The synergistic effect during biphasic SET-LRP in ethanol–nonpolar solvent–water mixtures

Abstract

Adding a nonpolar solvent to ethanol–water reaction mixtures transforms SET-LRP of BA from triphasic to biphasic exhibiting a synergistic effect.

SET-LRP in biphasic mixtures of fluorinated alcohols with water

“…42,43 SET-LRP of MA catalyzed by non-activated Cu(0) wire/Me 6 -TREN in TFE/water and TFP/water mixtures Previously, we reported the SET-LRP of MA and BA, using Cu(0) generated in situ by the reduction of Cu(II)Br 2 with NaBH 4 , in "programmed" bi(multi)phasic alcohol/water mixtures. 35,41 The selection of an alcohol solvent was determinant for the evolution of the SET-LRP reaction mixture. Whereas systems based on higher alcohols remained biphasic up to complete conversion, compositions based on methanol and ethanol transitioned, above a certain conversion and molecular weight, to a triphasic system.…”

“…These results support the tolerance of this biphasic system to a large excess of Cu(0) in the form of wire. The tolerance of these "interfacial" or "on water" SET-LRP processes [35][36][37][38][39][40][41] to high externally added Cu(II)Br 2 deactivator loadings was investigated by increasing the amount of Cu(II)Br 2 relative to the initiator from 5% to 10% and to 20% while maintaining a constant ratio [TREN] 0 /[CuBr 2 ] 0 = 2/1. As can be seen in Fig.…”

“…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 …”