Synthesis of ABC and CABAC Triphilic Block Copolymers by ATRP Combined with 'Click' Chemistry

ATRP using poly(propylene oxide) monofunctional macroinitiator was carried out with solketal methacrylate (SMA) and the non‐reactive PPO having two N3 terminal groups was removed by dissolution in an excess of n‐hexane. The resulting azido terminated AB diblock copolymer was ‘clicked’ with an α‐alkyne fluorinated compound, followed by acid hydrolysis of the SMA units, a triphilic ABC triblock copolymer was prepared. ATRP of SMA with a difunctional PPO macroinitiator to give ABA triblock copolymer was also carried out. The terminal Br was again exchanged with N3, ‘clicked’ with the α‐alkyne fluorinated compound and likewise hydrolyzed to give a triphilic CABAC pentablock copolymer, i.e., hydrophilic, oleophilic, and fluorophilic blocks were combined.