The influence of terminal hydrophobe branching on the micellar properties of Hydrophobically modified Ethoxylated URethanes (HEURs) is addressed through fluorescence, dynamic light scattering (DLS), solution rheology, and Raman spectroscopy. Model HEURs used in this study are monodisperse and fully substituted with hydrophobic groups of different structures. Two linear hydrophobes (l-C12H25 and l-C16H33) and three branched hydrophobes [b-(C12H26), b-(C16H34), and b-(C20H42)]are coupled to the hydroxyls of POE670 and POE195 through 4,4-methylene bis(dicyclohexyl)diisocyanate (H12MDI) units. Prior low molecular weight surfactant studies observed that a CH2 group, introduced as a branch from a linear hydrophobe, contributes approximately half to the surfactant's hydrophobicity that the same CH2 unit would add to the linear chain. Within hydrophobe equivalent comparisons, greater hydrophobic domains are indicated in pyrene's I1/I3 emission ratio for the linear hydrophobe HEURs, denoting a more hydrophilic core in branched HEURs. An increase in the number of -CH2-groups notably influences aqueous solution viscosities, as expected, but among equivalent hydrocarbon comparisons, the moderate-size linear hydrophobe is more viscosifying than the branched hydrophobe at high concentrations. Viscosity increases correlate with the aggregation sizes estimated from DLS studies as aggregate sizes approach 500 nm, covering small to large hydrophobes and different oxyethylene spacer lengths. Conformational differences (Raman spectroscopy) of poly(oxyethylenes) and HEURs under stagnant and flow conditions are also examined. The presence of byproduct impurities can markedly influence these results.

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In this study, the focus is on the spray behavior of latex coatings thickened with structurally different surfactant-modified, water-soluble polymers (associative thickeners of the hydrophobically modified, ethoxylated urethane [HEUR] type). Particle image velocimetry (PIV) profiles are considered in the perspective of the dynamic uniaxial extensional viscosity (DUEV) of the coatings and an effort to understand the results in terms of the structural aspects of the thickener molecules is undertaken. A high-M v hydroxyethyl cellulose (HEC) thickened formulation, with a significant DUEV, does not atomize well. Among the HEUR thickeners, the addition of larger hydrophobes in the terminal positions requires less thickener to achieve a 90 KU viscosity and produces lower DUEVs and lower viscosities at high-shear rates. This is necessary to produce formulations with acceptable spray characteristics (i.e., good atomization). The sprayability of these systems is reflected in their velocity profiles and particle size/particle size distributions. Poorer spray characteristics are reflected in ligaments and broad particles size distributions. This study highlights the ability to control the particle size/ size distribution and velocity profiles of coatings formulations through the use of structurally different HEUR associative thickeners. Variations in sprayability among different nozzle geometries are also studied.

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