Kinetics of heterogeneous polymerization of glycidol with B(C6F5)3 in toluene in the absence and presence of water

The synthesis of polyglycidol (or polyglycerol) using tris-(pentafluorophenyl)borane [B(C6F5)3] as a catalyst produces a branched structure with a cyclic core by a mechanism of zwitterionic ring expansion polymerization. The solvent choice is limited since the polymerization does not occur in good s...

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Autores: Gómez Urreizti, Eric, Gastearena, Xuban, Lam, Anabel, González de San Román, Estíbaliz, Miranda, José Ignacio, Matxain, Jon M., Barroso-Bujans, Fabienne
Tipo de documento: artigo
Estado:Versão publicada
Data de publicação:2024
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositório:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/387659
Acesso em linha:http://hdl.handle.net/10261/387659
Access Level:Acceso aberto
Palavra-chave:Polyglycidol
Polyglycerol
Cyclic polymer
Ring polymer
Polymerization mechanisms
DFT calculations
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spelling Kinetics of heterogeneous polymerization of glycidol with B(C6F5)3 in toluene in the absence and presence of waterGómez Urreizti, EricGastearena, XubanLam, AnabelGonzález de San Román, EstíbalizMiranda, José IgnacioMatxain, Jon M.Barroso-Bujans, FabiennePolyglycidolPolyglycerolCyclic polymerRing polymerPolymerization mechanismsDFT calculationsThe synthesis of polyglycidol (or polyglycerol) using tris-(pentafluorophenyl)borane [B(C6F5)3] as a catalyst produces a branched structure with a cyclic core by a mechanism of zwitterionic ring expansion polymerization. The solvent choice is limited since the polymerization does not occur in good solvents for polyglycidol (e.g. DMF, DMSO). In poor solvents for polyglycidol but good solvent for glycidol (e.g. toluene), the polymerization does occur but in a heterogeneous manner. The polymer precipitates during reaction forming two phases, the solution and precipitated phase. In the presence of water a competitive initiation mechanism consisting in the formation of hydronium ions by reaction between B(C6F5)3 and two water molecules, followed by the protonation of glycidol (Gly) epoxide is the responsible for the formation of analogous linear-core structures. In present study we evaluated the kinetic parameters of the initial stage of polymerization of Gly with B(C6F5)3 in the presence and absence of water by in situ 1H NMR monitoring in toluene-d8 phase. The results indicated first order kinetics with respect to Gly and B(C6F5)3, zero order with respect to water, similar initial rate constants for the polymerization initiated by B(C6F5)3 and H3O+ and similar activation energies for the polymerization in the absence and presence of water. The decrease in intensity of the 19F NMR signal relative to the initial value indicated that B(C6F5)3 goes to a precipitated phase just after the polymerization started due to a change in the solubility of the formed oligomeric active chains that carry the catalyst. In the precipitate, the reaction continued due to chain fusion events that take place increasing the molecular weight and producing a product with identical mass distribution as that of a polyglycidol produced under dry and solvent-free conditions. Density functional theory calculations supported the kinetic data by obtaining similar energy barriers and thermodynamic enthalpies for the reaction of Gly with B(C6F5)3 and H3O+.We gratefully acknowledge support from MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe” (grant PID2021-123438NB-I00), Basque Government (IT1584-22, IT1566-22 and PIBA 2021-1-0034) and Diputación Foral de Guipúzcoa (RED 2023-CIEN-000047-01). X.G. thanks the Basque Government for funding through the Fellowship Number PRE_2022_1_0235. A.L. also thanks DIPC program for visitors. Technical and human support provided by IZO-SGI, SGIker (UPV/EHU, MICINN, GV/EJ, ERDF, and ESF), is gratefully acknowledged.Peer reviewedElsevierAgencia Estatal de Investigación (España)Ministerio de Ciencia, Innovación y Universidades (España)Eusko JaurlaritzaDiputación Foral de GipuzkoaEuropean CommissionUniversidad del País VascoConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/387659reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-123438NB-I00The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1016/j.mtchem.2024.101993https://doi.org/10.1016/j.mtchem.2024.101993Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3876592026-05-22T06:33:51Z
dc.title.none.fl_str_mv Kinetics of heterogeneous polymerization of glycidol with B(C6F5)3 in toluene in the absence and presence of water
title Kinetics of heterogeneous polymerization of glycidol with B(C6F5)3 in toluene in the absence and presence of water
spellingShingle Kinetics of heterogeneous polymerization of glycidol with B(C6F5)3 in toluene in the absence and presence of water
Gómez Urreizti, Eric
Polyglycidol
Polyglycerol
Cyclic polymer
Ring polymer
Polymerization mechanisms
DFT calculations
title_short Kinetics of heterogeneous polymerization of glycidol with B(C6F5)3 in toluene in the absence and presence of water
title_full Kinetics of heterogeneous polymerization of glycidol with B(C6F5)3 in toluene in the absence and presence of water
title_fullStr Kinetics of heterogeneous polymerization of glycidol with B(C6F5)3 in toluene in the absence and presence of water
title_full_unstemmed Kinetics of heterogeneous polymerization of glycidol with B(C6F5)3 in toluene in the absence and presence of water
title_sort Kinetics of heterogeneous polymerization of glycidol with B(C6F5)3 in toluene in the absence and presence of water
dc.creator.none.fl_str_mv Gómez Urreizti, Eric
Gastearena, Xuban
Lam, Anabel
González de San Román, Estíbaliz
Miranda, José Ignacio
Matxain, Jon M.
