DE4125989A1 - SULFOSUCCINATE - Google Patents

Abstract

In order to obtain new sulphosuccinates, (a) fatty alcohol polyethylene glycolether having the formula (I): R<1>O-(CH2CH2O)nH, in which R<1> stands for an aliphatic hydrocarbon residue having 0, 1, 2 or 3 double bonds and n stands for numbers from 1 to 20, and having a narrow homologue distribution, are reacted with maleic acid or maleic anhydride in the presence of 0.1 to 5 wt % of an alkaline catalyser and (b) the resulting mono- or diesters are then sulphitized in a known manner. These products are characterized by a particularly advantageous foaming and thickening power and are suitable for preparing washing, rincing and cleaning products, as well as hair care and body care products.

Description

Field of the invention

The invention relates to novel sulfosuccinates obtainable by Reaction of fatty alcohol polyethylene glycol ethers containing a have narrow homolog distribution, with maleic acid or maleic anhydride and subsequent sulfitation of the resulting mono- or diesters, a process for their Production and their use in washing, rinsing and cleaning cleaning products and hair and body care products.

State of the art

Sulfosuccinates, which are also known as sulfosuccinic esters are anionic surfactants that are due to their excellent application properties and their good dermatological compatibility for the production of cleaning products in the broadest sense that are used with to come into contact with the human skin. The properties of sulfosuccinates are extensively do been documented; it is here on the reviews in Fats, soaps, Anstrich., 65, 748 (1963), Tens. Surf.  Det., 11, 202 (1974), Cosm. Toll., 104, 105 (1989) and R. Soc. Chem. (Ind. Appl. Surf.), 77, 77 (1990).

To prepare the sulfosuccinates is usually from Fatty alcohols or their ethylene oxide addition products, in the first step with maleic acid or maleic anhydride drid be converted into the mono- or diesters. From this Sulfosuccinic acid esters are obtained by reacting the double bond of the maleic acid esters bisulfite ad diert. Usually, for the preparation of sulfo succinate requires no catalysts, but it is Methods are known in which the esterification in the presence of alkali metal carbonates under pressure (JP 87 / 2 28 300).

Among the sulfosuccinates, the sulfosuccinic acid Monoesters have a special meaning, since they are opposite to the Diesters have a particularly good foaming power. From Disadvantage, however, is their comparatively lower water Solubility, which is usually compensated by the fact that one used as starting materials ethoxylated fatty alcohols. aq solutions of sulfosuccinates based on conventional Fatty alcohol polyglycol ethers can be prepared by adding Vis However, it is difficult to thicken cosity regulators Assembly of the products made with it exceptor difficult.

The object of the invention was thus, new sulfo to provide succinates whose aqueous solutions have improved thickenability.  

Description of the invention

The invention provides sulfosuccinates which are characterized gets by

• a) fatty alcohol polyethylene glycol ethers of the formula (I) R¹O- (CH₂CH₂O) _n H (I) in which R ^{1 is} an aliphatic hydrocarbon radical having 0, 1, 2 or 3 double bonds and n is a number from 1 to 20, and a narrow homolog distribution have, in the presence of 0.1 to 5 wt .-% of an alkali metal catalyst with maleic acid or maleic anhydride and
• b) the resulting mono- or diester then in sulfited in a known manner.

Surprisingly, it has been found that aqueous solutions of Sulfosuccinates based on fatty alcohol polyethylene glycol ethers with narrow homolog distribution to product not just conventional, broad homolog distribution easier, d. H. using smaller amounts of thickening agents, adjusted to an advantageous consistency but also more pronounced viscosity maxima show what extraordinary preparation for the preparation Partly. Furthermore, the inventive show Sulfosuccinate an improved foaming power in both hard as in soft water.  

Fatty alcohol polyethylene glycol ethers with concentrated homologs Distribution represent known substances and can be classified according to the relevant methods of preparative organic chemistry to be obtained. Are preferred for the preparation of sulfosuccinates according to the invention such Fettalkoholpoly Glycol ethers used by ethoxylation of Fettal boil in the presence of calcined hydrotalcite (DE 38 13 910 A1) or hydrophobicized hydrotalcite. The latter substances are, for example, by implementation of Hydrotalcite with fatty acids, in particular lauric acid, he hältlich.

