Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar masses

Autores
Soulé, Ezequiel Rodolfo; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose
Año de publicación
2005
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The scope of this study was to investigate the effect of a linear polymer dissolved in a reactive monomer on the kinetics of free-radical polymerization before the start of phase separation. The selected system was a solution of polyisobutylene (PIB) in isobornyl methacrylate (IBoMA), polymerized at 80 °C in the presence of benzoyl peroxide (BPO). A ternary phase diagram of PIB, IBoMA, and poly(isobornyl methacrylate) (PIBoMA) was built at 80 °C, both employing physical blends or determining the phase separation conversion in the course of polymerization. Cloud-point curves (CPC) obtained by both methods were coincident within experimental error. They were shifted to lower conversions when increasing the molar mass of PIB. Different PIBs exhibiting CPC at advanced conversions were selected for the kinetic study performed employing differential scanning calorimetry (DSC) at 80 °C. A simple kinetic model for free-radical polymerizations describing the relevant termination rate constant in terms of the free-volume theory provided a consistent fitting of the polymerization rates in the conversion range where the solution remained homogeneous. Increasing the molar mass of PIB led to an increase in polymerization rate due to the decrease in free volume and the corresponding decrease of the termination rate. Increasing the amount of a particular PIB in the initial formulation led to a less marked gel effect, explained by the smaller relative variation of free volume with conversion. The dimensionless free volume of PIB obtained from the kinetic model was found to increase with the volume concentration of chain ends, as expected. Under conditions where phase separation took place at very low conversions, the overall polymerization rate exhibited the presence of two maxima (gel effects), representing the polymerization in two different phases. The first maximum was associated with the polymerization taking place in the phase lean in PIB, and the second maximum was associated with the polymerization of the monomer that was initially fractionated with PIB.
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
Solution Polymerization
Free Volume
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:11336/28280
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/28280
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network_name_str CONICET Digital (CONICET)
spelling Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar massesSoulé, Ezequiel RodolfoBorrajo Fernandez, JulioWilliams, Roberto Juan JoseFree-Radical PolymerizationSolution PolymerizationFree Volumehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The scope of this study was to investigate the effect of a linear polymer dissolved in a reactive monomer on the kinetics of free-radical polymerization before the start of phase separation. The selected system was a solution of polyisobutylene (PIB) in isobornyl methacrylate (IBoMA), polymerized at 80 °C in the presence of benzoyl peroxide (BPO). A ternary phase diagram of PIB, IBoMA, and poly(isobornyl methacrylate) (PIBoMA) was built at 80 °C, both employing physical blends or determining the phase separation conversion in the course of polymerization. Cloud-point curves (CPC) obtained by both methods were coincident within experimental error. They were shifted to lower conversions when increasing the molar mass of PIB. Different PIBs exhibiting CPC at advanced conversions were selected for the kinetic study performed employing differential scanning calorimetry (DSC) at 80 °C. A simple kinetic model for free-radical polymerizations describing the relevant termination rate constant in terms of the free-volume theory provided a consistent fitting of the polymerization rates in the conversion range where the solution remained homogeneous. Increasing the molar mass of PIB led to an increase in polymerization rate due to the decrease in free volume and the corresponding decrease of the termination rate. Increasing the amount of a particular PIB in the initial formulation led to a less marked gel effect, explained by the smaller relative variation of free volume with conversion. The dimensionless free volume of PIB obtained from the kinetic model was found to increase with the volume concentration of chain ends, as expected. Under conditions where phase separation took place at very low conversions, the overall polymerization rate exhibited the presence of two maxima (gel effects), representing the polymerization in two different phases. The first maximum was associated with the polymerization taking place in the phase lean in PIB, and the second maximum was associated with the polymerization of the monomer that was initially fractionated with PIB.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 Society2005-06-11info: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/11336/28280Soulé, Ezequiel Rodolfo; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose; Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar masses; American Chemical Society; Macromolecules; 38; 14; 11-6-2005; 5987-59940024-9297CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/ma0502957info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ma0502957info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:04:19Zoai:ri.conicet.gov.ar:11336/28280instacron: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:34982025-10-22 11:04:19.701CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar masses
title Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar masses
spellingShingle Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar masses
Soulé, Ezequiel Rodolfo
