DE10029692A1 - Detergents useful for washing textiles comprise optionally alkoxylated oxo alcohols or their sulfates or phosphates - Google Patents

Abstract

Detergents comprising optionally alkoxylated oxo alcohols having 11-13 carbon (C) atoms or their sulfates or phosphates are new. Detergents comprising surfactants of formula (I) together with conventional detergent ingredients and optionally other surfactants are new: a = 11-13; R<1>, R<2> = H or 1-16C alkyl; R<3> = H, sulfato or phosphato; and x, y = 0-200.

Description

Detergents in the sense of this invention are generally used for washing more or less flexible materials, preferably those that are natural, contain synthetic or semi-synthetic fiber materials or best of them hen and consequently at least partially have a textile character.

Detergents of this type have been described many times in the prior art. A very good overview of the mode of action and the composition of detergents can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, vol. A8, (1986), pages 315 ff, keyword "detergents". The detergents contain one or more surfactants from the same or different surfactant groups and usually other auxiliary substances and additives, which are either required for packaging and / or which allow the detergents to be adapted to the specific intended use or the type of application (washing by hand or in machines). Components that can be used in many detergents in addition to the various surfactants in changing combinations and proportions are, for example, builders (sequestering agents) and co-builders, pH regulators, such as inorganic or organic acids, inorganic or organic bases and buffer systems , Ion exchangers, dispersants, soil release agents, thickening agents, enzymes, bleaching systems, hydrotropic compounds as solubilizers or solubilizers, such as. B. urea or alcohols, foam regulators for stabilizing or damping the foam, skin and corrosion inhibitor, disinfectant compounds or systems, such as those that contain iodine or release the chlorine or hypochlorous acid, such as. B. dichlorisocya nurate, perfume, dyes, optical (fluorescent) brighteners, graying inhibitors, adjusting and confectioning agents and biocides. The surfactants contained in the detergents described in the prior art have a significant share in the cleaning action. Ionic surfactants are used, both anionic such as alcohol sulfates, alcohol ether sulfates, alkylbenzenesulfonates, α-olefin sulfonates, sulfosuccinates and cationic surfactants, such as. B. for example C ₈ to C ₁₆ -di alkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with a long-chain alkyl radical.

The use of amphoteric surfactants, for example derivatives of secondary or tertiary amines such as. B. C ₆ -C ₁₈ alkyl betaines or C ₆ -C ₁₅ alkylsulfobetaines or amine oxides such as alkyldimethylamine oxides have already been described.

Also nonionic surfactants, especially alkoxylates and polyglycosides of long-chain and long-chain alkanols, in particular with 8 to 20 C Atoms and alkoxylates of alkylamines and alkylamides are described in Detergents used. In particular, it is also known to use oxo alcohols with 10 up to 13 carbon atoms in the form of their phosphoric or sulfuric acid esters and Al koxylates of these oxo alcohols directly or in the form of their phosphoric or Schwe rock acid esters as surfactants in detergents.

In the interest of the most economical use of materials, high economy and last but not least, the detergent manufacturers are striving for a lower environmental impact  after a constant improvement in the effectiveness of their products and in particular re of the surfactants it contains.

It has now surprisingly been found that the invention described below contemporary detergent compared to closest comparable known agents develop significantly superior effectiveness.

The present invention thus relates to a detergent comprising an effective proportion of one or more surfactants of the formula I.

wherein
a represents one of the numbers 11, 12 and 13,
R ¹ and R ^{2 are} different and each represent hydrogen or alkyl radicals of the formula C _n H _{2n + 1} -,
R ³ denotes hydrogen, or a sulfato or phosphate residue,
n stands for a number from 1 to 16, x for a number from 0 to 200 and y for a number from 0 to 200,
as well as other known auxiliaries and additives common in detergents and
optionally additional surfactants.

It is of considerable importance for the high effectiveness of the detergents according to the invention that the i-C _a H _{2a + 1} radical contained in the surfactants of the formula I is derived from an oxo alcohol obtained by hydroformylation of a decene, dodecene or a mixture of these olefins is, which in turn has been prepared by dimerization of n-pentene-2, hexene-3 or mixtures of these compounds.

The minimum proportion of the surfactants of formula I in the total weight of the Invention contemporary detergent is dimensioned so that there is a significant effect This addition shows.

The proportion of the tensi to be used according to the invention is expedient de adjusted so that in cooperation with the other components of the Detergent gives an optimal cleaning effect. Usually one good washing effect, especially a very good primary washing effect of the inventor detergent according to the invention achieved when the proportion of the surfactants of formula I in the detergent according to the invention, based on the total weight of the means, 0.01 to 50 wt .-%, preferably 0.1 to 40 wt .-%, in particular 0.5 to Is 30% by weight.

Preferred surfactants of the formula I are those in which a is 13.

Also preferred are surfactants of the formula I in which n is from 1 to 8, preferably from 1 to 4 in particular represents 1 or 2.

In a further preferred group of surfactants of the formula I, R ¹ and R ^{2 are} different and are each hydrogen, methyl, ethyl or propyl.

Furthermore, surfactants of the formula I are preferred in which x is from 1 to 50 in particular from 1 to 20 and y for a number from 0 to 50, in particular from 0 to 20 stands.

Furthermore, surfactants of the formula I are preferred in which the sum of x and y in the range from 1 to 200, preferably from 1 to 100, in particular from 1 to 50 lies.

In a further special embodiment, the cleaning agents according to the invention contain at least an effective proportion of compounds of formula I, but with the proviso that either the sum of x and y is at least 1 or R ^{3 is} not equal to hydrogen.

The x ether chain links of the formula -CH ₂ -CHR ¹ - and the y ether chain links of the formula -CH ₂ -CHR ² - in the compounds of the formula I can be arranged in blocks or randomly in the ether chain.

The compounds of the formula I can be uniform substances, but they can also be mixtures in which different substances falling under the formula I are mixed with one another. The components of these mixtures can differ in the meanings of R ¹ , R ² and also R ³ , and in the values of a, and in particular of x and y. This has the consequence that the analytical values obtained in the elementary analysis of the surfactants of the formula I, for example the C and H values obtained for the oxo alcohol assembly, and in particular the values of the alkoxy group determination when calculating back to the structural formula broken values for a, n, x and y. Of course, such mixtures of substances also represent surfactants according to the invention which fall under the formula I and which have the described advantages over the prior art.

Detergents in the sense of this invention are generally used for washing more or less flexible materials, preferably those that are natural, contain synthetic or semi-synthetic fiber materials or best of them hen and therefore usually at least partially a textile character exhibit. The fibrous or fibrous materials can principally occurring in everyone in use or manufacture and processing present form. For example, fibers can be disordered in the form of Flake or pile, arranged in the form of threads, yarns, threads, or in Form of fabrics such as fleeces, loden fabrics or felt, fabrics, ge act in all conceivable types of binding.

It can be raw fibers or fibers at any stage of processing act and natural protein or cellulose fibers such as wool, silk, Cotton, sisal, hemp, coconut fibers or synthetic fibers such as Po be polyester, polyamide or polyacrylonitrile fibers.

The detergents according to the invention can also be particularly advantageous in Within the processing of fiber materials are used for. B. to Ent greasing raw wool or desizing all kinds of fiber materials.

The detergents according to the invention can also be used to clean fiber conditions materials such. B. back-coated carpets with cut or uncut pile.

Of course, the compositions of the detergents are ver adapted for different purposes, as is known to the person skilled in the art is common. The detergents according to the invention can all be used for this purpose  speaking auxiliary and known from the above prior art Additives are added.

In many cases it is useful to use the surfactants of the invention Formula I with other nonionic surfactants, such as. B. alcohol alkoxylates, Al kylamine alkoxylates, alkyl amide alkoxylates, alkyl polyglucosides, or with ioni rule, preferably anionic, surfactants, such as. B. longer chain or long chain term alcohol sulfate / ether sulfates, alkylbenzenesulfonates, α-olefin sulfonates, Sulfosuccinates, or with amphoteric surfactants, such as. B. alkylamine oxides, or Combine betaines.

