Polypropylene Nanocomposites Attained by In Situ Polymerization Using SBA-15 Particles as Support for Metallocene Catalysts: Effect of Molecular Weight and Tacticity on Crystalline Details, Phase Transitions and Rheological Behavior

In this study, nanocomposites based on polypropylene are synthesized by the in situ polymerization of propene in the presence of mesoporous SBA-15 silica, which acts as a carrier of the catalytic system (zirconocene as catalyst and methylaluminoxane as cocatalyst). The protocol for the immobilizatio...

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Autores: Barranco-García, Rosa, García-Peñas, A., Blázquez-Blázquez, Enrique, Ressia, Jorge A., Quinzani, Lidia, Vallés, Enrique M., Gómez-Elvira González, José Manuel, Pérez, Ernesto, Cerrada, María L.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/310547
Acceso en línea:http://hdl.handle.net/10261/310547
Access Level:acceso abierto
Palabra clave:Polypropylene
SBA-15 silica
In situ polymerization
Hybrid particles
Metallocene catalysts
Nanocomposites
Crystallites
Confinement
Rheological percolation
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spelling Polypropylene Nanocomposites Attained by In Situ Polymerization Using SBA-15 Particles as Support for Metallocene Catalysts: Effect of Molecular Weight and Tacticity on Crystalline Details, Phase Transitions and Rheological BehaviorBarranco-García, RosaGarcía-Peñas, A.Blázquez-Blázquez, EnriqueRessia, Jorge A.Quinzani, LidiaVallés, Enrique M.Gómez-Elvira González, José ManuelPérez, ErnestoCerrada, María L.PolypropyleneSBA-15 silicaIn situ polymerizationHybrid particlesMetallocene catalystsNanocompositesCrystallitesConfinementRheological percolationIn this study, nanocomposites based on polypropylene are synthesized by the in situ polymerization of propene in the presence of mesoporous SBA-15 silica, which acts as a carrier of the catalytic system (zirconocene as catalyst and methylaluminoxane as cocatalyst). The protocol for the immobilization and attainment of hybrid SBA-15 particles involves a pre-stage of contact between the catalyst with cocatalyst before their final functionalization. Two zirconocene catalysts are tested in order to attain materials with different microstructural characteristics, molar masses and regioregularities of chains. Some polypropylene chains are able to be accommodated within the silica mesostructure of these composites. Thus, an endothermic event of small intensity appears during heating calorimetric experiments at approximately 105 °C. The existence of these polypropylene crystals, confined within the nanometric channels of silica, is corroborated by SAXS measurements obtained via the change in the intensity and position of the first-order diffraction of SBA-15. The incorporation of silica also has a very significant effect on the rheological response of the resultant materials, leading to important variations in various magnitudes, such as the shear storage modulus, viscosity and δ angle, when a comparison is established with the corresponding neat iPP matrices. Rheological percolation is reached, thus demonstrating the role of SBA-15 particles as filler, in addition to the supporting role that they exert during the polymerizations.This research was funded by MCIN/AEI/10.13039/501100011033, grant number PID2020-114930GB-I00, and also by the Madrid Government (Comunidad de Madrid, Spain) under the Multiannual Agreement with UC3M (“Fostering Young Doctors Research”, CICLAPNER-CM-UC3M), and in the context of the V PRICIT (Research and Technological Innovation Regional Programme). R. Barranco-García is recipient of a “Juan de la Cierva” contract (FJC2021-046585-I) funded by MCIN/AEI/10.13039/501100011033 and the European Union “NextGenerationEU”/PRTR. The authors also acknowledge the support received from the ALBA Synchrotron Light Facility.Peer reviewedMultidisciplinary Digital Publishing InstituteMinisterio de Ciencia, Innovación y Universidades (España)Agencia Estatal de Investigación (España)Comunidad de MadridEuropean CommissionALBA SynchrotronConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2023202320232023info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/310547reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-114930GB-I00https://doi.org/10.3390/molecules28114261Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3105472026-05-22T06:33:51Z
dc.title.none.fl_str_mv Polypropylene Nanocomposites Attained by In Situ Polymerization Using SBA-15 Particles as Support for Metallocene Catalysts: Effect of Molecular Weight and Tacticity on Crystalline Details, Phase Transitions and Rheological Behavior
title Polypropylene Nanocomposites Attained by In Situ Polymerization Using SBA-15 Particles as Support for Metallocene Catalysts: Effect of Molecular Weight and Tacticity on Crystalline Details, Phase Transitions and Rheological Behavior
