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1H-, 13C-NMR and ethylene polymerization studies of zirconocene/MAO catalysts : effect of the ligand structure on the formation of active intermediates and polymerization kinetics

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2003

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Bryliakov, Konstantin P.
Semikolenova, Nina V.
Yudaev, Dmitrii V.
Zakharov, Vladimir A.
Ystenes, Martin
Rytter, Erling
Talsi, Evgenii P.

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http://nbn-resolving.de/urn:nbn:de:bsz:352-238552
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https://doi.org/10.1016/S0022-328X(03)00443-1
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Journal of Organometallic Chemistry. 2003, 683(1), pp. 92-102. ISSN 0022-328X. Available under: doi: 10.1016/S0022-328X(03)00443-1

Zusammenfassung

Using 1H- and 13C-NMR spectroscopies, cationic intermediates formed by activation of L2ZrCl2 with methylaluminoxane (MAO) in toluene were monitored at Al/Zr ratios from 50 to 1000 (L2 are various cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands). The following catalysts were studied: (Cp-R)2ZrCl2 (R=Me, 1,2-Me2, 1,2,3-Me3, 1,2,4-Me3, Me4, Me5, n-Bu, t-Bu), rac-ethanediyl(Ind)2ZrCl2, rac-Me2Si(Ind)2ZrCl2, rac-Me2Si(1-Ind-2-Me)2ZrCl2, rac-ethanediyl(1-Ind-4,5,6,7-H4)2ZrCl2, (Ind-2-Me)2ZrCl2, Me2C(Cp)(Flu)ZrCl2, Me2C(Cp-3-Me)(Flu)ZrCl2 and Me2Si(Flu)2ZrCl2. Correlations between spectroscopic and ethene polymerization data for catalysts (Cp-R)2ZrCl2/MAO (R=H, Me, 1,2-Me2, 1,2,3-Me3, 1,2,4-Me3, Me4, Me5, n-Bu, t-Bu) and rac-Me2Si(Ind)2ZrCl2 were established. The catalysts (Cp-R)2ZrCl2/AlMe3/CPh3+B(C6F5)4− (R=Me, 1,2-Me2, 1,2,3-Me3, 1,2,4-Me3, Me4, n-Bu, t-Bu) were also studied for comparison of spectroscopic and polymerization data with MAO-based systems. Complexes of type (Cp-R)2ZrMe+←Me−-Al≡MAO (IV) with different [Me-MAO]− counteranions have been identified in the (Cp-R)2ZrCl2/MAO (R=n-Bu, t-Bu) systems at low Al/Zr ratios (50–200). At Al/Zr ratios of 500–1000, the complex [L2Zr(μ-Me)2AlMe2]+[Me-MAO]− (III) dominates in all MAO-based reaction systems studied. Ethene polymerization activity strongly depends on the Al/Zr ratio (Al/Zr=200–1000) for the systems (Cp-R)2ZrCl2/MAO (R=H, Me, n-Bu, t-Bu), while it is virtually constant in the same range of Al/Zr ratios for the catalytic systems (Cp-R)2ZrCl2/MAO (R=1,2-Me2, 1,2,3-Me3, 1,2,4-Me3, Me4) and rac-Me2Si(Ind)2ZrCl2/MAO. The data obtained are interpreted on assumption that complex III is the main precursor of the active centers of polymerization in MAO-based systems.

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540 Chemie

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Metallocene catalysts, 1H- and 13C-NMR, polyethylene, structure–property relations, transition metal chemistry

