Absolut “copper catalyzation perfected”; robust living polymerization of NIPAM: Guinness is good for SET-LRP

Abstract

The controlled polymerization of N-isopropyl acrylamide (NIPAM) is reported in a range of international beers, wine, ciders and spirits utilizing Cu(0)-mediated living radical polymerization (SET-LRP). Highly active Cu(0) is first formed in situ by the rapid disproportionation of [Cu(I)(Me 6-Tren)Br] in the commercial water-alcohol mixtures. Rapid, yet highly controlled, radical polymerization follows (Đ values as low as 1.05) despite the numerous chemicals of diverse functionality present in these solvents e.g. alpha acids, sugars, phenols, terpenoids, flavonoids, tannins, metallo-complexes, anethole etc. The results herein demonstrate the robust nature of the aqueous SET-LRP protocol, underlining its ability to operate efficiently in a wide range of complex chemical environments.

Aqueous SET-LRP catalyzed with “in situ” generated Cu(0) demonstrates surface mediated activation and bimolecular termination

“…3 Subsequently, SET-LRP was expanded to acrylates, [4][5][6][7][8][9][10][11][12][13][14][15][16][17] methacrylates, 8,[18][19][20][21][22][23][24][25] acrylamides, [26][27][28][29][30][31] methacrylamide, 32 acrylonitrile, 33,34 and monomers containing more complex water soluble side groups, such as sugars, 35,36 N-(2-hydroxypropyl) methacrylamide, 32 dimethylacrylamide, 26 N-isopropylacrylamide, 26,[37][38][39] oligo(ethylene oxide) methyl ether acrylate, 40 oligo(ethylene oxide) methyl ether methacrylate, 41 hydroxyethyl acrylate, 10 hydroxyethyl methacrylate 23 and acryloyl morpholine. 42 At the same time as these developments, the list of solvents used in SET-LRP was expanded to other solvents that in combination with aliphatic N-donor ligands, such as tris[(2-dimethylaminoethyl)...…”

Além da caipirinha: cachaça como solvente para síntese orgânica e extração de pigmento

“…Por outro lado, diversas bebidas alcoólicas foram empregadas como solventes alternativos em pesquisa química, como na reação de polimerização controlada da N-isopropil-acrilamida (Figura 1), 25 e como solventes em cromatografia em fase líquida de alta eficiência. 26 Nesse último caso, a cachaça aparece entre as bebidas investigadas como solvente cromatográfico.…”

Polymerisation of 2-acrylamido-2-methylpropane sulfonic acid sodium salt (NaAMPS) and acryloyl phosphatidylcholine (APC) via aqueous Cu(0)-mediated radical polymerisation

“…Primarily, the polymerisation has been shown to be tolerant of complex aqueous mixtures, 33,34 whilst ongoing work includes investigations into monomer compatibility as well as the degree of functionality present in the initiating species. To this end, functional initiators have been employed for the preparation of α-functional and α,ω-telechelic linear polymers capable of undergoing further chemistry at their chain terminii, such as conjugation to peptides and the introduction of hydrophobic moieties.…”