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Grafting well-defined polymers onto unsaturated PVDF using thiol-ene reactions

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dc.title Grafting well-defined polymers onto unsaturated PVDF using thiol-ene reactions en
dc.contributor.author Lin, Ting-Chih
dc.contributor.author Mocny, Piotr
dc.contributor.author Cvek, Martin
dc.contributor.author Sun, Mingkang
dc.contributor.author Matyjaszewski, Krzysztof
dc.relation.ispartof Polymer
dc.identifier.issn 0032-3861 Scopus Sources, Sherpa/RoMEO, JCR
dc.identifier.issn 1873-2291 Scopus Sources, Sherpa/RoMEO, JCR
dc.date.issued 2024
utb.relation.volume 297
dc.type article
dc.language.iso en
dc.publisher Elsevier Ltd
dc.identifier.doi 10.1016/j.polymer.2024.126848
dc.relation.uri https://www.sciencedirect.com/science/article/pii/S0032386124001836
dc.relation.uri https://www.sciencedirect.com/science/article/pii/S0032386124001836/pdfft?md5=8f0108c917e46bb6bf6c7eee0465be22&pid=1-s2.0-S0032386124001836-main.pdf
dc.subject poly(vinylidene fluoride) en
dc.subject controlled radical polymerization en
dc.subject thiol-ene en
dc.subject grafting-onto en
dc.description.abstract Poly(vinylidene fluoride) (PVDF) is commonly used in membranes, lithium-ion battery binders, and coatings due to its thermal and chemical robustness. Nevertheless, PVDF-based copolymers can broaden the application scope and performance capabilities of pristine PVDF. PVDF has been modified via grafting-from reactions. However, grafting density and graft length, two important properties of graft copolymers, cannot be accurately determined. Herein, we used grafting-onto thiol-ene reactions as a method to modify PVDF. The molar mass of pre-synthesized, thiol-terminated polymers were accurately determined, and grafting densities were calculated. Unsaturated sites were generated through dehydrofluorination and dehydrochlorination in PVDF and P(VDF-co-chlorotrifluoroethylene) (PVDF-CTFE). Various conditions were studied, including the molar mass and chemical structure of grafts, the degree of thiol substitution, and thiol-ene reaction mechanisms. Base-catalyzed Michael addition with secondary thiols performed best, with the highest grafting density calculated to be about 4 chains per PVDF chain. Despite the low grafting density, changes in material properties between the product and starting materials were observed, validating this controlled method for PVDF modification. en
utb.faculty University Institute
dc.identifier.uri http://hdl.handle.net/10563/1011969
utb.identifier.scopus 2-s2.0-85186757502
utb.identifier.wok 001205868100001
utb.identifier.coden POLMA
utb.source j-scopus
dc.date.accessioned 2024-04-17T13:13:06Z
dc.date.available 2024-04-17T13:13:06Z
dc.description.sponsorship National Science Foundation, NSF, (DMR 2202747); US-UK Fulbright Commission, (2022-21-1, RP/CPS/2022/007); Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung, SNF, (194385); Ministerstvo Školství, Mládeže a Tělovýchovy, MŠMT, (CHE-0130903, CHE-1039870, CHE-1726525)
dc.description.sponsorship NSF [DMR 2202747, CHE-0130903, CHE-1039870, CHE-1726525]; Swiss National Science Foundations (SNSF) [194385]; J. W. Fulbright Commission [2022-21-1]; DKRVO - MEYS of the Czech Republic [RP/CPS/2022/007]
dc.rights Attribution-NonCommercial 4.0 International
dc.rights.uri http://creativecommons.org/licenses/by-nc/4.0/
dc.rights.access openAccess
utb.ou Centre of Polymer Systems
utb.contributor.internalauthor Cvek, Martin
utb.fulltext.affiliation Ting-Chih Lin a, Piotr Mocny a, Martin Cvek a b, Mingkang Sun a, Krzysztof Matyjaszewski a a Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA, 15213, USA b Centre of Polymer Systems, Tomas Bata University in Zlín, Trida T. Bati 5678, 760 01, Zlin, Czech Republic
utb.fulltext.dates Received 20 September 2023 Received in revised form 25 February 2024 Accepted 26 February 2024 Available online 28 February 2024
utb.fulltext.sponsorship Financial support from NSF (DMR 2202747) is acknowledged. PM gratefully acknowledges financial support from Swiss National Science Foundations (SNSF, grant no. 194385). MC is grateful to the J. W. Fulbright Commission (2022-21-1) and project DKRVO (RP/CPS/2022/007), supported by MEYS of the Czech Republic. The NMR instrumentation at Carnegie Mellon University was partially supported by the NSF (CHE-0130903, CHE-1039870 and CHE-1726525). We would like to thank the Sodano group at the University of Michigan for their generous contribution of dehydrofluorinated PVDF.
utb.wos.affiliation [Lin, Ting-Chih; Mocny, Piotr; Cvek, Martin; Sun, Mingkang; Matyjaszewski, Krzysztof] Carnegie Mellon Univ, Dept Chem, 4400 Fifth Ave, Pittsburgh, PA 15213 USA; [Cvek, Martin] Tomas Bata Univ Zlin, Ctr Polymer Syst, Trida T Bati 5678, Zlin 76001, Czech Republic
utb.scopus.affiliation Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, 15213, PA, United States; Centre of Polymer Systems, Tomas Bata University in Zlín, Trida T. Bati 5678, Zlin, 760 01, Czech Republic
utb.fulltext.projects DMR 2202747
utb.fulltext.projects 194385
utb.fulltext.projects 2022-21-1
utb.fulltext.projects DKRVO (RP/CPS/2022/007)
utb.fulltext.projects CHE-0130903
utb.fulltext.projects CHE-1039870
utb.fulltext.projects CHE-1726525
utb.fulltext.faculty University Institute
utb.fulltext.ou Centre of Polymer Systems
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