Self-Assembly of amphiphilic polymers in water is promising to create precise yet dynamic micelles, hydrogels, and nanostructured materials. Recently, we have developed self-assembly systems of amphiphilic random or alternating copolymers carrying hydrophilic groups and hydrophobic groups as side chains in water or bulk/film state.

In this paper, we report recent advances on the self-assembly of amphiphilic random/alternating copolymers as new strategies to create controlled aggregates and soft materials as follows:

• Precision self-assembly into micelles in water

Typically, amphiphilic random copolymers bearing poly(ethylene glycol) (PEG) and alkyl groups self-fold and/or intermolecularly assembled via the association of the hydrophobic groups into unimer or multichain micelles in water. The random copolymer micelles are approximately 10 nm and smaller than general block copolymer micelles. The size and aggregation number of the micelles can be controlled by the composition, degree of polymerization, and side chains. 

(2) Dynamic self-sorting micelles and hydrogels. Binary mixtures of different random copolymers form discrete multichain micelles via the self-sorting of their polymer chains or fused micelles via the co-self-assembly of the polymers. Those micelles further induce dynamic yet selective exchange of the polymer chains. Self-healing and selectively adhesive hydrogels can be prepared using such dynamic random copolymer micelles as physical crosslinking units.

(3) Microphase separation into nanostructured materials. Amphiphilic random copolymers further induce pendant microphase separation into nanostructured materials/films.