Deuteron relaxation times T1 of polystyrenes deuterated at the backbone (PS-d3) and the phenyl ring (PS-d5), respectively, have been measured in solutions of benzene and diethyl malonate as a function of concentration and temperature. We conclude that the motion of the phenyl ring is faster than that of the backbone, the difference being smallest at high temperatures around 180°C. The temperatures dependence is discussed in relation to the activation energies in polystyrene.

Solutions of chain- (PS-d3) and phenyl ring (PS-d5) deuterated polystyrenes in perdeuterated PS-d8 have been investigated with 1H and 2D NMR relaxation and wide line methods. The intra- and intermolecular parts of the 1H second moments at −100°C are 3,7 G2 and 2,0 G2, respectively, for PS-d3, and 14,7 G2 and ca. 0 G2, respectively, for PS-d5. The intermolecular contribution to the 1H spin lattice relaxation rate, determined at 55 MHz between 150°C and 250°C, is about one third of the total rate in PS-d3, and negligible in PS-d5. We suggest that this contribution is caused by rotational fluctuations of the intermolecular H H vectors. The intramolecular 1H- and 2D-relaxation rates indicate th…