New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerism

Autores
Giussi, Juan Martín; Allegretti, Patricia Ercilia; Cortizo, Maria Susana
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The monomer 2-methyl-3-oxo-5-phenyl-4-pentenonitrile (MOP) was prepared by reaction of ethyl cinnamate and propionitrile in alkaline mixture. This monomer exhibits three possible tautomeric forms. The tautomeric equilibria of MOP and its copolymers with styrene in different solvents were analyzed by 1H NMR spectroscopy. The bulk and solution radical copolymerization behavior initiated with azobisisobutyronitrile was carried out at 60 ºC. The products were characterized by 1H NMR, 13C NMR, HSQC NMR, HMBC NMR and FTIR spectroscopies. The average molecular weight and polydispersity index were analyzed with size exclusion chromatography (SEC). The monomer reactivity ratios were obtained with the Fineman-Ross method, obtaining a value of r1r2 = 0.301. MOP copolymer composition as well as the nature of the solvent significantly affected the tautomeric equilibrium. Regression analysis of the copolymer composition with solvatochromic parameters showed a good linear correlation, as quantitatively expressed by means of the linear salvation energy relationship using the empirical set of Kamlet-Taft solvent parameters. This behavior could be attributed to polymer-polymer or polymer-solvent interactions prevalent in solvents of different polarity, which are responsible for changes in macromolecular chain conformations, as confirmed by FTIR and viscometric studies.
Fil: Giussi, Juan Martín. Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Departamento de Quimica. Laboratorio de Estudio de Compuestos Organicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Allegretti, Patricia Ercilia. Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Departamento de Quimica. Laboratorio de Estudio de Compuestos Organicos; Argentina
Fil: Cortizo, Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Departamento de Quimica. Laboratorio de Estudio de Compuestos Organicos; Argentina
Materia
Radical Polymerization
Beta-Ketonitrile
Tautomeric Equilibria
Nmr And Ftir Spectroscopies
Viscosity
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:11336/5463
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/5463
network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerismGiussi, Juan MartínAllegretti, Patricia ErciliaCortizo, Maria SusanaRadical PolymerizationBeta-KetonitrileTautomeric EquilibriaNmr And Ftir SpectroscopiesViscosityhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The monomer 2-methyl-3-oxo-5-phenyl-4-pentenonitrile (MOP) was prepared by reaction of ethyl cinnamate and propionitrile in alkaline mixture. This monomer exhibits three possible tautomeric forms. The tautomeric equilibria of MOP and its copolymers with styrene in different solvents were analyzed by 1H NMR spectroscopy. The bulk and solution radical copolymerization behavior initiated with azobisisobutyronitrile was carried out at 60 ºC. The products were characterized by 1H NMR, 13C NMR, HSQC NMR, HMBC NMR and FTIR spectroscopies. The average molecular weight and polydispersity index were analyzed with size exclusion chromatography (SEC). The monomer reactivity ratios were obtained with the Fineman-Ross method, obtaining a value of r1r2 = 0.301. MOP copolymer composition as well as the nature of the solvent significantly affected the tautomeric equilibrium. Regression analysis of the copolymer composition with solvatochromic parameters showed a good linear correlation, as quantitatively expressed by means of the linear salvation energy relationship using the empirical set of Kamlet-Taft solvent parameters. This behavior could be attributed to polymer-polymer or polymer-solvent interactions prevalent in solvents of different polarity, which are responsible for changes in macromolecular chain conformations, as confirmed by FTIR and viscometric studies.Fil: Giussi, Juan Martín. Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Departamento de Quimica. Laboratorio de Estudio de Compuestos Organicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Allegretti, Patricia Ercilia. Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Departamento de Quimica. Laboratorio de Estudio de Compuestos Organicos; ArgentinaFil: Cortizo, Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Departamento de Quimica. Laboratorio de Estudio de Compuestos Organicos; ArgentinaWiley2012-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/5463Giussi, Juan Martín; Allegretti, Patricia Ercilia; Cortizo, Maria Susana; New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerism; Wiley; Journal Of Polymer Science Part A: Polymer Chemistry; 50; 20; 10-2012; 4161-41690887-624Xenginfo:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/pola.26238/abstractinfo:eu-repo/semantics/altIdentifier/doi/10.1002/pola.26238info:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:42:20Zoai:ri.conicet.gov.ar:11336/5463instacron: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 09:42:20.281CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerism
title New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerism
spellingShingle New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerism
Giussi, Juan Martín
Radical Polymerization
Beta-Ketonitrile
