Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen

Autores
Soulé, Ezequiel Rodolfo; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose
Año de publicación
2004
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The kinetics of the free-radical polymerization of isobornyl methacrylate (IBoMA) at 80 °C, initiated by benzoyl peroxide (BPO), was determined by differential scanning calorimetry (DSC), using sample pans previously sealed in air or in nitrogen. The polymerization was arrested by vitrification at a final conversion close to 0.80. The kinetics in nitrogen could be fitted using initiation and propagation rate constants reported in the literature, a functionality of the termination rate constant controlled by translational diffusion based on the free-volume model, and an efficiency factor for the initiator decomposition that decreased with conversion in the medium-high conversion range. The presence of oxygen led to a significant decrease in the polymerization rate, an effect that was enhanced when decreasing the sample size (increasing the surface-to-volume ratio). The original finding was the presence of two maxima in the isothermal polymerization rate, a fact that was confirmed by replicating experiences in two different DSC devices and changing the amount of initiator in the formulation. The first maximum in the polymerization rate was explained by the decrease of the diffusion rate of macromolecular radicals to the oxygen-rich boundary, an effect that started at low conversions. The second maximum was related to the decrease in the solubility/diffusion of oxygen in the reaction medium, a phenomenon that was particularly severe at high conversions.
Fil: Soulé, Ezequiel Rodolfo. 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: Borrajo Fernandez, Julio. 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
Free-radical polymerization
Autoaceleration
Oxygen inhibition
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:11336/98897
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/98897
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by OxygenSoulé, Ezequiel RodolfoBorrajo Fernandez, JulioWilliams, Roberto Juan JoseFree-radical polymerizationAutoacelerationOxygen inhibitionhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1https://purl.org/becyt/ford/2.5https://purl.org/becyt/ford/2The kinetics of the free-radical polymerization of isobornyl methacrylate (IBoMA) at 80 °C, initiated by benzoyl peroxide (BPO), was determined by differential scanning calorimetry (DSC), using sample pans previously sealed in air or in nitrogen. The polymerization was arrested by vitrification at a final conversion close to 0.80. The kinetics in nitrogen could be fitted using initiation and propagation rate constants reported in the literature, a functionality of the termination rate constant controlled by translational diffusion based on the free-volume model, and an efficiency factor for the initiator decomposition that decreased with conversion in the medium-high conversion range. The presence of oxygen led to a significant decrease in the polymerization rate, an effect that was enhanced when decreasing the sample size (increasing the surface-to-volume ratio). The original finding was the presence of two maxima in the isothermal polymerization rate, a fact that was confirmed by replicating experiences in two different DSC devices and changing the amount of initiator in the formulation. The first maximum in the polymerization rate was explained by the decrease of the diffusion rate of macromolecular radicals to the oxygen-rich boundary, an effect that started at low conversions. The second maximum was related to the decrease in the solubility/diffusion of oxygen in the reaction medium, a phenomenon that was particularly severe at high conversions.Fil: Soulé, Ezequiel Rodolfo. 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: Borrajo Fernandez, Julio. 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; ArgentinaAmerican Chemical Society2004-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/98897Soulé, Ezequiel Rodolfo; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose; Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen; American Chemical Society; Macromolecules; 37; 4; 2-2004; 1551-15570024-9297CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/ma0350314info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ma0350314info:eu-repo/semantics/altIdentifier/url/https://arxiv.org/abs/1311.5448info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:35:24Zoai:ri.conicet.gov.ar:11336/98897instacron: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 09:35:25.129CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen
title Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen
spellingShingle Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen
Soulé, Ezequiel Rodolfo
Free-radical polymerization
Autoaceleration
Oxygen inhibition
title_short Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen
title_full Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen
title_fullStr Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen
title_full_unstemmed Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen
title_sort Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen
dc.creator.none.fl_str_mv Soulé, Ezequiel Rodolfo
Borrajo Fernandez, Julio
Williams, Roberto Juan Jose
author Soulé, Ezequiel Rodolfo
author_facet Soulé, Ezequiel Rodolfo
Borrajo Fernandez, Julio
Williams, Roberto Juan Jose
author_role author
author2 Borrajo Fernandez, Julio
Williams, Roberto Juan Jose
author2_role author
author
dc.subject.none.fl_str_mv Free-radical polymerization
Autoaceleration
Oxygen inhibition
topic Free-radical polymerization
Autoaceleration
Oxygen inhibition
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/2.5
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The kinetics of the free-radical polymerization of isobornyl methacrylate (IBoMA) at 80 °C, initiated by benzoyl peroxide (BPO), was determined by differential scanning calorimetry (DSC), using sample pans previously sealed in air or in nitrogen. The polymerization was arrested by vitrification at a final conversion close to 0.80. The kinetics in nitrogen could be fitted using initiation and propagation rate constants reported in the literature, a functionality of the termination rate constant controlled by translational diffusion based on the free-volume model, and an efficiency factor for the initiator decomposition that decreased with conversion in the medium-high conversion range. The presence of oxygen led to a significant decrease in the polymerization rate, an effect that was enhanced when decreasing the sample size (increasing the surface-to-volume ratio). The original finding was the presence of two maxima in the isothermal polymerization rate, a fact that was confirmed by replicating experiences in two different DSC devices and changing the amount of initiator in the formulation. The first maximum in the polymerization rate was explained by the decrease of the diffusion rate of macromolecular radicals to the oxygen-rich boundary, an effect that started at low conversions. The second maximum was related to the decrease in the solubility/diffusion of oxygen in the reaction medium, a phenomenon that was particularly severe at high conversions.
Fil: Soulé, Ezequiel Rodolfo. 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: Borrajo Fernandez, Julio. 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 The kinetics of the free-radical polymerization of isobornyl methacrylate (IBoMA) at 80 °C, initiated by benzoyl peroxide (BPO), was determined by differential scanning calorimetry (DSC), using sample pans previously sealed in air or in nitrogen. The polymerization was arrested by vitrification at a final conversion close to 0.80. The kinetics in nitrogen could be fitted using initiation and propagation rate constants reported in the literature, a functionality of the termination rate constant controlled by translational diffusion based on the free-volume model, and an efficiency factor for the initiator decomposition that decreased with conversion in the medium-high conversion range. The presence of oxygen led to a significant decrease in the polymerization rate, an effect that was enhanced when decreasing the sample size (increasing the surface-to-volume ratio). The original finding was the presence of two maxima in the isothermal polymerization rate, a fact that was confirmed by replicating experiences in two different DSC devices and changing the amount of initiator in the formulation. The first maximum in the polymerization rate was explained by the decrease of the diffusion rate of macromolecular radicals to the oxygen-rich boundary, an effect that started at low conversions. The second maximum was related to the decrease in the solubility/diffusion of oxygen in the reaction medium, a phenomenon that was particularly severe at high conversions.
publishDate 2004
dc.date.none.fl_str_mv 2004-02
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/11336/98897
Soulé, Ezequiel Rodolfo; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose; Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen; American Chemical Society; Macromolecules; 37; 4; 2-2004; 1551-1557
0024-9297
CONICET Digital
CONICET
url http://hdl.handle.net/11336/98897
identifier_str_mv Soulé, Ezequiel Rodolfo; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose; Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen; American Chemical Society; Macromolecules; 37; 4; 2-2004; 1551-1557
0024-9297
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/ma0350314
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ma0350314
info:eu-repo/semantics/altIdentifier/url/https://arxiv.org/abs/1311.5448
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
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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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