DE2844451A1 - NEW QUARTAERE AMMONIUM COMPOUNDS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A TEXTILE SOFTENER - Google Patents

Description

"New quaternary ammonium compounds, a process too

Their manufacture and their use as fabric softeners "The invention relates to new quaternary ammonium compounds with two or three long-chain hydroxyalkyloxyalkyl radicals, a process for their production and their use as a fabric softener Active ingredient.

It has long been known that tetraalkyl quaternary ammonium compounds with two long-chain, i.a.

C16-C18 alkyl residues give washed textiles a soft feel if they are added to the final rinse bath when washing clothes. These Fabric softeners are widely used by both commercial laundries and also used for laundry in the household. It is believed that these cationic Quaternary ammonium compounds easily on the textile substrate because of their positive charge wind up.

The most frequently used textile softener in this class of compounds is ditallow alkyl or distearyldimethylammonium chloride. This fabric softener Although it has excellent plasticizing properties, it also has some Disadvantages on. The textiles treated with it have a difference compared to the untreated ones Tissues decreased absorbency, something that the consumer - especially in the case of overdosing of the fabric softener - e.g. B. in clothing that comes into contact with the skin and can be perceived as uncomfortable when using terry towels. Such textile softeners can often not be completely removed from the laundry Remove tissue again so that it sometimes closes - even with the correct dosage there is an accumulation of the emollient active ingredients, which also decreases The suction effect of the textiles is connected. Further serious disadvantages of these textile softeners are their relatively high manufacturing costs because of expensive secondary fatty amines it must be assumed that one predominantly consists of native fatty acids or fatty alcohols of frequently fluctuating quality.

There has been no lack of attempts to overcome these disadvantages. It is known from US Pat. No. 3,636,114 that the use of quaternary Ammonium compounds with 2 long-chain 2-hydroxyalkyl radicals improve the absorbency can be. From DE-OS 22 56 234 are quaternary ammonium compounds with 2 long chains 2-hydroxy-3-alkoxypropyl groups are known. The 16 19 043 known from DE-AS Softeners contain quaternary ammonium compounds with only a long one Alkyl radical and three short alkyl radicals, the 3 short alkyl radicals hydroxyl and May contain ether groups. In Dutch patent application 68/08958 and US Pat. No. 3,591,405, quaternary ammonium compounds are described, their hydrophobic Radicals hydroxyalkyl groups or linked to the nitrogen via ethoxy groups Represent alkyl groups. However, these attempts at solving the problem could not witness because either the modified quaternary ammonium compounds are poor in terms of preparation were accessible and therefore out of the question for a practical application, or because the softening effect was too little.

The present invention was therefore based on the object of new quaternary Provide ammonium compounds in a simple manner from readily available cheap raw materials can be obtained with the textiles treated with them good softening effect, the absorbency is preserved and residue-free remove the laundry from the textiles.

Another task was the provision of new tertiary amines as preliminary products from which the quaternary ammonium compounds are formed by quaternization can be produced.

It has now been found that the quaternary ammonium compounds of the formula I in which R¹ is an aliphatic hydrocarbon group having 1 to 21 carbon atoms and R2 is H or R¹, the sum of the carbon atoms of R1 and R2 being 6 to 22 and in the case R2 = H the group R1 has 6-21 carbon atoms, R3 is an alkyl group or Hydroxyalkyl group with 1 to 4 carbon atoms or a radical of the formula R4 denotes an alkyl group with 1 to 4 carbon atoms, X and Y denote hydrogen or the methyl group, but X and Y in the same ethoxy group are not both methyl, m, n and p denote integers between 1 and 20 and A 8 denotes a Anion stands, are easily accessible preparatively and at the same time have excellent laundry-enhancing properties. AO means an anion split off from the quaternizing agent, e.g. B.

a chloride or methyl sulfate anion. However, the anion can also be another anion customary in quaternary ammonium compounds, e.g. B. be the bromide or ethyl sulfate anion. The compounds of the formula I can be prepared in a simple manner from cheap starting materials in high yield via the tertiary amine of the formula II, in which R1, R2, R3, X, Y, m and n have the abovementioned meaning. The invention therefore also relates to the provision of the compounds of formula II as valuable intermediates. The invention therefore also provides a process for the preparation of the new quaternary ammonium compounds and the new tertiary amines of the formula II on which they are based Compounds of the formula I with 2 or 3 long radicals, in which R1 is an alkyl group with preferably 8-18 carbon atoms and R2 is the hydrogen atom, can be used particularly well as textile softeners with regard to the balance of their application properties. Depending on the desired hydrophilicity, the compounds can contain 1-20 ethoxy or propoxy groups in each long radical, products whose long radicals containing 1-3 ethoxy groups, in particular 1 ethoxy group, are preferred, typical compounds of formula I are z. B.

