Crystallization kinetics of a thermotropic liquid crystalline polyimide derived from 1,3-bis[4-(4′-aminophenoxy) cumyl] benzene

Abstract

We have studied the nonisothermal and isothermal crystallization kinetics of an aromatic thermotropic liquid crystalline polyimide synthesized from 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA) and 1,3-bis[4-(4′-aminophenoxy) cumyl] benzene (BACB) by means of differential scanning calorimetry (DSC). Polarized light microscopy (PLM) and wide-angle X-ray diffraction (WAXD) results confirm that this polyimide exhibits a smectic texture. Nonisothermal crystallization showed two strong and one weak exothermic peaks during cooling. The phase transition from isotropic melt to liquid crystalline state is extremely fast which completes in several seconds. The mesophase transition has a small Avrami parameter, n, of approximate 1. The isothermal crystallization of 253-258 °C has been examined. The average value n is about 2.6 and the temperature-dependent rate constant k changes about two orders of magnitude in the crystallization temperature range of 6°C. The slope of In k versus 1/ (TcΔT) is calculated to be -2.4 × 105, which suggests nucleation control, via primary and/or secondary nucleation for the crystallization process. During the annealing process, a new phase (slow transition) is induced, which grows gradually with annealing time. At lower annealing temperatures ( 220-230°C), the slow transition process seems not to be influenced by the crystals formed during cooling process and its Avrami parameter n is ca. 0.3-0.4. However, the slow transition was hindered by the crystals formed during cooling process when annealed at higher temperature (230-240°C). © 1998 John Wiley & Sons, Inc.