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Examining the Influence of Anion Nucleophilicity on the Polymerisation Initiation Mechanism of Phenyl Glycidyl Ether

The reaction of phenyl glycidyl ether (PGE) with 1-ethyl-3-methylimidazolium acetate and 1-ethyl-3-methylimidazolium thiocyanate to initiate the polyetherification reaction was examined using thermal and spectral analysis techniques. The influence of the nucleophilicity of the anions on the deproton...

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Detalles Bibliográficos
Autores principales: Binks, Fiona C., Cavalli, Gabriel, Henningsen, Michael, Howlin, Brendan J., Hamerton, Ian
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6523680/
https://www.ncbi.nlm.nih.gov/pubmed/30974878
http://dx.doi.org/10.3390/polym11040657
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author Binks, Fiona C.
Cavalli, Gabriel
Henningsen, Michael
Howlin, Brendan J.
Hamerton, Ian
author_facet Binks, Fiona C.
Cavalli, Gabriel
Henningsen, Michael
Howlin, Brendan J.
Hamerton, Ian
author_sort Binks, Fiona C.
collection PubMed
description The reaction of phenyl glycidyl ether (PGE) with 1-ethyl-3-methylimidazolium acetate and 1-ethyl-3-methylimidazolium thiocyanate to initiate the polyetherification reaction was examined using thermal and spectral analysis techniques. The influence of the nucleophilicity of the anions on the deprotonation of the 1-ethyl-3-methylimidazolium cation determined the reaction pathway. The thermal degradation of the ionic liquid liberated the acetate ion and led, subsequently, to the deprotonation of the acidic proton in the imidazole ring. Thus, polymerisation of PGE occurred via a carbene intermediate. The more nucleophilic thiocyanate anion was not sufficiently basic to deprotonate the 1-ethyl-3-methylimidazolium cation, and thus proceeded through direct reaction with the PGE, unless the temperature was elevated and a competing carbene mechanism ensued.
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spelling pubmed-65236802019-06-03 Examining the Influence of Anion Nucleophilicity on the Polymerisation Initiation Mechanism of Phenyl Glycidyl Ether Binks, Fiona C. Cavalli, Gabriel Henningsen, Michael Howlin, Brendan J. Hamerton, Ian Polymers (Basel) Article The reaction of phenyl glycidyl ether (PGE) with 1-ethyl-3-methylimidazolium acetate and 1-ethyl-3-methylimidazolium thiocyanate to initiate the polyetherification reaction was examined using thermal and spectral analysis techniques. The influence of the nucleophilicity of the anions on the deprotonation of the 1-ethyl-3-methylimidazolium cation determined the reaction pathway. The thermal degradation of the ionic liquid liberated the acetate ion and led, subsequently, to the deprotonation of the acidic proton in the imidazole ring. Thus, polymerisation of PGE occurred via a carbene intermediate. The more nucleophilic thiocyanate anion was not sufficiently basic to deprotonate the 1-ethyl-3-methylimidazolium cation, and thus proceeded through direct reaction with the PGE, unless the temperature was elevated and a competing carbene mechanism ensued. MDPI 2019-04-10 /pmc/articles/PMC6523680/ /pubmed/30974878 http://dx.doi.org/10.3390/polym11040657 Text en © 2019 by the authors. 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 (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Binks, Fiona C.
Cavalli, Gabriel
Henningsen, Michael
Howlin, Brendan J.
Hamerton, Ian
Examining the Influence of Anion Nucleophilicity on the Polymerisation Initiation Mechanism of Phenyl Glycidyl Ether
title Examining the Influence of Anion Nucleophilicity on the Polymerisation Initiation Mechanism of Phenyl Glycidyl Ether
title_full Examining the Influence of Anion Nucleophilicity on the Polymerisation Initiation Mechanism of Phenyl Glycidyl Ether
title_fullStr Examining the Influence of Anion Nucleophilicity on the Polymerisation Initiation Mechanism of Phenyl Glycidyl Ether
title_full_unstemmed Examining the Influence of Anion Nucleophilicity on the Polymerisation Initiation Mechanism of Phenyl Glycidyl Ether
title_short Examining the Influence of Anion Nucleophilicity on the Polymerisation Initiation Mechanism of Phenyl Glycidyl Ether
title_sort examining the influence of anion nucleophilicity on the polymerisation initiation mechanism of phenyl glycidyl ether
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6523680/
https://www.ncbi.nlm.nih.gov/pubmed/30974878
http://dx.doi.org/10.3390/polym11040657
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