In the ethoxylation of fatty alcohols finds no selek tive addition of a discrete number of Ethylenoxidmole each molecule of the alcohol instead, the reaction rather follows statistical laws and leads to a Ge mixed homologous addition products, their degrees of ethoxylation a broad spectrum. Under a restricted homolo genverteilung here is to understand that the proportion never and higher homologs as well as of free fatty alcohol in the product mixture in favor of those homologs signifi kant is reduced, their degree of ethoxylation by average degree of ethoxylation in terms of the maximum Gaussian distribution is equal or at least approximate.

Typical examples of fatty alcohol polyethylene glycol ethers with restricted homolog distribution, which are used as starting materials for the sulfosuccinates according to the invention come into consideration are Addition products of on average 1 to 20, preferably 2 to 5 moles of ethylene oxide with caproic alcohol, capryl alcohol hol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl  alcohol, palmitoleyl alcohol, stearyl alcohol, oleyl alcohol, Elaidyl alcohol, linolyl alcohol, linolenyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol.

As is customary in the field of fat chemistry, these can be used as an insert fatty alcohol polyethylene glycol ethers also used by Addition products of ethylene oxide to technical Fettalko oil fractions, for example based on coconut oil or Derive beef tallow.

Sulfosuccinic acid esters, in particular monoesters which are derived from fatty alcohol polyethylene glycol ethers of the formula (I) in which R ^{1 is} an alkyl radical having 12 to 18 carbon atoms and n is a number from 2 to 5, are distinguished by a particularly advantageous thickening behavior of their aqueous Solutions and a stable base foam and are therefore preferred.

Another object of the invention relates to a method for the preparation of sulfosuccinates, characterized draws that one

• a) fatty alcohol polyethylene glycol ethers of the formula (I) R¹O- (CH₂CH₂O) _n H (I) in which R ^{1 is} an aliphatic hydrocarbon radical having 0, 1, 2 or 3 double bonds and n is a number from 1 to 20, and a narrow homolog distribution in the presence of 0.1 to 5 wt .-% of an alkaline catalyst with maleic acid or maleic anhydride and reacts
• b) the resulting mono- or diester then in sulfited in a known manner.

For the preparation of the sulfosuccinates are first the fat alcohol polyglycol ether with maleic acid or maleic anhydride reacted, wherein the molar use ratio 3: 1 to Can be 1: 3. For the production of the preferred Monoester is recommended polyglycol ether and maleic acid or maleic anhydride in a molar ratio of 1: 1 to 1: 2 and the esterification at temperatures of 60 up to 100 ° C. For the production of Sulfobern Stearic acid diesters, it has proved to be optimal, the Esterification at temperatures of 80 to 100 ° C with a To carry out excess of polyglycol ether and the Reacti continuously remove water from equilibrium.

While it is possible to prepare sulfosuccinic acid esters based on fatty alcohols or conventional polyglycol ethers without the use of an esterification catalyst, it has proven compulsory for the preparation of the sulfo-succinates according to the invention to carry out the reaction in the presence of alkaline catalysts, since otherwise products having unsatisfactorily low sulfitation degrees result. By alkaline catalysts are meant substances selected from the group consisting of alkali and alkaline earth hydroxides, carbonates and C ₁ -C ₄ -alkylates and zinc hydroxide. Typical examples of these are sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, sodium methoxide, sodium carbonate, potassium carbonate and calcium carbonate.

The alkaline catalysts can be used in quantities of 0.1 to 5, preferably 0.3 to 3 wt .-% - based on the polyglycol ether - be used.

The sulfitation of the maleic acid mono- or diesters can in be carried out in a known manner. Usually If the reaction is carried out using a hydrogen sulfite, For example, sodium hydrogen sulfite, which in methanolic Solution added to the double bond of the maleic acid ester becomes. In a preferred embodiment, the leads Sulfitation at temperatures of 60 to 100 ° C in aqueous Solution using alkali metal sulfite, especially Na triumsulfite, in which the hydrogen sulfite formed in situ will, through. Here, the molar use ratio of Maleic acid ester to sulfite 1: 1 to 1: 2. In Ab dependence of the sulphitizing agent used are the Sulfosuccinates subsequently as solutions of their alkali salts, preferably their sodium or magnesium salts.

The sulfosuccinates according to the invention are surface-active and have excellent detergent properties. You för the wetting of hard surfaces and the emulsification of hydrophobic substances in water. Because she has a pronounced Foaming power and dermatologically well tolerated are suitable for the production of washing, rinsing and Detergents and for hair and body products Care in which they are from 0.1 to 25, preferably 1 to 10 Wt .-% - based on the means - may be included.  

