Graft copolymers by the combination of ATRP and photochemical acylation process by using benzodioxinones

Synthesis of graft copolymers by combination of atom transfer radical polymerization (ATRP) and photoinduced reaction of benzodioxinone was reported. First, statistical copolymers of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) were prepared by ATRP process. Then, the other component, namely benzodioxinone functional polystyrene (PS-B) was prepared independently by the etheriflcation reaction of hydroxyl benzodioxinone (HDPD) with polystyrene (PS-Br) obtained by ATRP by using K₂ CO₃ in acetone. Photolysis of poly(hydroxyethyl methacrylate-co-methyl methacrylate) (P(HEMA-co-MMA)) and (PS-B) pre-polymers in CH₂C1₂ at λ_inc > 300 nm yielded graft copolymers. The graft copolymers and the intermediates were characterized in detail by using ¹H NMR, GPC, UV, FT-IR, DSC, and AFM measurements.