DE2452033A1 - Methoxyalkyl sulphate surfactant combinations - have a high cleaning capacity, are mild to skin, biologically degradable and innocuous to marine life - Google Patents

Abstract

A surfactant combination for use in washing/cleaning compsns. consists of 50-70 wt. % cpd (I) 30-50 wt. % cpd(II) (where R is (un)branched 8020C alkyl and M is Na, K, NH4 or the cation of an org. ammonium base). The combination has a high cleaning capacity (higher than each alone) esp. for wool and synth. fibres. It is mild to skin and may therefore be used in dish-washing compsns. shampoos and hand-cleaning compsns. (cf. US 3639291 which contains alkyl benzene sulphonates, known skin irritants). It is biologically degradable and is innocuous to marine life.

Description

"Surfactant combination suitable for use in detergents and cleaning agents and process for their preparation" German Offenlegungsschrift 1 910 765 discloses active washing substances which are obtained from higher molecular weight internal epoxides or the internal vicinal diols derived therefrom with the introduction of solubilizing groups. The internal vicinal methoxy sulfates of the general formula derived from these diols or epoxides are also used with x and y = 0-26 and x + y = 0-26, preferably 8-20 and M = cation. These are isomer mixtures which, however, should have less than 2 Vo of terminal isomers. It can be shown that the washing and cleaning power of these compounds with internal sulfate and methoxy groups is unsatisfactory.

American patent 3,639,291 describes vicinal ether sulfates of the formula with x and y - 0 - 15 and x + y = 13 - 15, R = alkyl group with 1 - 8 carbon atoms and Me = cation mentioned. They can exist as isomer mixtures and are used together with alkylbenzenesulfonates in liquid detergents and cleaning agents. The patent does not contain any information on the structure and composition of the isomer mixtures.

The use of vicinal methoxyalkyl sulfates according to above formula in phosphate-free, containing sodium silicate as a builder Detergents are also known from German Offenlegungsschrift No. 2,242,093. More information about the structure and isomer distribution of the ether sulfates used cannot be found in this reference either.

There was now a surfactant combination based on isomeric methoxyalkyl sulfates found, which is characterized by a high washing power, especially with regard to textiles made of wool and synthetic fibers, the effect of the mixture being that of the Substances significantly outperforms.

The invention relates to a surfactant combination suitable for use in detergents and cleaning agents, characterized in that it consists of 50 to 70% by weight of a 1-methoxyalkyl sulfate-2 of the formula (I) and from 30 to 50% by weight of a 2-methoxyalkyl sulfate-1 of the formula (II) where R is a straight-chain or branched alkyl radical having 8 to 20 carbon atoms and M is Na, K, NH4 or the cation of an organic ammonium base.

R preferably stands for a straight-chain alkyl radical. The number of Carbon atoms is preferably 10 to 18.

Of particular practical interest are the sodium salts of the compounds. The weight ratio of the compound (I) to the compound (II) should be particularly in the range of about 60:40, i.e. H. between 55:45 and 65:35.

The methoxyalkyl sulfates can be prepared in a known manner by sulfation the corresponding primary and secondary ether alcohols with strong sulphonation agents, such as sulfur trioxide, chlorosulfonic acid or sulfamic acid and subsequent neutralization shown and combined with each other in the given proportions. It However, it has surprisingly been found that when a mixture of 50 up to 70% by weight of 1-methoxyalkanols-2 and 50 to 30% by weight of 2-methoxyalkanols-1 comparatively high sulfation yield and a particularly light-colored sulfation product is achieved even when no solvents or diluents are present.

The invention therefore also provides a process for the preparation of mixtures of methoxyalkyl sulfates according to the above definition of the invention, characterized in that a mixture of 50 to 70% by weight of ether alcohol of the formula (III R - CHOH - CH2-OCH3 (III) and 50 to 30 parts by weight of ether alcohol of the formula (IV) in the absence of solvents with strong sulfonating agents, which are used in amounts of 1 to 1.3 mol, based on mol of sulfatable substance, sulfated at temperatures between 10 ° and 50 ° C. and then neutralized in a manner known per se.

