Comparison of the local chain dynamics in a series of bulk polymers at temperatures well above the glass transition temperature

Abstract

13C n.m.r. spin-lattice relaxation times and excimer fluorescence data obtained on a series of bulk polymers at temperatures well above the glass transition temperature have been analysed in terms of local dynamics. Results thus obtained have shown that the intramolecular conformational changes of the excimer-forming probes are mostly governed by the segmental motions of the polymer chains involved in the glass transition phenomenon. Moreover, the frequency of these intramolecular motions is controlled by the monomeric friction coefficient of the surrounding matrix. Simultaneous analysis of 13C n.m.r. spin-lattice relaxation times and excimer fluorescence data has led to an estimation of the displacement associated with the segmental motion of the chain. The jump amplitude is determined by the precise chemical nature of the polymer chain. In addition, 13C n.m.r. data have shown that, in all the polymers investigated, libration of the C-H vector is superposed on the conformational reorientation. The libration amplitude depends on the chemical structure of the polymer and, for a given polymer, on the steric hindrance at the site of each carbon considered.