Synthesis and solution properties of sulfate-type hybrid surfactants with a benzene ring

Nine novel sulfate-type hybrid surfactants, CmF2m+1C6H4CH(OSO3Na)CnH2n+1 (FmPHnOS: m=4, 6, 8; n=3, 5, 7; C6H4: p-phenylene), with a benzene ring in their molecules were synthesized. Alkanoyl chlorides were allowed to react with iodobenzene in the presence of aluminum chloride to give the corresponding aromatic ketones. The reaction of the ketones with perfluoroalkyl iodides yielded 1-[4-(perfluoroalkyl)phenyl]-1-alkanones as intermediates. The intermediates were allowed to react with methanol in tetrahydrofuran in the presence of sodium borohydride to yield 1-[4-(perfluoroalkyl)phenyl]-1-alkanols. The desired hybrid surfactants were obtained by the reaction of 1-[4-(perfluoroalkyl)phenyl-1-alkanols with sulfur trioxide/pyridine complex in pyridine and by the subsequent neutralization of the products with sodium hydroxide solution. When compared with the conventional hybrid surfactants, CmF2m+1C6H4COCH(SO3Na)CnH2n+1 (FmHnS: m=4, 6; n=2, 4, 6; C6H4: p-phenylene), the new hybrid surfactants thus synthesized were found to have a comparable ability to lower the surface tension of water and a high hydrophilicity. The cmc of FmPHnOS obeyed Kleven’s rule and their occupied areas per molecule increased with increasing m and n with the values between 0.66 and 1.05 nm2. The aggregation number for FmPHnOS micelles ranged from 6 to 45 and the hydrodynamic radius of the micelles was in the range of 1.4–3.1 nm.