Thermoresponsive Microgel-Based Free-Standing Membranes: Influence of Different Microgel Cross-Linkers on Membrane Function.

In this study we show a possibility to produce thermoresponsive, free-standing microgel membranes based on N -isopropylacrylamide (NIPAM) and the UV-sensitive comonomer 2-hydroxy-4-(methacryloyloxy)benzophenone (HMABP). To influence the final network structure and functionality of the membranes, we use different cross-linkers in the microgel syntheses and characterize the resulting structural microgel properties and the swelling behavior by means of AFM, FTIR, and PCS measurements. Varying the cross-linker results in significant changes in the structure and swelling behavior of the individual microgels and has an influence on the incorporation of the comonomer, which is essential for subsequent photochemical membrane formation. We investigate the ion transport through the different membranes by temperature-dependent resistance measurements revealing a sharp increase in resistance when the copolymer microgels reach their collapsed state. The resistance of the membranes can be adjusted by different cross-linkers and the associated incorporation of the comonomer. Furthermore, we show that transferring a reversible cross-linker from a cross-linked state to an un-cross-linked state strongly influences the membrane properties and even reverses the switching behavior, while the mechanical stability of the membrane is maintained.