The effect of polymer chain ordering on the transport properties of the polymer membrane was examined for the semi-crystalline heterocyclic polyetherimide (PEI) BPDA-P3 based on 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and diamine 1,4-bis [4-(4-aminophenoxy)phenoxy]benzene (P3). All-atom Molecular Dynamics (MD) simulations were used to investigate the gas diffusion process carried through the pores of a free volume several nanometers in size. The long-term (~30 μs) MD simulations of BPDA-P3 were performed at T = 600 K, close to the experimental value of the melting temperature (Tm ≈ 577 K). It was found during the simulations that the transition of the PEI from an amorphous state to an ordered one occurred. We determined a decrease in solubility for both the gases examined (CO2 and CH4), caused by the redistribution of free volume elements occurring during the structural ordering of the polymer chains in glassy state (Tg ≈ 481 K). By analyzing the diffusion coefficients in the ordered state, the presence of gas diffusion anisotropy was found. However, the averaged values of the diffusion coefficients did not differ from each other in the amorphous and ordered states. Thus, permeability in the observed system is primarily determined by gas solubility, rather than by gas diffusion.
Keywords: gas separation; membranes; molecular dynamic; polyimide; simulations; structure ordering.