Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical study

Autores
Franceschini, Fernando C.; Tavares, Tatiana T. Da R.; Dos Santos, João H. Z.; Ferreira, María Luján; Soares, João B.P.
Año de publicación
2006
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Me2Si(Ind)2ZrCl2 was in situ immobilized onto SMAO and used for ethylene and propylene polymerization in the presence of TEA or TIBA as cocatalyst. The catalytic system Me2Si(Ind) 2ZrCl2/SMAO exhibited different behavior depending on the amount and nature of the alkylaluminum employed and on the monomer type. The catalyst activity was nearly 0,4 kg polymer · g cat-1 · h-1 with both cocatalysts for propylene polymerization. Similar activities were observed for ethylene polymerization in the presence of TIBA. When ethylene was polymerized using TEA at an Al/Zr molar ratio of 250, the activity was 10 times higher. Polyethylenes made by in situ supported or homogeneous catalyst systems had practically the same melting point (T m). On the other hand, poly(propylenes) made using in situ supported catalyst systems had a slightly lower Tm than poly(propylenes) made using homogeneous catalyst systems. The nature and amount of the alkylaluminum also influenced the molar mass. The poly(propylene) molar mass was higher when TIBA was the cocatalyst. The opposite behavior was observed for the polyethylenes. Concerning the alkylaluminum concentration, the molar mass of the polymers decreased as the amount of TEA increased. In the presence of TIBA, the polyethylene's molar mass was almost the same, independent of the alkylaluminum concentration, and the poly(propylene) molar mass increased with increasing amounts of cocatalyst. The deconvolution of the GPC curves showed 2 peaks for the homogeneous system and 3 peaks for the heterogeneous in situ supported system. The only exception was observed when TEA was used at an Al/Zr molar ratio of 500, where the best fit was obtained with 2 peaks. Based on the GPC deconvolution results and on the theoretical modeling, a proposal for the active site structure was made.
Fil: Franceschini, Fernando C.. Ipiranga Petroquímica S.a.; Brasil
Fil: Tavares, Tatiana T. Da R.. Ipiranga Petroquímica S.a.; Brasil
Fil: Dos Santos, João H. Z.. Universidade Federal do Rio Grande do Sul; Brasil
Fil: Ferreira, María Luján. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Fil: Soares, João B.P.. University Of Waterloo; Canadá
Materia
Gpc Deconvolution
In Situ Immobilization
Metallocene Catalysts
Modeling
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:11336/36737

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spelling Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical studyFranceschini, Fernando C.Tavares, Tatiana T. Da R.Dos Santos, João H. Z.Ferreira, María LujánSoares, João B.P.Gpc DeconvolutionIn Situ ImmobilizationMetallocene CatalystsModelinghttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2Me2Si(Ind)2ZrCl2 was in situ immobilized onto SMAO and used for ethylene and propylene polymerization in the presence of TEA or TIBA as cocatalyst. The catalytic system Me2Si(Ind) 2ZrCl2/SMAO exhibited different behavior depending on the amount and nature of the alkylaluminum employed and on the monomer type. The catalyst activity was nearly 0,4 kg polymer · g cat-1 · h-1 with both cocatalysts for propylene polymerization. Similar activities were observed for ethylene polymerization in the presence of TIBA. When ethylene was polymerized using TEA at an Al/Zr molar ratio of 250, the activity was 10 times higher. Polyethylenes made by in situ supported or homogeneous catalyst systems had practically the same melting point (T m). On the other hand, poly(propylenes) made using in situ supported catalyst systems had a slightly lower Tm than poly(propylenes) made using homogeneous catalyst systems. The nature and amount of the alkylaluminum also influenced the molar mass. The poly(propylene) molar mass was higher when TIBA was the cocatalyst. The opposite behavior was observed for the polyethylenes. Concerning the alkylaluminum concentration, the molar mass of the polymers decreased as the amount of TEA increased. In the presence of TIBA, the polyethylene's molar mass was almost the same, independent of the alkylaluminum concentration, and the poly(propylene) molar mass increased with increasing amounts of cocatalyst. The deconvolution of the GPC curves showed 2 peaks for the homogeneous system and 3 peaks for the heterogeneous in situ supported system. The only exception was observed when TEA was used at an Al/Zr molar ratio of 500, where the best fit was obtained with 2 peaks. Based on the GPC deconvolution results and on the theoretical modeling, a proposal for the active site structure was made.Fil: Franceschini, Fernando C.. Ipiranga Petroquímica S.a.; BrasilFil: Tavares, Tatiana T. Da R.. Ipiranga Petroquímica S.a.; BrasilFil: Dos Santos, João H. Z.. Universidade Federal do Rio Grande do Sul; BrasilFil: Ferreira, María Luján. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Soares, João B.P.. University Of Waterloo; CanadáWiley VCH Verlag2006-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/36737Franceschini, Fernando C.; Tavares, Tatiana T. Da R.; Dos Santos, João H. Z.; Ferreira, María Luján; Soares, João B.P.; Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical study; Wiley VCH Verlag; Macromolecular Materials and Engineering (print); 291; 3; 12-2006; 279-2871438-7492CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/mame.200500360info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/mame.200500360/abstractinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:09:58Zoai:ri.conicet.gov.ar:11336/36737instacron: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 10:09:59.1CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical study
title Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical study
spellingShingle Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical study
Franceschini, Fernando C.
Gpc Deconvolution
In Situ Immobilization
Metallocene Catalysts
Modeling
title_short Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical study
title_full Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical study
title_fullStr Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical study
title_full_unstemmed Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical study
title_sort Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical study
dc.creator.none.fl_str_mv Franceschini, Fernando C.
