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Insight into the Intermolecular Interaction and Free Radical Polymerizability of Methacrylates in Supercritical Carbon Dioxide

1
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education and School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China
2
College of Chemistry and Chemical Engineering, Shaanxi University of Science & Technology, Xi’an 710021, China
3
School of Materials Science & Engineering, Shaanxi Normal University, Xi’an 710119, China
*
Authors to whom correspondence should be addressed.
These authors contributed equally to this work.
Polymers 2020, 12(1), 78; https://doi.org/10.3390/polym12010078
Received: 2 December 2019 / Revised: 14 December 2019 / Accepted: 16 December 2019 / Published: 2 January 2020
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 scCO2 were systematically investigated. Interestingly, the previously proposed mechanism of intermolecular-interaction dynamically-induced solvation effect (IDISE) of monomer in scCO2 is expected to be well verified/corroborated in view that the predicted solubility order of the monomers in scCO2 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 (–CF3) may effectively enhance the intermolecular hydrogen bonding and restrain the diffusion of the monomer in scCO2. More importantly, the strong electron-withdrawing inductive effect of –CF3 to C=C may distinctly decrease the atomic charge of the carbon atom in the methylene (=CH2). 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 scCO2. View Full-Text
Keywords: intermolecular interaction; free radical polymerization; methacrylate monomer; supercritical carbon dioxide (scCO2); theoretical calculation intermolecular interaction; free radical polymerization; methacrylate monomer; supercritical carbon dioxide (scCO2); theoretical calculation
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MDPI and ACS Style

Li, R.-Q.; Wang, M.-X.; Zhang, Q.-Y.; Chen, J.-G.; Wang, K.; Zhang, X.-Y.; Shen, S.; Liu, Z.-T.; Liu, Z.-W.; Jiang, J. Insight into the Intermolecular Interaction and Free Radical Polymerizability of Methacrylates in Supercritical Carbon Dioxide. Polymers 2020, 12, 78.

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