Synthesis and characterization of side-chain liquid-crystalline polyacrylates containing azobenzene moieties

Syntheses of novel liquid‐crystalline polymers containing azobenzene moieties were performed by a convenient route with an acrylate backbone. The azobenzenes were key intermediates of the monomers, and side‐chain liquid‐crystalline polymers were prepared, that is, poly[α‐{4‐[(4‐acetylphenyl)azo]phenoxy}alkyloxy]acrylates, for which the spacer length was 3 or 11 methylene units. In addition, poly[3‐{4‐[(3,5‐dimethylphenyl)azo]phenoxy}propyloxy]acrylate was prepared with a spacer length of 3 methylene units. The structures of the precursors, monomers, and polymers were characterized with Fourier transform infrared, 1H‐NMR, and 13C‐NMR techniques. The polymers were obtained by conventional free‐radical polymerization with 2,2′‐azobisisobutyronitrile as an initiator. The phase‐transition temperatures of the polymers were studied with differential scanning calorimetry, and the phase structures were evaluated with a polarizing optical microscopy technique. The results showed that two of the monomers and their corresponding polymers exhibited nematic liquid‐crystalline behavior, and one of the monomers and its corresponding polymer showed smectic liquid‐crystalline behavior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2653–2661, 2002