Polystyrene-block-poly(2-cinnamoylethyl methacrylate) (PS-b-PCEMA) formed micelles in THF/cyclohexane or chloroform/cyclohexane mixtures with the PCEMA block as the core. Depending on the relative length of the PS and PCEMA block, star and crewcut micelles were prepared. Upon UV irradiation, the PCEMA block selectively cross-linked to form star polymers and nanospheres from the corresponding star and crewcut micelles. The cross-linked micelles were characterized by solution and solid-state NMR, FTIR, GPC, TEM, and dynamic and static light scattering.

Polystyrene-block-poly(2-cinnamoylethyl methacrylate) (PS-b-PCEMA) samples with n/m larger than 9.0, where n and m stand for the numbers of styrene and of CEMA units in a chain, formed essentially star micelles and those with n/m between 7 and 8.2 formed mixtures of star and long cylindrical micelles in cyclopentane with PCEMA as the core and PS as the shell. UV cross-linking of the PCEMA cores of these micelles at 50 °C yielded star polymers and nanofibers. This probably represents the first preparation of cross-linked block copolymer cylindrical micelles or nanofibers in the solution phase. While we have previously prepared star polymers using this approach, this study shows the robustness of this method in producing star polymers with as many as 4.5 × 102 arms and a molar mass of 9.9 × 107 g/mol. Detailed study showed that UV cross-linking only locked in the structure of the micelles and did not change their aggregation numbers. This allowed us to determine the molar masses of the cross-linked micelles in toluene, in which uncross-linked micelles would have disintegrated, and to equate them to those of the uncross-linked micelles in cyclopentane. The aggregation numbers of the star micelles in cyclopentane were found to follow theoretical scaling laws.

Polystyrene-block-poly(2-cinnamoylethyl methacrylate) (PS-b-PCEMA) of different block lengths have been synthesized. These polymers were adsorbed via the anchoring of the insoluble PCEMA block on silica, in the brush conformation, from cyclohexane/THF or cyclopentane/THF mixtures when cyclohexane or cyclopentane contents were high. The adsorbed amount could be increased or decreased by increasing or decreasing the cyclohexane or cyclopentane content. In a given solvent mixture, number surface coverages ρ∞ increased as n/m decreased, where n and m are the numbers of repeat units for the PS and PCEMA blocks, respectively. The trend that ρ∞ increased with decreasing n/m is contradictory to previous experimental observations but can be well explained by the scaling relation derived by Marques et al. for block copolymer adsorption from a micellar solution in the buoy-dominated regime.

Rich heteroatom-doped conjugated nanoporous polymers with uniform microspherical morphology exhibit remarkably high capacity up to 450 wt% for removing iodine from the vapor phase (at 348 K and atmospheric pressure).