New architecture of supported metallocene catalysts for alkene polymerization

Autores
Velilla, Teresa; Delgado, Katherine; Quijada, Raúl; Bianchini, Daniela; Barrera Galland, Griselda; Dos Santos, João Henrique Z.; Fasce, Diana Patricia; Williams, Roberto Juan Jose
Año de publicación
2007
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report the synthesis of a supported metallocene catalyst that exhibits the same activity as a homogeneous catalyst for ethylene polymerization reactions. The key to this new catalytic system is a hybrid organic-inorganic polymer obtained by the cocondensation of an organotrialkoxysilane (OTAS; 40 mol %) with tetraethoxysilane (TEOS; 60 mol %). The particular organic group of OTAS enabled us to avoid gelation when the hydrolytic condensation was performed with a thermal cycle attaining 150 °C. The resulting product [soluble functionalized silica (SFS)] was a glass at room temperature that was soluble in several organic solvents such as tetrahydrofuran and toluene. The 29Si NMR spectrum of SFS showed that the OTAS units were fully condensed (T3 species), whereas the TEOS units were mainly present as tricondensed (Q3) and tetracondensed (Q4) units. SFS was grafted onto activated silica through a reaction of silanol groups. The metallocene [(nBuCp)2ZrCl2] was covalently bonded to the SFS-modified support. The polymerization of ethylene was carried out in toluene in the presence of methylaluminoxane. The activity of the supported catalyst was similar to that of the metallocene catalyst in solution. The simplest explanation accounting for this fact is that most of the metallocene was grafted to SFS species issuing from the surface of the support through a reaction with their silanol groups. This improved the accessibility of the monomer to the reaction sites. Specific interactions of the metallocene species with neighboring organic branches of SFS might also affect the catalytic activity.
Fil: Velilla, Teresa. Universidad de Chile; Chile
Fil: Delgado, Katherine. Universidad de Chile; Chile
Fil: Quijada, Raúl. Universidad de Chile; Chile
Fil: Bianchini, Daniela. Universidade Federal do Rio Grande do Sul; Brasil
Fil: Barrera Galland, Griselda. Universidade Federal do Rio Grande do Sul; Brasil
Fil: Dos Santos, João Henrique Z.. Universidade Federal do Rio Grande do Sul; Brasil
Fil: Fasce, Diana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina
Fil: Williams, Roberto Juan Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina
Materia
Catalytic Activity
Ethylene Polymerization
Metallocene Catalysts
Polyethylene
Soluble Functionalized Silica
Supported Metallocene Catalysts
Supports
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/76069
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/76069
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling New architecture of supported metallocene catalysts for alkene polymerizationVelilla, TeresaDelgado, KatherineQuijada, RaúlBianchini, DanielaBarrera Galland, GriseldaDos Santos, João Henrique Z.Fasce, Diana PatriciaWilliams, Roberto Juan JoseCatalytic ActivityEthylene PolymerizationMetallocene CatalystsPolyethyleneSoluble Functionalized SilicaSupported Metallocene CatalystsSupportshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report the synthesis of a supported metallocene catalyst that exhibits the same activity as a homogeneous catalyst for ethylene polymerization reactions. The key to this new catalytic system is a hybrid organic-inorganic polymer obtained by the cocondensation of an organotrialkoxysilane (OTAS; 40 mol %) with tetraethoxysilane (TEOS; 60 mol %). The particular organic group of OTAS enabled us to avoid gelation when the hydrolytic condensation was performed with a thermal cycle attaining 150 °C. The resulting