Polymer solubility in ionic liquids: dominated by hydrogen bonding

Polymer solubility in ionic liquids (ILs) cannot be predicted by the solubility parameter approach based on the "like dissolves like" principle. According to the Kamlet-Abraham-Taft (KAT) multi-parameter polarity scale, ILs can be categorized on the basis of hydrogen-bond acidity or basicity ones. The experimental observations, that acidic ILs easily dissolve basic polymers and basic ILs dissolve acidic polymers, reflect the complementary nature of hydrogen-bonding interactions. A quantitative hydrogen-bonding analysis is proposed for predicting the solubility by taking the product of Δ α Δ β as an indicator of the competition between cross-association and self-association hydrogen bonding (H-bonding), where Δ α is the difference of acidity parameters between the polymer and IL, and Δ β is the difference of basicity. This solubility criterion has been validated by the solubility data of 19 polymers (11 acidic and 8 basic) in 11 ILs (7 acidic and 4 basic). These principles based on KAT parameters can be applied to other systems dominated by hydrogen bonding. The product of H-bond acidity ( α ) and basicity parameter ( β ) reflects the complementary nature of the H-bonding interactions. Strong cross-association and weak self-association favor the solubility of polymer in ILs, therefore the product of Δ α Δ β < 0.