External Stress-Free Reversible Multiple Shape Memory Polymers

The present work is focused on developing external stress-free two-way triple shape memory polymers (SMPs). Accordingly, a series of innovative approaches are proposed for the material design and preparation. Polyurethane prepolymers carrying crystalline polytetrahydrofuran (PTMEG) and poly­(ε-caprolactone) (PCL) as the switching phases are respectively synthesized in advance and then cross-linked to produce the target material. The stepwise method is believed to be conducive to manipulation of the relative contribution of PCL and PTMEG. Moreover, the chain extender, 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol (UPy), is incorporated to establish hydrogen bonds among the macromolecules. By straightforward stretching treatment at different temperatures, the hydrogen bond networks are successfully converted into an internal stress provider, which overcomes the challenge of stress relaxation of the melted low melting temperature polymer (i.e., PTMEG) and increases the efficiency of stress transfer. Meanwhile, the contraction force of the switching phases is tuned to match the internal tensile stress. As a result, the internal stress provider can closely collaborate with melting/recrystallization of the crystalline domains, leading to the repeated multiple shape memory effects. The cross-linked polyurethane is thus able to reversibly morph among three shapes and displays its potentials as soft robot and actuator. The strategy reported here has the advantages of easily accessible raw materials, simple reaction, and facile programing/deprograming/reprograming, so that it possesses wide applicability.