DE2625945A1 - Long chain branched alkyl quat. ammonium cpds. - useful as textile softeners, having antistatic and antimicrobial properties - Google Patents

Abstract

Quat. ammonium cpds. of formula (I): R1CH2CH2.CHR2.CH2N(R3)(R4).Y X- and intermediate of formula (IVa): (R1CH2CH2CHR2.CH2)2NH (IVa), (R1 and R2 = 6-20C alkyl, R3 and R4 = 1-3C alkyl or substd. ethyl or propyl. Y = 1-3C alkyl or CH2CHR2.CH2CH2R1, X = an anion). (I) are prepd. from (IVa), or the corresp. prim. amine, by alkylation to the tert. amine, then quaternisation. In an example, bis(2-decyltetradecyl)dimethylammonium chloride was prepd. by reacting di(2-decyltetradecyl)amine with CH3I in isopropanol. (I) are textile softeners useful for application after washing. They have minimal effect on the absorption capacity of the textiles and also possess antistatic and antimicrobial properties.

Description

"New quaternary ammonium compounds and their use as textile softeners" The invention relates to new quaternary ammonium compounds with one or two long chain aliphatic hydrocarbon radicals, a process for their preparation as well as their use in textile treatment agents.

Quaternary ammonium compounds that have one or two long-chain and contain three or two short-chain aliphatic hydrocarbon radicals in the molecule, such as the compound ditallowalkyldimethylammonium chloride, are already used as fabric softeners Used for treating textiles, especially for post-treating washed laundry. This treatment gives the textile pieces a soft and fluffy feel. In use, however, the textile material treated in this way shows a marked deterioration Suction capacity compared to the untreated goods. Terrycloth textiles, tea towels or diapers, for example, that keep using these quaternary after washing Ammonium compounds have been treated, show a reduced or

delayed water absorption, reducing the performance properties be affected. It is believed that this has an adverse effect on it are due to the fact that the quaternary ammonium compounds applied to the fibers are not or not completely removed during the subsequent washing and therefore the repeated post-treatment leads to an accumulation on the fiber.

It has now been found that the quaternary ammonium compounds of Formula I l3 R1-CH2-CH2-C1H-CH2-NY, x0 (i) R2 R4 in which the radicals R1 and R2 are alkyl groups with 6-20, the radicals R3 and R4 are alkyl groups with 1-3 carbon atoms, Y is a lower alkyl group such as R or R4 or the radical -CH2-CHR2-CH2-CH2R1 and X - an anion mean, surprisingly have excellent laundry finishing properties and are therefore suitable for textile treatment, in particular for use in laundry aftertreatment agents, without having the disadvantages described above. Accordingly, it is a particular advantage of the new fabrics that, in addition to their good fabric softening effect, they only have a negligible effect on the absorbency of the treated fabric. In addition, the new substances act as antistatic agents; ie the unwanted static charging of the textiles during their drying or use, especially in the case of textiles made of synthetic fibers, is prevented by the treatment with the new active ingredients. In addition, the new active ingredients have valuable antimicrobial properties. The compounds of the formula I can be mixed with other fabric softeners, antimicrobials, optical brighteners, nonionic and cationic surfactants without problems and, in particular, made up into liquid preparations.

The alkyl groups, corresponding to the radicals R1 and R2 in formula I, can be of synthetic or natural origin. They go back to the alcohols of the formula II R1- (or R2) H2-CH2OH (II) from synthetic or natural sources, whereby the radicals R1 and R2 can be identical. These alcohols are converted into the corresponding Guerbet alcohols of the formula III by means of the Guerbet reaction ie converted into primary alcohols with d-alkyl branching.

The Guerbet reaction also makes it possible to utilize such aliphatic ones Alcohols that have a carbon chain that is too short for the direct synthesis of surfactants exhibit.

Such alcohols with in particular 4-10 carbon atoms fall in technical fat processing via the so-called first run fatty acids on and are also found in the pre-distillates of synthetically produced longer-chain ones Alkanols.

The radicals R3 and R4, which are identical or different in formula I can be, it is the methyl, ethyl, propyl, isopropyl, hydroxyethyl, 2-hydroxypropyl and 2,3-dihydroxypropyl groups, of which the methyl group of of particular practical interest.

Under the anion X (3, due to what is described below Manufacturing process, especially the chloride or bromide anion or the methyl sulfate anion Understood. However, the salts of the formula I can also be used by exchanging the anions in salts with sulfate, borate, phosphate, perchlorate anions or in salts of organic, non-capillary acids are transferred, if this is desired.

The compounds of the formula I are liquids that are viscous at normal temperature, which can be dissolved or dispersed in water. They are also readily soluble in the lower alcohols such as methanol, ethanol, ispropyl alcohol.

