Fabrication of Liquid Crystalline Polyurethane Networks with a Pendant Azobenzene Group to Access Thermal/Photoresponsive Shape-Memory Effects.

Herein, we report a novel thermal/photoresponsive shape-memory polyurethane network with a pendant azobenzene group by utilizing its anisotropic-isotropic phase transitions and photoresponsive feature concurrently. To achieve this goal, the side-chain liquid crystalline polyurethane networks based on the pendant azobenzene group [SCLCPU(AZO)-Ns] were developed in a well-defined architecture. The smectic C nature of an LC phase in the polyurethane networks was confirmed by differential scanning calorimetry, polarized optical microscopy, and one-dimensional and two-dimensional wide-angle X-ray diffraction. The well-defined architecture-made SCLCPU(AZO)-N displays two distinct transition temperatures (Ttrans) (Tg and Tcl), with a difference of about 40 °C. Consequently, the excellent triple-shape-memory effect in this network was demonstrated by cyclic thermomechanical analysis. By making full use of the trans-cis photoisomerization of azobenzene, the reversible bending and unbending behaviors were realized under the light irradiation with wavelengths of 450 and 550 nm, respectively.