Copoly(o-hydroxyamide)s (HPA) and copoly(o-hydroxyamide-amide)s (PAA) have been synthesized to be used as continuous phases in mixed matrix membranes (MMMs). These polymeric matrices were blended with different loads (15 and 30 wt.%) of a relatively highly microporous porous polymer network (PPN). SEM images of the manufactured MMMs exhibited good compatibility between the two phases for all the membranes studied, and their mechanical properties have been shown to be good enough even after thermal treatment. The WAX results show that the addition of PPN as a filler up to 30% does not substantially change the intersegmental distance and the polymer packing. It seems that, for all the membranes studied, the free volume that determines gas transport is in the high end of the possible range. This means that gas flow occurs mainly between the microvoids in the polymer matrix around the filler. In general, both HPA- and PAA-based MMMs exhibited a notable improvement in gas permeability, due to the presence of PPN, for all gases tested, with an almost constant selectivity. In summary, although the thermal stability of the PAA is limited by the thermal stability of the polyamide side chain, their mechanical properties were better. The permeability was higher for the PAA membranes before their thermal rearrangement, and these values increased after the addition of moderate amounts of PPN.
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