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This is an analytical review on kinetics and mechanism of threedimensional radical polymerization (TDRP) of multifunctional vinyl monomers (oligomers) having two or more double bonds per molecule. The period (1960 - 1977) of establishing the fundamental kinetic law of TDRP and the principal characteristics of its mechanism, i.e., microheterogeneity, is briefly described. New intense progress in the field of TDRP (during the recent decade) resulting from the development of new technologies based on this technique (fiber-optic engineering, information technology, etc.) has received much consideration. The methodological peculiarities of investigations on TDRP kinetics and mechanism, which are a result of the complex conditions of highly structured reaction media inherent in TDRP processes, are described. Particular attention is given to techniques of structuralphysical investigation (a consistent complex of methods including ESR, NMR, diffusion and radiation probing, mechanics and thermomechanics) sensitive to structural microheterogeneity in the range 10-6 - 10-4 cm. The perspectives of macromolecular design based on TDRP data are analyzed including latest approaches as the employment of a ‘living’ chain mode. This review covers three monographs in Russian, reflecting three sequential stages of TDRP development from 1960 till 1995 using acrylic oligomers as an example (most of the investigations were carried out at the Institute of Chemical Physics RAS). The bibliography includes 197 references.

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