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Novel methacrylate and a-chloroacrylate side-chain polymers in which the mesogenic moieties are based on the 4-n-alkoxyphenyl-4-(4"-methylhexyloxy) benzoates have been characterized by differential scanning calorimetry, optical microscopy and X-ray diffraction. Polymethacrylates give smectic A phases although the homologue where n = 1 1 exhibits a smectic C*-smectic A transition. There is no real evidence for liquid-crystalline properties in the poly-a-chloroacrylates where n = 2 or 6. The poly-a-chloroacrylate for which n = 1 1 exhibits a layer structure with the side chains orthogonal to the layer planes as in the smectic A phase. However, this smectic phase has a higher order of the molecules within the layers; the chlorine atoms do impose a local ordering of the mesogenic side groups.

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