Steric hindrance surfactants

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 azo coupling reaction proceeds by the electrophilic aromatic substitution mechanism. In the case of 4-chlorobenzenediazonium compound with l-naphthol-4-sulfonic acid [84-87-7] the reaction is not base-catalyzed, but that with l-naphthol-3-sulfonic acid and 2-naphthol-8-sulfonic acid [92-40-0] is moderately and strongly base-catalyzed, respectively. The different rates of reaction agree with kinetic studies of hydrogen isotope effects in coupling components. The magnitude of the isotope effect increases with increased steric hindrance at the coupler reaction site. The addition of bases, even if pH is not changed, can affect the reaction rate. In polar aprotic media, reaction rate is different with alkyl-ammonium ions. Cationic, anionic, and nonionic surfactants can also influence the reaction rate (27). 

In order to study the effect of substituents near the hydrolyzable bond, four fatty acid ethoxylates with different degrees of steric hindrance near the ester bond, see Fig. 4, have been synthesized [18]. The homologue pure surfactants were prepared by reacting the appropriate acid chlorides with a large excess of tetra(ethylene glycol) in the presence of pyridine. 

The stability of the ester surfactants against enzymatic hydrolysis by two different microbial Upases, Mucor miehei lipase (MML) and Candida antarc-tica lipase B (CALB) added separately to the surfactant solutions, was also investigated, see Fig. 5 [19]. It is obvious that hydrolysis of the unsubstituted surfactant is much faster with both CALB and MML than that of the substituted surfactants, i.e., increased steric hindrance near the ester bond leads to decreased hydrolysis rate. Since the specificity of the enzyme against its substrate is determined by the structure of the active site, it can be concluded, as expected, that the straight chain surfactant most easily fits into the active site of both enzymes. 

Nonionic surfactants produce the same interfacial films in the interface in a similar fashion as that mentioned above. As expected, there is no charge repulsion contribution to the stability of the emulsion. However, the polar groups of the surfactants (i.e., polyoxyethylene) are hydrated and bulky, causing steric hindrance among droplets and preventing coalescence. 

Hybrid silica materials were prepared via a sol-gel pathway at pH 9. The influence of anionic surfactant (SDS) was studied by comparing templated materials (TbSn series) with hybrid materials obtained without surfactant (Tbn series). Two mechanisms of mesostructure formation can be considered as represented on Fig. 2. The pka of aminopropyl chain is about 10.6 in the reaction mixture propyl-amines are partially protonated. Electrostatic interactions between dodecylsulfate anion and NH and sodium cation neutralization may then occur, resulting in the condensation of the silica structure around surfactant micelles and aminopropyl groups at the surface of the pores. The other mechanism is SDS chains complex-ation by P-CD cavity, which wonld result in P-CD gronps located at the surface of the pores and aminopropyl less accessible, due to steric hindrance caused by P-CD bulky groups. A complete characterization of the prodncts and adsorption capacities will help nnderstanding the formation mechanism of mesoporons hybrid silica. 

From the results of Figure 14.3, interestingly, the protein extraction behaviour by dilinoleyl phosphoric acid (DLIPA) is distinct from the result obtained by DOLPA, in spite of the similar hydrophobic chain. The oleyl and linoleyl groups are unsaturated C18 chains. The former has one unsaturated cis-double bond at the position between C9 and CIO, while the latter has two at the position between C9 and CIO and between C12 and Cl 3. The two double bonds in the hydrophobic part of the surfactant DLIPA provide some inflexibility in the chain, which can lead to steric hindrance and to solvation by the organic phase (Figure 14.5). 

