The gas permeation behavior of poly(dialkylfumarate)s (PDAF)s with various bulky ester side chains has been studied. The thermal molecular motion and intermolecular distances depended on the bulkiness of ester side groups. The permeation behavior was strongly influenced by thermal molecular motion and density of PDAFs. The magnitude of permeability for O2, N2, and CO is in the order of 10−10-10−9cm3(STP)·cm cm−1s−1cmHg−1at 298 K. The magnitude of separation factor of O2 to CO was above 10 at 298 K and remained high below the β-relaxation temperature.
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