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ATRP of methyl methacrylate initiated with a bifunctional initiator bearing bromomethyl functional groups: Synthesis of the block and graft copolymers

Öztürk, Temel | Yılmaz-Savaşkan, Sevil | Hazer, Baki | Menceloğlu, Yusuf Z.

Article | 2010 | Journal of Polymer Science, Part A: Polymer Chemistry48 ( 6 ) , pp.1364 - 1373

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 bls(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 In ([M o]/[Mt]) versus reaction time are linear, corresp . . .onding 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(MMAg-RSS-3) graft copolymers. Swelling ratio values (q v) 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), gelpermeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and the fractional precipitation (?) techniques. © 2010 Wiley Periodicals, Inc Daha fazlası Daha az

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

Öztürk, Temel | Yılmaz-Savaşkan, Sevil | Hazer, Baki

Article | 2008 | Journal of Macromolecular Science, Part A: Pure and Applied Chemistry45 ( 10 ) , pp.811 - 820

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 init . . .iators 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 Daha fazlası Daha az

Synthesis and characterization of a novel macromonomer initiator for reversible addition fragmentation chain transfer (RAFT). Evaluation of the polymerization kinetics and gelation behaviors

Öztürk, Temel | Hazer, Baki

Article | 2010 | Journal of Macromolecular Science, Part A: Pure and Applied Chemistry47 ( 3 ) , pp.265 - 272

Reversible addition fragmentation chain transfer, RAFT, self condensing a novel macromonomer initiator polymerization and copolymerization with methyl methacrylate, MMA, in the presence of 2,2' -azobisisobutyronitrile, AIBN, has been reported. RAFT-MIM was obtained from potassium salt of the ethyl xanthegonate and the terminally brominated poly (ethylene glycol) methacrylate (v-PEG-Br) which was synthesized by the reaction of poly (ethylene glycol) methacrylate, v-PEG-OH with Mn = 526 Dalton and 3-bromopropionyl chloride. Self condensing RAFT-MIM polymerization and copolymerization with MMA gave highly branched and cross-linked amph . . .iphilic copolymers. The kinetic parameters were evaluated by changing some polymerization conditions such as monomer, initiator and solvent concentration, polymerization time and polymerization temperature. The plots of ln (M0/M) versus reaction time are linear, corresponding to first-order kinetics. The overall polymerization rate constant, k, was calculated as 7.9 10-5 s-1. The products were characterized by 1H-NMR and TGA. Swelling ratio values of the crosslinked products in CHCl3 were also determined Daha fazlası Daha az


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