Entangled Azobenzene‐Containing Polymers with Photoinduced Reversible Solid‐to‐Liquid Transitions for Healable and Reprocessable Photoactuators

<jats:title>Abstract</jats:title><jats:p>Photoactuators based on liquid crystal elastomers or networks are smart materials that show photoinduced motions. However, their crosslinked networks make their repair or reprocessing difficult. Here, a healable and reprocessable photoactuator is fabricated using entangled high‐molecular‐weight azobenzene‐containing polymers (azopolymers) that are non‐crosslinked. A series of linear liquid crystal azopolymers with different molecular weights are synthesized. The low‐molecular‐weight azopolymers (5–53 kg mol<jats:sup>−1</jats:sup>) cannot form freestanding photoactuators because their polymer chains lack entanglements, which makes them hard and brittle. In contrast, flexible and stretchable actuators are fabricated using high‐molecular‐weight azopolymers (80–100 kg mol<jats:sup>−1</jats:sup>) that exhibit good processability because of the polymer chain entanglements. The azopolymer photoactuators show photoinduced bending based on photoinduced <jats:italic>trans</jats:italic>–<jats:italic>cis</jats:italic> isomerization of the azopolymers on the irradiated side. The experiments show not only photoinduced phase transitions or changes in the order parameters but also photoinduced solid‐to‐liquid transition of the azopolymers resulting in shape changes and mechanical responses. Thus, photoinduced solid‐to‐liquid transition is a new mechanism for the design of photoactuators. Moreover, the azopolymer photoactuators are healable and reprocessable via solution processing or light irradiation. Healability and reprocessability prolong lifetimes of photoactuators are important for materials reusage and recycling, and represent a new strategy for the preparation of smart materials.</jats:p>