AN NMR-STUDY OF STRUCTURE AND DYNAMICS OF POLY(FUMARATE)S IN THE SOLID-STATE

C-13 cross polarization/magic angle spinning (CP/MAS) NMR spectra and partially-relaxed C-13 NMR spectra of poly(diisopropyl fumarate) (PDiPF) and poly(dicyclohexyl fumarate) (PDCHF) in the solid state were measured over a wide range of temperatures. On the basis of these experiments, C-13 spin-lattice relaxation times (T1C) for the polymers were determined as a function of temperature. From these results, the molecular motion of the main chain and side chains of the polymers was clearly elucidated. In addition, H-1 spin-lattice relaxation times (T1H) and H-1 spin-lattice relaxation times in the rotating frame (T1rho(H)) of the polymers were measured by H-1 pulse NMR over a wide range of temperatures. From these results, dynamics of the main chain and side chains of these polymers was elucidated. The reorientation frequency of the main chain of PDiPF is about 43 kHz at 120-degrees-C, while that of PDCHF at 120-degrees-C is less than this. These pulse NMR results do not conflict with the CP/MAS NMR results.