Supramolecular Chemistry in the Formation of Self-Assembled Nanostructures from a High-Molecular-Weight Rod-Coil Block Copolymer

The self‐assembled nanostructures of a high‐molecular‐weight rod–coil block copolymer, poly(styrene‐block‐(2,5‐bis[4‐methoxyphenyl]oxycarbonyl)styrene) (PS‐b‐PMPCS), in p‐xylene are studied. The cylindrical micelles, long segmental cylindrical micelle associates, spherical micelles, and spherical micelle associates are observed with increased copolymer concentration. The high molecular weight of PS leads to the entanglement between PS chains from different micelles, which is the force for supramolecular interactions. Short cylindrical micelles are connected end‐to‐end via this supramolecular chemistry to form long segmental cylindrical micelle associates, analogue to the condensation polymerization process, with direction and saturation. On the other hand, spherical micelles assemble via supramolecular chemistry to form spherical micelle associates, yet without any direction due to their isotropic properties. The self‐assembly of a high‐molecular‐weight rod–coil copolymer, PS620‐b‐PMPCS1000, in p‐xylene is studied. The self‐assembled cylindrical micelles or spherical micelles can undergo supramolecular chemistry to form segmental cylindrical micelle associates or spherical micelles associates. The driving force for this supramolecular chemistry is the chain entanglement between the long polystyrene (PS) coils.