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

Abstract

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 40°C. 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 (γ) techniques. The reaction schemes were also performed using the HYPERCHEM 7.5 program. The mechanical properties of the products were investigated.

Keywords:

• Atom transfer radical polymerization
• free radical polymerization
• macroperoxy initiators
• block and graft copolymers
• mechanical properties
• swelling ratio

Acknowledgement

Thanks to Professor Ahmet Ugur Turhan for mechanical tests.

Notes

^a for CuCl/bpy initiating system.

^b for CuBr/bpy initiating system.