This contribution reports an efficient method for the production and use of biocide-loaded cellulose acetate nanoparticles. As well-known model biocides 4-Hexylresorcinol and Triclosan were used for in situ nanoparticle loading during a nanoprecipitation process. We show that the nanoparticle size can be well-controlled by variation of the cellulose acetate concentration during nanoprecipitation. Apart from strong evidence suggesting cellulose acetate particle formation according to a nucleation-aggregation mechanism, we further show that the biocide loading of the particles occurs by a diffusion process and not via co-precipitation. The quantity of particle loading was analyzed by ¹H-NMR spectroscopy of re-dissolved nanoparticles, and it was observed that a decisive factor for high packaging efficiency is the use of a biocide with low water solubility and high hydrophobicity. SEM studies showed no influence on the particle morphology or size by both biocides 4-Hexylresorcinol and Triclosan. Finally, an aqueous nanoparticle dispersion can be coated onto model paper sheets to yield pronounced antimicrobial surface-properties. Nanoparticles loaded with the biocide Triclosan showed a high antimicrobial activity against Bacillus subtilis, a cellulase producing bacteria, if applied to model paper substrates, even at extremely low coating weights of 1–5 g/m², respectively. Additional long-term efficacy renders these nanoparticles ideal for various applications.

Hydrophobic coatings are of utmost importance for many applications of paper-based materials. However, to date, most coating methods demand vast amounts of chemicals and solvents. Frequently, fossil-based coating materials are being used and multiple derivatization reactions are often required to obtain desired performances. In this work, we present a solvent-free paper-coating process, where olive oil as the main biogenic component is being used to obtain a hydrophobic barrier on paper. UV-induced thiol-ene photocrosslinking of olive oil was pursued in a solvent-free state at a wavelength of 254 nm without addition of photoinitiator. Optimum reaction conditions were determined in advance using oleic acid as a model compound. Paper coatings based on olive oil crosslinked by thiol-ene reaction reach water contact angles of up to 120°. By means of Fourier transform infrared spectroscopy and differential scanning calorimetry, a successful reaction and the formation of a polymer network within the coating can be proven. These results show that click-chemistry strategies can be used to achieve hydrophobic polymeric paper coatings while keeping the amount of non-biobased chemicals and reaction steps at a minimum.

For a wide range of applications, paper materials require effective protection against the destructive effect of water, which is most effectively realized by superhydrophobic coatings. In recent years, a considerable amount of scientific research has been carried out in this area, focusing particularly on biogenic resources. With this contribution, we go one step further and examine how biogenic materials can be transferred into aqueous dispersions and coated onto paper via existing technologies. With this paper coating, based on a hydrophobic cellulose derivative in combination with a structurally similar wax, thermally regenerable flower-like surface morphologies are obtained via self-assembly, where the hydrophobic cellulose polymer acts as a structural template for the co-crystallization of the wax component. Such hydrophobic structures in the low micrometer range ensure perfectly water-repellent paper surfaces with contact angles > 150° starting from coating weights of 5 g/m². The dispersion can be successfully applied to a variety of commercially available paper substrates, whereby the effects of different roughness, porosity, and hydrophobicity were investigated. In this context, a certain roughness of the base paper (S_a ~ 1.5–3 µm) was found to be beneficial for achieving the highest possible contact angles. Furthermore, the approach proved to be paper process-compatible, recyclable, and regenerable, whereby the processing temperatures allow the coating properties to be thermally generated in situ. With this work, we demonstrate how biogenic waxes are very well suited for superhydrophobic, regenerative coatings and, importantly, how they can be applied from aqueous coatings, enabling simple transfer into the paper industry.