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Article

Solute Diffusion into Polymer Swollen by Supercritical CO2 by High-Pressure Electron Paramagnetic Resonance Spectroscopy and Chromatography

1
Faculty of Chemistry, Lomonosov Moscow State University, Leninskiye Gory, 1-3, 119991 Moscow, Russia
2
Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, Russia
3
Institute of Physical Chemistry, RWTH Aachen University, 52056 Aachen, Germany
4
Federal Scientific Research Centre “Crystallography and Photonics” RAS, Institute of Photon Technologies, Pionerskaya Str. 2, Troitsk, 108840 Moscow, Russia
*
Author to whom correspondence should be addressed.
Academic Editor: Boqi Xiao
Polymers 2021, 13(18), 3059; https://doi.org/10.3390/polym13183059
Received: 5 August 2021 / Revised: 31 August 2021 / Accepted: 6 September 2021 / Published: 10 September 2021
(This article belongs to the Special Issue Heat and Mass Transfer in Porous Polymers)
High-pressure electron paramagnetic resonance (EPR) was used to measure translational diffusion coefficients (Dtr) of a TEMPONE spin probe in poly(D,L-lactide) (PDLLA) and swollen in supercritical CO2. Dtr was measured on two scales: macroscopic scale (>1 μm), by measuring spin probe uptake by the sample; and microscopic scale (<10 nm), by using concentration-dependent spectrum broadening. Both methods yield similar translational diffusion coefficients (in the range 5–10 × 10−12 m2/s at 40–60 °C and 8–10 MPa). Swollen PDLLA was found to be homogeneous on the nanometer scale, although the TEMPONE spin probe in the polymer exhibited higher rotational mobility (τcorr = 6 × 10−11 s) than expected, based on its Dtr. To measure distribution coefficients of the solute between the swollen polymer and the supercritical medium, supercritical chromatography with sampling directly from the high-pressure vessel was used. A distinct difference between powder and bulk polymer samples was only observed at the start of the impregnation process. View Full-Text
Keywords: poly(D,L-lactide); supercritical fluid; carbon dioxide; diffusion; electron paramagnetic resonance poly(D,L-lactide); supercritical fluid; carbon dioxide; diffusion; electron paramagnetic resonance
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MDPI and ACS Style

Gromov, O.I.; Kostenko, M.O.; Petrunin, A.V.; Popova, A.A.; Parenago, O.O.; Minaev, N.V.; Golubeva, E.N.; Melnikov, M.Y. Solute Diffusion into Polymer Swollen by Supercritical CO2 by High-Pressure Electron Paramagnetic Resonance Spectroscopy and Chromatography. Polymers 2021, 13, 3059. https://doi.org/10.3390/polym13183059

AMA Style

Gromov OI, Kostenko MO, Petrunin AV, Popova AA, Parenago OO, Minaev NV, Golubeva EN, Melnikov MY. Solute Diffusion into Polymer Swollen by Supercritical CO2 by High-Pressure Electron Paramagnetic Resonance Spectroscopy and Chromatography. Polymers. 2021; 13(18):3059. https://doi.org/10.3390/polym13183059

Chicago/Turabian Style

Gromov, Oleg I., Mikhail O. Kostenko, Alexander V. Petrunin, Anastasia A. Popova, Olga O. Parenago, Nikita V. Minaev, Elena N. Golubeva, and Mikhail Y. Melnikov. 2021. "Solute Diffusion into Polymer Swollen by Supercritical CO2 by High-Pressure Electron Paramagnetic Resonance Spectroscopy and Chromatography" Polymers 13, no. 18: 3059. https://doi.org/10.3390/polym13183059

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