Linear segmented polyurethanes. I. A kinetics study

Autores
Polo, Mara Lis; Spontón, Marisa Elisabet; Jaramillo, Franklin; Estenoz, Diana Alejandra; Meira, Gregorio Raul
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
This work investigates the two-step polymerization between methylene diphenyl diisocyanate (MDI), two different poly(tetramethylene oxide) macrodiols, and 1,4-butanediol (BD) as chain extender. At the end of the prepolymerization, the reaction mixture contains MDI in excess and a prepolymer with isocyanate end group. Then, BD and a solvent (tetrahydrofuran) were added to start the finishing stage under nominal stoichiometric equilibrium. The reaction was analyzed by Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance (1H-NMR), and size exclusion chromatography. 1H-NMR was employed to follow global concentrations of unreacted isocyanate end groups and internal urethane groups. This information enabled to estimate the following ?effective? rate constants: k1 = 1.07 × 10−3 L mol−1 s−1 for the prepolymerization; and k2 = 1.94 × 10−4 L mol−1 s−1 for the finishing stage. These values are subject to errors caused by biases introduced in the recipe, in the measurements, in the reaction conditions, in the quality of reagents, and in the reaction mechanism assumptions. Such errors also explain the dispersion of the published rate constants values. The 1H-NMR measurements also enabled to estimate the evolution (with extent of reaction) of the number-average number of structural units along the prepolymerization and finishing stages; and such estimates reasonably verify Flory´s classical expressions.
Fil: Polo, Mara Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Spontón, Marisa Elisabet. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Jaramillo, Franklin. Universidad de Antioquia; Colombia
Fil: Estenoz, Diana Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Meira, Gregorio Raul. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Materia
Nmr
Polyurethanes
Reaction Kinetics
Sec
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:11336/27281
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/27281
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Linear segmented polyurethanes. I. A kinetics studyPolo, Mara LisSpontón, Marisa ElisabetJaramillo, FranklinEstenoz, Diana AlejandraMeira, Gregorio RaulNmrPolyurethanesReaction KineticsSechttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2This work investigates the two-step polymerization between methylene diphenyl diisocyanate (MDI), two different poly(tetramethylene oxide) macrodiols, and 1,4-butanediol (BD) as chain extender. At the end of the prepolymerization, the reaction mixture contains MDI in excess and a prepolymer with isocyanate end group. Then, BD and a solvent (tetrahydrofuran) were added to start the finishing stage under nominal stoichiometric equilibrium. The reaction was analyzed by Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance (1H-NMR), and size exclusion chromatography. 1H-NMR was employed to follow global concentrations of unreacted isocyanate end groups and internal urethane groups. This information enabled to estimate the following ?effective? rate constants: k1 = 1.07 × 10−3 L mol−1 s−1 for the prepolymerization; and k2 = 1.94 × 10−4 L mol−1 s−1 for the finishing stage. These values are subject to errors caused by biases introduced in the recipe, in the measurements, in the reaction conditions, in the quality of reagents, and in the reaction mechanism assumptions. Such errors also explain the dispersion of the published rate constants values. The 1H-NMR measurements also enabled to estimate the evolution (with extent of reaction) of the number-average number of structural units along the prepolymerization and finishing stages; and such estimates reasonably verify Flory´s classical expressions.Fil: Polo, Mara Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Spontón, Marisa Elisabet. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Jaramillo, Franklin. Universidad de Antioquia; ColombiaFil: Estenoz, Diana Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Meira, Gregorio Raul. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaJohn Wiley & Sons Inc2017-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/27281Polo, Mara Lis; Spontón, Marisa Elisabet; Jaramillo, Franklin; Estenoz, Diana Alejandra; Meira, Gregorio Raul; Linear segmented polyurethanes. I. A kinetics study; John Wiley & Sons Inc; Journal of Applied Polymer Science; 135; 4; 9-2017; 1-13; 457470021-8995CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/app.45747/abstractinfo:eu-repo/semantics/altIdentifier/doi/10.1002/app.45747info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:26:41Zoai:ri.conicet.gov.ar:11336/27281instacron: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:34982025-10-22 11:26:42.089CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Linear segmented polyurethanes. I. A kinetics study
title Linear segmented polyurethanes. I. A kinetics study
spellingShingle Linear segmented polyurethanes. I. A kinetics study
Polo, Mara Lis
Nmr
Polyurethanes
Reaction Kinetics
Sec
