Development of humidity-responsive self-healing zwitterionic polyurethanes for renewable shape memory applications

This paper reports a novel humidity-responsive self-healing material based on zwitterionic polyurethanes. The material was synthesized from N,N-bis(2-hydroxylethyl) isonicotinamide (BINA), hexamethylene diisocyanate (HDI) and 1,3-propanesultone (PS). The self-healing of its structure, its mechanical properties and shape memory properties were carefully investigated. Results demonstrate that self-healing zwitterionic polyurethanes contain pyridine type sulfobetaines and that strong electrostatic interactions are formed between zwitterions acting as physical crosslinkers. The aggregation of zwitterions strongly influences the phase transition behavior of polyurethane. Bulk polyurethane shows a phase-separated structure with an amorphous soft phase. The damaged zwitterionic polyurethane structure can self-heal several times in the presence of moisture without any additive or external energy. As the proportion of zwitterions increases, the self-healing efficiency increases. The self-healing efficiency results are higher when the relative humidity is increased. The self-healing mechanism is ascribed to the improved ionic mobility upon hydration and to electrostatic forces which occur during drying. Furthermore, pyridine based zwitterionic polyurethanes also show good self-healing of their shape memory properties. Self-healed polyurethanes show both a good shape fixity and recovery. This work paves the way to develop stimulus-responsive self-healing materials for renewable shape memory applications.