The invention further relates to a process for the preparation of the new substances of the formula I. This process is characterized in that an amine of the formula IY, in which the radicals R1 and R2 have the meanings given in formula 1, and the radical Z is hydrogen or the group -CH2-CHR2-CH2-CH2-R1, alkylated with an alkylating agent introducing the radicals R3 and optionally R4 up to the tertiary amine stage and then quaternized to the ammonium stage.

The alkyl halides, the alkyl sulfates, are suitable as alkylating agents and the epoxy compounds ethylene oxide, propylene oxide and glycide. When using Alkyl halides such as methyl chloride, methyl bromide or alkyl sulfates such as dimethyl sulfate or diethyl sulfate can start the alkylation from the primary or secondary amine can be carried out in one go up to the ammonium stage. For the alkylation of the primary or secondary amine of the formula IV to the tertiary amine is the reductive method Methylation of amines with formaldehyde and formic acid according to Leuckart-Wallach in particular suitable. In this way, from the primary or secondary amines Formula IV obtained the corresponding tertiary methyl-substituted amines.

Suitable for the preparation of the active ingredients of the formula I according to the invention primary amines of the formula IV are, for example, the compounds: 2-hexyldecylamine, 2-octyldodecylamine, 2-decyltetradecylamine, 2-dodecylhexadecylamine, 2-tetradecyloctadecylamine, 2-hexadecyleicosylamine, as well as those from hydrogenated, natural fatty acid fish derived amines, such as 3. nocosguerbetalkylamine and tallowguerbetalkylamine.

Let through reductive methylation with formaldehyde and formic acid the tertiary amines with 2 methyl groups result from the aforementioned primary amines produce, for example, the compounds N, N-dimethyl-N- (2-hexyldecyl) amine, N, N-dimethyl-N- (2-octyldodecyl) -amine, N, N-dimethyl-N- (2-decyltetradecyl) -amine, etc.

By reaction with the abovementioned epoxyalkanes, for example the tertiary amines N> N-bis (2-hydroxyethyl) -N- (2-hexyldecyl) -amine, N, N-bis (2-hydroxypropyl) -N- (2-octyldodecyl) ) -amine, N, N-bis (2,3-dihydroxypropyl) -N- (2-hexyldecyl) -amine, etc.

Of particular importance are the new substances of the formula I, which are im Molecule contain 2 long-chain Guerbetalkyl radicals (Y = -CH2-CHR2-CH2-CH2R1), and which are consequently derived from the secondary amines of the formula IV. With these secondary amines are symmetrical compounds if one originally starts from a primary alcohol of a certain chain length. In however, alcohol mixtures with straight-chain alcohols are often used in practice start out of different chain lengths in order to produce the Guerbet alcohol of the formula III. This shows that when processing alcohol mixtures to Guerbet alcohols the formula III arrives in which the R1 and R2 radicals are alkyl groups mean different chain length (so-called crossed Guerbetization), and that is why the resulting via the primary Guerbetamine by condensation under Secondary amines of the formula IV produced asymmetric mixtures represent established connections.

Typical representatives of the secondary amines of the formula IV are, for example single compounds (R1 = R2 in formula IV).

Bis (2-hexyldecyl) amine, bis (2-octyldodecyl) amine 5 bis (2-decyltetradecyl ) -amine and the compounds bis-cocosguerbetalkylamine and bis-tallowguerbetalkylamine, represent the corresponding mixtures.

By methylation according to the Leuckart-Wallach method or by Alkoxylation can use the corresponding secondary amines of the formula IV tertiary amines, which then have to be quaternized to give the compounds of formula I. are to be produced. Examples include: N-methyl-N, N-bis-cocosguerbetalkylamine, N- (2-hydroxyethyl) -N, N-bis (2-hexyldodecyl) amine, N- (2,3-dihydroxypropyl) -N, N-bist2-octyldodecyl) amine.

The quaternary produced from the secondary amines of the formula IV Ammonium compounds of the formula I are preferred because they are particularly good plasticizers or have antimicrobial properties.

A method for producing the active ingredients is particularly preferred of the formula I, in which a secondary amine of the formula IV is used in an inert solvent dissolves, mixed with an acid-binding additive and, preferably in a closed System, at 80-130 ° C with a 1 to 3-fold molar excess of an alkylation and Quaternierungsmitteis and the reaction stops at the latest when the reaction mixture no longer contains any titratable amine.

The lower C1, for example, are suitable as inert solvents -C4 alcohols, especially isopropyl alcohol.

