Surfactant moieties

The two distinctive affinities in the surfactant molecule mentioned above serve as the basis for the commonly accepted definition of surfactant groups. According to the charge of their hydrophilic moiety, surfactants can be classified into four categories anionic, non-ionic, cationic and amphoteric. 

Hydrophobic and hydrophilic are categories of solvation effects in aqueous liquids. Classical ions such as Na" " or polar molecules such as NH3 are easily recognized hydrophilic solutes. In contrast, the interactions of hydrophobic solutes or groups with water molecules do not display classic electrostatic or specific chemical interactions. Primitive hydrophobic solutes are inert gases and simple hydrocarbons that are sparingly soluble in water. However, much of the interest in hydrophobic effects is associated with more complex solutes that contain both hydrophobic and hydrophilic moieties. Surfactant species, for example the decanoate anion, include both hydrophobic and hydrophilic parts and are called amphiphilic. 

The detergent range alcohols and their derivatives have a wide variety of uses ia consumer and iadustrial products either because of surface-active properties, or as a means of iatroduciag a long chain moiety iato a chemical compound. The major use is as surfactants (qv) ia detergents and cleaning products. Only a small amount of the alcohol is used as-is rather most is used as derivatives such as the poly(oxyethylene) ethers and the sulfated ethers, the alkyl sulfates, and the esters of other acids, eg, phosphoric acid and monocarboxyhc and dicarboxyhc acids. Major use areas are given ia Table 11. 

The principal constituents of rosin (qv) are abietic and related acids. Tall oil (qv) is a mixture of unsaturated fatty and aHcycHc acids of the abietic family. Refined tall oil may be high in rosin acids or unsaturated acids, depending on the refining process. Ethoxylates of rosin acids, eg, dehydro abietic acid, are similar to fatty acid ethoxylates in surfactant properties and manufacture, except for thek stabiHty to hydrolysis. No noticeable decomposition is observed when a rosin ester of this type is boiled for 15 min in 10% sulfuric acid or 25% sodium hydroxide (90). Steric hindrance of the carboxylate group associated with the aHcycHc moiety has been suggested as the cause of this unexpectedly great hydrolytic stabiHty. 

The stmcture of individual block polymers is deterrnined by the nature of the initiator (1,2-propanediol above), the sequence of addition of propylene and ethylene oxides, and the percentage of propylene and ethylene oxides in the surfactant. Thus, when the order of addition is reversed, a different stmcture is obtained in which the hydrophobic moieties are on the outside of the molecule. With ethylene glycol as the initiator, the reactions are as foUows ... 

In some cases, dye-forming moieties attached to a polymeric backbone, called a polymeric coupler, can replace the monomeric coupler in coupler solvent (51). In other reports, very small particles of coupler solubilized by surfactant micelles can be formed through a catastrophic precipitation process (58). Both approaches can eliminate the need for mechanical manipulation of the coupler phase. 

The electrostatic impasse mentioned can be circumvented (Moss and Rav-Acha, 1980) if a cationic surfactant is functionalized with an arenediazonium ion moiety. The azo coupling with the micellar diazonium ion surfactant 12.160 was found to be faster than the azo coupling with the model diazonium ion 12.161 by factors of 122 and 244, in reactions with 2-naphthol and with 2-naphthol-6-sulfonate respectively. 

In the simplest case a surfactant is composed of an organic hydrophobic part and a hydrophilic part (Fig. 3). In an alkyl sulfate the hydrophobic part is derived from a fatty alcohol and the sodium sulfate moiety as the hydrophilic counterpart. (Only small variations concerning the fatty chain are possible in this special kind of structure.)... 

This kind of ester acts as a nonionic surfactant if the alkanol groups contain hydrophilic moieties. If only two molecules of alkanoles are added to the phosphoric acid molecule an acid or secondary dialkyl phosphoric acid ester is formed that are an amphiphilic molecule by itself see Eq. (5). 

