Regularities of the synthesis of triblock random copolymers based on styrene and acrylic acid in the presence of styrene-acrylic acid different composition copolymers containing a tritiocarbonate group in DMF and 1,4-dioxane are studied. It is shown that the composition of copolymer reversible chain transfer agents affects the chain microstructure of the central block of the resulting copolymer. The structure and physicochemical properties of the synthesized block random copolymers are studied by AFM, turbidimetric titration, and contact angle measurements. It is demonstrated that the properties of block copolymers (aggregate stability with worsening of the thermodynamic quality of the solvent, water contact angle of the polymer film) are determined by the chemical composition of the central block, the length of which significantly exceeds the length of the end blocks. At the same time, with a certain difference in the central and end blocks in the composition of the copolymers, their microphase segregation in the solution and at the interface is possible.

The regularities of the controlled synthesis of amphiphilic copolymers of styrene and acrylic acid mediated by dithiobenzoate and trithiocarbonates as reversible addition fragmentation chain transfer agents in a 1,4-dioxane solution are considered. The influence of the general composition and chain microstructure on the dispersion stability and hydrodynamic sizes of polymer particles of copolymers containing from 40 to 90 mol % of acrylic acid units is studied. It is shown that in dilute aqueous media random copolymers are dispersed to individual compacted coils owing to the intrachain hydrophobic association of styrene units. The addition of two poly(acrylic acid) blocks to such a copolymer improves its dispersibility in water, and the attachment of two polystyrene blocks makes it insoluble in water because of the interchain association of polystyrene units. The synthesized copolymers possess surface activity, and when applied to a hydrophilic glass surface, they moderately hydrophobize it. In general, this synthetic approach opens up broad prospects for obtaining a wide range of new polymer macromolecules with different properties from one pair of traditional monomers.