WO1995029890A1

WO1995029890A1 - Process for producing long-shelf-life sulphosuccinates and sulphosuccinamates

Info

Publication number: WO1995029890A1
Application number: PCT/EP1995/001499
Authority: WO
Inventors: Ansgar Behler; Werner Seipel; Wilhelm Barlage; Almud Folge
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1994-04-28
Filing date: 1995-04-20
Publication date: 1995-11-09
Also published as: DE4414863B4; DE4414863A1

Abstract

The proposal is for a process for producing long-shelf-life sulphosuccinates and sulphosuccinamates in which fatty alcohols or fatty amines or their alkylene oxide adducts are reacted with maleic acid anhydride in the presence of 0,5 to 3 wt. % of a polyol and the resultant esters or amides sulphited in the prior art manner.

Description

Process for the preparation of stable sulfosuccinates and sulfosuccinamates

Field of the Invention

The invention relates to a process for the preparation of sulfosuccinates or sulfosuccinamates with improved storage stability, in which fatty alcohols or fatty amines or their alkylene oxide adducts are reacted with maleic anhydride in the presence of polyols and the reaction products are then known in a manner known per se sulfites.

Status of the * »r: hτιi

Sulfosuccinates and sulfosuccinamates are anionic surfactants which are characterized by high foaming power, excellent wetting properties and high dermatological compatibility. They are used as textile and flotation aids, in hand dishwashing detergents and in the field of cosmetic products. They are usually prepared from fatty alcohols or fatty amines or their ethylene oxide adducts, which are esterified or amidated in the first stage with maleic anhydride and then subsequently added to the sulfoberstein stones by addition of hydrogen sulfite. acid esters or amides are implemented. T.Schoenburg in Cosm, for example, provides overviews on this topic. Toxl. 104, 105 (1989) or B. Fabry in Seifen-Öle-Fette-Wwachs, 117, 3 (1991).

Although the substances mentioned are established anionic surfactants, their production is not free from problems. One difficulty, for example, is that the sulfitation of the reaction products formed in the first reaction stage - the esterification or amidation - results in a high viscosity and the sulfitation can therefore only be carried out with strong shear.

In addition, sulfosuccinates and sulfosuccinamates are not sufficiently stable in storage at low temperatures. For example, initially clearly dissolved products cloud out below 10 ° C. within 2 to 4 weeks and form insoluble precipitates or sediments when stored further.

The object of the invention was therefore to provide a process for the production of sulfosuccinates or sulfosuccinamates which on the one hand solves the viscosity problems during sulfitation and on the other hand leads to products with improved storage stability.

Description of the invention

The invention relates to a process for the preparation of storage-stable sulfosuccinates and sulfosuccinamates by reacting fatty alcohols or fatty amines or their alkyls. Lenoxide adducts with maleic anhydride and subsequent sulfation of the resulting esters or amides, in which the esterification or amidation is carried out in the presence of 0.5 to 3 and preferably 1 to 2% by weight of a polyol.

Surprisingly, it was found that the addition of small amounts of polyol, preferably glycerol, in the esterification or amidation significantly reduces the viscosity of the reaction products and the resulting sulfitation products remain clear and do not become cloudy even after prolonged storage, for example for 10 weeks at 8 ° C.

Polvole

For the purposes of the process according to the invention, suitable polyols are compounds having at least two, preferably three, hydroxyl groups:

*** glycerin,

*** Alkylene glycols such as ethylene glycol, ethylene glycol, propylene glycol, addition products from

Ethylene oxide on alkylene glycols; *** Technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50

% By weight; *** methyl compounds, such as in particular trimethylolethane,

Trimethylolpropa, trimethylolbutane, pentaerythritol and

Dipentaerythritol; *** Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical such as methyl and butyl glucoside;

*** sugar alcohols with 5 to 12 carbon atoms such as sorbitol or mannitol,

*** Sugar with 5 to 12 carbon atoms such as glucose or sucrose;

*** Aminosugars such as glucamine.

Feedstocks

Examples of suitable starting materials are fatty alcohols and their ethylene oxide adducts which follow the formula (I)

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 6 to 22 and preferably 12 to 18 carbon atoms and 0 and / or 1 to 3 double bonds, and n is 0 or numbers from 1 to 30, preferably 2 to 7.

