N ematic and Cholesteric Thermotropic Polyesters with Azoxybenzene Mesogenie Units and Flexible Spacers in the Main Chain

Properties of linear polyesters based on azoxybenzene and 2,2'-methylazoxybenzene moieties with linear, flexible spacers based on mixtures of dodecanedioic acid (DDA) and methyladipic acid (MAA), chiral or racemic, of various compositions (system MAA/DDA-8 and MAA/DDA-9, respectively) have been described. Substitution of methyl groups in the 2,2' or 3,3' positions of the mesogenic core Ieads to soluble and relatively low-melting-point polyesters. The viscosity law for (MAA/DDA-9) polyesters in 1,1,2,2 tetrachloroethane gives an exponent 0.76, indicating well-solvated, coiled chain conformations in dilute solution. Calorimetric data show an increase in isotropization entropy ßSNI with increasing average length of the spacer. This suggests a nonrandom conformation of the spacer in the nematic melt with a degree of order superiortothat of low-molecular-weight analogs. X-ray data obtained with an oriented nematic glass quenched from the nematic melt of DDA-9 subjected to a magnetic field of 10-12 T also support the extended-chain model in the nematic phase of DDA-9. Oriented fibers can be produced by subjecting nematic melts of polyesters 8 and 9 either to magnetic fields of high intensity or to shear fields. The x-ray data obtained from these fibers also support the extended-chain model. Cholesteric systems do not orient in the magnetic field of 10-12 T. The study ofmesophases ofsystems 8 and 9 indicates a dramatic influence of the position of the ester group on the stability of the mesophase in the azoxybenzene polyesters. The results are interpreted in terms of geometric factors influencing the colinearity of the mesogenic core and of the extended spacer.