Mesoscopic Detection of the Influence of a Third Component on the Self-Assembly Structure of A₂B Star Copolymer in Thin Films

The most common self-assembly structure for A₂B copolymer is the micellar structure with B/A segments being the core/corona, which greatly limits its application range. Following the principle of structure deciding the properties, a reformation in the molecular structure of A₂B copolymer is made by appending three segments of a third component C with the same length to the three arms, resulting (AC)₂CB 3-miktoarm star terpolymer. A reverse micellar structure in self-assembly is expected by regulating the C length and the pairwise repulsive strength of C to A/B, aiming to enrich its application range. Keeping both A and B lengths unchanged, when the repulsion strength of C to A is much stronger than C to B, from the results of mesoscopic simulations we found, with a progressive increase in C length, (AC)₂CB terpolymer undergoes a transition in self-assembled structures, from a cylindrical structure with B component as the core, then to a deformed lamellar structure, and finally to a cylindrical structure with A component as the core. This reverse micellar structure is formed with the assistance of appended C segments, whose length is longer than half of B length, enhancing the flexibility of three arms, and further facilitating the aggregation of A component into the core. These results prove that the addition of a third component is a rational molecular design, in conjunction with some relevant parameters, enables the manufacturing of the desired self-assembly structure while avoiding excessive changes in the involved factors.