title_short Linear segmented polyurethanes. I. A kinetics study
title_full Linear segmented polyurethanes. I. A kinetics study
title_fullStr Linear segmented polyurethanes. I. A kinetics study
title_full_unstemmed Linear segmented polyurethanes. I. A kinetics study
title_sort Linear segmented polyurethanes. I. A kinetics study
dc.creator.none.fl_str_mv Polo, Mara Lis
Spontón, Marisa Elisabet
Jaramillo, Franklin
Estenoz, Diana Alejandra
Meira, Gregorio Raul
author Polo, Mara Lis
author_facet Polo, Mara Lis
Spontón, Marisa Elisabet
Jaramillo, Franklin
Estenoz, Diana Alejandra
Meira, Gregorio Raul
author_role author
author2 Spontón, Marisa Elisabet
Jaramillo, Franklin
Estenoz, Diana Alejandra
Meira, Gregorio Raul
author2_role author
author
author
author
dc.subject.none.fl_str_mv Nmr
Polyurethanes
Reaction Kinetics
Sec
topic Nmr
Polyurethanes
Reaction Kinetics
Sec
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv This work investigates the two-step polymerization between methylene diphenyl diisocyanate (MDI), two different poly(tetramethylene oxide) macrodiols, and 1,4-butanediol (BD) as chain extender. At the end of the prepolymerization, the reaction mixture contains MDI in excess and a prepolymer with isocyanate end group. Then, BD and a solvent (tetrahydrofuran) were added to start the finishing stage under nominal stoichiometric equilibrium. The reaction was analyzed by Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance (1H-NMR), and size exclusion chromatography. 1H-NMR was employed to follow global concentrations of unreacted isocyanate end groups and internal urethane groups. This information enabled to estimate the following ?effective? rate constants: k1 = 1.07 × 10−3 L mol−1 s−1 for the prepolymerization; and k2 = 1.94 × 10−4 L mol−1 s−1 for the finishing stage. These values are subject to errors caused by biases introduced in the recipe, in the measurements, in the reaction conditions, in the quality of reagents, and in the reaction mechanism assumptions. Such errors also explain the dispersion of the published rate constants values. The 1H-NMR measurements also enabled to estimate the evolution (with extent of reaction) of the number-average number of structural units along the prepolymerization and finishing stages; and such estimates reasonably verify Flory´s classical expressions.
Fil: Polo, Mara Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Spontón, Marisa Elisabet. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Jaramillo, Franklin. Universidad de Antioquia; Colombia
Fil: Estenoz, Diana Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Meira, Gregorio Raul. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
description This work investigates the two-step polymerization between methylene diphenyl diisocyanate (MDI), two different poly(tetramethylene oxide) macrodiols, and 1,4-butanediol (BD) as chain extender. At the end of the prepolymerization, the reaction mixture contains MDI in excess and a prepolymer with isocyanate end group. Then, BD and a solvent (tetrahydrofuran) were added to start the finishing stage under nominal stoichiometric equilibrium. The reaction was analyzed by Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance (1H-NMR), and size exclusion chromatography. 1H-NMR was employed to follow global concentrations of unreacted isocyanate end groups and internal urethane groups. This information enabled to estimate the following ?effective? rate constants: k1 = 1.07 × 10−3 L mol−1 s−1 for the prepolymerization; and k2 = 1.94 × 10−4 L mol−1 s−1 for the finishing stage. These values are subject to errors caused by biases introduced in the recipe, in the measurements, in the reaction conditions, in the quality of reagents, and in the reaction mechanism assumptions. Such errors also explain the dispersion of the published rate constants values. The 1H-NMR measurements also enabled to estimate the evolution (with extent of reaction) of the number-average number of structural units along the prepolymerization and finishing stages; and such estimates reasonably verify Flory´s classical expressions.
publishDate 2017
dc.date.none.fl_str_mv 2017-09
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/11336/27281
Polo, Mara Lis; Spontón, Marisa Elisabet; Jaramillo, Franklin; Estenoz, Diana Alejandra; Meira, Gregorio Raul; Linear segmented polyurethanes. I. A kinetics study; John Wiley & Sons Inc; Journal of Applied Polymer Science; 135; 4; 9-2017; 1-13; 45747
0021-8995
CONICET Digital
CONICET
url http://hdl.handle.net/11336/27281
identifier_str_mv Polo, Mara Lis; Spontón, Marisa Elisabet; Jaramillo, Franklin; Estenoz, Diana Alejandra; Meira, Gregorio Raul; Linear segmented polyurethanes. I. A kinetics study; John Wiley & Sons Inc; Journal of Applied Polymer Science; 135; 4; 9-2017; 1-13; 45747
0021-8995
CONICET Digital
CONICET
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/app.45747/abstract
info:eu-repo/semantics/altIdentifier/doi/10.1002/app.45747
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 John Wiley & Sons Inc
publisher.none.fl_str_mv John Wiley & Sons Inc
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 12.982451

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