The following are examples of different types of surfactants suitable for combination:
Examples of suitable nonionic surfactants are alkoxylated C ₈ to C ₂₂ alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which preferably contain at least two molecules of an alkylene oxide mentioned above can be used as surfactants. Here, too, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol. Ethylene oxide is preferably used as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst, alkoxylates with a broad or narrow alkylene oxide homolog distribution can be obtained.

Another class of suitable nonionic surfactants are alkylphenol alkoxylates such as alkylphenol ethoxylates with C ₆ to C ₁₄ alkyl chains and 5 to 30 mol alkylene oxide units.

Another class of nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. This connection gene usually contain 1 to 20, preferably 1.1 to 5 glucoside units.

Another class of nonionic surfactants are N-alkyl glucamides of the general structures

where B ^{1 is} a C ₆ - to C ₂₂ -alkyl, B ^{2 is} hydrogen or C ₁ - to C ₄ -alkyl and D is a polyhydroxyalkyl radical having 5 to 12 C atoms and at least 3 hydroxy groups. B ¹ is preferably C ₁₀ to C ₁₈ alkyl, B ^{2 is} CH ₃ and D is a C ₅ or C ₆ radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C ₁₀ to C ₁₈ carboxylic acids.

Further suitable nonionic surfactants are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A 95/11225

R ¹ -CO-NH- (CH ₂ ) _y -O- (A ¹ O) _x -R ²

in the
R ¹ denotes a C ₅ to C ₂₁ alkyl or alkenyl radical,
R ^{2 represents} a C ₁ to C ₄ alkyl group,
A ^{1 represents} C ₂ to C ₄ alkylene,
y denotes the number 2 or 3 and
x has a value from 1 to 6.

Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₃ -C ₄ H ₉ with methyl dodecanoate or the reaction products of ethyl tetraglycolamine of the formula H ₂ N- (CH ₂ - CH ₂ -O) ₄ -C ₂ H ₅ with a commercially available mixture of saturated C ₈ - to C ₁₈ -fatty acid methyl esters.

Block copolymers are also suitable as nonionic surfactants Ethylene oxide, propylene oxide and / or butylene oxide (Pluronic® and Tetronic® Brands of BASF), polyhydroxy or polyalkoxy fatty acid derivatives such as Polyhy hydroxy fatty acid amides, N-alkoxy or N-aryloxypolyhydroxy fatty acid amides, Fatty acid amide ethoxylates, especially end-capped, and fatty acid realkanolamide alkoxylates.

The additional nonionic surfactants ("nonionic surfactants") are in the invention detergents according to the invention, preferably in an amount of 0.01 to 30% by weight, in particular 0.1 to 25% by weight, especially 0.5 to 20% by weight.

Individual nonionic surfactants or a combination of different nonionic surfactants can be used. Nonionic surfactants from only one class can be used, in particular only alkoxylated C ₈ to C ₂₂ alcohols, but surfactant mixtures from different classes can also be used.

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18, carbon atoms, e.g. B. C ₉ - to C ₁₁ alcohol sulfates, C ₁₂ - to C ₁₄ alcohol sulfates, C ₁₂ -C ₁₈ alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated ethoxylated C ₈ to C ₂₂ alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by firstly using a C ₈ - to C ₂₂ -, preferably a C ₁₀ - to C ₁₈ alcohol, e.g. B. a fatty alcohol, alkoxylated and the alkoxylation product then sulfated. For the alkoxylation, preference is given to using ethylene oxide, with 1 to 50, preferably 1 to 20, mol of ethylene oxide being used per mol of alcohol. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Such alkoxylated C ₈ are suitable also - to C ₂₂ alcohols, the ethylene oxide and propylene oxide or ethylene oxide and butylene oxide or ethylene oxide and propylene oxide and butylene oxide. The alkoxylated C ₈ to C ₂₂ alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution. Depending on the type of alkoxylation catalyst, alkyl ether sulfates with a broad or narrow alkylene oxide homolog distribution can be obtained.

Other suitable anionic surfactants are alkanesulfonates such as C ₈ - to C ₂₄ -, preferably C ₁₀ - to C ₁₈ -alkanesulfonates and soaps such as the Na and K salts of C ₈ - to C ₂₄ -carboxylic acids.

Further suitable anionic surfactants are linear C ₈ to C ₂₀ alkylbenzenesulfonates ("LAS"), preferably linear C ₉ to C ₁₃ alkylbenzenesulfonates and alkyltoluenesulfonates.

Still further, C ₈ suitable anionic surfactants - to C ₂₄ olefin sulfonates and disulfonates, which may also be mixtures of alkene and hydroxyalkane sulfonates and disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol lyglykolethersulfate, fatty acid glycerol, Alkylphenolpo, paraffin sulfonates with about 20 to approx. 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyl taurates, acyl methyl taurates, alkyl amber acids, alkenyl succinic acids or their half esters or half amides, alkyl sulfosuccinic acids or their amides, mono- and diesters of sulfosuccinic acids, acyl sarcosinates, sulfated alkyl polyglucosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

The anionic surfactants are preferably in the form of Added salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium salts such as e.g. B. Hydroxyethy lammonium, di (hydroxyethyl) ammonium and Tri (hydroxyethyl) ammonium salts.

The anionic surfactants are present in the detergents according to the invention preferably in an amount of up to 30% by weight, for example from 0.1 to 30% by weight, especially 1 to 25% by weight, in particular 3 to 20% by weight. -% in front. If C ₉ to C ₂₀ linear alkylbenzenesulfonates (LAS) are also used, they are usually used in an amount of up to 15% by weight, in particular up to 10% by weight.

Individual anionic surfactants or a combination of different anionic surfactants can be used. Anionic surfactants from only one class can be used, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but it is also possible to use surfactant mixtures from different classes, e.g. B. a mixture of fatty alcohol sulfates and alkylbenzenesulfonates. Further, according to the invention to be employed surfactants of the formula I with cationic surfactants, usually in an amount up to 25 wt .-%, vorzugswei se 1 to 15 wt .-%, for example C ₈ - to C ₁₆ - Dialkyldimethylammoniumhalogeniden, Dialkoxydimethylammoniumhalogeni the or imidazolinium salts having a long-chain Alkyl radical; and / or with amphoteric surfactants, usually in an amount up to 15 wt .-%, preferably 1 to 10 wt .-%, for example derivatives of secondary or tertiary amines such as. B. C ₆ -C ₁₈ alkyl betaines or C ₆ -C ₁₅ alkyl sulfobetaines or amine oxides such as alkyldimethylamine oxides can be combined.

As a rule, the surfactants of formula I to be used according to the invention are included Builders (sequestrants) such as B. polyphosphates, polycarboxylates, Phosphonates, complexing agents, e.g. B. methylglycinediacetic acid and its salts, Nitrilotriacetic acid and its salts, ethylenediaminetetraacetic acid and its salt ze and optionally combined with co-builders.

Individual builder substances which are well suited for combination with the surfactants of the formula I to be used according to the invention are listed below:
Suitable inorganic builders are, above all, crystalline or amorphous aluminosilicates with ion-exchanging properties, such as, in particular, zeolites. Various types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially replaced by other cations such as Li, K, Ca, Mg or ammonium . Suitable zeolites are described, for example, in US-A-4604224.

Suitable crystalline silicates as builders are, for example, disilicates or layered silicates, e.g. B. δ-Na ₂ Si ₂ O ₅ or β-Na ₂ Si ₂ O ₅ (SKS 6 or SKS 7). The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates. Amorphous silicates such as sodium metasilicate, which has a polymeric structure, or amorphous disilicate (Britesil® H 20 manufacturer: Akzo) can also be used.

