Polymers of intrinsic microporosity (PIMs) are a class
of promising
gas separation materials due to their high membrane permeabilities
and reasonable selectivities. When processed into thin film composite
(TFC) membranes, their high gas throughput aligns closely with industrial
requirements, but they are prone to physical aging and plasticization
effects. TFC membranes based on the prototypical PIM-1 and its carboxylated
derivative cPIM-1 exhibit temperature-dependent gas permeation behavior,
which has not been extensively studied before. In single CO
2
permeation tests, measurable physical aging occurred when the temperature
was raised to 55 °C within a period of 90 min, and the aging
rate accelerated as temperature was raised further. TFC membranes
prepared from cPIM-1 exhibited a faster aging rate compared to PIM-1
at the same temperature. The decreased permeance could be at least
partially recovered through a 5 day methanol vapor treatment. In mixed
gas experiments, all membranes showed decreased permselectivities
at elevated temperatures. The plasticization pressure of TFC membranes
occurred at around 1 bar of CO
2
partial pressure, independent
of temperature. Significant plasticization was particularly evident
for cPIM-1 TFC membranes under CO
2
/CH
4
conditions
with increasing temperature, which resulted in increased gas permeance
for both components.