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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...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2019
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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. |
format | Online Article Text |
id | pubmed-6523680 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
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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