Bist5-hydroxy-3-oxa-pentadecyl) dimethyl ammonium methyl sulfate, bis (5-hydroxy-3-oxa-heptadecyl) -dimethyl-ammonium methyl sulfate, bis (5-hydroxy-3-oxa-C15 / 17-alkyl) -dimethyl-ammonium methyl sulfate, Bis (5-hydroxy-3-oxa-C19 / 21-alkyl) -dimethyl-ammonium methyl sulfate, bis (5-hydroxy-3-oxa-C1 5/1 7-alkyl) methyl (2-hydroxyethylammonium methyl sulfate, bis (5-hydroxy-3-oxa-undecyl) -dimethyl-ammonium chloride, bis (5-hydroxy-3-oxa-4-hexyl-tridecyl) -2-hydroxyethylmethyl-ammonium chloride, Bis (5-hydroxy-3-oxa-4-octyl-nonadecyl) -dimethyl-ammonium chloride, bis (5-hydroxy-3-oxa-2-methyl-heptadecyl) -dimethyl-ammonium chloride, bis (11-hydroxy-3,6t9-trioxa-tricosyl) -dimethyl-ammonium chloride, Tris (5-hydroxy-3-oxa-pentadecyl) -methyl-ammonium chloride, Tris (5-hydroxy-3-oxa-pentadecyl) -methyl-ammonium methyl sulfate, Tris (5-hydroxy-3-oxa-C15 / 17-alkyl) -methyl-ammoinum chloride, Tris (5-hydroxy-3-oxa-heptadecyl) -methyl-ammonium methyl sulfate, tris (5-hydroxy-3-oxa-C19 / 21-alkyl) -methyl-ammonium chloride, Tris (5-hydroxy-3-oxa-undecyl) -methyl-ammonium chloride, Tris (5-hydroxy-3-oxa-undecyl) -2-hydroxyethyl-ammonium chloride, tris (5-hydroxy-3-oxa-4-octyl-heptadecyl) -ethyl-ammonium chloride, Trisf5-hydroxy-3-oxa-4-pentadecyl-hexyl) -methyl-ammonium methyl sulfate, Tris (5-hydroxy-3-oxa-2-methyl-nonadecyl) -methyl-ammonium chloride 1 Tris (14-hydroxy-tetrapropoxy-pentacosyl) -methyl-ammonium methyl sulfate.

The process for the preparation of quaternary ammonium compounds of the formula I via the tertiary amines of the formula II is characterized in that an epoxyalkane of the formula III in which R1 and R2 have the meanings given above with a polyalkanolamine of the formula IV in which R5 denotes an alkyl group with 1-4 carbon atoms or a radical of the formula H (-OCHX-CHY) p-, where X, Y, m, n and p have the abovementioned meanings, in the presence of a catalyst under normal pressure and at an elevated level Temperature to form the tertiary amine of the formula II and then quaternized with an alkylating agent which introduces the group R4 defined in formula I of claim 1.

The epoxyalkanes and alkanolamines to be used as starting materials are cheap and available in large quantities.

The epoxyalkanes are prepared in a known manner from the corresponding olefins or olefin mixtures obtained. The 1,2-epoxyalkanes are obtained via 1,2-monoolefins, the for example by polymerizing ethylene with organic ones Aluminum compounds as catalysts or by thermal cracking of paraffin hydrocarbons can be obtained. Examples of preferably usable epoxyalkanes are the compounds 1,2-epoxy dodecane, 1,2-epoxy tetradecane, 1,2-epoxy decane, 1,2-epoxy octadecane and epoxy mixtures such as B. C -1,2-epoxy with approx.

12/14 70% by weight of C12 and approx. 30% by weight of C14 epoxyalkane or C16 / 18-1,2 epoxy with approx. 40% by weight of C16 and approx. 60% by weight of Cl 8 epoxyalkane.

The internal epoxyalkanes are obtained, for example, by epoxidation of olefins or olefin mixtures produced by catalytic dehydrogenation or by Chlorination / dehydrogenation of linear paraffinic hydrocarbons can be produced. Monoolefins with an internal double bond can also be isomerized by d \ -olefins are produced. Internal epoxyalkanes used with preference a C11 / 14 olefin fraction contained approx.

