Mitigating of Thin-Film Composite PTMSP Membrane Aging by Introduction of Porous Rigid and Soft Branched Polymeric Additives

This work was focused on the mitigation of physical aging in thin-film composite (TFC) membranes (selective layer ~1 μm) based on polymer intrinsic microporosity (PTMSP) by the introduction of both soft, branched polyethyleneimine (PEI), and rigid, porous aromatic framework PAF-11, polymer additives. Self-standing mixed-matrix membranes of thicknesses in the range of 20-30 μm were also prepared with the same polymer and fillers. Based on 450 days of monitoring, it was observed that the neat PTMSP composite membrane underwent a severe decline of its gas transport properties, and the resultant CO₂ permeance was 14% (5.2 m³ (STP)/(m²·h·bar)) from the initial value measured for the freshly cast sample (75 m³ (STP)/(m²·h·bar)). The introduction of branched polyethyleneimine followed by its cross-linking allowed to us to improve the TFC performance maintaining CO₂ permeance at the level of 30% comparing with day zero. However, the best results were achieved by the combination of porous, rigid and soft, branched polymeric additives that enabled us to preserve the transport characteristics of TFC membrane as 43% (47 m³ (STP)/(m²·h·bar) after 450 days) from its initial values (110 m³ (STP)/(m²·h·bar)). Experimental data were fitted using the Kohlrausch-Williams-Watts function, and the limiting (equilibrium) values of the CO₂ and N₂ permeances of the TFC membranes were estimated. The limit value of CO₂ permeance for neat PTMSP TFC membrane was found to be 5.2 m³ (STP)/(m²·h·bar), while the value of 34 m³(STP)/(m²·h·bar) or 12,600 GPU was achieved for TFC membrane containing 4 wt% cross-linked PEI, and 30 wt% PAF-11. Based on the N₂ adsorption isotherms data, it was calculated that the reduction of the free volume was 1.5-3 times higher in neat PTMSP compared to the modified one. Bearing in mind the pronounced mitigation of physical aging by the introduction of both types of fillers, the developed high-performance membranes have great potential as support for the coating of an ultrathin, selective layer for gas separation.