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

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...

Descripción completa

Detalles Bibliográficos
Autores: Soulé, Ezequiel Rodolfo, Borrajo Fernandez, Julio, Williams, Roberto Juan Jose
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2005
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/28280
Acceso en línea:http://hdl.handle.net/11336/28280
Access Level:acceso abierto
Palabra clave:Free-Radical Polymerization
Solution Polymerization
Free Volume
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
id AR_cdd125935a9355c752b3c1933fae20b0
oai_identifier_str oai:ri.conicet.gov.ar:11336/28280
network_acronym_str AR
network_name_str Argentina
repository_id_str
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
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
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
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
topic Free-Radical Polymerization
Solution Polymerization
Free Volume
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
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
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
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
_version_ 1799194734638399488
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 Técnicas2024-05-08T13:35:15Zoai: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:34982024-05-08 13:35:15.783CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
score 15,812429

Similares en LA Referencia