Nonequilibrium Lattice Fluid Modeling of Gas Solubility in HAB-6FDA Polyimide and Its Thermally Rearranged Analogues
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Galizia et al_Modeling TR polymers_revised manuscript.pdf
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Author(s)
Galizia, Michele
Stevens, Kevin A.
Paul, Donald R.
Freeman, Benny D.
Smith, Zachary P
Date Issued
November 2016
Journal
Macromolecules
Publisher
American Chemical Society (ACS)
Citation
Galizia, Michele et al. “Nonequilibrium Lattice Fluid Modeling of Gas Solubility in HAB-6FDA Polyimide and Its Thermally Rearranged Analogues.” Macromolecules 49, 22 (November 2016): 8768–8779 © 2016 American Chemical Society
Version
Original manuscript
Abstract
For the first time, a theoretical analysis of gas sorption, based on the nonequilibrium lattice fluid (NELF) model, in chemically imidized HAB-6FDA polyimide and its thermally rearranged analogues is presented. Because of the inaccessibility of pVT data in the rubbery region, the characteristic lattice fluid parameters of the polymers considered in this study were obtained from a collection of infinite dilution solubility data at multiple temperatures. Hydrogen, nitrogen, and methane sorption isotherms at 35 °C were fit to the NELF model using one adjustable parameter, i.e., the polymer–penetrant binary interaction parameter, k₁₂. The optimal value of k₁₂ for each polymer–penetrant pair was used to predict hydrogen, nitrogen, and methane sorption isotherms at other temperatures and at pressures up to 6 MPa. For carbon dioxide, a second adjustable parameter, the swelling coefficient, was introduced to account for sorption-induced matrix dilation. The ideal solubility–selectivity is also predicted for several gas pairs. The increase in gas sorption in thermally rearranged samples relative to their polyimide precursor is essentially due to entropic effects, i.e., to the increase in nonequilibrium fractional free volume during thermal rearrangement.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
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DOI of Published Version
https://doi.org/10.1021/acs.macromol.6b01479