Suitable carbonate-based inorganic builder substances are carbonates and hydrogen carbonates. These can be in the form of their alkali metal, alkaline earths tall or ammonium salts are used. Na, Li and Mg carbonates or bicarbonates, especially sodium carbonate and / or Sodium bicarbonate used.

Common phosphates used as inorganic builders are alkali orthophosphates and / or polyphosphates such. B. pentasodium triphosphate. The builder components mentioned can be used individually or in mixtures each other.

Furthermore, it is advisable in many cases to add co-builders to the detergents according to the invention. Examples of suitable substances are listed below:
In a preferred embodiment, the detergents according to the invention contain, in addition to the inorganic builders, 0.05 to 20% by weight, in particular 1 to 10% by weight, organic cobuilders in the form of low molecular weight, oligomeric or polymeric carboxylic acids, in particular polycarboxylic acids, or Phosphonic acids or their salts, especially Na or K salts.

Examples of suitable low-molecular carboxylic acids or phosphonic acids as organic cobuilders are:
Phosphonic acids such as B. 1-hydroxyethane-1,1-diphosphonic acid, amino tris (methylenephosphonic acid), ethylenediamine-tetra (methylenephosphonic acid), hexamethylenediamine-tetra (methylenephosphonic acid) and diethylenetriamine penta (methylenephosphonic acid);
C _{4 to} C ₂₀ di, tri and tetracarboxylic acids such as. B. succinic acid, propane tri carboxylic acid, butane tetracarboxylic acid, cyclopentane tetracarboxylic acid and alkyl and alkenyl succinic acids with C ₂ - to C ₁₆ alkyl or alkenyl radicals;
C ₄ - to C ₂₀ hydroxycarboxylic acids such. B. malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;
Aminopolycarboxylic acids such as. B. nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, alkylethylenediaminetriacetate, N, N-bis (carboxymethyl) glutamic acid, ethylenediaminedi succinic acid and N- (2-hydroxyethyl) iminodiacetic acid, methyl.

Examples of suitable oligomeric or polymeric carboxylic acids as organic cobuilders are:
Oligomaleic acids, as described for example in EP-A 451508 and EP-A 396303;
Copolymers and terpolymers of unsaturated C ₄ to C ₈ dicarboxylic acids, the comonomers being monoethylenically unsaturated monomers from group (i) below in amounts of up to 95% by weight, from group (ii) in amounts of up to 60% by weight and from group (iii) in amounts of up to 20% by weight can be polymerized.

Examples of unsaturated C ₄ - to C ₈ -dicarboxylic acids here are maleic acid, fumaric acid, itaconic acid and citraconic acid. Malic acid is preferred.

Group (i) includes monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids such as. As acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. Before are added from group (i) acrylic acid and methacrylic acid.

Group (ii) includes monoethylenically unsaturated C ₂ to C ₂₂ olefins, vinyl alkyl ethers with C ₁ to C ₈ alkyl groups, styrene, vinyl esters of C ₁ to C ₈ carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C ₂ -C ₆ -olefins, vinyl alkyl ethers having C ₁ -C ₄ -alkyl groups, vinyl acetate and vinyl propionate.

If the polymers of group (ii) contain vinyl esters in copolymerized form, these also partially or completely hydrolyzed to vinyl alcohol structural units available. Suitable copolymers and terpolymers are, for example, from US-A 3887806 and DE-A 43 13 909 known.

Group (iii) comprises (meth) acrylic esters of C ₁ to C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of C ₁ to C ₈ amines, N-vinylformamide and N-vinylimidazole.

Also suitable as organic cobuilders are homopolymers of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids such as. B. acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid, especially acrylic acid and methacrylic acid,
Copolymers of dicarboxylic acids such as e.g. B. copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, particularly preferably those in a weight ratio of 30:70 to 90:10 with molecular weights of 1,000 to 150,000;
Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C ₁ -C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), the weight ratio of Acrylic acid to vinyl ester can vary in the range from 30:70 to 70:30;
Copolymers of maleic acid with C ₂ -C ₈ olefins in a molar ratio of 40:60 to 80:20, copolymers of maleic acid with ethylene, propylene or isobutene in a molar ratio of 50:50 being particularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates, cf. US-A 5227446, DE-A 44 15 623 and DE-A 43 13 909 are also suitable as organic cobuilders.

Suitable unsaturated carboxylic acids include maleic acid, Fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid and mixtures of acrylic acid and maleic acid, which in Amounts of 40 to 95 wt .-%, based on the component to be grafted on be grafted.

For modification, up to 30% by weight, based on the additional grafting component, other monoethylenically unsaturated monomers are polymerized. Suitable modifying monomers are those above called monomers of groups (ii) and (iii).

Degraded polysaccharides such as e.g. B. acidic or enzymatically degraded starches, inulins or cellulose, protein hydrolysates and reduced (hydrogenated or hydrated aminated) degraded polysaccharides such as. B. mannitol, sorbitol, aminosorbitol and N-alkylglucamine suitable as well as Polyalkylengly cole with molecular weights with up to M _w = 5000 such. B. polyethylene glycols, ethylene oxide / propylene oxide or ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyvalent C ₁ - to C ₂₂ alcohols. (See. US-A-5756456)

Polyglyoxylic acids suitable as organic cobuilders are, for example, be wrote in EP-B-001004, US-A-5399286, DE-A-41 06 355 and EP-A-656914. The end groups of the polyglyoxylic acids can have different structures point.

Polyamidocarboxylic acids suitable as organic cobuilders and modified Polyamidocarboxylic acids are known for example from EP-A-454126, EP-B-511037, WO-A-94/01486 and EP-A-581452.

As organic cobuilders in particular polyaspartic acids or cocondensates of aspartic acid are used with other amino acids, C ₄ - to C ₂₅ - mono- or dicarboxylic acids and / or C ₄ - to C ₂₅ -mono- or -diamines. Be Sonders are preferably prepared in phosphorus-containing acids, with C ₆ - to C ₂₂ used modified mono- or diamines, polyaspartic acids - to C ₂₂ -mono- or -dicarboxylic acids or with C. ₆

Iminodisuccinic acid, oxydi, are also suitable as organic cobuilders succinic acid, aminopolycarboxylates, alkyl polyaminocarboxylates, aminopo lyalkylene phosphonates, polyglutamates, hydrophobically modified citric acid such as e.g. B. agaricic acid, poly-α-hydroxyacrylic acid, N-acylethylenediamine triacetates such as Lauroylethylenediamine triacetate and alkylamides of ethylenediaminetetraacetic acid like EDTA tallow amide.

Oxidized starches can also be used as organic cobuilders become.  

In a further preferred embodiment, the inventive Detergents in addition, in particular in addition to the inorganic builders, the anionic surfactants and / or the nonionic surfactants, 0.5 to 20% by weight, in particular 1 to 10 wt .-%, glycine-N, N-diacetic acid derivatives, as in WO 97/19159 are described.

It is often also expedient to use the bleaching detergents according to the invention stems consisting of bleaches, such as. B. perborate, percarbonate and given if necessary bleach activators such. B. tetraacetylethylenediamine, + bleach stabilizer close gates.

In these cases, the detergents according to the invention additionally contain 0.5 to 30% by weight, in particular 5 to 27% by weight, especially 10 to 23% by weight of bleach medium in the form of percarboxylic acids, e.g. B. Diper-oxododecanedicarboxylic acid, Phthalimidopercaproic acid or monoperoxophthalic acid or terephthalic acid, Adducts of hydrogen peroxide with inorganic salts, e.g. B. sodium perborate Monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or Na triumphosphate perhydrate, adducts of hydrogen peroxide with organic ver ties, e.g. B. urea perhydrate, or of inorganic peroxo salts, e.g. B. Alkali metal persulfates, or -peroxodisulfates, optionally in combination with 0 to 15% by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 8 % By weight, bleach activators.

