Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complex

Autores
De Queiroz, Alvaro A. A.; Franca, Ecio J.; Abraham, Gustavo Abel; Román, Julio S.
Año de publicación
2002
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The ring-opening polymerization of ε-caprolactone (ε-CL) catalyzed by iodine (I2) was studied. The formation of a charge-transfer complex (CTC) among triiodide, I3-, and ε-CL was confirmed with ultraviolet-visible spectroscopy. The monomer ε-CL was polymerized in bulk using I2 as a catalyst to form the polyester having apparent weight-average molecular weights of 85,900 and 45,500 at polymerization temperatures of 25 and 70 °C, respectively. The reactivity of both, ε-CL monomer and ε-CL:I2 CTC, was interpreted by means of the potential energy surfaces determined by semiempirical computations (MNDO-d). The results suggest that the formation of the ε-CL:I2 CTC leads to the ring opening of the ε-CL structure with the lactone protonation and the formation of a highly polarized polymerization precursor (ε-CL)+. The band gaps approximated from an extrapolation of the oligomeric polycaprolactone (PCL) structures were computed. With semiempirical quantum chemical calculations, geometries and charge distributions of the protonated polymerization precursor (ε-CL)+ were obtained. The calculated band gap (highest occupied molecular orbit/lowest unoccupied molecular orbit differences) agrees with the experiment. The analysis of the oligomeric PCL isosurfaces indicate the existence of a weakly lone pair character of the C=O and C - O bonds suggesting a ε-CL ring-opening specificity. © 2002 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys.
Fil: De Queiroz, Alvaro A. A.. Escola Federal de Engenharia de Itajubá; Brasil
Fil: Franca, Ecio J.. Escola Federal de Engenharia de Itajubá; Brasil
Fil: Abraham, Gustavo Abel. 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; Argentina. Consejo Superior de Investigaciones Científicas; España
Fil: Román, Julio S.. Consejo Superior de Investigaciones Científicas; España
Materia
Catalysts
Charge Transfer
Polyesters
Ring-Opening Polymerization
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:11336/54234
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/54234
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complexDe Queiroz, Alvaro A. A.Franca, Ecio J.Abraham, Gustavo AbelRomán, Julio S.CatalystsCharge TransferPolyestersRing-Opening Polymerizationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The ring-opening polymerization of ε-caprolactone (ε-CL) catalyzed by iodine (I2) was studied. The formation of a charge-transfer complex (CTC) among triiodide, I3-, and ε-CL was confirmed with ultraviolet-visible spectroscopy. The monomer ε-CL was polymerized in bulk using I2 as a catalyst to form the polyester having apparent weight-average molecular weights of 85,900 and 45,500 at polymerization temperatures of 25 and 70 °C, respectively. The reactivity of both, ε-CL monomer and ε-CL:I2 CTC, was interpreted by means of the potential energy surfaces determined by semiempirical computations (MNDO-d). The results suggest that the formation of the ε-CL:I2 CTC leads to the ring opening of the ε-CL structure with the lactone protonation and the formation of a highly polarized polymerization precursor (ε-CL)+. The band gaps approximated from an extrapolation of the oligomeric polycaprolactone (PCL) structures were computed. With semiempirical quantum chemical calculations, geometries and charge distributions of the protonated polymerization precursor (ε-CL)+ were obtained. The calculated band gap (highest occupied molecular orbit/lowest unoccupied molecular orbit differences) agrees with the experiment. The analysis of the oligomeric PCL isosurfaces indicate the existence of a weakly lone pair character of the C=O and C - O bonds suggesting a ε-CL ring-opening specificity. © 2002 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys.Fil: De Queiroz, Alvaro A. A.. Escola Federal de Engenharia de Itajubá; BrasilFil: Franca, Ecio J.. Escola Federal de Engenharia de Itajubá; BrasilFil: Abraham, Gustavo Abel. 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; Argentina. Consejo Superior de Investigaciones Científicas; EspañaFil: Román, Julio S.. Consejo Superior de Investigaciones Científicas; EspañaJohn Wiley & Sons Inc2002-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/54234De Queiroz, Alvaro A. A.; Franca, Ecio J.; Abraham, Gustavo Abel; Román, Julio S.; Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complex; John Wiley & Sons Inc; Journal of Polymer Science Part B: Polymer Physics; 40; 8; 12-2002; 714-7220887-6266CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/polb.10133info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.10133info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:42:05Zoai:ri.conicet.gov.ar:11336/54234instacron: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 09:42:05.932CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complex
title Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complex
spellingShingle Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complex
De Queiroz, Alvaro A. A.
Catalysts
Charge Transfer
Polyesters
Ring-Opening Polymerization
title_short Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complex
title_full Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complex
title_fullStr Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complex
title_full_unstemmed Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complex
title_sort Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complex
dc.creator.none.fl_str_mv De Queiroz, Alvaro A. A.