spellingShingle Polypropylene Nanocomposites Attained by In Situ Polymerization Using SBA-15 Particles as Support for Metallocene Catalysts: Effect of Molecular Weight and Tacticity on Crystalline Details, Phase Transitions and Rheological Behavior
Barranco-García, Rosa
Polypropylene
SBA-15 silica
In situ polymerization
Hybrid particles
Metallocene catalysts
Nanocomposites
Crystallites
Confinement
Rheological percolation
title_short Polypropylene Nanocomposites Attained by In Situ Polymerization Using SBA-15 Particles as Support for Metallocene Catalysts: Effect of Molecular Weight and Tacticity on Crystalline Details, Phase Transitions and Rheological Behavior
title_full Polypropylene Nanocomposites Attained by In Situ Polymerization Using SBA-15 Particles as Support for Metallocene Catalysts: Effect of Molecular Weight and Tacticity on Crystalline Details, Phase Transitions and Rheological Behavior
title_fullStr Polypropylene Nanocomposites Attained by In Situ Polymerization Using SBA-15 Particles as Support for Metallocene Catalysts: Effect of Molecular Weight and Tacticity on Crystalline Details, Phase Transitions and Rheological Behavior
title_full_unstemmed Polypropylene Nanocomposites Attained by In Situ Polymerization Using SBA-15 Particles as Support for Metallocene Catalysts: Effect of Molecular Weight and Tacticity on Crystalline Details, Phase Transitions and Rheological Behavior
title_sort Polypropylene Nanocomposites Attained by In Situ Polymerization Using SBA-15 Particles as Support for Metallocene Catalysts: Effect of Molecular Weight and Tacticity on Crystalline Details, Phase Transitions and Rheological Behavior
dc.creator.none.fl_str_mv Barranco-García, Rosa
García-Peñas, A.
Blázquez-Blázquez, Enrique
Ressia, Jorge A.
Quinzani, Lidia
Vallés, Enrique M.
Gómez-Elvira González, José Manuel
Pérez, Ernesto
Cerrada, María L.
author Barranco-García, Rosa
author_facet Barranco-García, Rosa
García-Peñas, A.
Blázquez-Blázquez, Enrique
Ressia, Jorge A.
Quinzani, Lidia
Vallés, Enrique M.
Gómez-Elvira González, José Manuel
Pérez, Ernesto
Cerrada, María L.
author_role author
author2 García-Peñas, A.
Blázquez-Blázquez, Enrique
Ressia, Jorge A.
Quinzani, Lidia
Vallés, Enrique M.
Gómez-Elvira González, José Manuel
Pérez, Ernesto
Cerrada, María L.
author2_role author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
Agencia Estatal de Investigación (España)
Comunidad de Madrid
European Commission
ALBA Synchrotron
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Polypropylene
SBA-15 silica
In situ polymerization
Hybrid particles
Metallocene catalysts
Nanocomposites
Crystallites
Confinement
Rheological percolation
topic Polypropylene
SBA-15 silica
In situ polymerization
Hybrid particles
Metallocene catalysts
Nanocomposites
Crystallites
Confinement
Rheological percolation
description In this study, nanocomposites based on polypropylene are synthesized by the in situ polymerization of propene in the presence of mesoporous SBA-15 silica, which acts as a carrier of the catalytic system (zirconocene as catalyst and methylaluminoxane as cocatalyst). The protocol for the immobilization and attainment of hybrid SBA-15 particles involves a pre-stage of contact between the catalyst with cocatalyst before their final functionalization. Two zirconocene catalysts are tested in order to attain materials with different microstructural characteristics, molar masses and regioregularities of chains. Some polypropylene chains are able to be accommodated within the silica mesostructure of these composites. Thus, an endothermic event of small intensity appears during heating calorimetric experiments at approximately 105 °C. The existence of these polypropylene crystals, confined within the nanometric channels of silica, is corroborated by SAXS measurements obtained via the change in the intensity and position of the first-order diffraction of SBA-15. The incorporation of silica also has a very significant effect on the rheological response of the resultant materials, leading to important variations in various magnitudes, such as the shear storage modulus, viscosity and δ angle, when a comparison is established with the corresponding neat iPP matrices. Rheological percolation is reached, thus demonstrating the role of SBA-15 particles as filler, in addition to the supporting role that they exert during the polymerizations.
publishDate 2023
dc.date.none.fl_str_mv 2023
2023
2023
2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/310547
url http://hdl.handle.net/10261/310547
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-114930GB-I00
https://doi.org/10.3390/molecules28114261
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Multidisciplinary Digital Publishing Institute
publisher.none.fl_str_mv Multidisciplinary Digital Publishing Institute
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
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collection DIGITAL.CSIC. Repositorio Institucional del CSIC
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