Intramolecular Folding or Intermolecular Self-Assembly of Amphiphilic Random Copolymers: On-Demand Control by Pendant Design

Amphiphilic random copolymers comprising different hydrophilic poly­(ethylene glycol) (PEG, average number of oxyethylene units = 4.5 or 8.5) and hydrophobic butyl or dodecyl pendants were designed to investigate self-folding and self-assembly behavior in water. The copolymers with controlled composition and chain length were synthesized by ruthenium-catalyzed living radical copolymerization. We revealed that the pendant design was one of the most critical factors to selectively induce intramolecular self-folding or intermolecular self-assembly. In the case of 30 mol % hydrophobic monomers, random copolymers bearing short PEG (on average 4.5 oxyethylene units) and butyl pendants intramolecularly self-folded into unimer micelles in water, independent of chain length. The size of unimer micelles thus increased with increasing chain length. In contrast, random copolymers bearing long dodecyl pendants intermolecularly self-assembled into uniform multichain micelles; the size depended on composition and PEG length. Additionally, the polymer micelles showed thermoresponsive solubility in water. The cloud point temperature was effectively controlled by the pendant structure, composition, and chain length