Structural Analysis of Bottlebrush Block Copolymer Micelles Using Small-Angle X‑ray Scattering

We present structural analysis of spherical diblock copolymer micelles where core blocks have bottlebrush architecture. The dependence of the core radius (R_core) and the corona thickness (L_corona) on the core block length (N_core) is investigated using small-angle X-ray scattering (SAXS) and discussed in terms of the stiffness of a core-forming polymer posed by its long fluoroalkyl side chains. The conformation of the core block is strongly stretched, and the measured exponents α and β from power-law correlations, R_core ∼ N_core^α and L_corona ∼ N_core^β, respectively, are greater than those from any scaling predictions for block copolymer micelles with a flexible, linear core-block. Such deviations are attributed to the appreciable chain stiffness of the bottlebrush core block, and a simple model is suggested to understand how the core block stiffness influences both the dimensions of core and corona.