Solvent‐Assisted Recovery and Shape Memory in Self‐Healable Liquid Crystal Elastomers

To synthesize a dynamic, self‐healable polymer network, a highly branched polymer was designed using a controlled Michael addition reaction, followed by free radical polymerization. For shape memory functionality, instead of relying on high‐temperature dynamic bond exchange, an entropic strategy involving solvent‐assisted programming and reprogramming of shapes was employed. The ability of the liquid crystal elastomer (LCE) film to memorize a temporary shape primarily stems from chain entanglement forces. When the LCE film is well swollen in a solvent, the entangled polymer chains are released, forming a loosened network. Upon solvent removal, the rearranged polymer chains become fixed in their new configuration, effectively “memorizing” the temporary folded shape. This process exemplifies the solvent‐assisted shape memory mechanism and the memory reprocessing of the LCEs. In this study, a polymer side‐chain entanglement design is used to enable straightforward self‐healing and shape memory capabilities in soft mechanical materials. This advancement has significant promise for the future development of soft actuators and flexible robotic components. The synergistic interaction between the dynamics of side‐chain physical entanglement and solvent‐assisted chain relaxation enables the system to achieve reversible shape fixation (R ƒ > 97%) and rapid self‐healing under mild conditions without relying on high‐temperature triggering mechanisms.