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Partially Hydrolyzed Alkylaluminums as the Active Heterogenized Components of Metallocene Catalysts

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Abstract

The heterogenized reaction products of the partial hydrolysis of the organoaluminum compounds AlMe3 and Al(i-Bu)3 with water as a constituent of highly hydrated supports, zeolite (ZSM-5-H2O) and montmorillonite (MMT-H2O), have been synthesized. The thermal degradation of the resulting heterogenized methylalumoxane compound and methylalumoxane (MAO) in a solid state is studied by temperature-programmed desorption with the mass-spectrometric analysis of liberated gaseous products, and the structural identity of the above compounds is found. Alkylalumoxanes prepared immediately on the surface of a support form heterogenized complexes with the metallocenes Cp2ZrCl2 and Et(Ind)2ZrCl2. These heterogenized complexes exhibit high activity in the reactions of ethylene and propylene polymerization. For this reason, MAO can be replaced by AlMe3 or Al(i-Bu)3 and the additional introduction of MAO or another alkylaluminum for zirconocene activation is unnecessary. It has been found that, upon the immobilization of commercial MAO on dehydrated SiO2, the MAO molecule loses a portion of its most reactive methyl groups and, as a result of this, becomes incapable of activating metallocenes.

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Authors and Affiliations

  1. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, 117977, Russia

    L. A. Novokshonova, N. Yu. Kovaleva, T. M. Ushakova, I. N. Meshkova, V. G. Krasheninnikov & T. A. Ladygina

  2. Institute of Energy Problems of Chemical Physics, Russian Academy of Sciences, Moscow, 117829, Russia

    I. O. Leipunskii, A. N. Zhigach & M. L. Kuskov

Authors
  1. L. A. Novokshonova
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  2. N. Yu. Kovaleva
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  3. T. M. Ushakova
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  4. I. N. Meshkova
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  5. V. G. Krasheninnikov
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  6. T. A. Ladygina
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  7. I. O. Leipunskii
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  8. A. N. Zhigach
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  9. M. L. Kuskov
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__________

Translated from Kinetika i Kataliz, Vol. 46, No. 6, 2005, pp. 901–908.

Original Russian Text Copyright © 2005 by Novokshonova, Kovaleva, Ushakova, Meshkova, Krasheninnikov, Ladygina, Leipunskii, Zhigach, Kuskov.

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Novokshonova, L.A., Kovaleva, N.Y., Ushakova, T.M. et al. Partially Hydrolyzed Alkylaluminums as the Active Heterogenized Components of Metallocene Catalysts. Kinet Catal 46, 853–860 (2005). https://doi.org/10.1007/s10975-005-0147-z

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  • DOI: https://doi.org/10.1007/s10975-005-0147-z

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