Publikation: 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
Dateien
Datum
Autor:innen
Herausgeber:innen
ISSN der Zeitschrift
Electronic ISSN
ISBN
Bibliografische Daten
Verlag
Schriftenreihe
Auflagebezeichnung
URI (zitierfähiger Link)
DOI (zitierfähiger Link)
Internationale Patentnummer
Link zur Lizenz
Angaben zur Forschungsförderung
Projekt
Open Access-Veröffentlichung
Sammlungen
Core Facility der Universität Konstanz
Titel in einer weiteren Sprache
Publikationstyp
Publikationsstatus
Erschienen in
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.
Zusammenfassung in einer weiteren Sprache
Fachgebiet (DDC)
Schlagwörter
Konferenz
Rezension
Zitieren
ISO 690
BRYLIAKOV, 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)00443-1BibTex
@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.} }
RDF
<rdf:RDF xmlns:dcterms="http://purl.org/dc/terms/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#" xmlns:foaf="http://xmlns.com/foaf/0.1/" xmlns:void="http://rdfs.org/ns/void#" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/server/rdf/resource/123456789/23855"> <dc:language>eng</dc:language> <dc:contributor>Talsi, Evgenii P.</dc:contributor> <dcterms:issued>2003</dcterms:issued> <dc:rights>terms-of-use</dc:rights> <dc:contributor>Semikolenova, Nina V.</dc:contributor> <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/> <dcterms:bibliographicCitation>Journal of Organometallic Chemistry ; 683 (2003), 1. - S. 92-102</dcterms:bibliographicCitation> <dc:creator>Bryliakov, Konstantin P.</dc:creator> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-07-24T19:16:31Z</dcterms:available> <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/23855/2/Bryliakov_238452.pdf"/> <foaf:homepage rdf:resource="http://localhost:8080/"/> <dc:creator>Brintzinger, Hans-Herbert</dc:creator> <dcterms:abstract xml:lang="eng">Using <sup>1</sup>H- and <sup>13</sup>C-NMR spectroscopies, cationic intermediates formed by activation of L<sub>2</sub>ZrCl<sub>2</sub> with methylaluminoxane (MAO) in toluene were monitored at Al/Zr ratios from 50 to 1000 (L<sub>2</sub> are various cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands). The following catalysts were studied: (Cp-R)<sub>2</sub>ZrCl<sub>2</sub> (R=Me, 1,2-Me<sub>2</sub>, 1,2,3-Me<sub>3</sub>, 1,2,4-Me<sub>3</sub>, Me<sub>4</sub>, Me<sub>5</sub>, n-Bu, t-Bu), rac-ethanediyl(Ind)<sub>2</sub>ZrCl<sub>2</sub>, rac-Me<sub>2</sub>Si(Ind)<sub>2</sub>ZrCl<sub>2</sub>, rac-Me<sub>2</sub>Si(1-Ind-2-Me)<sub>2</sub>ZrCl<sub>2</sub>, rac-ethanediyl(1-Ind-4,5,6,7-H<sub>4</sub>)<sub>2</sub>ZrCl<sub>2</sub>, (Ind-2-Me)<sub>2</sub>ZrCl<sub>2</sub>, Me<sub>2</sub>C(Cp)(Flu)ZrCl<sub>2</sub>, Me<sub>2</sub>C(Cp-3-Me)(Flu)ZrCl<sub>2</sub> and Me<sub>2</sub>Si(Flu)<sub>2</sub>ZrCl<sub>2</sub>. Correlations between spectroscopic and ethene polymerization data for catalysts (Cp-R)<sub>2</sub>ZrCl<sub>2</sub>/MAO (R=H, Me, 1,2-Me<sub>2</sub>, 1,2,3-Me<sub>3</sub>, 1,2,4-Me<sub>3</sub>, Me<sub>4</sub>, Me<sub>5</sub>, n-Bu, t-Bu) and rac-Me<sub>2</sub>Si(Ind)<sub>2</sub>ZrCl<sub>2</sub> were established. The catalysts (Cp-R)<sub>2</sub>ZrCl<sub>2</sub>/AlMe<sub>3</sub>/CPh<sub>3</sub>+B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub><sup>−</sup> (R=Me, 1,2-Me<sub>2</sub>, 1,2,3-Me<sub>3</sub>, 1,2,4-Me<sub>3</sub>, Me<sub>4</sub>, n-Bu, t-Bu) were also studied for comparison of spectroscopic and polymerization data with MAO-based systems. Complexes of type (Cp-R)<sub>2</sub>ZrMe<sup>+</sup>←Me<sup>−</sup>-Al≡MAO (IV) with different [Me-MAO]<sup>−</sup> counteranions have been identified in the (Cp-R)<sub>2</sub>ZrCl<sub>2</sub>/MAO (R=n-Bu, t-Bu) systems at low Al/Zr ratios (50–200). At Al/Zr ratios of 500–1000, the complex [L<sub>2</sub>Zr(μ-Me)<sub>2</sub>AlMe<sub>2</sub>]<sup>+</sup>[Me-MAO]<sup>−</sup> (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)<sub>2</sub>ZrCl<sub>2</sub>/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)<sub>2</sub>ZrCl<sub>2</sub>/MAO (R=1,2-Me<sub>2</sub>, 1,2,3-Me<sub>3</sub>, 1,2,4-Me<sub>3</sub>, Me<sub>4</sub>) and rac-Me<sub>2</sub>Si(Ind)<sub>2</sub>ZrCl<sub>2</sub>/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> <dc:creator>Rytter, Erling</dc:creator> <dc:creator>Talsi, Evgenii P.</dc:creator> <dc:creator>Yudaev, Dmitrii V.</dc:creator> <dc:contributor>Rytter, Erling</dc:contributor> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-07-24T19:16:31Z</dc:date> <dc:contributor>Zakharov, Vladimir A.</dc:contributor> <dc:creator>Semikolenova, Nina V.</dc:creator> <dc:contributor>Yudaev, Dmitrii V.</dc:contributor> <dc:creator>Zakharov, Vladimir A.</dc:creator> <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/> <dc:contributor>Ystenes, Martin</dc:contributor> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/23855"/> <dc:contributor>Brintzinger, Hans-Herbert</dc:contributor> <dc:creator>Ystenes, Martin</dc:creator> <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/23855/2/Bryliakov_238452.pdf"/> <dcterms: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</dcterms:title> <dc:contributor>Bryliakov, Konstantin P.</dc:contributor> </rdf:Description> </rdf:RDF>