ATRP of methyl methacrylate initiated with a bifunctional initiator bearing bromomethyl functional groups: Synthesis of the block and graft copolymers
2010
Ozturk, Temel | Yilmaz, Sevil Savaskan | Hazer, Baki | Menceloglu, Yusuf Z.
This article reports the synthesis of the block and graft copolymers using peroxygen-containing poly(methyl methacrylate) (poly-MMA) as a macroinitiator that was prepared from the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in the presence of bis(4,4′-bromomethyl benzoyl peroxide) (BBP). The effects of reaction temperatures on the ATRP system were studied in detail. Kinetic studies were carried out to investigate controlled ATRP for BBP/CuBr/bpy initiating system with MMA at 40 °C and free radical polymerization of styrene (S) at 80 °C. The plots of ln ([Mo]/[Mt]) versus reaction time are linear, corresponding to first-order kinetics. Poly-MMA initiators were used in the bulk polymerization of S to obtain poly (MMA-b-S) block copolymers. Poly-MMA initiators containing undecomposed peroygen groups were used for the 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 (qv) of the graft copolymers in CHCl₃ were calculated. The characterizations of the polymers were achieved by Fourier-transform infrared spectroscopy (FTIR), ¹H-nuclear magnetic resonance (¹H NMR), gel-permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and the fractional precipitation (γ) techniques.
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