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Some main-chain liquid-crystalline polymers were synthesized with pendent sulfonic acid groups (0-6 wt %) on the polymer backbone. The solution viscosity behavior, the chemical structures, and the liquid-crystalline (LC) properties were characterized with Fourier transform infrared spectroscopy, elemental analysis, 1 H-NMR, differential scanning calorimetry, polarizing optical microscopy, and X-ray measurements. All the polymers displayed a smectic mesophase with a mesogenic range of 142-1558C and good thermal stability. With an increasing concentration of sulfonic acid groups in the polymer systems, some of the polymers exhibited two kinds of mesophases, including smectic and nematic phases. The glass-transition temperatures and isotropic-transition temperature were elevated slightly, whereas the temperature of the smectic-nematic phase transition changed a little. For polymers with a few sulfonated benzene groups, the regular mesogen/soft matrix structures led to a smectic structure because of microdomains between the mesogenic moieties and the soft main-chain matrix, whereas for polymers with an increased number of sulfonic groups, the ionic groups were distributed in both the soft matrix and the LC microphase. Although the increased ionic interactions between mesogens led to more crystalline phases, the strong electrostatic interactions in the ionic group/mesogen/soft matrix systems may have been tangled in domains. Therefore, they disturbed the regular mesogen/soft matrix smectic phase structure, leading to the appearance of a smectic-nematic transition.

A series of side-chain liquid crystalline polysiloxanes bearing different chiral groups were synthesized with a cholesteric liquid crystalline monomer cholesteryl 2-(4-allyloxy-benzoxy)-succinate and a chiral monomer 2-isopropyl-5-methyl-cyclohexyl 4-allyloxy-benzoate. All the chiral polymers showed cholesteric mesophase with very wide mesophase temperature ranges. Along with phase morphology varied from solid state to isotropic state, the sample exhibited varied spectroscopic images, indicating different phase behaviors between mesophase and isotropic state. Optical properties of the polymers were characterized with circular polarization spectra and optical rotation analysis. The specific rotations of the chiral liquid crystalline polymers were all negative values and increased with increase of menthyl component in the polymer systems. As compared with corresponding monomers, the polymers showed significantly lower specific rotations, suggesting that the existence of polysiloxane main chains affect the molecule polarity. The selective light reflection maximum wavelength of the polymers at the same temperature shifted to short wavelength with decrease of cholesteryl component, indicating that the helical pitch becomes shorter due to induction of menthyl groups with high chiral properties. The temperature dependence of selective light reflection maximum wavelength was shifted to a longer wavelength region as the temperature decreased.

A series of side-chain liquid crystalline (LC) oligomers bearing glycidyl ether groups were synthesized with cholest-5-en-3-ol(3 β)-4-(2-propenyloxy) benzoate, octyl 4-(4-allyloxy-benzoyloxy)-benzoate and epoxy monomer allyl glycidyl ether. The chemical structures and LC properties of the monomers and oligomers were characterized by use of various experimental techniques. All the chiral LC oligomers showed cholesteric mesophase with very wide mesophase temperature ranges. All the synthesized LC oligomers were cured with 4,4'-diaminodiphenylmethane at the same curing conditions. The thermal behaviors, mesomorphic phase and optical properties of the thermosets were characterized. The synthesized thermosets have high thermal stability. The cholesteric phases of LC oligomers were frozen in the polymer networks. Compared with those of corresponding oligomers, the reflection located at wide angles of thermosets became more diffuse, and the peak intensity decreased in X-ray diffraction analysis. The selective light reflection maximum λmax of the thermosets at room temperature shifted slightly to short wavelengths as the LC monomer bearing cholesteryl component was increased, indicating that the helical pitch P becomes shorter due to more chiral groups in the polymer network systems. The temperature dependences of both reflection wavelength and optical rotation under the influence of the crosslinking reaction were also investigated.

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