SET-LRP of acrylates catalyzed by a 1 penny copper coin

Abstract

Controlled polymerization of acrylates can be catalyzed by one of the cheapest catalysts, a 1 pence coin.

Cu(0)-RDRP of styrene: balancing initiator efficiency and dispersity

“…[12][13][14][15][16][17][18][19][20] Among these techniques, Cu(0)-wire RDRP 21 (single electron transfer living radical polymerisation (SET LRP) 22 or supplemental activator and reducing agent (SARA) ATRP) 23 has attracted considerable attention as a versatile and robust methodology demonstrating broad monomer scope, yielding polymers with high end group fidelity even at near-quantitative conversions. 24,25 Perhaps the most significant advantage of Cu(0)-RDRP is its simplicity 26 as the reactions can often be carried out in a disposable vial (rather than Schlenk tubes) with simple deoxygenation via nitrogen bubbling for a few minutes being sufficient for a controlled polymerisation, rather than time-consuming freeze-pump-thaw cycles. In addition, the majority of the Cu(0)-wire catalyst can be removed post-polymerisation by simply removing the wire and stirrer it is wrapped around.…”

“…This results in a polymerisation product mixture with only ppm concentrations of copper, which can subsequently be simply removed, circumventing the perceived issues of product metal contamination and any associated residual colour. 27,28 To date, Cu(0)-RDRP has been extensively explored for the synthesis of poly(acrylates) demonstrating an impressive monomer scope, initiator, ligand and solvent choice. 21 Importantly, polyacrylates can be easily prepared over a wide range of molecular weights and architectures which is exemplified by the synthesis of high-ordered complex materials.…”

Transformation of Thioester‐Initiated Star Polymers into Linear Arms via Native Chemical Ligation

“…Complimentarily, amide‐based initiators such as 2‐chloropropionamide or 2‐bromo‐2‐N‐phenyl‐propionamide can also be applied as initiators for Cu‐mediated polymerization techniques . Last but not the least, multifunctional initiators based on these structural varieties have also been widely reported in the literature, and the search for functional initiator structures is still going on, as they allow the preparation of functional polymers with high chain end fidelity …”

“…[14,15] Last but not the least, multifunctional initiators based on these structural varieties have also been widely reported in the literature, and the search for functional initiator structures is still going on, as they allow the preparation of functional polymers with high chain end fidelity. [16,17] Although there are investigations looking into activation rate constants (k act ) of initiators with different halogens and substituents, no evaluation of the "neighboring group effect" (the effect of X group in Scheme 1) has been reported, yet. [18,19] Here, a comparison of ester, thioester, and an amide initiator is made for the first time to investigate their polymerization behavior.…”

A versatile and rapid coating method via a combination of plasma polymerization and surface‐initiated SET‐LRP for the fabrication of low‐fouling surfaces

“…Cu(0)‐mediated living radical polymerization (LRP), which is known as single electron transfer living radical polymerization (SET‐LRP) has drawn attention due to its fast reaction rate and high tolerance to atmospheric oxygen . Conventionally, the reaction is carried out using copper wire (Cu(0)) or powder as the catalyst, generating in situ Cu(I) which instantaneously disproportionates into highly active “nascent” Cu(0) and Cu(II) . The nascent Cu(0) activates alkyl halides through a fast outer sphere electron transfer while the Cu(II) deactivates the propagating radical to provide control over the polymerization .…”