Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts
Autor(a) principal: | |
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Data de Publicação: | 2010 |
Outros Autores: | , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UFRN |
Texto Completo: | https://repositorio.ufrn.br/jspui/handle/123456789/29091 |
Resumo: | A series of hybrid-supported catalysts was prepared by sequentially grafting Cp2ZrCl2 and (nBuCp)2ZrCl2 (1:3 ratio) onto synthesized silica–zirconia xerogel, alumino-silicates, alumina, chrysotile and commercial MAO (methylaluminoxane)-modified silica. Supported catalysts were characterized by Rutherford backscattering spectrometry, atomic force microscopy, extended X-ray absorption fine structure spectroscopy, X-ray diffraction and nitrogen adsorption. The grafted metal content was between 0.21 and 1.00 wt.% Zr/SiO2 or Zr/Al2O3. All of the systems were shown to be active in ethylene polymerization with methylaluminoxane as the cocatalyst. The catalyst activity and polymer molecular weight depended on the effects of the textural characteristics of the supports on the structure of the generated supported catalyst species. The highest activity in ethylene polymerization (ca. 6560 kgPE molZr−1 h−1) was reached with the supported catalyst using commercial MAO-modified silica and also presented the lowest surface roughness. Correlation between EXAFS data and polymer characteristics was extracted: the production of polyethylenes with higher molecular weight was associated with the reduction in the interatomic Zr–O distance of the supported catalysts, which was shown to be dependent on the nature of the support. |
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Silveira, Fernando TobiasAlves, Maria do Carmo MartinsStedile, Fernanda ChiarelloPergher, Sibele Berenice CastellãSantos, João Henrique Zimnoch dos2020-05-28T13:58:39Z2020-05-28T13:58:39Z2010-01-15SILVEIRA, Fernando; ALVES, Maria do Carmo Martins; STEDILE, Fernanda C.; PERGHER, Sibele B. C.; SANTOS, João Henrique Zimnoch dos. Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts. Journal Of Molecular Catalysis A: Chemical, [s. l.], v. 315, n. 2, p. 213-220, 15 jan. 2010. ISSN 1381-1169, DOI https://doi.org/10.1016/j.molcata.2009.09.014. Disponível em: https://www.sciencedirect.com/science/article/abs/pii/S1381116909004506?via%3Dihub. Acesso em: 28 maio 2020.1381-1169https://repositorio.ufrn.br/jspui/handle/123456789/2909110.1016/j.molcata.2009.09.014ElsevierAttribution-NonCommercial-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nc-nd/3.0/br/info:eu-repo/semantics/openAccessSupported metallocenePolyethyleneMicroporous supportsMesoporous supportsEXAFSMicroporous and mesoporous supports and their effect on the performance of supported metallocene catalystsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleA series of hybrid-supported catalysts was prepared by sequentially grafting Cp2ZrCl2 and (nBuCp)2ZrCl2 (1:3 ratio) onto synthesized silica–zirconia xerogel, alumino-silicates, alumina, chrysotile and commercial MAO (methylaluminoxane)-modified silica. Supported catalysts were characterized by Rutherford backscattering spectrometry, atomic force microscopy, extended X-ray absorption fine structure spectroscopy, X-ray diffraction and nitrogen adsorption. The grafted metal content was between 0.21 and 1.00 wt.% Zr/SiO2 or Zr/Al2O3. All of the systems were shown to be active in ethylene polymerization with methylaluminoxane as the cocatalyst. The catalyst activity and polymer molecular weight depended on the effects of the textural characteristics of the supports on the structure of the generated supported catalyst species. The highest activity in ethylene polymerization (ca. 6560 kgPE molZr−1 h−1) was reached with the supported catalyst using commercial MAO-modified silica and also presented the lowest surface roughness. Correlation between EXAFS data and polymer characteristics was extracted: the production of polyethylenes with higher molecular weight was associated with the reduction in the interatomic Zr–O distance of the supported catalysts, which was shown to be dependent on the nature of the support.engreponame:Repositório Institucional da UFRNinstname:Universidade Federal do Rio Grande do Norte (UFRN)instacron:UFRNORIGINALMicroporousMesoporousSupports_Pergher_2010.pdfMicroporousMesoporousSupports_Pergher_2010.pdfapplication/pdf1078801https://repositorio.ufrn.br/bitstream/123456789/29091/1/MicroporousMesoporousSupports_Pergher_2010.pdf6e558bcdaa40c468c1f637c108e2436cMD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8811https://repositorio.ufrn.br/bitstream/123456789/29091/2/license_rdfe39d27027a6cc9cb039ad269a5db8e34MD52LICENSElicense.txtlicense.txttext/plain; charset=utf-81484https://repositorio.ufrn.br/bitstream/123456789/29091/3/license.txte9597aa2854d128fd968be5edc8a28d9MD53TEXTMicroporousMesoporousSupports_Pergher_2010.pdf.txtMicroporousMesoporousSupports_Pergher_2010.pdf.txtExtracted texttext/plain35228https://repositorio.ufrn.br/bitstream/123456789/29091/4/MicroporousMesoporousSupports_Pergher_2010.pdf.txtaecf1e4af8113ff2ffbcfb0e6ce7bf91MD54THUMBNAILMicroporousMesoporousSupports_Pergher_2010.pdf.jpgMicroporousMesoporousSupports_Pergher_2010.pdf.jpgGenerated Thumbnailimage/jpeg1746https://repositorio.ufrn.br/bitstream/123456789/29091/5/MicroporousMesoporousSupports_Pergher_2010.pdf.jpg06df62573311ef77baeca7c95bbab82aMD55123456789/290912021-02-15 15:57:05.355oai:https://repositorio.ufrn.br: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Repositório de PublicaçõesPUBhttp://repositorio.ufrn.br/oai/opendoar:2021-02-15T18:57:05Repositório Institucional da UFRN - Universidade Federal do Rio Grande do Norte (UFRN)false |