Typical examples are capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolenyl alcohol, linolenyl alcohol, linolenyl alcohol and erucyl alcohol and their technical mixtures, which are used, for example, in the high pressure hydrogenation of technical see methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Further examples are the adducts of the fatty alcohols mentioned with 1 to 10 and preferably 2 to 7 moles of ethylene oxide. It is particularly preferred to use an adduct of 1 to 3 moles of ethylene oxide with a technical C12 14 or Cχ2 / i8 ^-κ ° cosfatty alcohol fraction.

Technical fatty alcohols with 12 to 18 carbon atoms such as coconut, palm, palm kernel or tallow fatty alcohol are preferred.

Also suitable as feedstocks are fatty amines and their ethylene oxide adducts which follow the formula (II)

R3

I

in the R ^ for a linear or branched aliphatic hydrocarbon radical having 6 to 22 and preferably 12 to 18 carbon atoms and 0 and / or 1 to 3 double bonds, R ^ for hydrogen or a (CH2CH2θ) _n H group and m and n independently of one another stands for 0 or numbers from 1 to 30, preferably 2 to 7.

Typical examples are laurylamine, cocoalkylamine and tallow alkylamine. Esterification or amidation

To prepare the sulfosuccinates or sulfosuccinamates, the fatty alcohols or fatty amines or their alkylene oxide adducts (“fatty substances”) are first reacted with maleic acid, preferably maleic anhydride, the molar ratio being 3: 1 to 1: 3. For the preparation of the preferred monoesters, it is advisable to use the fatty substances and the maleic anhydride in a molar ratio of 1: 1 to 1: 2 and to carry out the esterification or amidation at temperatures from 60 to 100 ° C. A further finding of the invention is that it is advantageous for the production of particularly storage-stable products to use an excess of about 5 to 20 mol% of maleic anhydride, based on the fatty substances.

For the production of sulfosuccinic acid diesters or amides, it has also proven to be advantageous to carry out the esterification or amidation at temperatures from 80 to 100 ° C. with an excess of the fatty substances and to remove the water of reaction continuously from equilibrium .

Sulfitation

The sulfitation of the maleic acid monoesters or amides can be carried out in a manner known per se. The reaction is usually carried out using a hydrogen sulfite, for example sodium hydrogen sulfite, which in methanolic solution adds to the double bond of the maleic acid ester becomes. In a preferred embodiment, the sulfonation is carried out at temperatures from 60 to 100 ° C. in an aqueous solution using alkali sulfite, in particular sodium sulfite, at which the hydrogen sulfite is formed in situ. The molar ratio of maleic acid ester or amide to sulfite can be 1: 1 to 1: 2. Depending on the sulfitizing agent used, the sulfosuccinates or sulfosuccinamates are subsequently present as solutions of their alkali metal salts, preferably their sodium salts.

Industrial applicability

The sulfosuccinates or sulfosuccinamates obtainable by the process according to the invention are surface-active and have excellent detergent properties. They promote the wetting of hard surfaces and the emulsification of hydrophobic substances in water. Since they have a pronounced foaming power and are well tolerated by dermatology, they are suitable for the production of detergents, dishwashing detergents and cleaning agents and for products for hair and body care, in which they contain 0.1 to 25, preferably 1 to 10 wt .-% - based on the agent - may be included.

