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Mechanistic study of Atom Transfer Radical Polymerization in the Presence of an Inimer: Toward Highly Branched Controlled Macromolecular Architectures through One-Pot Reaction

Highly branched polymethacrylates have recently offered new perspectives in lithographic performance and drug delivery. The control of branching remains yet challenging and requires fundamental investigation to consider new applications. Therefore, an advanced study of the formation mechanism of branched polymers synthesized by self-condensing vinyl copolymerization (SCVCP) of a methacrylic AB* inimer, 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM), with methyl methacrylate (MMA) via atom transfer radical polymerization (ATRP) has been performed. Evidence of branched structures was obtained with a conventional GPC apparatus equipped with a multiangle light scattering detector and detailed 1H NMR analyses. A three-step reaction scheme is suggested according to the dependence of molecular weight with conversion. Controlled radical polymerization mainly occurs until moderate conversions, with the participation of inimer as chain initiator. Then the polymerization of small macromolecules, through consumpti...

Authors:   Florence Bally; Esma Ismailova; Cyril Brochon; Christophe A. Serra; Georges Hadziioannou
Journal:   Macromolecules
Year:   2011
DOI:   10.1021/ma2011443
Publication date:   24-Aug-2011
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