A number of temperature and kinetic parameters of thermal degradation of polyimides over the temperature range from 20 to 1000° have been determined on the basis of thermogravimetric investigations of a polyimide sample obtained from pyromellitic dianhydride and diaminodiphenyl ether. It was shown that such kinetic parameters as the reaction order and the activation energy of thermal degradation are directly dependent on the conditions under which the thermal analysis is carried out. It was found that when the static and dynamic conditions of the environment of a polymer sample are varied, the thermochemical processes occurring in a polyimide over the temperature range investigated are drastically changed.
The results of thermoanalytical investigations of polyimides are considered. It is shown that combined application of methods of thermal analysis makes it possible not only to determine the thermal and structural characteristics of polyimide articles but also to observe the formation of polyimides, their thermal degradation and transformation into new structures under the influence of high temperatures.
Thermogravimetry of polyimides based on dianhydrides of pyromellitic, diphenyl- and diphenyloxidetetracarboxylic acids and a series of diamines has been used to determine their temperature characteristics and calculate their activation energies. The dependence of the thermal stability of the polyimides on the structure of their diamine component was established. It was shown that the effect of the thermal stability of the polyimides progressively weakens with the increase in the rigidity of their chemical structure.
Authors:N. A. Shirokov, S. A. Dauengauer, and Yu. N. Sazanov
Some features of DTA in platinum crucibles in air related to the catalytic activity of platinum in many oxidation reactions have been considered. This property of platinum should be taken into account in the interpretation of the DTA curves.
Authors:Yu. N. Sazanov, L. A. Shibaev, and T. A. Antonova
The method of comparative thermal analysis has been used to determine the thermal stability of polyimides and their model compounds. The extent of defects in the investigated polyimides was determined by gas chromatography. The dependence of the extent of the defects on the chemical structure of the initial components and the supermolecular structure of the polyimides was established.
Authors:S. A. Agranova, G. A. Polotskaya, N. A. Shirokov, V. G. Baranov, and Yu. N. Sazanov
The effect of introduction of the comonomer methylthiirane (MT) into the main chain of polyacrylonitrile (PAN) on the thermal transformations of the macromolecules in dilute DMF solution was studied. For this purpose, statistical copolymers of acrylonitrile and MT were synthetized and their pyrolysis in solution was investigated. It was found that introduction of the thioether group into the main chain of PAN results in essential changes in the thermal behaviour of the copolymers as compared to the homopolymer. The results of rheological, thermal and spectral studies on the solutions suggest that the direction of the thermochemical reaction changes on introduction of the thioether group into the PAN molecule. In such copolymers the reaction will preferably proceed by the -C≡N groups forming conjugated cyclic structures.