Zwitterionic ring expansion polymerization of tert-butyl glycidyl ether with B(C6F5)3 towards the generation of cyclic chains
dc.contributor.author | Pagnacco, Carlo Andrea | |
dc.contributor.author | Gastearena, Xuban | |
dc.contributor.author | González de San Román, Estibaliz | |
dc.contributor.author | Matxain Beraza, Jon Mattin | |
dc.contributor.author | Barroso Bujans, Fabienne | |
dc.date.accessioned | 2024-07-04T16:33:24Z | |
dc.date.available | 2024-07-04T16:33:24Z | |
dc.date.issued | 2024-06 | |
dc.identifier.citation | Journal of Polymer Science 62(12) : 2704-2715 (2024) | es_ES |
dc.identifier.issn | 2642-4150 | |
dc.identifier.issn | 2642-4169 | |
dc.identifier.uri | http://hdl.handle.net/10810/68771 | |
dc.description.abstract | The synthesis of cyclic polymers via zwitterionic ring expansion polymerization is limited to a few number of monomer and catalyst pairs. Herein we report the synthesis of cyclic poly(tert-butyl glycidyl ether) through the polymerization of tert-butyl glycidyl ether (tBGE) with B(C6F5)3 in different reaction conditions that include different solvents, monomer to initiator ratio, monomer concentration and temperature. We found that bimodal molecular weight distribution is formed in almost all reaction conditions caused by cyclization of short chains. Subsequent chain elongation leads to the formation of cycles of higher molecular weight, particularly in cyclohexane and under bulk conditions. The formation of non-cyclic byproducts is common in all the systems investigated. Low molecular weight cyclic chains (Mn = 0.7 kDa, Ð = 1.1) of high topological purity were successfully isolated by preparative gel permeation chromatography. By using a click scavenging protocol, the non-cyclic byproducts were eliminated from the high molecular weight fraction (Mn = 3 kDa, Ð = 1.3) generating pure cyclic chains. Mechanistic investigation using density functional theory calculations was performed on the formation of zwitterionic intermediates and the transfer reaction to the monomer, which notably affects chain growth by the attack of the glycidyl oxygen of the monomer on the growing chain. | es_ES |
dc.description.sponsorship | We gratefully acknowledge support from MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe” (PID2021-123438NB-I00), and Basque Government (IT1584-22, IT1566-22 and PIBA 2021-1-0034). Xuban Gastearena thanks the Basque Government for funding through the Fellowship Number PRE_2022_1_0235. | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | Wiley | es_ES |
dc.relation | info:eu-repo/grantAgreement/MICINN/PID2021-123438NB-I00 | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by/3.0/es/ | * |
dc.subject | B(C 6 F5 ) 3 | es_ES |
dc.subject | cyclic polymers | es_ES |
dc.subject | DFT calculations | es_ES |
dc.subject | Lewis acid | es_ES |
dc.subject | ring-opening polymerization | es_ES |
dc.title | Zwitterionic ring expansion polymerization of tert-butyl glycidyl ether with B(C6F5)3 towards the generation of cyclic chains | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.rights.holder | © 2024 The Authors. Journal of Polymer Science published by Wiley Periodicals LLC. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. | es_ES |
dc.rights.holder | Atribución 3.0 España | * |
dc.relation.publisherversion | https://onlinelibrary.wiley.com/doi/10.1002/pol.20240112 | es_ES |
dc.identifier.doi | 10.1002/pol.20240112 | |
dc.departamentoes | Polímeros y Materiales Avanzados: Física, Química y Tecnología | es_ES |
dc.departamentoeu | Polimero eta Material Aurreratuak: Fisika, Kimika eta Teknologia | es_ES |
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Except where otherwise noted, this item's license is described as © 2024 The Authors. Journal of Polymer Science published by Wiley Periodicals LLC. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.