Post-polymerization modification (PPM) through the para -fluoro-thiol reaction (PFTR) represents a powerful strategy for the selective functionalization of electron-deficient aromatic polymers. Herein, we report the synthesis of poly(pentafluorophenyl acrylamide) (pPFPAA), an acrylamide-based reactive polymer, via both free radical polymerization and reversible addition–fragmentation chain transfer (RAFT) polymerization, which offers the possibility for a PPM by the PFTR. The kinetics of RAFT polymerization of PFPAA was investigated and the process afforded well-defined polymers with controlled molar masses ( M n = 25–70 kg mol –1 ) and narrow dispersities ( Đ < 1.2). The resulting pPFPAA exhibited a high glass transition temperature ( T g = 155 °C), hydrolytic stability, and solubility in common organic solvents. Quantitative para -fluoro substitution was achieved with five primary thiols under mild conditions at room temperature within 1 h, without detectable side reactions. The versatility of pPFPAA toward PPM enabled dual-sequence modification when employed in the synthesis of block copolymers with poly(pentafluorophenyl acrylate) (pPFPA) known for its functionalization via amidation, thereby providing orthogonal functionalization pathways. The physicochemical properties of the synthesized polymers were characterized by FT-IR and 1 H, 13 C, and 19 F NMR spectroscopy, as well as gel permeation chromatography (GPC), confirming successful modification and stability of the polymer backbone. Thermal analysis of the polymers before and after PPM by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) revealed changes in the thermal properties depending on the structure of the thiol employed in the PFTR. This work introduces pPFPAA as a versatile platform for selective PPM via the PFTR. Beyond expanding the scope of para -fluoro-thiol chemistry, pPFPAA serves as a new synthetic tool to enrich the library of multifunctional polymers, opening pathways toward precision material design and advanced macromolecular architectures.
Орлова et al. (Fri,) studied this question.