Thermosensitive Ionic Microgels via Surfactant-Free Emulsion Copolymerization and in Situ Quaternization Cross-Linking

A type of thermosensitive ionic microgel was successfully prepared via the simultaneous quaternized cross-linking reaction during the surfactant-free emulsion copolymerization of N-isopropylacrylamide (NIPAm) as the main monomer and 1-vinylimidazole or 4-vinylpyridine as the comonomer. 1,4-Dibromobutane and 1,6-dibromohexane were used as the halogenated compounds to quaternize the tertiary amine in the comonomer, leading to the formation of a cross-linking network and thermosensitive ionic microgels. The sizes, morphologies, and properties of the obtained ionic microgels were systematically investigated by using transmission electron microscopy (TEM), dynamic and static light scattering (DLS and SLS), electrophoretic light scattering (ELS), thermogravimetric analyses (TGA), and UV-visible spectroscopy. The obtained ionic microgels were spherical in shape with narrow size distribution. These ionic microgels exhibited thermosensitive behavior and a unique feature of poly(ionic liquid) in aqueous solutions, of which the counteranions of the microgels could be changed by anion exchange reaction with BF4K or lithium trifluoromethyl sulfonate (PFM-Li). After the anion exchange reaction, the ionic microgels were stable in aqueous solution and could be well dispersed in the solvents with different polarities, depending on the type of counteranion. The sizes and thermosensitive behavior of the ionic microgels could be well tuned by controlling the quaternization extent, the type of comonomer, halogenated compounds, and counteranions. The ionic microgels showed superior swelling properties in aqueous solution. Furthermore, these ionic rnicrogels also showed capabilities to encapsulate and release the anionic dyes, like methyl orange, in aqueous solutions.