Nitroxide-Mediated Alternating Copolymerization of Vinyl Acetate with tert-Butyl-2-trifluoromethacrylate Using a SG1-Based Alkoxyamine

International audience; Unique alternating copolymers based on vinylacetate (VAc) and tert-butyl-2-trifluoromethacrylate (MAFTBE,a nonhomopolymerizable monomer under radicalconditions) have been synthesized by nitroxide-mediatedpolymerization (NMP) using a SG1-based BlocBuilderalkoxyamine (MAMA-SG1) at moderate temperature (at 40°C) in dimethyl sulfoxide. First-order kinetics and linearevolutions of the molecular weight (up to 17100 g mol−1),maintaining low dispersity values (Đ ≤ 1.33), confirmed thecontrolled nature of the copolymerization. Interestingly, noneof the starting monomers could undergo homopolymerizationunder the NMP condition initiated by MAMA-SG1. Theresulting alternating copolymers were characterized by 1H, 13C, 19F, and 31P NMR spectroscopies and size exclusionchromatography (SEC). The poly(VAc-alt-MAF-TBE) copolymer is amorphous and exhibited a single glass transitiontemperature of 59 °C. This is the first report of nitroxide-mediated (co)polymerization of VAc leading to well-definedcopolymers with satisfactory yields. The results presented in this study established a new route via NMP toward the synthesis ofstrictly 1:1 alternating fluorocopolymers that can display diverse functionalities.