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The phenomenon of ionic liquid (IL) nanoconfinement within a copolymer/IL membrane reportedly enhances membrane selectivity, solubility, and transport in gas separations. Also, the copolymer/IL membrane morphology has been found to affect IL stability at high transmembrane pressures. In this work, a combined mesoscopic dynamics simulation and hybrid grand canonical Monte Carlo/molecular dynamics (GCMC-MD) simulations were carried out to investigate the morphologies, as well as CO2/CH4 gas diffusivities, solubilities, and selectivities of polystyrene-b-poly(ethylene oxide) (PS-b-PEO)/1-Ethyl-3-methylimidazolium thiocyanate ([EMIM][SCN]) and PS-b-PEO/1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf2N]) membranes. The latter simulations focused on nanoconfined ILs in the copolymer/IL phase boundaries at 2.5 and 5 nm confinement lengths. The investigated systems were four nanoconfined ILs, i.e., PS/[EMIM][SCN]/PEO (the IL forming a separate microphase, denoted IL-Micro), PS/[EMIM][Tf2N]/PEO, PS/[EMIM][SCN]-PEO/PS (the IL distributed in the PEO phase, denoted IL-PEO), and PS/[EMIM][Tf2N]-PEO/PS, and five control systems, i.e., PS/PEO/PS, bulk PS, bulk PEO, bulk [EMIM][SCN], and bulk [EMIM][Tf2N]. Based on the mesoscopic dynamics simulation results, the dominant membrane morphologies at IL loadings of <50 vol % were lamellar or cylindrical (favorable for both IL stability at high transmembrane pressures if the bedding planes are horizontal, i.e. at 90° to the nominal direction of the transmembrane pressure gradient) with the IL-PEO or IL-Micro phases. Also, there was an overall 50% match between the observed PS-b-PEO/[EMIM][SCN] and PS-b-PEO/[EMIM][Tf2N] membrane morphologies. Based on the MD simulation results, both CO2 and CH4 diffusivities were the smallest in the bulk PS (control) and highest in the PS/[EMIM][Tf2N]/PEO system (IL-Micro between the PS and PEO phases) at both confinement lengths. The CO2 diffusivities were, on average, larger when the confinement length increased to 5 nm. The GCMC-MD results indicated that the CO2 solubility in the IL-Micro phases was higher than in the corresponding bulk ILs at both confinement lengths, with the PS/[EMIM][Tf2N]/PEO system exhibiting the highest CO2 solubility, followed by the PS/[EMIM][SCN]/PEO system. Additionally, the permselectivities of the nanoconfined IL systems were, on average, 40–50% larger than those of the bulk systems, with the highest permselectivity observed for PS/[EMIM][Tf2N]/PEO at the confinement length of 5 nm. Overall, the IL nanoconfinement between the PS and PEO phases (IL-Micro) leads to significant improvements in the CO2/CH4 permselectivities, suggesting that strategies to create nanoconfined IL morphologies in the copolymer/IL membranes are very promising for optimizing the membrane gas separation performance. 

Abstract Reversible addition‐fragmentation chain transfer (RAFT) polymerization has proven itself as a powerful polymerization technique affording facile control of molecular weight, molecular weight distribution, architecture, and chain end groups ‐ while maintaining a high level of tolerance for solvent and monomer functional groups. RAFT is highly suited to water as a polymerization solvent, with aqueous RAFT now utilized for applications such as controlled synthesis of ultra‐high molecular weight polymers, polymerization induced self‐assembly, and biocompatible polymerizations, among others. Water as a solvent represents a non‐toxic, cheap, and environmentally friendly alternative to organic solvents traditionally utilized for polymerizations. This, coupled with the benefits of RAFT polymerization, makes for a powerful combination in polymer science. This perspective provides a historical account of the initial developments of aqueous RAFT polymerization at the University of Southern Mississippi from the McCormick Research Group, details practical considerations for conducting aqueous RAFT polymerizations, and highlights some of the recent advances aqueous RAFT polymerization can provide. Finally, some of the future opportunities that this versatile polymerization technique in an aqueous environment can offer are discussed, and it is anticipated that the aqueous RAFT polymerization field will continue to realize these, and other exciting opportunities into the future.