(393b) Versatile Polymer Nanoparticle Synthesis Using Initiated Chemical Vapor Deposition (iCVD)

Polymerization of monomers to form nanoparticles (i.e., bottom-up synthesis) is commonly performed in liquid environments which confers restrictions to monomer chemistries and particle shape based on solubility and procedures that are commonly driven by surface tension. Here, we report the synthesis of polymer nanoparticles (PNPs) through a technique performed in a chemical vapor deposition apparatus that traditionally forms thin film polymer coatings. By utilizing an initiated chemical vapor deposition (iCVD) reactor, the synthesis process is afforded the advantages of an all-dry process, enabling PNPs made of insoluble polymers (e.g., hydrophobic and heavily cross-linked) and a variety of chemistries (zwitterionic, fluorinated, functionalizable, etc.) using the same technique. Furthermore, the solvent-free process enables control of the PNP diameters across an impressively broad range, from below 10 nm to above 1 µm. This approach delivers unprecedented synthetic capability for PNPs with control over particle size without relying on laborious nanofabrication of templates, which are commonly required for particle size control in existing procedures. The approach is also substrate-independent, such that it can be performed on any type of material, turning PNPs into nanostructured thin films in situ. This technique is compatible with a library of over 70 functional monomers developed to date for iCVD. The chemical versatility, combined with the broad yet precise control of particle sizes, renders this approach a promising route to generating PNPs from materials inaccessible in liquid-based methods, thus opening new avenues for PNP applications.