Modification of model ethylene-butene copolymers using an organic peroxide

Autores
Pérez, Claudio Javier; Valles, Enrique Marcelo; Failla, Marcelo Daniel
Año de publicación
2005
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Well-characterized linear ethylene-butene-1 copolymers with polydispersities lower than 1.1 were modified using an organic peroxide with the purpose of assessing the relative importance of chain-linking processes. The copolymers used in this work were obtained by hydrogenation of polybutadienes, which were synthesized by anionic polymerization of butadiene. All the copolymers were modified in the molten state using 2,5-dimethyl-2,5 di(terbutyl peroxy)-hexane with concentrations varying on a ample range. The changes in the molecular structure of the polymers due to the chemical attack of the peroxide were evaluated combining selective solvent extraction and GPC-MALLS techniques. As expected, the critical concentration required for the onset of gelation, Cc, decreases with average molecular mass of the original copolymer. When concentrations of peroxide below Cc are employed, the weight-average molecular mass of the modified copolymers augments and the molecular mass distribution gets wider as the concentration of peroxide added to the copolymer increases. Although, the chain-linking reactions govern the modification process, there is a fraction of molecular chains that suffers scission. The measurable fraction of molecules having molecular mass lower than the original quasi-monodisperse copolymers ranges between 15% and 24% of the total mass when the copolymers were modified with concentrations of peroxide below Cc. Beyond the onset of gelation, the gel amount increases continuously with the peroxide concentration added to the copolymers. At a given peroxide concentration, the amount of gel produced for a given polymer is higher the greater is the initial molecular mass of the modified polymer. The limiting amount of gel was between 90% and 98% of the total mass, which was reached using concentrations 20 times larger than the critical one. The efficiency of the peroxide as cross-linking agent seems to be dependent on the concentration of peroxide.
Fil: Pérez, Claudio Javier. 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: Valles, Enrique Marcelo. 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: Failla, Marcelo Daniel. 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
Materia
Crosslinking
Etylene-Butene Copolymers
Organic Peroxide
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:11336/78982
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/78982
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Modification of model ethylene-butene copolymers using an organic peroxidePérez, Claudio JavierValles, Enrique MarceloFailla, Marcelo DanielCrosslinkingEtylene-Butene CopolymersOrganic Peroxidehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Well-characterized linear ethylene-butene-1 copolymers with polydispersities lower than 1.1 were modified using an organic peroxide with the purpose of assessing the relative importance of chain-linking processes. The copolymers used in this work were obtained by hydrogenation of polybutadienes, which were synthesized by anionic polymerization of butadiene. All the copolymers were modified in the molten state using 2,5-dimethyl-2,5 di(terbutyl peroxy)-hexane with concentrations varying on a ample range. The changes in the molecular structure of the polymers due to the chemical attack of the peroxide were evaluated combining selective solvent extraction and GPC-MALLS techniques. As expected, the critical concentration required for the onset of gelation, Cc, decreases with average molecular mass of the original copolymer. When concentrations of peroxide below Cc are employed, the weight-average molecular mass of the modified copolymers augments and the molecular mass distribution gets wider as the concentration of peroxide added to the copolymer increases. Although, the chain-linking reactions govern the modification process, there is a fraction of molecular chains that suffers scission. The measurable fraction of molecules having molecular mass lower than the original quasi-monodisperse copolymers ranges between 15% and 24% of the total mass when the copolymers were modified with concentrations of peroxide below Cc. Beyond the onset of gelation, the gel amount increases continuously with the peroxide concentration added to the copolymers. At a given peroxide concentration, the amount of gel produced for a given polymer is higher the greater is the initial molecular mass of the modified polymer. The limiting amount of gel was between 90% and 98% of the total mass, which was reached using concentrations 20 times larger than the critical one. The efficiency of the peroxide as cross-linking agent seems to be dependent on the concentration of peroxide.Fil: Pérez, Claudio Javier. 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: Valles, Enrique Marcelo. 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: Failla, Marcelo Daniel. 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; ArgentinaElsevier2005-01-26info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/78982Pérez, Claudio Javier; Valles, Enrique Marcelo; Failla, Marcelo Daniel; Modification of model ethylene-butene copolymers using an organic peroxide; Elsevier; Polymer; 46; 3; 26-1-2005; 725-7320032-3861CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0032386104012145info:eu-repo/semantics/altIdentifier/doi/10.1016/j.polymer.2004.11.085info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:39:15Zoai:ri.conicet.gov.ar:11336/78982instacron: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 09:39:15.549CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Modification of model ethylene-butene copolymers using an organic peroxide
title Modification of model ethylene-butene copolymers using an organic peroxide
spellingShingle Modification of model ethylene-butene copolymers using an organic peroxide
Pérez, Claudio Javier
Crosslinking
Etylene-Butene Copolymers
Organic Peroxide
