KINETIC FEATURES OF CARBENE TRANSFORMATIO NS IN POLYMERS

Kinetics and mechanisms of the carbene-initiated radical reactions in solid polymers are considered. The dispersion of cell distances betwee n carbene centers and C-H bonds of macromolecules determines the kinet ic inequivalence of triplet carbene states in the low-temperature reac tion of hydrogen atom detachment. The interaction of arylcarbenes in t he clusters at low temperatures leads to the formation of biradicals. The yield of biradicals is a measure of inhomogeneity of the distribut ion of carbene precursors in polymers. Structural modification of a po lymer as a result of filling produces a strong effect upon the kinetic s of the thermal loss of carbenes. The kinetic data allow the thicknes s of boundary layers in the filled polymers to be determined.