Confined Space Enables Spontaneous Liquid Separation by Molecular Size: Selective Absorption of Alkanes into a Polyolefin Cast Film

The depletion force has been used to explain phase separation phenomena in colloidal systems. Here, we showed that depletion force can explain not only phase separation of large and small colloidal particles but also preferential absorption of larger molecules from a mixture of large and small molecules in a liquid state. When a polyolefin cast film was immersed in a mixture of long and short normal alkanes, the longer molecules were selectively absorbed into the film. This experimental result was explained from the viewpoint of depletion force. The main finding was the use of confined space to emphasize the separation tendency caused by the force. In general, the increase in entropy may serve as a driving force to mix molecules. However, if sufficiently narrow pores are present, large and small molecules are separated naturally by size as the entropy increases. This finding will lead to size exclusion chromatography of low-mass molecules, similar to gel permeation chromatography of macromolecules. In order to demonstrate the effect of depletion force, we selected and experimented with a system based on a polyolefin isotactic poly­(4-methyl-1-pentene) (P4MP1) film and a normal alkane mixture and realized high molecular selectivity. The P4MP1 film we used can be prepared simply by evaporating the solvent from the solution and casting the film. On the basis of the Asakura–Oosawa theory, we concluded that spontaneous and high molecular selectivity is attributed to the depletion force provided by the small sub-nanopores with uniform size in the film.