Synthesis of graft copolymers by combination of radical photopolymerization and iniferter process

Abstract

Various PS-based graft copolymers including polystyrene-graft-poly(methyl methacrylate) and poly(styrenegraft-poly(ethylene glycol) methacrylate) are prepared via subsequent visible light radical photopolymerization and iniferter processes. Thus, poly(styrene-co-4-chloromethylstyrene) P(S-co-VBC) is synthesized by light induced free-radical polymerization. Then, chloride moieties are substituted with triphenylmethyl (trityl) groups to give trityl-substituted PS (PS-trityl) under visible light irradiation using dimanganese decacarbonyl (Mn 2 (CO) 10 ) photochemistry. Side chains are then grafted from PS-trityl backbone via iniferter process to give desired graft copolymers in a controlled manner. The precursor intermediates and the final graft copolymers are analyzed by 1 H NMR, FT-IR, and GPC measurements.

Synthesis of hyperbranched polymers by combination of self‐condensing vinyl polymerization and iniferter process

“…Among various iniferter agents, trityl was purposely chosen based on its appropriate activation–deactivation properties. Thus, a novel synthetic protocol has been added to the previous synthesis methods 24,27 utilizing this group for the synthesis of various complex macromolecular structures.…”

“…to the previous synthesis methods 24,27 utilizing this group for the synthesis of various complex macromolecular structures.…”

“…Among them triphenylmethane (trityl) systems are remarkable thermal iniferters based on their adequate activation‐deactivation cycles resulting in narrow molecular weight distributed polymers 19,26 . In a previous study, we have reported a mechanistic transformation protocol for the synthesis of graft copolymers by combining visible light radical photopolymerization and iniferter processes using triphenylmethane 27 …”

“…19,26 In a previous study, we have reported a mechanistic transformation protocol for the synthesis of graft copolymers by combining visible light radical photopolymerization and iniferter processes using triphenylmethane. 27 Herein, we report a straightforward and effective one-step method for the synthesis of HBPs by combination of SCVP and iniferter concepts. In the process deliberately designed 2,2,2-(triphenylethyl)styrene (TPES) plays a key role as inimer.…”