Versatile and Rapid Synthesis of Polymer Nanodomes via Template- and Solvent-free Condensed Droplet Polymerization

Nonspherical polymer nanoparticles (PNPs) represent an emerging class of materials with novel functions such as self-assembly of metamaterials and programmable pharmacokinetics/immune response. Common solution-based synthesis techniques like emulsion polymerization primarily produce spherical particles. Although nonspherical PNPs have been obtained with additional templating, fabrication, and purification steps, the labor-intensive and costly solution-based synthetic protocols limit the fundamental and applied research on their properties and functions. Furthermore, these approaches are only applicable to a small selection of monomers, restricting the functionality that is accessible by PNPs. Here, we report the rapid, solvent-, and template-free synthesis of nonspherical PNPs via the fresh idea of coupled condensation and polymerization, realized using a novel technique, namely, condensed droplet polymerization (CDP). Using polymer nanodomes as a proof of principle, we demonstrate continuous variation of particle dimensions (from sub-20 nm to above 1 μm) and the complete syntheses of nanodomes composed of a variety of functional polymers within seconds to minutes. The vapor-based CDP approach renders the technique scalable for the manufacturing of soft nonspherical nanoparticles, promising advanced applications.