Synthesis and characterization of fluorinated ionizable copolymers by controlled radical polymerization as precursors for advanced hydrogel materials

Functional polymeric materials with tailored chemical properties are increasingly relevant for environmental applications, particularly in the development of platforms capable of interacting with emerging organic contaminants. In this work, we report the synthesis and characterization of fluorinated ionizable copolymers designed as versatile precursors for the fabrication of advanced hydrogel-based materials. Copolymers based on tert-butyl acrylate (tBA) and 2,2,2-trifluoroethyl methacrylate (TFEMA) were synthesized through copper-mediated reversible deactivation radical polymerization (Cu(0)-RDRP). This strategy enables control over polymer composition while incorporating fluorinated segments with potential affinity toward hydrophobic molecules and protected acrylic functionalities suitable for post-polymerization modification. The obtained poly(tert-butyl acrylate-co-fluorinated methacrylate) materials were subsequently converted into poly(acrylic acid-co-fluorinated methacrylate) derivatives through acid-mediated hydrolysis of tert-butyl ester groups. The influence of polymerization conditions and monomer composition on molecular characteristics and chemical structure was evaluated by proton nuclear magnetic resonance spectroscopy (¹H NMR), Fourier transform infrared spectroscopy (FTIR), and size exclusion chromatography (SEC). The successful conversion of tert-butyl ester functionalities into carboxylic acid groups was assessed through spectroscopic analysis. Thermal properties and material behavior were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), while preliminary water interaction properties were evaluated through swelling and solubility studies. The resulting fluorinated ionizable copolymers constitute a modular platform for subsequent processing into porous hydrogel architectures using physical templating and radiation-induced crosslinking approaches. This work represents an initial step toward the development of tailored polymeric materials combining controlled synthesis, chemical functionality, and processability for future water remediation applications.