SET-LRP of hydrophobic and hydrophilic acrylates in tetrafluoropropanol

Self-regulated disproportionation of in situ generated Cu(i)X in the presence of the N-containing ligand Me₆-TREN to produce the "nascent" Cu(0) activator together with CuX₂/L deactivator and the ability to solubilize various hydrophobic and hydrophilic monomers as well as the resulting polymers in 2,2,3,3-tetrafluoropropanol (TFP) make it an excellent solvent for hydrazine-activated Cu(0) wire mediated single electron transfer-living radical polymerization (SET-LRP). The results reported here demonstrate that SET-LRP conducted in TFP results in well-defined polymers with narrow molecular weight distribution from a large diversity of acrylates containing hydrophobic and hydrophilic substituents, including methyl acrylate (MA), n-butyl acrylate (nBA), tert-butyl acrylate (tBA) with methyl 2-bromopropionate (MBP) as initiator, and 2-hydroxyethyl acrylate (HEA) with 2-ethylbromoisopropionate (EBiB) as initiator.