product [soluble functionalized silica (SFS)] was a glass at room temperature that was soluble in several organic solvents such as tetrahydrofuran and toluene. The 29Si NMR spectrum of SFS showed that the OTAS units were fully condensed (T3 species), whereas the TEOS units were mainly present as tricondensed (Q3) and tetracondensed (Q4) units. SFS was grafted onto activated silica through a reaction of silanol groups. The metallocene [(nBuCp)2ZrCl2] was covalently bonded to the SFS-modified support. The polymerization of ethylene was carried out in toluene in the presence of methylaluminoxane. The activity of the supported catalyst was similar to that of the metallocene catalyst in solution. The simplest explanation accounting for this fact is that most of the metallocene was grafted to SFS species issuing from the surface of the support through a reaction with their silanol groups. This improved the accessibility of the monomer to the reaction sites. Specific interactions of the metallocene species with neighboring organic branches of SFS might also affect the catalytic activity.Fil: Velilla, Teresa. Universidad de Chile; ChileFil: Delgado, Katherine. Universidad de Chile; ChileFil: Quijada, Raúl. Universidad de Chile; ChileFil: Bianchini, Daniela. Universidade Federal do Rio Grande do Sul; BrasilFil: Barrera Galland, Griselda. Universidade Federal do Rio Grande do Sul; BrasilFil: Dos Santos, João Henrique Z.. Universidade Federal do Rio Grande do Sul; BrasilFil: Fasce, Diana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Williams, Roberto Juan Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaJohn Wiley & Sons Inc2007-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/76069Velilla, Teresa; Delgado, Katherine; Quijada, Raúl; Bianchini, Daniela; Barrera Galland, Griselda; et al.; New architecture of supported metallocene catalysts for alkene polymerization; John Wiley & Sons Inc; Journal of Polymer Science Part A: Polymer Chemistry; 45; 23; 12-2007; 5480-54860887-624XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/pola.22292info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/pola.22292info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:18:18Zoai:ri.conicet.gov.ar:11336/76069instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-22 11:18:18.858CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv New architecture of supported metallocene catalysts for alkene polymerization
title New architecture of supported metallocene catalysts for alkene polymerization
spellingShingle New architecture of supported metallocene catalysts for alkene polymerization
Velilla, Teresa
Catalytic Activity
Ethylene Polymerization
Metallocene Catalysts
Polyethylene
Soluble Functionalized Silica
Supported Metallocene Catalysts
Supports
title_short New architecture of supported metallocene catalysts for alkene polymerization
title_full New architecture of supported metallocene catalysts for alkene polymerization
title_fullStr New architecture of supported metallocene catalysts for alkene polymerization
title_full_unstemmed New architecture of supported metallocene catalysts for alkene polymerization
title_sort New architecture of supported metallocene catalysts for alkene polymerization
dc.creator.none.fl_str_mv Velilla, Teresa
Delgado, Katherine
Quijada, Raúl
Bianchini, Daniela
Barrera Galland, Griselda
Dos Santos, João Henrique Z.
Fasce, Diana Patricia
Williams, Roberto Juan Jose
author Velilla, Teresa
author_facet Velilla, Teresa
Delgado, Katherine
Quijada, Raúl
Bianchini, Daniela
Barrera Galland, Griselda
Dos Santos, João Henrique Z.
Fasce, Diana Patricia
Williams, Roberto Juan Jose
author_role author
author2 Delgado, Katherine
Quijada, Raúl
Bianchini, Daniela
Barrera Galland, Griselda
Dos Santos, João Henrique Z.