Franca, Ecio J.
Abraham, Gustavo Abel
Román, Julio S.
author De Queiroz, Alvaro A. A.
author_facet De Queiroz, Alvaro A. A.
Franca, Ecio J.
Abraham, Gustavo Abel
Román, Julio S.
author_role author
author2 Franca, Ecio J.
Abraham, Gustavo Abel
Román, Julio S.
author2_role author
author
author
dc.subject.none.fl_str_mv Catalysts
Charge Transfer
Polyesters
Ring-Opening Polymerization
topic Catalysts
Charge Transfer
Polyesters
Ring-Opening Polymerization
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 ring-opening polymerization of ε-caprolactone (ε-CL) catalyzed by iodine (I2) was studied. The formation of a charge-transfer complex (CTC) among triiodide, I3-, and ε-CL was confirmed with ultraviolet-visible spectroscopy. The monomer ε-CL was polymerized in bulk using I2 as a catalyst to form the polyester having apparent weight-average molecular weights of 85,900 and 45,500 at polymerization temperatures of 25 and 70 °C, respectively. The reactivity of both, ε-CL monomer and ε-CL:I2 CTC, was interpreted by means of the potential energy surfaces determined by semiempirical computations (MNDO-d). The results suggest that the formation of the ε-CL:I2 CTC leads to the ring opening of the ε-CL structure with the lactone protonation and the formation of a highly polarized polymerization precursor (ε-CL)+. The band gaps approximated from an extrapolation of the oligomeric polycaprolactone (PCL) structures were computed. With semiempirical quantum chemical calculations, geometries and charge distributions of the protonated polymerization precursor (ε-CL)+ were obtained. The calculated band gap (highest occupied molecular orbit/lowest unoccupied molecular orbit differences) agrees with the experiment. The analysis of the oligomeric PCL isosurfaces indicate the existence of a weakly lone pair character of the C=O and C - O bonds suggesting a ε-CL ring-opening specificity. © 2002 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys.
Fil: De Queiroz, Alvaro A. A.. Escola Federal de Engenharia de Itajubá; Brasil
Fil: Franca, Ecio J.. Escola Federal de Engenharia de Itajubá; Brasil
Fil: Abraham, Gustavo Abel. 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; Argentina. Consejo Superior de Investigaciones Científicas; España
Fil: Román, Julio S.. Consejo Superior de Investigaciones Científicas; España
description The ring-opening polymerization of ε-caprolactone (ε-CL) catalyzed by iodine (I2) was studied. The formation of a charge-transfer complex (CTC) among triiodide, I3-, and ε-CL was confirmed with ultraviolet-visible spectroscopy. The monomer ε-CL was polymerized in bulk using I2 as a catalyst to form the polyester having apparent weight-average molecular weights of 85,900 and 45,500 at polymerization temperatures of 25 and 70 °C, respectively. The reactivity of both, ε-CL monomer and ε-CL:I2 CTC, was interpreted by means of the potential energy surfaces determined by semiempirical computations (MNDO-d). The results suggest that the formation of the ε-CL:I2 CTC leads to the ring opening of the ε-CL structure with the lactone protonation and the formation of a highly polarized polymerization precursor (ε-CL)+. The band gaps approximated from an extrapolation of the oligomeric polycaprolactone (PCL) structures were computed. With semiempirical quantum chemical calculations, geometries and charge distributions of the protonated polymerization precursor (ε-CL)+ were obtained. The calculated band gap (highest occupied molecular orbit/lowest unoccupied molecular orbit differences) agrees with the experiment. The analysis of the oligomeric PCL isosurfaces indicate the existence of a weakly lone pair character of the C=O and C - O bonds suggesting a ε-CL ring-opening specificity. © 2002 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys.
publishDate 2002
dc.date.none.fl_str_mv 2002-12
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/11336/54234
De Queiroz, Alvaro A. A.; Franca, Ecio J.; Abraham, Gustavo Abel; Román, Julio S.; Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complex; John Wiley & Sons Inc; Journal of Polymer Science Part B: Polymer Physics; 40; 8; 12-2002; 714-722
0887-6266
CONICET Digital
CONICET
url http://hdl.handle.net/11336/54234
identifier_str_mv De Queiroz, Alvaro A. A.; Franca, Ecio J.; Abraham, Gustavo Abel; Román, Julio S.; Ring-opening polymerization of ε-caprolactone by iodine charge-transfer complex; John Wiley & Sons Inc; Journal of Polymer Science Part B: Polymer Physics; 40; 8; 12-2002; 714-722
0887-6266
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/polb.10133
info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.10133
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 13.070432

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