Having established that bilayer flexibility and bilayer interaction are the mesoscopic determinants, the next question is whether these determinants can be coupled to molecular parameters. In fact, this has been done to quite some extent. In general, bilayer flexibility can be shown (both experimentally as well as theoretically by simulation methods) to be directly related to bilayer thickness, lateral interaction between heads and tails of the surfactants, type of head group (ethoxylate, sugar, etc.), type of tail (saturated, unsaturated) and specific molecular mixes (e.g. SDS with or without pen-tanol). The bilayer interaction is known to be related to characteristics such as classical electrostatics. Van der Waals, Helfrich undulation forces (stemming from shape fluctuations), steric hindrance, number, density of bilayers, ionic strength, and type of salt. Two examples will be dicussed. 

Steric hindrance When a nonionic surfactant adsorbs on an interface between oil and water, the hydrophobic part of the molecule wUl orient itself towards the oily phase, while the hydrophUic part will stick out into the aqueous phase. One can envisage the interface, therefore, as having a coat of hydrophihc chains sticking out of the interface. When two oil droplets approach each other, the two coats would first make contact. The only way that the two droplets can coalesce is when the nonionic surfactant molecules move away from the contact point. However, they are strongly adsorbed and therefore impede the coalescence. Hence, when two droplets with such a layer approach each other, the coats will repel each other. Thus, the droplets will move apart again, and coalescence is prevented. 

Very small particles that are not completely wetted by either the continuous or the dispersed phase have the tendency to adsorb onto the interface between the two phases. This can cause stabilisation of the interface the particles partially stick out of the interface, giving steric hindrance for coalescence, just as non-ionic surfactants do. The stabilisation is better when the particles stick out further, that is, they act better when they are wetted better by the continuous phase. Also here a form of the Bancroft rule applies the phase that wets the particles best wiU be the continuous phase (see Figure 15.3)... 

Therefore, it is conceivable that the micropore and macropore are interparticle pores, while the mesopore presumably is the intra-particle pore. During the course of calcination, the connection of interparticle was destroyed and this finally resulted in the vanishing of macropore. Because the mesopore was the intraparticle pores, it had relative fine thermal stability though the pore size was enlarged in the calcination. The reasons may be attributed to the steric dispersant effect of non-ionic surfactant PEG [12]. In the synthesis course, PEG gave steric hindrance to the assembling of mesophase and improved the pore structure. 

Steric hindrance due to adsorption of an oriented non-ionic surfactant or polyelectrolyte... 

Adsorption of a non-ionic polymer (gum or cellulosic) or surfactant (polysorbate 80) of sufficient chain length creates steric hindrance and prevents adjacent suspended particles from coming close enough to join each other. Steric stabilization has the advantage over electrostatic stabilization in that it is relatively insensitive to the presence of electrolyte in the aqueous vehicle. 

This potential force occurs in microstructured fluids like microemulsions, in cubic phases, in vesicle suspensions and in lamellar phases, anywhere where an elastic or fluid boundary exists. Real spontaneous fluctuations in curvature exist, and in liposomes they can be visualised in video-enhtuiced microscopy [59]. Such membrane fluctuations have been invoked as a mechanism to account for the existence of oil- or water-swollen lamellar phases. Depending on the natural mean curvature of the monolayers boimding an oil region - set by a mixture of surfactant and alcohol at zero -these swollen periodic phases can have oil regions up to 5000A thick With large fluctuations the monolayers are supposed to be stabilised by steric hindrance. Such fluctuations and consequent steric hindrance play some role in these systems and in a complete theory of microemulsion formation. 

Pure water/oil-emulsions are unstable. For this reason, surface active agents (surfactants) are added, which adsorb at the interface between the two immiscible liquids and decreasing the interfacial tension. In this way, the stability of a water droplet in oil will be increased. In addition, there is a second stabilizing effect by steric hindrance which will be explained later (4). 

By addition of surface active agents, a so called "steric hindrance" occurs. In this case, a mutual approach of two particles will be prevented by the lipophilic tails of the surfactants, which can be understood as a mechanical barrier with the same function as the adsorbed colloids as described in the previous section (see Figure 3). 

Figure 3. Steric hindrance monolayer films of different surfactants between two flattened droplets.

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