New liquid-crystalline polyesters 1 with 4-(pheny1azo)azobenzene moities as mesogenic side groups and a polyester backbone structure characterized by a systematic variation of the length of the flexible non-mesogenic main-chain segments were synthesized. The polyesters were investigated by differential scanning calorimetry, polarizing microscopy, miscibility studies and X-ray diffraction. With increasing number of methylene groups in the backbone spacer, the thermal stability of the nematic and/or smectic phases first decreases and then increases.
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