DE4300325A1 - Prepn. of oligo:glycerol ester sulphate from fatty alcohol oligo:glycerol ester - Google Patents

Abstract

Oligoglycerol ester sulphates (I) obtd. by reacting fatty acid oligoglycerol esters of formula R1-CO-O-(CH2-(O)-CH-CH2O)nH (II) with a sulphating agent, followed by neutralising are claimed wherein R1CO = 6-22C aliphatic acyl gp. with 0-3, C=C bonds and n = 1.5-10.Pref. in (II), R1CO = 12-18C acyl gp. and n = 2-5.Sulphation is in a continuous falling-film reactor, using C1S3OH or gaseous SO3 as sulphating agent, in a molar ratio of (II): sulphating agent of 1:0.5-2.0, at 30-90 deg. C. Neutralisation is with 5-55 wt. % aq. alkali metal hydroxides, alkaline earth (hydr)oxides, NH4OH, 2-4C mono-, di- or tri-alkanolamines, 1-4C prim. sec. or tert. alkylamines or glucamines.

Description

Field of the invention

The invention relates to oligoglycerol ester sulfates, a Ver drive to their preparation, which involves fatty acid oligo glycerol ester with sulfating agents and Neutralisationsbasen um , detergent mixtures and surfactants Oligoglycerinestersulfate contain as well as the use of the Oligoglycerinestersulfate for the production of oberflächak effective means.

State of the art

Ether sulfates are important anionic surfactants that exist all as mild ingredients for cosmetic products and Hand dishwashing detergents find use. To her manufacturer One usually starts with fatty alcohols, which are too next with ethylene oxide in fatty alcohol polyglycol over leads and then with sulfur trioxide or chlorosulfonic acid be sulfated. Finally, the acid sulfonated products neutralized with aqueous bases. An overview of this topic is, for example, M.J. Schwuger in HENKEL Lectures 20, 22 (1984). About manufacture and  Importance is also in numerous together reports. Representative is here on the review in chemistry i.u. Time 25, 214 (1991).

However, classical ether sulfates show two disadvantages: one is needed for their production of ethylene oxide, which high demands on health and safety at work, and to of which one observes as by-product of sulfation the partial degradation of the polyglycol ether chain to form Dioxane.

The object of the invention was now new anionic Surfactants with sulfate structure to develop, although through high skin compatibility, good foam and cleaning ability, easy thickening and high ecotoxicological Compatibility, but free of ethylene oxide as should be hydrophilic unit.

Description of the invention

The invention relates Oligoglycerinestersulfate since obtainable by using fatty acid oligoglycerol esters of Formula (I)

in which R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and n is a number from 1.5 to 10, reacted with sulfating agents and then neutralized with bases.

Surprisingly, it has been found that the inventive Sulfation products have excellent detergent properties and classically in terms of application technology at least equal to ether sulphates. From the Um was that no ethylene oxide required for their preparation is, results in a significant reduction of the otherwise usual high technical effort for occupational safety measure men. The absence of unwanted by-products, such as For example, ethylene oxide or dioxane, eventually leads compared to the prior art to toxicologically improved Products.

Another object of the invention further relates to a Process for the preparation of oligoglycerol ester sulfates, in fatty acid oligoglycerol esters of the formula (I)

in which R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and n is from 1.5 to 10, reacted with sulfating agents and then neutralized with bases.

Fettsäureoligoglycerinester

Fatty acid oligoglycerol esters are known substances which according to the relevant procedures of preparative organic Chemistry can be obtained. Usually you go to ith rer production of fatty acids and technical oligoglycerin mixed in the presence of basic catalysts at condensed at elevated temperature [FR-A 15 75 466, Eastman Kodak].

Typical examples of fatty acid oligoglycerol esters known as Starting materials for the preparation of the inventive Oligoglycerinestersulfate come into consideration are esters of Caproic acid, caprylic acid, 2-ethylhexylic acid, capric acid, Lauric, myristic, palmitic, palmitic, Stearic acid, isostearic acid, oleic acid, elaidic acid, petro selenic, linoleic, linolenic, elaeostearic, ara cholic acid, gadoleic acid, behenic acid and erucic acid as well their technical mixtures, such as those in the Pressure splitting of natural fats and oils occur with Self-condensation products of glycerol, which in turn an average condensation degree n of 1.5 to 10 can have.

