Bis(formylphenolato)cobalt(II)-Mediated Alternating Radical Copolymerization of tert-Butyl 2-Trifluoromethylacrylate with Vinyl Acetate

The organometallic-mediated radical polymerization (OMRP) of vinyl acetate (VAc) and its OMR copolymerization (OMRcoP) with tert-butyl 2-trifluoromethylacrylate (MAF-TBE) mediated by Co(SAL)(2) (SAL = 2-formylphenolato or deprotonated salicylaldehyde) produced relatively well-defined PVAc and poly(VAc-alt-MAF-TBE) copolymers at moderate temperature (<40 degrees C) in bulk. The resulting alternating copolymer was characterized by H-1-, C-13- and F-19-nuclear magnetic resonance (NMR) spectroscopies, and by size exclusion chromatography. The linear first-order kinetic plot, the linear evolutions of the molar mass with total monomer conversion, and the relatively low dispersity (D similar to 1.55) of the resulting copolymers suggest that this cobalt complex provides some degree of control over the copolymerization of VAc and MAF-TBE. Compared to the previously investigated cobalt complex OMRP mediators having a fully oxygen-based first coordination sphere, this study emphasizes a few peculiarities of Co(SAL)(2): a lower ability to trap radical chains as compared to Co(acac)(2) and the absence of catalytic chain transfer reactions, which dominates polymerizations carried in the presence of 9-oxyphenalenone cobalt derivative.