The role of dormant sites in propene polymerization using methylalumoxane activated metallocene catalysts

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1995
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Jüngling, Stephan
Mülhaupt, Rolf
Stehling, Udo
Fischer, David
Langhauser, Franz
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Macromolecular Symposia ; 97 (1995), 1. - pp. 205-216. - ISSN 1022-1360. - eISSN 1521-3900
Abstract
Propene polymerization of methylalumoxane (MAO) activated rac-Me2Si(Benz[e]Indenyl)2ZrCl2 (BI) and rac-Me2Si(2-Me-Benz[e]Indenyl)2ZrCl2 (MBI) was studied to investigate the influence of the ligand substitution pattern and the role of dormant sites. Poly(propene) end group composition as well as regio- and stereoirregularities were examined by means of 1H- and 13C-NMR spectroscopy. Dormant sites, resulting from 2, 1-propene insertion, were reactivated either by β-hydrogen transfer to propene, yielding 2-butenyl end groups, or by 1, 2-insertion of propene, yielding regioirregularities. Propene polymerization in the presence of hydrogen gave n-butyl end groups and less regioirregularities as expected for hydrogenolysis of such dormant sites. Methyl substitution in 2-position of the benz[e]indenyl ligand suppressed β-hydrogen transfer to propene, and increased molecular weight with increasing propene concentration. Also, activation energy increased from 30 kJ/mol (BI/MAO) to 59 kJ/mol (MBI/MAO). For both catalysts activity depended on propene concentration. The order of reaction relative to propene was 1.7.
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ISO 690JÜNGLING, Stephan, Rolf MÜLHAUPT, Udo STEHLING, Hans-Herbert BRINTZINGER, David FISCHER, Franz LANGHAUSER, 1995. The role of dormant sites in propene polymerization using methylalumoxane activated metallocene catalysts. In: Macromolecular Symposia. 97(1), pp. 205-216. ISSN 1022-1360. eISSN 1521-3900. Available under: doi: 10.1002/masy.19950970121
BibTex
@article{Jungling1995dorma-24062,
  year={1995},
  doi={10.1002/masy.19950970121},
  title={The role of dormant sites in propene polymerization using methylalumoxane activated metallocene catalysts},
  number={1},
  volume={97},
  issn={1022-1360},
  journal={Macromolecular Symposia},
  pages={205--216},
  author={Jüngling, Stephan and Mülhaupt, Rolf and Stehling, Udo and Brintzinger, Hans-Herbert and Fischer, David and Langhauser, Franz}
}
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    <dcterms:abstract xml:lang="eng">Propene polymerization of methylalumoxane (MAO) activated rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(Benz[e]Indenyl)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt; (BI) and rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(2-Me-Benz[e]Indenyl)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt; (MBI) was studied to investigate the influence of the ligand substitution pattern and the role of dormant sites. Poly(propene) end group composition as well as regio- and stereoirregularities were examined by means of &lt;sup&gt;1&lt;/sup&gt;H- and &lt;sup&gt;13&lt;/sup&gt;C-NMR spectroscopy. Dormant sites, resulting from 2, 1-propene insertion, were reactivated either by β-hydrogen transfer to propene, yielding 2-butenyl end groups, or by 1, 2-insertion of propene, yielding regioirregularities. Propene polymerization in the presence of hydrogen gave n-butyl end groups and less regioirregularities as expected for hydrogenolysis of such dormant sites. Methyl substitution in 2-position of the benz[e]indenyl ligand suppressed β-hydrogen transfer to propene, and increased molecular weight with increasing propene concentration. Also, activation energy increased from 30 kJ/mol (BI/MAO) to 59 kJ/mol (MBI/MAO). For both catalysts activity depended on propene concentration. The order of reaction relative to propene was 1.7.</dcterms:abstract>
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