One-Step Formation of Double Emulsions Stabilized by PNIPAM-based Microgels: The Role of Co-monomer
Tong Zhang, To Ngai
Abstract
Microgels have been widely used as particulate emulsifiers to stabilize emulsions due to their multiresponsiveness and deformability. Generally, microgels stabilize oil-in-water (o/w) emulsions, whereas occasionally water-in-oil (w/o) emulsions are reported using oils like n-octanol in which microgels can swell. However, the use of microgels to stabilize double emulsions (DEs) remains scarce. In this work, we report a special poly(N-isopropylacrylamide)- (PNIPAM-) based microgel to obtain water-in-oil-in-water (w/o/w) DEs in one step with the introduction of 1-vinylimidazole (VIM) as comonomer and hydroxy silicone oil as the oily phase. By comparison, when methacrylic acid (MAA) is used, an o/w emulsion will be obtained. The same holds true even when we freeze-dry and redisperse the microgels in the oil. Compared with PNIPAM-co-MAA microgel, PNIPAM-co-VIM microgel achieves a lower interfacial tension (IFT) when dispersed in the aqueous phase. This interfacial affinity of PNIPAM-co-VIM is believed to result from acid–base interaction between VIM and hydroxyl groups of the silicone oil, the same interaction used for preparing silica–vinyl polymer composite particles. Increasing the particle concentrations from 0.05% to 0.9% (w/v), we observe the inversion from w/o to o/w/o and w/o/w emulsions. When the oil fraction is changed from 0.1 to 0.9, the emulsion morphology evolves from o/w and w/o/w to w/o emulsions. At last, we examine the emulsifying ability of PNIPAM-co-VIM microgel with other oils and find that w/o/w emulsions are obtained with edible oils as well. Considering the similarity between microgels and biopolymers, the discovery in this work will help in designing food-grade emulsifiers to form edible DEs.