Emulsion Stabilized by Biocompatible and Stimuli-Responsive Poly(N‑vinylcaprolactam)-Based Microgels: Effects of Electrostatic Repulsion and Deformability on Emulsion Stability

Microgels have been widely used for stabilizing emulsions due to their softness and stimulus responsiveness. Although ultrastable emulsions have been prepared by microgel nanoparticles, the role of electrostatic interactions on emulsion stability is still a controversial topic and further investigation of the effect of microgel deformability is required. In the present study, neutral poly­(N-vinylcaprolactam) (PVCL) and charged poly­(N-vinylcaprolactam)-co-methacrylic acid (P­(VCL-co-MAA)) microgels were synthesized and further used as emulsifiers to stabilizing emulsion. The P­(VCL-co-MAA) microgel has a swelling ratio larger than that of the PVCL microgel in water. The nanomechanical properties of the microgels in water were characterized by atomic force microscopy with using the tip of different radii. The result reveals that the P­(VCL-co-MAA) microgel is more deformable than the PVCL counterpart. Stability tests of the emulsions showed that below the volume phase transition temperature (VPTT) of the microgels, both microgel types can stabilize the emulsions under various conditions. Unexpectedly, most of the emulsions still remain stable above the VPTT. Further increasing the temperature to 60 °C, P­(VCL-co-MAA) microgel emulsions remained stable at a pH value above the pK a of MAA while the emulsion was unstable below the pK a. However, phase separation occurs in PVCL microgel-stabilized emulsions at 60 °C. These results demonstrate that electrostatic repulsion and deformability of the microgels can enhance the emulsion stability, providing insights into the rational design and preparation of ultrastable Pickering emulsions.