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Cobalt-Mediated Radical Copolymerization of Vinylidene Fluoride and 2,3,3,3-Trifluoroprop-1-ene

New copolymers based on vinylidene fluoride (VDF) and 2,3,3,3-tetrafluoroprop-1-ene (1234yf) were synthesized by organometallic-mediated radical copolymerization (OMRcP) using the combination of bis(tert-butylcyclohexyl) peroxydicarbonate initiator and bis(acetylacetonato)cobalt(II), (Co(acac)(2)) a...

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Autores principales: Falireas, Panagiotis G., Ameduri, Bruno
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8402042/
https://www.ncbi.nlm.nih.gov/pubmed/34451216
http://dx.doi.org/10.3390/polym13162676
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author Falireas, Panagiotis G.
Ameduri, Bruno
author_facet Falireas, Panagiotis G.
Ameduri, Bruno
author_sort Falireas, Panagiotis G.
collection PubMed
description New copolymers based on vinylidene fluoride (VDF) and 2,3,3,3-tetrafluoroprop-1-ene (1234yf) were synthesized by organometallic-mediated radical copolymerization (OMRcP) using the combination of bis(tert-butylcyclohexyl) peroxydicarbonate initiator and bis(acetylacetonato)cobalt(II), (Co(acac)(2)) as a controlling agent. Kinetics studies of the copolymerization of the fluoroalkenes copolymers were monitored by GPC and (19)F NMR with molar masses up to 12,200 g/mol and dispersities (Đ) ranging from 1.33 to 1.47. Such an OMRcP behaves as a controlled copolymerization, evidenced by the molar mass of the resulting copolymer-monomer conversion linear relationship. The reactivity ratios, r(i), of both comonomers were determined by using the Fineman-Ross and Kelen-Tüdos fitting model leading to r(VDF) = 0.384 ± 0.013 and r(1234yf) = 2.147 ± 0.129 at 60 °C, showing that a lower reactivity of VDF integrated in the copolymer to a greater extent leads to the production of gradient or pseudo-diblock copolymers. In addition, the Q (0.03) and e (0.06 and 0.94) parameters were assessed, as well as the dyad statistic distributions and mean square sequence lengths of PVDF and P1234yf.
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spelling pubmed-84020422021-08-29 Cobalt-Mediated Radical Copolymerization of Vinylidene Fluoride and 2,3,3,3-Trifluoroprop-1-ene Falireas, Panagiotis G. Ameduri, Bruno Polymers (Basel) Article New copolymers based on vinylidene fluoride (VDF) and 2,3,3,3-tetrafluoroprop-1-ene (1234yf) were synthesized by organometallic-mediated radical copolymerization (OMRcP) using the combination of bis(tert-butylcyclohexyl) peroxydicarbonate initiator and bis(acetylacetonato)cobalt(II), (Co(acac)(2)) as a controlling agent. Kinetics studies of the copolymerization of the fluoroalkenes copolymers were monitored by GPC and (19)F NMR with molar masses up to 12,200 g/mol and dispersities (Đ) ranging from 1.33 to 1.47. Such an OMRcP behaves as a controlled copolymerization, evidenced by the molar mass of the resulting copolymer-monomer conversion linear relationship. The reactivity ratios, r(i), of both comonomers were determined by using the Fineman-Ross and Kelen-Tüdos fitting model leading to r(VDF) = 0.384 ± 0.013 and r(1234yf) = 2.147 ± 0.129 at 60 °C, showing that a lower reactivity of VDF integrated in the copolymer to a greater extent leads to the production of gradient or pseudo-diblock copolymers. In addition, the Q (0.03) and e (0.06 and 0.94) parameters were assessed, as well as the dyad statistic distributions and mean square sequence lengths of PVDF and P1234yf. MDPI 2021-08-11 /pmc/articles/PMC8402042/ /pubmed/34451216 http://dx.doi.org/10.3390/polym13162676 Text en © 2021 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Falireas, Panagiotis G.
Ameduri, Bruno
Cobalt-Mediated Radical Copolymerization of Vinylidene Fluoride and 2,3,3,3-Trifluoroprop-1-ene
title Cobalt-Mediated Radical Copolymerization of Vinylidene Fluoride and 2,3,3,3-Trifluoroprop-1-ene
title_full Cobalt-Mediated Radical Copolymerization of Vinylidene Fluoride and 2,3,3,3-Trifluoroprop-1-ene
title_fullStr Cobalt-Mediated Radical Copolymerization of Vinylidene Fluoride and 2,3,3,3-Trifluoroprop-1-ene
title_full_unstemmed Cobalt-Mediated Radical Copolymerization of Vinylidene Fluoride and 2,3,3,3-Trifluoroprop-1-ene
title_short Cobalt-Mediated Radical Copolymerization of Vinylidene Fluoride and 2,3,3,3-Trifluoroprop-1-ene
title_sort cobalt-mediated radical copolymerization of vinylidene fluoride and 2,3,3,3-trifluoroprop-1-ene
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8402042/
https://www.ncbi.nlm.nih.gov/pubmed/34451216
http://dx.doi.org/10.3390/polym13162676
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