Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type CoII complexes
Autor(a) principal: | |
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Data de Publicação: | 2021 |
Outros Autores: | , , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1016/j.eurpolymj.2021.110757 http://hdl.handle.net/11449/222556 |
Resumo: | In this study, we synthesized the complex [Co(BuSalen)] using the novel tetradentate BuSalen ligand and analyzed its ability as a controlling agent for the photo-induced organometallic-mediated radical polymerization (photo-OMRP) of butyl acrylate (BA) using diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) as photo-initiator. BA polymerization with [Co(BuSalen)] reached significant control levels using the [BA]/[CoII]/TPO molar ratio of 600/1/1. The [Co(Salen)] and [Co(Bu2Salen)] complexes were also obtained following literature methods aiming a comparison in the mediating ability in photo-OMRP. [Co(BuSalen)] and [Co(Bu2Salen)] showed better controlling ability, as observed in the copolymerization study (Đ= 2.64, 1.50, and 1.26 for complexes [Co(Salen)], [Co(BuSalen)] and [Co(Bu2Salen)], respectively). Kinetics studies and computational investigations support a reversible termination (RT) mechanism and a tailorable CoII complex reactivity mainly altered by Schiff-base steric factors. Calculated thermodynamic parameters agree with the controlling degree delivered by these complexes, since the polymerization control increases with increasing the ΔG values for the formation of dormant species. |
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Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type CoII complexesButyl acrylateCoII complexesPhoto-OMRPTetradentate Schiff-baseIn this study, we synthesized the complex [Co(BuSalen)] using the novel tetradentate BuSalen ligand and analyzed its ability as a controlling agent for the photo-induced organometallic-mediated radical polymerization (photo-OMRP) of butyl acrylate (BA) using diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) as photo-initiator. BA polymerization with [Co(BuSalen)] reached significant control levels using the [BA]/[CoII]/TPO molar ratio of 600/1/1. The [Co(Salen)] and [Co(Bu2Salen)] complexes were also obtained following literature methods aiming a comparison in the mediating ability in photo-OMRP. [Co(BuSalen)] and [Co(Bu2Salen)] showed better controlling ability, as observed in the copolymerization study (Đ= 2.64, 1.50, and 1.26 for complexes [Co(Salen)], [Co(BuSalen)] and [Co(Bu2Salen)], respectively). Kinetics studies and computational investigations support a reversible termination (RT) mechanism and a tailorable CoII complex reactivity mainly altered by Schiff-base steric factors. Calculated thermodynamic parameters agree with the controlling degree delivered by these complexes, since the polymerization control increases with increasing the ΔG values for the formation of dormant species.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG)Faculdade de Ciências e Tecnologia UNESP – Univ. Estadual PaulistaInstituto de Química Universidade Federal de Uberlândia, P.O. Box 593Faculdade de Ciências e Tecnologia UNESP – Univ. Estadual PaulistaFAPESP: 2018/06340-1FAPESP: 2018/19395-9FAPESP: 2019/03354-4CNPq: 307443/2015-9FAPEMIG: CEX - APQ-03017-16Universidade Estadual Paulista (UNESP)Universidade Federal de Uberlândia (UFU)Oliveira, Larissa F. [UNESP]Bignardi, Camila [UNESP]Pesqueira, Naralyne M. [UNESP]Riga-Rocha, Beatriz A. [UNESP]Machado, Antonio E.H.Carvalho-Jr, Valdemiro P. [UNESP]Goi, Beatriz E. [UNESP]2022-04-28T19:45:24Z2022-04-28T19:45:24Z2021-10-05info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://dx.doi.org/10.1016/j.eurpolymj.2021.110757European Polymer Journal, v. 159.0014-3057http://hdl.handle.net/11449/22255610.1016/j.eurpolymj.2021.1107572-s2.0-85116349418Scopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengEuropean Polymer Journalinfo:eu-repo/semantics/openAccess2022-04-28T19:45:24Zoai:repositorio.unesp.br:11449/222556Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T14:02:59.131980Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type CoII complexes |