It is preferable to use fatty acid oligoglycerol esters of the formula (I) in which R ¹ CO represents acyl radicals having 12 to 18 carbon atoms and n represents numbers of 2 to 5. Particularly preferred are caprylic acid diglycerol esters, coconut or tallow fatty acid di-, tri- and pentaglycerol esters.

Sulfation and neutralization

The sulfation of fatty acid oligoglycerol esters can be found in the for fatty acid lower alkyl ester known way [J. Falbe (ed.), "Surfactants in consuer products", Springer Verlag, Berlin-Heidelberg, 1987, 5. 61], whereby reactors, which work on the falling film principle, are preferred. When Sulfurizing agents come chlorosulfonic acid and especially gas shaped sulfur trioxide into consideration. The latter is übli cherweise with an inert gas, preferably air or Nitrogen diluted and in the form of a gas mixture, which the sulfating agent in a concentration of 1 to 8, esp special contains 2 to 5 vol .-%, used.

The molar use ratio of fatty acid oligoglycerol ester Sulfurizing agent may be 1: 0.5 to 1: 2.0 and preferably 1: 0.95 to 1: 1.5. Usually the sulphate is tion at temperatures of 30 to 90 ° C performed. In the Hin look at the viscosity of the starting materials on the one hand and the Color quality of the resulting sulfation products ande On the other hand, it has proved to be optimal for the reaction in to carry out a temperature range of 35 to 70 ° C.

The acid sulfonation products obtained during sulfation are neutralized together with aqueous bases. In a preferred embodiment of the invention, the neutralization is carried out at a pH of 7 to 8 in order to largely avoid undesired hydrolysis of the ester bond. Subsequently, the products are adjusted to a pH of 6.5 to 7.5. As bases for the neutralization come alkali metal hydroxides such as sodium, potassium and lithium hydroxide, alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, mono-, di- and tri-C _2-4 alkanol amine, for example Mono-, di- and triethanolamine, primary, secondary or tertiary C _1-4 alkylamines and glucamines into consideration. The neutralization bases are preferably added in the form of 5 to 55% strength by weight aqueous solutions, with 5 to 25% strength by weight aqueous sodium hydroxide solutions being preferred.

The sulfation products can after neutralization in an known manner by the addition of hydrogen peroxide or sodium hypochlorite solution. In doing so, based on the solids content in the solution of the sulphate tion products, 0.2 to 2 wt .-% hydrogen peroxide, calculated as 100% substance, or equivalent amounts of sodium hy used pochlorite. The pH of the solutions may be below Use of suitable buffering agents, eg. B. with sodium phosphate or citric acid are kept constant. To stabilize tion against bacterial attack is also recommended a Kon Serving, z. With formaldehyde solution, p-hydroxybenzoate, Sorbic acid or other known preservatives.

Sulfation leads to the addition of sulfur trioxide to the free hydroxyl groups of the oligoglycerol body. This reaction follows the statistics, ie one or more hydroxyl groups of a molecule can be sulfated. If the fatty acid body is unsaturated, it may also - albeit subordinate - come to an electrophilic addition of the SO ₃ molecule to the double bond, sulfonates are formed.

Detergent mixtures

Another object of the invention relates Detergensge mix containing a content of the oligoglycerol invention ester sulfates and other anionic, nonionic, cat ionic and / or amphoteric or zwitterionic surfactants respectively.

Typical examples of anionic surfactants are alkylbenzene sulfonates, alkanesulfonates, olefinsulfonates, alkylethersul fonates, glycerol ether sulfonates, α-methyl ester sulfonates, Sul fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glyce amine ether sulfates, hydroxymethylene ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, Sulfosuccinamates, sulfotriglycerides, amide soaps, ethercar acids, isethionates, sarcosinates, taurides, alkyl oligo lucoside sulfates and alkyl (ether) phosphates. Unless the anioni surfactants contain polyglycol ether chains, they can a conventional, but preferably a restricted Ho have moloenverteilung.

Typical examples of nonionic surfactants are fatty alcohol holpolyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, alk (en) yloligo glycosides, fatty acid glucamides, polyol fatty acid esters, sugars esters, sorbitan esters and polysorbates. Unless the nonioni surfactants contain polyglycol ether chains, they can a conventional, but preferably a restricted Ho have molecular distribution.  

Typical examples of cationic surfactants are quaternary amines monium compounds and quaternized difatty acid trialkanol aminester.

Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, amino glycinates, imidazolinium betaines and sulfobetaines.

The surfactants mentioned are exclusively known compounds. Regarding structure and production these substances are included in relevant reviews for example J. Falbe (ed.), "Surfactants in Consuaer Pro ducts ", Springer Verlag, Berlin, 1987, pp. 54-124 or J. Faibe (ed.), "Catalysts, Surfactants and Mineral Oil Additives", Thieme Verlag, Stuttgart, 1978, pp. 123-217.

The detergent mixtures may contain the oligoglycerol ester sulfates in Amounts of 1 to 99, preferably 10 to 80 and in particular 25 to 75 wt .-% included. The offer forms are Pul ver, granules and preferably aqueous solutions or di Sparsions with a solids content of 5 to 75, preferably Wise 25 to 70 wt .-% into consideration.

Industrial Applicability

The oligoglycerol ester sulfates according to the invention have upper surface active properties. This is how you promote example Wetting of solid surfaces, form an energy creamy foam and do not otherwise emulsify mutually miscible liquid phases. They are also under  aerobic conditions are well biodegradable and have one high skin-cosmetic compatibility. Other items The invention therefore relates to surfactants which a content of the oligoglycerol ester sulfates according to the invention and which are defined in more detail below:

• - Powdered universal detergents containing 10 to 30 Wt .-% - based on the agent Oligoglycerinestersulfate and customary auxiliary and Zu set materials.
• Liquid universal detergents containing 10 to 70 Wt .-% - based on the agent Oligoglycerinestersulfate and customary auxiliary and Zu set materials.
• Liquid mild detergents containing 10 to 50% by weight based on the medium - Oligoglycerinestersulfate as well usual auxiliaries and additives.
• Hand dishwashing detergent containing 10 to 50% by weight based on the medium - Oligoglycerinestersulfate as well usual auxiliaries and additives.
• Rinse aid containing 10 to 50 wt .-% - based on the middle - Oligoglycerinestersulfate as well as usual Auxiliaries and additives.
• - Liquid detergents and disinfectants, containing 10 to 30% by weight, based on the agent, of oligoglyce Rinestersulfate and customary auxiliaries and additives.  
• - Hair shampoos, containing 10 to 30 wt .-% - based on the middle - Oligoglycerinestersulfate as well as usual Auxiliaries and additives.
• - Hair rinses, containing 10 to 30 wt .-% - based on the middle - Oligoglycerinestersulfate as well as usual Auxiliaries and additives.
• - Foam baths containing 10 to 30 wt .-% - based on the middle - Oligoglycerinestersulfate as well as usual Auxiliaries and additives.

Auxiliaries and additives

Washing, rinsing, cleaning and softening preparations based on Oligoglycerinestersulfate invention can be used as auxiliary and additives, for example, other surfactants, builders, Salts, bleaches, bleach activators, optical brighteners, Grayness inhibitors, solubilizers and enzymes enthal th.

Common builders are sodium aluminum silicates (zeolites), Phosphates, phosphonates, ethylenediaminetetraacetic acid, Ni tri-tri-acetate, citric acid and / or polycarboxylates. When Salts or adjusting agents are, for example, sodium sulfate, Sodium carbonate or sodium silicate (water glass) into consideration. As typical individual examples of other additives are Sodium Borate, Starch, Sucrose, Polydextrose, TAED, Style benverbindungen, methyl cellulose, toluenesulfonate, cumolsul  fonat, long-chain soaps, silicones, mixed ethers, lipases and To name proteases.

Hair shampoos, hair lotions or bubble baths based on the he Oligoglycerinestersulfate according to the invention can be used as auxiliary and additives, for example, other surfactants, emulsifiers, Oil components, fats and waxes, thickeners, overfat agents, biogenic agents, film formers, fragrances, Dyes, pearlescing agents, preservatives and pH re gulatoren included.

