Nitroxyl-mediated reversible inhibition of free-radical copolymerization of styrene with acrylic monomers

The kinetics of the quasi-living radical copolymerization of styrene (active monomer) with methylacrylate (inactive monomer) was studied at various ratios of the comonomers under the conditions of reversible inhibition by 2,2,6,6-tetramethyl-1-peridinyloxy (TEMPO) radicals. It was shown that the copolymerization proceeds at the background of the stationary concentration of TEMPO and is characterized by a reduction in the rate of reaction during the process. The equilibrium constant for the dissociation of the terminal bonds of the copolymer to radicals was determined, and the kinetic model of copolymerization was suggested.