The frequent breaking and reforming of the labile intermolecular interactions stabilizing the reversed micelles maintain in thermodynamic equilibrium a more or less wide spectrum of aggregates differing in size and/or shape whose relative populations are controlled by some internal (nature and shape of the polar group and of the apolar molecular moiety of the amphiphile, nature of the apolar solvent) and external parameters (concentration of the amphiphile, temperature, pressure) [11], The tendency of the surfactants to form reversed micelles is, obviously, more pronounced in less polar solvents. 

An extraordinary way of stabilizing RUO2-coated CdS colloids for H2 generation was chosen by Fendler and co-workers The colloidal particles were generated in situ in surfactant vesicles of dioctadecyldimethylammonium chloride and dihexa-decyl phosphate. Thiophenol as a membrane permeable electron donor acted as a sacrificial additive. Later, a surface active re-usable electron donor (n-C,gH3,)2N — (CHj)—CH2—CHj—SH, Br was incorporated into the vesicles. Its R—SS—R oxidation product could be chemically reduced by NaBH to regenerate the active electron donor. The H2 yields in these systems were only 0.5 %. However, yields up to 10% were later reported for a system in which CdS was incorporated into a polymerizable styrene moiety, (n-C,jH3jC02(CH2)2) N (CH3) (CH2CgH4CH=CH2>, CP, and benzyl alcohol was used as the electron donor. 

Of interest here is the question relating to the value for the slope coefficient, k, from equation (1), when surfactant structures incorporating both ionic (say sulphonate) and nonionic moieties are included together. The Ghanges in electric double layer effects imparted from salt addition might dominate the packing constraints and therefore the phase inversion process, or perhaps oxyethylene dehydration effects from the presence of toluene could also play a role. 

Surfactants are separated according to adsorption or partitioning differences with a polar stationary phase in NPLC. This retention of the polar surfactant moiety allows for the separation of the ethylene oxide distribution. Of all the NPLC packings that have been utilized to separate nonionic surfactants, the aminopropyl-bonded stationary phases have been shown to give the best resolution (Jandera et al., 1990). The separation of the octylphenol ethoxylate oligomers on an amino silica column is shown in Fig. 18.4. Similar to the capabilities of CE for ionic surfactants, the ethylene oxide distribution can be quantitatively determined by NPLC if identity and response factors for each oligomer are known. 

A surfactant was defined in Chapter 8 as an agent, soluble or dispersible in a liquid, which reduces the surface tension of the liquid [1]. It is helpful to visualise surfactant molecules as being composed of opposing solubility tendencies. Thus, those effective in aqueous media typically contain an oil-soluble hydrocarbon-based chain (the hydrophobe) and a smaller water-solubilising moiety which may or may not confer ionic character (the hydrophile). The limitations of space do not permit a comprehensive detailed treatment of the chemistry of surfactants. The emphasis is therefore on a broad-brush discussion of the principal types of surfactant encountered in textile preparation and coloration processes. Comprehensive accounts of the chemistry and properties of surfactants are available [2-13]. A useful and lucid account of the chemistry and technology of surfactant manufacturing processes is given by Davidsohn and Milwidsky [ 14] ... 

More complex hydrophilic moieties are sometimes encountered, however, such as mono-, di- and tri-ethanolamine and the corresponding isopropanolamines in anionic surfactants. Morpholine, once employed, is now obsolete owing to its toxicity. 

The most common hydrophobes used as the basis for surfactants are those containing eight to eighteen carbon atoms, such as those listed as carboxylates in Table 9.1. Some hydrophobes are aromatic (benzene or naphthalene) moieties, often containing lower alkyl substituents dodecylbenzene (9.1) is a common example. Alkyl-substituted toluenes, xylenes and phenols, and mono- and di-alkylated naphthalenes (9.2 and 9.3), are also used. 

Modified carboxylates, in which the carboxylate moiety forms part of a carboxymethoxy group, are also available. These are made by reaction of selected nonionic surfactants with chloroacetic acid. The result is a useful hybrid range, lacking the sensitivity of simple... 

Fig. 4.23 Preparation of mesoporous silica materials with chirally twisted rod-like structures by using surfactant with a chiral amino acid moiety as a structure-directing reagent.

---