Molecular Dynamics Simulation Study of Organic Solvents Confined in PIM-1 and P84 Polyimide Membranes

Organic solvent nanofiltration (OSN) has recently proved to be a promising separation process thanks to the development of membrane materials with suitable resistance toward organic solvents. Among those materials, P84 polyimide membranes are currently the most used in OSN while PIM-1 membranes have recently attracted attention due to their high permeance in apolar solvents and alcohols. Both P84 and PIM-1 membranes have nanosized free volumes, and their separation performance is finely connected to polymer/solvent interactions. Consequently, modeling OSN membranes at the molecular scale is highly desirable in order to rationalize experimental observations and gain a deeper insight into the molecular mechanisms ruling solvent and solute permeation. A prerequisite for understanding solvent transport through OSN membranes is therefore to characterize the membrane/solvent interactions at the molecular level. For that purpose, we carried out molecular simulations of three different solvents, acetone, methanol, and toluene in contact with P84 and PIM-1 membranes. The solvent uptake by both membranes was found to be correlated to the degree of confinement of the solvent, the polymer swelling ability and polymer/solvent interactions. The translational dynamics of the solvent molecules in the PIM-1 membrane was found to be correlated with the solvent viscosity due to the relatively large pores of this membrane. That was not the case with the P84 membrane, which has a much denser structure than the PIM-1 membrane and for which it was observed that the translational dynamics of the confined solvent molecules was directly correlated to the affinity between the P84 polymer and the solvent.

Automated summary

Organic solvent nanofiltration (OSN) is a promising separation process, and P84 polyimide membranes and PIM-1 membranes are commonly used in OSN due to their suitable resistance toward organic solvents. In order to understand the molecular mechanisms of solvent and solute permeation, molecular simulations were conducted on acetone, methanol, and toluene in contact with P84 and PIM-1 membranes. It was found that the solvent uptake by the membranes was influenced by solvent confinement, polymer swelling ability, and polymer/solvent interactions.