JPS6254097B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a process for the preparation of mixtures of sulfosuccinic acid half esters based on Alba oil. German Patent No. 2039745 discloses that whale oil or spermaceti oil is first saponified into fatty alcohols and fatty acids, or reacted with monohydric fatty alcohols having 1 to 3 carbon atoms to form fatty acids. from the alcohol and the corresponding fatty acid alkyl ester, followed by the liberated acid or its alkyl ester to the acyl alkanolamide in the presence of the liberated fatty alcohol, and finally from the fatty alcohol and the acyl alkanolamide obtained. by reaction of a mixture of with maleic anhydride and sulfite to give a sulfosuccinic acid half ester, the general formula as well as (In the formula, R is a hydrocarbon chain of a fatty alcohol contained in whole whale oil or spermaceti oil, R' is a hydrocarbon chain of a fatty acid contained in whole whale oil or spermaceti oil, and X is at least A straight or branched hydrocarbon chain having 2 carbon atoms, R'' means a hydrogen atom, an alkyl group or a hydroxyalkyl group, the total number of carbon atoms in X and R'' being from 2 to 6, M means the equivalent of the cation which makes the product water-soluble suitable for cleaning purposes, Y means a hydrogen atom and Y' means the group SO ₃ M or Y and Y' vice versa. A method for preparing a mixture of sulfosuccinic acid half esters having the following formula is described. The mixture of sulfosuccinic acid half esters obtained in this method has excellent foam-forming properties, but
Since very little whale oil or spermaceti oil is available as a raw material these days, alternatives to this versatile raw material are being actively sought. The present inventors discovered that when using sulfur whale oil or spermaceti oil instead of spermaceti oil in the method described in German Patent No. 2039745, sulfosuccinic acid having similar properties which are superior in many respects It has been found that a mixture of half esters is obtained. In the present invention, the main component has the general formula CH ₃ (CH ₂ ) ₇ CH=CH(CH ₂ ) _x CH ₂ −O−CO−(CH ₂ ) _y CH=CH(CH ₂ ) ₇ CH ₃ (in the formula are the numbers 9, 11 and 13, and y is the number 7, 9 and 11
) is first saponified into fatty alcohols and fatty acids, or is reacted with monohydric fatty alcohols having 1 to 3 carbon atoms. fatty alcohol and the corresponding fatty acid alkyl ester, followed by converting the liberated acid or its alkyl ester into an acyl alkanolamide in the presence of the liberated fatty alcohol, and converting the resulting fatty alcohol and acyl alkanolamide into General formula, characterized in that the mixture is converted into a sulfosuccinic acid half ester by reaction with maleic anhydride and a sulfite. as well as (In these formulas, R ₁ is the hydrocarbon chain of the fatty alcohol contained in the oil, R′ ₁ is the hydrocarbon chain of the fatty acid contained in the oil, and X is a straight chain having at least 2 carbon atoms. A linear or branched hydrocarbon chain, R″ means a hydrogen atom, an alkyl group or a hydroxyalkyl group, where X and
The total number of carbon atoms in R'' is from 2 to 6, M means the equivalent of the cation suitable for cleaning purposes and imparting water solubility to the product, Y is a hydrogen atom and Y' is a radical.
This is a process for producing a mixture of sulfosuccinic acid half esters represented by SO ₃ M or Y and Y' having the opposite meanings. The oil is a wax ester, and its composition was determined by JAO by Yermanos and Dunkan.
CS53, page 80 (1976) shows the following molecular chain distribution as an extreme value in research conducted in 1973 and 1974.

Table: Simmondsia chinensis oil is a pale yellow, almost odorless liquid obtained from the seeds of Simmondsia chinensis by a common mechanical expression process used for the separation of oil from, for example, peanuts, soybeans, and other oil seeds. It is. As reported in the literature, the main component of the oil ester is composed almost entirely of linear acids and alcohols, and the acids are eicosanoic acid (C ₂₀ ) and docosanoic acid (C ₂₂ ). It is a mixture containing small amounts of palmitoleic acid (C ₁₈ ) and oleic acid (C ₁₆ ). The alcohol is a mixture of eicosanol and docosanol, containing small amounts of hexacosanol and lower molecular weight alcohols. The acids and alcohols that make up the oil are:
Each has one double bond. All these double bonds are present in the ω ₉ -position (ie between the 9th and 10th carbon atoms counting from the terminal methyl group). The main component of the oil is expressed by the general formula CH ₃ (CH ₂ ) ₇ CH=CH(CH ₂ ) _x CH ₂ −O−CO−(CH ₂ ) _y CH=CH(CH ₂ ) ₇ CH ₃ (in the formula are the numbers 9, 11 and 13, and y is the number 7, 9 and 11
(meaning the number of ). The mixture of sulfosuccinic acid esters derived from Alba oil produced according to the invention is water-soluble and has further excellent cleaning action and good skin tolerance and is therefore suitable for use in utensil cleaners, household detergents and shampoos. eminently suitable for use in This mixture, optionally mixed with inorganic salts, can be dried to fluidity and thus, together with other known and commercially available materials, produces a soap/interface with excellent calcium soap dispersion power. It can be used in the production of activator detergents. The reaction of saponification or transesterification products is
Based on the procedure described above, which is carried out directly and without separation of the fatty alcohols, mixtures of alkanolamides of fatty acids contained in fatty alcohols, glycerin and oils are obtained in almost quantitative yields,
The glycerin can be washed away from this using a salt solution. Although this washing is not necessary, the removal of glycerin improves the color and odor of the product as well as the economy of subsequent processing steps. Particular preference is given to reacting the butternut oil, for example by reaction with methanol, to form a mixture of fatty alcohol and fatty acid methyl ester, with removal of the lower glycerol layer, which can be separated from the upper layer by decanting. This reaction is preferably carried out using an excess of alcohol. Sulfosuccinic acid half ester (SB
-J) was tested in comparison with sulfosuccinic acid half ester (SB-S) prepared by the method described in DE 2039745. The starting conditions for each of the following tests were the same. (1) Foaming power and foam stability according to Ross-Miles (as a 0.1% solution at 40°C, directly/after 5 minutes) SB-J 75/65 SB-S 165/160 (2) Wetting power according to DIN 53901, distillation As a 0.1% solution in water SB-J 12 seconds SB-S 10 seconds (3) Calcium soap dispersion power according to DIN 53903 SB-J 10 SB-S 11 (4) Cleaning power WFK - Cotton standard (Washing Research Institute, Krefeld) The detergency was tested using an artificially soiled test fabric. 5g per cloth at 60℃ using an automatic rotary washing machine
Wash with a washing solution containing active substances. The washed test fabric pieces were measured using a Fotovolt, New York 670-Color and Glossmeter.

