Solution and solid-state NMR characterization of poly(p-phenylene terephthalamide)

NMR spectroscopy has been used to characterize poly(p-phenylene terephthalamide) in the solid state and in solution in sulfuric acid. Solid-state ¹³C NMR spectra illustrate that the chain structure is highly ordered in the solid state and is of lower symmetry than in solution. Solid-state ¹³C and ¹H NMR results show that only very limited motion takes place over the temperature range of ?170 to +200°C. High-resolution NMR spectra can be observed only in very dilute isotropic solutions because it is the overall rotational motion of the polymer, not segmental motion, that averages the nuclear spin interactions to their isotropic values. These results demonstrate that previous solution NMR studies that were interpreted as reflecting the presence of isotropic and anisotropic high-molecular-weight polymer phases over a wide range of concentrations actually are representative of polymer degradation.