Tautomeric Equilibria
Nmr And Ftir Spectroscopies
Viscosity
title_short New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerism
title_full New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerism
title_fullStr New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerism
title_full_unstemmed New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerism
title_sort New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerism
dc.creator.none.fl_str_mv Giussi, Juan Martín
Allegretti, Patricia Ercilia
Cortizo, Maria Susana
author Giussi, Juan Martín
author_facet Giussi, Juan Martín
Allegretti, Patricia Ercilia
Cortizo, Maria Susana
author_role author
author2 Allegretti, Patricia Ercilia
Cortizo, Maria Susana
author2_role author
author
dc.subject.none.fl_str_mv Radical Polymerization
Beta-Ketonitrile
Tautomeric Equilibria
Nmr And Ftir Spectroscopies
Viscosity
topic Radical Polymerization
Beta-Ketonitrile
Tautomeric Equilibria
Nmr And Ftir Spectroscopies
Viscosity
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The monomer 2-methyl-3-oxo-5-phenyl-4-pentenonitrile (MOP) was prepared by reaction of ethyl cinnamate and propionitrile in alkaline mixture. This monomer exhibits three possible tautomeric forms. The tautomeric equilibria of MOP and its copolymers with styrene in different solvents were analyzed by 1H NMR spectroscopy. The bulk and solution radical copolymerization behavior initiated with azobisisobutyronitrile was carried out at 60 ºC. The products were characterized by 1H NMR, 13C NMR, HSQC NMR, HMBC NMR and FTIR spectroscopies. The average molecular weight and polydispersity index were analyzed with size exclusion chromatography (SEC). The monomer reactivity ratios were obtained with the Fineman-Ross method, obtaining a value of r1r2 = 0.301. MOP copolymer composition as well as the nature of the solvent significantly affected the tautomeric equilibrium. Regression analysis of the copolymer composition with solvatochromic parameters showed a good linear correlation, as quantitatively expressed by means of the linear salvation energy relationship using the empirical set of Kamlet-Taft solvent parameters. This behavior could be attributed to polymer-polymer or polymer-solvent interactions prevalent in solvents of different polarity, which are responsible for changes in macromolecular chain conformations, as confirmed by FTIR and viscometric studies.
Fil: Giussi, Juan Martín. Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Departamento de Quimica. Laboratorio de Estudio de Compuestos Organicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Allegretti, Patricia Ercilia. Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Departamento de Quimica. Laboratorio de Estudio de Compuestos Organicos; Argentina
Fil: Cortizo, Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Departamento de Quimica. Laboratorio de Estudio de Compuestos Organicos; Argentina
description The monomer 2-methyl-3-oxo-5-phenyl-4-pentenonitrile (MOP) was prepared by reaction of ethyl cinnamate and propionitrile in alkaline mixture. This monomer exhibits three possible tautomeric forms. The tautomeric equilibria of MOP and its copolymers with styrene in different solvents were analyzed by 1H NMR spectroscopy. The bulk and solution radical copolymerization behavior initiated with azobisisobutyronitrile was carried out at 60 ºC. The products were characterized by 1H NMR, 13C NMR, HSQC NMR, HMBC NMR and FTIR spectroscopies. The average molecular weight and polydispersity index were analyzed with size exclusion chromatography (SEC). The monomer reactivity ratios were obtained with the Fineman-Ross method, obtaining a value of r1r2 = 0.301. MOP copolymer composition as well as the nature of the solvent significantly affected the tautomeric equilibrium. Regression analysis of the copolymer composition with solvatochromic parameters showed a good linear correlation, as quantitatively expressed by means of the linear salvation energy relationship using the empirical set of Kamlet-Taft solvent parameters. This behavior could be attributed to polymer-polymer or polymer-solvent interactions prevalent in solvents of different polarity, which are responsible for changes in macromolecular chain conformations, as confirmed by FTIR and viscometric studies.
publishDate 2012
dc.date.none.fl_str_mv 2012-10
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/11336/5463
Giussi, Juan Martín; Allegretti, Patricia Ercilia; Cortizo, Maria Susana; New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerism; Wiley; Journal Of Polymer Science Part A: Polymer Chemistry; 50; 20; 10-2012; 4161-4169
0887-624X
url http://hdl.handle.net/11336/5463
identifier_str_mv Giussi, Juan Martín; Allegretti, Patricia Ercilia; Cortizo, Maria Susana; New copolymers of a tautomerizable beta-ketonitrile monomer: synthesis, characterization and solution tautomerism; Wiley; Journal Of Polymer Science Part A: Polymer Chemistry; 50; 20; 10-2012; 4161-4169
0887-624X
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/pola.26238/abstract
info:eu-repo/semantics/altIdentifier/doi/10.1002/pola.26238
info:eu-repo/semantics/altIdentifier/doi/
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 Wiley
publisher.none.fl_str_mv Wiley
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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