Effect of double quaternary ammonium groups on micelle formation of partially fluorinated surfactant.

To investigate the effect of divalency on the micelle properties, we synthesized divalent cationic surfactants composed of fluorocarbons and double quaternary ammonium groups N,N-dimethyl-N-[2-(N'-trimethylammonium)ethyl]-1-(3-perfluoroalkyl-2-hydroxypropyl) ammonium bromide [C(n)(F)C(3)-2Am; where n (=8 or 10) represents the number of carbon atoms in the fluorocarbon chain]. The double quaternary ammonium groups are continuously combined by the ethylene spacer in the surfactant head group, which clearly distinguishes the molecular design of the surfactant from those of the other typical divalent surfactants, bolaform and gemini types. The presence of the divalent head group results in an advantageous increase in their solubility [i.e., rise in the critical micelle concentration (cmc)]; however, the extra electrostatic repulsion between divalent cations decreases the surface activity in comparison with monovalent homologous fluorinated surfactants. The cmc, surface tension at cmc, and area occupied by a surfactant molecule in aqueous solution at 298.2K are 4.32 mM, 30.6 mN m(-1), and 0.648 nm(2 )molecule(-1), respectively, for C(8)(F)C(3)-2Am, and 1.51 mM, 30.4 mN m(-1), and 0.817 nm(2) molecule(-1), respectively, for C(10)(F)C(3)-2Am. The micellar size and shape were investigated by dynamic light scattering and freeze-fracture transmission electron microscopy (TEM). The TEM micrographs show that C(n)(F)C(3)-2Am (n=8 and 10) mainly forms ellipsoidal micelles approximately 10-100 nm in size for n=8 and approximately 10-20 nm in size for n=10. The degree of counterion binding to micelle was determined by selective electrode potential measurements, and the results of 0.7-0.8 agree with the average values for conventional monovalent ionic surfactants.