Suitable bleach activators are:

• - polyacylated sugars, e.g. B. Pentaacetylglucose;
• Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, e.g. B. sodium p-nonanoyloxybenzenesulfonate or sodium p- benzoyloxybenzenesulfonate;  
• - N, N-diacylated and N, N, N ', N'-tetraacylated amines, e.g. B. N, N, N ', N'- Tetraacetyl methylenediamine and ethylenediamine (TAED), N, N- Diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin;
• - N-alkyl-N-sulfonylcarbonamides, e.g. B. N-methyl-N-mesylacetamide or N- Methyl-N-mesylbenzamide;
• - N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. B. Mo. noacetyl maleic acid hydrazide;
• - O, N, N-trisubstituted hydroxylamines, e.g. B. O-Benzoyl-N, N succinylhydroxylamine, O-acetyl-N, N-succinylhydroxylamine or O, N, N- Triacetylhydroxylamine;
• - N, N'-diacylsulfurylamides, e.g. B. N, N'-Dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionyisulfurylamide;
• - Acylated lactams such as acetylcaprolactam, octanoylcapro lactam, benzoylcaprolactam or carbonyl biscaprolactam;
• - Anthranil derivatives such as B. 2-methylanthranil or 2-phenylanthranil;
• - Triacylcyanurate, e.g. B. triacetyl cyanurate or tribenzoyl cyanurate;
• - Oxime esters and bisoxime esters such as. B. O-acetylacetone oxime or bisisopro pyliminocarbonate;
• - Carboxylic anhydrides, e.g. B. acetic anhydride, benzoic anhydride, m- Chlorobenzoic anhydride or phthalic anhydride;
• - enol esters such as B. isopropenyl acetate;
• - 1,3-diacyl-4,5-diacyloxy imidazolines, e.g. B. 1,3-diacetyl-4,5- diacetoxyimidazoline;
• - tetraacetylglycoluril and tetrapropionylglycoluril;
• - Diacylated 2,5-diketopiperazines, e.g. B. 1,4-diacetyl-2,5-diketopiperazine;  
• - Ammonium substituted nitriles such as. B. N-methylmorpholinium acetonitrile methyl sulfate;
• - acylation products of propylene diurea and 2,2-dimethyl propylene diurea, e.g. B. tetraacetylpropylene diurea;
• - α-Acyloxypolyacylmalonamide, e.g. B. α-acetoxy-N, N'-diacetylmalonamide;
• - Diacyl-dioxohexahydro-1,3,5-triazines, e.g. B. 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine;
• - Benz- (4H) 1,3-oxazin-4-one with alkyl radicals, e.g. B. methyl, or aromati rests z. B. phenyl, in the 2-position.

The described bleaching system consisting of bleaching agents and bleach activators can optionally also contain bleach catalysts. Suitable bleaching catalyst ren are, for example, quaternized imines and sulfonimines, for example are described in US-A 5 360 569 and EP-A 453 003. Particularly effective Bleaching catalysts are manganese complexes that are used, for example, in the WO-A 94/21777 are described. Such connections are made in the event of their use in detergents at most in amounts up to 1.5% by weight, in particular up to 0.5% % By weight, in the case of very active manganese complexes in amounts of up to 0.1 % By weight.

In addition to the bleaching system described, consisting of bleaching agents, bleach activators and optionally bleaching catalysts for the detergents according to the invention also the use of systems with enzymatic peroxide release or photo-activated bleaching systems possible.

For a number of applications, it is useful if the fiction modern detergents contain enzymes. Preferably used in detergents set enzymes are proteases, amylases, lipases and cellulases. From the En  Zymmen are preferably amounts of 0.1 to 1.5 wt .-%, especially before preferably 0.2 to 1.0 wt .-%, of the finished enzyme added. Suitable Proteases are e.g. B. Savinase and Esperase (manufacturer: Novo Nordisk). A ge suitable lipase is e.g. B. Lipolase (manufacturer: Novo Nordisk). A suitable Cel lulase is e.g. B. Celluzym (manufacturer: Novo Nordisk). Even the use of Peroxidases to activate the bleaching system are possible. One can single Use enzymes or a combination of different enzymes. Given if the detergent according to the invention can also enzyme stabilizers, for. B. Calcium propionate, sodium formate or boric acids or their salts, and / or Oxidation preventers included.

The components of detergents are known in principle to the person skilled in the art. The The above and the following lists of suitable components only give an exemplary section of the known suitable components again.

In addition to the main components mentioned above, the detergents according to the invention can also contain the following further customary additives in the customary amounts:
Known dispersants, such as. B. naphthalenesulfonic acid condensates or poly carboxylates, soil release agents, soil release agents, such as. B. polyether esters, incrustation inhibitors, pH-regulating compounds such. B. alkalis or alkali donors (NaOH, KOH, pentasodium metasilicate, sodium carbonate) or acids (hydrochloric acid, phosphoric acid, amidosulfuric acid, citric acid) Buffer system, such as. As acetate or phosphate buffer, ion exchanger, perfume, dyestuff, graying inhibitors, optical (fluorescent) brighteners, color transfer inhibitors such. B. polyvinylpyrrolidone, biocides such. B. isothiazolinones or 2-bromo-2-nitro-1,3-propanediol, hydrotropic compounds as a solvent or solubilizers, such as. B. cumene sulfonates, toluenesulfonates, short chain ge fatty acids, urea, alcohols or phosphoric acid alkyl / aryl esters, foam regulators for stabilizing or damping the foam z. As silicone oils, skin and anti-corrosion agents, disinfectant compounds or systems such. B. those that release chlorine or hypochlorous acid such. B. dichlorisocya nurat or containing iodine, thickeners and adjusting and confectioning agents.

The detergents are usually, but not exclusively, in solid form; powder form, and then usually contain additional usual adjusting means, which give them good flowability, meterability and solubility and that prevent caking and dusting, such as. B. sodium sulfate or Ma magnesium sulfate.

The powder detergents have a through in the conventional form average bulk density of approx. 450 g / l. Compact or ultra Compact detergents and extrudates have a bulk density of <600 g / l. These are becoming increasingly important.

If they are to be used in liquid form, they can be used as aqueous Mi kroemulsions, emulsions or solutions are present. In liquid detergents can also solvents such. B. ethanol, i-propanol, 1,2- Propylene glycol, or butyl glycol can be used.

In the case of gel detergents according to the invention, thickeners, such as B. polysaccharides and / or weakly crosslinked polycarboxylates (example Carbopol® from Goodrich) can be used.

In the case of tablet detergents, tableting aids such as e.g. B. polyethylene glycols with molecular weights <1000 g / mol, polymer dispersions, and  Tablet disintegrants such. B. cellulose derivatives, crosslinked polyvinylpyrrolidone, cross-linked polyacrylates or combinations of acids, e.g. B. citric acid + Na triumbicarbonate, to name just a few.

The detergents according to the invention are surprisingly considerably superior in their detergent action to comparable detergents. As the comparison carried out in the context of the exemplary embodiments shows, they have clear advantages, in particular in the primary washing action, compared to the known C ₁₃ oxo alcohol surfactants which have been prepared on the basis of trimerized butenes.

Another object of the present invention is the use of the Ten side of formula I in the manufacture of detergents.

Another object of the invention is a washing process using of a detergent according to the invention.

The structure of the radical C _a H _{2a + 1} O- is obviously of decisive importance for the surprisingly high effectiveness of the surfactants of the formula I used according to the invention compared with compounds which can be compared as closely as possible.

This surprisingly effective structure of the ten side to be used according to the invention is obtained if they are prepared by

• a) subjecting a C ₄ olefin mixture to metathesis,
• b) separating olefins having 5 and 6 carbon atoms from the metathesis mixture,  
• c) the separated olefins individually or as a mixture to dimerize Olefin mixtures with 10 to 12 carbon atoms,
• d) the olefin mixture obtained, optionally after fractionation, the Derivatization to a mixture of oxo alcohols (surfactant alcohols) un throws and
• e) optionally alkoxylating the oxo alcohols obtained,
• f) optionally those obtained in the manufacturing steps d) or e) Oxo alcohols or oxo alcohol alkoxylates in the acidic sulfuric acid or transferred to phosphoric acid esters.

