Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniques

Autores
Ninago, Mario Daniel; Satti, Angel Jose; Ressia, Jorge Aníbal; Ciolino, Andrés Eduardo; Villar, Marcelo Armando; Valles, Enrique Marcelo
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The controlled synthesis of poly(dimethylsiloxane) homopolymers (PDMS) using hexamethyl(cyclotrisiloxane) monomer (D 3 ), a mixture of ciclohexane/tetrahydrofuran 50/50 v/v and sec-Bu - Li + as initiator was studied using different experimental conditions, and whole-sealed glass reactors according to standards procedures in high-vacuum anionic polymerization. It was observed that polydispersity indexes (PD) and conversions strongly depend on temperature and reaction times. For PDMS homopolymers with molar masses below 100,000 g/mol, high conversion (>90%) and PD < 1.1 can be achieved at long reaction times (24 h) and mild temperature conditions (below or up to 30 °C). On the other hand, to synthesize PDMS homopolymers with molar masses higher than 100,000 g/mol and PD < 1.1 it is necessary to increase the temperature up to 50 °C and decrease the reaction time (8 h). However, under these reaction conditions, it was observed that the conversion decreases (about 65-70% conversion is achieved). Apparently, the competition between propagation and secondary reactions (redistribution, backbiting, and reshuffling) depends on the molar masses desired. According to the results obtained in this study-which were compared with others found in the scientific literature-propagation is favored when M n < 100,000 g/mol, whereas secondary reactions seem to become important for higher molar masses. Nevertheless, model PDMS homopolymers with high molar masses can still be obtained increasing the reaction temperature and shortening the total reaction time. It seems that the combined effect of these two facts favors propagation against secondary reactions, and provides model PDMS homopolymers with molar masses quite close to the expected ones.
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: Satti, Angel Jose. 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: Ressia, Jorge Aníbal. 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: 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
Fil: Valles, Enrique Marcelo. 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
High-Vacuum Anionic Polymerization Techniques
Model Homopolymers
Narrow Molar Masses Distribution
Poly(Dimethylsiloxane)
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:11336/83562
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/83562
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network_name_str CONICET Digital (CONICET)
spelling Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniquesNinago, Mario DanielSatti, Angel JoseRessia, Jorge AníbalCiolino, Andrés EduardoVillar, Marcelo ArmandoValles, Enrique MarceloHigh-Vacuum Anionic Polymerization TechniquesModel HomopolymersNarrow Molar Masses DistributionPoly(Dimethylsiloxane)https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The controlled synthesis of poly(dimethylsiloxane) homopolymers (PDMS) using hexamethyl(cyclotrisiloxane) monomer (D 3 ), a mixture of ciclohexane/tetrahydrofuran 50/50 v/v and sec-Bu - Li + as initiator was studied using different experimental conditions, and whole-sealed glass reactors according to standards procedures in high-vacuum anionic polymerization. It was observed that polydispersity indexes (PD) and conversions strongly depend on temperature and reaction times. For PDMS homopolymers with molar masses below 100,000 g/mol, high conversion (>90%) and PD < 1.1 can be achieved at long reaction times (24 h) and mild temperature conditions (below or up to 30 °C). On the other hand, to synthesize PDMS homopolymers with molar masses higher than 100,000 g/mol and PD < 1.1 it is necessary to increase the temperature up to 50 °C and decrease the reaction time (8 h). However, under these reaction conditions, it was observed that the conversion decreases (about 65-70% conversion is achieved). Apparently, the competition between propagation and secondary reactions (redistribution, backbiting, and reshuffling) depends on the molar masses desired. According to the results obtained in this study-which were compared with others found in the scientific literature-propagation is favored when M n < 100,000 g/mol, whereas secondary reactions seem to become important for higher molar masses. Nevertheless, model PDMS homopolymers with high molar masses can still be obtained increasing the reaction temperature and shortening the total reaction time. It seems that the combined effect of these two facts favors propagation against secondary reactions, and provides model PDMS homopolymers with molar masses quite close to the expected ones.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: Satti, Angel Jose. 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: Ressia, Jorge Aníbal. 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: 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; ArgentinaFil: Valles, Enrique Marcelo. 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; ArgentinaJohn Wiley & Sons Inc2009-09-05info: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/11336/83562Ninago, Mario Daniel; Satti, Angel Jose; Ressia, Jorge Aníbal; Ciolino, Andrés Eduardo; Villar, Marcelo Armando; et al.; Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniques; John Wiley & Sons Inc; Journal of Polymer Science Part A: Polymer Chemistry; 47; 18; 5-9-2009; 4774-47830887-624XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/pola.23530info:eu-repo/semantics/altIdentifier/doi/10.1002/pola.23530info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:22:38Zoai:ri.conicet.gov.ar:11336/83562instacron: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 10:22:38.988CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniques
title Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniques
spellingShingle Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniques
Ninago, Mario Daniel
High-Vacuum Anionic Polymerization Techniques
Model Homopolymers
