Ruiu Andrea, Bouilhac Cécile, Gimello Olinda, Seaudeau-Pirouley Karine, Senila Marin, Jänisch Thorsten, Lacroix-Desmazes Patrick
ICGM, Univ. Montpellier, CNRS, ENSCM, 34293 Montpellier, France.
Innovation Fluides Supercritiques, Batiment INEED, 26300 Alixan, France.
Polymers (Basel). 2022 Jun 30;14(13):2698. doi: 10.3390/polym14132698.
The synthesis and characterization of a platform of novel functional fluorinated gradient copolymers soluble in liquid and supercritical CO 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 (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. All the investigated metal-complexing copolymers are soluble in dense CO 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, 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.
报道了一种可溶于液体和超临界CO的新型功能性氟化梯度共聚物平台的合成与表征。这些功能性共聚物带有不同类型的络合单元（吡啶、三苯基膦、乙酰丙酮、硫代乙酸酯和硫醇），它们是各种金属的著名配体。它们通过可逆加成-断裂链转移（RAFT）聚合制备，以获得结构明确的梯度共聚物。通过质子核磁共振（H-NMR）光谱、基质辅助激光解吸/电离飞行时间（MALDI-TOF）质谱、热重分析（TGA）、动态扫描量热法（DSC）以及在致密CO中的浊点测量对共聚物进行了表征。所有研究的金属络合共聚物在温和条件下（压力低于30 MPa，温度高达65°C）可溶于致密CO，证实了它们在诸如致密CO中的金属催化反应、金属浸渍（例如负载型催化剂的制备）或从各种底物（固体或液体流出物）中提取金属等过程中的潜在应用。特别是，与更传统的火法和湿法冶金方法相比，它为从废催化剂中回收金属开辟了更绿色、能耗更低的工艺途径。