Fig. 1 illustrates this synthetic route to the invention einzu releasing surfactants of the formula I.

The main features of the metathesis used in process step a) are for example in Ullmann's Ecyclopedia of Industrial Chemistry, 5th ed., volume A18, pp. 235/236. Further information on implementation for example, K. J. Ivin, "Olefin Metathesis, Academic Press, London, (1983); Houben-Weyl, E18, 1163-1223; R.L. Banks, Discovery and Development of Olefin Disproportionation, CHEMTECH (1986), February, 112-117.

When applying metathesis to the main constituents butene-1 and butene-2 contained in the C ₄ -olefin streams, olefins having 5 to 10 C atoms, preferably having 5 to 8 C atoms, but in particular, are used in the presence of suitable catalysts Pentene-2 and hexene-3 formed.

Suitable catalysts are preferably molybdenum, tungsten or rhenium compounds. It is particularly expedient to carry out the reaction under heterogeneous catalysis, the catalytically active metals being used in particular in conjunction with supports composed of Al ₂ O ₃ or SiO ₂ . Examples of such catalysts are MoO ₃ or WO ₃ on SiO ₂ , or Re ₂ O ₇ on Al ₂ O ₃ .

It is particularly favorable to perform the metathesis in the presence of a rhenium catalyst to carry out, since in this case particularly mild reaction conditions are possible are. In this case, the metathesis can take place at a temperature of 0 to 50 ° C and be carried out at low pressures of about 0.1 to 0.2 MPa.

The dimerization of the olefins or olefin mixtures obtained in the metathesis step gives dimerization products which have particularly favorable components and a particularly advantageous composition with regard to the further processing on surfactant alcohols, if a dimerization catalyst is used which contains at least one element of subgroup VIII of the periodic system contains
and the catalyst composition and the reaction conditions are selected so that a dimer mixture is obtained which contains less than 10% by weight of compounds which have a structural element of the formula I (vinylidene group)

wherein A ¹ and A ^{2 are} aliphatic hydrocarbon radicals.

Preferred for the dimerization are those in the metathesis product contained internal, linear pentenes and hexenes. Especially the use of 3-hexene is preferred.

The dimerization can be homogeneously catalyzed or heterogeneously catalyzed be performed. The heterogeneous procedure is preferred, since here On the one hand, the catalyst separation is simplified, and the process is therefore simplified is more economical, on the other hand, no environmentally harmful wastewater generated, as usually in the separation of dissolved catalysts, for Example by hydrolysis. Another advantage of the heterogeneous Process is that the dimerization product does not contain halogens, especially chlorine or fluorine. Contain homogeneously soluble catalysts generally ligands containing halide or they are used in combination with halogen-containing cocatalysts used. From such catalyst systems can halogen be incorporated into the dimerization products, which both the Product quality as well as further processing, especially the Hydroformylation to surfactant alcohols significantly impaired.

Combinations of oxi are expediently used for heterogeneous catalysis those of metals of subgroup VIII with aluminum oxide on support materials s made of silicon and titanium oxides, such as from DE-A-43 39 713 are known used. The heterogeneous catalyst can be in a fixed bed - then before preferably in coarse-grained form as 1 to 1.5 mm grit - or suspended (Parti size 0.05 to 0.5 mm) can be used. The dimerization is hetero general implementation expediently at temperatures of 80 to 200 ° C, preferably from 100 to 180 ° C, below that at the reaction temperature pressure, possibly also under an inert gas pressure, in ge closed system. The Reak tion mixture several times in a circle, continuously a certain  Proportion of the circulating product removed and through starting material is replaced.

Mixtures become monounsaturated during dimerization Obtained hydrocarbons, the components of which are predominantly double Have chain length like the starting olefins.

The dimerization catalysts and the reaction conditions are in Conveniently chosen within the scope of the above information so that at least 80 % of the components of the dimerization mixture in the range from 1/4 to 3/4, preferably from 1/3 to 2/3, the chain length of their main chain one Have branching, or two branches on adjacent carbon atoms.

Their high degree is very characteristic of the olefin mixtures produced in this way some - usually over 75%, especially over 80% - of components with Ramifications and the low proportion - usually under 25, especially under 20% - unbranched olefins. Another characteristic is that at the Branches of the main chain predominantly groups with (y-4) and (y-5) C- Atoms are bound, where y is the number of carbon atoms for the Dimerization monomer used. The value (y-5) = 0 means that none Side chain is present.

In the C ₁₂ olefin mixtures prepared in this way, the main chain preferably carries methyl or ethyl groups at the branching points.

The position of the methyl and ethyl groups on the main chain is also characteristic: With mono substitution there are the methyl or Ethyl groups in position P = (n / 2) -m of the main chain, where n is the length of the  Main chain and m is the carbon number of the side groups, at Disubstitution products there is a substituent in position P, the others at the neighboring C atom P + 1. The shares of Mono substitution products (single branch) on the invention The olefin mixture produced is characteristically overall in the range from 40 to 75 wt .-%, the proportions of double-branched components in the Range from 5 to 25% by weight.

It was also found that the dimerization mixtures can be derivatized particularly well if the position of the double bond meets certain requirements. In these advantageous olefin mixtures, the position of the double bonds relative to the branches is characterized in that the ratio of the "aliphatic" hydrogen atoms to "olefinic" hydrogen atoms in the H _aliph. : H _olefin. = (2.n-0.5): 0.5 to (2.n-1.9) 1.9, where n is the number of carbon atoms of the olefin obtained in the dimerization.

("Aliphatic" hydrogen atoms are those which are attached to Carbon atoms are bound that are not attached to a C = C double bond (Pi Binding) are involved, as "olefinic" hydrogen atoms those attached to a Carbon atom is bound, which activates a pi bond.)

Dimerization _mixtures in which the ratio H _aliph. : H _olefin. = (2.n-1.0): 1 to (2.n-1.6): 1.6.

The olefin mixtures thus produced are first reacted with Carbon monoxide and hydrogen in the presence of suitable, preferably  cobalt- or rhodium-containing catalysts for surfactant alcohols (oxo alcohols), branched primary alcohols, hydroformylated.

A good overview of the hydroformylation process with numerous Further references can be found, for example, in the extensive Review by Beller et al. in Journal of Molecular Catalysis, A104 (1995) 17-85 or in Ullmanns Encyclopedia of Industrial Chemistry, Vol. A5 (1986), page 217 ff., page 333, as well as the relevant references.

The comprehensive information given there enables the person skilled in the art to also hydroformylate the branched olefins according to the invention. In this reaction, CO and hydrogen are attached to olefinic double bonds, mixtures of aldehydes and

Alkanols are obtained:

(A ³ = hydrocarbon residue)

The molar ratio of n- and iso compounds in the reaction mixture is, depending on the process conditions chosen for the hydroformylation and the catalyst used, generally in the range from 1: 1 to 20: 1. The hydroformylation is normally in the temperature range from 90 to 200 ° C. and at a CO / H ₂ pressure of 2.5 to 35 MPa (25 to 350 bar). The mixing ratio of carbon monoxide to hydrogen depends on whether alkanals or alkanols should preferably be produced. The process is advantageously carried out in the range CO: H from 10: 1 to 1:10, preferably 3: 1 to 1: 3, the range of low hydrogen partial pressures being used for the production of alkanals and the range of high hydrogen partial pressures, for example the production of alkanols. B. CO: H ₂ = 1: 2.

Particularly suitable catalysts are metal compounds of the general formula HM (CO) ₄ or M ₂ (CO) ₈ , where M is a metal atom, preferably a cobalt, rhodium or ruthenium atom.

