Accelerated Ambient‐Temperature ATRP of Methyl Acrylate in Alcohol–Water Solutions with a Mixed Transition‐Metal Catalyst System

Abstract

The current trend in developing next‐generation LRP systems and in particular ATRP involves reduction, elimination, and/or replacement of toxic and highly expensive catalysts and solvents with environmently friendly ones. Here, the unexpected, accelerated, ambient‐temperature ATRP of methyl acrylate catalyzed by a Fe(0)/CuBr2/Me6TREN system in a mixture of water and inexpensive and environmentally more friendly alcohols (methanol, ethanol, and 1‐propanol) is reported. The data presented open up the possibility of using fast ATRP catalyzed by a mixed transition‐metal catalyst system in solvents that are inexpensive, eco‐friendly, and have low boiling points.

Cyclopentyl methyl ether: A new green co‐solvent for supplemental activator and reducing agent atom transfer radical polymerization

“…(b) with Supporting Information Fig. SF(b)], as it was observed for other water‐containing solvent mixtures used in SARA ATRP . The structure of the well‐defined Br‐terminated PMA was confirmed by 1 H NMR spectroscopy (Fig.…”

“…There are several reports on the controlled polymerization of MA (used as model monomer) . In this study, the SARA ATRP of MA was first investigated using the catalytic system Cu(0)/CuBr 2 /Me 6 TREN .…”

“…SF), proving the usefulness of the CPME as a green co‐solvent for the SARA ATRP of MA. Aiming to achieve a complete harmless reaction solvent mixture, DMSO was replaced by the EtOH, which has also been used for the SARA ATRP of different monomers . In this case, the addition of a small amount of water was also required to allow a complete dissolution of the catalytic complex.…”

“…Supplemental activator and reducing agent (SARA) ATRP is one of the most recent developed ATRP variations and it is considered to be a very attractive technique since it allows the use of a low concentration of soluble catalyst (e.g., 100 ppm). With this approach, zero valent metals or Food and Drug Administration (FDA)‐approved inorganic sulfites have been successfully used as SARA agents. The role of these species is to continuously regenerate the activator (e.g., CuX; X: halide) by deactivator reduction (e.g., CuX 2 ) and to slowly generate growing radicals by supplemental activation (Scheme ) …”

“…This strategy aims to potentiate the implementation of ATRP at an industrial scale, as well as to provide harmless reaction conditions for the preparation of polymers for the biomedical field. On this matter, it is worth to notice that the SARA ATRP of acrylates, methacrylates, and acrylamides has also been successfully performed in alcohol/water mixtures or even in aqueous medium …”