Synthesis and characterization of the block copolymers using the novel bifunctional initiator by RAFT and FRP technics: evaluation of the primary polymerization parameters

Synthesis of poly(styrene-b-methyl methacrylate) block copolymers were obtained via reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene using RAFT-macro agent. For this purpose, 4-bromomethyl benzoyl chloride was obtained using 4-methylbenzoyl chloride and N-bromosuccinimide. The mono functional bromomethyl benzoyl t-butyl peroxy ester (t-BuBP) was obtained by reaction of 4-bromomethyl benzoyl chloride with t-butyl hydroperoxide. Terminally brominated poly(methyl methacrylate) (PMMA-Br) was synthesized using t-BuBP and methyl methacrylate via free-radical polymerization. RAFT-macro agent was acquired by reaction of PMMA-Br and potassium ethyl xanthogenate. By reacting RAFT-macro agent and styrene, block copolymers were obtained. The primary parameters, for example concentration, and time that affect reaction were evaluated. The products were characterized by FT-IR, ¹H-NMR, GPC, and TGA. The multi instruments studies of the obtained block copolymers show that the copolymers easily formed as a result of RAFT. Mn,GPC values of the copolymers were between 24,900 g.mol⁻¹ and 74,100 g.mol⁻¹.