| Summary: | A novel initiator, bromoester modified 4-<i>n</i>-butylresorcinol (4nBREBr<sub>2</sub>), was prepared and utilized in controlled atom transfer radical polymerization (ATRP) to obtain three series of amphiphilic copolymers. The V-shaped copolymers of methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (HEMA), and poly(ethylene glycol) methyl ether methacrylate (MPEGMA), abbreviated to P(HEMA–<i>co</i>–MMA), P(HEMA–<i>co</i>–MPEGMA), and P(MMA–<i>co</i>–MPEGMA), were synthesized. Moreover, P((HEMA–<i>graft</i>–PEG)–<i>co</i>–MMA) graft copolymers were prepared by combining the pre-polymerization modification of HEMA and a “click” reaction using a “grafting onto” approach. All copolymers could form micelles with encapsulated active substances (vitamin C (VitC), vitamin E (VitE), arbutin (ARB)), which are used in cosmetology. In vitro studies carried out in a PBS solution (pH 7.4) demonstrates that in most cases the maximum release of active substance was after 1 h. The polymeric systems presenting satisfactory encapsulation characteristics and release profiles are attractive micellar carriers of cosmetic substances, which show a positive effect on the skin condition.
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