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Highly Active Bipyridine-Based Ligands for Atom Transfer Radical Polymerization
Journal article

Highly Active Bipyridine-Based Ligands for Atom Transfer Radical Polymerization

Andrew J. D. Magenau, Yungwan Kwak, Kristin Schroeder and Krzysztof Matyjaszewski
ACS macro letters, v 1(4), pp 508-512
17 Apr 2012
PMID: 35585751

Abstract

Physical Sciences Polymer Science Science & Technology
A series of 2,2'-bipyridines with 4,4'-substituents (R-bpy) were investigated for atom transfer radical polymerization (ATRP) of methyl acrylate (MA) and methyl methacrylate (MMA). Ligand substituents with a large range of Hammett parameters (R = Cl, H, Me, dinonyl (dN), MeO, and (Me)(2)N) were studied with cyclic voltammetry (CV), revealing that increasing the strength of electron donating groups (EDGs) resulted in more stable Cu-II complexes and larger ATRP equilibrium constants. Normal ATRP experiments confirmed the obtained CV data by showing the fastest rates of polymerization with R-bpy ligands containing EDGs ((Me)(2)N and MeO) and the slowest with electron withdrawing Cl. A 400-fold increase in the polymerization rate was observed with bpy ligands containing p-(Me)(2)N compared to H substituents. Linear increases in molecular weight with monomer conversion, and narrow molecular weight distributions were obtained with (Me)(2)N-bpy and MeO-bpy ligands. Low catalyst concentrations of 50 to 100 parts-per-million (ppm) were successfully employed with highly active R-bpy ligands (R = MeO and (Me)(2)N) and found to be effective in polymerizing MA and MMA, respectively, with narrow molecular weight distributions <1.3.

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Polymer Science
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