New highly cross-linked polysiloxanes were prepared by sol−gel
polymerization of 1,6-bis(diethoxymethylsilyl)hexane (1) and
1,4-bis(diethoxymethylsilyl)benzene (2).
Hydrolysis
and condensation of 1 and 2 under acidic and
basic conditions with 4 equiv of water led to
the rapid formation of hexylene- and phenylene-bridged polysiloxane
gels. The dry gels
(xerogels) were intractable, insoluble materials that were noticeably
hydrophobic, exhibiting
no swelling in organic solvents or water. Most of the xerogels
were high surface area,
mesoporous materials. Hexylene-bridged polysiloxanes prepared
under acidic conditions
were always nonporous regardless of whether they were
processed to afford xerogels or
supercritically dried as aerogels. Hexylene-bridged polysiloxanes
prepared under basic
conditions and all of the phenylene-bridged polysiloxanes were
mesoporous with surface
areas as high as 1025 m2/g.
Two new surfactant molecules are reported that contain thermally labile Diels-Alder adducts connecting the hydrophilic and hydrophobic sections of each molecule. The two surfactants possess identical hydrophobic dodecyl tail segments but have phenol and carboxylic acid hydrophilic headgroups, respectively. Deprotonation with potassium hydroxide affords the formation of water-soluble surfactants. Room temperature aqueous solutions of both surfactants exhibit classical surface-active agent behavior similar to common analagous alkylaryl surfactant molecules. Critical micelle concentrations have been determined for each surfactant through dynamic surface tension and dye solubilization techniques. Small-angle neutron scattering measurements of the aqueous surfactant solutions indicate the presence of spherical micelles with radii of 16.5 angstroms for the carboxylate and 18.8 angstroms for the phenolate. When these surfactants are exposed to elevated temperatures (>50 degrees C), the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments. Aqueous solutions of each surfactant subsequently exhibit a loss of all surface-active behavior and the micellar aggregates are no longer detectable.
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