Anomalous swelling of a polystyrene matrix in organic solvents

Abstract

Swelling behavior of a commercial linear polystyrene, containing a small amount (<5% wt) of mineral oil, has been studied in three different classes of organic solvents (alkanes, alcohols and carboxylic acids) using both gravimetry and light microscopy. A comparison has been made with the results presented in earlier publications using a different linear polystyrene, without mineral oil. It is shown that the polystyrene containing mineral oil absorbs much higher amounts of solvent at lower temperatures then at higher temperatures. This anomalous behavior sharply contrasts with the polystyrene without mineral oil, which at lower temperatures absorbs much less solvent. Light microscopy of the diffusion layer reveals that in the polymer with mineral oil precipitation occurs during diffusion at low temperatures, but not at high temperatures. These results clearly show that the presence of small amounts of mineral oil (in quantities below the detection limit of FTIR) can cause significant changes in the sorption behavior of polymers. These results are interpreted by pre-existing nano-inhomogeneities, formed by the mineral oil, limited miscibility of oil in the polymer phase and high miscibility of solvent in the oil phase.