SET-LRP of hydrophobic and hydrophilic acrylates in trifluoroethanol

Efficient disproportionation of CuBr-Me-6-TREN in 2,2,2-trifluoroethanol (TFE) to produce "nascent" Cu(0) and CuBr2-Me-6-TREN indicates that this semifluorinated alcohol has the potential to be an excellent solvent for Cu(0) mediated single electron transfer-living radical polymerization (SET-LRP). Herein, we report the SET-LRP of a range of hydrophobic and hydrophilic acrylates, including methyl acrylate (MA), n-butyl acrylate (nBA), tert-butyl acrylate (tBA), 2-ethylhexyl acrylate (EHA) and 2-hydroxyethyl acrylate (HEA) using 2-bromopropionate (MBP) and 2-ethylbromoisopropionate (EBiB) as initiators, and Me-6-TREN as ligand in TFE. Analysis of the kinetics of polymerization and of the polymer chain ends by a combination of H-1 NMR, GPC, MALDI-TOF and chain-end functionalization by "thio-bromo" click reaction demonstrated the synthesis of perfect or near-perfect chain-end functional polyacrylates by SET-LRP in TFE.