Suitable for binding the acid released during the alkylation e.g. sodium carbonate, potassium carbonate, sodium bicarbonate. As both alkylating like quaternizing agent, methyl chloride1, mathyl bromide, ethyl chloride, Ethyl bromide or dimethyl or diethyl sulfate into consideration.

The reaction is advantageously carried out in an autoclave which a device for taking samples to determine the end point of the reaction to be able It has been shown that it is useful to list the reaction by rapid Then stop cooling if there are still small amounts of titratable amine in the reaction mixture are included. In this way a particularly light-colored product is obtained.

The reaction mixture is worked up in the customary manner by filtering off the insoluble salts and distilling off the solvent and excess alkylating agent.

The process product thus obtained is a mixture of quaternary Ammonium compound, amine hydrochloride and amine.

In this form it shows the desired fabric softening and antimicrobial properties Properties and is without further cleaning measures for application-technical Purposes.

Accordingly, unless expressly stated otherwise, as new quaternary ammonium compounds of the formula I defined above, there are also those technical products are understood to be in addition to a predominant proportion of quaternary ammonium compound also has a proportion of non-quaternized amine precursors contain.

The active compounds according to the invention include, for example, the compounds of the formula I, Table 1 listed below in Table 1 Active ingredient of formula I. 1 2-hexyldecyl-trimethylammonium chloride 2 2-octyldodecyl trimethylammonium chloride 3 2-decyltetradecyl trimethylammonium chloride 4 2-hexadecylecosyl trimethylammonium chloride 5 Tallowgouerbet alkyl trimethylammonium chloride 6 2-Octadecyldocosyl-trimethylammonium chloride 7 bis (2-hexyl-decyl) -dimethylammonium methyl sulfate 8 bis (2-octyl-dodecyl) -dimethylammonium chloride 9 bis (2-decyl-tetradecyl) -dimethylammonium chloride 10 bis (2-dodecyl-hexadecyl) -dimethylammonium chloride 11 bis (cocosguerbetalkyl) dimethylammonium chloride 12 Bis (2-tetradecyl-octadecyl) -dimethylammonium chloride 13 | Bis (tallow-goat alkyl) -dimethylammonium chloride 14 Talguerbetalkyl bis (2-hydroxyethyl) methylammonium chloride 15 Cocosguerbetalkyl bis (2,3-dihydroxypropyl) methyl ammonium chloride In the context of this invention, the secondary amines of the formula IV a in which the radicals R1 and R2 are alkyl groups with 4 - 20 carbon atoms, claimed as new substances.

Except for the production of the quaternaries already described above These secondary amines are also suitable as ammonium compounds of the formula I Starting materials for the production of surfactants of the amine oxide type, the betaines and the polyethylene glycol ether. Furthermore, the secondary amines of the formula IV a for use in antimicrobial agents, bitumen auxiliaries and as Corrosion inhibitors suitable.

The new secondary amines of the formula IV a are prepared by condensation of the primary amine with elimination of ammonia. In this process, a primary amine of the formula IV b in which the radicals R1 and R2 have the meaning given under IV a, mixed with a hydrogenation catalyst, preferably Raney nickel, and under a hydrogen atmosphere until a molar equivalent of ammonia is split off to a temperature in the range of 100-200, in particular 150- Heated to 180 OC.

The primary amine required as starting material for this reaction of the formula IV b is known per se from the Guerbet alcohol of the formula III Way, for example by reaction with ammonia under a hydrogen pressure from 250 - 260 atm at 280 - 320 OC on a zinc chrome or zinc aluminum contact manufactured.

Finally, the invention also relates to the use of the active ingredients of formula I as a fabric softener. According to the invention, the new substances of the formula I as a textile softener in, in particular, liquid textile treatment agents use 1 - 40 wt. Hg of these active ingredients and at least one diluent and optionally contain other common ingredients of textile treatment agents.

The treatment of textiles with those containing the active ingredients of the formula I. Agents can be used in the textile industry, in commercial laundries and in private Households are carried out.

Textile goods are treated once in the textile industry for the purpose of reducing the frictional resistance of the textile material during processing and to provide the textile material with a pleasant, soft and smooth handle Softeners are mostly used in the textile industry by padding (padding) applied; According to this method, the plasticizer is made in a short liquor -Water and / or an organic solvent applied. Because of the good solubility of the compounds of the formula I, these are particularly good for the padding method suitable.