[Table] (5) Swelling values in synthetic detergents SB-J 12% SB-S 15% The sulfosuccinic acid half esters based on bittersweet oil have a distinctly low foaming power which is favorable for a range of applications. Get noticed. The essentially low swelling values in synthetic detergents are also particularly advantageous compared to sulfosuccinic acid esters based on whale oil. (6) DRAIZE eye test (mucosal tolerance) Substance concentration 20% according to the Food and Drug Administration guidelines SB-J (invention) <10 (no irritation) SB-S (comparison) 15-20 (irritation) ) The skin tolerability of the substance SB-J obtained according to the invention is significantly improved compared to the comparative substance SB-S. The irritation value by DRAIZE (mucosal tolerance) is reduced by the present invention to about half of the comparative product. The mixtures produced according to the invention can be used in the form obtained in the manufacturing operation or with other substances such as inorganic salts and phosphates, so-called preservatives, bleaching agents, as well as fatty acid amides and fatty acid alkanolamides which act as foaming agents. It can be used in admixture with fatty amine oxides and amphoteric and other anionic surfactants. Furthermore, various organic solvents, supergreasing agents and other materials commonly used in detergents, such as urea and carboxymethylcellulose, fragrances or deodorizers, protective substances and disinfectants, such as esters of paraoxybenzoic acid or chlorinated phenols. For example, it is also possible to mix with p-chloro-m-cresol and dichloro-m-xylol. Example: 100g of soybean oil and 10g of monoethanolamine
g and 0.1 g of sodium methylate as a catalyst.
The reaction is carried out with stirring in the presence of g, with the reaction temperature gradually rising to 140°C. Care is taken to ensure that free alkali is present, and if necessary some sodium methylate is added later. After 2 hours of reaction, a wax-like substance is formed that is solid at room temperature, shows no ester bonds in the IR spectrum, and consists of a mixture of fatty acid monoethanolamide and fatty alcohol. 80 g of this reaction mixture is reacted with 26 g of maleic anhydride by known means to form a half-ester mixture;
and directly 34 g of sodium sulfite in 310 g of water.
Sulfonate using A milky-white dispersion containing 30% solids is obtained, which on dilution with water gives an almost clear viscous liquid.

Claims (1)

[Claims] 1 The main components have the general formula CH ₃ (CH ₂ ) ₇ CH=CH(CH ₂ ) _x CH ₂ −O−CO−(CH ₂ ) _y CH=CH(CH ₂ ) ₇ CH ₃ ( In the formula, x is a number of 9, 11 and 13, and y is a number of 7, 9 and 11
) is first saponified into fatty alcohols and fatty acids, or is reacted with monohydric fatty alcohols having 1 to 3 carbon atoms. a fatty alcohol and the corresponding fatty alkyl ester, followed by converting the liberated acid or its alkyl ester to an acyl alkanolamide in the presence of the liberated fatty alcohol;
and the resulting mixture of fatty alcohol and acyl alkanolamide is converted into a sulfosuccinic acid half ester by reaction with maleic anhydride and sulfite. as well as (In these formulas, R ₁ is the hydrocarbon chain of the fatty alcohol contained in the oil, R′ ₁ is the hydrocarbon chain of the fatty acid contained in the oil, and X is a straight chain having at least 2 carbon atoms. A linear or branched hydrocarbon chain, R″ means a hydrogen atom, an alkyl group or a hydroxyalkyl group, where X and
The total number of carbon atoms in R'' is from 2 to 6, M means the equivalent of the cation suitable for cleaning purposes and imparting water solubility to the product, Y is a hydrogen atom and Y' is a radical.
A method for preparing a mixture of sulfosuccinic acid half esters represented by SO ₃ M or Y and Y' having the opposite meanings.