Amphiphilic Copolymers of Acrylic Acid and n-Butyl Acrylate with the Predetermined Microstructure: Synthesis and Properties

Features of the synthesis of n-butyl acrylate copolymers with acrylic acid in 1,4-dioxane by free radical reversible addition-fragmentation chain transfer (RAFT) polymerization mediated by symmetric trithiocarbonates are considered. It is shown that the living mechanism of polymerization is realized in the studied systems. The chemical nature of the RAFT agent dictates different chain microstructures (random block or random) of the copolymers. The effect of chain microstructure on the properties of the copolymers containing about 90 mol % of acrylic acid units is studied by differential scanning calorimetry, contact angle measurements, turbidimetry, potentiometric titration, and dynamic light scattering. It is demonstrated that all the copolymers in the solid phase have similar properties: a single glass transition temperature close to the glass transition temperature of polyacid and a good water wettability. In dilute aqueous solutions, the properties of the copolymers are different: at the inherent pH, random copolymer macromolecules form large associates, while random block copolymers are dispersed into individual coils or micelles. All the copolymers are weaker polyacids compared with PAA; the random block copolymers are characterized by the compaction of macromolecules at small degrees of ionization. Our studies provide evidence that reversible addition-fragmentation chain transfer polymerization is an efficient tool for the targeted insertion of nonpolar units into a polyelectrolyte chain and it can be used for the fine-tuning of its properties.