Suitable sulfonating agents are oleum, sulfur trioxide, preferably in gaseous, with air or an inert gas to a content of 0.2 to 8 percent by volume Is used diluted, sulfamic acid and especially chlorosulfonic acid.

The sulphonation can be carried out batchwise or continuously devices that operate according to the thin-film or atomization principle work are particularly suitable.

The temperature during the sulfation is preferably 15 to 30 ° C, although this is generally somewhat lower when using chlorosulfonic acid can be kept than when using 503. To dissipate the heat of reaction the reaction vessel can be equipped with cooling devices. Preferably is the molar ratio of sulfonating agent to ether alcohol 1.02: 1 to 1.15: 1 Excess of SO3 or

that remaining in the reaction mixture during the reaction with chlorosulfonic acid Hydrogen chloride is expediently removed after the reaction has ended by directs a stream of air or inert gas through the reaction material or this by applying degassed in a vacuum.

The neutralization can be carried out with customary alkalis, e.g. B. the hydroxides, Carbonates and bicarbonates of sodium or potassium, with ammonia or organic Amines or ammonium bases take place. Suitable organic neutralizing agents are z. B. mono-, di- or trialkanolamines, especially ethanolamines, also guanidine, Morpholine and N-methylmorpholine. Before or after neutralization, the sulfonation products, sòfernJ! P! »brave, with the usual oxidative or reductive acting Bleaches are bleached, for example with hypochlorites, chlorites or with hydrogen peroxide.

The surfactant combination according to the invention, in particular that after The mixture produced by the method according to the invention is characterized by a number of merits. It has a high cleaning power, especially against Wool and synthetic fibers, which are comparable substances, especially the of the individual components. It is skin-friendly and therefore suitable excellent for the production of detergents for manual dishwashing, Shampoos and skin cleansers. It outperforms the US patent blends in this regard 3,639,291, which contain alkylbenzenesulfonates, which are known to be irritating to the skin and are therefore less recommended for manual washing and cleaning.

The good biodegradability and harmlessness should also be emphasized against organisms living in water.

The claimed surfactant combination can stand alone, for example in liquid preparations or in connection with other cleansing agents Substances are used, in particular with so-called. Builder substances, which the To bind calcium hardness of the water or to be able to complex metal ions.

Other suitable, additional components of the mixture are anionic, zwitterionic or nonionic surfactants as well as other commonly used in detergents, Active ingredients contained in detergents and cleaning agents, e.g. B. washing alkalis, bleaching active compounds as well as stabilizers and / or activators for bleaches, Graying inhibitors, optical brighteners, enzymes, biocides, foam inhibitors or -stabilizers, fabric softeners as well as dyes and fragrances.

If the surfactant combination according to the invention together with builder substances used is the mixing ratio between the surfactant combination and the structural substance ae according to application area 5: 95 to 90: 10.

The structural substances include the carbonates and silicates of potassium and especially of sodium, the latter having a ratio of SiO2 to Na20 of 1: 1 to 3.5: 1. The polymer phosphates are also particularly suitable the pentasodium triphosphate, which in a mixture with its hydrolysis products, the mono- and diphosphates, and more highly condensed phosphates, e.g. B. the tetraphosphates, may exist. As a further structural substance, particularly suitable for mild detergents Sodium sulfate is an option.

The polymer phosphates can also be wholly or partly by organic, aminopolycarboxylic acids with a complexing action be replaced. These include in particular Alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. Suitable are also the salts of dietary triaminopentaacetic acid and the higher homologues of the mentioned kainopolyzarboxylic acids. These homologues can, for example, by Polymerization of an ester, amide or nitrile of N-acetic acid aziridine and then Saponification to carboxylic acids Salts or by reacting polyethyleneimine made with chloroacetic acid or bromoacetic acid salts in an alkaline environment will. Other suitable aminopolycarboxylic acids are poly (N-succinic acid) ethyleneimine, Poly (N-tricarballyic acid) ethylene imine and poly (N-butane-2, 3, 4-tricarboxylic acid) ethylene imine, which are available analogously to the N-acetic acid derivatives.

