SET-LRP in Biphasic Mixtures of the Nondisproportionating Solvent Hexafluoroisopropanol with Water

The fluorinated alcohol 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) is an especially effective solvent for solubilizing a wide range of polymers. However, the performance of HFIP as SET-LRP solvent has classically been questioned due to its poor Cu(I)X disproportionating properties. Taking advantage of the fast and quantitative disproportionation of Cu(I)X in water, SET-LRP in organic solvent/water mixtures rids the organic solvent of mediating this fundamental event. Here, the Cu(0) wire-catalyzed SET-LRP synthesis of well-defined poly(methyl acrylate)s and poly(butyl acrylate)s with narrow molecular weight distribution and near perfect bromine chain end functionality is reported in HFIP/water mixtures. The results reported here support the potential of HFIP/water mixtures in the preparation of more complex architectures including polymers with dual control over molecular weight and tacticity. Since HFIP is also a classic solvent for the denaturation of proteins this SET-LRP system is also expected to find applications in the grafting of protein.