The effect of high pressure on the phenyl group motion in amorphous polystyrene (PS-ds) has been studied using 2H n.m.r, quadrupole echo spectroscopy. The spectra are superpositions of two contributions from phenyl groups performing relatively slow and fast 180 ° flipping motion, respectively. The motion of the phenyl groups is characterized by a distribution of correlation times. The mean correlation times of the slowly flipping groups vary from milliseconds to microseconds and are in good agreement with data from other relaxation techniques. The effect of pressure on the molecular motion is strong in the glassy state. The reorientational activation volume is of the same order as the volume required for the rotation of a phenyl group. Above the glass transition temperature the effect of pressure is much weaker. We have no evidence that the phenyl group motion is dependent on the main chain motion.
Посилання на статтю:
2H n.m.r, study of high pressure effects on the molecular dynamics in polystyrene: 2. Phenyl group motion / A. S. Kulik* and K. O. Prins // Polymer. – 1993. – Vol 34. – P. 4635-4641.