Common oil components are substances such as paraffin oil, Pflan zenoyl, fatty acid esters, squalane and 2-octyldodecanol while as fats and waxes, for example, spermaceti, beeswax, mon tan wax, paraffin and cetylstearyl alcohol find use. As Überfettungsmittel substances such as polyethoxylated lanolin derivatives, lecithin derivatives and fat acid alkanolamides are used, the latter simultaneously serve as foam stabilizers. Suitable Ver Thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar, alginates and tyloses, Carboxymethylcellulose and hydroxyethylcellulose, further hermolecular polyethylene glycol mono- and diesters of fat acids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrole lidon and electrolytes such as table salt and ammonium chloride. Among biogenic agents are, for example, Pflanzenex tracts, protein hydrolysates and vitamin complexes. Common film formers are for example polyvinylpyr rolidon, vinylpyrrolidone-vinyl acetate copolymers, polymers the acrylic acid series, quaternary cellulose derivatives and the like connections. As preservatives are suitable  For example, formaldehyde solution, p-hydroxybenzoate or sorbin acid. For example, glycol diols are used as pearlescing agents stearic acid esters such as ethylene glycol distearate, as well Fatty acid monoglycol esters. As dyes can the sub-appropriate and approved for cosmetic purposes For example, in the pub likation "Cosmetic Dyes" of the Dye Commission the Deutsche Forschungsgemeinschaft, published in Ver Chemie, Weinheim, 1984, 5.81-106. These dyes are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the total mixture, a set.

Another object of the invention finally relates the use of the oligoglycerol ester of the invention fate for the production of detergents, dishwashing detergents and cleaning agents and hair and body care products in which they are used in Amounts from 1 to 70, preferably 10 to 30 wt .-% - related may be included in the funds.

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

Examples I. General preparation instructions

In a 1-liter sulfonation reactor with jacket cooling and Gaseinlei guide tube 1 mol fatty acid oligoglycerol were initially charged and heated to 35 to 70 ° C. Within 20 to 50 minutes now 0.5 to 1.9 moles of gaseous sulfur trioxide were passed. The amount of SO ₃ had previously been expelled from an appropriate amount of 65 wt .-% oleum and diluted with nitrogen to a concentration of 3 vol .-%. After completion of the sulfation, the crude product was neutralized together with a 25 wt .-% aqueous sodium hydroxide solution at pH = 7.5. Finally, the resulting fatty acid oligoglycerol ester sulfate sodium salts were adjusted to pH = 7 with the addition of 1% by weight of citric acid as buffer and preservative.

Used starting materials A) Caprylic acid diglycerol ester n = 2 B) C _12/14 coconut fatty acid diglycerol ester n = 2 C) C _12/14 coconut fatty acid triglycerol ester n = 3 D) C _12/14 coconut fatty acid pentaglycerol ester n = 5 E) C _16/18 tallow fatty acid diglycerol ester n = 2

The starting materials mentioned are tech niche products, d. H. the specified degree of self-condensation tion (n) represents a statistical average.  

The anionic surfactant content (WAS) as well as the unsulfonated portions (US) according to the DGF standard methods, Stuttgart 1950- 1984, H-III-10 and G-II-6b determined. The salinity was calculated as sodium sulfate, the water content over the Troc kenrückstand determined.

Table 1

test results

Percentages as weight%

II. Formulation Examples Example 9

Liquid detergent with softening properties Dehydol ^(R) ) LT 7 15% by weight Estersulfat according to Ex. 3 44% by weight Plantaren ^(R) APG-600 15% by weight Dehyquart ^(R) AM 36 8% by weight Cumene sulfonate sodium salt 4% by weight water ad 100

The agent has excellent washing and avivage properties and also causes an antistatic equipment of the treated textiles.

Example 10

Disinfectant cleaner Plantar ^(R) APG-225 7% by weight Estersulfat according to Ex. 3 3% by weight Dehyquart ^(R) AM 36 10% by weight water ad 100

The agent has excellent cleaning properties simultaneous disinfection on.  

Example 11

Universal detergents Plantaren ^(R) APG-600 10% by weight Ester sulfate according to Ex. 8 9.5% by weight sodium tripolyphosphate 45% by weight sodium 20% by weight sodium 15% by weight protease 0.5% by weight

The powder has very good washing and cleaning properties on.

Example 12

duty detergent Plantaren ^(R) APG-600 12% by weight Estersulfat gem. Ex. 8 4% by weight Dehyquart ^(R) AM 36 4% by weight water ad 100

The detergent mixture combines the properties of a fine detergent with that of a softener.