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 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, which is softened during the text of the drying process draws on the laundry. However, at present the laundry mostly dried hanging; the use of the plasticizer therefore also predominates in the last rinsing bath of the washing process for hand and especially machine washing. Such amounts of the agent according to the invention are dissolved in the rinsing liquor, that the concentration of the active ingredient of the formula I 0.05-1.5 g / l, preferably 0.1 - is 1.0 g / l. r As a diluent for liquid textile treatment agents water and / or water-soluble organic solvents are suitable. Useful water-soluble organic solvents are the lower alcohols with 1 - 5 carbon atoms, like z ß. Methanol, methanol, propanol, isopropyl alcohol, n-butanol, isobutanol, Amyl alcohol, also the lower ketones acetone and methyl ethyl ketone and ethylene glycol, Propylene glycol, diethylene glycol and their mono- or diether derivatives with in particular Methyl and ethyl residues.

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 active ingredients, acidic Additives, solubilizers, dyes and fragrances.

The fabric softening and antimicrobial effects of the compounds of formula I is influenced by the length of the carbon chains of the radicals R1 and R2. It has been observed that the compounds of the formula I with alkyl radicals from the middle and the upper half of the claimed chain length range from C4 - C20 an optimum show an emollient effect, while the antimicrobial effect of the compounds is pronounced with shorter-chain alkyl radicals. In mixtures of compounds of the Formula I with different chain lengths in the claimed range can be so the desired softening and antibacterial effect can be set.

The compounds of formula 1 can also be used together with known textile softeners of the type of quaternary ammonium compounds, such as, for example, 5. Ditallowalkyldimethylammonium chloride, or with known textile softeners with an amide structure of the fatty acid condensation product type with hydroxyalkyl polyamines, for example the condensation product of 1 mole of tallow and 1 mole of 2-hydroxyethylethylenediamine, are combined. Also the addition of well-known, antimicrobial suitable for the packaging in textile treatment agents Active ingredients of the antimicrobial quaternary ammonium compound type, such as benzyldodecyldimethylammonium chloride, as well as antimicrobial nitro alcohols respectively.

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% by weight of 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, b other common ingredients of laundry treatment 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 Medium-related zengen be present: 0.2 - 5.0 wt .-% other, of the active ingredient of the formula I various textile softeners, 0.2-3.0% by weight of others, of the active ingredient of the formula I various antimicrobial active ingredients, 0.2 - 6.0 wt. acidic additive, 0.01-0.5% by weight cotton brightener, 0.01-0.5% by weight, 4 polyamide brighteners, 0.01 - 0.5% by weight of fragrance, 0.00001-0.05% by weight of dye.

In the following, those in the textile treatment agents in addition to Active ingredient of formula 1 still contained components 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 ("Nonionleszt") are particularly suitable. These include products that demonstrate their hydrophilic properties to the presence of polyether chains, Amine oxide, sulfoxide or phosphine oxide groups, alkylolamide groups and also whole generally owe to an accumulation of hydroxyl groups. Contain such nonionics in the molecule at least one hydrophobic residue of 8-26, preferably 10-20 and in particular 12-18 carbon atoms, and at least one nonionic water-solubilizing agent Group. The preferably saturated hydrophobic radical is usually more aliphatic, if appropriate also alicyclic in nature; he can work with the water-solubilizing groups directly or connected via intermediate links. There are e.g. benzene rings as intermediate links, Carboxylic acid ester or carbonamide groups, ether-like or ester-like radicals polyhydric alcohols, such as those of ethylene glycol, propylene glycol, des Glycerine or corresponding polyether residues in question.

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 especially 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 contain 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 alkylolamides, 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, up to 4 carbon atoms each containing alkyl and / or alkylol radicals containing amines derived products.

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, for example, solid or liquid polyethylene glycols, Ethylene oxide adducts of glycerin and other polyalcohols, etc .; to the latter e.g. partial fatty acid glycerides or not or

not completely water-soluble alkoxylation products, e.g.

those with 2 - 5 ethylene glycol ether residues in the molecule.

Inorganic and non-surface-active substances become acidic additives organic acids with 2 - 8 carbon atoms, such as amidosulfonic acid, urea compounds -der orthophosphoric acid, boric acid, oxalic acid, lactic acid, ß glycolic acid, citric acid, Tartaric acid, benzoic acid, phthalic acid, gluconic acid, acetic acid and propionic acid as well the benzene-J toluene or xylene sulfonic acids, sulfoacetic acid or sulfobenzoic acids, respectively.

understood acidic alkali salts of these acids.

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, Organic radical containing double bonds in the molecule. examples for such antimicrobial quaternary ammonium compounds are the following: dimethyl-benzyl-dodecylammonium chloride, Dimethyl-benzyltetradecylammonium chloride, dimethyl "(ethylbenzyl) -dodecylammonium chloride, Dimethyl-benzyl-decylammonium bromide, diethylbenzyl-dodecylammonium chloride, diethyl-benzyl-octyl-ammonium chloride, - Dibutyl-allyl, methyl-ethyl-benzyl, ethyl-cyclohexyl-allyl and ethyl-crotyl-diethylaminoethyl-dodecylammonium chloride.

