Synthesis: Amphiphilic Random Copolymer Micelles: Design, Self‐Assembly, and Functional Materials

Herein, we report the design, self-assembly, and functional materials of amphiphilic random copolymer micelles bearing hydrophilic poly(ethylene glycol) chains or ionic groups and hydrophobic alkyl or related groups. The random copolymers induce self-folding or intermolecular self-assembly in water via the association of the hydrophobic side chains to form small micelles, where the size, aggregation number, chain exchange behavior, and cloud point temperature can be controlled by the primary structures, such as composition, chain length, and side chain/main chain structures. This chapter is especially focused on the following topics: (1) Precision self-assembly of PEG/alkyl-bearing random copolymers into unimer or multichain micelles and related aggregates in water; (2) dynamic self-sorting or switchable co-self-assembly of the binary random copolymer mixtures into discrete or fused micelles; and (3) design of functional materials, including thermoresponsive micelles and gels, self-healing/selectively adhesive hydrogels, polymer catalysts, and protein conjugation or encapsulation materials.