The first report on phosphonate-based homopolymers combining both chelating and thermosensitive properties of gadolinium: synthesis and evaluation

Abstract

International audienc

Exploring the role of polymer hydrophobicity in polymer–metal binding thermodynamics

“…Several such approaches (e.g., polymer-enhanced ultrafiltration) use metal-chelating polymers to selectively bind and extract REEs. 3,4 Thus, quantifying metal binding thermodynamics in aqueous solution is critical, but the interactions among metal-ion, polymer, and water are complex. [5][6][7] To probe these complexities, the thermodynamics (DG, DH, and DS) of the polymer-metal interaction have been studied: Binding is entropy driven, suggesting the critical role of water in REE chelation.…”

Synthesis and self-assembly of carbamoylmethylphosphonate acrylamide-based diblock copolymers: new valuable thermosensitive materials

“…It is important to specify that the cloud point of P(CPAAm6C) prepared by free radical polymerization was 42.5 °C (M n = 31 000 g mol −1 determined by SEC in DMF + LiCl 0.1 wt%). 13 Comparable CP values were found for P(CPAAm6C)-CTA synthesized by RAFT polymerization except for the shortest polymer (M n = 3800 g mol −1 determined by SEC in DMF + LiCl 0.1 wt%) with a CP equal to 35 °C. This difference was attributed to the lauryl hydrophobic polymer chain end which had a non-negligible influence in the case of this very low molecular weight polymer, lowering the CP value.…”

“…10,12 More recently, the synthesis of homopolymers combining both chelating groups and thermosensitivity from a single original monomer, diethyl-6-(acryl-amido)hexylcarbamoylmethylphosphonate (CPAAm6C), was described. 13 The carbamoylmethylphosphonate moiety was of interest as it was proved that this functional group efficiently sorbed lanthanides, 14 especially gadolinium (Gd). 13 Polymerization of CPAAm6C was achieved by a free radical process.…”

“…13 The carbamoylmethylphosphonate moiety was of interest as it was proved that this functional group efficiently sorbed lanthanides, 14 especially gadolinium (Gd). 13 Polymerization of CPAAm6C was achieved by a free radical process. As a consequence, it was impossible to control the molecular weight and build complex architectures for the produced polymers.…”

“…Such materials could be useful owing to both their thermosensitive properties 28,29 and ability to complex gadolinium (Gd(III)). 13 We first determined the experimental conditions allowing the control of the RAFT polymerization of the diethyl-6-(acryl-amido)hexylcarbamoyl methylphosphonate (CPAAm6C) monomer. The reaction was carried out at 80 °C in DMSO using 2-cyano-2-propyl dodecyl trithiocarbonate and AIBN as the chain transfer agent (CTA) and the initiator, respectively (Scheme 1).…”