Other useful antimicrobial agents are the by both Bromine as well as lower alcohols substituted by the nitro group or DJoie-mit 3 - 5 carbon atoms such as the compounds 2-bromo-2-nitro-propane-1,3-diol, 1-bromo-1-nitro-3,3,3-trichloro-2-propanol, 2-bromo-2-nitrobutanol.

Phenolic compounds are also suitable as antimicrobial agents of the type of halogenated phenols unit 1 - 5 halogen substituents, in particular chlorinated phenols; Alkyl, cycloalkyl, aralkyl and phenyl phenols with 1 - 12 Carbon atoms in the alkyl radicals and with 1 - 4 halogen substituents, in particular Chlorine and bromine in the molecule; Alkylenebisphenols, in particular with 2 - 6 halogen atoms and optionally lower alkyl or trifluoromethyl groups substituted derivatives, with an alkylene bridge member consisting of 1 to 10 carbon atoms; Hydroxybenzoic acids or their esters and amides, in particular anilides, die.im benzoic acid and / or aniline radical in particular substituted by 2 or 3 halogen atoms and / or trifluoromethyl groups -could be; o-Phenoxyphenols, by 1 - 7, preferably 2 - 5 halogen atoms and / or the hydroxyl, cyano, carbomethoxy and carboxyl groups or lower alkyl be substituted. can; a particularly preferred derivative of o-phenoxyphenol 2-Hydroxy-2 ', 4,4'-trichlorodiphenyl ether is one of the antimicrobial agents In a broader sense, additives such as formaldehyde, sorbic acid, sodium fluoride are also used understood, which serve to preserve the preparations.

B e i s p i e I e First the manufacture of the new secondary Amines of the formula IV a described: Example 1: Preparation of bis (2-hexyldecyl ) -aiain a) 2-Hexyldecylamine In the oven of a hydrogenation apparatus (volume: approx. 14 1) 12 l of a zinc chrome contact was filled in and reduced (cf. DT-PS 1 543 676, page 3, example-2 B).

Then a hydrogen atmosphere was created and so much ammonia added until the cycle gas contained approx. 5-10% by volume of ammonia. The circulation speed was 200 printing liters / hour. After heating the contact furnace to 280 ° C a total pressure of 260 atmospheres is set and 1 1 of 2-hexyldecanol (OHZ 214; COZ 2.5; SZ 0.6) * and at the same time 400 g of liquid ammonia were fed in. From the The pressure separator was switched off every hour for approx.

1 1 colorless amine relaxed. Some water of reaction separated on standing that was saturated with ammonia. The amine was poured off from the water of reaction and degassed in a water jet vacuum at 60 ° C. The fractional distillation gave an amine with XP 98 ° C and AZ = 232 (calc. 233) in 92% yield. 0.1 * 0HZ = hydroxyl number; COZ = carbonyl number; SZ = acid number; AZ = amine number; b) bis (2-hexyldecyl) amine 1084 g (4.5 moles) of the 2-hexyldecylamine along with 11 g of anhydrous methanolic Raney nickel in a 2 1 - three-necked flask, which is equipped with a stirrer, thermometer, Radiator and gas inlet pipe was fitted.

The cooler was connected to an immersion pipe, with the help of which an overpressure of 600 mm water column was set. The air in the apparatus was replaced by hydrogen. It was then heated to 160 ° C. with stirring, a slow flow of hydrogen gas was maintained. After about 2 hours the ammonia split was complete. After the separation of the Raney nickel was distilled. The main fraction distilled at bp 0.1 205-210 ° C; AZ = 119 (calc. 120); Freezing point approx.

-50 0C.

Example 2: Preparation of bis (2-octyldodecyl) amine a) 2-octyldodecylamine As described in Example 1 a), the total pressure was hourly at 320 ° C. and 260 atmospheres 1 1 technical 2-octyldecanol-1 (OHZ 175; VZ 2.4; SZ 7.2,) as well as 400 g liquid Pumped in ammonia. Gas circulation: 200 pressure liters per hour.

Work-up as in Example 1 a). The product was distilled by vacuum cleaned. AZ = 186 (calc. 188).

b) Bis (2-octyldodecyl) amine 1785 g of the 2-octyldodecylamine was obtained reacted as described in Example 1 b) with 20 g of Raney nickel. The analog work-up resulted in a product with the characteristics: 228-230 ° C; AZ = 96 (calc. 97); Freezing point -32 C.

Example 3: bis (2-decyltetradecyl) amine As described in Example 2, the primary amine 2-decyltetradecylamine was first produced from 2-decyltetradecanol (Bp 0.05 162-164 OC; AZ = 157.2, calc. 157.8) The conversion to the secondary amine took place according to the method of Example 1 b). Reaction temperature: 175 OC; Reaction time.