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ISO 690BRYLIAKOV, Konstantin P., Nina V. SEMIKOLENOVA, Dmitrii V. YUDAEV, Vladimir A. ZAKHAROV, Hans-Herbert BRINTZINGER, Martin YSTENES, Erling RYTTER, Evgenii P. TALSI, 2003. 1H-, 13C-NMR and ethylene polymerization studies of zirconocene/MAO catalysts : effect of the ligand structure on the formation of active intermediates and polymerization kinetics. In: Journal of Organometallic Chemistry. 2003, 683(1), pp. 92-102. ISSN 0022-328X. Available under: doi: 10.1016/S0022-328X(03)00443-1
BibTex
@article{Bryliakov2003ethyl-23855,
  year={2003},
  doi={10.1016/S0022-328X(03)00443-1},
  title={<sup>1</sup>H-, <sup>13</sup>C-NMR and ethylene polymerization studies of zirconocene/MAO catalysts : effect of the ligand structure on the formation of active intermediates and polymerization kinetics},
  number={1},
  volume={683},
  issn={0022-328X},
  journal={Journal of Organometallic Chemistry},
  pages={92--102},
  author={Bryliakov, Konstantin P. and Semikolenova, Nina V. and Yudaev, Dmitrii V. and Zakharov, Vladimir A. and Brintzinger, Hans-Herbert and Ystenes, Martin and Rytter, Erling and Talsi, Evgenii P.}
}
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    <dcterms:abstract xml:lang="eng">Using &lt;sup&gt;1&lt;/sup&gt;H- and &lt;sup&gt;13&lt;/sup&gt;C-NMR spectroscopies, cationic intermediates formed by activation of L&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt; with methylaluminoxane (MAO) in toluene were monitored at Al/Zr ratios from 50 to 1000 (L&lt;sub&gt;2&lt;/sub&gt; are various cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands). The following catalysts were studied: (Cp-R)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt; (R=Me, 1,2-Me&lt;sub&gt;2&lt;/sub&gt;, 1,2,3-Me&lt;sub&gt;3&lt;/sub&gt;, 1,2,4-Me&lt;sub&gt;3&lt;/sub&gt;, Me&lt;sub&gt;4&lt;/sub&gt;, Me&lt;sub&gt;5&lt;/sub&gt;, n-Bu, t-Bu), rac-ethanediyl(Ind)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;, rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(Ind)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;, rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(1-Ind-2-Me)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;, rac-ethanediyl(1-Ind-4,5,6,7-H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;, (Ind-2-Me)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;, Me&lt;sub&gt;2&lt;/sub&gt;C(Cp)(Flu)ZrCl&lt;sub&gt;2&lt;/sub&gt;, Me&lt;sub&gt;2&lt;/sub&gt;C(Cp-3-Me)(Flu)ZrCl&lt;sub&gt;2&lt;/sub&gt; and Me&lt;sub&gt;2&lt;/sub&gt;Si(Flu)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;. Correlations between spectroscopic and ethene polymerization data for catalysts (Cp-R)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;/MAO (R=H, Me, 1,2-Me&lt;sub&gt;2&lt;/sub&gt;, 1,2,3-Me&lt;sub&gt;3&lt;/sub&gt;, 1,2,4-Me&lt;sub&gt;3&lt;/sub&gt;, Me&lt;sub&gt;4&lt;/sub&gt;, Me&lt;sub&gt;5&lt;/sub&gt;, n-Bu, t-Bu) and rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(Ind)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt; were established. The catalysts (Cp-R)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;/AlMe&lt;sub&gt;3&lt;/sub&gt;/CPh&lt;sub&gt;3&lt;/sub&gt;+B(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt; (R=Me, 1,2-Me&lt;sub&gt;2&lt;/sub&gt;, 1,2,3-Me&lt;sub&gt;3&lt;/sub&gt;, 1,2,4-Me&lt;sub&gt;3&lt;/sub&gt;, Me&lt;sub&gt;4&lt;/sub&gt;, n-Bu, t-Bu) were also studied for comparison of spectroscopic and polymerization data with MAO-based systems. Complexes of type (Cp-R)&lt;sub&gt;2&lt;/sub&gt;ZrMe&lt;sup&gt;+&lt;/sup&gt;←Me&lt;sup&gt;−&lt;/sup&gt;-Al≡MAO (IV) with different [Me-MAO]&lt;sup&gt;−&lt;/sup&gt; counteranions have been identified in the (Cp-R)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;/MAO (R=n-Bu, t-Bu) systems at low Al/Zr ratios (50–200). At Al/Zr ratios of 500–1000, the complex [L&lt;sub&gt;2&lt;/sub&gt;Zr(μ-Me)&lt;sub&gt;2&lt;/sub&gt;AlMe&lt;sub&gt;2&lt;/sub&gt;]&lt;sup&gt;+&lt;/sup&gt;[Me-MAO]&lt;sup&gt;−&lt;/sup&gt; (III) dominates in all MAO-based reaction systems studied. Ethene polymerization activity strongly depends on the Al/Zr ratio (Al/Zr=200–1000) for the systems (Cp-R)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;/MAO (R=H, Me, n-Bu, t-Bu), while it is virtually constant in the same range of Al/Zr ratios for the catalytic systems (Cp-R)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;/MAO (R=1,2-Me&lt;sub&gt;2&lt;/sub&gt;, 1,2,3-Me&lt;sub&gt;3&lt;/sub&gt;, 1,2,4-Me&lt;sub&gt;3&lt;/sub&gt;, Me&lt;sub&gt;4&lt;/sub&gt;) and rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(Ind)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;/MAO. The data obtained are interpreted on assumption that complex III is the main precursor of the active centers of polymerization in MAO-based systems.</dcterms:abstract>
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