A reverse degradation vs. temperature relationship for a carbonate-containing gemini surfactant

Abstract

The rate of hydrolysis of cleavable surfactant is known to have a strong temperature dependence. A nonionic gemini surfactant with a readily hydrolysable carbonate bond as spacer unit has been synthesized and evaluated. A carbonate linkage is special as spacer unit in a gemini surfactant because the hydrolysis results in two identical molecules, in this case a hydroxy-substituted nonionic surfactant, along with carbon dioxide. The critical micelle concentration for the gemini surfactant was an order of magnitude lower than that of the degradation product. The degradation of the new surfactant and specifically the effect of temperature on the rate of hydrolysis was investigated in detail. It was found that alkaline hydrolysis was rapid at 15 °C but very slow at 30 °C, i.e. there was a reverse relationship between rate of hydrolysis and temperature. The same behavior was found for monomeric nonionic carbonate-containing surfactants that were synthesized and used as references. This unusual behavior, which can be of practical use, is explained by the reverse solubility vs. temperature profile for amphiphiles carrying a polyoxyethylene chain.