Smart Copolymer Microgels with High Volume Phase Transition Temperatures: Composition, Swelling, and Morphology

The thermosensitivity and microstructure of microgels made by copolymerizing standard microgel-forming monomers with more hydrophilic comonomers are investigated, with the aim of increasing the volume phase transition temperature (VPTT). We precisely determine the incorporation of N-(hydroxymethyl)acrylamide (HMAM) and purpose-synthesized N-(2-hydroxyisopropyl)acrylamide (HIPAM) into microgels, neither of which forms microgels on its own by precipitation polymerization. The swelling properties and microstructure of the resulting copolymer microgels with N-isopropylacrylamide (NIPAM, LCST of ∼32 °C) and N-isopropylmethacrylamide (NIPMAM, LCST of ∼44 °C) are then characterized via turbidimetry, DLS, and AFM. At low comonomer contents, all microgel particles exhibit moderate growth. Beyond a system-specific threshold, we observe a significant increase in size and smoother swelling behavior. For NIPAM-HIPAM, the size increase is linked to a strong increase in swelling capacity and the formation of a thick corona. The effect of the hydrophilic comonomers on the VPTT correlates linearly with their true composition, allowing us to extrapolate the VPTT of hypothetical pure HMAM and HIPAM microgels. This leads to values of 99 °C for HMAM and 68 °C for HIPAM for the respective VPTT. These numbers can be seen as useful indicators of the effect of these monomers on the VPTT in the copolymerized microgels. The observed changes in VPTT, swelling, size, and morphology suggest that high-VPTT microgels possess unique internal molecular composition gradients, likely due to hydrophobic interactions during synthesis. Our results have potential implications for developing temperature-sensitive microgel-based membranes that can self-adapt their permeability at higher operating temperatures in energy applications.