Effect of Copolymer Structure on Rare-Earth-Element Chelation Thermodynamics

Rare-earth elements (REEs) are crucial to modern technology, leading to a high demand for materials capable of REE extraction and purification. Metal-chelating polymers (e.g., polycarboxylic acids, polyamines, and others) are particularly useful in these applications due to their synthetic accessibility and high selectivity. Copolymers with varied mole fractions of acrylic acid and methyl acrylate are synthesized and isothermal titration calorimetry (ITC) to measure the thermodynamics of REE binding for each material is used. Across a series of copolymer compositions, entropically driven binding thermodynamics (∆G, ∆H, and ∆S) that appear to be independent of χ_{Acrylic Acid} are found. ITC stoichiometry data reveal that each copolymer requires between four and five repeat units to bind each REE. These data suggest that alterations in the copolymer structure do not affect the overall binding thermodynamics of REEs to these copolymers.