Vesicle templated emulsion polymerization is a special form of emulsion polymerization where the polymer is grown from the outside of the vesicle, leading to nanocapsules. Cost effective nanocapsules synthesis is in high demand due to phasing out of older methods for capsule synthesis. Although the first indications of this route being successful were published some 10 years ago, until now a thorough understanding of the parameters controlling the morphologies resulting from the template emulsion polymerization was lacking. Most often a mixture of different morphologies was obtained, ranging from solid particles to pro-trusion structures to nanocapsules. A high yield of nanocapsules was not achieved until now. In this paper, the influence of initial vesicle dispersion, choice of the Reversible Addition-Fragmentation chain Transfer (RAFT) species and oligomer, monomer and crosslinker have been investigated. It turns out that good initial vesicle dispersion, molecular control of the RAFT process, a not too hydrophobic monomer and some crosslinking is needed to result in high yield of nanocapsules. In previous work, the level of RAFT control was often suboptimal and not properly verified and although nanocapsules were shown, other morphologies were also present. We now believe we have a full understanding of vesicle templated nanocapsules synthesis, relevant to many applications.
A simple and straightforward approach to synthesize oil-in-water (O/W) emulsions under high salinity and temperature using zwitterion-functionalized latexes are presented in this work. First, well-defined functionalized latexes were synthesized by emulsifier-free emulsion copolymerization in the presence of precursor sulfobetaine comonomer using brine as a continuous phase. The surface-functionalized latex particles were then characterized by DLS, SEM, TEM, XPS, and TGA. The functionalized latex exhibited antipolyelectrolyte behavior in high salinity brine and at high temperatures. The effects of salinity, temperature, and pH on the long-term stability of the particles were investigated. Further, to evaluate the potential in high salinity brine and high temperature, the saltphilic functionalized latexes were utilized to stabilize the oil/brine (O/W) interface without any other additives. The latex enabled the formation of a stable Pickering emulsion system with low solid content (<0.02% w/w) in the presence of 50% v/v n-decane. The functionalized latexes were self-assembled at the O/W interface as a spherical colloidosome in high salinity brine through hydrophobic interactions and irreversible adsorption. The supraparticles were imaged with SEM, providing an insight that the exterior of the emulsion droplets is stabilized by the saltphilic latex particles, forming a protective layer at the oil−water interface through electrostatic repulsion. The antipolyelectrolyte latex can be utilized as a novel emulsion stabilizer, which can provide a versatile alternative for applications in a complex environment such as high salinity, temperature, and low or high pH.
A facile and simple synthetic route towards functionalized non-spherical polymer particles (NSP) with tunable morphologies and iridescence is presented. Monodisperse particles with unique zwitterionic functionality were synthesized via emulsifier-free emulsion polymerization in a single step process. The sulfobetaine comonomer was utilized to induce phase separation in the course of polymerization to achieve anisotropic NSP with controlled morphologies such as quasi-spherical with protruding structures like bulge, eye-ball, and snowman-like nanostructures. Both SEM and TEM analyses revealed anisotropic particles, and phase-separated protrusion morphology with a small increase in aspect ratio. By taking advantage of the monodisperse, colloidally stable NSPs, template free photonic crystal arrays were fabricated through a bottom-up approach. The particles readily self-assemble and exhibit a photonic bandgap with vivid structural colors that arise from ordered structures of different morphologies. Additionally, the salt-responsive photonic crystals also possess tunable color-changing characteristics. † Electronic supplementary information (ESI) available: The detailed experiment section with the characterization of PS/PSB particles, DLS, SEM, TEM, XPS, FTIR, and TGA. See
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