Narrow Molar Masses Distribution
Poly(Dimethylsiloxane)
title_short Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniques
title_full Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniques
title_fullStr Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniques
title_full_unstemmed Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniques
title_sort Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniques
dc.creator.none.fl_str_mv Ninago, Mario Daniel
Satti, Angel Jose
Ressia, Jorge Aníbal
Ciolino, Andrés Eduardo
Villar, Marcelo Armando
Valles, Enrique Marcelo
author Ninago, Mario Daniel
author_facet Ninago, Mario Daniel
Satti, Angel Jose
Ressia, Jorge Aníbal
Ciolino, Andrés Eduardo
Villar, Marcelo Armando
Valles, Enrique Marcelo
author_role author
author2 Satti, Angel Jose
Ressia, Jorge Aníbal
Ciolino, Andrés Eduardo
Villar, Marcelo Armando
Valles, Enrique Marcelo
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv High-Vacuum Anionic Polymerization Techniques
Model Homopolymers
Narrow Molar Masses Distribution
Poly(Dimethylsiloxane)
topic High-Vacuum Anionic Polymerization Techniques
Model Homopolymers
Narrow Molar Masses Distribution
Poly(Dimethylsiloxane)
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 controlled synthesis of poly(dimethylsiloxane) homopolymers (PDMS) using hexamethyl(cyclotrisiloxane) monomer (D 3 ), a mixture of ciclohexane/tetrahydrofuran 50/50 v/v and sec-Bu - Li + as initiator was studied using different experimental conditions, and whole-sealed glass reactors according to standards procedures in high-vacuum anionic polymerization. It was observed that polydispersity indexes (PD) and conversions strongly depend on temperature and reaction times. For PDMS homopolymers with molar masses below 100,000 g/mol, high conversion (>90%) and PD < 1.1 can be achieved at long reaction times (24 h) and mild temperature conditions (below or up to 30 °C). On the other hand, to synthesize PDMS homopolymers with molar masses higher than 100,000 g/mol and PD < 1.1 it is necessary to increase the temperature up to 50 °C and decrease the reaction time (8 h). However, under these reaction conditions, it was observed that the conversion decreases (about 65-70% conversion is achieved). Apparently, the competition between propagation and secondary reactions (redistribution, backbiting, and reshuffling) depends on the molar masses desired. According to the results obtained in this study-which were compared with others found in the scientific literature-propagation is favored when M n < 100,000 g/mol, whereas secondary reactions seem to become important for higher molar masses. Nevertheless, model PDMS homopolymers with high molar masses can still be obtained increasing the reaction temperature and shortening the total reaction time. It seems that the combined effect of these two facts favors propagation against secondary reactions, and provides model PDMS homopolymers with molar masses quite close to the expected ones.
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: Satti, Angel Jose. 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: Ressia, Jorge Aníbal. 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: 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
Fil: Valles, Enrique Marcelo. 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 The controlled synthesis of poly(dimethylsiloxane) homopolymers (PDMS) using hexamethyl(cyclotrisiloxane) monomer (D 3 ), a mixture of ciclohexane/tetrahydrofuran 50/50 v/v and sec-Bu - Li + as initiator was studied using different experimental conditions, and whole-sealed glass reactors according to standards procedures in high-vacuum anionic polymerization. It was observed that polydispersity indexes (PD) and conversions strongly depend on temperature and reaction times. For PDMS homopolymers with molar masses below 100,000 g/mol, high conversion (>90%) and PD < 1.1 can be achieved at long reaction times (24 h) and mild temperature conditions (below or up to 30 °C). On the other hand, to synthesize PDMS homopolymers with molar masses higher than 100,000 g/mol and PD < 1.1 it is necessary to increase the temperature up to 50 °C and decrease the reaction time (8 h). However, under these reaction conditions, it was observed that the conversion decreases (about 65-70% conversion is achieved). Apparently, the competition between propagation and secondary reactions (redistribution, backbiting, and reshuffling) depends on the molar masses desired. According to the results obtained in this study-which were compared with others found in the scientific literature-propagation is favored when M n < 100,000 g/mol, whereas secondary reactions seem to become important for higher molar masses. Nevertheless, model PDMS homopolymers with high molar masses can still be obtained increasing the reaction temperature and shortening the total reaction time. It seems that the combined effect of these two facts favors propagation against secondary reactions, and provides model PDMS homopolymers with molar masses quite close to the expected ones.
publishDate 2009
dc.date.none.fl_str_mv 2009-09-05
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/11336/83562
Ninago, Mario Daniel; Satti, Angel Jose; Ressia, Jorge Aníbal; Ciolino, Andrés Eduardo; Villar, Marcelo Armando; et al.; Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniques; John Wiley & Sons Inc; Journal of Polymer Science Part A: Polymer Chemistry; 47; 18; 5-9-2009; 4774-4783
0887-624X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/83562
identifier_str_mv Ninago, Mario Daniel; Satti, Angel Jose; Ressia, Jorge Aníbal; Ciolino, Andrés Eduardo; Villar, Marcelo Armando; et al.; Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniques; John Wiley & Sons Inc; Journal of Polymer Science Part A: Polymer Chemistry; 47; 18; 5-9-2009; 4774-4783
0887-624X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/pola.23530
info:eu-repo/semantics/altIdentifier/doi/10.1002/pola.23530
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 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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