22% by weight C11-, approx. 30% by weight C12-, approx. 26% by weight C13-, approx. 22% by weight C14 epoxyalkane. An epoxyalkane mixture of a C15 / 18 olefin fraction, which is also preferably used, contains approx. 26% by weight of C15, approx. 35% by weight of C16, approx. 32% by weight of C17 and approx. 7% by weight of C18 epoxyalkane.

Di- or trialkanolamines which are preferably used are, for example N-methyl-diethanolamine or triethanolamine.

The use of alkoxylated alkanolamines can reduce the hydrophilicity of the end products varied within certain limits and adapted to the desired application will.

As a catalyst for the conversion of epoxyalkanes of the formula III with polyalkanolamines of the formula IV, sodium alcoholate, especially sodium methylate, has been found proven.

The catalyst is preferably used in amounts of 0.1-1.0% by weight, used based on the total reaction mixture.

The reaction of the epoxyalkane with the alkanolamine proceeds without any noteworthy results Formation of by-products with high yield. You lead the implementation to connections of formula I expediently with such a ratio of epoxyalkane to Alkanolamine by using one alkanol equivalent per mole of epoxyalkane, d. That is, one mole of epoxyalkane with 1/2 mole of dialkanolamine or 1/3 mole of trialkanolamine implements. With an excess of alkanolamine or with incomplete conversion as a result Mixtures of compounds with R3 in formula I are obtained with a shortened reaction time = Alkyl on the one hand and hydroxyalkyl on the other. These technical mixtures show after their quaternization also the desired fabric softening properties while maintaining the absorbency of the softened textiles; possibly not converted starting products are expediently removed from the reaction product at low Distilled off under pressure and low temperature. This avoids that the Conversion products become dark.

Suitable alkylating agents are e.g. B. methyl chloride, methyl bromide, Dimethyl sulfate, diethyl sulfate, but especially methyl chloride and dimethyl sulfate. When carrying out the quaternization with methyl chloride as the alkylating agent works one expediently under a pressure of up to 10 bar, preferably 3-6 bar and a temperature between preferably 80-120 ° C., optionally in the presence from solvents such as isopropyl alcohol and / or water. The quaternization with dimethyl sulfate as the alkylating agent, at normal pressure and temperatures between 50 and 100 ° C, preferably 60-80 ° C.

A quaternization is also possible by reacting the amines with a lower one Epoxy and subsequent acid treatment to introduce the anion possible.

The new products can be easily put in water and in mixtures dispersing from water and lower alcohols to form stable dispersions; treated with it Textiles have a soft, fluffy feel with good absorbency at the same time and good wettability.

The compounds of the formula I can be used as fabric softeners and optionally together with other fabric softeners, antimicrobials, optical Brighteners, nonionic and cationic surfactants and optionally others Mix and match the usual ingredients of textile softeners without any problems especially for liquid preparations. The use of the new quaternary Ammonium compounds as textile softeners in liquid agents in particular Post-laundry treatment in the rinsing bath of the washing process for hand or machine washing and in the tumble dryer, the agents 1 to 40% by weight of the compounds of the formula I and at least one diluent and, if appropriate, other customary additives for liquid laundry aftertreatment agents is therefore a further subject matter the invention.

The use of the fabric softening agents according to the invention in Laundries and households for the post-treatment of washed laundry can be on done in different ways, depending on the choice of drying method. Is in dried in a tumble dryer, so you can wash the laundry directly with an active ingredient dispersion spray or bring the active ingredient into contact with the laundry via a carrier, for example by spraying the inner walls of the drying device with the liquid Means before loading the device with laundry, or by loading one with the liquid Medium-impregnated carrier with a large surface area, with the fabric softener during of the drying process draws on the laundry. Currently will however, most of the laundry was left hanging; therefore it also outweighs the Application of the softening agent in the last rinse bath of the washing process in the Hand and especially machine wash. Such amounts of the invention Means dissolved in the rinsing solution that the concentration of the active ingredient of the formula I is 0.05-1.5 g / l, preferably 0.1-1.0 g / l.

