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Insight into the Intermolecular Interaction and Free Radical Polymerizability of Methacrylates in Supercritical Carbon Dioxide
High pressure in situ Fourier transfer infrared/near infrared technology (HP FTIR/NIR) along with theoretical calculation of density functional theory (DFT) method was employed. The solvation behaviors and the free radical homopolymerization of methyl methacrylate (MMA), methacrylate acid (MAA), tri...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7023658/ https://www.ncbi.nlm.nih.gov/pubmed/31906565 http://dx.doi.org/10.3390/polym12010078 |
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author | Li, Rui-Qing Wang, Ming-Xi Zhang, Qi-Yu Chen, Jian-Gang Wang, Kuan Zhang, Xiao-Yong Shen, Shukun Liu, Zhao-Tie Liu, Zhong-Wen Jiang, Jinqiang |
author_facet | Li, Rui-Qing Wang, Ming-Xi Zhang, Qi-Yu Chen, Jian-Gang Wang, Kuan Zhang, Xiao-Yong Shen, Shukun Liu, Zhao-Tie Liu, Zhong-Wen Jiang, Jinqiang |
author_sort | Li, Rui-Qing |
collection | PubMed |
description | High pressure in situ Fourier transfer infrared/near infrared technology (HP FTIR/NIR) along with theoretical calculation of density functional theory (DFT) method was employed. The solvation behaviors and the free radical homopolymerization of methyl methacrylate (MMA), methacrylate acid (MAA), trifluoromethyl methacrylate (MTFMA) and trifluoromethyl methacrylate acid (TFMAA) in scCO(2) were systematically investigated. Interestingly, the previously proposed mechanism of intermolecular-interaction dynamically-induced solvation effect (IDISE) of monomer in scCO(2) is expected to be well verified/corroborated in view that the predicted solubility order of the monomers in scCO(2) via DFT calculation is ideally consistent with that observed via HP FTIR/NIR. It is shown that MMA and MAA can be easily polymerized, while the free radical polymerizability of MTFMA is considerably poor and TFMAA cannot be polymerized via the free radical initiators. The α trifluoromethyl group (–CF(3)) may effectively enhance the intermolecular hydrogen bonding and restrain the diffusion of the monomer in scCO(2). More importantly, the strong electron-withdrawing inductive effect of –CF(3) to C=C may distinctly decrease the atomic charge of the carbon atom in the methylene (=CH(2)). These two factors are believed to be predominantly responsible for the significant decline of the free radical polymerizability of MTFMA and the other alkyl 2-trifluoromethacrylates in scCO(2). |
format | Online Article Text |
id | pubmed-7023658 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-70236582020-03-11 Insight into the Intermolecular Interaction and Free Radical Polymerizability of Methacrylates in Supercritical Carbon Dioxide Li, Rui-Qing Wang, Ming-Xi Zhang, Qi-Yu Chen, Jian-Gang Wang, Kuan Zhang, Xiao-Yong Shen, Shukun Liu, Zhao-Tie Liu, Zhong-Wen Jiang, Jinqiang Polymers (Basel) Article High pressure in situ Fourier transfer infrared/near infrared technology (HP FTIR/NIR) along with theoretical calculation of density functional theory (DFT) method was employed. The solvation behaviors and the free radical homopolymerization of methyl methacrylate (MMA), methacrylate acid (MAA), trifluoromethyl methacrylate (MTFMA) and trifluoromethyl methacrylate acid (TFMAA) in scCO(2) were systematically investigated. Interestingly, the previously proposed mechanism of intermolecular-interaction dynamically-induced solvation effect (IDISE) of monomer in scCO(2) is expected to be well verified/corroborated in view that the predicted solubility order of the monomers in scCO(2) via DFT calculation is ideally consistent with that observed via HP FTIR/NIR. It is shown that MMA and MAA can be easily polymerized, while the free radical polymerizability of MTFMA is considerably poor and TFMAA cannot be polymerized via the free radical initiators. The α trifluoromethyl group (–CF(3)) may effectively enhance the intermolecular hydrogen bonding and restrain the diffusion of the monomer in scCO(2). More importantly, the strong electron-withdrawing inductive effect of –CF(3) to C=C may distinctly decrease the atomic charge of the carbon atom in the methylene (=CH(2)). These two factors are believed to be predominantly responsible for the significant decline of the free radical polymerizability of MTFMA and the other alkyl 2-trifluoromethacrylates in scCO(2). MDPI 2020-01-02 /pmc/articles/PMC7023658/ /pubmed/31906565 http://dx.doi.org/10.3390/polym12010078 Text en © 2020 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 Li, Rui-Qing Wang, Ming-Xi Zhang, Qi-Yu Chen, Jian-Gang Wang, Kuan Zhang, Xiao-Yong Shen, Shukun Liu, Zhao-Tie Liu, Zhong-Wen Jiang, Jinqiang Insight into the Intermolecular Interaction and Free Radical Polymerizability of Methacrylates in Supercritical Carbon Dioxide |
title | Insight into the Intermolecular Interaction and Free Radical Polymerizability of Methacrylates in Supercritical Carbon Dioxide |
title_full | Insight into the Intermolecular Interaction and Free Radical Polymerizability of Methacrylates in Supercritical Carbon Dioxide |
title_fullStr | Insight into the Intermolecular Interaction and Free Radical Polymerizability of Methacrylates in Supercritical Carbon Dioxide |
title_full_unstemmed | Insight into the Intermolecular Interaction and Free Radical Polymerizability of Methacrylates in Supercritical Carbon Dioxide |
title_short | Insight into the Intermolecular Interaction and Free Radical Polymerizability of Methacrylates in Supercritical Carbon Dioxide |
title_sort | insight into the intermolecular interaction and free radical polymerizability of methacrylates in supercritical carbon dioxide |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7023658/ https://www.ncbi.nlm.nih.gov/pubmed/31906565 http://dx.doi.org/10.3390/polym12010078 |
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