Mechanistic interactions in polystyrene-block-poly(N-hydroxyethylacrylamide) diblock copolymer-based nano-corona toward elucidation of solvation responses

Diblock copolymers consisting of higher hydrophobic styrene and hydrophilic N-hydroxyethylacrylamide (HEAAm) segments were successfully synthesized via direct two-step atom transfer radical polymerization. Polystyrene (PS) homopolymers were synthesized using methyl 4-(bromo-methyl) benzoate initiator in N,N′- dimethylformamide (DMF) in the presence of Cu(I)Br/pentamethyldiethylene tetramine (PMDETA) catalyst system at 90 and 110 °C in nitrogen atmosphere. PS was used as macro-initiator for the synthesis of PS-b-PHEAAm polymer. Block copolymerizations were carried out in pure DMF in the presence of the same catalyst system at 110 °C while argon was used for deoxygenation and inert environment. Block copolymer was purified through dialysis into deionized water using a dialysis tubing (MWCO 3500, cellulose membrane). The number average molecular weight of PS polymers (Mn = 2240, 3250 and 10,800 Da) was determined by size exclusion chromatography using tetrahydrofuran (THF) as eluent. The chemical structures, functional groups and actual compositions of copolymer were determined using instrumental data, c.f. elemental analysis, attenuated total reflectance infra-red and proton—nuclear magnetic resonance (¹H-NMR) spectroscopy analysis. Thermo-gravimetric analysis confirms that diblock copolymer has higher thermal stability than PS homopolymer. Co-solvent effect on particle formation was investigated by regulating dielectric constant. It is revealed that THF/DMF (9:1) provides susceptible environment for the formation of smallest size (13 ± 4 nm) particle. This synthetic route would establish a direct synthesis of diblock copolymer with antagonistic segments for advanced technological applications.