The following examples are intended to form the subject of the invention explain it in more detail without restricting it to it.

Examples starting materials A) Dehydol® LS-3:

Addition product of an average of 3 moles of ethylene oxide to a technical C _12/14 coconut fatty alcohol. The alkoxy lation of Kokosfettalkohols in the presence of 0.5 wt .-% - based on the fatty alcohol - a 30 wt .-% solution of sodium methylate in methanol Runaway leads.
Hydroxyl number of the product: 175.

B) Dehydol® LS-3, neutral:

Corresponds to A). After alkoxylation, the product became neutralized with lactic acid.

C) Arlypon® F:

Addition product of an average of 2.5 moles of ethylene oxide to a technical C _12/14 coconut fatty alcohol. The alkoxylation of coconut fatty alcohol was carried out in the presence of 0.5 wt .-% - based on the fatty alcohol - calcined hydrotalcite according to the German patent application DE 38 13 910 A1. The product has a narrow homolog distribution compared to A) and B).
Hydroxyl number of the product: 184.5

II. Production Examples Comparative Example V1: a) Preparation of the maleic acid monoester:

In a 500 ml three-necked flask equipped with stirrer and internal thermometers were 235.9 g (0.735 mol) of Dehy dol® LS-3, neutral (B) and 30 min under ver reduced pressure (20 mbar) at a temperature of 120 ° C dried; then the vacuum was introduced by introducing broken by nitrogen. The dried polyglycol ether was heated to 60 ° C and over a period of 30 min in portions with 72.1 g (0.735 mol) of maleic anhydride added. Thereafter, the reaction mixture was at 80 to Heated to 85 ° C and held at this temperature (about 2 h) until the content of free maleic acid remained constant. The maleic acid monoester was used as a clear liquid keep the following metrics:

acid number 137 (theory 134) Content of free maleic acid 2.0% by weight

b) Preparation of sulfosuccinate

In a 1 liter three-necked flask, 97.6 g (0.735 mol) of sodium sulfite (95% purity) was dissolved in 594.4 g of water. The solution was heated to 80 to 85 ° C and the maleic acid monoester from a) added in portions. After 3 h, the reaction was stopped and traces of unreacted sulfite were destroyed by the addition of H ₂ O ₂ . The sulfosuccinate was obtained as a clear liquid; the degree of sulfitation was 78.6% of theory.

Characteristics of the product Sulfosuccinic acid di-sodium salt 31.5% by weight Sulfosuccinic trisodium salt 2.4% by weight Unsulfitiertes 6.6% by weight sodium sulphate 0.7% by weight water 58.8% by weight

Comparative Example V2:

Analogously to Comparative Example C1 a), 235.9 g of Dehydol® were used LS-3 (A) and 72.1 g of maleic acid in the presence of 2.8 g of a 30 wt .-% solution of sodium methylate in methanol - ent speaking a concentration of 0.5 wt .-% based on the Dehydol® LS-3 - implemented. The monoester had the following Key figures on:

acid number 134 (theory 134) Content of free maleic acid 0.8% by weight

The sulfitation was similar to Comparative Example V1 b) with a solution of 97.6 g of sodium sulfite in 594.4 g of water guided. The sulfosuccinate was in the form of a clear liquid obtained; the degree of sulfitation was 82.7% of Theory.

Characteristics of the product Sulfosuccinic acid di-sodium salt 27.2% by weight Sulfosuccinic trisodium salt 4.2% by weight Unsulfitiertes 6.6% by weight sodium sulphate 0.6% by weight water 66.6% by weight

Comparative Example C3:

Comparative Example C2 was carried out using 0.4 g of the 30 % by weight solution of sodium methylate in methanol - correspond of an amount used of 0.1 wt .-% based on the Dehydol® LS 3 repeated. The resulting sulfosuccinate had a degree of sulfitation of 82.5% of theory.

