Synthesis of Amphiphilic Three-Armed Star Random Copolymers via Living Radical Polymerization and their Unimolecular Folding Properties in Water

Summary Amphiphilic three‐armed star random copolymers were synthesized by ruthenium‐catalyzed living radical copolymerization of hydrophilic poly(ethylene glycol) methyl ether methacrylate (PEGMA) and hydrophobic dodecyl methacrylate (DMA). Their amphiphilic star random copolymers with 10‐50 mol% DMA efficiently self‐folded in water with intramolecular hydrophobic interaction to form compact unimolecular micelles. Owing to PEG segments, star copolymers were thermoresponsive to induce lower critical solution temperature‐type phase separation in water.