dc.title.pt_BR.fl_str_mv |
Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts |
title |
Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts |
spellingShingle |
Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts Silveira, Fernando Tobias Supported metallocene Polyethylene Microporous supports Mesoporous supports EXAFS |
title_short |
Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts |
title_full |
Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts |
title_fullStr |
Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts |
title_full_unstemmed |
Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts |
title_sort |
Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts |
author |
Silveira, Fernando Tobias |
author_facet |
Silveira, Fernando Tobias Alves, Maria do Carmo Martins Stedile, Fernanda Chiarello Pergher, Sibele Berenice Castellã Santos, João Henrique Zimnoch dos |
author_role |
author |
author2 |
Alves, Maria do Carmo Martins Stedile, Fernanda Chiarello Pergher, Sibele Berenice Castellã Santos, João Henrique Zimnoch dos |
author2_role |
author author author author |
dc.contributor.author.fl_str_mv |
Silveira, Fernando Tobias Alves, Maria do Carmo Martins Stedile, Fernanda Chiarello Pergher, Sibele Berenice Castellã Santos, João Henrique Zimnoch dos |
dc.subject.por.fl_str_mv |
Supported metallocene Polyethylene Microporous supports Mesoporous supports EXAFS |
topic |
Supported metallocene Polyethylene Microporous supports Mesoporous supports EXAFS |
description |
A series of hybrid-supported catalysts was prepared by sequentially grafting Cp2ZrCl2 and (nBuCp)2ZrCl2 (1:3 ratio) onto synthesized silica–zirconia xerogel, alumino-silicates, alumina, chrysotile and commercial MAO (methylaluminoxane)-modified silica. Supported catalysts were characterized by Rutherford backscattering spectrometry, atomic force microscopy, extended X-ray absorption fine structure spectroscopy, X-ray diffraction and nitrogen adsorption. The grafted metal content was between 0.21 and 1.00 wt.% Zr/SiO2 or Zr/Al2O3. All of the systems were shown to be active in ethylene polymerization with methylaluminoxane as the cocatalyst. The catalyst activity and polymer molecular weight depended on the effects of the textural characteristics of the supports on the structure of the generated supported catalyst species. The highest activity in ethylene polymerization (ca. 6560 kgPE molZr−1 h−1) was reached with the supported catalyst using commercial MAO-modified silica and also presented the lowest surface roughness. Correlation between EXAFS data and polymer characteristics was extracted: the production of polyethylenes with higher molecular weight was associated with the reduction in the interatomic Zr–O distance of the supported catalysts, which was shown to be dependent on the nature of the support. |
publishDate |
2010 |
dc.date.issued.fl_str_mv |
2010-01-15 |
dc.date.accessioned.fl_str_mv |
2020-05-28T13:58:39Z |
dc.date.available.fl_str_mv |
2020-05-28T13:58:39Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
SILVEIRA, Fernando; ALVES, Maria do Carmo Martins; STEDILE, Fernanda C.; PERGHER, Sibele B. C.; SANTOS, João Henrique Zimnoch dos. Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts. Journal Of Molecular Catalysis A: Chemical, [s. l.], v. 315, n. 2, p. 213-220, 15 jan. 2010. ISSN 1381-1169, DOI https://doi.org/10.1016/j.molcata.2009.09.014. Disponível em: https://www.sciencedirect.com/science/article/abs/pii/S1381116909004506?via%3Dihub. Acesso em: 28 maio 2020. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufrn.br/jspui/handle/123456789/29091 |
dc.identifier.issn.none.fl_str_mv |
1381-1169 |
dc.identifier.doi.none.fl_str_mv |
10.1016/j.molcata.2009.09.014 |
identifier_str_mv |
SILVEIRA, Fernando; ALVES, Maria do Carmo Martins; STEDILE, Fernanda C.; PERGHER, Sibele B. C.; SANTOS, João Henrique Zimnoch dos. Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts. Journal Of Molecular Catalysis A: Chemical, [s. l.], v. 315, n. 2, p. 213-220, 15 jan. 2010. ISSN 1381-1169, DOI https://doi.org/10.1016/j.molcata.2009.09.014. Disponível em: https://www.sciencedirect.com/science/article/abs/pii/S1381116909004506?via%3Dihub. Acesso em: 28 maio 2020. 1381-1169 10.1016/j.molcata.2009.09.014 |
url |
https://repositorio.ufrn.br/jspui/handle/123456789/29091 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ info:eu-repo/semantics/openAccess |
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Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Elsevier |
publisher.none.fl_str_mv |
Elsevier |
dc.source.none.fl_str_mv |
reponame:Repositório Institucional da UFRN instname:Universidade Federal do Rio Grande do Norte (UFRN) instacron:UFRN |
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Universidade Federal do Rio Grande do Norte (UFRN) |
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UFRN |
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UFRN |
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Repositório Institucional da UFRN |
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Repositório Institucional da UFRN |
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