THE FORMATiON AND SiGNIFICANCE OF POLYCONJUGATED SYSTEMS iN THERMAL AND THERMO-OXIDATIVE PROCESSES

The processes of formation of polyconjugatcd fragments during thermal oxidation of polymers and the reactions of low molecular compounds yielding polymers with an extended system of conjugation are considered. It is shown from the experimental data that the polyconjugated system (PCS) formed during thermal oxidation and thermolysis exerts initiating or activating action during the process. The cause of such properties of the PCS is the existence in macromolecules of stable biradicals capable of complex formation with dia-magnetic molecules. in this complex the radical reactivity is enhanced due to an increased probability of ST transfer (effect of local activation). Initiation of hydroperoxide decomposition caused by the PCS explains the high syner-getic action of mixtures of polyconjugated polymers formed during thermal oxidation or thermolysis of monomeric inhibitors (bisphenols, aromatic amines, etc.) and initial monomers not subjected to such treatment. It is shown that during thermolysis along with paramagnetic centres (PMC), the activ