title_short Modification of model ethylene-butene copolymers using an organic peroxide
title_full Modification of model ethylene-butene copolymers using an organic peroxide
title_fullStr Modification of model ethylene-butene copolymers using an organic peroxide
title_full_unstemmed Modification of model ethylene-butene copolymers using an organic peroxide
title_sort Modification of model ethylene-butene copolymers using an organic peroxide
dc.creator.none.fl_str_mv Pérez, Claudio Javier
Valles, Enrique Marcelo
Failla, Marcelo Daniel
author Pérez, Claudio Javier
author_facet Pérez, Claudio Javier
Valles, Enrique Marcelo
Failla, Marcelo Daniel
author_role author
author2 Valles, Enrique Marcelo
Failla, Marcelo Daniel
author2_role author
author
dc.subject.none.fl_str_mv Crosslinking
Etylene-Butene Copolymers
Organic Peroxide
topic Crosslinking
Etylene-Butene Copolymers
Organic Peroxide
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Well-characterized linear ethylene-butene-1 copolymers with polydispersities lower than 1.1 were modified using an organic peroxide with the purpose of assessing the relative importance of chain-linking processes. The copolymers used in this work were obtained by hydrogenation of polybutadienes, which were synthesized by anionic polymerization of butadiene. All the copolymers were modified in the molten state using 2,5-dimethyl-2,5 di(terbutyl peroxy)-hexane with concentrations varying on a ample range. The changes in the molecular structure of the polymers due to the chemical attack of the peroxide were evaluated combining selective solvent extraction and GPC-MALLS techniques. As expected, the critical concentration required for the onset of gelation, Cc, decreases with average molecular mass of the original copolymer. When concentrations of peroxide below Cc are employed, the weight-average molecular mass of the modified copolymers augments and the molecular mass distribution gets wider as the concentration of peroxide added to the copolymer increases. Although, the chain-linking reactions govern the modification process, there is a fraction of molecular chains that suffers scission. The measurable fraction of molecules having molecular mass lower than the original quasi-monodisperse copolymers ranges between 15% and 24% of the total mass when the copolymers were modified with concentrations of peroxide below Cc. Beyond the onset of gelation, the gel amount increases continuously with the peroxide concentration added to the copolymers. At a given peroxide concentration, the amount of gel produced for a given polymer is higher the greater is the initial molecular mass of the modified polymer. The limiting amount of gel was between 90% and 98% of the total mass, which was reached using concentrations 20 times larger than the critical one. The efficiency of the peroxide as cross-linking agent seems to be dependent on the concentration of peroxide.
Fil: Pérez, Claudio Javier. 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: Valles, Enrique Marcelo. 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: Failla, Marcelo Daniel. 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
description Well-characterized linear ethylene-butene-1 copolymers with polydispersities lower than 1.1 were modified using an organic peroxide with the purpose of assessing the relative importance of chain-linking processes. The copolymers used in this work were obtained by hydrogenation of polybutadienes, which were synthesized by anionic polymerization of butadiene. All the copolymers were modified in the molten state using 2,5-dimethyl-2,5 di(terbutyl peroxy)-hexane with concentrations varying on a ample range. The changes in the molecular structure of the polymers due to the chemical attack of the peroxide were evaluated combining selective solvent extraction and GPC-MALLS techniques. As expected, the critical concentration required for the onset of gelation, Cc, decreases with average molecular mass of the original copolymer. When concentrations of peroxide below Cc are employed, the weight-average molecular mass of the modified copolymers augments and the molecular mass distribution gets wider as the concentration of peroxide added to the copolymer increases. Although, the chain-linking reactions govern the modification process, there is a fraction of molecular chains that suffers scission. The measurable fraction of molecules having molecular mass lower than the original quasi-monodisperse copolymers ranges between 15% and 24% of the total mass when the copolymers were modified with concentrations of peroxide below Cc. Beyond the onset of gelation, the gel amount increases continuously with the peroxide concentration added to the copolymers. At a given peroxide concentration, the amount of gel produced for a given polymer is higher the greater is the initial molecular mass of the modified polymer. The limiting amount of gel was between 90% and 98% of the total mass, which was reached using concentrations 20 times larger than the critical one. The efficiency of the peroxide as cross-linking agent seems to be dependent on the concentration of peroxide.
publishDate 2005
dc.date.none.fl_str_mv 2005-01-26
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/11336/78982
Pérez, Claudio Javier; Valles, Enrique Marcelo; Failla, Marcelo Daniel; Modification of model ethylene-butene copolymers using an organic peroxide; Elsevier; Polymer; 46; 3; 26-1-2005; 725-732
0032-3861
CONICET Digital
CONICET
url http://hdl.handle.net/11336/78982
identifier_str_mv Pérez, Claudio Javier; Valles, Enrique Marcelo; Failla, Marcelo Daniel; Modification of model ethylene-butene copolymers using an organic peroxide; Elsevier; Polymer; 46; 3; 26-1-2005; 725-732
0032-3861
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0032386104012145
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.polymer.2004.11.085
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
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
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 13.070432

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