Optimizing Chain Topology of Bottle Brush Copolymer for Promoting the Disorder-to-Order Transition

The order-disorder transitions (ODT) of core-shell bottle brush copolymer and its structural isomers were investigated by dissipative particle dynamics simulations and theoretically by random phase approximation. Introducing a chain topology parameter [Formula: see text] which parametrizes linking points between M diblock chains each with N monomers, the degree of incompatibility at ODT ([Formula: see text]; [Formula: see text] being the Flory–Huggins interaction parameter between constituent monomers) was predicted as a function of chain topology parameter ([Formula: see text]) and the number of linked diblock chains per bottle brush copolymer (M). It was found that there exists an optimal chain topology about [Formula: see text] at which [Formula: see text] gets a minimum while the domain spacing remains nearly unchanged. The prediction provides a theoretical guideline for designing an optimal copolymer architecture capable of forming sub-10 nm periodic structures even with non-high [Formula: see text] components.