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Keywords = triptycene diamine

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18 pages, 3174 KB  
Article
Gas Separation by Mixed Matrix Membranes with Porous Organic Polymer Inclusions within o-Hydroxypolyamides Containing m-Terphenyl Moieties
by Cenit Soto, Edwin S. Torres-Cuevas, Alfonso González-Ortega, Laura Palacio, Ángel E. Lozano, Benny D. Freeman, Pedro Prádanos and Antonio Hernández
Polymers 2021, 13(6), 931; https://doi.org/10.3390/polym13060931 - 18 Mar 2021
Cited by 15 | Viewed by 4635
Abstract
A hydroxypolyamide (HPA) manufactured from 2,2-bis(3-amino-4-hydroxy phenyl)-hexafluoropropane (APAF) diamine and 5′-terbutyl-m-terphenyl-4,4′′-dicarboxylic acid chloride (tBTpCl), and a copolyimide produced by stochiometric copolymerization of APAF and 4,4′-(hexafluoroisopropylidene) diamine (6FpDA), using the same diacid chloride, were obtained and used as polymeric matrixes in mixed [...] Read more.
A hydroxypolyamide (HPA) manufactured from 2,2-bis(3-amino-4-hydroxy phenyl)-hexafluoropropane (APAF) diamine and 5′-terbutyl-m-terphenyl-4,4′′-dicarboxylic acid chloride (tBTpCl), and a copolyimide produced by stochiometric copolymerization of APAF and 4,4′-(hexafluoroisopropylidene) diamine (6FpDA), using the same diacid chloride, were obtained and used as polymeric matrixes in mixed matrix membranes (MMMs) loaded with 20% (w/w) of two porous polymer networks (triptycene-isatin, PPN-1, and triptycene-trifluoroacetophenone, PPN-2). These MMMs, and also the thermally rearranged membranes (TR-MMMs) that underwent a thermal treatment process to convert the o-hydroxypolyamide moieties to polybenzoxazole ones, were characterized, and their gas separation properties evaluated for H2, N2, O2, CH4, and CO2. Both TR process and the addition of PPN increased permeability with minor decreases in selectivity for all gases tested. Excellent results were obtained, in terms of the permeability versus selectivity compromise, for H2/CH4 and H2/N2 separations with membranes approaching the 2008 Robeson’s trade-off line. The best gas separation properties were obtained when PPN-2 was used. Finally, gas permeation was characterized in terms of chain intersegmental distance and fraction of free volume of the membrane along with the kinetic diameters of the permeated gases. The intersegmental distance increased after TR and/or the addition of PPN-2. Permeability followed an exponential dependence with free volume and a quadratic function of the kinetic diameter of the gas. Full article
(This article belongs to the Special Issue State-of-the-Art Polymer Science and Technology in Spain (2020,2021))
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18 pages, 6667 KB  
Article
Synthesis and Gas-Permeation Characterization of a Novel High-Surface Area Polyamide Derived from 1,3,6,8-Tetramethyl-2,7-diaminotriptycene: Towards Polyamides of Intrinsic Microporosity (PIM-PAs)
by Giuseppe Genduso, Bader S. Ghanem, Yingge Wang and Ingo Pinnau
Polymers 2019, 11(2), 361; https://doi.org/10.3390/polym11020361 - 19 Feb 2019
Cited by 23 | Viewed by 7062
Abstract
A triptycene-based diamine, 1,3,6,8-tetramethyl-2,7-diamino-triptycene (TMDAT), was used for the synthesis of a novel solution-processable polyamide obtained via polycondensation reaction with 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) (6FBBA). Molecular simulations confirmed that the tetrasubstitution with ortho-methyl groups in the triptycene building block reduced rotations around the C–N [...] Read more.
A triptycene-based diamine, 1,3,6,8-tetramethyl-2,7-diamino-triptycene (TMDAT), was used for the synthesis of a novel solution-processable polyamide obtained via polycondensation reaction with 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) (6FBBA). Molecular simulations confirmed that the tetrasubstitution with ortho-methyl groups in the triptycene building block reduced rotations around the C–N bond of the amide group leading to enhanced fractional free volume. Based on N2 sorption at 77 K, 6FBBA-TMDAT revealed microporosity with a Brunauer–Emmett–Teller (BET) surface area of 396 m2 g−1; to date, this is the highest value reported for a linear polyamide. The aged 6FBBA-TMDAT sample showed moderate pure-gas permeabilities (e.g., 198 barrer for H2, ~109 for CO2, and ~25 for O2) and permselectivities (e.g., αH2/CH4 of ~50) that position this polyamide close to the 2008 H2/CH4 and H2/N2 upper bounds. CO2–CH4 mixed-gas permeability experiments at 35 °C demonstrated poor plasticization resistance; mixed-gas permselectivity negatively deviated from the pure-gas values likely, due to the enhancement of CH4 diffusion induced by mixing effects. Full article
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