Copper(0)‐mediated living radical polymerization of acrylonitrile: SET‐LRP or AGET‐ATRP

Abstract

Cu(0)‐mediated living radical polymerization was first extended to acrylonitrile (AN) to synthesize polyacrylonitrile with a high molecular weight and a low polydispersity index. This was achieved by using Cu(0)/hexamethylated tris(2‐aminoethyl)amine (Me6‐TREN) as the catalyst, 2‐bromopropionitrile as the initiator, and dimethyl sulfoxide (DMSO) as the solvent. The reaction was performed under mild reaction conditions at ambient temperature and thus biradical termination reaction was low. The rapid and extensive disproportionation of Cu(I)Br/Me6‐TREN in DMSO/AN supports a mechanism consistent with a single electron transfer‐living radical polymerization (SET‐LRP) rather than activators generated by electron transfer atom transfer radical polymerization (AGET ATRP). 1H NMR analysis and chain extension experiment confirm the high chain‐end functionality of the resultant polymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

“Nascent” Cu(0) nanoparticles‐mediated single electron transfer living radical polymerization of acrylonitrile at ambient temperature

“…As noted previously, a variety of nitrogen‐based ligands, including N,N,N',N',N' ‐pentamethyldiethylenetriamine (PMDETA), tris[2‐(dimethylamino)‐ethyl] amine (Me 6 TREN), and bpy have been successfully employed for copper‐mediated LRP of AN 58–62. The choose of an appropriate ligand significantly affected Zn(0)‐ppm concentrations of Cu(II) mediated‐radical polymerization of AN at ambient temperature.…”

Activation of alkyl halides at the Cu0 surface in SARA ATRP: An assessment of reaction order and surface mechanisms

“…Since the use of Cu 0 in ATRP was first demonstrated in 1997, great developments have been made with regards to reaction scope and mechanistic understanding. It has successfully been utilized in the polymerization of acrylates, methacrylates, styrenes, acrylonitrile, and acrylamides with varying macromolecular architectures . This widespread control has been achievable in a broad range of reaction media including both aqueous and organic solvents …”

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)...…”