Claims (24)

1. Oligoglycerol ester sulfates obtainable by reacting fatty acid oligoglycerol esters of the formula (I) in which R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and n is from 1.5 to 10, reacted with sulfonating agents and then neutralized with bases. 2. A process for the preparation of Oligoglycerinestersulfa th, wherein fatty acid oligoglycerol esters of the formula in which R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and n is from 1.5 to 10, reacted with sulfonating agents and then neutralized with bases. 3. The method according to claim 2, characterized in that one uses fatty acid oligoglycerol ester of the formula (I) in which R ¹ CO for acyl radicals having 12 to 18 Kohlenstoffato men and n is from 2 to 5 numbers. 4. Process according to claims 2 and 3, characterized marked records that as the sulfonating agent chlorosulfonic acid or gaseous sulfur trioxide. 5. Process according to claims 2 to 4, characterized marked characterized in that the sulfation in a continuous union reactor performs, according to the falling film principle is working. 6. Process according to claims 2 to 5, characterized marked records that the fatty acid oligoglycerol esters and the sulfonating agent in a molar ratio of 1: 0.5 to 1: 2.0 starts. 7. Process according to claims 2 to 6, characterized marked characterized in that the sulfation at temperatures of 30 to 90 ° C performs. 8. Process according to claims 2 to 7, characterized in that the neutralization with 5 to 55 wt .-% aqueous bases of the alkali metal hydroxides, alkaline earth metal oxides and hydroxides, ammonia, mono-, di- and tri-C _2-4 alkanolamines and primary, secondary and tertiary C _1-4 alkylamines and glucamines formed group performed. 9. Detergent mixtures containing Oligoglycerinestersulfate according to claim 1 and further anionic, nonionic, cationic and / or amphoteric or zwitterionic Ten side.   10. detergent mixtures according to claim 9, characterized net, that they have a content of anionic surfactants which are selected from the group proposed by Al alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, Alkyl ether sulfonates, glycerol ether sulfonates, α-methyl estersulfonates, sulfo-fatty acids, alkyl sulfates, fat alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fat acid amide (ether) sulfates, sulfosuccinates, sulfosuc cinamates, sulfotriglycerides, amide soaps, ethercarbon acids, isethionates, sarcosinates, taurides, alkyloli goglucoside sulfates and alkyl (ether) phosphates becomes. 11. detergent mixtures according to claim 9, characterized gekennzeich net that they contain a content of nonionic surfactants which are selected from the group consisting of Fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide poly glycol ethers, fatty amine polyglycol ethers, alkoxylated Triglycerides, alk (en) yloligoglycosides, fatty acid glut camiden, polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates is formed. 12. detergent mixtures according to claim 9, characterized gekennzeich net, that they have a content of cationic surfactants which are selected from the group of quaternary ammonium compounds and quaternized di fatty acid trialkanolamine esters is formed.   13. detergent mixtures according to claim 9, characterized gekennzeich net, that they have a content of cationic surfactants which are selected from the group proposed by Al kylbetaines, alkylamidobetaines, aminopropionates, ami noglycinates, imidazolinium betaines and sulfobetaines is formed. 14. detergent mixtures according to claims 9 to 13, characterized characterized in that they contain the oligoglycerol ester sulfates in Amounts of 1 to 99 wt .-% included. 15. Powdered universal detergents containing 10 to 30 % By weight of the funds Oligoglycerinestersulfate and customary auxiliary and Zu set materials. 16. Universal liquid detergents containing 10 to 70 Wt .-% - based on the means Oligoglycerinestersulfate and customary auxiliary and Zu set materials. 17. Liquid mild detergents containing 10 to 50% by weight - based on the middle oligoglycerol ester sulfates as well as usual auxiliaries and additives. 18. Hand dishwashing detergent containing 10 to 50% by weight - based on the middle oligoglycerol ester sulfates as well as usual auxiliaries and additives.   19. rinse aid, containing 10 to 50 wt .-% - based on the means - Oligoglycerinestersulfate as well as usual Auxiliaries and additives. 20. Liquid cleaners and disinfectants containing 10 to 30 wt .-% - based on the means - Oligoglyce Rinestersulfate and customary auxiliaries and additives. 21. Hair shampoos, containing 10 to 30 wt .-% - based on the means - Oligoglycerinestersulfate as well as usual Auxiliaries and additives. 22. Hair rinses containing 10 to 30 wt .-% - based on the means - Oligoglycerinestersulfate as well as usual Auxiliaries and additives. 23. foam baths containing 10 to 30 wt .-% - based on the means - Oligoglycerinestersulfate as well as usual Auxiliaries and additives. 24. Use of Oligoglycerinestersulfaten according to claim 1 for the production of washing, rinsing and Reinigungsmit hair and body care products.