Abstract
A series of chain liquid crystalline copolymers of 4‐cyanophenyl 4′‐(6‐methacryloyloxyhexyloxy)benzoate and 2‐methacryloyloxyethyl β‐(1‐naphthyl)‐propenoate were prepared by free radical polymerization. The corresponding polyacrylates could not be prepared in the same way and an alternative method was used for their preparation involving the synthesis of copolymers of the mesogenic monomer and 2‐hydroxyethyl acrylate followed by treatment of the resulting polymers with β‐(1‐naphthyl)propenoyl chloride. The materials are of interest as photoactive liquid crystalline polymers. The effect of introducing a bulky nonmesogenic group into a liquid crystalline copolymer generally lowers the clearing temperature and raises T^g^ but also gives rise to contrasting phase behaviour in these two series of polymers. Polymethacrylates which show mesomorphism have sharp transitions and continue to exhibit a highly ordered smectic phase over the bulk of their liquid crystal range. Polyacrylates, on the other hand, exhibit a weakening and broadening‐out of their thermal transitions consistent with a lowering of order. These results emphasize the effect of the polymer backbone on phase behaviour.