1 1/2 hours. The product was purified by vacuum distillation. AZ = 80.8 (calc. 81.4).

Example 4: Bis [2- (C14 / C16-alkyl) - (C18 / C20-alkyl)] - amine as starting material served technical Guerbet alcohol, made from the C16 / C18 cut of tallow alcohol. The initially obtained tallow betamine (AZ = 104; calc. 103.5) was used in the example 1 b) described way (temperature 160 -t165 OC; duration 2 1/2 hours) in the secondary Amin transferred. AZ = 55 (calc. 56.2).

The preparation of the new quaternary ammonium compounds of the formula 1 is illustrated by the following examples: Example 5 Bis (2decyltetradecyl ) -d imethylammoniumchlorid 200 g of di- (2-decyltetradecyl) -amine were together with Put 70 g of sodium bicarbonate and 200 g of isopropanol in a 1 liter stirred autoclave, which was provided with a dip tube for sampling. Then there were 70 g of methyl chloride pressed from a filling bomb under nitrogen pressure into the autoclave. After that it was the contents of the autoclave are heated to 100 ° C. with stirring and the temperature is within about 1 hour increased from 100 to 120 ° C.

A sample was then taken every 30 minutes, the Inorganic salt filtered off and then diluted with isopropyl alcohol and countered titrated by n / 10 HCl (indicator bromophenol blue). After a total reaction time of The consumption of n / 10 HCl per 1 g of solution of the autoclave contents was less than 3 hours 1 ml dropped. The reaction was then terminated by cooling the autoclave. During work-up, the inorganic salt was filtered off and the isopropyl alcohol and the excess methyl chloride removed. The reaction product was called viscous yellowish liquid (viscosity at 25 ° C approx. 260 cp) obtained.

The product had the following characteristics: N = 1.9% by weight; Cl = 4.7 Wt%; Refractive index at 50 ° C nD50 = 1.4554.

Example 6 Bis (2-hexyldecyl) dimethylammonium chloride According to the method of Example 1 were 200 g of bis (2-hexyldecyl) amine with 80 g of sodium bicarbonate and 80 g of methyl chloride reacted. The reaction product became a yellowish liquid obtained with the following characteristics: N = 2.1% by weight; Cl = 5.3 wt%; 4 ° = 1.4526.

Example 7 Bis (2-octyldodecyl) dimethylammonium chloride 200 g of bis (2-octyldodecyl) amine were described in Example 1 with 75 g of sodium bicarbonate and 75 g of methyl chloride implemented.

The reaction product was as a yellowish viscous liquid with the the following characteristics were obtained: N = 2.05% by weight; Cl = 4.75 wt%; nD50 = 1.4545.

Example 8 Tallow uerbetalkyltrimethzvlammonilmchlorid 1 mole tallowguerbetalkylamine (539 g) was taken up in 2.5 liters of isopropyl alcohol. After adding 3.6 mol of 85 % formic acid (195 g) was heated to 60 ° C. and a 37% strength aqueous formaldehyde solution (194 g corresponding to 2.4 mol) were added dropwise with stirring over the course of 30 minutes. It was. heated to boiling after 1.2 hours and then by adding 10% sodium hydroxide solution up to pH 9, the amine is shielded as the (upper) liquid phase. The amine phase was dried and the tallow guerbetalkyldimethylamine obtained in this way for quaternization dissolved in isopropyl alcohol. The quaternization took place by reaction with methyl chloride in the autoclave, initially saturating the solution with methyl chloride at 4 atmospheres and then heated to 80 ° C. for 2 hours. After cooling, the solvent became distilled off and the quaternary salt obtained as a residue.

Melting point 64-67 ° C.

Example 9: N- (2-Hexyldecyl) -N, N, N-trimethylammonium chloride 255 g 2-Hexyldecylanine were initially carried out according to the method described in Example 8 Dimethylation converted into the tertiary amine. Bp 0.05 95 ° C; AZ = 201 (calc. 208). For quaternization, 199 g of the tertiary amine were dissolved in 104 g of isopropyl alcohol. Then 5 atmospheres of methyl chloride were injected into the autoclave at 70-75 ° C. and this Maintain pressure for 5 hours. For the quaternary salt obtained during processing 10.15% chlorine (calc. 11.1%) was determined; nD50 = 1 4664.

Example 10: N- (2-Octyldodecyl) -N, N, N-trimethylammonium chloride Production in analogy to Examples 8 and 9 via the tertiary amine (AZ = 170). 9.2% chlorine (calc. 9.4%) was determined for the end product by elemental analysis Follow the manufacturing instructions described in Examples 5-10 the other active ingredients of the formula I can also be prepared analogously; nD50 = 1 4681.

