Enhanced understanding and implementation of the self-assembly of fluorosilicone double-hydrophobic diblock copolymers in dilute solutions from thermodynamic perspective: The effect of different preparation factors

The aggregate properties of the fluorosilicone double-hydrophobic poly(dimethylsiloxane)-b-poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate) diblock copolymers (PDMS-b-PHFBMA) in organic solvents were investigated experimentally in this article. Different factors such as the composition of the solvents, polymer concentration, copolymer block length as well as the removal of the common solvent in the system were investigated. Besides, a classical thermodynamic model for surfactant self-assembly was applied to describe the mechanism of the formation and transition between different morphologies. It was found that the transfer free energy, the aggregate core-solvent interfacial free energy, the deformation free energy of the non-soluble block as well as the soluble block steric interactions had their specific contributions to the formation and transition of different morphologies induced from the self-assembly behavior of PDMS-b-PHFBMA. As a whole, the qualitative description of the mechanism of self-assembly and morphology transition behavior in macromolecular system can be easily achieved using the classical thermodynamic approach for surfactant self-assembly, while it still needs to be further improved.