Characteristics of the product Sulfosuccinic acid di-sodium salt 30.5% by weight Sulfosuccinic trisodium salt 7.7% by weight Unsulfitiertes 6.6% by weight sodium sulphate 0.5% by weight water 58.4% by weight

Comparative Example V4:

Analogously to Comparative Example C1 a), 230.8 g (0.76 mol) Arlypon® F (C) and 74.4 g (0.76 mol) of maleic anhydride implemented. The maleic acid monoester precipitated as a colorless, clear Liquid and had the following characteristics:

acid number 149.6 (theory 139.6) Content of free maleic acid 1.9% by weight

The sulfitation was similar to Comparative Example V1 b) with a solution of 100.7 g (0.76 mol) of sodium sulfite in 800 g Water performed. The sulfosuccinate was in the form of a clear, easily gelling liquid; the Sulfitierungsgrad amounted to only 49.6% of theory.  

Characteristics of the product Sulfosuccinic acid di-sodium salt 17.1% by weight Sulfosuccinic trisodium salt 4.3% by weight Unsulfitiertes 13.2% by weight sodium sulphate 0.5% by weight water 64.9% by weight

Examples 1 to 6

As in Comparative Example C4, 230.8 g of Arlypon® F in Presence of 0.3 to 3 wt .-% - based on the Arlypon® F - The catalysts I to V implemented. The monoesters were then, as also described as under V4, with 100.1 g of sodium sulfite sulfite in 800 g of water. The results The experiments are summarized in Table 1.

Sulfosuccinate content (anionic surfactant) and unsulfitated (US) according to the DGF standard methods, Stuttgart 1950- 1984, H-III-10 and G-II-6b determined. The water determination was done according to the Fischer method.  

Table 1

Sulfosuccinates based on Arlypon® F (percentages by weight)

III. Application examples a) Foaming behavior

The foaming behavior of the sulfosuccinates according to the invention was investigated in a foam test according to DIN 53 902 at 20 ° C., 0 ° d and 20 ° d (3.57 mmol / l Ca ²⁺ ) and a concentration of 1 g active substance per liter. The results of the foam measurements are summarized in Tab. 2.

Table 2

foam measurements

b) Thickening behavior

The thickening behavior of the sulfosuccinates was determined by aqueous solutions of the test products (sulfosuccinate content: 15 wt .-% based on the solution) examined by the Addition of 5 wt .-% Arlypon® F and 5 to 8 wt .-% sodium chloride - in each case based on the sulfosuccinate content - ver were thickened. The viscosity measurement was at 20 ° C in a Ball drop viscometer after Höppler determined. The results are summarized in Tab. 3.

Thickening behavior after addition of x wt .-% NaCl

Claims (7)

1. Sulfosuccinates, obtainable by reacting

• a) fatty alcohol polyethylene glycol ethers of the formula (I) R¹O- (CH₂CH₂O) _n H (I) in which R ^{1 is} an aliphatic hydrocarbon radical having 0, 1, 2 or 3 double bonds and n is a number from 1 to 20, and the one concentrated Have homolog distribution, in the presence of 0.1 to 5 wt .-% of an alkaline catalyst with maleic acid or maleic anhydride and
• b) subsequently sulfiting the resulting mono- or diesters in a manner known per se.

2. A process for the preparation of sulfosuccinates, characterized in that

• a) fatty alcohol polyethylene glycol ethers of the formula (I) R¹O- (CH₂CH₂O) _n H (I) in which R ^{1 is} an aliphatic hydrocarbon radical having 0, 1, 2 or 3 double bonds and n is a number from 1 to 20, and the one concentrated Have homolog distribution, in the presence of 0.1 to 5 wt .-% of an alkaline catalyst with maleic acid or maleic anhydride and
• b) subsequently sulfiting the resulting mono- or diesters in a manner known per se.

3. The method according to claim 2, characterized in that fatty alcohol polyethylene glycol ethers of the formula (I) with restricted homolog distribution, which one through Ethoxylation of fatty alcohols in the presence of calci hydrotalcite or hydrophobized hydrotalcite holds. 4. Process according to claims 2 and 3, characterized marked characterized in that the fatty alcohol polyethylene glycol ethers and maleic acid or maleic anhydride in mo ratio of 3: 1 to 1: 3. 5. The method according to at least one of claims 1 to 3, characterized in that alkaline catalysts selected from the group consisting of alkali metal and Erdalka lihydroxiden, carbonates and -C ₁ -C ₄ alkylates and zinc hydroxide is used. 6. Use of sulfosuccinates according to claim 1 for Her washing, rinsing and cleaning agents as well as Hair and body care products. 7. Use of sulfosuccinates according to the method according to to claims 2 to 5 for the production of washing, rinsing and cleaning products as well as hair and body products perpflege.