A new macromonomer initiator for atom transfer radical polymerization (ATRP-MIM) based on polyethylene glycol (Mn= 660 Da) (PEG) was synthesized by the reaction of hydroxyl end of the mono-methacryloyl polyethylene glycol with 2-bromopropanoyl chloride leading to methacryloyl polyethylene glycol 2-bromopropanoyl ester (v-PEG-Br). Poly(ethylene glycol) functionalized with methacrylate at one end was reacted with 2-bromopropionyl chloride to form a macromonomeric initiator for ATRP. Self condensing ATRP-MIM polymerization yielded branched PEG with low cross-linked fraction (3-29 wt%). In the same polymerization condition, self condensing ATRP-MIM polymerization was found faster than that of conventional free radical macromonomer initiators which behave as macro crosslinker, macro initiator and macromonomer. Besides the PEG obtained has still unreacted double bonds and halides leading to the further branching. In the second step, ATRP of methyl methacrylate was initiated by the MIM-ATRP using the copper coordination complex CuBr / N,N,N',N',N'' -pentamethyl diethylenetriamine (PMDETA). The ATRP-MIM and the chloroform soluble branched polymers obtained were characterized by 1H NMR spectroscopy and gel permeation chromatography (GPC). Variation of gel polymer content, molecular weight of the soluble parts and conversion of the monomers with the changingpolymerization conditions were also discussed.
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