Acetone–water biphasic mixtures as solvents for ultrafast SET-LRP of hydrophobic acrylates

Abstract

Transformation of SET-LRP catalyzed with Cu(0) wire from single phase (acetone/water = 9/1, v/v) into biphase (acetone/water = 8/2, v/v).

Ultra-low volume oxygen tolerant photoinduced Cu-RDRP

“…b Determined by THF SEC analysis and expressed as molecular weight equivalents to PMMA narrow molecular weight standards. Owing to the diverse properties of hydrophobic [54][55][56][57] and semi-fluorinated 58,59 materials we were then interested in polymerizing tert-butyl (t-BA), hexyl (HA, C6), lauryl (LA, C12) and trifluoroethyl (meth)acrylates (TFEA and TFEMA). However, DMSO has been reported as an unsuitable solvent leading to insoluble final polymeric materials and subsequent loss of control.…”

SET-LRP in biphasic mixtures of fluorinated alcohols with water

“…16,[32][33][34] Our laboratory recently developed a library of "programmed" multiphasic SET-LRP systems based on mixtures of organic solvents with water. [35][36][37][38][39][40][41] Previous experiments that inspired this concept will be discussed in a later subchapter. This approach relies on the unexpected immiscibility between a solution of water containing Cu(II)Br 2 and a ligand with organic solvents, including water miscible organic solvents, containing a monomer and a polymer.…”

“…To support this statement, we reported relevant examples of SET-LRP synthesis of hydrophobic polymers in biphasic aqueous mixtures of non-polar and polar-non-disproportionation solvents. [35][36][37][38] This approach can also be applied to solvents with good disproportionation capabilities such as alcohols as well as dipolar aprotic solvents (i.e. DMSO, sulfolane, NMP, DMAC and DMF).…”

Facile preparation of superhydrophobic and oleophobic surfaces via the combination of Cu(0)‐mediated reversible‐deactivation radical polymerization and click chemistry

“…Since the disproportionation of Cu(I) is the crucial step of SET‐LRP, the solvent dependency of this process is a limitation of the technique. However, the development of multiphase SET‐LRP has expanded the solvent classes that can be used, including less disproportionating solvents, such as acetonitrile and acetone, and even the mixture of ethanol and water with non‐disproportionating solvents, such as hexanes, cyclohexane, ethyl acetate, diethyl carbonate, toluene, and anisole . These improvements together with the intrinsic advantages of the Cu(0)‐mediated RDRP process, such as high reaction rates, tolerance to air, impurities, and radical inhibitors, and near perfect chain‐end fidelity, make it a method of choice for performing surface initiated RDRP reactions …”