Manipulation of the Ligand Structure as an Effective and Versatile Tool for Modification of Active Site Properties in Homogeneous Ziegler-Natta Catalyst Systems

  • Abbas Razavi
  • Dominique Vereecke
  • Lilian Peters
  • Katty Den Dauw
  • Léa Nafpliotis
  • Jerry L. Atwood


The molecular structures of a series of group 14 metallocenes with prochiral and chiral ligand frameworks have been determined by single crystal X-ray diffraction. Correlation of the polymerization behavior of these catalyst precursors with the properties of the polymers they produce has demonstrated that relatively minor steric perturbations (caused by cyclopentadienyl substituents or by slight modification in the bridge) have a pronounced effect on the mechanism of their polymerization, and the microtacticity of the resulting poly olefins. The pair-wise comparison of the molecular structures, polymerization behaviors, and polymer properties of four metallocenes: Isopropylidene(cyclopentadienyl- fluoreny 1)ZrCl2, isopropylidene(3-methylcyclopentadienyl-fluoreny 1)ZrCl2, isopropylidene (3-t-butylcyclopentadienyl-fluorenyl)ZrCl2, and [1,2-(cyclopentadienyl-fluorenyl)ethane] ZrCl2, all having the same basic molecular skeleton with mixed aromatic ligand framework, has lead to the determination of the impact of the steric bulk of the positional substituents on the regio- and stereoselectivity of the final catalysts. By employing the molecular structure of the monoalkyl cation, [isopropylidene(cyclopentadienyl-fluorenyl) ZrMe]+ as a “close-to-reality” model for the active site and application of the generally accepted stereodifferentiation principles, the relevance of different structural factors becomes evident. It has been shown that for the described catalyst precursors, the syndiospecificity, hemiisospecificity, and isospecificity is further dependent on the dynamically selective behavior of the chain with the free, restricted, or inhibited migration (a mechanism which prevails throughout the entire polymerization processes).


Isotactic Polypropylene Versatile Tool Ligand Structure Propylene Polymerization Methyl Region 
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Copyright information

© Springer-Verlag Berlin Heidelberg 1995

Authors and Affiliations

  • Abbas Razavi
    • 1
  • Dominique Vereecke
    • 1
  • Lilian Peters
    • 1
  • Katty Den Dauw
    • 1
  • Léa Nafpliotis
    • 1
  • Jerry L. Atwood
    • 2
  1. 1.Fina Research, Centre de Recherche du Groupe PetrofinaZone Industrielle CFeluyBelgium
  2. 2.Department of ChemistryThe University of AlabamaTuscaloosaUSA

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