Unraveling mechanistic events in solids-stabilized emulsion polymerization by monitoring the concentration of nanoparticles in the water phase.

The fate of nanoparticles used as stabilizers in solids-stabilized, or Pickering, emulsion polymerization for the formation of armored hybrid polymer latexes was studied. We showed that disk centrifugation can be used as a powerful quantitative tool to analyze and determine the concentration of nanoparticles in the water phase throughout solids-stabilized emulsion polymerizations. We performed a series of emulsion polymerizations using vinyl acetate, vinyl pivalate, methyl methacrylate, or butyl acrylate in presence of silica nanoparticles (Ludox TM-40, ca. 25 nm in diameter). The developed method to quantify the number of silica nanoparticles in the water phase proved to be an invaluable tool for determining key features of the polymerization process. The obtained concentration profiles versus monomer conversion explained the existence of limited coalescence of armored particles in the later stages of the solids-stabilized emulsion polymerization process of vinyl acetate, leading to nonspherical structures. Moreover, we demonstrated that the correlation of the measured number of silica nanoparticles present in the water phase with the average particle sizes of the latex particles provided excellent predictions for the coverage of the armored layer of nanoparticles on the surfaces of the polymer particles, corresponding to observed packing patterns.

Packing patterns of silica nanoparticles on surfaces of armored polystyrene latex particles.

Fascinating packing patterns of identical spherical and discotic objects on curved surfaces occur readily in nature and science. Examples include C(60) fullerenes, (1, 2) 13-atom cuboctahedral metal clusters, (3) and S-layer proteins on outer cell membranes. (4) Numerous situations with surface-arranged objects of variable size also exist, such as the lenses on insect eyes, biomineralized shells on coccolithophorids, (5) and solid-stabilized emulsion droplets (6) and bubbles. (7) The influence of size variations on these packing patterns, however, is studied sparsely. Here we investigate the packing of nanosized silica particles on the surface of polystyrene latex particles fabricated by Pickering miniemulsion polymerization of submicrometer-sized armored monomer droplets. We are able to rationalize the experimental morphology and the nearest-neighbor distribution with the help of Monte Carlo simulations. We show that broadening of the nanoparticle size distribution has pronounced effects on the self-assembled equilibrium packing structures, with original 12-point dislocations or grain-boundary scars gradually fading out.

Multilayered nanocomposite polymer colloids using emulsion polymerization stabilized by solid particles.

We report a versatile emulsion polymerization process in which solid nanoparticles are used as stabilizer, thereby replacing the role of surfactants, allowing for simple fabrication of armored nanocomposite polymer latexes. Use of a second conventional seeded emulsion polymerization step provides a straightforward route to more complex multilayered nanocomposite polymer colloids.

Tuning the hydrophilicity of gold nanoparticles templated in star block copolymers.

We report on a simple procedure to tune the hydrophilicity of hybrid gold nanoparticles. The nanoparticles have been prepared in the core of a poly(ethylene glycol)-block-poly(epsilon-caprolactone) (PEG-b-PCL) five-arm star block copolymer. A hydrophilic corona was then added to these hybrid gold nanoparticles by direct chemisorption of trithiocarbonate-containing poly(acrylic acid) chains. These polymers were synthesized by RAFT polymerization with a trithiocarbonate as the chain-transfer agent. The efficiency of the grafting was evidenced by TEM, AFM, and DLS and by the successful transfer of these nanoparticles from organic solvent to water.