Synthesis and Phase Behavior of a Platform of CO 2 -Soluble Functional Gradient Copolymers Bearing Metal-Complexing Units.

The synthesis and characterization of a platform of novel functional fluorinated gradient copolymers soluble in liquid and supercritical CO 2 is reported. These functional copolymers are bearing different types of complexing units (pyridine, triphenylphosphine, acetylacetate, thioacetate, and thiol) which are well-known ligands for various metals. They have been prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization in order to obtain well-defined gradient copolymers. The copolymers have been characterized by proton nuclear magnetic resonance ( 1 H-NMR) spectroscopy, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry, thermal gravimetric analysis (TGA), dynamical scanning calorimetry (DSC) and cloud point measurements in dense CO 2 . All the investigated metal-complexing copolymers are soluble in dense CO 2 under mild conditions (pressure lower than 30 MPa up to 65 °C), confirming their potential applications in processes such as metal-catalyzed reactions in dense CO 2 , metal impregnation, (e.g., preparation of supported catalysts) or metal extraction from various substrates (solid or liquid effluents). Particularly, it opens the door to greener and less energy-demanding processes for the recovery of metals from spent catalysts compared to more conventional pyro- and hydro-metallurgical methods.