Shape Memory Polymers with Patternable Recovery Onset Regulated by Light

Abstract Shape memory polymers (SMPs) show attractive prospects in emerging fields such as soft robots and biomedical devices. Although their typical trigger‐responsive character offers the essential shape‐changing controllability, having to access external stimulation is a major bottleneck toward many applications. Recently emerged autonomous SMPs exhibit unique stimuli‐free shape‐shifting behavior with its controllability achieved via a delayed and programmable recovery onset. Achieving multi‐shape morphing in an arbitrary fashion, however, is infeasible. In this work, a molecular design that allows to spatio‐temporally define the recovery onset of an autonomous shape memory hydrogel (SMH) is reported. By introducing nitrocinnamate groups onto an SMH, its crosslinking density can be adjusted by light. This affects greatly the phase separation kinetics, which is the basis for the autonomous shape memory behavior. Consequently, the recovery onset can be regulated between 0 to 85 min. With masked light, multiple recovery onsets in an arbitrarily defined pattern which correspondingly enable multi‐shape morphing can be realized. This ability to achieve highly sophisticated morphing without relying on any external stimulation greatly extends the versatility of SMPs.