Model Amphiphilic Polymer Conetworks in Water: Prediction of Their Ability for Oil Solubilization

[Image: see text] In this work, we computationally explored the ability of water-swollen, model ionizable ABA triblock copolymer-based amphiphilic polymer conetworks (APCNs) to solubilize a water-immiscible organic solvent (oil), via Gibbs free energy minimization. This was done as a function of the conetwork hydrophobe (A-blocks) mol fraction and the degree of ionization of the hydrophilic B-blocks. Expectedly, highest oil solubilization capacities were calculated for the most hydrophobic and least ionized APCNs, which could absorb up to 6.4 times more oil than water and exhibited a lamellar morphology. Our results also included a phase diagram, which indicated transitions from spheres to cylinders, lamellae, and unimers in oil, as the hydrophobe content increased and the degree of ionization decreased. All of these transitions were accompanied by discontinuous changes in the degrees of swelling in the aqueous and oil nanophases, discontinuous changes in the asymmetry ratios (for the anisotropic morphologies), and discontinuous changes in the oil solubilization capacities. This is the first time that a dual discontinuous volume phase transition is reported within a polymer gel.