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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/28280
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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 Técnicas2025-09-29T09:36:15Zoai: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:34982025-09-29 09:36:15.552CONICET 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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1844613135449718784 |
score |
13.070432 |