Cyclo Dehydration Reaction of Polyhydrazides. I. Kinetic Parameters Obtained with Nonisothermal Thermogravimetry

The thermal conversion reaction of poly-(1,3-phenyl-1,4-phenyl)-hydrazide into poly-(1,3phenyl-1,4-phenyl)-1,3,4-oxadi~le has been studied using thermogravimetry (TG). For the evaluation of the energie of activation and other kinetic parameters of this cyclo dehydration reaction a method developed by Ozawa was used, where polymer samples are heated with different constant heating rates. With this method the energy of activation can be determined accurately as a function of the degree of conversion. In this way a parallel reaction could be obaerved starting at the end of the nonisothermal conversion process. The polymer was used in two different morphological states, a powder and a film. A slightly higher energy of activation and a considerably higher pre-exponential factor were observed for the film indicating a dependency of the kinetics on the morphological state or on the history of the polymer sample.