Furthermore, complexing polyphosphonic acid salts can be present be, e.g. the alkali salts of aminopolyphosphonic acids, especially aminotri- (methyienphosphonic acid), 1-Hydroxyäthan- 1, 1 -diphosphonic acid, methylenediphosphonic acid, ethylenediphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Mixtures too the aforementioned complexing agents can be used, of particular importance are nitrogen- and phosphorus-free and form complex salts with calcium ions Polycarboxylic acids, including polymers containing carboxyl groups. Suitable are citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid. Polycarboxylic acids containing carboxymethyl ether groups can also be used, such as 2,2t-oxydisuccinic acid as well as partially or completely etherified with glycolic acid polyhydric alcohols or hydroxycarboxylic acids, for example triscarboxymethyl glycerine, bicarbboxymethylglyceric acid and carboxymethylated or oxidized polysaccharides. The polymeric carboxylic acids with a molecular weight of at least 350 in the form of the water-soluble sodium or potassium salts, such as polyacrylic acid, Polymethacrylic acid, polyoc-hydroxyacrylic acid, polymaleic acid, polyitaconic acid, Poly-, esroconic acid, polybutenetricarboxylic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, propylene, isobutylene, vinyl methyl ether or furan.

Complexing agents which are insoluble in water can also be used. These include phosphorylated cellulose and graft polymers of acrylic acid or methacrylic acid on cellulose, which can be in the form of woven or non-woven fabrics. Furthermore are spatially cross-linked and thus water-insoluble copolymers of acrylic, methacrylic, Crotonic and maleic acid and other polymerizable polycarboxylic acids, if necessary with other ethylenically unsaturated compounds in the form of sodium or potassium salts suitable as a sequestering agent. These insoluble copolymers can be used as tiles, Swim or in the form of finely ground, specifically light foams with open-celled foam Structure.

Alkali aluminum silicates are also suitable as water-insoluble builder substances and alkali borosilicates, which may contain bound water and a calcium binding capacity have at least 50 mg CaO / g active substance. This includes connections in particular of the formula (Na 2 O) x Al 2 O 3 (SiO 2) y, where x is a number from 0.7 to 1.5 and y is a number from 1.3 to 4 mean. You can use the agents according to the invention as a finely divided powder be added. Also mixtures of the aforementioned water-soluble and water-insoluble ones Framework substances are useful.

Except for the invention to be used lflethoxyalkyl sulfates and The detergents can contain structural substances as well as other common detergent constituents contain.

These include the known anionic, nonionic and zwitterionic Surfactants, bleaching agents, anti-graying substances, optical brighteners, biocides, Fragrances and dyes as well as other common auxiliaries and additives.

Suitable surfactants are those of the sulfonate or sulfate type, for example Alkylbenzenesulfonates, in particular n-dodecylbenzenesulfonate, also olefin sulfonates, Alkyl sulfonates, ac sulfo fatty acid esters, primary and secondary alkyl.

sulfates and the sulfates of ethoxylated or propoxylated higher molecular weight Alcohols.

Further compounds of this class which may be present in the detergents are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali metal salts of the monoalkyl ethers or the monofatty acid esters of glycerol monozzoic acid ester or

of 1,2-dioxropane sulfonic acid. Furthermore, sulfates come from ethoxylated or propoxylated fatty acid araids and alkylphenols and fatty acid taurides and Fatty acid ethers in question. Other suitable anionic surfactants are alkali soaps of fatty acids of natural or synthetic origin, e.g. sodium soaps of coconut, palm kernel or tallow fatty acids.

Zwitterionic surfactants are alkyl betaines and, in particular, alkyl sulfobetaines in question, e.g. 3- (N, N-dimethyl-N-alkylnmmonium) -propane-1-sulfonate and 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropan-1-sulfonate.

