Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines

Autores
Lyu, Ya; Rachita, Eric; Pogharian, Nicholas; Froimowicz, Pablo; Ishida, Hatsuo
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Three isomers of benzoxazine monomers based on m-alkoxyphenol and 4,4′-methylenedianiline were synthesized and successfully isolated by column chromatography. The molecular structures of benzoxazine monomers were confirmed by proton nuclear magnetic resonance (1H NMR) and Fourier-transform infrared (FT-IR) spectroscopy. The polymerization behavior evaluated by differential scanning calorimetry (DSC) shows that the asymmetric isomer, which has a methoxy group at the 5-position and 7-positions (5,7′MO-ddm), has only one exothermic peak between temperatures of the other two symmetric isomers. The 1H NMR spectrum of monomers shows that the type and position of alkoxy groups can exert different effects on the electron density of the oxazine ring, and may result in a sensitive trend of ring-opening. The difference in electron densities was verified by the Gaussian simulation calculation results of natural charges. In this work, we provide a fundamental molecular-level understanding of the polymerization mechanism of asymmetric bis-benzoxazines, which can provide possibilities for designing new benzoxazines in order to solve the potential disadvantages of benzoxazines/polybenzoxazines and/or enhance their advantages.
Fil: Lyu, Ya. Case Western Reserve University; Estados Unidos
Fil: Rachita, Eric. Case Western Reserve University; Estados Unidos
Fil: Pogharian, Nicholas. Case Western Reserve University; Estados Unidos
Fil: Froimowicz, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Tecnología en Polímeros y Nanotecnología. Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnología en Polímeros y Nanotecnología; Argentina
Fil: Ishida, Hatsuo. Case Western Reserve University; Estados Unidos
Materia
BENZOXAZINES
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:11336/135240
Acceder
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spelling Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazinesLyu, YaRachita, EricPogharian, NicholasFroimowicz, PabloIshida, HatsuoBENZOXAZINEShttps://purl.org/becyt/ford/2.5https://purl.org/becyt/ford/2Three isomers of benzoxazine monomers based on m-alkoxyphenol and 4,4′-methylenedianiline were synthesized and successfully isolated by column chromatography. The molecular structures of benzoxazine monomers were confirmed by proton nuclear magnetic resonance (1H NMR) and Fourier-transform infrared (FT-IR) spectroscopy. The polymerization behavior evaluated by differential scanning calorimetry (DSC) shows that the asymmetric isomer, which has a methoxy group at the 5-position and 7-positions (5,7′MO-ddm), has only one exothermic peak between temperatures of the other two symmetric isomers. The 1H NMR spectrum of monomers shows that the type and position of alkoxy groups can exert different effects on the electron density of the oxazine ring, and may result in a sensitive trend of ring-opening. The difference in electron densities was verified by the Gaussian simulation calculation results of natural charges. In this work, we provide a fundamental molecular-level understanding of the polymerization mechanism of asymmetric bis-benzoxazines, which can provide possibilities for designing new benzoxazines in order to solve the potential disadvantages of benzoxazines/polybenzoxazines and/or enhance their advantages.Fil: Lyu, Ya. Case Western Reserve University; Estados UnidosFil: Rachita, Eric. Case Western Reserve University; Estados UnidosFil: Pogharian, Nicholas. Case Western Reserve University; Estados UnidosFil: Froimowicz, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Tecnología en Polímeros y Nanotecnología. Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnología en Polímeros y Nanotecnología; ArgentinaFil: Ishida, Hatsuo. Case Western Reserve University; Estados UnidosRoyal Society of Chemistry2020-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/135240Lyu, Ya; Rachita, Eric; Pogharian, Nicholas; Froimowicz, Pablo; Ishida, Hatsuo; Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines; Royal Society of Chemistry; Polymer Chemistry; 11; 4; 1-2020; 800-8091759-9962CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/c9py01641dinfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2020/PY/C9PY01641D#!divAbstractinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:04:25Zoai:ri.conicet.gov.ar:11336/135240instacron: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:34982025-09-03 10:04:26.086CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines
title Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines
spellingShingle Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines
