Abstract
A comprehensive investigation into the effect of molecular size of the substituent group of softwood modified with linear chain carboxylic acid anhydrides, namely acetic, propionic, butyric, valeric, hexanoic, upon the sorption of water vapour has been performed. The sorption isotherms for untreated and chemically modified wood were analysed using the Hailwood–Horrobin model. The experimental analysis of the sorption isotherms showed that esterification affects the total, polymolecular and monomolecular sorption. The effect of molecular size of the substituent group on site accessibility was addressed by comparing the effect on water vapour sorption produced by adducts with differences in molecular size. Similar levels of cell-wall bulking were produced at different levels of hydroxyl substitution. Analysis of the sorption isotherms at comparable weight percentage gain revealed that the five anhydrides used show similar effectiveness in both total, polymolecular and monomolecular sorption, despite the substantial difference in the proportion of hydroxyl groups reacted. It is concluded that the reduction in total, polymolecular and monomolecular sorption produced by the linear chain anhydrides is primarily determined by the volume of adduct deposited in the cell wall (bulking) rather than by the number of hydroxyl groups that have been substituted. The validity of the Hailwood–Horrobin model is questioned.
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