Green electrospinning is a relatively new promising technology in which a polymer (latex) can be spun from an aqueous dispersion with the help of a template polymer. This method is a green, clean and safe technology that is able to spin hydrophobic polymers using water as an electrospinning medium. In this article, a systematic study that investigates the influence of the template polymer molar mass, the total solids content of the initial dispersion and the particle/template ratio is presented. Furthermore, the influence of the surfactant used to stabilize the polymer particles, the surface functionality of the polymer particles and the use of a bimodal particle size distribution on the final fiber morphology is studied for the first time. In green electrospinning, the viscosity of the initial complex blend depends on the amount and molar mass of the template polymer but also on the total solids content of the dispersion to be spun. Thus, both parameters must be carefully taken into account in order to fine-tune the final fiber morphology. Additionally, the particle packing and the surface chemistry of the polymer particles also play an important role in the obtained nanofibers quality.

2‐Octyl acrylate (2‐OA) is a very promising bio‐based monomer that is a great candidate to substitute the widely used (but oil‐based) 2‐ethylhexyl acrylate (2‐EHA). In this work, the homopolymerization of these two monomers along with their methacrylic analogues (2‐octyl methacrylate, 2‐OMA and 2‐ethylhexyl methacrylate, 2‐EHMA) is compared to analyze their performance in detail. Very similar polymerization kinetics are observed, both in conversion and particle size. However, there are important differences in the microstructure (molar mass distribution, gel content, and degree of branching). Both acrylates form high amounts of gel (2‐OA higher than 2‐EHA) while the methacrylates do not form any. It is found that the most likely reason for the higher amount of gel on 2‐OA lies on the second abstractable labile hydrogen in the side chain presented in this monomer, that is more reactive in 2‐OA than in 2‐EHA. This is supported by the molar mass distributions, that show that 2‐octyl esters have higher molar mass than their respective 2‐ethylhexyl counterparts (both in acrylates and methacrylates), as a result of a higher amount of long chain branches.

In this work, solvent‐free waterborne polyurethane‐poly(meth)acrylate hybrid dispersions that can be used to formulate anticorrosive paints are synthesized. To achieve the anticorrosive protection, a phosphate containing polymerizable surfactant, Sipomer PAM 200 is incorporated to the hybrids. The presence of phosphate groups can produce an iron phosphate passivation layer to provide coatings with anticorrosive properties. These properties are tested in both mild and harsh corrosive environments. It is observed that when the films are dried at 60% relative humidity conditions, very poor anticorrosive protection is achieved because no phosphatization is obtained, but increasing the humidity to 85% during the drying step allows the formation of the passivation layer providing good anticorrosive properties.

The emulsion copolymerization between vinyl acetate (VAc) and vinyl alkoxysilanes is an interesting yet not well-understood process. In the present work, the copolymerization between VAc and vinyl trimethoxysilane (VTMS) is taken as a model system and studied using different polymerization techniques in order to understand the underlying mechanism that governs the emulsion polymerization kinetics. The solution and bulk copolymerization kinetics can be explained by the reactivity ratios of the monomers determined in this work (r_VTMS = 0, r_VAc = 0.211). However, the emulsion copolymerization kinetics presents features that cannot be explained by the reactivity ratios, as VTMS concentrations above 5 wt% stopped the emulsion polymerization when initiated with hydrophilic initiators (such as persulfates). This was a consequence of the slow propagating radicals terminating in the aqueous phase, decreasing the concentration of surface-active radicals and thus radical entry. When more hydrophobic vinyl alkoxysilanes such as vinyl triethoxysilane are used, the inhibiting effect was less prominent, because the silane concentration in the aqueous phase was smaller. Using Density Functional Theory calculations it was found that the hydrolyzed version of the alkoxysilane monomers had a different reactivity ratio.