Stabilizing Phases of Block Copolymers with Gigantic Spheres via Designed Chain Architectures.

It is generally believed that the spherical domains self-assembled from -type block copolymers are composed of the minority blocks with a volume fraction of < 1/2. Breaking this generic rule so that the spherical domains are formed by the majority blocks ( > 1/2) requires mechanisms to drastically expand the stable region of spherical packing phases. Self-consistent field theory predicts that dendron-like -type block copolymers, composed of - 1 generations of blocks connected with the outermost generation of blocks, exhibit a stable region of spherical packing phases extending to ∼ 0.7. The extremely expanded spherical regions shed light on the mechanisms governing the self-assembly of amphiphilic macromolecules, as well as provide opportunities to engineer complex spherical packing phases.