Synthesis of a new macroperoxy initiator with methyl methacrylate and t-butyl peroxy ester by atom transfer radical polymerization and copolymerization with conventional vinyl monomers

In this study, we present the synthesis of poly-MMA macroperoxy initiators obtained by the ATRP of MMA with bromo methyl benzyl t-butyl peroxy ester (t-BuBP) as an initiator, and CuX (X:Br or Cl)/2,2'-bipyridine (bpy) as a catalyst system at 0, 20, 30 and 40C. The peroxygen groups do not decompose during the ATRP reaction, because low reaction temperatures used for the ATRP reaction are not enough to decompose them. The peroxygen groups of poly-PMMA macroperoxy initiators can lead them to react with a monomer by using appropriate reaction conditions to obtain the block or graft copolymers. For this purpose, poly-MMA macroperoxy initiators were used to synthesize poly(MMA-b-S) block copolymers with S and used for graft copolymerization of polybutadiene (PBd) and natural rubber (RSS-3) to obtain crosslinked poly(MMA-g-PBd) and poly(MMA-g-RSS-3) graft copolymers. Swelling ratio values of the crosslinked graft copolymers in CHCl3 were calculated. The characterizations of the polymers were achieved by FT-IR, 1H-NMR, GPC, DSC, SEM, and the fractional precipitation () techniques. The reaction schemes were also performed using the HYPERCHEM 7.5 program. The mechanical properties of the products were investigated