THE ROLE OF A MOLECULAR SPONGE IN HETEROPHASE CHAIN-REACTIONS OF BLOCK POLYMERS (ILLUSTRATED BY POLYSTYRENE ARYLATION WITH DIBENZOYL PEROXIDE)

Certain peculiarities of dibenzoyl peroxide interaction with amorphous polystyrene, remained unexplained within the homogeneous mechanism, a re interpreted in terms of a heterophase kinetic scheme involving two conjugate reaction chains localized in separated structural zones of t he polymeric matrix. The reaction scheme is set up on the basis of the micellar-skeleton model of the supramolecular organization, which dis tinguishes two kinds of zones in the structure of spongy molecular cel ls. Differing in the fluctuation dynamics of polymer units and in the size of micropores - reactive particle traps, these zones also differ by conditions for initiation, propagation, and termination of reaction chains. The principle of inter-zone conjugation of kinetic chains is demonstrated for the case of fluctuation dynamics of molecular sponge units limited by the supramolecular skeleton.