Can be used as a diluent for liquid textile treatment agents Water and / or water-soluble organic solvents in question. Usable water soluble organic solvents are the lower alcohols with 1 - 5 carbon atoms, such as B. methanol, ethanol, propanol, isopropyl alcohol, n-butanol, isobutanol, Amyl alcohol, also the lower ketones acetone and methyl ethyl ketone as well as ethylene glycol, Propylene glycol, diethylene glycol and their mono- or diether derivatives with in particular Methyl and ethyl radicals.

The active ingredients of the formula I are also suitable for packaging of free-flowing textile aftertreatment agents in powder form. As a diluent such powdery agents are, for example, urea, acetamide, Sodium sulfate and any other common ingredients, if any these are in solid form.

Other common components of textile treatment agents are considered to be for example dispersants, optical brighteners; antimicrobial agents, acidic Additives, solubilizers, dyes and fragrances.

The connections of the. Formula I can also be used together with known Textile softeners of the quaternary ammonium compound type, such as. B. Ditallowalkyldimethylammonium chloride, or with known textile softeners with amide structure from Type of the fatty acid condensation products with hydroxyalkyl polyamines, for example the Condensation product of 1 mole of tallow and 1 mole of 2-hydroxyethylethylenediamine, combined will. Also the addition of well-known ones for the assembly in textile treatment agents suitable antimicrobial agents of the antimicrobial quaternary type Ammonium compounds, such as. B. Benzyldodecyldimethylammonium chloride, as well as antimicrobial Nitro alcohols or phenol derivatives or carbamates etc. are possible.

The composition of liquid laundry aftertreatment agents of particular interest, in which the new active ingredients of the formula I can be used lies in general in the range of the following formulation: 2.0-30.0, preferably 5.0-25.0 5 weight percent active ingredient of formula I, 0.2-6.0, preferably 0.5-3.0% by weight of dispersants, 0.0-30.0, preferably 1.0 - 15.0% by weight of water-soluble organic solvents, 0.0 - 10.0, preferably 0.3 - 7.5% by weight of other common constituents of laundry aftertreatment agents, Rest water.

As other common constituents of laundry aftertreatment agents may include at least one of the following components in the specified, on the whole Agent-related amounts are present: 0.2-5.0% by weight of other, of the active ingredient of the formula I various textile softeners, 0.2-3.0% by weight of antimicrobial agents, 0.2 - 6.0 acidic additive, 0.01 - 0.5% by weight cotton whitening agent, 0.01 - 0.5% by weight Polyamide brighteners, 0.01-0.5% by weight fragrance, 0.00001-0.05 % By weight dye.

In the following, those in the textile treatment agents in addition to Active ingredient of the formula I still containing ingredients sorted according to substance classes described in more detail.

As dispersants, such as those in liquid and powdery textile treatment agents can be contained, the nonionic surfactants ("Nonionics2") are particularly suitable.

This includes products that have their hydrophilic properties of presence of polyether chains, amine oxide, sulfoxide or phosphine oxide groups, alkylolamide groups as well as an accumulation of hydroxyl groups in general. Such nonionics contain at least one hydrophobic radical from 8 to 26 in the molecule, preferably 10-20 and especially 12-18 carbon atoms, and at least one nonionic water-solubilizing group. The preferably saturated hydrophobic residue is mostly aliphatic, optionally also alicyclic, in nature; he can with the water-solubilizing Groups can be connected directly or via intermediate links. Come as intermediate links z. B. benzene rings, carboxylic acid ester or carbonamide groups, ether- or ester-like bonded residues of polyhydric alcohols, such as. B. those of ethylene glycol, propylene glycol, of glycerine or corresponding polyether residues.

Of particular practical interest are those caused by the addition of Ethylene oxide and / or glycide on fatty alcohols, alkylphenols, fatty acids, fatty amines, Fatty acid or sulfonic acid amides, these nonionics 4 - 100, preferably 6-40 and in particular 8-20 ether residues, especially ethylene glycol ether residues may contain per molecule. In addition, in these polyether chains or on the ends of which are propylene or butylene glycol ether residues or polyether chains be.

The nonionics also include products that are made from water-insoluble ones Polypropylene glycols or from water-insoluble propoxylated lower, 1 - 8, preferably 3 - 6 carbon atoms containing aliphatic alcohols or from water-insoluble propoxylated alkenediamines are obtained by adding them to solubility in water ethoxylated.

The nonionics also include fatty acid or sulfonic acid alkylolamines, for example from mono- or diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, for example the glycamines. You let by amides from higher primary or secondary alkylamines and polyhydroxycarboxylic acids substitute.

