Controlled radical polymerization of styrene and n-butyl acrylate mediated by trithiocarbonates

The free-radical bulk homopolymerization of styrene and n-butyl acrylate at 80°C mediated by dibenzyl trithiocarbonate, poly(styryl) trithiocarbonate, or poly(n-butyl acrylate) trithiocarbonate as reversible addition-fragmentation chain-transfer agents has been studied. It has been shown that the use of low-and high-molecular-mass reversible addition-fragmentation chain-transfer agents makes it possible to efficiently control the molecular-mass characteristics of polymers. In the case of styrene, the rate of polymerization slightly depends on the concentration of the addition-fragmentation chain-transfer agent. In contrast, for the polymerization of n-butyl acrylate, the rate significantly decreases with the concentration of the chain-transfer agent. Formation of radical intermediates during the polymerization of styrene and n-butyl acrylate mediated by trithiocarbonates has been studied by ESR spectroscopy. It has been demonstrated that the polymeric chain-transfer agents are efficient for the synthesis of block copolymers with the controlled block length.