Effect of crosslinking structure on sorption of CO2 in photocrosslinked PVCA film

The sorption behavior of CO₂ gas in photocrosslinked poly(vinyl cinnamate) film was examined under atmospheric pressure. The sorption isotherm was well described by the Langmuir equation, suggesting that sorption of CO₂ is mainly governed by adsorption in the microvoids. The amount of sorbed CO₂ was significantly affected by the degree of crosslinking. The CO₂ sorption was enhanced at a lower degree of crosslinking but was decreased at a higher degree of crosslinking. The unexpected increase in the amount of adsorbed CO₂ correlated with the increase in the number of microvoids that occurred as a result of the crosslinking reaction. However, further crosslinking led to a decrease in the mean size of the microvoids. The smaller microvoids, in comparison to CO₂ molecules, did not act as adsorption sites, so that the amount of sorbed CO₂ decreased. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1744–1750, 2000