Example 11 The usefulness of the new substances of the formula I as effective Ingredients of textile treatment agents were made with a preparation of the following Composition proven: 6 wt .-% active ingredient of the formula I, 24 wt .- isopropyl alcohol, 70 wt. Water.

To determine the softening effect, the preparation was on a Application concentrate of 0.3 g of active ingredient of formula 1 per liter of washing liquor diluted. Cloths made of cotton terry fabric were used as textile samples, which had previously been carried out by Treatment in a washing machine for 120 hours with a 2 g / l sodium triphosphate containing wash liquor had been pre-cured at 95 0C. This in a more defined Wise pre-hardened fabric samples were assigned the handle grade 6 (= very hard handle).

In contrast, the handle grade 1 (= full and very soft handle) on new, de-treated cotton terry fabric, which is treated with a solution of 0.5 g / l Ditallowalkyldimethylammonium chloride. The hard tissue samples with handle mark 6 were 5 minutes in the treatment bath (temperature 20 0C; liquor ratio 1: 7) submerged. The samples were then spun and dried while hanging. The grip assessment was carried out independently by 4 experienced people and expressed in grades between the limits 1 and 6 defined above. To the For comparison, a treatment bath containing 0.3 g / l of ditallowalkyldimethylammonium chloride was used contained. The mean values calculated from the grip evaluations are shown in the table below II listed. A single treatment of the pre-hardened ones leads to these values Tissue samples with the agents according to the invention to a full and soft grip, that as practically the same soft or slightly softer than the one with the comparison substance effect achieved was assessed.

T able II Active ingredient handle note 1 bis (2-octyldodecyl) dimethyl 3,4 ammonium chloride 2 bis (2-decyltetradecyl) dimethyl 2.8 ammonium chloride 3 Ditallowalkyldiiaethylainmonium- 3.2 chloride (reference substance) 4 Untreated sample 6.0 Example 12 This example shows the good absorbency of the fabrics treated with the agents according to the invention. The influence of the active ingredients of the formula I on the absorbency of the tissue samples was determined by measuring the height of rise using the method of H. Jörder, Zeitschrift für die Gesamt Textilindustrie, 64, 593-596 (1962); ibid. 67, 222-224 (1965) determined. New cotton fabric was used as the test material, which was first extracted with methanol and dichloromethane. Strips 20 cm long and 2 cm wide of this pretreated fabric were agitated for one hour at room temperature in a treatment bath which had been prepared by diluting the preparation given in Example 6 to an active ingredient concentration of 0.5 g / l. The strips were then spun, dried and ironed between filter paper.

After air conditioning at 20 ° C. and 65 ffi relative humidity For 24 hours, these strips were soaked with the lower end in distilled water hung up and the height of the water rises measured after 30 minutes. As comparison used tissue that had only been treated with water, as well as one with 0.5 g / l ditallow alkyldimethylammonium chloride tissue treated as reference substance. The obtained from 8 parallel measurements Average values are given in Table III below. From these numerical values It can be seen that those tissues, which with an active ingredient of the formula I containing Remedies have been treated have a much better ability to sing than the fabrics treated with the known textile softener. While by the well-known Textile softeners, the fabrics are strongly hydrophobized, have those with the invention Agent treated tissue has a singing power that is very similar to that of untreated tissue comes close.

T able III Active ingredient rise in cm 1 bis (2-octyldodecyl) dimethyl-11.1 ammonium chloride 2 bis (2-decyltetradecyl) dimethyl 8.0 ammonium chloride | 3 Ditalgal1gyldimethylrmmonillm- 2.2 chloride (reference substance) 4 4 Untreated sample 13.5 The following Examples 13-15 describe liquid laundry aftertreatment agents. When they were formulated, the active ingredient of the formula I was mixed together with the dispersant and the organic solvent at 40-60 ° C. until homogeneous. Optical brightener and acidic additive, if provided, were dissolved in water and this aqueous solution was added to the above solution with stirring. The preparations obtained in this way are distinguished by good pourability and spreadability in cold water. Fragrances and dyes can be added to the preparations.

Example 13 5% by weight of bis (2-hexyldecyl) dimethylammonium chloride, 2 % By weight adduct of 1 mol of oleyl / cetyl alcohol + 10 mol of ethylene oxide, 1% by weight of citric acid, Rest water.

Example 14 20% by weight bis (2-octyldodecyl) dimethylammonium chloride, 2% by weight adduct of 1 mole coconut alcohol (C12-C18) + 4 moles ethylene oxide, 1% by weight glycolic acid, 20% by weight isopropyl alcohol, the remainder being water.

