Effect of the degree of crosslinking on penetrant transport in polystyrene

The effect of the degree of crosslinking of glassy polymers on the transport mechanism of penetrants was investigated using a series of divinyl benzene (DVB)-crosslinked polystyrenes of nominal crosslinking ratio X from 0.001 38 to 0.060 mol DVB/mol styrene. The number average molecular weight between crosslinks, $\text{M}\text{?}{}_{\mathrm{<mtext>c</mtext>}}$, was determined from equilibrium swelling experiments in cyclohexane. Dynamic swelling experiments with cyclohexane at 30°C showed that the mechanism of penetrant transport was anomalous. An overshoot in the penetrant uptake was observed, characteristic of macromolecular relaxations and of changing solubility of the cyclohexane in the continuously swelling polystyrene. Photographs of various samples during the swelling process showed that solvent crazing occurred predominantly in loosely crosslinked samples.