In general, under hydroformylation conditions, catalytically active species of the general formula H _x M _y (CO) _z L _{q are} formed from the catalysts or catalyst precursors used in each case, where M is a metal from subgroup VIII, L is a ligand which is a phosphine or phosphite , Amine, pyridine or any other donor compound, also in polymeric form, and q, x, y and z are integers, depending on the valency and type of the metal and the binding force of the ligand L, where q is also 0 can be.

The metal M is preferably cobalt, ruthenium, Rhodium, palladium, platinum, osmium or iridium and in particular around cobalt, Rhodium or ruthenium.

Suitable rhodium compounds or complexes are e.g. B. Rhodium (II) - and Rhodium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) -  sulfate, potassium rhodium sulfate, rhodium (II) or rhodium (III) caboxylate, Rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of Rhodium (III) acid, such as. B. Trisammonium hexachlororhodate (III). Farther rhodium complexes such as rhodium biscarbonyl acetylacetonate are suitable, Acetylacetonato-bisethylene-rhodium- (I). Preferably be Rhodium biscarbonyl acetylacetonate or rhodium acetate used.

Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) carbonate, cobalt (II) nitrate, their amine or hydrate complexes, Cobalt carbocylates such as cobalt acetate, cobalt ethyl hexanoate, cobalt naphthanoate, and the cobalt caprolactamate complex. Here too they can Carbonyl complexes of cobalt such as dicobalt octocarbonyl, Tetrakobaltdodecacarbonyl and Hexakobalthexadecacarbonyl be used.

The compounds of cobalt, rhodium and ruthenium mentioned are in Principle known and adequately described in the literature, or they can prepared by a person skilled in the art analogously to the already known compounds become.

The hydroformylation can be carried out with the addition of inert solution or Diluents or be carried out without such addition. Suitable Inert additives are, for example, acetone, methyl ethyl ketone, cyclohexanone, Toluene, xylene, chlorobenzene, methylene chloride, hexane, petroleum ether, acetonitrile and the high-boiling fractions from the hydroformylation of the Dimerization products.

If the hydroformylation product obtained has too high an aldehyde content has, this can easily by hydrogenation, for example with  Hydrogen in the presence of Raney nickel or using others for Hydrogenation reactions of known, especially copper, zinc, cobalt, nickel, Catalysts containing molybdenum, zirconium or titanium can be eliminated. there the aldehyde fractions are largely hydrogenated to alkanols. A practical one Complete removal of aldehyde fractions in the reaction mixture can be if desired by post-hydrogenation, for example under particularly gentle and economical conditions with an alkali borohydride, to reach.

The alkanols thus prepared can be used in different ways non-ionic or anionic surfactants can be produced.

Nonionic surfactants are obtained by reacting the alkanols with

Alkylene oxides (alkoxylation) of the formula II
wherein R ^{1 is} hydrogen or a straight-chain or branched aliphatic radical of the formula C _n H _{2n + 1} and n is a number from 1 to 16, preferably from 1 to 8. In particular, R ^{1 is} hydrogen, methyl, ethyl or propyl.

The alkanols of the invention can be used with a single alkylene oxide species or implemented with several different ones. When implementing the Alkanols with the alkylene oxides form compounds which in turn have an OH Wear group and therefore can react again with an alkylene oxide molecule. Therefore, depending on the molar ratio of alkanol to alkylene oxide Reaction products get the more or less long polyether chains  exhibit. The polyether chains can contain 1 to approx. 200 alkylene oxide assemblies contain. Compounds whose polyether chains 1 to 50 are preferred Contain alkylene oxide assemblies.

The chains can consist of the same chain links or they can have different acylene oxide assemblies which differ from one another in terms of their radical R ¹ . These different assemblies can exist within the chain in statistical distribution or in the form of blocks.

The following reaction scheme is intended to illustrate the alkoxylation of the alkanols described above using the example of a reaction with two different alkylene oxides which are used in different molar amounts x and y.

R ¹ and R ² are different radicals within the scope of the definitions given above for R ¹ and R-OH is a branched oxo alcohol described above.

The alkoxylation is preferably catalyzed by strong bases which are advantageously added in the form of an alkali metal hydroxide or alkaline earth metal hydroxide, generally in an amount of 0.1 to 1% by weight, based on the amount of the alkanol R ² -OH. (See G. Gee et al., J. Chem. Soc. (1961), p. 1345; B. Wojtech, Makromol. Chem. 66, (1966), p. 180).

Acid catalysis of the addition reaction is also possible. In addition to Bronsted acids, Lewis acids such as. B. AlCl ₃ or BF ₃ . (See PH Plesch, The Chemistry of Cationic Polymerization, Pergamon Press, New York (1963).

The addition reaction is carried out at temperatures of about 120 to about 220 ° C. preferably from 140 to 160 ° C, carried out in a closed vessel. The Alkylene oxide or the mixture of different alkylene oxides is added to the mixture from the alkanol mixture according to the invention and alkali under that in the selected Reaction temperature prevailing vapor pressure of the alkylene oxide mixture fed. If desired, the alkylene oxide can contain up to about 30 to 60% be diluted with an inert gas. This adds security against explosive polyaddition of the alkylene oxide.

If an alkylene oxide mixture is used, polyether chains are formed in which the different alkylene oxide building blocks are practically statistically distributed. There are variations in the distribution of the building blocks along the polyether chain due to different reaction speeds of the components and can also be done arbitrarily by continuous addition of an alkylene oxide mixture program-controlled composition can be achieved. Will the different alkylene oxides are reacted one after the other to obtain Polyether chains with block-like distribution of the alkylene oxide building blocks.  

The length of the polyether chains varies within the reaction product statistically around an average that essentially derives from the Additional amount resulting stoichiometric value.

Both the alkanol mixtures resulting from synthesis step d) and the polyethers optionally produced therefrom in synthesis step e) can be in anionic surfactants are converted by using them in a manner known per se with sulfuric acid or sulfuric acid derivatives to give acidic alkyl sulfates or Alkyl ether sulfates or with phosphoric acid or its derivatives to acidic Alkyl phosphates or alkyl ether phosphates esterified (sulfated or phosphated).

Sulfation reactions of alcohols have already been described e.g. B. in US-A-3,462,525, 3,420,875 or 3,524,864. Details on how to do this Reaction can also be found in "Ullmann's Encyclopedia of Industrial Chemistry", 5th edition vol. A25 (1994), pages 779-783 and in those specified there References.

If sulfuric acid itself is used for the esterification, one uses expediently a 75 to 100% by weight, preferably 85 to 98% by weight Acid (so-called "concentrated sulfuric acid" or "monohydrate"). The Esterification can be done in a solvent or diluent if it is for the control of the reaction, e.g. B. heat generation is desired. As a rule, the alcoholic reactant is presented, and that Sulphating agent gradually added with constant mixing. If a complete esterification of the alcohol component is desired the sulfating agent and the alkanol in a molar ratio of 1: 1 to 1: 1.5, preferably from 1: 1 to 1: 1.2. Lower levels of sulfating agent can be advantageous if mixtures of alkanol according to the invention  alkoxylates used and combinations of neutral and anionic Surfactants are to be produced. The esterification is usually at Temperatures from room temperature to 85 ° C, preferably in the range of 45 up to 75 ° C.

It may be appropriate to lower the esterification in a low boiling, water-immiscible solvents and diluents to carry out its boiling point, the resulting from the esterification Water is distilled off azeotropically.

Instead of sulfuric acid of the concentration given above can Sulphation of the alkanol mixtures according to the invention also, for example Sulfur trioxide, sulfur trioxide complexes, solutions of sulfur trioxide in Sulfuric acid ("oleum"), chlorosulfonic acid, sulfuryl chloride or else Amidosulfonic acid can be used. The reaction conditions are then adapt accordingly.

If sulfur trioxide is used as the sulfating agent, the reaction can also advantageously in a falling film reactor in countercurrent, if desired also run continuously.