The capillary-active amine oxides include, for example, those of higher tertiary, one hydrophobic alkyl radical and two shorter ones, up to 4 carbon atoms each containing amines containing alkyl and / or alkylol radicals.

In addition to the mostly water-soluble surfactants, non-ionic ones are also suitable Dispersants optionally also water-soluble or emulsifiable in water or dispersible compounds that either do not have any hydrophobic radicals as defined above contain nonionic surfactants described, or where the nature or the Number of hydrophilic groups to achieve complete water solubility not suffice. The former include e.g. B. solid or liquid polyethylene glycols, which are called condensation polymers of ethylene oxide with ethylene glycol or water can understand ethylene oxide adducts of glycerin and other polyalcohols, etc .; to the latter z. B. partial fatty acid glycerides or not or not completely water-soluble alkoxylation products, e.g. B. those with 2-5 ethylene glycol ether residues in the molecule.

Acidic additives are inorganic and non-surface-active organic acids with 2 - 8 carbon atoms, such as B. sulfamic acid, larnea compounds orthophosphoric acid, boric acid, oxalic acid, lactic acid, glycolic acid, citric acid, Tartaric acid, benzoic acid, phthalic acid, gluconic acid, acetic acid and propionic acid as well the benzene, toluene or xylene sulfonic acids, sulfoacetic acid or sulfobenzoic acids or acidic alkali salts of these acids. Are glycolic acid and citric acid acids preferred because of their easy accessibility and non-toxicity.

Antimicrobial agents here are bactericidal or bacteriostatic or fungicidal or fungistatic compounds understood. These active ingredients should be water-soluble either as such or in the form of their salts. Both antimicrobial quaternary ammonium compounds suitable as additives are involved in particular those that have a long-chain aliphatic and two short-chain aliphatic hydrocarbon radicals an aromatic, over a aliphatic carbon atom linked to the nitrogen atom, or an aliphatic, Contain organic radical having double bonds in the molecule. examples for such antimicrobial quaternary ammonium compounds are the following: dimethyl-benzyl-dodecylammonium chloride, Dimethylbenzyl-tetradecylammonium chloride, dimethyl- (ethylbenzyl) -dodecyl-ammonium chloride, Dimethyl-benzyl-decylammonium bromide, diethyl-benzyl-dodecylammonium chloride, diethylbenzyl-octyl-ammonium chloride, Dibutyl-allyl, methylethyl-benzyl-, ethyl-cyclohexyl-allyl- and ethyl-crotyldiethylaminoethyl-dodecyl-ammonium chloride Further useful antimicrobial agents are those by both bromine and by the nitro group substituted lower alcohols or diols with 3 to 5 carbon atoms such as B. the compounds 2-bromo-2-nitropropane-1,3-diol, 1-bromo-1-nitro-3,3 r 3-trichloro-2-propanol, 2-bromo-2-nitro-butanol.

Phenolic compounds are also suitable as antimicrobial agents of the halogenated phenol type with 1-5 halogen substituents, especially chlorinated ones Phenols; Alkyl, cycloalkyl, aralkyl and phenylphenols with 1-12 carbon atoms in the alkyl radicals and with 1-4 halogen substituents, in particular chlorine and bromine in the molecule; Alkyl bisphenols, in particular with 2 - 6 halogen atoms and optionally lower alkyl or trifluoromethyl substituted derivatives with an alkylene bridge member consisting of 1 - 10 carbon atoms; Hydroxybenzoic acids or their esters and Amides, especially anilides; those in the benzoic acid and / or aniline radical in particular can be substituted by 2 or 3 halogen atoms and / or trifluoromethyl groups; o-Phenoxyphenols, by 1 - 7, preferably 2 - 5 halogen atoms and / or the Hydroxy, cyano, carbomethoxy and carboxyl groups or lower alkyl substituted could be; a particularly preferred derivative of o-phenoxyphenol is 2-hydroxy-2 ', 4,4'-trichlorodiphenyl ether, Antimicrobial agents in the broader sense also include additives, such as. B. formaldehyde, sorbic acid, sodium fluoride understood to preserve the Serving preparations.

Examples The following is first the description of the production of the new connections.

