Double long-chain cationic surfactants

The rhodium/TPPTS-catalyzed hydroformylation of higher olefins in organic/ aqueous biphasic system in the presence of double long-chain cationic surfactants (37) was studied at 100 °C and 20 bar CO H2 = 1 1 pressure. The reaction rate was comparable with that in homogeneous catalysis system [111]. 

Rotational dynamics of a fluorescent dye adsorbed at the interface provides useful information concerning the rigidity of the microenvironment of liquid-liquid interface in terms of the interfacial viscosity. The rotational relaxation time of the rhodamine B dye was studied by the time-resolved total internal reflection fluorescent anisotropy. In-plane rotational relaxation time of octadecylrhodamine B cation was evaluated under the presence or absence of a surfactant [26]. Table 2.8 shows that by adding a surfactant, the relaxation time and the interfadal viscosity increased. Anionic surfactants SDS and HDHP (hydrogen dihexadecylphosphate) were more effective in reducing the rotational motion, because of the electrostatic interaction. HDHP with double long chains hindered the interfacial rotation more [40]. 

The information includes location of double bonds In fatty acids, indentlficatlon of components in complex lipids, determination of compositions of anionic and cationic surfactants, and identification of long-chained alkyl substituents on phosphonium and ammonium ions. 

Atomic force microscopy (AFM) [19-21] provides a more detailed molecular picture of adsorbates at concentrations above the CMC. Adsorbed cationic surfactant C14TAB (tetradecyltrimethylammo-nium bromide) was arranged in surface micelles on silica and in long cylinders on mica. Double-chained DDAB was organized in bdayers on mica. These structures result from the balance of adsorbate-surface interactions and aggregate curvature controlled by intermolecular interactions. 

Water-soluble l,3-bis(di(hydroxyalkyl)phosphino)propane derivatives were thoroughly studied as components of Pd-catalysts for CO/ethene (or other a-olefins) copolymerization and for the terpolymerization of CO and ethene with various a-olefins in aqueous solution (Scheme 7.17) [59], The ligands with long hydroxyalkyl chains consistently gave catalysts with higher activity than sulfonated DPPP and this was even more expressed in copolymerization of CO with a-olefins other than ethene (e.g. propene or 1-hexene). Addition of anionic surfactants, such as dodecyl sulfate (potassium salt) resulted in about doubling the productivity of the CO/ethene copolymerization in a water/methanol (30/2) solvent (1.7 kg vs. 0.9 kg copolymer (g Pd)" h" under conditions of [59]) probably due to the concentration of the cationic Pd-catalyst at the interphase region or around the micelles which solubilize the reactants and products. Unfortunately under such conditions stable emulsions are formed which prevent the re-use... 

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