Lyu, Ya
BENZOXAZINES
title_short Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines
title_full Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines
title_fullStr Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines
title_full_unstemmed Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines
title_sort Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines
dc.creator.none.fl_str_mv Lyu, Ya
Rachita, Eric
Pogharian, Nicholas
Froimowicz, Pablo
Ishida, Hatsuo
author Lyu, Ya
author_facet Lyu, Ya
Rachita, Eric
Pogharian, Nicholas
Froimowicz, Pablo
Ishida, Hatsuo
author_role author
author2 Rachita, Eric
Pogharian, Nicholas
Froimowicz, Pablo
Ishida, Hatsuo
author2_role author
author
author
author
dc.subject.none.fl_str_mv BENZOXAZINES
topic BENZOXAZINES
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.5
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Three isomers of benzoxazine monomers based on m-alkoxyphenol and 4,4′-methylenedianiline were synthesized and successfully isolated by column chromatography. The molecular structures of benzoxazine monomers were confirmed by proton nuclear magnetic resonance (1H NMR) and Fourier-transform infrared (FT-IR) spectroscopy. The polymerization behavior evaluated by differential scanning calorimetry (DSC) shows that the asymmetric isomer, which has a methoxy group at the 5-position and 7-positions (5,7′MO-ddm), has only one exothermic peak between temperatures of the other two symmetric isomers. The 1H NMR spectrum of monomers shows that the type and position of alkoxy groups can exert different effects on the electron density of the oxazine ring, and may result in a sensitive trend of ring-opening. The difference in electron densities was verified by the Gaussian simulation calculation results of natural charges. In this work, we provide a fundamental molecular-level understanding of the polymerization mechanism of asymmetric bis-benzoxazines, which can provide possibilities for designing new benzoxazines in order to solve the potential disadvantages of benzoxazines/polybenzoxazines and/or enhance their advantages.
Fil: Lyu, Ya. Case Western Reserve University; Estados Unidos
Fil: Rachita, Eric. Case Western Reserve University; Estados Unidos
Fil: Pogharian, Nicholas. Case Western Reserve University; Estados Unidos
Fil: Froimowicz, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Tecnología en Polímeros y Nanotecnología. Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnología en Polímeros y Nanotecnología; Argentina
Fil: Ishida, Hatsuo. Case Western Reserve University; Estados Unidos
description Three isomers of benzoxazine monomers based on m-alkoxyphenol and 4,4′-methylenedianiline were synthesized and successfully isolated by column chromatography. The molecular structures of benzoxazine monomers were confirmed by proton nuclear magnetic resonance (1H NMR) and Fourier-transform infrared (FT-IR) spectroscopy. The polymerization behavior evaluated by differential scanning calorimetry (DSC) shows that the asymmetric isomer, which has a methoxy group at the 5-position and 7-positions (5,7′MO-ddm), has only one exothermic peak between temperatures of the other two symmetric isomers. The 1H NMR spectrum of monomers shows that the type and position of alkoxy groups can exert different effects on the electron density of the oxazine ring, and may result in a sensitive trend of ring-opening. The difference in electron densities was verified by the Gaussian simulation calculation results of natural charges. In this work, we provide a fundamental molecular-level understanding of the polymerization mechanism of asymmetric bis-benzoxazines, which can provide possibilities for designing new benzoxazines in order to solve the potential disadvantages of benzoxazines/polybenzoxazines and/or enhance their advantages.
publishDate 2020
dc.date.none.fl_str_mv 2020-01
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/11336/135240
Lyu, Ya; Rachita, Eric; Pogharian, Nicholas; Froimowicz, Pablo; Ishida, Hatsuo; Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines; Royal Society of Chemistry; Polymer Chemistry; 11; 4; 1-2020; 800-809
1759-9962
CONICET Digital
CONICET
url http://hdl.handle.net/11336/135240
identifier_str_mv Lyu, Ya; Rachita, Eric; Pogharian, Nicholas; Froimowicz, Pablo; Ishida, Hatsuo; Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines; Royal Society of Chemistry; Polymer Chemistry; 11; 4; 1-2020; 800-809
1759-9962
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/c9py01641d
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2020/PY/C9PY01641D#!divAbstract
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 Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 13.13397

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