Journal of Polymer Science Part B: Polymer Physics, Vol.37, No.6, 505-522, 1999
The influence of annealing on thermal transitions in a nematic copolyester
Thermal transitions of a glassy, main chain, liquid crystalline, random copolyester, HIQ-40, have been characterized. HIQ-40 is made from 40 mol percent p-hydroxybenzoic acid (HBA) and 30 mol % each of p-hydroquinone (HQ) and isophthalic acid (IA). This polymer is soluble in organic solvents, permitting the preparation of thin, solution-cast films that are in a glassy, metastable, optically isotropic state. On first heating of an isotropic HIQ-40 film in a calorimeter, one glass transition is observed at low temperature (approximately 42 degrees C), and is ascribed to the glass/rubber transition of the isotropic polymer. A cold crystallization exotherm centered near 150 degrees C is observed. This is associated with the development of low levels of crystalline order. A broad melting endotherm is centered at about 310 degrees C; this endotherm marks the melting of crystallites and the transformation to a nematic fluid. A nematic to isotropic transition was not observed by calorimetry. After quenching from the nematic melt, a T-g is observed in the range of 110-115 degrees C and is associated with the glass/rubber transition of the nematically ordered polymer. Annealing optically isotropic films at temperatures above the isotropic glass transition results in the systematic development of axial order. In these annealed samples, T-g increases rapidly until it is near the annealing temperature, then T-g increases more slowly at longer annealing times. In as-cast films annealed at 120-135 degrees C, the light intensity transmitted through a sample held between crossed polarizers in an optical microscope (a qualitative measure of birefringence and, in turn, axial order) initially increases rapidly and uniformly throughout the sample and, at longer annealing times, approaches asymptotic values that are higher at higher annealing temperatures. The increase in transmitted intensity is ascribed to the development of axial order. The uniform increase in transmitted intensity suggests that ordering occurs by a rather global process and not via a nucleation and growth mechanism.
Keywords:LIQUID-CRYSTALLINE POLYMERS;DYNAMIC-MECHANICAL ANALYSIS;THERMOTROPIC POLYESTERS;POLY(PARA-OXYBENZOATE-CO-PARA-PHENYLENE ISOPHTHALATE);AROMATIC POLYESTERS;LOCAL DYNAMICS;CHAIN;TRANSPORT;NMR