Example 15 6.0% by weight bis (cocosguerbetalkyl) 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-2,2s-disulfonic acid, sodium salt, 1.0% by weight benzyldodecyldimethylammonium chloride, 10.0% by weight isopropyl alcohol, remainder Water.

Example 12: Powdered laundry aftertreatment agent 15.0% by weight Bis (2-octyldodecyl) dimethylammonium chloride, 3.0% by weight adduct from 1 mole of nonylphenol + 9.5 mol of ethylene oxide, 1.5% by weight of glycolic acid, 55.0% by weight of urea, 25.5% by weight Na2SO4, anhydrous.

Claims (16)

P a t e n t a n s s r u c h e (1.) Quaternary ammonium compounds of the formula I in which the radicals R1 and R2 are alkyl groups with 6-20 carbon atoms, the radicals R3 and R4 are alkyl groups with 1-3 carbon atoms or substituted ethyl and propyl groups, Y is a lower alkyl group with 1-3 carbon atoms or the group -CH2-CHR2-CH2 -CH2R1 and X - mean an anion. 2. Compounds of the formula I according to claim 1, characterized in that that the radicals R3 and R4 denote the methyl, ethyl, propyl or isopropyl group. 3. Compounds of formula 1 according to claim 1, characterized in that that at least one of the radicals R3 and R4 is 2-hydroxyethyl, 2-hydroxypropyl or means the 2,3-dihydroxypropyl group. 4. Compounds of formula 1 according to claim 1 and 2, characterized in that that the radicals R3 and R4 represent the methyl group. 5. Compounds of formula I according to claim 1 to 4, characterized in that that the anion X Ç) means the chloride, bromide, methyl sulfate or ethyl sulfate anion. 6. Compounds of formula I according to claim 5, characterized in that that X- is a chloride or bromide anlon. 7. Compounds of formula I according to claim 1 to 6, characterized in that that Y is the group -CH2-CHR2-CH2-CH2R1. 8. A process for the preparation of the ammonium compounds of the formula I according to Claims 1 to 7, characterized in that an amine of the formula IV is used in which the radicals R1 and R2 have the meanings given in formula I in claim 1, and the radical Z is hydrogen or the group -CH2-C.ER2-CH2-CH2R1, with an alkylating agent introducing the radicals R3 and optionally R4 up to tertiary amine stage and then quaternized with the same or a different alkylating agent to the ammonium stage. 9. The method according to claim 8, characterized in that one of starts from an amine of the formula IV in which Z is the group -CH2-CHR2-CH2-CH2R1. 10. The method according to claim 8 and 9, characterized in that one methylated with formaldehyde / formic acid up to the tertiary amine stage. and the tertiary Amine quaternized. 11. The method according to claim 8 and 9, characterized in that one a secondary amine of the formula IV, in which Z is the group -CH2-CHR2-CH2-CH2R1, dissolves in an inert solvent, mixed with an acid-binding additive and, preferably in a closed system, at 80 - 130 0C with a 1 to 3-fold molar excess of an alkylating and substituting agent introducing the radicals R3 and R4 converts and the reaction stops at the latest when the reaction mixture does not titrable amine contains more. 12. Compounds of the formula IV a in which the radicals R1 and R2 are alkyl groups with 4 to 20 carbon atoms. 13. A process for the preparation of the compounds of the formula IV a according to claim 12, characterized in that a primary amine of the formula IV b in which the radicals R1 and R2 have the meaning given under formula IV a, mixed with a hydrogenation catalyst, preferably Raney nickel, and under a hydrogen atmosphere until a molar equivalent of ammonia is split off at a temperature in the range from 100-200, in particular 150 - 180 0C heated. 14.Textile treatment agents, especially liquid laundry aftertreatment agents, characterized by a content of 1 - 40% by weight of those used as textile softeners Quaternary ammonium compound of the formula I according to Claims 1-11, and at least a diluent and, if necessary, other customary ingredients of Textile treatment agents. 15. Liquid laundry aftertreatment agent according to claim 14, characterized by the following composition: 2.0-30.0, preferably 5.0-25.0% by weight of quaternary Ammonium compound of formula 1, 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 ingredients in laundry aftertreatment agents, Rest water. 16. Liquid laundry aftertreatment agent according to claim 15, characterized in that characterized in that as other common ingredients at least one of the following Components present in the specified amounts based on the total agent is: 0.2 - 5.0% by weight of other textile softeners different from the active ingredient of the formula I, 0.2-3.0% by weight of other antimicrobial agents other than the active ingredient of the formula I Active ingredient, 0.2-6.0% by weight acidic additive, 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.