Fasce, Diana Patricia
Williams, Roberto Juan Jose
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Catalytic Activity
Ethylene Polymerization
Metallocene Catalysts
Polyethylene
Soluble Functionalized Silica
Supported Metallocene Catalysts
Supports
topic Catalytic Activity
Ethylene Polymerization
Metallocene Catalysts
Polyethylene
Soluble Functionalized Silica
Supported Metallocene Catalysts
Supports
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We report the synthesis of a supported metallocene catalyst that exhibits the same activity as a homogeneous catalyst for ethylene polymerization reactions. The key to this new catalytic system is a hybrid organic-inorganic polymer obtained by the cocondensation of an organotrialkoxysilane (OTAS; 40 mol %) with tetraethoxysilane (TEOS; 60 mol %). The particular organic group of OTAS enabled us to avoid gelation when the hydrolytic condensation was performed with a thermal cycle attaining 150 °C. The resulting product [soluble functionalized silica (SFS)] was a glass at room temperature that was soluble in several organic solvents such as tetrahydrofuran and toluene. The 29Si NMR spectrum of SFS showed that the OTAS units were fully condensed (T3 species), whereas the TEOS units were mainly present as tricondensed (Q3) and tetracondensed (Q4) units. SFS was grafted onto activated silica through a reaction of silanol groups. The metallocene [(nBuCp)2ZrCl2] was covalently bonded to the SFS-modified support. The polymerization of ethylene was carried out in toluene in the presence of methylaluminoxane. The activity of the supported catalyst was similar to that of the metallocene catalyst in solution. The simplest explanation accounting for this fact is that most of the metallocene was grafted to SFS species issuing from the surface of the support through a reaction with their silanol groups. This improved the accessibility of the monomer to the reaction sites. Specific interactions of the metallocene species with neighboring organic branches of SFS might also affect the catalytic activity.
Fil: Velilla, Teresa. Universidad de Chile; Chile
Fil: Delgado, Katherine. Universidad de Chile; Chile
Fil: Quijada, Raúl. Universidad de Chile; Chile
Fil: Bianchini, Daniela. Universidade Federal do Rio Grande do Sul; Brasil
Fil: Barrera Galland, Griselda. Universidade Federal do Rio Grande do Sul; Brasil
Fil: Dos Santos, João Henrique Z.. Universidade Federal do Rio Grande do Sul; Brasil
Fil: Fasce, Diana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina
Fil: Williams, Roberto Juan Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina
description We report the synthesis of a supported metallocene catalyst that exhibits the same activity as a homogeneous catalyst for ethylene polymerization reactions. The key to this new catalytic system is a hybrid organic-inorganic polymer obtained by the cocondensation of an organotrialkoxysilane (OTAS; 40 mol %) with tetraethoxysilane (TEOS; 60 mol %). The particular organic group of OTAS enabled us to avoid gelation when the hydrolytic condensation was performed with a thermal cycle attaining 150 °C. The resulting product [soluble functionalized silica (SFS)] was a glass at room temperature that was soluble in several organic solvents such as tetrahydrofuran and toluene. The 29Si NMR spectrum of SFS showed that the OTAS units were fully condensed (T3 species), whereas the TEOS units were mainly present as tricondensed (Q3) and tetracondensed (Q4) units. SFS was grafted onto activated silica through a reaction of silanol groups. The metallocene [(nBuCp)2ZrCl2] was covalently bonded to the SFS-modified support. The polymerization of ethylene was carried out in toluene in the presence of methylaluminoxane. The activity of the supported catalyst was similar to that of the metallocene catalyst in solution. The simplest explanation accounting for this fact is that most of the metallocene was grafted to SFS species issuing from the surface of the support through a reaction with their silanol groups. This improved the accessibility of the monomer to the reaction sites. Specific interactions of the metallocene species with neighboring organic branches of SFS might also affect the catalytic activity.
publishDate 2007
dc.date.none.fl_str_mv 2007-12
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/76069
Velilla, Teresa; Delgado, Katherine; Quijada, Raúl; Bianchini, Daniela; Barrera Galland, Griselda; et al.; New architecture of supported metallocene catalysts for alkene polymerization; John Wiley & Sons Inc; Journal of Polymer Science Part A: Polymer Chemistry; 45; 23; 12-2007; 5480-5486
0887-624X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/76069
identifier_str_mv Velilla, Teresa; Delgado, Katherine; Quijada, Raúl; Bianchini, Daniela; Barrera Galland, Griselda; et al.; New architecture of supported metallocene catalysts for alkene polymerization; John Wiley & Sons Inc; Journal of Polymer Science Part A: Polymer Chemistry; 45; 23; 12-2007; 5480-5486
0887-624X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/pola.22292
info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/pola.22292
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv John Wiley & Sons Inc
publisher.none.fl_str_mv John Wiley & Sons Inc
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 12.982451

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