Vinylated polyhedral oligomeric silsesquioxane (POSS-M) was prepared by the reaction of POSS containing amine groups with
acrylic acid. Azobenzene liquid crystalline copolymer (LCP-POSS) was then synthesized with 6.0 mol% POSS-M and 94.0 mol% acrylate
monomer containing azobenzene liquid crystalline moiety (Azo-M) by free-radical copolymerization. Homopolymer of Azo-M (LCP)
was also synthesized under the same conditions. Their thermal properties and liquid crystallinity were characterized by Thermal
gravimetric analysis (TG), differential scanning calorimetry (DSC), Wide-angle X-ray diffraction experiments (XRD) and polarized
optical micrographs (POM). The results showed that LCP-POSS has higher thermal stability and glass transition temperature
than pure LCP due to the incorporation of the rigid cage-like POSS. Especially, LCP-POSS exhibits enantiotropic smectic and
nematic liquid crystalline behaviors, its smectic-nematic transition temperature (TSN) and nematic-isotropic transition temperature (TNI) are higher than those of pure LCP, which may promote and extend its applications on stimuli-responsive materials and devices.