Azopolyesters with Intrinsic Crystallinity and Photoswitchable Reversible Solid-to-Liquid Transitions

Herein, we introduce a variety of azopolyesters (azobenzene-based polyesters) with remarkable intrinsic crystallinity and photoinduced reversible solid-to-liquid transition abilities from copolymerization of azobenzene-based epoxides with cyclic anhydrides. The length of the soft alkyl side-chain inlaid with azobenzenes and stereoregularity of main-chain of azopolymers have tremendous effects on crystallization properties of the resulting polyesters with melting temperature (T_m) in the range of 51–251 °C. Moreover, some of azopolyesters possess excellently photoinduced reversible solid-to-liquid transition performance thanks to trans-cis photoisomerization of azobenzenes. Trans-azopolyesters are yellow solids with T_ms or glass transition temperatures (T_gs) above room temperature, whereas cis-polymers are red liquids with T_gs below −20 °C. These azopolyesters could be applied as novel light-switchable adhesives for quartz/quartz, wood/wood and quartz/wood adhesion, with the strength in the range of 0.73–0.89 MPa for trans-polymers. Conversely, the adhesion strength of liquefied cis-azopolyesters generated from the irradiation of trans-polymers by UV light was about 0.1 MPa, which shows light enable to control the adhesion process with high spatiotemporal resolution.