This article focuses on the adequate surfactant concentration regime in which MMA droplets are stabilized sufficiently against coalescence during high-pressure homogenization but still no diffusion processes from droplets to micelles take place in the polymerization. Monomer miniemulsions with different surfactant concentrations were prepared with different energy inputs. Emulsions result that depend either on the surfactant concentration or on the energy input of the homogenization process. For both cases, the occupancy of the interface is compared as a function of the droplet size. It is shown that the surfactant concentration needed for the stabilization of a specified interface area decreases with increasing droplet size. For the dependence of droplet size on the energy input, it is shown that more surfactant can be applied before emulsion polymerization starts, but the applicable surfactant concentration is lower than the cmc and also depends on droplet size.

Hydrophilic silica particles need to be hydrophobized to be encapsulated in a polymeric environment, which can be achieved by different methods. We report on the relationship between different hydrophobization techniques of silica and the final structure of poly(methyl methacrylate)/silica hybrid nanoparticles obtained by miniemulsion polymerization. Hydrophobization by cetyltrimethylammonium chloride (CTMA-Cl) uses the ionic interaction between the positively charged ammonium salt and the negatively charged silica surface, as shown by isothermal titration calorimetry. In this case, the interaction between polymer and silica surface needs to be enhanced, so 4-vinylpyridine (4-VP) was used as a co-monomer. Alternatively, the condensation reactions of 3-methacryloxypropyltrimethoxysilane (MPS) and octadecyltrimethoxysilane (ODTMS) were used to provide a covalent bond to the silica surface. The condensation reaction of the trimethoxysilane groups onto the silica surface was proven by Fourier transform infrared spectroscopy and thermogravimetric analysis. Hybrid nanoparticles were successfully formed with silica particles functionalized with the different functionalization agents. However, the structure of the resulting hybrid particles (i.e., the distribution of the silica particles within the polymer matrix) depends on the agent. The MPS-functionalized silica particles copolymerize with poly(methyl methacrylate), leading to a fixation of the silica particles inside the polymer and to a homogeneous distribution. The CTMA-Cl-and ODTMSfunctionalized silica particles cannot copolymerize, but aggregate at the interface, leading to a Janus-like structure.

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The surfactant concentration in miniemulsion polymerization is a very important parameter. At surfactant concentrations lower than a critical value, coalescence of monomer droplets changes their size, whereas concentrations too high lead to the formation of micelles and micellar nucleation in the polymerization step. Inorganic particles dispersed in the monomer phase, with the goal to produce hybrid particles, infl uence the surfactant concentration needed as shown in this contribution. Values for the ideal surfactant concentration have been determined for different combinations of particles and surfactant. Underlying mechanisms for the required adjustment of surfactant concentration are discussed.