SELF-ASSEMBLY BEHAVIOR OF SUPRAMOLECULAR DIBLOCK COPOLYMER/HOMOPOLYMER MIXTURES WITH NON-COVALENT BONDING INTERACTIONS IN SELECTIVE SOLVENTS

Self-assembly of supramolecular AB diblock copolymer/C homopolymer mixtures in selective solvents was examined by real-space self-consistent field theory. The non-covalent bond is formed between the free end of hydrophobic B block of amphiphilic AB diblock copolymer and one end of hydrophobic C homopolymer,, and thereby the mixtures consist of unbonded AB diblock copolymers, unbonded C homopolymers and supramolecular ABC triblock copolymers. The constitutions of the mixtures are dependent on the non-covalent bonding strength and the initial AB/C mixing ratio, which are essential to the morphologies of the self-assembled micelles. The AB diblock copolymer/C homopolymer mixtures are self-assembled into a variety of micelles such as core-shell-corona micelles and wormlike micelles in selective solvents. With increasing the bonding strength, the volume fraction of supramolecular ABC triblock copolymers increases, and that of unbonded AB diblock copolymers and C homopolymers decreases. In this process, transitions from core-shell-corona micelles to wormlike micelles were observed. In the core-shell-corona micelles, the bonded C homopolymers are distributed at the hydrophobic/hydrophilic interface, while the unbonded C homopolymers are dispersed in solvents due to their weak hydrophobic property. In the wormlike micelles, most bonded C homopolymers localize between two cores in one micelle, while the unbonded C homopolymers transit to the center of C domains. With increasing the volume fraction of homopolymers, the volume fraction of supramolecular ABC triblock copolymers increases to a maximum and then decreases. The morphological transitions of these micelles were also observed as a function of the volume fraction of homopolymers. The work provided an insight into the effect of non-covalent bonds on the morphology of supramolecular micelles.