In this review, the results of modern theoretical and experimental investigations of three dimen sional reversible deactivation radical polymerization are discussed. The most important factors affecting the critical gelation conversion, the probability of cyclization, and the topological structures of polymers are underlined. Examples of the most promising application of the reversible deactivation radical polymerization to produce new polymer materials are given.
It is shown that branched and highly branched vinyl polymers can be prepared by three dimen sional radical polymerization in the presence of dissolved oxygen, as exemplified by the oxidative copolymer ization of styrene and divinylbenzene. The conditions of synthesis of highly branched polymers with a high yield-the ratio between monovinyl and divinyl comonomers and the rate of oxygen bubbling-are deter mined. The kinetics of formation of branched polystyrenes and the features of their molecular mass distribu tion are studied. Elemental analysis data show that the polymeric product contains 22-24 wt % oxygen, which, according to the IR data, enters into the composition of carbonyl, hydroxyl, and peroxide groups. The thermal decomposition of polymeric products is investigated via the TGA-DSC method. The main exother mal peak at ~145°C is associated with the decomposition of peroxide groups, which is accompanied by the evolution of formaldehyde.
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