Self-assembly of hydrophobic–amphiphilic diblock copolymers in solution

Abstract

Thermoresponsive polymers are usually characterized by a locally amphiphilic chain structure and their self-assembly in solution is controlled, in particular, by the surface activity of the monomer units or side chains. We theoretically study the condensed state of a single diblock copolymer molecule consisting of a hydrophobic block and amphiphilic block with hydrophobic groups in the backbone and pendant polar groups. The equilibrium parameters of the polymer globules of different shapes are determined using the mean-field approach to determine the most favorable structure. Morphological diagrams of condensed macromolecules are presented depending on the chain length, amphiphilic block fraction, interaction parameters, and pendant volume and length. The diagrams are compared with those of a copolymer molecule with the same fraction of amphiphilic monomer units which are regularly distributed along the chain. The diblock copolymer molecule is found to form a single spherical or flattened particle, with the core from the hydrophobic block, or a granular micelle consisting of spherical or nearly spherical particles, in agreement with the experimental data in the literature. The optimal chain parameters for self-assembly into a stable single core–shell particle are predicted.