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

Examples 1 to 5:

a) Preparation of the maleic acid half-ester (sulfosuccinate precursor). 731.6 g (2.31 mol) of Ci2 / i4 coconut fatty alcohol 3EO adduct (Dehydol ( ^R) LS3, Henkel KGaA, Düsseldorf / FRG) and 249.0 g (2.54 mol) of maleic anhydride were in the presence of each 12.5 g

al) glycerin, a2) oligoglycerin (diglycerol content 42% by weight), a3) butyl glucoside, a4) sorbitol and a5) ethylene glycol

- Corresponding to 1.3 wt .-% based on the starting materials - 4 h at 80 ° C stirred.

b) Preparation of the sulfosuccinic acid ester (sulfosuccinate). 245 g (1.89 mol) of sodium sulfite dissolved in 1430 g of water were placed in a stirrer and 800 g (1.92 mol) of the five monoesters from a) were added. The mixtures were then stirred at 75 ° C. under nitrogen for 2 h. After completion of the reaction, unreacted sodium sulfite was destroyed by adding hydrogen peroxide.

In all cases, products with an anionic surfactant content of approx. 34% by weight were obtained, which remained clear even after a storage period of 10 weeks at 8 ° C. Examples 6 to 10

a) Preparation of the maleic acid halamide (sulfosuccinainate precursor). 422.6 g (2.31 mol) of Ci2 / 14 coconut fatty amine and 249.0 g (2.54 mol) of maleic anhydride were in the presence of 6.5 g each

- Correspondingly 1 wt .-% based on the starting materials - stirred at 80 ° C for 4 h.

b) Preparation of the sulfosuccinic acid amide (sulfosuccinate). 245 g (1.89 mol) of sodium sulfite dissolved in 1430 g of water were placed in a stirrer and 546 g (1.9 mol) of the five monoamides from a) were added. The mixtures were then stirred at 75 ° C. under nitrogen for 2 h. After completion of the reaction, unreacted sodium sulfite was destroyed by adding hydrogen peroxide.

In all cases, products with an anionic surfactant content of approx. 30% by weight were obtained, which remained clear even after a storage period of 10 weeks at 8 ° C. Comparative Example 1:

Example 1 was repeated, but section a) was carried out without the addition of glycerol. A product with an anion content of approx. 34% by weight was obtained which, however, became cloudy after a storage period of 10 weeks at 8 ° C. and formed a sediment.

Comparative Example 2:

Example 5 was repeated, but section a) was carried out without the addition of glycerol. A product with an anion content of approx. 30% by weight was obtained which, however, became cloudy after a storage period of 10 weeks at 8 ° C. and formed a sediment.

Claims

1. Process for the preparation of storage-stable sulfosuccinates and sulfosuccinamates by reacting fatty alcohols or fatty amines or their alkylene oxide adducts with maleic anhydride and subsequent sulfitation of the resulting esters or amides, characterized in that the esterification or amidation is carried out in Presence of 0.5 to 3 wt .-% of a polyol.

2. The method according to claim 1, characterized in that polyols are used which are selected from the group formed by glycerol, alkylene glycols, technical oligoglycerol mixtures, methylol compounds, lower alkyl glucosides, sugar alcohols, sugars and amino sugars.

3. Process according to claims 1 and 2, characterized gekenn¬ characterized in that fatty alcohols and their ethylene oxide adducts are used which follow the formula (I),

R ¹ 0 (CH ₂ CH2θ) _n H (I)

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 6 to 22 and preferably 12 to 18 carbon atoms and 0 and / or 1 to 3 double bonds and n is 0 or numbers from 1 to 30, preferably 2 to 7 . Process according to claims 1 and 2, characterized gekenn¬ characterized in that fatty amines and their ethylene oxide adducts are used which follow the formula (II),

R3

I R2-N (CH ₂ CH2θ) _1I1 H (II)

in the R ^ for a linear or branched aliphatic hydrocarbon radical with 6 to 22 carbon atoms and 0 and / or 1 to 3 double bonds, R ^ for hydrogen or a (CH2CH2θ) _n H group and m and n un ¬ depends on each other for 0 or numbers from 1 to 30.

Process according to Claims 1 to 4, characterized in that an excess of 5 to 20 mol% of maleic anhydride, based on the fatty substances, is used in the esterification or amidation.