Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components

Autores
Meizoso Loureiro, Roi; Carballeira Amareloa, Tánia; Paz Abuin, Senen; Soulé, Ezequiel Rodolfo; Williams, Roberto Juan Jose
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
An analysis of the kinetics of the epoxy-thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted.
Fil: Meizoso Loureiro, Roi. No especifíca;
Fil: Carballeira Amareloa, Tánia. No especifíca;
Fil: Paz Abuin, Senen. No especifíca;
Fil: Soulé, Ezequiel Rodolfo. Universidad Nacional de Mar del Plata. Facultad de Ingenieria; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigación en Ciencia y Tecnología de Materiales (i); Argentina
Fil: Williams, Roberto Juan Jose. Universidad Nacional de Mar del Plata. Facultad de Ingenieria; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigación en Ciencia y Tecnología de Materiales (i); Argentina
Materia
CLICK CHEMISTRY
DSC
EPOXY-THIOL REACTION
INDUCTION PERIOD
KINETICS
TERTIARY AMINE
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:11336/2757
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/2757
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional componentsMeizoso Loureiro, RoiCarballeira Amareloa, TániaPaz Abuin, SenenSoulé, Ezequiel RodolfoWilliams, Roberto Juan JoseCLICK CHEMISTRYDSCEPOXY-THIOL REACTIONINDUCTION PERIODKINETICSTERTIARY AMINEhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1An analysis of the kinetics of the epoxy-thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted.Fil: Meizoso Loureiro, Roi. No especifíca;Fil: Carballeira Amareloa, Tánia. No especifíca;Fil: Paz Abuin, Senen. No especifíca;Fil: Soulé, Ezequiel Rodolfo. Universidad Nacional de Mar del Plata. Facultad de Ingenieria; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigación en Ciencia y Tecnología de Materiales (i); ArgentinaFil: Williams, Roberto Juan Jose. Universidad Nacional de Mar del Plata. Facultad de Ingenieria; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigación en Ciencia y Tecnología de Materiales (i); ArgentinaElsevier Science2015-08-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/2757Meizoso Loureiro, Roi; Carballeira Amareloa, Tánia ; Paz Abuin, Senen; Soulé, Ezequiel Rodolfo; Williams, Roberto Juan Jose; Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components; Elsevier Science; Thermochimica Acta; 616; 8-8-2015; 79-860040-6031enginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0040603115003263info:eu-repo/semantics/altIdentifier/doi/10.1016/j.tca.2015.08.012info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-05T10:20:30Zoai:ri.conicet.gov.ar:11336/2757instacron: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:34982025-11-05 10:20:30.44CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components
title Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components
spellingShingle Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components
Meizoso Loureiro, Roi
CLICK CHEMISTRY
DSC
EPOXY-THIOL REACTION
INDUCTION PERIOD
KINETICS
TERTIARY AMINE
title_short Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components
title_full Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components
title_fullStr Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components
title_full_unstemmed Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components
title_sort Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components
dc.creator.none.fl_str_mv Meizoso Loureiro, Roi
Carballeira Amareloa, Tánia
Paz Abuin, Senen
Soulé, Ezequiel Rodolfo
Williams, Roberto Juan Jose
author Meizoso Loureiro, Roi
author_facet Meizoso Loureiro, Roi
Carballeira Amareloa, Tánia
Paz Abuin, Senen
Soulé, Ezequiel Rodolfo
Williams, Roberto Juan Jose
author_role author
author2 Carballeira Amareloa, Tánia
Paz Abuin, Senen
Soulé, Ezequiel Rodolfo
Williams, Roberto Juan Jose
author2_role author
author
author
author
dc.subject.none.fl_str_mv CLICK CHEMISTRY
DSC
EPOXY-THIOL REACTION
INDUCTION PERIOD
KINETICS
TERTIARY AMINE
topic CLICK CHEMISTRY
DSC
EPOXY-THIOL REACTION
INDUCTION PERIOD
KINETICS
TERTIARY AMINE
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv An analysis of the kinetics of the epoxy-thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted.
Fil: Meizoso Loureiro, Roi. No especifíca;
Fil: Carballeira Amareloa, Tánia. No especifíca;
Fil: Paz Abuin, Senen. No especifíca;
Fil: Soulé, Ezequiel Rodolfo. Universidad Nacional de Mar del Plata. Facultad de Ingenieria; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigación en Ciencia y Tecnología de Materiales (i); Argentina
Fil: Williams, Roberto Juan Jose. Universidad Nacional de Mar del Plata. Facultad de Ingenieria; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigación en Ciencia y Tecnología de Materiales (i); Argentina
description An analysis of the kinetics of the epoxy-thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted.
publishDate 2015
dc.date.none.fl_str_mv 2015-08-08
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/11336/2757
Meizoso Loureiro, Roi; Carballeira Amareloa, Tánia ; Paz Abuin, Senen; Soulé, Ezequiel Rodolfo; Williams, Roberto Juan Jose; Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components; Elsevier Science; Thermochimica Acta; 616; 8-8-2015; 79-86
0040-6031
url http://hdl.handle.net/11336/2757
identifier_str_mv Meizoso Loureiro, Roi; Carballeira Amareloa, Tánia ; Paz Abuin, Senen; Soulé, Ezequiel Rodolfo; Williams, Roberto Juan Jose; Kinetics of the epoxy-thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components; Elsevier Science; Thermochimica Acta; 616; 8-8-2015; 79-86
0040-6031
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0040603115003263
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.tca.2015.08.012
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
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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
_version_ 1847977804500566016
score 13.087074

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