Example 1 Preparation of tris (5-hydroxy-3-oxa-C15 / 17-alkyl) methylammonium chloride To 298.4 g (2 mol) of triethanolamine and 6 g of 30% strength by weight methanolic sodium methylate solution were at 180 ° C under a nitrogen atmosphere and with stirring within 30 minutes 1194 g (6 mol) of 1,2-epoxyalkane with approx. 70% by weight of C12 and approx. 30% by weight of C14-epoxyalkane added and stirred for 1 h. Then at 0.8 mbar and a bottom temperature from 240 ° 80 g forerun distilled off.

1407 g of tris (5-hydroxy-3-oxa-C15 / 17-alkyl) amine remained as residue in the distillation flask with an amine number of 84.4. This product totaled 664.7 g (1 mole) with 95.4 g of water and 143 g of isopropyl alcohol in an evacuated 2-liter autoclave moved in. At 100 ° C., 5 bar of methyl chloride were injected. After 4 1/4 h it was the quaternization almost completely completed (quaternary content 93.5% by weight, amine number a sample 2,3).

After cooling to room temperature and equalizing the pressure, one obtained 75% strength by weight solution of tris (5-hydroxy-3-oxa-C1 5/1 7-alkyl) -methylainmoniumchlorid.

Example 2 Preparation of bis (5-hydroxy-3-oxa-C1 9/2 1-alkyl) dimethylammonium methyl sulfate At room temperature, 276.8 g (1 mol) of 1,2-epoxyalkane with a proportion of approx. 40% by weight of C16 and approx.

60 wt% C18 epoxyalkane to 59.5 g (0.5 mole) N-methyldiethanolamine and added 1.5 g of 30 wt% methanolic Sodium methylate solution added. The reaction was carried out after heating with stirring and a nitrogen blanket to 180 ° C within 7 h.

This was followed by a pressure of 0.4 mbar and a sump temperature from 240 ° C 25.6 g of first runnings are distilled off. 314 g (0.5 mol) of the reaction product Bis (5-hydroxy-3-oxa-C1 9,21-alkyl) methylamine with an amine number of 92.6 g remained as residue in the distillation flask.

Without further purification, this reaction product became quaternized 63.1 g (0.5 mol) of dimethyl sulfate are added dropwise at 70 ° C. with stirring and stirred at 70 ° C. for 2 h. The quaternized product was made with 75.4 g of isopropyl alcohol and 50.3 g of water were added. The resulting 75% strength by weight solution was used for tests used.

The reaction product of Example 1 wes before the quaternization in IR spectrum no longer shows any epoxy band at 831 cm; this showed that the epoxyalkane was fully implemented. Instead, the ether band appeared at 1120 cm 1.

The maxima characteristic of the structure were in the NMR spectrum at # = 4.3; 3.6; 2.7 and 0.9 ppm. The integration ratio was 1: 5: 2: 3. When heavy water was added, the maximum at S = -4.3 ppm disappeared.

This maximum could thus be assigned to the hydroxyl group. The maxima at 1.3 and 0.9 ppm are the methylene and methyl groups of the long one To be assigned to alkyl esters.

The maximum at & = 3.6 ppm is assigned to the hydrogen atoms, which are bonded to the carbon atoms adjacent to the oxygen atom. That The maximum at & = 2.7 ppm is assigned to the hydrogen atoms attached to the Nitrogen atoms adjacent carbon atoms are bonded. Of course the signal of the hydrogen atoms appears as the most intense maximum at 1.3 ppm Methylene groups of the long alkyl residue.

Theoretically, the not yet quaternized reaction product should be from Example 1 in the NMR spectrum maxima at 6 = 4-5 ppm, and at 6 = 3.4; 2.7 and 0.9 ppm, the integration ratio being 1: 5: 2: 3. The location the maximum of the measured NMR spectrum and the integration ratio are correct so agrees very well with the theoretical values for this compound.

The NMR spectrum of the reaction product from Example 2 shows before Quaternization, as expected, in addition to the other maxima, which are also in the spectrum of the product of Example 1 are present, a maximum at 6 = 2.3 ppm, which is characteristic of the N-CH3 group. The measured integration ratio 2: 10: 4: 3: 6 agrees with the theoretical integration ratio for this Connection also match.

Example 3 The product from Example 1 was tested for its softening properties Effect and on the wetting behavior of fabrics treated with this product checked. The wetting behavior provides information about the absorbency of Textiles, which are mainly used for terry towels and clothing that comes into contact with the Skin is worn plays an important role.

