Hydration and swelling: a theoretical investigation on the cooperativity effect of H-bonding interactions between p-hydroxy hydroxymethyl calix[4]/[5]arene and H2O by many-body interaction and density functional reactivity theory.

In order to explore the nature of the hydration and swelling of superabsorbent resin, a theoretical investigation into the cooperativity effect of the H-bonding interactions in the hydrates of four model compounds that can be regarded as the units of hydroquinone formaldehyde resin (HFR) (i.e., O-hydroxymethyl-1,4-dihydroxybenzene, methylene di-O-hydroxymethyl-1,4-dihydroxybenzene, p-hydroxy hydroxymethyl calix[4]arene and p-hydroxy hydroxymethyl calix[5]arene) was carried out by many-body interaction and density functional reactivity theory. The HFR···H2O···H2O complexes, in which the H2O···H2O moieties are bound with both the hydroxyl groups of HFR, are the most stable. For the HFR(H2O)n clusters, the interaction energy per building block is increased as the number of the size n increases, indicating the cooperativity effect. Therefore, a deduction is given that the cooperativity effects of the H-bonding interactions play an important role in the process of the hydration and swelling of HFR, and the swelling behavior is mainly attributed to the cooperativity effects which arised from the interactions between the H2O molecules. The origin of the cooperativity effect was examined employing several information-theoretic quantities in the density functional reactivity theory. The degree of swelling of HFR was quantitated using a measure of volume. Graphical abstract.