synopsisThe kinetics and parameters of thermal and acidic degradation of poly-1,s-dioxolane were investigated in order to elucidate the mechanism of degradation and to obtain information on the nature of active centers. Both homolytic and heterolytic breaking of a macromolecule were shown to be random and occur a t the acetal bond. Thermal degradation was found to proceed in two stages, depending on temperature and involving active centers of a different nature, i.e., macroions and macroradicals. The rate-determining step of thermal degradation appears to be one involving the radical component, similarly to thermal degradation of olefin polyoxides. Acidic degradation occurs solely by the depolymerization mechanism, as in the case of polyaldehydes. It was concluded that the degradation mechanism depends not only on the chain structure and the thermodynamic properties of the system, but also on the nature of active centers.

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