After the esterification, the batches are neutralized by adding alkali and, if necessary after removal of excess alkali sulfates and any existing ones Solvent worked up.

In an analogous manner, alkanols and alkanol ethers and mixtures thereof can be used Phosphating agents also converted into acidic phosphoric acid esters (phosphated).  

Phosphating acid, polyphosphoric acid and phosphorus pentoxide are particularly suitable as phosphating agents, but also POCl ₃ if the remaining acid chloride functions are subsequently hydrolysed. The phosphating of alcohols has been described, for example, in Synthesis 1985, pages 449 to 488.

The following embodiments illustrate the manufacture and Use of the surfactants to be used according to the invention.

example 1 Production of C ₅ / C ₆ olefins from C ₄ olefin streams by metathesis

A butadiene-free C ₄ fraction with a total butene content of 84.2% by weight and a molar ratio of 1-butene: 2-butene of 1.06 (“Raffinate II”) is continuously at 40 ° C. and 10 bar by a with Re ₂ O ₇ / Al ₂ O ₃ heterogeneous contact fed tube reactor. The catalyst load is set to 4500 kg / (m ² .h). The reactor discharge is separated by distillation and contains the following components (details in percent by mass):
Ethene: 1.15%, propene: 18.9%, butane: 15.8%, 2-butene: 19.7%, 1-butene: 13.3%, i-butene: 1.00%, 2- Pentene: 19.4%, methylbutene: 0.45%, 3-hexene 10.3%.

Examples 2A and 2B Heterogeneously catalyzed dimerization of 3-hexene. 2A. Fixed bed procedure.

An isothermally heatable reactor with a diameter of 16 mm was filled with 100 ml of a catalyst of the following composition:
50 wt.% NiO, 34 wt.% SiO ₂ , 13 wt.% TiO ₂ , 3 wt.% Al ₂ O ₃ (according to DE-A-43 39 713), 24 hours at 160 ° C conditioned in N ₂ , used as 1 to 1.5 mm grit.

5 experiments were carried out, 3-hexene (99.9% by weight, 0.1% by weight of C ₇ to C ₁₁ fractions) being produced by the catalyst bed specified in a rate based on the reactor volume (WHSV) of 0.25 kg / lh passed and discharged at a rate of 24 to 28 g / h. The reaction temperature or the operating time of the experiment was varied in the individual experiments.

The following Table 1 shows the test conditions of the five tests and the results obtained.  

Table 1

Process conditions and results in the fixed bed process

The discharged product was fractionally distilled and the framework isomers of the C ₁₂ fraction were determined. The analysis showed 14.2% by weight of n-dodecenes, 31.8% by weight of 5-methylundecenes, 29.1% by weight of 4-ethyldecenes, 6.6% by weight of 5,6-dimethyldecenes, 9 , 3% by weight of 4-methyl-5-ethylnonene and 3.7% by weight of diethyloctene.

B. Suspension process (fluid bed process)

An isothermally heatable reactor with a diameter of 20 mm and a volume of 157 ml was filled with 30 g of a catalyst of the following composition:
50 wt.% NiO, 34 wt.% SiO ₂ , 13 wt.% TiO ₂ , 3 wt.% Al ₂ O ₃ (according to DE-A-43 39 713), 24 hours at 160 ° C conditioned in N ₂ , used as 0.05 to 0.5 mm spray material.

6 experiments were carried out, 3-hexene (99.9% by weight, 0.1% by weight of C ₇ to C ₁₁ fractions) being passed through the catalyst fluidized bed from the bottom in a rate based on the reactor volume of 0.25 kg / lh was passed. The reaction product emerging from the reactor was largely recycled (recycling: feed quantity varies between about 45 and 60). The reaction temperature, the feed quantity, the circulation flow, the recirculation rate and the WHSV of the experiment were also varied in the individual experiments. The test lasted 8 hours.

Tables 2A and 2B below show the experimental conditions of the six Trials and the results obtained.  

Tables 2

Test conditions and results in the suspension process

Table 2A

Test conditions

Table 2B

Composition of the reaction discharge

The discharged product was fractionally distilled and the framework isomers of the C ₁₂ fraction were determined. The analysis showed 14% by weight of n-dodecenes, 32% by weight of 5-methylundecenes, 29% by weight of 4-ethyldecenes, 7% by weight of 5,6-dimethyldecenes, 9% by weight of 4-methyl 5-ethylnonenes and 4% by weight diethyloctenes.

Example 3 Hydroformylation of a dodecene mixture

750 g of the dodecene mixture prepared according to Example 2B are mixed with 3.0 g of Co ₂ (CO) ₈ at 185 ° C. and 280 bar CO / H ₂ (volume ratio = 1: 1.5) with the addition of 75 g of H ₂ O hydroformylated for 5 hours in a 2.5 liter autoclave. The reaction product is decobated oxidatively with 10% by weight acetic acid with introduction of air at 90 ° C. The oxo product is hydrogenated with the addition of 10% by weight of water in a 2.5 l stirred autoclave with 50 g of Raney nickel at 125 ° C. and 280 bar hydrogen pressure for 10 hours. The reaction discharge is fractionally distilled.

450 g of a tridecanol fraction produced in this way are rehydrated with 3.5 g of NaBH ₄ .

The OH number of the tridecanol obtained is 277 mg KOH / g.
¹ H NMR spectroscopy determined an average degree of branching of 2.3 methyl groups / molecule, corresponding to a degree of branching of 1.3.

Example 3A Hydroformylation of a dodecene mixture

2.12 kg of the dodecene mixture prepared according to Example 2A are mixed with 8 g of Co ₂ (CO) ₈ at 185 ° C. and 280 bar CO / H ₂ (volume ratio 1: 1) with the addition of 210 g of water in a 5-liter rotary autoclave 5 Hours hydroformylated. The reaction product is decobated oxidatively with 10% by weight acetic acid with introduction of air at 90 ° C. The oxo product obtained is hydrogenated in a 5-liter tubular reactor in a trickle mode over a Co / Mo fixed bed catalyst at 175 ° C. and 280 bar hydrogen pressure with the addition of 10% by weight of water. The alcohol mixture is worked up by distillation. The tridecanol obtained has an OH number of 279 mg KOH / g; A mean degree of branching of 1.53 is measured by ¹ H-NMR spectroscopy.

Example 3B Hydroformylation of a dodecene mixture

50 mg of rhodium biscarbonyl acetylacetonate, 4.5 g of a polyethyleneimine of molecular weight M _W = 460,000, in which 60% of all nitrogen atoms are acylated with lauric acid, 800 g of a dodecene mixture prepared according to Example 2A and 196 g of toluene are in a 2.5- l Stirring autoclave heated to 150 ° C for 7 hours under a pressure of 280 bar CO / H ₂ (volume ratio 1: 1). Then the autoclave is cooled, relaxed and emptied. A conversion of the olefin of 93% is determined by gas chromatography of the reaction product obtained. The oxo product obtained is hydrogenated in a 2.5 liter tubular reactor in a trickle mode on a Co / Mo fixed bed catalyst at 175 ° C. and 280 bar hydrogen pressure with the addition of 10% by weight of water and the alcohol mixture formed is worked up by distillation. The tridecanol obtained has an OH number of 279 mg KOH / g; An average degree of branching of 1.63 is measured by ¹ H-NMR spectroscopy.

Example 3C Hydroformylation of a dodecene mixture

50 mg of rhodium biscarbonyl acetylacetonate, 4.5 g of a polyethyleneimine of molecular weight M _W = 460,000, in which 60% of all nitrogen atoms are acylated with lauric acid, 800 g of a dodecene mixture prepared according to Example 2A and 196 g of toluene are in a 2.5- l Stirring autoclave heated to 160 ° C for 7 hours under a pressure of 280 bar CO / H ₂ (volume ratio 1: 1). Then the autoclave is cooled, relaxed and emptied. A conversion of the olefin of 94% is determined by gas chromatography of the reaction product obtained. The oxo product obtained is hydrogenated in a 2.5 liter tubular reactor in a trickle mode on a Co / Mo fixed bed catalyst at 175 ° C. and 280 bar hydrogen pressure with the addition of 10% by weight of water and the alcohol mixture formed is worked up by distillation. The tridecanol obtained has an OH number of 279 mg KOH / g; An average degree of branching of 1.69 is measured by ¹ H-NMR spectroscopy.

