Mapping the Extra Solvent Power of Ionic Liquids for Monomers, Polymers, and Dry/Wet Globular Single-Chain Polymer Nanoparticles.

Ionic liquids (ILs) have shown advantages in organic synthesis and catalysis, energy storage and conversion, and a variety of pharmaceutical applications. Understanding the miscibility behavior of IL/monomer, IL/polymer, and IL/polymer nanoparticle mixtures is critical for the use of ILs as green solvents in polymerization processes as well as to rationalize recent observations concerning the superior solubility of some proteins in ILs when compared to standard solvents. In this work, the most relevant results obtained in terms of extended three-component Flory-Huggins theory concerning the extra solvent power (ESP) of ILs when compared to traditional nonionic solvents for monomeric solutes (Case I), linear polymers (Case II), dry (i.e., without IL inside) globular single-chain polymer nanoparticles (SCNPs) (Case III), and wet (i.e., with IL inside) globular SCNPs (Case IV) are presented. Moreover, useful ESP maps are drawn for the first time for IL mixtures corresponding to Cases I, II, III, and IV at a constant temperature and pressure. Finally, a potential pathway to improve the miscibility of nonionic polymers in ILs is proposed.