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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...

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Autores principales: 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
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2020
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).
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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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