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Effect of substituents on the catalytic properties of bis(cyclopentadienyl)zirconium dichloride complexes with polymethylaluminoxane and AlBu1 3/CPh3B(C6F5)4 cocatalysts in ethylene polymerization

  • Physical Chemistry
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Abstract

The catalytic properties of the complexes (RCp)2ZrCl2 (R=H, Me, Pri, Bun, Bui, Me3Si,cyclo-C6H11), and Me2SiCp*NBuiZrCl2 (Cp*=C5(CH3)4) combined with the AlBui 3−CPh3B(C6F5)4 cocatalyst in ethylene polymerization were studied. The specific activity of the substituted bis-cyclopentadienyl complexes decreases in the sequence: Me>Pri>Bun>Bui>Me3Si>cyclo-C6H11, which corresponds to the activity sequence for these complexes activated by polymethylaluminoxane (MAO) but is 4–20 times lower in absolute value. Comparison of the polyethylene samples obtained in the presence of the same complexes with MAO and AlBui 3−CPh3B(C6F5)4 cocatalysts showed that polyethylene with much higher molecular mass, melting point, and crystallinity is formed in the presence of the ternary catalytic systems, and this indicates a different nature of the active sites of the catalytic systems. The effective activation energy of polymerization (≈3.6 kcal mol−1), first order with respect to monomer and ≈0.4 order with respect to organoaluminum component, was found for the (PriCo)2ZrCl2−AlBui 3−CPh3B(C6F5)4 catalytic system. It was proposed on the basis of the kinetic data that AliBu3 enters into the composition of the active site to form a bridged heteronuclear cationic complex.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432, Chernogolovka, Moscow Region, Russian Federation

    A. N. Panin, O. N. Babkina & N. M. Bravaya

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  1. A. N. Panin
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  2. O. N. Babkina
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  3. N. M. Bravaya
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp 301–307, February, 2000.

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Panin, A.N., Babkina, O.N. & Bravaya, N.M. Effect of substituents on the catalytic properties of bis(cyclopentadienyl)zirconium dichloride complexes with polymethylaluminoxane and AlBu1 3/CPh3B(C6F5)4 cocatalysts in ethylene polymerization. Russ Chem Bull 49, 303–309 (2000). https://doi.org/10.1007/BF02494677

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  • DOI: https://doi.org/10.1007/BF02494677

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