Unusual Phase Transition Behavior of Poly(N-isopropylacrylamide)-co-Poly(tetrabutylphosphonium styrenesulfonate) in Water: Mild and Linear Changes in the Poly(N-isopropylacrylamide) Part.

In this paper, one LCST-type thermoresponsive poly(ionic liquid) (PIL), poly(tetrabutylphosphonium styrenesulfonate) (P[P4,4,4,4][SS]), was introduced to poly(N-isopropylacrylamide) (PNIPAM) by two different ways, mixing and copolymerization. Interestingly, they show distinct thermoresponsive phase transition behaviors, evidenced by temperature-variable (1)H nuclear magnetic resonance and Fourier transform infrared in combination with the perturbation correlation moving window (PCMW) technique. The PNIPAM/P[P4,4,4,4][SS] mixture exhibits a sharp and drastic phase transition, similar to that of pure PNIPAM. In the statistical copolymer, PNIPAM-co-P[P4,4,4,4][SS], the thermosensitivity of P[P4,4,4,4][SS] is largely suppressed, resulting in a linear, mild, and incomplete phase transition, which has never been reported before. This abnormal phenomenon is shown to arise from the outstanding hydration ability of P[P4,4,4,4][SS]. Our findings should be conducive to improving our understanding of the interaction between LCST-type polymers with distinct structures and provide a new perspective for preparing thermoresponsive materials with linear phase transition behavior.