Rapidly self-deoxygenating controlled radical polymerization in water via in situ disproportionation of Cu(i)

Abstract

The rapidly self-deoxygenating Cu-RDRP in aqueous media is investigated.

Fully oxygen-tolerant atom transfer radical polymerization triggered by sodium pyruvate

“…However, the use of high copper concentration (2000-8000 ppm relative to NIPAM) was necessary to attain high monomer conversions and low dispersity values. 73 Herein, we demonstrate the rst fully oxygen tolerant, photoinduced ICAR ATRP of NIPAM with ppm level of Cu catalyst in water, enabling a quantitative conversion of the monomer in less than 30 min. This simplied, non-enzymatic ATRP system uses sodium pyruvate as both a hydrogen peroxide scavenger and a "fuel" for the continuous regeneration of the catalyst and can be easily transferred to organic solvents.…”

Well-defined polyacrylamides with AIE properties via rapid Cu-mediated living radical polymerization in aqueous solution: thermoresponsive nanoparticles for bioimaging

“…The Haddleton group introduced a novel synthetic route to perform aqueous copper-mediated RDRP via the in situ formation of Cu containing catalysts exploiting the rapid disproportionation (<10 seconds) as an advantageous driving force. [32][33][34] ATRP in water has often been described as being problematic with a Cu/tris(2-pyridylmethyl)amine (TPMA) complex being described as being the best and most versatile catalyst to employ in water 35 even though the quite popular Me 6 Tren has been shown to be efficient. [32][33][34] This rapid rate of polymerization requires a high radical concentration at any moment in time, however, the excellent control we were seeking is often thought to require a low concentration of radicals, which is somewhat contradictory.…”

Aqueous copper-mediated reversible deactivation radical polymerization (RDRP) utilizing polyetheramine derived initiators

“…This is due to the fact that Cu-RDRP has been considered as one of the most robust strategies due to successful implementation under various conditions (e.g. in the presence of oxygen/air, [13][14][15] in various reaction media [16][17][18] ) and also due to the wide of range of materials that can be synthesized (i.e. polyacrylates, polymethacrylates, polystyrene, polyacrylamides) with excellent control over their (macro)molecular characteristics.…”

“…One of the main advantages of Cu-RDRP is its successful implementation in aqueous media, with excellent control over the macromolecular characteristics of the synthesized polymers. 15,18,19,21,30,31 In the presence of multidentate aliphatic amine ligands (e.g. tris [2-(dimethylamino)ethyl]amine, Me 6 TREN) and in aqueous media, Cu(I) is highly unstable towards rapid disproportionation, leading to Cu(II) and nascent, highly active Cu(0).…”