Thermal Decomposition of Vulcanized Structures of Deformed Vulcanizates Containing Various Accelerators

According to the hypotheses developed by the authors, vulcanized rubber is a system in which the molecular chains are united by local molecular and chemical bonds of varying intensity. The concentration, distribution, and strength of these bonds determine the principal physical and mechanical properties of the vulcanizates. Consequently the study of the structure of the vulcanizate is of primary practical value. The explanation of the nature of the bonds in a vulcanizate by chemical methods is very difficult, mainly because of the impossibility of distinguishing the specific chemical groups which enter into the composition of the different molecular chains from those bonds between the chains which are responsible for the development of spatial structures. From this view point, the thermo-mechanical method described below, which is based on the study of stress relaxation at different temperatures, is of great significance. As was shown by Dogadkin and Reznikovskii˘, the delayed stress relaxation in a vulcanizate at temperatures up to 70° C is caused by rupture of the local intermolecular bonds and the regrouping of the structural elements of the polymeric chains without destruction of the chemical bonds between them. Accordingly, after some time at these temperatures, a practically balanced stress is established, which depends on the number of the stronger bonds remaining. At temperatures above 70° C, rupture of the chemical bonds between the chains takes place; its speed increases with decrease of the energy activating the rupture of the given type of bond. Particularly in the case of sulfur vulcanizates, we can assume that the following types of bonds exist between the chains of the rubber: (1) —C—C—, which develop as a result of the polymerizationprocesses; (2) —C—S—C— monosulfide; (3) —C—S—S—C— disulfide, and (4) —C—Sn—C— polysulfide, formed as a result of the direct participation of the vulcanizing agent, sulfur, in the process of joining of the molecular chains. The energy of these chains can be estimated as 62.7 kcal, per mole for C—C, 54.5 kcal. per mole for C—S, and 27.5 kcal. per mole for the —S—S bond. Naturally, the heat stability of a vulcanizate will depend on which of the indicated types of bonds predominates.