Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal Behavior

Autores
Ninago, Mario Daniel; De Freitas, Augusto G. O.; Hanazumi, Vivina; Muraro, Paulo I. R.; Schmidt, Vanesa; Giacomelli, Cristiano; Ciolino, Andrés Eduardo; Villar, Marcelo Armando
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Branched copolymers are a special class of polymeric materials in which are refl ected the combined effects of polymer segments and architectural constraints of the branched architecture. This study employed two methodologies to obtain copolymers with different branching density. In the fi rst case, poly(hydroxyethyl methacrylate- graft- poly(ε-caprolactone)- block -poly(ε- caprolactone), P(HEMA- g -PCL)- b -PCL, copolymers were synthesized by a “grafting through” method in a three-step reaction pathway involving ring opening polymerization (ROP) and radical addition fragmentation transfer (RAFT) polymerization. In the second case, a combination of simultaneous “grafting through” and “grafting from” methods in a one-pot RAFT and ROP reaction afforded P(HEMA- co -HEMA- g -PCL)- b -PCL comb-like copolymers with comparatively less dense branching. Samples with molar masses between 5500 and 46 000 g mol −1 and polydispersity indexes ( Mw / Mn ) lower than 1.3 were successfully obtained through both approaches. According to thermal analyses, the presence of branches reduces PCL melting temperature by as much as 20 °C, without affecting thermal stability. This fact was particularly evident for the most densely branched copolymers with higher molar masses. Nonisothermal crystallization process was successfully described using Ozawa’s method, which showed a clear dependence of crystallization rate and cooling on grafting density.
Fil: Ninago, Mario Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Fil: De Freitas, Augusto G. O.. Universidade Federal de Santa María; Brasil
Fil: Hanazumi, Vivina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Fil: Muraro, Paulo I. R.. Universidade Federal de Santa María; Brasil
Fil: Schmidt, Vanesa. Universidade Federal de Santa María; Brasil
Fil: Giacomelli, Cristiano. Universidade Federal de Santa María; Brasil
Fil: Ciolino, Andrés Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Fil: Villar, Marcelo Armando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Materia
Branched Copolymers
Poly(2- Hydroxyethylmethacrylate) (Phema)
Poly(E-Caprolactone) (Pcl)
Raft And Rop Polymerization
Thermal Behavior
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:11336/18285
Acceder
id CONICETDig_940062f884e21e09d417fbce966429db
oai_identifier_str oai:ri.conicet.gov.ar:11336/18285
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal BehaviorNinago, Mario DanielDe Freitas, Augusto G. O.Hanazumi, VivinaMuraro, Paulo I. R.Schmidt, VanesaGiacomelli, CristianoCiolino, Andrés EduardoVillar, Marcelo ArmandoBranched CopolymersPoly(2- Hydroxyethylmethacrylate) (Phema)Poly(E-Caprolactone) (Pcl)Raft And Rop PolymerizationThermal Behaviorhttps://purl.org/becyt/ford/2.5https://purl.org/becyt/ford/2Branched copolymers are a special class of polymeric materials in which are refl ected the combined effects of polymer segments and architectural constraints of the branched architecture. This study employed two methodologies to obtain copolymers with different branching density. In the fi rst case, poly(hydroxyethyl methacrylate- graft- poly(ε-caprolactone)- block -poly(ε- caprolactone), P(HEMA- g -PCL)- b -PCL, copolymers were synthesized by a “grafting through” method in a three-step reaction pathway involving ring opening polymerization (ROP) and radical addition fragmentation transfer (RAFT) polymerization. In the second case, a combination of simultaneous “grafting through” and “grafting from” methods in a one-pot RAFT and ROP reaction afforded P(HEMA- co -HEMA- g -PCL)- b -PCL comb-like copolymers with comparatively less dense branching. Samples with molar masses between 5500 and 46 000 g mol −1 and polydispersity indexes ( Mw / Mn ) lower than 1.3 were successfully obtained through both approaches. According to thermal analyses, the presence of branches reduces PCL melting temperature by as much as 20 °C, without affecting thermal stability. This fact was particularly evident for the most densely branched copolymers with higher molar masses. Nonisothermal crystallization process was successfully described using Ozawa’s method, which showed a clear dependence of crystallization rate and cooling on grafting density.Fil: Ninago, Mario Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: De Freitas, Augusto G. O.. Universidade Federal de Santa María; BrasilFil: Hanazumi, Vivina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Muraro, Paulo I. R.. Universidade Federal de Santa María; BrasilFil: Schmidt, Vanesa. Universidade Federal de Santa María; BrasilFil: Giacomelli, Cristiano. Universidade Federal de Santa María; BrasilFil: Ciolino, Andrés Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Villar, Marcelo Armando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaWiley Vch Verlag2015-11-17info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/18285Ninago, Mario Daniel; De Freitas, Augusto G. O.; Hanazumi, Vivina; Muraro, Paulo I. R.; Schmidt, Vanesa; et al.; Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal Behavior; Wiley Vch Verlag; Macromolecular Chemistry And Physics; 216; 17-11-2015; 2331-23431022-1352CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/macp.201500248info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/macp.201570075/epdfinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:06:56Zoai:ri.conicet.gov.ar:11336/18285instacron: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 10:06:56.902CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal Behavior
title Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal Behavior
spellingShingle Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal Behavior
Ninago, Mario Daniel
Branched Copolymers
Poly(2- Hydroxyethylmethacrylate) (Phema)
Poly(E-Caprolactone) (Pcl)
Raft And Rop Polymerization
Thermal Behavior
title_short Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal Behavior
title_full Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal Behavior
title_fullStr Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal Behavior
title_full_unstemmed Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal Behavior
title_sort Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal Behavior
dc.creator.none.fl_str_mv Ninago, Mario Daniel
De Freitas, Augusto G. O.
