Deuteron NMR study of molecular order and motion of the mesogenic side groups in liquid‐crystalline polymers

Abstract

AbstractThe molecular order and mobility of two liquid‐crystalline polyacrylates with phenyl benzoate moieties as mesogenic side groups and (CH2)m spacers (m = 2 and m = 6) were investigated by pulsed 2H NMR. The mesogenic side groups were isotopically labelled at the terminal phenylene ring. In the glassy state the orientational distribution function was characterized from the angular dependence of the 2H NMR line shape of samples macroscopically ordered in their nematic phase by the 8,4 T magnetic field of an NMR spectrometer. It was found to be Gaussian with widths of ± 18,5° and ± 10,5° for the m = 2 frozen nematic and m = 6 frozen smectic system, respectively. The phenylene rings undergo 180° jumps about their local C2‐axes in the glassy state. The time‐scale of this process, however, was found not to be uniform. Instead, the analysis of 2H NMR line shapes and their intensities as a function of temperature yielded a log‐Gaussian distribution with correlation times characteristic of amorphous solids, 2,2 versus 2,5 decades in width and mean activation energy ĒA = 42 versus 47 kJ/mol for the m = 2 and m = 6 system, respectively. The correlation times for the centre of the distribution agree with those obtained by dielectric relaxation measurements of the same systems, suggesting that reorientation of the whole mesogenic group is detected via the phenylene rings.