ABSTRACT
A novel investigation of the effects of the hydrophilic and hydrophobic segments of hydrophobically modified ethoxylated urethanes (HEURs) on the rheological properties of their aqueous solutions, latex-based emulsions, and waterborne paints is demonstrated. Different HEUR thickeners were produced by varying the poly(ethylene glycol) (PEG) molecular weight and terminal hydrophobic size. Results reveal that the strength of hydrophobic associations and, consequently, the rheological properties of HEUR formulations can be effectively controlled by modifying the structure of the hydrophobic segment, specifically, the combination of diisocyanate and monoalcohol. This allows for the on-demand attainment of diverse rheological behaviors ranging from predominantly Newtonian profiles exhibiting lower viscosities to markedly pseudoplastic behaviors with significantly higher viscosities. The length of the hydrophilic group appears to affect viscosity only marginally up to a molecular weight of 23,000 g/mol, with more notable effects at 33,000 g/mol. Additionally, it was indicated that the rheological responses observed in water solutions provide a reliable forecast of their behavior in latex-based emulsions and waterborne paints. Coarse-grained molecular dynamics (CG-MD) simulations were also applied to gain insight into HEUR micelle dynamics in aqueous solutions. Guided by the DBSCAN algorithm, the simulations successfully captured the concentration-dependent behavior and the impact of hydrophilic chain length, aligning with the experimental viscosity trends. Various metrics were employed to provide a comprehensive analysis of the micellization process, including the hydrophobic cluster volume, the total micellar volume, the aggregation number, and the number of chains interconnecting with other micelles.
ABSTRACT
In this work, mixtures of increasing viscosity (from 0.9 to ≈720 mPas) are sonicated directly using an ultrasonic horn at 30 kHz to investigate the effect of viscosity on the ultrasound field both from an experimental and numerical point of view. The viscosity of the mixtures is modified by preparing water-polyethylene glycol solutions. The impact of the higher viscosity on the acoustic pressure distribution is studied qualitatively and semi-quantitatively using sonochemiluminescence. The velocity of light scattering particles added in the mixtures is also explored to quantify acoustic streaming effects using Particle Image Velocimetry (PIV). A numerical model is developed that is able to predict cavitationally active zones accounting for both thermoviscous and cavitation based attenuation. The results show that two cavitation zones exist: one directly under the horn tip and one around the part of the horn body that is immersed in the liquid. The erosion patterns on aluminum foil confirm the existence of both zones. The intensity of the cavitationally active zones decreases considerably with increasing viscosity of the solutions. A similar reduction trend is observed for the velocity of the particles contained in the jet directly under the tip of the horn. Less erratic flow patterns relate to the high viscosity mixtures tested. Finally, two numerical models were made combining different boundary conditions related to the ultrasonic horn. Only the model that includes the radial horn movements is able to qualitatively predict well the location of the cavitation zones and the decrease of the zones intensity, for the highest viscosities studied. The current findings should be taken into consideration in the design and modelling phase of horn based sonochemical reactors.
ABSTRACT
In this work, we report for the first time on the influence of the quality of reactants and reaction conditions on the production of hydrophobically modified ethoxylated urethanes (HEURs) and selected prepolymers without the use of solvents. We show that the polyol water concentration is detrimental to the progress of the main urethane forming reaction, confirming the necessity of carefully drying the reactants below 1000 ppm to suppress the consumption of diisocyanate toward urea during HEUR synthesis. Increasing the mixing speed (≈30 to 750 rpm), reaction temperature (80-110 °C), and catalyst concentration (0.035-2.1 wt % bismuth carboxylate) can significantly increase the rate of molecular weight buildup, but their effect decreases with time as the bulk viscosity increases and mixing limitations eventually take over, leading to the Weissenberg effect and chain growth termination. Consequently, for the selected formulation, the maximum product molecular weight attained lies in the range of ≈20â¯000-22â¯000 g/mol, irrespective of the specific process conditions applied.
