The application of atypical experimental methods such as conductivity measurements, optical microscopy, and nonstirred polymerizations to investigations of the 'classical' batch ab initio emulsion polymerization of styrene revealed astonishing facts. The most important result is the discovery of spontaneous emulsification leading to monomer droplets even in the quiescent styrene in water system. These monomer droplets with a size between a few and some hundreds of nanometers, which are formed by spontaneous emulsification as soon as styrene and water are brought into contact, have a strong influence on the particle nucleation, the particle morphology, and the swelling of the particles. Experimental results confirm that micelles of low-molecular-weight surfactants are not a major locus of particle nucleation. Brownian dynamics simulations show that the capture of matter by the particles strongly depends on the polymer volume fraction and the size of the captured species (primary free radicals, oligomers, single monomer molecules, or clusters).

Radical desorption is one of the most important physical processes influencing the kinetics of free-radical emulsion polymerization. Desorption of any molecule from a polymer particle can only take place if the molecule reaches the particle surface during its random diffusion through the polymer phase. For doing this the molecule must survive all possible competitive reactions taking place simultaneously inside the particle. Once at the surface it must also overcome a certain energy barrier in order to leave the particle. This energy barrier is determined mainly by the difference in the chemical potential of the molecule between the particle and the continuous phase (including interfacial tension effects) and by additional barriers such as the presence of a stabilizer layer. In this molecular picture of the desorption process all molecules inside the polymer particle can desorb from the particle at a rate determined by its energy barrier and diffusion coefficient. It is for this reason that desorption of the smaller and more hydrophilic molecules is predominant. In this paper we propose the use of Brownian dynamics (BD) algorithms for simulating the desorption of radicals from polymer particles and estimate the corresponding desorption rate coefficients. The results obtained in simple systems are found to be in very good agreement with the rate coefficients of desorption determined theoretically. For more complex systems, such as core-shell particles, nonspherical particles, hollow particles, or particles with a gradient in monomer concentration, BD simulations open the possibility to obtain easy, reliable estimations of the desorption rate coefficients, which are difficult to obtain using the experimental or theoretical methods currently available. This article is also intended to be a comprehensive and critical review of the different available theories of radical desorption in emulsion polymerization.

Food packaging materials are commonly derived from petroleum that increases global contamination; this raises the interest to evaluate raw material from renewable sources such as whey protein for the development of packaging materials, especially to produce active films. This research aimed to evaluate whey protein-based film properties when natamycin, nanoemulsioned α-tocopherol, or both were added. An oil-in-water (O/W) nanoemulsion of antioxidant (α-tocopherol) was prepared by microfluidization technique. Four films were prepared with different levels of natamycin and nanoemulsified α-tocopherol and were characterized in terms of physicochemical, mechanical, optical-properties, water vapor barrier, FTIR, microstructure, antioxidant and antimicrobial activity. The natamycin, nanoemulsified α-tocopherol, or both did not modify the moisture content of the films. Moreover lead to a significant reduction of tensile strength and elastic modulus, while presenting growth in the elongation at break. Film opacity, the total color difference, the UV-Vis light barrier, and the water vapor permeability values increased when compounds were incorporated into the film. The microstructure studies showed uniformly distributed porosity throughout the films. The addition of nanoemulsioned α-tocopherol into whey protein-based films provoked antioxidant activity and the addition of natamycin produced films with effectivity against C. albicans, P. chrysogenum, and S. cerevisiae, allowing develop a material appropriate for use as active food packaging.

The kinetics of collision between primary persulfate radicals and colloidal polymer particles, a key issue in emulsion polymerization modeling, is determined by the simulation of Brownian dynamics using a Monte Carlo random flight algorithm. The results obtained confirm the ideal behavior predicted by Smoluchowski's kinetic equation only in colloidal dispersions of very low polymer volume fractions (<0.1%), while at higher values, significant deviations from ideality are observed. This deviation from ideality, designated as the Smoluchowski number (Sm), is found to increase almost linearly with the volume fraction of the dispersion. The kinetic model considering the effect of volume fraction is compared with previous experimental data. A satisfactory explanation for the different functional dependences of the radical entry rate on particle diameter is obtained. It is concluded that the polymer volume fraction in the dispersion plays a major role in the mechanism of radical capture by polymer particles.

Nanostructured thermosets were achieved by mixing an unsaturated polyester (UP) resin with an amphiphilic poly[(ethylene oxide)b-(propylene oxide)-b-(ethylene oxide)] block copolymer (EPE). Differential scanning calorimetry and dynamic light scattering were used to study the miscibility and molecular dynamics of nonreactive mixtures. Obtained results indicated that the formation of the nanostructured thermosets followed a self-assembly mechanism. Atomic force microscopy was used to study the morphology of the thermosets. It was found that mixtures cured at 25 °C nanostructured with smaller domains had higher transparency if compared to the mixtures cured at 35 °C. The mechanical properties of nanostructured thermosets showed that UP resin was significantly toughened by addition of the EPE. Results indicated that, for an EPE content of 15 wt %, the critical stress intensity factor, K Ic , of the mixture increased ca. 40%, if compared to the neat UP thermoset.

Styrene is the classical monomer obeying zero-one kinetics in radical emulsion polymerization. Accordingly, particles that are less than 100 nm in diameter contain either one or no growing radical(s). We describe a unique photoinitiated polymerization reaction accelerated by snowballing radical generation in a continuous flow reactor. Even in comparison to classical emulsion polymerization, these unprecedented snowballing reactions are rapid and high-yielding, with each particle simultaneously containing more than one growing radical. This is a consequence of photoinitiator incorporation into the nascent polymer backbone and repeated radical generation upon photo-irradiation.

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