Alcohol ethoxylates synthesis

Figure 1. Synthesis route to secondary alcohol ethoxylates from n-paraffins...

Sulphosuccinic acid esters should be grouped into mono- and diesters. The first step of the monoester sulphosuccinate synthesis is the esterification of a hydroxyl-bearing stock material by maleic acid anhydride. As stock materials, long-chain primary alcohols, ethoxylated alcohols, ethoxylated alkylphenols, alkanolamides, ethoxylated alkanolamides, or monoglycerides are generally used [10, p. 405 ff 75, 76]. 

There are two important methods for the synthesis of ether carboxylates from ethoxylated fatty alcohols ... 

There are some means for synthesis of defined primary or secondary esters. Monoester salts of phosphoric acid, for instance, are prepared by addition of alcohol or ethoxylated alcohol, alkali fluoride, and pyrophosphoryl chloride (C12P0)20 in a molar ratio of 0.9-1.5 0.05-1 1.0 at -50 to +10°C and hydrolysis of the Cl-containing intermediates with base. Thus, 32.3 g (C12P0)20 was treated at -50°C with 23.9 g lauryl alcohol in the presence of 0.7 g KF and the mixture was slowly warmed to room temperature and hydrolyzed with H20 and 40% NaOH to give 83% sodium monolauryl phosphate. The monoester salts showed comparable or better washing and foaming efficiency than a commercial product [12]. 

Quatemized imidazolines with an amido moiety are suitable formulations for general oil and gas field applications. The synthesis of such compounds is detailed in the literature [1218]. For aqueous systems that contain sulfide compounds, a mixture has been described [262] that consists of an aqueous solution of an alcohol such as diethylene glycol monobutyl ether, butyl cellosolve, additional orthophosphoric acid, a fatty acid (from tall oil), substituted imidazoline, an ethoxylated fatty diamine (polyamines such as ethylenediamine, diethylenetriamine, etc.), and a molybdate compound. 

Chemistry and general properties. Sulphosuccinates are made in a two-stage synthesis. Firstly an ester is made by reacting maleic anhydride with an alcohol or an ethoxylated alcohol (Figure 4.12). If the molar ratio of alcohol to maleic anhydride is 1 1, the product is called the half-ester, but where 2 mol of alcohol is used per mole of anhydride, the product is a diester. 

Symmetrical sulfides are obtained in 70-90% yields by refluxing aqueous alcoholic solutions of halides with sodium sulfide. The nonahydrate of sodiiun sulfide is a satisfactory reagent for the reac-tion. Tetramethylene and pentamethylene halides give cyclic sulfides, e.g., tetramethylene sulfide (tetrahydrothiophene) (64%). Halides containing several other important functional groups have been employed. Typical examples include methallyl chloride, and halides with hydroxyl, ethoxyl, carboxyl, and diethylamino groups in the beta position. A dry synthesis of phenyl sulfide from calcium oxide, sulfur, and chlorobenzene at 300° has been reported. ... 

Elimination of bromine and ethoxyl groups with zinc is much the same as the elimination of two adjacent halogen atoms. The /6-bromo ether is heated with a stirred suspension of powdered zinc or zinc-copper couple in 90-95% ethanol, n-propyl alcohol, or isopropyl alcohol. The preparation of 3 Octene fails in n-propyl alcohol. In several cases the products have been shown to be mixtures of cis and trans isomers. The yields for the first two steps of the synthesis are 70-90%. The coupling of the a,/S-dibromo ethers with primary Grignard reagents takes place in 50-80% yields, whereas with secondary Grignard reagents only 30-55% yields are obtained. 

In the synthesis of nonionic surfactants (ethoxylated fatty alcohols), it was observed that in acidic catalysis (HBF4, BF3 etherate, SbF5, HSbF6, HPF6, HC104) a more uniform distribution of EO sequences per hydroxyl groups takes places, compared to the ethoxylation in anionic catalysis. 

The model reaction kinetics for the propoxylation or ethoxylation of fatty alcohols and nonylphenol, for surfactant synthesis, was developed successfully by Santacesaria and co-workers [45-50]. Of course, it is clear that, in principle, there are many similarities between the propoxylation of a fatty alcohol and the propoxylation of polyols, but there are some small differences. 

The dodecyl penta(oxyethylene glycol) monoether was synthesized from Aldrich dodecyl alcohol (98%) by adding 5 mol of ethylene oxide per mol of alcohol this reaction produces the typical distribution in degree of ethoxylation. The synthesis of nonylphenyl methacrylate was by a straightforward reaction of methacryloyl chloride (Aldrich) and nonylphenol (Kodak). Proton NMR spectroscopy just before use indicated 77% double bonds the rest were alkyl hydrogens, presumably because of polymerization. 

This synthesis is usually carried out in the presence of alkaline catalysts. The catalyst is neutralized and at least partially remains in the final product. Primary Cg-Cig long-chain alcohols are generally used for ethoxylation. The alcohols may be of synthetic (Ziegler or oxo alcohols), vegetable and animal origin. Other hydroxo compounds can be subjected to ethoxylation, for example diols, such as 2,4,7,9- tetramethyl-5-decyne-4,7-diol ( Surfinol ), vegetable sterols, lanoline fractions enriched by sterols and fatty alcohols [34]. Ethoxylated alcohols and mercaptanes modified by a subsequent addition of propylene oxide or ethoxylated and propoxylated alcohols mentioned before (section 1.2.2) are of some industrial importance. 

The resultants, 1,1,2,2-tetrahydroperfluoroalkyl iodides, can be easily converted, e.g., into alcohols, thiols, carboxylic acids and ethoxylated products. Thus, direct hydrolysis of 2-perfluoroalkyl iodides leads to perfIuoroalkyl-2-ethanols which show surface activity in non-aqueous solvents. Such approaches to fluorosurfactant synthesis have been put on stream by Du Pont, Ciba-Geigy, Hoechst, Asahi Glass and Daikin Kogyo. 

Figure 5.4 Synthesis of an ethoxylated fatty alcohol acrylate.

Malodors in raw materials contribute to unacceptable products as well as the need to use higher levels of fragrance. One such example was the synthesis of sodium lauryl ethoxy sulfate (SLES), a major surfactant used in personal care products. This material is produced by ethoxylation of lauryl alcohol followed by sulfonation. Often it is necessary to add a final bleaching step to minimize... 

E sulfonates d alcools gras ethoxyl s Because fatty alcohol ether sulfates are sensitive to - hydrolysis it is attractive to use f., where the sulfur is directly linked to the carbon. There are several possibilities for synthesis but none of them gained large-scale importance. 

Kajtna and Sebenik described the synthesis of pressure-sensitive adhesives based on polyacrylates by suspension polymerization. The monomers used were 2-ethylhexyl acrylate (2-EHA) and ethyl acrylate (EA), and dibenzoyl peroxide (DBF) was used as initiator. Surface-active agents [modified ester of sulfocarboxylic acid (SCA) and ethoxylated oleyl alcohol (EOA)], chain transfer agent (w-dodecanethiol) (CTA) and suspension stabilizer [poly(vinyl alcohol) (PVA)] were also used. Various organically modified montmorillonites were used as fillers. It was observed that the kinetics of suspension polymerization were independent of the presence of the montmorillonite in the system, as shown in Figure 1.8. 

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