title |
Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type CoII complexes |
spellingShingle |
Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type CoII complexes Oliveira, Larissa F. [UNESP] Butyl acrylate CoII complexes Photo-OMRP Tetradentate Schiff-base |
title_short |
Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type CoII complexes |
title_full |
Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type CoII complexes |
title_fullStr |
Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type CoII complexes |
title_full_unstemmed |
Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type CoII complexes |
title_sort |
Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type CoII complexes |
author |
Oliveira, Larissa F. [UNESP] |
author_facet |
Oliveira, Larissa F. [UNESP] Bignardi, Camila [UNESP] Pesqueira, Naralyne M. [UNESP] Riga-Rocha, Beatriz A. [UNESP] Machado, Antonio E.H. Carvalho-Jr, Valdemiro P. [UNESP] Goi, Beatriz E. [UNESP] |
author_role |
author |
author2 |
Bignardi, Camila [UNESP] Pesqueira, Naralyne M. [UNESP] Riga-Rocha, Beatriz A. [UNESP] Machado, Antonio E.H. Carvalho-Jr, Valdemiro P. [UNESP] Goi, Beatriz E. [UNESP] |
author2_role |
author author author author author author |
dc.contributor.none.fl_str_mv |
Universidade Estadual Paulista (UNESP) Universidade Federal de Uberlândia (UFU) |
dc.contributor.author.fl_str_mv |
Oliveira, Larissa F. [UNESP] Bignardi, Camila [UNESP] Pesqueira, Naralyne M. [UNESP] Riga-Rocha, Beatriz A. [UNESP] Machado, Antonio E.H. Carvalho-Jr, Valdemiro P. [UNESP] Goi, Beatriz E. [UNESP] |
dc.subject.por.fl_str_mv |
Butyl acrylate CoII complexes Photo-OMRP Tetradentate Schiff-base |
topic |
Butyl acrylate CoII complexes Photo-OMRP Tetradentate Schiff-base |
description |
In this study, we synthesized the complex [Co(BuSalen)] using the novel tetradentate BuSalen ligand and analyzed its ability as a controlling agent for the photo-induced organometallic-mediated radical polymerization (photo-OMRP) of butyl acrylate (BA) using diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) as photo-initiator. BA polymerization with [Co(BuSalen)] reached significant control levels using the [BA]/[CoII]/TPO molar ratio of 600/1/1. The [Co(Salen)] and [Co(Bu2Salen)] complexes were also obtained following literature methods aiming a comparison in the mediating ability in photo-OMRP. [Co(BuSalen)] and [Co(Bu2Salen)] showed better controlling ability, as observed in the copolymerization study (Đ= 2.64, 1.50, and 1.26 for complexes [Co(Salen)], [Co(BuSalen)] and [Co(Bu2Salen)], respectively). Kinetics studies and computational investigations support a reversible termination (RT) mechanism and a tailorable CoII complex reactivity mainly altered by Schiff-base steric factors. Calculated thermodynamic parameters agree with the controlling degree delivered by these complexes, since the polymerization control increases with increasing the ΔG values for the formation of dormant species. |
publishDate |
2021 |
dc.date.none.fl_str_mv |
2021-10-05 2022-04-28T19:45:24Z 2022-04-28T19:45:24Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://dx.doi.org/10.1016/j.eurpolymj.2021.110757 European Polymer Journal, v. 159. 0014-3057 http://hdl.handle.net/11449/222556 10.1016/j.eurpolymj.2021.110757 2-s2.0-85116349418 |
url |
http://dx.doi.org/10.1016/j.eurpolymj.2021.110757 http://hdl.handle.net/11449/222556 |
identifier_str_mv |
European Polymer Journal, v. 159. 0014-3057 10.1016/j.eurpolymj.2021.110757 2-s2.0-85116349418 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
European Polymer Journal |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.source.none.fl_str_mv |
Scopus reponame:Repositório Institucional da UNESP instname:Universidade Estadual Paulista (UNESP) instacron:UNESP |
instname_str |
Universidade Estadual Paulista (UNESP) |
instacron_str |
UNESP |
institution |
UNESP |
reponame_str |
Repositório Institucional da UNESP |
collection |
Repositório Institucional da UNESP |
repository.name.fl_str_mv |
Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP) |
repository.mail.fl_str_mv |
|
_version_ |
1808128309132787712 |