Nanostructured polyurethane perylene bisimide ester assemblies with tuneable morphology and enhanced stability

Size control has been successfully achieved in inorganic materials, but it remains a challenge in polymer nanomaterials due to their polydispersity. Here, we report a facile approach to tailor the diameters of polyurethane (PU) nanoparticles (490 nm, 820 nm and 2.1 µm) via perylene bisimide (PBI) assisted self-assembly. The formed morphologies such as spindle, spherical and core-shell structures depend on the ratio of PBI and polymer concentrations. It is shown that the formation of PU nanoparticles is directed by π-π stacking of PBI and the morphology transition is not only affected by the amount of PBI incorporated, but also influenced by solvent, which controls the initial evaporation balance. Furthermore, the prepared PUs exhibit retained optical stability and enhanced thermal stability. The PUs, designed to have conjugated PBI segments in backbones, were synthesized via ring-opening and condensation reactions. Compared with the neat PU, gel permeation chromatography shows narrower molecular weight distribution. Fluorescence spectra and ultraviolet-visible spectra indicate retained maximum emission wavelength of PBI at 574 nm and 5.2% quantum yields. Thermo-gravimetric analysis and differential scanning calorimetry reveal 79°C higher decomposition temperature and 22°C higher glass transition temperature. This study provides a new way to fabricate well-defined nanostructures of functionalized PUs.