The anionic surfactants can be in the form of the sodium, potassium and ammonium salts and as salts of organic bases such as mono-, di- or triethanolamine. If the anionic and zwitterionic compounds mentioned are aliphatic Have hydrocarbon radical, this should preferably be straight-chain and 8 to Have 22 carbon atoms. In the compounds with an araliphatic hydrocarbon residue the preferably unbranched alkyl chains contain an average of 6 to 16 carbon atoms. - As nonionic surface-active surfactants come first Line of polyglycol ether derivatives of alcohols, fatty acids and alkylphenols in question, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical contain. Polyglycol ether derivatives in which the number of Ethylene glycol ether groups is 5 to 15 and their hydrocarbon radicals of straight-chain, primary alcohols with 12 to 18 carbon atoms or of alkylphenols derive with a straight-chain alkyl chain having 6 to 14 carbon atoms.

Other suitable nonionic surfactants are the water-soluble, Containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups Polyethylene oxide adducts with polypropylene glycol, ethylene diamino poly propylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. the compounds mentioned usually contain 1 to per propylene glycol unit 5 ethylene glycol units. Also nonionic compounds of the amine oxide type and sulfoxides, which can optionally also be ethoxylated, can be used.

Oxygen-releasing bleaches are another component of the mixture, such as alkali perborates, percarbonates, perpyrophosphates and persilicates as well as urea perhydrate in question.

Sodium perborate is preferably used in anhydrous form or as tetrahydrate. To stabilize the per compounds, the agents can contain magnesium silicate, for example in amounts of 3 to 20 wt., based on the amount of perborate, Means to be used for washing textiles at temperatures below 70 ° C., so-called Cold detergents, bleach activators from the class of N- or O-acyl compounds, especially tetraacetylethylenediamine or Tetraacetyl glycoluril, contained as a powder component.

Those consisting of the bleach activator or the per compound Powder particles can be coated with coating substances such as water-soluble polymers or fatty acids be coated to allow interaction between the per compound and the activator to avoid during storage.

The detergents can also contain optical brighteners, in particular Derivatives of diaminostilbene disulfonic acid or

their alkali metal salts. For example, salts of 4,4'-bis - (- 2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2'-disulfonic acid are suitable or similarly structured compounds, 'which instead of the morpholino group a Diethanolamino group, a methylamino group or a ß-methoxyethylamino group wear. Furthermore, brighteners of the diarylpyrazoline type are used as brighteners for polyamide fibers in question, for example 1- (p-sulfonamidophenyl) -5- (p-chloropnenyl) - t2-pyrazoline as well as similarly structured compounds which, instead of the sulfonamido group, have a Carboxymethyl or acetylamino groups. Substituted ones can also be used Aminocoumarins, e.g. 4-methyl-7-dimethylamino- or 4-methyl-7-diethylaminocoumarin. The compounds 1- (2-benzimidazolyl) -2- ( 1-hydroxyethyl-2-benzimidazolyl) -ethylene and 1-0thyl-3-phenyl-7-diethylamino-carbostyril useful. The compounds are used as brighteners for polyester and polyamide fibers 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphtho [2, u, 3-g -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) -ethylene are suitable. You can also use brighteners of the substituted diphenylstyrile type be present. Also mixtures of the aforementioned Brighteners can be used.

Particularly suitable graying inhibitors are carboxymethyl cellulose, Methyl cellulose, as well as water-soluble polyesters and polyamides made from polyvalent ones Carboxylic acids and glycols or diamines, the free carboxyl groups capable of forming salts, Have betaine groups or sulfobetaine groups as well as colloidally soluble in water Polymers or copolymers of vinyl alcohol, vinyl pyrrolidone, acrylamide and acrylonitrile.

The agents can also include enzymes from the class of the proteases, lipases and amylases or mixtures thereof. Bacterial strains are particularly suitable or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus obtained enzymatic active ingredients, which oppose alkali, percompounds and anionic Active washing substances are relatively stable and also at temperatures between 500 and 700C are not yet significantly inactivated.

