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Hydrogen Effects in Propylene Polymerization with Ti-Based Ziegler-Natta Catalysts. Chemical Mechanism

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Organometallic Catalysts and Olefin Polymerization

Abstract

The hydrogen activation effect in propylene polymerization reactions with Ti—based catalysts is usually explained in the literature as a consequence of the secondary insertion of a propylene molecule into the Ti—CH2CH(CH3)—Polymer bond resulting in the formation of a sleeping active center. This article proposes a different mechanism of the hydrogen activation effect. It is based on the assumption that propylene insertion into the Ti—H bond has poor regioselectivity, in contrast to its insertion into the Ti—C bond, which is highly regioselective. Ti—CH(CH3)2 species formed after the secondary insertion of propylene into the Ti—H bond is stable due to the ß—agostic interaction between the H atom of its CH3 group and the Ti atom. However, the Ti—H bond is restored in a reaction with hydrogen. Validity of this mechanism is demonstrated in the study of ethylene/α—olefin copolymerization reactions with two Ti—based catalysts. GC analysis of ethylene—propylene co—oligomers prepared in the presence of hydrogen showed that the probability of the secondary insertion of a propylene molecule into the Ti—H bond is only 3-4 times lower than the probability of its primary insertion.

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Author information

Authors and Affiliations

  1. Rutgers University, Department of Chemistry, 610 Taylor Rd, Piscataway, NJ, 08854-8087, USA

    Yury V. Kissin

  2. Semenov Institute of Chemical Physics, 117977, Moscow, Kosygin st. 4, Russia

    Laura A. Rishina

Authors
  1. Yury V. Kissin
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  2. Laura A. Rishina
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Editor information

Editors and Affiliations

  1. Hydrocarbon Process Chemistry, Sintef Applied Chemistry, PO.Box 124, Blindern, N-0314, Oslo, Norway

    Richard Blom

  2. Borealis AS, 3960, Stathelle, Norway

    Arild Follestad

  3. Institute of Chemical Engineering, NTNU, 7491, Trondheim, Norway

    Erling Rytter

  4. Department of Chemistry, University of Oslo, P.O.Box 1033, Blindern, 0315, Oslo, Norway

    Mats Tilset

  5. Department of Chemistry, NTNU, N-7491, Trondheim, Norway

    Martin Ystenes

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© 2001 Springer-Verlag Berlin Heidelberg

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Kissin, Y.V., Rishina, L.A. (2001). Hydrogen Effects in Propylene Polymerization with Ti-Based Ziegler-Natta Catalysts. Chemical Mechanism. In: Blom, R., Follestad, A., Rytter, E., Tilset, M., Ystenes, M. (eds) Organometallic Catalysts and Olefin Polymerization. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-59465-6_19

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  • DOI: https://doi.org/10.1007/978-3-642-59465-6_19

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-642-63987-6

  • Online ISBN: 978-3-642-59465-6

  • eBook Packages: Springer Book Archive

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