Tavares, Tatiana T. Da R.
Dos Santos, João H. Z.
Ferreira, María Luján
Soares, João B.P.
author Franceschini, Fernando C.
author_facet Franceschini, Fernando C.
Tavares, Tatiana T. Da R.
Dos Santos, João H. Z.
Ferreira, María Luján
Soares, João B.P.
author_role author
author2 Tavares, Tatiana T. Da R.
Dos Santos, João H. Z.
Ferreira, María Luján
Soares, João B.P.
author2_role author
author
author
author
dc.subject.none.fl_str_mv Gpc Deconvolution
In Situ Immobilization
Metallocene Catalysts
Modeling
topic Gpc Deconvolution
In Situ Immobilization
Metallocene Catalysts
Modeling
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Me2Si(Ind)2ZrCl2 was in situ immobilized onto SMAO and used for ethylene and propylene polymerization in the presence of TEA or TIBA as cocatalyst. The catalytic system Me2Si(Ind) 2ZrCl2/SMAO exhibited different behavior depending on the amount and nature of the alkylaluminum employed and on the monomer type. The catalyst activity was nearly 0,4 kg polymer · g cat-1 · h-1 with both cocatalysts for propylene polymerization. Similar activities were observed for ethylene polymerization in the presence of TIBA. When ethylene was polymerized using TEA at an Al/Zr molar ratio of 250, the activity was 10 times higher. Polyethylenes made by in situ supported or homogeneous catalyst systems had practically the same melting point (T m). On the other hand, poly(propylenes) made using in situ supported catalyst systems had a slightly lower Tm than poly(propylenes) made using homogeneous catalyst systems. The nature and amount of the alkylaluminum also influenced the molar mass. The poly(propylene) molar mass was higher when TIBA was the cocatalyst. The opposite behavior was observed for the polyethylenes. Concerning the alkylaluminum concentration, the molar mass of the polymers decreased as the amount of TEA increased. In the presence of TIBA, the polyethylene's molar mass was almost the same, independent of the alkylaluminum concentration, and the poly(propylene) molar mass increased with increasing amounts of cocatalyst. The deconvolution of the GPC curves showed 2 peaks for the homogeneous system and 3 peaks for the heterogeneous in situ supported system. The only exception was observed when TEA was used at an Al/Zr molar ratio of 500, where the best fit was obtained with 2 peaks. Based on the GPC deconvolution results and on the theoretical modeling, a proposal for the active site structure was made.
Fil: Franceschini, Fernando C.. Ipiranga Petroquímica S.a.; Brasil
Fil: Tavares, Tatiana T. Da R.. Ipiranga Petroquímica S.a.; Brasil
Fil: Dos Santos, João H. Z.. Universidade Federal do Rio Grande do Sul; Brasil
Fil: Ferreira, María Luján. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Fil: Soares, João B.P.. University Of Waterloo; Canadá
description Me2Si(Ind)2ZrCl2 was in situ immobilized onto SMAO and used for ethylene and propylene polymerization in the presence of TEA or TIBA as cocatalyst. The catalytic system Me2Si(Ind) 2ZrCl2/SMAO exhibited different behavior depending on the amount and nature of the alkylaluminum employed and on the monomer type. The catalyst activity was nearly 0,4 kg polymer · g cat-1 · h-1 with both cocatalysts for propylene polymerization. Similar activities were observed for ethylene polymerization in the presence of TIBA. When ethylene was polymerized using TEA at an Al/Zr molar ratio of 250, the activity was 10 times higher. Polyethylenes made by in situ supported or homogeneous catalyst systems had practically the same melting point (T m). On the other hand, poly(propylenes) made using in situ supported catalyst systems had a slightly lower Tm than poly(propylenes) made using homogeneous catalyst systems. The nature and amount of the alkylaluminum also influenced the molar mass. The poly(propylene) molar mass was higher when TIBA was the cocatalyst. The opposite behavior was observed for the polyethylenes. Concerning the alkylaluminum concentration, the molar mass of the polymers decreased as the amount of TEA increased. In the presence of TIBA, the polyethylene's molar mass was almost the same, independent of the alkylaluminum concentration, and the poly(propylene) molar mass increased with increasing amounts of cocatalyst. The deconvolution of the GPC curves showed 2 peaks for the homogeneous system and 3 peaks for the heterogeneous in situ supported system. The only exception was observed when TEA was used at an Al/Zr molar ratio of 500, where the best fit was obtained with 2 peaks. Based on the GPC deconvolution results and on the theoretical modeling, a proposal for the active site structure was made.
publishDate 2006
dc.date.none.fl_str_mv 2006-12
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/11336/36737
Franceschini, Fernando C.; Tavares, Tatiana T. Da R.; Dos Santos, João H. Z.; Ferreira, María Luján; Soares, João B.P.; Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical study; Wiley VCH Verlag; Macromolecular Materials and Engineering (print); 291; 3; 12-2006; 279-287
1438-7492
CONICET Digital
CONICET
url http://hdl.handle.net/11336/36737
identifier_str_mv Franceschini, Fernando C.; Tavares, Tatiana T. Da R.; Dos Santos, João H. Z.; Ferreira, María Luján; Soares, João B.P.; Ethylene and propylene polymerization using in situ supported Me 2Si(Ind)2ZrCl2 Catalyst: Experimental and theoretical study; Wiley VCH Verlag; Macromolecular Materials and Engineering (print); 291; 3; 12-2006; 279-287
1438-7492
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/mame.200500360
info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/mame.200500360/abstract
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 Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
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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