Further components contained in the agents according to the invention are neutral salts, especially sodium sulphate, bacteriostatic substances, such as halogenated phenolic ethers and thioethers, halogenated carbanilides and salicylanilides as well as halogenated diphenylmethanes, dyes and fragrances, liquids can also contain hydrotopic substances and solvents, such as alkali salts benzene, toluene or xylene sulfonic acid, urea, glycerine, polyglycerine, di- or triglycol, polyethylene glycol, ethanol, i-propanol and ether alcohols.

If appropriate, the detergents can also be known foam suppressants contain, such as saturated fatty acids or their alkali metal soaps with 20 to 24 Carbon atoms, higher molecular fatty acid esters or triglycerides, paraffins, Trialkyl melamines and silicone antifoams.

Examples 1. Preparation of the methoxy ether sulfates Example 1 In 272 g (1 mol) of a mixture of 60% by weight of 1-methoxyhexadecanol-2 and 40% by weight of 2-methoxyhexadecanol-1 was in a 1 liter round bottom flask at a temperature of 22 ° C in the course introduced for 30 minutes with vigorous stirring, a stream of air, the 3 percent by volume Contained SO3.

After 88 g of SO3 (1.1 mol) had been introduced, air was introduced continued for another 3 minutes. The light yellow, viscous product became vivid under Stirring and cooling with ice, poured into a solution of 42 g (1.05 mol) of NaOH in 200 ml of water. The solution, which had been adjusted to a pH of approx. 8, was then spray-dried. The spray product was yellowish-tinged white and had a degree of sulfation of 96%.

Example 2 274 g (1 mol) of a mixture of 60% by weight of 1-methoxyalkanol-2 and 40% by weight of 2-methoxyalkanol-1, the hydrocarbon radicals of which have 15 to 18 carbon atoms (mean chain length c16.1) were in a 1 liter flask at an initial temperature of 15 0C in the course of 10 minutes under brisk Stirring mixed with 128 g (1.1 mol) of chlorosulfonic acid, the temperature with Ice-water cooled reaction vessel rose briefly to 23 ° C. After completion of the The sulfonation reaction became vigorous with vigorous stirring for 5 minutes Air flow passed through the reaction mixture to remove the remaining hydrogen chloride to remove. The neutralization with 44 g (1.1 mol) of NaOH in 200 ml of water and the Work-up was carried out as indicated in Example 1.

The product was slightly yellowish to colorless and had a ~~ Sulfiergraa! ~ Ff! N-! 8 ~% on. on.

2. Technical application test With those prepared according to Examples 1 and 2 Washing tests were carried out with surfactant combinations. As comparison substances were used: A. a vicinal sodium methoxysulphate with a linear C15-C18 hydrocarbon residue (mean chain length C16 5), in which the adjacent methoxy and sulfate group are statistically distributed over the hydrocarbon chain (reference substance according to DOS 1 910 765), B. Comparative substance of structure A, but with a linear Cl 1-C14 hydrocarbon radical (average chain length C13, 5), C. a 1-methoxyalkyl sulfate-2 with a linear C15-C18 hydrocarbon radical (Average chain length C16.5 D. a from primary C12-C14 fatty alcohols through conversion sodium alkyl diglycol ether sulfate obtained with 2 moles of ethylene glycol and subsequent sulfation.

