13C n.m.r. analysis of fluorinated polyimides and poly (amic acid)s

Abstract The fine structure of poly (amic acid) (PAA) and the structural changes caused by thermal imidization are investigated by 13 C n.m.r. spectroscopy of fluorinated PAA and polyimides cured under various conditions. Split signals reflecting the isomerism of PAA are assigned by measuring model compounds, and the proportions of isomeric units are estimated. Signals assigned to the end groups of PAA are found in the spectrum of samples cured at 120°C. Depolymerization at amide groups thus occurs at low curing temperatures and the molecular weight of the polymer decreases considerably. This low-molecular-weight polymer is, however, converted into high-molecular-weight polyimide by subsequent curing at 300°C. These depolymerization and polycondensation processes are also supported by measuring the viscosity of PAA and polyimide solutions.