Morphology-controlled synthesis of poly(oxyethylene)silicone or alkylsilicone surfactants with explicit, atomically defined, branched, hydrophobic tails.
Silicone surfactants are widely used in commerce because of the unusual surface activity when compared with fluorocarbon or hydrocarbon surfactants. However, most silicone surfactants are comprised of ill-defined mixtures, which preclude the development of an understanding of structure-surface activity relationships. Herein, we report a synthetic strategy that permits exquisite control over silicone structure by using the B(C(6)F(5))(3)-catalyzed condensation of hydro- and alkoxysilanes. Six different, precise hydrophobes were then mated to hydrophilic poly(oxyethylene)s of three different molecular weights by a metal-free click cyclization to generate a library of explicit silicone surfactants. These compounds were calculated to have a relatively linear value range of the hydrophilic-lipophilic balance, ranging from about 8 to about 15. The solubility of some of the compounds was too low to measure a critical micelle concentration (CMC). The others exhibited a broad range of surface tension values at the CMC that depend both on the length of the hydrophilic tail and, more importantly, the nature of the hydrophobic head group. Subtle distinctions in surfactant-related properties, which can be attributed to the three-dimensional structures, can be seen for compounds with comparable numbers of hydrocarbons and silicon groups.
Department of Chemistry and Chemical Biology, McMaster University, 1280 Main Street W., Hamilton, ON L8S4 M1, Canada. gonzaga@mcmaster.ca
Ferdinand
F
Gonzaga
John B
JB
Grande
Michael A
MA
Brook