The softening effect was tested by going through several times Washing hard-made fabrics made of cotton or

Polyacrylonitrile in an aqueous liquor (liquor ratio 1:20), which contained 0.5% by weight (based on the tissue) of active substance, 3 minutes Room temperature moved slightly, the fabric then in a spin dryer from adhering Treatment liquor largely freed and air-dried. The softness of the dried tissue was haptically assessed by a group of people who Have experience in this type of test.

The wettability was measured on 2 x 2 cm, as described above, Treated cotton fabrics are tested by placing the samples on a water surface and measured the time after which the sample begins to sink downwards.

For comparison, a cationic one was commercially available as the active ingredient Textile softeners of the ditallow alkyl dimethyl ammonium chloride type are used.

Result: cotton and polyacrylonitrile textiles that come with the product from Example 1 and the comparative product were treated by the Test subjects all judged to be soft; there were only slight graduals Differences found.

The following values were measured for wettability (Table 1): Table 1 Treatment with product wettability from example 1 1 sec. Ditallowalkyl-dimethylammonium-> 300 sec. chloride Untreated <1 sec.

These values show that the wettability of the inventive Connections treated tissue is extraordinarily good.

Further recipe examples follow.

Example 4 5% by weight bis (5-hydroxy-3-oxa-C19 / 21-alkyl) -dimethylammonium chloride 1% by weight adduct of 1 mole oleyl / cetyl alcohol + 10 moles ethylene oxide 1% by weight citric acid Rest water.

Example 5 20% by weight bis (5-hydroxy-3-oxa-C19 / 21-alkyl) -dimethylammonium chloride 2 parts by weight of adduct of 1 mole of coconut alcohol (C12-C18) + 4 moles of ethylene oxide and 1% by weight of glycolic acid 20% by weight isopropyl alcohol, remainder water.

Example 6 6.0 wt% bis (5-hydroxy-3-oxa-C19 / 21-alkyl) -dimethylammonium chloride 1.0% by weight adduct of 1 mole of oleyl / cetyl alcohol + 10 moles of ethylene oxide 0.5% by weight Citric acid 0.1% by weight cotton whitening agent 4,4-bis- (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid, sodium salt 1.0 wt .- * Benzyldodecyldimethylammonium chloride 10.0 wt .- t isopropyl alcohol remainder Water.

Examples 9-13 The product from Example 1 was used to produce fully made-up laundry aftertreatment agents with the following composition (data in% by weight): Table 2 Component example 9 10 11 12 13 Tris (5-hydroxy-3-oxa-C15 / 17-6.0 6.0 9.0 9.0 12.0 alkyl) methylammonium chloride Polyglycol ethers, molecular | 2.0 | 0.5 | 1.5 | 1.5 | 1.0 weight 400 Lauryltrimethylammonium- | - | 1.0 | - | - | 1.5 | chloride C12 / 14 fatty alcohol ethoxylate | - | - | - | 0.5 | 0.2 with 3 moles of ethylene oxide Glycolic acid 1.0 1.0 - - - Citric acid - - 0.5 0.5 0.5 Na acetate - - - - 0.1 Optical brightener 0.1 - - 0.1 - - for polyamide Isopropyl alcohol 0.5 - 0.5 0.3 - Dutstoff 0.1 0.1 0.1 0.1 0.1 Dye - 0.01 - 0.01 - Rest water The items of laundry treated with these formulations exhibited good absorbency in addition to a good handle.

Claims (19)

