What dominates the interfacial properties of extended surfactants: Amphipathicity or surfactant shape?

The properties of conventional surfactants (c-surfactants) are generally accepted to be amphipathicity-dominated, but extended surfactants (e-surfactants) are additionally polypropylene oxide (PPO)-dependent; this additional property makes us wonder how an intramolecular PPO spacer would be "extended" at various interfaces and what is responsible for the excellent all-round properties of e-surfactants.

A series of novel sodium medium alkyl chain PPO-b-PEO sulfates (2-ethylhexyl polypropylene oxide-block-polyethylene oxide sulfates, C₈P_pE_eS) were designed, synthesized and structurally identified. Tensiometry was applied to estimate the surfactant shape at the air/water surface. Surface tension, interfacial tension, emulsifying power, electrolyte tolerance, adsorption onto oil sands and thermal hydrolysis stability were measured to evaluate the effect of the PPO coil on the interfacial and micellar properties of the e-surfactants.

On the basis of obtaining greater values for e-surfactants than c-surfactants for both surface area (a_m) per surfactant molecule and the corresponding shape factor (S), we were surprised to find that e-surfactants form a rugby ball shape not only at the air/water surface but also at the oil/water interface; this result is potentially explained by the PPO spacer coiling and collapsing to produce dense packing at the monolayer adsorption, which is rationally borrowed by other interfaces. Many positive or negative correlations were observed between the interfacial/micellar properties of C₈P_pE_eS and a_m values, which seems that the surfactant shape dominants the properties of the e-surfactants. In fact, the properties of C₈P_pE_eS are dominated by the dynamic amphipathicity and assisted by the rugby ball shape of the molecules because of both being driven by the dynamic biphasic affinity of the PPO coil in response to the external environment; these findings provide soft interfacial materials specially adapted for surfactant flooding.