Barroso-Bujans, Fabienne
author Gómez Urreizti, Eric
author_facet Gómez Urreizti, Eric
Gastearena, Xuban
Lam, Anabel
González de San Román, Estíbaliz
Miranda, José Ignacio
Matxain, Jon M.
Barroso-Bujans, Fabienne
author_role author
author2 Gastearena, Xuban
Lam, Anabel
González de San Román, Estíbaliz
Miranda, José Ignacio
Matxain, Jon M.
Barroso-Bujans, Fabienne
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación (España)
Ministerio de Ciencia, Innovación y Universidades (España)
Eusko Jaurlaritza
Diputación Foral de Gipuzkoa
European Commission
Universidad del País Vasco
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Polyglycidol
Polyglycerol
Cyclic polymer
Ring polymer
Polymerization mechanisms
DFT calculations
topic Polyglycidol
Polyglycerol
Cyclic polymer
Ring polymer
Polymerization mechanisms
DFT calculations
description The synthesis of polyglycidol (or polyglycerol) using tris-(pentafluorophenyl)borane [B(C6F5)3] as a catalyst produces a branched structure with a cyclic core by a mechanism of zwitterionic ring expansion polymerization. The solvent choice is limited since the polymerization does not occur in good solvents for polyglycidol (e.g. DMF, DMSO). In poor solvents for polyglycidol but good solvent for glycidol (e.g. toluene), the polymerization does occur but in a heterogeneous manner. The polymer precipitates during reaction forming two phases, the solution and precipitated phase. In the presence of water a competitive initiation mechanism consisting in the formation of hydronium ions by reaction between B(C6F5)3 and two water molecules, followed by the protonation of glycidol (Gly) epoxide is the responsible for the formation of analogous linear-core structures. In present study we evaluated the kinetic parameters of the initial stage of polymerization of Gly with B(C6F5)3 in the presence and absence of water by in situ 1H NMR monitoring in toluene-d8 phase. The results indicated first order kinetics with respect to Gly and B(C6F5)3, zero order with respect to water, similar initial rate constants for the polymerization initiated by B(C6F5)3 and H3O+ and similar activation energies for the polymerization in the absence and presence of water. The decrease in intensity of the 19F NMR signal relative to the initial value indicated that B(C6F5)3 goes to a precipitated phase just after the polymerization started due to a change in the solubility of the formed oligomeric active chains that carry the catalyst. In the precipitate, the reaction continued due to chain fusion events that take place increasing the molecular weight and producing a product with identical mass distribution as that of a polyglycidol produced under dry and solvent-free conditions. Density functional theory calculations supported the kinetic data by obtaining similar energy barriers and thermodynamic enthalpies for the reaction of Gly with B(C6F5)3 and H3O+.
publishDate 2024
dc.date.none.fl_str_mv 2024
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/387659
url http://hdl.handle.net/10261/387659
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-123438NB-I00
The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1016/j.mtchem.2024.101993
https://doi.org/10.1016/j.mtchem.2024.101993
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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