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 review addresses the synthesis of copolymers with the controlled distribution of monomer units (random, gradient, block-random, block-gradient, multiblock copolymers) by reversible deactivation radical polymerization and the ways of purposeful variation in the sequence of units in macromolecules during the synthesis. The effect of chain microstructure on the properties of these copolymers is discussed.

The laws of dispersion polymerization of n-butyl acrylate in an aqueous-alcoholic medium in the presence of a hydrophilic reversible addition-fragmentation chain-transfer poly(acrylic acid)-based polymeric agent with a trithiocarbonate group within the chain are investigated. It is shown that the portioned introduction of the monomer into the synthesis makes it possible to achieve higher maximum conversions. The resulting block copolymers are characterized by a relatively narrow molecular weight distribution and their number-average molecular weight increases linearly with increasing monomer concentration. The obtained dispersions of triblock copolymer poly(acrylic acid)–block-poly(n-butyl acrylate)–block-poly(acrylic acid) have a unimodal particle size distribution that persists after dialysis against water. It is shown that the synthesized dispersions may be used as a polymer matrix for immobilizing zinc oxide nanoparticles and as a polymer precursor in the process of the seeded polymerization of styrene.

Certain quantitative parameters characterizing the Cu(0)-mediated SET polymerization of methyl acrylate, that is, the kinetic orders of the polymerization rate with respect to the concentration of the monomer and initiator and the rate constants of initiation under various conditions, are determined. A method for the separate determination of Cu(I) and Cu(II) ions during polymerization is developed. A new effective form of the catalyst, a copper mirror, is proposed, which makes it possible to multiply the specific rate of polymerization and decrease the residual copper content in the polymer.

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.

The tuning of the relative monomer reactivities of styrene and acrylic acid in a solution of N,N-dimethylformamide by using polymeric RAFT agents.

Narrowly dispersed hydrophilic block and random copolymers of acrylic acid and N -isopropylacrylamide of various compositions and molecular masses are synthesized for the first time by controlled radical polymerization via the reversible addition-fragmentation chain-transfer mechanism. The copolymers are used for the synthesis of ternary copolymers with n -butyl acrylate. As shown by dynamic light scattering, the resulting amphiphilic copolymers can form stable dispersions in diluted aqueous solutions. It is found that the effective hydrodynamic radii of dispersion particles may be controlled via variation both in the primary structure of the ternary copolymer, i.e., the amount and sequence of hydrophilic and hydrophobic units, and in the external stimuli, i.e., the temperature and pH of a solution.

The radical polymerization of n-butyl acrylate in organic, aqueous, and water–alcohol media in the presence of poly(acrylic acid) containing a trithiocarbonate group within the chain is studied for the first time. It is shown that in nonselective solvents (1,4-dioxane and DMF) poly(acrylic acid) serves as a reversible addition–fragmentation chain-transfer agent and the triblock copolymer poly(acrylic acid)–block–poly(n-butyl acrylate)-–block-poly(acrylic acid) is formed. In aqueous and aqueous–organic media (under conditions of emulsion, dispersion, and miniemulsion polymerizations as well as polymerization-induced selfassembly), the block copolymer being formed additionally serves as a stabilizer of polymer–monomer particles. The sizes of these particles and the molecular-mass characteristics of the resulting polymers may be controlled via variation in the concentration ratio of the components. It is found that, during polymerization in aqueous media, there is the formation of spherical polymer particles that preserve their morphology in thin films prepared via precipitation of the synthesized dispersion.

The formation of copolymers of vinyl acetate and n-butyl acrylate via polymerization mediated by di-tert-butyl trithiocarbonate and dibenzyl trithiocarbonate as reversible addition-fragmentation chain-transfer agents is studied. Copolymerization mediated by low-molecular-mass reversible addition-fragmentation chain-transfer agents and by the copolymers formed in their presence proceeds via the pseudoliving mechanism. As a result, the controlled synthesis of narrowly dispersed copolymers of various compositions and desired molecular masses may be implemented. Variation in the compositions of the copolymers with conversion is investigated, and the reactivity ratios of the comonomers are found to differ significantly (r VA = 0.01 and r BA = 5.38). Our experimental data make it possible to infer that gradient copolymers are formed in the systems of interest in a wide range of comonomer mixture compositions.