Surfactant modulated interactions of hydrophobically modified ethoxylated urethane (HEUR) polymers with penetrable surfaces

Hypothesis Adsorption of hydrophobically modified ethoxylated urethane polymers (HEURs) at the soft colloid interfaces of emulsion droplets will stabilise oil-in-water emulsions (a) via steric stabilisation induced by adsorption of the polymer at the droplet surfaces through the hydrophobic groups, and (b) via continuous phase viscosity enhancement through polymer self-association. Both of these mechanisms will be modulated by the presence of the surfactant, sodium dodecylsulfate (SDS). Experiments Dodecane-in-water emulsions stabilised by three HEUR polymers with different structural composition were examined in the absence and presence of SDS by NMR spectroscopy and small-angle neutron scattering (SANS). The effect of adsorption of the polymer to the dodecane droplet surfaces, and the conformation of the self-associating polymer in the aqueous solution were quantified. Findings All emulsions were stable for days-weeks. Diffusion data showed the formation of oil droplets of hundreds of nm in size in the presence of all three HEURs, here denoted C6-L-(EO100-L)9-C6, C10-L-(EO200-L)4-C10, and C18-L-(EO200-L)7-C18, where EOx represents a block of ethylene oxide of x monomers, L denotes the linker group, and Cn the length of the hydrophobic end-group. No significant changes in droplet size across this series of polymers was observed. Collectively, the results point to adsorption of the polymer to the droplet surfaces, which results in a small decrease in the effective polymer solution concentration, thereby driving to significant changes in the structure and dynamics of the system. Evident in the SANS data in particular, is a subtle balance between the characteristic features reflecting polymer self-association, and those associated with polymer structures commensurate with a larger length-scale, dependent on the system composition. Surprisingly, the polymer and polymer/SDS complex in the presence of oil show slightly greater diffusive rates relative to the analogous systems in the absence of the oil. Finally, the partitioning of the three polymers in phase-separated samples was studied by 1H NMR, and it was shown that the C18-L-(EO200-L)7-C18 exhibited a greater partitioning in the oil phase compared with C6-L-(EO100-L)9-C6 and C10-L-(EO200-L)4-C10, an observation that may be understood in terms of the structural composition of the HEURs. The SDS showed a positive correlation between its partitioning in the two layers with the polymer partitioning, evidence of a strong interaction between the surfactant and the polymer, consistent with the behaviour observed in the oil-free system