Creation of Thermal Response Ordered Mesostructure Polymer Particles Using Diblock Copolymers via 3D Confined Self-Assembly

Advancements in nanotechnology and materials science have led to an increased demand for specific material functions, preparation, and design of polymer particles with ordered internal and surface mesostructures. In this work, well-shaped spheres of poly(2,2,2-trifluoroethyl methacrylate)-b-poly(2-vinylpyridine) with four different molecular weights are prepared by 3D confined self-assembly. After thermal annealing, these spheres exhibit ordered internal and surface mesostructure. Analytical studies suggest that the internal mesoporous structure is formed by the microphase separation properties of the diblock copolymers, while the formation of ordered mesopores on the surface is caused by the decomposition of the PTFEMA domains under electron irradiation. Other microphase-separated structures, such as cylindrical and lamellar ones, are observed using solution casting and non-solution casting methods in the same diblock copolymer, indicating that the 3D confined environment induces the formation of internal ordered spherical microphase-separated structures in the particles.