Thermoresponsive and co-nonsolvency behavior of poly(N-vinyl isobutyramide) and poly(N-isopropyl methacrylamide) as poly(N-isopropyl acrylamide) analogs in aqueous media

Sets of the nonionic polymers poly(N-vinyl isobutyramide) (pNVIBAm) and poly(N-isopropyl methacrylamide) (pNIPMAm) are synthesized by radical polymerization covering the molar mass range from about 20,000 to 150,000 kg mol⁻¹, and their thermoresponsive and solvent-responsive behaviors in aqueous solution are studied. Both polymers feature a lower critical solution temperature (LCST) apparently of the rare so-called type II, as characteristic for their well-studied analogue poly(N-isopropyl acrylamide) (pNIPAm). Moreover, in analogy to pNIPAm, both polymers exhibit co-nonsolvency behavior in mixtures of water with several co-solvents, including short-chain alcohols as well as a range of polar aprotic solvents. While the cloud points of the aqueous solutions are a few degrees higher than those for pNIPAm and increase in the order pNIPAm < pNVIBAm < pNIPMAm, the co-nonsolvency behavior becomes less pronounced in the order pNIPAm > pNVIBAm > pNIPMAm. Exceptionally, pNIPMAm does not show co-nonsolvency in mixtures of water and N,N-dimethylformamide. Graphical Abstract: [Figure not available: see fulltext.].