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Updated: Sep 22, 2025

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Nitroxide-Mediated Alternating Copolymerization of Vinyl Acetate with tert-Butyl-2-trifluoromethacrylate Using a
Sanjib Banerjee1, Ilaria Domenichelli2,3, Bruno Ameduri1
1Ingénierie et Architectures Macromoléculaires, Institut Charles Gerhardt, UMR 5253 CNRS, UM, ENSCM, Place Eugéne Bataillon, 34095 Montpellier Cedex 5, France.
Abstract:
Unique alternating copolymers based on vinyl acetate (VAc) and tert-butyl-2-trifluoromethacrylate (MAF-TBE, a nonhomopolymerizable monomer under radical conditions) have been synthesized by nitroxide-mediated polymerization (NMP) using a SG1-based BlocBuilder alkoxyamine (MAMA-SG1) at moderate temperature (at 40 °C) in dimethyl sulfoxide. First-order kinetics and linear evolutions of the molecular weight (up to 17100 g mol-1), maintaining low dispersity values (Đ ≤ 1.33), confirmed the controlled nature of the copolymerization. Interestingly, none of the starting monomers could undergo homopolymerization under the NMP condition initiated by MAMA-SG1. The resulting alternating copolymers were characterized by 1H, 13C, 19F, and 31P NMR spectroscopies and size exclusion chromatography (SEC). The poly(VAc-alt-MAF-TBE) copolymer is amorphous and exhibited a single glass transition temperature of 59 °C. This is the first report of nitroxide-mediated (co)polymerization of VAc leading to well-defined copolymers with satisfactory yields. The results presented in this study established a new route via NMP toward the synthesis of strictly 1:1 alternating fluorocopolymers that can display diverse functionalities.
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