Free-Radical Polymerization
Solution Polymerization
Free Volume
title_short Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar masses
title_full Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar masses
title_fullStr Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar masses
title_full_unstemmed Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar masses
title_sort Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar masses
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
Solution Polymerization
Free Volume
topic Free-Radical Polymerization
Solution Polymerization
Free Volume
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The scope of this study was to investigate the effect of a linear polymer dissolved in a reactive monomer on the kinetics of free-radical polymerization before the start of phase separation. The selected system was a solution of polyisobutylene (PIB) in isobornyl methacrylate (IBoMA), polymerized at 80 °C in the presence of benzoyl peroxide (BPO). A ternary phase diagram of PIB, IBoMA, and poly(isobornyl methacrylate) (PIBoMA) was built at 80 °C, both employing physical blends or determining the phase separation conversion in the course of polymerization. Cloud-point curves (CPC) obtained by both methods were coincident within experimental error. They were shifted to lower conversions when increasing the molar mass of PIB. Different PIBs exhibiting CPC at advanced conversions were selected for the kinetic study performed employing differential scanning calorimetry (DSC) at 80 °C. A simple kinetic model for free-radical polymerizations describing the relevant termination rate constant in terms of the free-volume theory provided a consistent fitting of the polymerization rates in the conversion range where the solution remained homogeneous. Increasing the molar mass of PIB led to an increase in polymerization rate due to the decrease in free volume and the corresponding decrease of the termination rate. Increasing the amount of a particular PIB in the initial formulation led to a less marked gel effect, explained by the smaller relative variation of free volume with conversion. The dimensionless free volume of PIB obtained from the kinetic model was found to increase with the volume concentration of chain ends, as expected. Under conditions where phase separation took place at very low conversions, the overall polymerization rate exhibited the presence of two maxima (gel effects), representing the polymerization in two different phases. The first maximum was associated with the polymerization taking place in the phase lean in PIB, and the second maximum was associated with the polymerization of the monomer that was initially fractionated with PIB.
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 scope of this study was to investigate the effect of a linear polymer dissolved in a reactive monomer on the kinetics of free-radical polymerization before the start of phase separation. The selected system was a solution of polyisobutylene (PIB) in isobornyl methacrylate (IBoMA), polymerized at 80 °C in the presence of benzoyl peroxide (BPO). A ternary phase diagram of PIB, IBoMA, and poly(isobornyl methacrylate) (PIBoMA) was built at 80 °C, both employing physical blends or determining the phase separation conversion in the course of polymerization. Cloud-point curves (CPC) obtained by both methods were coincident within experimental error. They were shifted to lower conversions when increasing the molar mass of PIB. Different PIBs exhibiting CPC at advanced conversions were selected for the kinetic study performed employing differential scanning calorimetry (DSC) at 80 °C. A simple kinetic model for free-radical polymerizations describing the relevant termination rate constant in terms of the free-volume theory provided a consistent fitting of the polymerization rates in the conversion range where the solution remained homogeneous. Increasing the molar mass of PIB led to an increase in polymerization rate due to the decrease in free volume and the corresponding decrease of the termination rate. Increasing the amount of a particular PIB in the initial formulation led to a less marked gel effect, explained by the smaller relative variation of free volume with conversion. The dimensionless free volume of PIB obtained from the kinetic model was found to increase with the volume concentration of chain ends, as expected. Under conditions where phase separation took place at very low conversions, the overall polymerization rate exhibited the presence of two maxima (gel effects), representing the polymerization in two different phases. The first maximum was associated with the polymerization taking place in the phase lean in PIB, and the second maximum was associated with the polymerization of the monomer that was initially fractionated with PIB.
publishDate 2005
dc.date.none.fl_str_mv 2005-06-11
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/11336/28280
Soulé, Ezequiel Rodolfo; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose; Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar masses; American Chemical Society; Macromolecules; 38; 14; 11-6-2005; 5987-5994
0024-9297
CONICET Digital
CONICET
url http://hdl.handle.net/11336/28280
identifier_str_mv Soulé, Ezequiel Rodolfo; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose; Kinetics of the free-radical polymerization of isobornyl methacrylate in the presence of polyisobutylenes of different molar masses; American Chemical Society; Macromolecules; 38; 14; 11-6-2005; 5987-5994
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/ma0502957
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ma0502957
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 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 12.982451

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