Poly(2-propyl-2-oxazoline)s in Aqueous Methanol: To Dissolve or not to Dissolve

At room temperature, poly(N-isopropylacrylamide) (PNIPAM) is soluble in water and methanol, but it is not soluble in certain water/methanol mixtures. This phenomenon, known as cononsolvency, has been explored in great detail experimentally and theoretically in an attempt to understand the complex interactions occurring in the ternary PNIPAM/water/co-nonsolvent system. Yet little is known about the effects of the polymer structure on cononsolvency. To address this point, we investigated the temperature-dependent solution properties in water, methanol, and mixtures of the two solvents of poly(2-cyclopropyl-2-oxazoline) (PcyPOx) and two structural isomers of PNIPAM (M _n ∼ 11 kg/mol): poly(2-isopropyl-2-oxazoline) (PiPOx) and poly(2-n-propyl-2-oxazoline) (PnPOx). The phase diagram of the ternary water/methanol/poly(2-propyl-2-oxazolines) (PPOx) systems, constructed based on cloud point (T _CP) measurements, revealed that PnPOx exhibits cononsolvency in water/methanol mixtures. In contrast, methanol acts as a cosolvent for PiPOx and PcyPOx in water. The enthalpy, ΔH, and temperature, T _max, of the coil-to-globule transition of the three polymers in various water/methanol mixtures were measured by high-sensitivity differential scanning calorimetry. T _max follows the same trends as T _CP, confirming the cononsolvency of PnPOx and the cosolvency of PiPOx and PcyPOx. ΔH decreases linearly as a function of the methanol content for all PPOx systems. Ancillary high-resolution ¹H NMR spectroscopy studies of PPOx solutions in D₂O and methanol-d ₄, coupled with DOSY and NOESY experiments revealed that the n-propyl group of PnPOx rotates freely in D₂O, whereas the rotation of the isopropyl and cyclopropyl groups of PiPOx and PcyPOx, respectively, is limited due to steric restriction. This factor appears to play an important role in the case of the PPOxs/water/methanol ternary system.