chadwick, R. Duchateau, N. Friederichs, Chem. Rev. 105 (11), 4073 (2005).

    Google Scholar 

  13. www.dow.com/elastomers/products/engage.htm.

  14. www.exxonmobilchemical.com/Chem-English/brands/exact-plastomers.aspx?ln=productsservices.

  15. www.exxonmobilchemical.com/Chem-English/brands/vistamaxx-propylene-based-elastomers.aspx?ln=productsservices.

  16. C. Stephens, B. Poon, P. Ansems, S. Chum, A. Hiltner, E. Baer, J. Appl. Polym. Sci. 100, 1651 (2006).

    Google Scholar 

  17. T. Boussie, G. Diamond, C. Goh, K. Hall, A. LaPointe, M. Leclerc, M. Vince, J. Shoemaker, H. Turner, R. Rosen, J. Stevens, F. Alfano, V. Busico, R. Cipullo, G. Talarico, Angew. Chem. Int. Ed. 45, 3278 (2006); see also www.dow.com/versify.

    Google Scholar 

  18. P.S. Chum, K.W. Swogger, Prog. Polym. Sci. 33, 797 (2008).

    Google Scholar 

  19. J. Seppälä, M. Härkonen, L. Luciani, Makromol. Chem. 190, 2535 (1989).

    Google Scholar 

  20. P. Jerschow, H. Janeschitz-Kriegl, Int. Polym. Proc. 12, 72 (1997).

    Google Scholar 

  21. R. Pantani, L. Balzano, G.W.M. Peters, Macromol. Mater. Eng. 296, 740 (2011).

    Google Scholar 

  22. V. Busico, R. Cipullo, Prog. Polym. Sci. 26, 443 (2001).

    Google Scholar 

  23. M. Gahleitner, C. Bachner, E. Ratajski, G. Rohaczek, W. Neißl, J. Appl. Polym. Sci. 73, 2507 (1999).

    Google Scholar 

  24. A. Andoni, J.C. Chadwick, H.J.W. Niemantsverdriet, P.C. Thüne, J. Catal. 257, 81 (2008).

    Google Scholar 

  25. T. Garoff, V. Virkkunen, P. Jääskeläinen, T. Vestberg, Eur. Polym. J. 39, 1679 (2003).

    Google Scholar 

  26. J.C. Chadwick, F.P.T.J. van der Burgt, S. Rastogi, V. Busico, R. Cipullo, G. Talarico, J.J.R. Heere, Macromolecules 37, 9722 (2004).

    Google Scholar 

  27. A. Schöbel, E. Herdtweck, M. Parkinson, B. Rieger, Chem. Eur. J. 18, 4174 (2012).

    Google Scholar 

  28. M. Gahleitner, P. Jääskeläinen, E. Ratajski, C. Paulik, J. Reussner, J. Wolfschwenger, W. Neißl, J. Appl. Polym. Sci. 95, 1073 (2005).

    Google Scholar 

  29. C. De Rosa, F. Auriemma, P. Vollaro, L. Resconi, S. Guidotti, I. Camurati, Macromolecules 44, 540 (2011).

    Google Scholar 

  30. H. Schwager, Kunststoffe 82, 499 (1992).

    Google Scholar 

  31. G. Cecchin, G. Morini, G. Pelliconi, Macromol. Symp. 173, 195 (2001).

    Google Scholar 

  32. F. Ramsteiner, G. Kanig, W. Heckmann, W. Gruber, Polymer 24, 365 (1983).

    Google Scholar 

  33. C. Grein, K. Bernreitner, A. Hauer, M. Gahleitner, W. Neißl, J. Appl. Polym. Sci. 87, 1702 (2003).

    Google Scholar 

  34. P. Doshev, R. Lach, G. Lohse, A. Heuvelsland, W. Grellmann, H.-J. Radusch, Polymer 46, 9411 (2005).

    Google Scholar 

  35. D. Bouzid, T.F.L. McKenna, Macromol. Chem. Phys. 207, 13 (2006).

    Google Scholar 

  36. W. Kaminsky, A. Funck, K. Wiemann, Macromol. Symp. 239, 1 (2006)

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Markus Gahleitner.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Gahleitner, M., Resconi, L. & Doshev, P. Heterogeneous Ziegler-Natta, metallocene, and post-metallocene catalysis: Successes and challenges in industrial application. MRS Bulletin 38, 229–233 (2013). https://doi.org/10.1557/mrs.2013.47

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1557/mrs.2013.47

Navigation