Hanazumi, Vivina
Muraro, Paulo I. R.
Schmidt, Vanesa
Giacomelli, Cristiano
Ciolino, Andrés Eduardo
Villar, Marcelo Armando
author Ninago, Mario Daniel
author_facet Ninago, Mario Daniel
De Freitas, Augusto G. O.
Hanazumi, Vivina
Muraro, Paulo I. R.
Schmidt, Vanesa
Giacomelli, Cristiano
Ciolino, Andrés Eduardo
Villar, Marcelo Armando
author_role author
author2 De Freitas, Augusto G. O.
Hanazumi, Vivina
Muraro, Paulo I. R.
Schmidt, Vanesa
Giacomelli, Cristiano
Ciolino, Andrés Eduardo
Villar, Marcelo Armando
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Branched Copolymers
Poly(2- Hydroxyethylmethacrylate) (Phema)
Poly(E-Caprolactone) (Pcl)
Raft And Rop Polymerization
Thermal Behavior
topic Branched Copolymers
Poly(2- Hydroxyethylmethacrylate) (Phema)
Poly(E-Caprolactone) (Pcl)
Raft And Rop Polymerization
Thermal Behavior
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.5
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Branched copolymers are a special class of polymeric materials in which are refl ected the combined effects of polymer segments and architectural constraints of the branched architecture. This study employed two methodologies to obtain copolymers with different branching density. In the fi rst case, poly(hydroxyethyl methacrylate- graft- poly(ε-caprolactone)- block -poly(ε- caprolactone), P(HEMA- g -PCL)- b -PCL, copolymers were synthesized by a “grafting through” method in a three-step reaction pathway involving ring opening polymerization (ROP) and radical addition fragmentation transfer (RAFT) polymerization. In the second case, a combination of simultaneous “grafting through” and “grafting from” methods in a one-pot RAFT and ROP reaction afforded P(HEMA- co -HEMA- g -PCL)- b -PCL comb-like copolymers with comparatively less dense branching. Samples with molar masses between 5500 and 46 000 g mol −1 and polydispersity indexes ( Mw / Mn ) lower than 1.3 were successfully obtained through both approaches. According to thermal analyses, the presence of branches reduces PCL melting temperature by as much as 20 °C, without affecting thermal stability. This fact was particularly evident for the most densely branched copolymers with higher molar masses. Nonisothermal crystallization process was successfully described using Ozawa’s method, which showed a clear dependence of crystallization rate and cooling on grafting density.
Fil: Ninago, Mario Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Fil: De Freitas, Augusto G. O.. Universidade Federal de Santa María; Brasil
Fil: Hanazumi, Vivina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Fil: Muraro, Paulo I. R.. Universidade Federal de Santa María; Brasil
Fil: Schmidt, Vanesa. Universidade Federal de Santa María; Brasil
Fil: Giacomelli, Cristiano. Universidade Federal de Santa María; Brasil
Fil: Ciolino, Andrés Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Fil: Villar, Marcelo Armando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
description Branched copolymers are a special class of polymeric materials in which are refl ected the combined effects of polymer segments and architectural constraints of the branched architecture. This study employed two methodologies to obtain copolymers with different branching density. In the fi rst case, poly(hydroxyethyl methacrylate- graft- poly(ε-caprolactone)- block -poly(ε- caprolactone), P(HEMA- g -PCL)- b -PCL, copolymers were synthesized by a “grafting through” method in a three-step reaction pathway involving ring opening polymerization (ROP) and radical addition fragmentation transfer (RAFT) polymerization. In the second case, a combination of simultaneous “grafting through” and “grafting from” methods in a one-pot RAFT and ROP reaction afforded P(HEMA- co -HEMA- g -PCL)- b -PCL comb-like copolymers with comparatively less dense branching. Samples with molar masses between 5500 and 46 000 g mol −1 and polydispersity indexes ( Mw / Mn ) lower than 1.3 were successfully obtained through both approaches. According to thermal analyses, the presence of branches reduces PCL melting temperature by as much as 20 °C, without affecting thermal stability. This fact was particularly evident for the most densely branched copolymers with higher molar masses. Nonisothermal crystallization process was successfully described using Ozawa’s method, which showed a clear dependence of crystallization rate and cooling on grafting density.
publishDate 2015
dc.date.none.fl_str_mv 2015-11-17
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/11336/18285
Ninago, Mario Daniel; De Freitas, Augusto G. O.; Hanazumi, Vivina; Muraro, Paulo I. R.; Schmidt, Vanesa; et al.; Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal Behavior; Wiley Vch Verlag; Macromolecular Chemistry And Physics; 216; 17-11-2015; 2331-2343
1022-1352
CONICET Digital
CONICET
url http://hdl.handle.net/11336/18285
identifier_str_mv Ninago, Mario Daniel; De Freitas, Augusto G. O.; Hanazumi, Vivina; Muraro, Paulo I. R.; Schmidt, Vanesa; et al.; Synthesis of Grafted Block Copolymers Based on e-Caprolactone: Influence of Branches on Their Thermal Behavior; Wiley Vch Verlag; Macromolecular Chemistry And Physics; 216; 17-11-2015; 2331-2343
1022-1352
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/macp.201500248
info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/macp.201570075/epdf
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
application/pdf
dc.publisher.none.fl_str_mv Wiley Vch Verlag
publisher.none.fl_str_mv Wiley Vch Verlag
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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