Self-Assembly of a Thermally Responsive Double-Hydrophilic Copolymer in Ethanol-Water Mixtures: The Effect of Preferential Adsorption and Co-Nonsolvency.

Lower alcohols can induce a combined collapse-swelling de-mixing transition (lower critical solution temperature (LCST)-type co-nonsolvency) in aqueous solutions of poly( N-isopropylacrylamide) (PNIPAM) by interacting with the polymer's amide groups. This interaction results in an increase of the total surface area of hydrophobic sites and destabilizes the chains. Here, we make use of this phenomenon to drive the counterintuitive self-assembly of a PNIPAM-containing double-hydrophilic graft copolymer in water-ethanol mixtures at T ≪ LCST.