Diblock copolymer nanostructures

Polystyrene‐ block ‐poly(2‐cinnamoylethyl methacrylate) (PS‐ b ‐PCEMA) and poly(acrylic acid)‐ block ‐poly(2‐cinnamoylethyl methacrylate) (PAA‐ b ‐PCEMA) were synthesized. These polymers formed micelles with PCEMA as the core in solvents poor for the PCEMA block but good for the other blocks. When the PS block was much longer than the PCEMA block, star micelles were prepared. The PCEMA cores of these micelles were then photo‐crosslinked to yield PS star polymers. Nanospheres of PCEMA were obtained by photolyzing crew‐cut micelles of PAA‐ b ‐PCEMA, in which the water‐soluble PAA block was much shorter than the water‐insoluble PCEMA block. PS‐ b ‐PCEMA self‐assembled at silica and their THF/cyclopentane micellar solution interfaces to form diblock monolayers called polymer brushes, in which the insoluble PCEMA block spread like a melt on the silica surface and the chains of the soluble PS block stretched into the solution phase like bristles of a brush. By tuning the relative composition, PCEMA in bulk formed cylindrical micro‐domains dispersed in the continuous PS matrix. Irradiation of the PS‐ b ‐PCEMA brushes enabled our preparation of crosslinked PS‐ b ‐PCEMA monolayers. Nanofibers were prepared by dissolving in THF the irradiated PS‐ b ‐PCEMA films with crosslinked cylindrical PCEMA micro‐domains.