Self-assembly of poly(4-methylstyrene)-g-poly(methacrylic acid) graft copolymer in selective solvents for grafts: scattering and molecular dynamics simulation study.

Poly(4-methylstyrene)-g-poly(methacrylic acid) (P4MS-g-PMAA) graft copolymer was synthesized by the grafting-onto method from poly(4-methylstyrene), selectively brominated on methyl groups, and "living" poly(tert-butyl methacrylate). The average degree of polymerization of the backbone and the grafts and the average number of grafts per backbone were 251, 21, and 25, respectively. The self-assembly of P4MS-g-PMAA was studied in methanol and aqueous buffers (selective solvents for grafts). Micelles of P4MS-g-PMAA in methanol were studied by a combination of static and dynamic light scattering, TEM and SAXS. It was found that their spherical core/shell morphology resembles that of diblock copolymer micelles but they have a very low aggregation number (approximately 3) and a high cmc (approximately 0.8 mg/mL). The spherical core-shell structure revealed by SAXS was confirmed by the molecular dynamics study emulating an associate of comblike copolymers with structural parameters close to those of the experimentally studied system. Because P4MS-g-PMAA was not directly soluble in water, its aqueous solutions had to be prepared by dialysis of the methanolic solutions. In aqueous solutions, unlike in methanol, small P4MS-g-PMAA micelles (approximately 20 nm in diameter) form large secondary aggregates (approximately 100-400 nm).