Example 4 Preparation of a C ₁₃ oxo alcohol ethoxylate with 5 mol of ethylene oxide

400 g of C ₁₃ oxo alcohol (prepared according to Example 3B) are introduced into a dry 2 l autoclave with 1.5 g of NaOH. The contents of the autoclave are heated to 150 ° C. and 440 g of ethylene oxide are pressed into the autoclave under pressure. After the entire amount of ethylene oxide is in the autoclave, the autoclave is kept at 150 ° C. for 30 minutes. After cooling, the catalyst is neutralized with acetic acid.

The surfactant obtained has a cloud point of 58.5 ° C., measured 1% in 10% butyl diglycol solution according to DIN 53 917. The surface tension at a concentration of 1 g / l is 26.7 mN / m, measured according to DIN 53 914.

Example 5 Preparation of a C ₁₃ oxo alcohol ethoxylate with 2.75 mol of ethylene oxide

500 g of C ₁₃ oxo alcohol (prepared according to Example 3B) are introduced into a dry 2 l autoclave with 1.5 g of NaOH. The contents of the autoclave are heated to 150 ° C. and 300 g of ethylene oxide are pressed into the autoclave under pressure. After the entire amount of ethylene oxide is in the autoclave, the autoclave is kept at 150 ° C. for 30 minutes. After cooling, the catalyst is neutralized with acetic acid.

The surfactant obtained has a cloud point of 35 ° C., measured 1% in 10 % butyl diglycol solution according to DIN 53 917. The surface tension at a concentration of 1 g / l is 25.8 mN / m, measured according to DIN 53 914.

Example 6 (comparison) Preparation of a C ₁₃ oxo alcohol ethoxylate with 5 mol ethylene oxide

400 g of C ₁₃ oxo alcohol (produced by trimerization of n-butenes and subsequent hydroformylation) are introduced into a dry 2 l autoclave with 1.5 g of NaOH. The contents of the autoclave are heated to 150 ° C. and 440 g of ethylene oxide are pressed into the autoclave under pressure. After the entire amount of ethylene oxide is in the autoclave, the autoclave is kept at 150 ° C. for 30 minutes. After cooling, the catalyst is neutralized with acetic acid.

The surfactant obtained has a cloud point of 61 ° C., measured 1% in 10 % butyl diglycol solution according to DIN 53 917. The surface tension at a concentration of 1 g / l is 27.2 mN / m, measured according to DIN 53 914.

Example 7 (comparison) Preparation of a C ₁₃ oxo alcohol ethoxylate with 2.75 mol ethylene oxide

500 g of C ₁₃ oxo alcohol (produced by trimerization of n-butenes and subsequent hydroformylation) are introduced into a dry 2 l autoclave with 1.2 g of NaOH. The contents of the autoclave are heated to 150 ° C. and 300 g of ethylene oxide are pressed into the autoclave under pressure. After the entire amount of ethylene oxide is in the autoclave, the autoclave is kept at 150 ° C. for 30 minutes. After cooling, the catalyst is neutralized with acetic acid.

The surfactant obtained has a cloud point of 39.5 ° C., measured 1% in 10% butyl diglycol solution according to DIN 53 917. The surface tension at a concentration of 1 g / l is 26.7 mN / m, measured according to DIN 53 914.

Example 8 Washing tests

The washing tests were carried out in a Launderometer LP 2 from Atlas with the following recipe:
19% by weight surfactant
30% by weight zeolite A
12% by weight sodium carbonate
3% by weight sodium silicate
1.2% by weight carboxymethyl cellulose (Tylose® CR 1500 p (based on active substance))
14.4% by weight sodium perborate monohydrate
4% by weight TAED
5% by weight polycarboxylate (Sokalans® CP 5)
0.5% by weight of soap
4% by weight sodium sulfate
6.9% by weight of water
Amount of detergent: 4 g / l
Fleet ratio: 1: 12.5
Water hardness: 3 mmol
Ca: Mg: HCO ₃ ^- : 4:18
Washing time: 30 min

The washing tests were carried out using test material EMPA 101 (manufacturer: EMPA Test material, Mövenstraße 12, CH 9015 St. Gallen) and with test fabric wfk 10 D (manufacturer: wfk-Testgewebe GmbH, Christenfeld 10, 41375 Brueggen) guided.

Pollution

EMPA 101: carbon black / olive oil on cotton
wfk 10 D: wfk pigment / skin fat on cotton.

The following table shows the washing tests at 40 ° C and at 60 ° C results obtained. The values measured after washing are given in each case Degree of reflectance in [%] of the incident light quantity.

The reflectance is measured using the Elrepho 2000 device from datacolor AG.

table

Washing results

Fig. 1 illustrates schematically the preparation of the surfactants used according to the invention of formula I.

FIGS. 2a and 2b illustrate the is in the table of Example 8 given context between the plotted on the ordinate alkoxy lierungsgrad (alkylene oxide) content in moles of alkylene oxide per mole of alkoxylated Ver compound (EO [mol / mol]) and the the abscissa applied wash result - expressed by the degree of remission in%.

FIG. 2a shows the washing result when using the EMPA 101 test material, FIG. 2b shows the washing result when using the wfk 10 D test material. The reference numerals given in FIGS . 2a and 2b have the following meanings:
E40 washing with surfactants according to the invention at 40 ° C.,
E60 washing with surfactants according to the invention at 60 ° C.,
V40 laundry with known comparable surfactants at 40 ° C,
V60 washing with closest comparable known surfactants at 60 ° C.

Claims (10)

1. Detergent comprising an effective proportion of one or more ten side of the formula I.
wherein
a represents one of the numbers 11, 12 and 13,
R ¹ and R ^{2 are} different and each represent hydrogen or alkyl radicals of the formula C _n H _{2n + 1} -,
R ³ denotes hydrogen, or a sulfato or phosphate residue,
n stands for a number from 1 to 16, x for a number from 0 to 200 and y for a number from 0 to 200,
as well as other known auxiliaries and additives customary in detergents,
and
optionally additional surfactants. 2. Detergent according to claim 1, characterized in that the i - C _a H _{2a + 1} radical contained in the surfactants of the formula I is derived from an oxo alcohol which is obtained by hydroformylation of a decene, dodecene or a mixture of these olefins, which in turn has been produced by dimerization of n-pentene-2, hexene-3 or mixtures of these compounds. 3. Detergent according to claims 1 and 2, characterized in that the minimum proportion of the surfactants of formula I in the total weight of he detergent according to the invention is such that there is a significant Effect of this addition shows. 4. Detergent according to claim 3, characterized in that the proportion the surfactants of formula I in the detergent according to the invention, bezo to the total weight of the agent, 0.01 to 50 wt .-%, preferably 0.1 to 40% by weight. 5. Detergent according to claims 1 to 4, characterized in that in the surfactants of the formula I a is 13. 6. Detergent according to claims 1 to 5, characterized in that in the surfactants of the formula I n stands for a number from 1 to 8. 7. Detergent according to claims 1 to 6, characterized in that in the surfactants of the formula IR ¹ and R ^{2 are} different and in each case what is hydrogen, methyl, ethyl or propyl. 8. Detergent according to claims 1 to 7, characterized in that in particular in the surfactants of the formula I x for a number from 1 to 50 from 1 to 20 and y for a number from 0 to 50, in particular from 0 to 20 stands. 9. Process for the production of detergents, characterized in that that one uses surfactants of formula I. 10. Washing method, characterized in that the detergent of claim 1 can be used.