Liquid crystalline comb-like polyimides with biphenyl-based side groups

We have synthesized series of comb-like polyimides with mesogenic units in their side groups. Such comb-like polyimides were obtained by polycondensation of aromatic diamines bearing biphenyl-based mesogenic moieties with bicyclo2,2,2]oct-7-ene 2,3,5,6-tetracarboxylic dianhydride (BCDA). The different diamines, with two lengths of spacer (with 6 and 11 methylene groups), were synthesized in three steps using as mesogenic groups: biphenyl, 4-cyanobiphenyl and 4-(2-methyl-1-butoxy)biphenyl. The synthesis of the polyimides was performed in two steps: polycondensation of a dianhydride with a diamine in N-methyl-2-pyrrolidone at room temperature giving the corresponding polyamic acid, followed by thermal cyclization into the corresponding polyimide. The comb-like polyimides were studied by X-ray diffraction between room temperature and 250°C. Two types of smectic structure were established: SmA₁ for the long spacer and SmC₁ for the short spacer.