Microporous and mesoporous supports and their effect on the performance of supported metallocene catalysts

Detalhes bibliográficos
Autor(a) principal: Silveira, Fernando Tobias
Data de Publicação: 2010
Outros Autores: Alves, Maria do Carmo Martins, Stedile, Fernanda Chiarello, Pergher, Sibele Berenice Castellã, Santos, João Henrique Zimnoch dos
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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spelling 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:123456789/29091Tk9OLUVYQ0xVU0lWRSBESVNUUklCVVRJT04gTElDRU5TRQoKCkJ5IHNpZ25pbmcgYW5kIGRlbGl2ZXJpbmcgdGhpcyBsaWNlbnNlLCBNci4gKGF1dGhvciBvciBjb3B5cmlnaHQgaG9sZGVyKToKCgphKSBHcmFudHMgdGhlIFVuaXZlcnNpZGFkZSBGZWRlcmFsIFJpbyBHcmFuZGUgZG8gTm9ydGUgdGhlIG5vbi1leGNsdXNpdmUgcmlnaHQgb2YKcmVwcm9kdWNlLCBjb252ZXJ0IChhcyBkZWZpbmVkIGJlbG93KSwgY29tbXVuaWNhdGUgYW5kIC8gb3IKZGlzdHJpYnV0ZSB0aGUgZGVsaXZlcmVkIGRvY3VtZW50IChpbmNsdWRpbmcgYWJzdHJhY3QgLyBhYnN0cmFjdCkgaW4KZGlnaXRhbCBvciBwcmludGVkIGZvcm1hdCBhbmQgaW4gYW55IG1lZGl1bS4KCmIpIERlY2xhcmVzIHRoYXQgdGhlIGRvY3VtZW50IHN1Ym1pdHRlZCBpcyBpdHMgb3JpZ2luYWwgd29yaywgYW5kIHRoYXQKeW91IGhhdmUgdGhlIHJpZ2h0IHRvIGdyYW50IHRoZSByaWdodHMgY29udGFpbmVkIGluIHRoaXMgbGljZW5zZS4gRGVjbGFyZXMKdGhhdCB0aGUgZGVsaXZlcnkgb2YgdGhlIGRvY3VtZW50IGRvZXMgbm90IGluZnJpbmdlLCBhcyBmYXIgYXMgaXQgaXMKdGhlIHJpZ2h0cyBvZiBhbnkgb3RoZXIgcGVyc29uIG9yIGVudGl0eS4KCmMpIElmIHRoZSBkb2N1bWVudCBkZWxpdmVyZWQgY29udGFpbnMgbWF0ZXJpYWwgd2hpY2ggZG9lcyBub3QKcmlnaHRzLCBkZWNsYXJlcyB0aGF0IGl0IGhhcyBvYnRhaW5lZCBhdXRob3JpemF0aW9uIGZyb20gdGhlIGhvbGRlciBvZiB0aGUKY29weXJpZ2h0IHRvIGdyYW50IHRoZSBVbml2ZXJzaWRhZGUgRmVkZXJhbCBkbyBSaW8gR3JhbmRlIGRvIE5vcnRlIHRoZSByaWdodHMgcmVxdWlyZWQgYnkgdGhpcyBsaWNlbnNlLCBhbmQgdGhhdCB0aGlzIG1hdGVyaWFsIHdob3NlIHJpZ2h0cyBhcmUgb2YKdGhpcmQgcGFydGllcyBpcyBjbGVhcmx5IGlkZW50aWZpZWQgYW5kIHJlY29nbml6ZWQgaW4gdGhlIHRleHQgb3IKY29udGVudCBvZiB0aGUgZG9jdW1lbnQgZGVsaXZlcmVkLgoKSWYgdGhlIGRvY3VtZW50IHN1Ym1pdHRlZCBpcyBiYXNlZCBvbiBmdW5kZWQgb3Igc3VwcG9ydGVkIHdvcmsKYnkgYW5vdGhlciBpbnN0aXR1dGlvbiBvdGhlciB0aGFuIHRoZSBVbml2ZXJzaWRhZGUgRmVkZXJhbCBkbyBSaW8gR3JhbmRlIGRvIE5vcnRlLCBkZWNsYXJlcyB0aGF0IGl0IGhhcyBmdWxmaWxsZWQgYW55IG9ibGlnYXRpb25zIHJlcXVpcmVkIGJ5IHRoZSByZXNwZWN0aXZlIGFncmVlbWVudCBvciBhZ3JlZW1lbnQuCgpUaGUgVW5pdmVyc2lkYWRlIEZlZGVyYWwgZG8gUmlvIEdyYW5kZSBkbyBOb3J0ZSB3aWxsIGNsZWFybHkgaWRlbnRpZnkgaXRzIG5hbWUgKHMpIGFzIHRoZSBhdXRob3IgKHMpIG9yIGhvbGRlciAocykgb2YgdGhlIGRvY3VtZW50J3MgcmlnaHRzCmRlbGl2ZXJlZCwgYW5kIHdpbGwgbm90IG1ha2UgYW55IGNoYW5nZXMsIG90aGVyIHRoYW4gdGhvc2UgcGVybWl0dGVkIGJ5CnRoaXMgbGljZW5zZQo=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
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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
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