To test the wool washability, wool strands of 4 g weight soiled with dust and skin fat were washed in a laboratory washing machine (launderometer) with 200 ml washing liquor with little mechanical processing of the laundry using a mixture of 1 g / l active washing substance and 3 g / l Na2SO4. The washing temperature was 30 ° C., the water hardness was 16 OdH, the weight ratio of textiles to the washing liquor was 1:50, and the washing time was 15 minutes. The samples were then rinsed three times with tap water and dried, and the percentage lightening (non-soiled material 100%, “soiled material = 0 to”) was determined photometrically. Pensid% brightening according to example 78 compare A 71 compare BO Compare C 76 Compare D 68 Tab. 1 In a second series of tests, samples of a mixed fabric consisting of equal parts of finished cotton and polyester fiber and soiled with dust and sebum were washed in the launderometer. The detergent used was a mixture of 36.7% by weight of active washing substance and 63.3% by weight of pentasodium triphosphate. The detergent concentration was 2.75 g / l, the liquor ratio 1:30, the water hardness 16 ° dH and the temperature 60 ° C. After a washing time of 30 minutes including the heating-up period, it was rinsed 4 times with tap water. The remission determined photometrically compared to a whiteness standard (magnesium oxide) is given in Table 2 below. Surfactant worth it according to example 1 61 according to example 2 62 Compare A 52 Compare B 44 he is equal to C 60 Compare D 54 Tab. 2 The zein test (cf. Aesthetic Medicine 15, year 1966, pages 313-319) was used to determine skin tolerance. To this end, 2 g of zein are added to 40 ml of a neutral 1% solution of a washing active substance, warmed to 35 ° C. and located in a 50 ml narrow-necked bottle, and the temperature is kept at 35 ° C. for 2 hours with constant mixing. After filtering off the undissolved zein, the nitrogen content of the solution is determined according to Ejeldahl. The zein value is given in mg N per 100 ml of solution. Non-irritating substances have a zein value of less than 300. A zein value of 350 is generally assumed as the limit value for good skin tolerance.

The following zein values were found using this method: washing active substance Zeinwert I 310 II 305 C12-14-alkyl diglycol ether sulfate 324 n-dodecylbenzenesulfonate The tests show that the agents according to the invention are different from the comparison substances characterized by better washing power and increased skin tolerance.

Claims (12)

Claims Oil Surfactant combination suitable for use in detergents and cleaning agents, characterized in that it consists of 50 to 70% by weight of a 1-methoxyalkyl sulfate-2 of the formula (I) and from 30 to 50% by weight of a 2-methoxyalkyl sulfate-1 of the formula (II) where R is a straight-chain or branched alkyl radical having 8 to 20 carbon atoms and M is Na, K, NH4 or the cation of an organic ammonium base. 2. Means according to claim 1, characterized in that R is for one straight-chain alkyl radical. 3. Means according to claim 1 and 2, characterized in that R 10 has to 18 carbon atoms. 4. Means according to claim 1-3, characterized in that M is sodium stands. 5. Means according to claim 1 to 4, characterized in that it is too 55 to 65% by weight of the compound of formula (I) and to. 45 to 35% by weight of the compound according to formula. II exists. 6. Process for the preparation of the agent according to claim 1, characterized in that a mixture of 50 to 70 wt. Ether alcohol of the formula (III) R - CHOH - CH2 - OCH3 (III) and 50 to 30 wt. Ether alcohol is used Formula (IV) in the absence of solvents with strong sulfonating agents, which are used in amounts of 1 to 1.3 mol, based on moles of sulfatable substance, sulfated at temperatures between 10 and 50 ° C and then neutralized in a manner known per se. 7. The method according to claim 6, characterized in that as Sulphuring agent with air or inert gas to a content of 0.2 to 6 percent by volume diluted sulfur trioxide is used. 8. The method according to claim 6, characterized in that as The sulfating agent used is chlorosulfonic acid. 9. The method according to claim 6 to 8, characterized in that the The molar ratio of sulphonation agent to ether alcohol is 1.02 1 to 1.15: 1. 10. The method according to claim 6 to 9, characterized in that one the sulfonation is carried out at temperatures between 15 and 40 ° C. 11. Use of the agents according to Claims 1 to 5 in detergents and cleaning agents with a content of structural substances that reduce the hardness of lime in water or metal ions able to bind in a complex manner. 12. Use according to claim 1-1, characterized in that it the mixing ratio of surfactant combination to structural substance 5: 95 to 90: 10 is.