A multiphase SET-LRP system using the in situ generated Cu(0) by reduction of Cu(ii)Br2 with NaBH4 in various alcohols containing water was developed and used for SET-LRP of hydrophobic acrylates. From left to right: a solution of methanol/water containing Cu(ii)Br2, the same solution after addition of BA and its SET-LRP.

The two kinetic regime, low conversion and low chain end functionality seen in copper catalyzed polymerization of acrylates in acetonitrile was transformed into a SET-LRP kinetic, to complete conversion and quantitative chain end functionality in a biphasic mixture containing 10% water.