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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/76069
Ver los metadatos del registro completo
id |
CONICETDig_4d92018b8d65a86ecbce8ed3d3ea3a7e |
---|---|
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 Técnicas2025-09-29T09:48:53Zoai: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:34982025-09-29 09:48:53.673CONICET 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 |
_version_ |
1844613515942297600 |
score |
13.070432 |