"New quaternary ammonium compounds, a process for their production and their use as textile softeners" Patent claims 12 quaternary ammonium compounds of the formula I. in which R1 is an aliphatic hydrocarbon group with 1 to 21 carbon atoms and R2 is H or R1, the sum of the carbon atoms of R1 and R2 being 6 to 22 and, if R2 = H, the group R1 has 6-21 carbon atoms, R3 an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms or a radical of the formula R4 denotes an alkyl group with 1 to 4 carbon atoms, X and Y denote hydrogen or the methyl group, but X and Y in the same ethoxy group are not both methyl, m, n and p denote integers between 1 and 20 and A # stands for an anion. 2. Compounds according to formula I of claim 1, characterized in that that R3 is an alkyl group or a hydroxyalkyl group having 1-4 carbon atoms means. 3. Compounds according to formula I of claim 1, characterized in that R3 is a radical of the formula denotes, where R1, R2, X, Y and p have the meaning given in claim 1. 4. Compounds according to claim 1-3, characterized in that R1 denotes an alkyl group having 1 to 21, preferably 8 to 18 carbon atoms. 5. Compounds according to claim 1-4, characterized in that R2 = H means. 6. Compounds according to claim 1-5, characterized in that X = Y = H means. 7. Compounds according to claim 1-6, characterized in that the Indices m, n and p each denote a number from 1 to 3, in particular the number 1. 8. Compounds according to claim 1-7, characterized in that A0 of the formula I an anion from the group consisting of chloride, bromide, methyl sulfate, Means ethyl sulfate, in particular chloride or methyl sulfate. 9. Compounds according to claim 1-8, characterized in that R1 is an alkyl group with 8-18 carbon atoms, R2 = X = Y = H, R3 is a radical of the formula R4 = methyl, m = n = p = 1 and A denotes the chloride or methyl sulfate anion. 10. Compounds according to claim 1-8, characterized in that R1 is an alkyl group with 8-18 carbon atoms, R2 = X = = H, R3 = R4 = methyl, m = n = 1 and A is the chloride or methyl sulfate anion. 11. Compounds of the formula II in which R1, R2, R3, X, Y, m and n are as defined in claim 1, in particular as defined in claims 2-10. 12 * Process for the preparation of compounds of the formula I according to claims 1-10, characterized in that an epoxyalkane of the formula III in which R1 and R2 have the meanings given in claims 1-10 with a polyalkanolamine of the formula IV in which R5 is an alkyl group with 1-4 carbon atoms or a radical of the formula H (-OCHX-CHY) p-, where X, Y, m, n and p have the meanings given in claims 1-10, in the presence of one The catalyst is reacted under normal pressure and at an elevated temperature to form the tertiary amine of the formula II according to claim 11 and then quaternized with an alkylating agent which introduces the group R defined in formula I of claim 1. 13. The method according to claim 12, characterized in that as Alkylating agent a compound selected from the group consisting of methyl chloride, Methyl bromide, dimethyl sulfate, diethyl sulfate, especially methyl chloride or dimethyl sulfate used. 14. The method according to claim 12 and 13, characterized in that the quaternization is preferably carried out at 80.degree.-1200.degree. C., if appropriate with increased Carries out pressure and optionally in the presence of solvents. 15. The method according to claim 12-14, characterized in that one an epoxyalkane of the formula III, in which R1 and R2 are those specified in claims 1-10 Have meanings with a polyalkanolamine of the formula IV in which X and Y have the in Claim 1, preferably have the meaning given in claim 6, R5 is a methyl or ethyl group or a group of the formula H (-OCHX-CHY) p-, in, n and p are integers between 1 and 3, in particular 1, in the presence of a sodium alcoholate as Catalyst at normal pressure and a temperature of 150 - 250 ° C within 2 Reacts for 10 hours, preferably for 3 to 6 hours, and at 50-150 ° C with dialkyl sulfate under normal pressure or with alkyl chloride at a pressure of up to 10 bar, preferably 3 - 6 bar, quaternized. 16. Use of the compounds of the formula I of claims 1-10 as a textile softener. 17. Use of the compounds of the formula I of claims 1-10 according to claim 16 in in particular liquid agents for the aftertreatment of washed Wash in the rinsing bath of the washing process for hand washing or, in particular, machine washing and in the tumble dryer, the agents 1 to 40% by weight of the compounds of the formula I and at least one diluent and, if appropriate, other customary ingredients contained in laundry aftertreatment agents. 18. Use of quaternary ammonium compounds according to the claims 16 and 17 in liquid laundry treatment agents of the following composition: 2.0-30.0, preferably 5.0-25.0% by weight of quaternary ammonium compounds of the formula I 0.2-6.0, preferably 0.5-3.0% by weight of dispersants 0-30.0, preferably 1.0-15.0% by weight of water-soluble organic solvents, O-10.0, preferably 0.3 - 7.5 tonnes by weight of other common constituents of laundry aftertreatment agents Rest water. 19. Use of quaternary ammonium compounds in liquid laundry aftertreatment agents according to claims 16-18, characterized in that the other usual components at least one of the following components in the specified, on the total agent related quantities is present: 0.2 - 5.0 wt. t of other, of the active ingredient of the formula I various textile softeners 0.2-3.0% by weight of antimicrobial active ingredient 0.2 - 6.0 wt. G of acidic additives 0.01-0.5% by weight cotton whitening agent 0.01-0.5% by weight polyamide brightener 0.01-0.5% by weight fragrance 0.00001-0.05% by weight Dye.