DE2723120C2 - Production of quaternary ammonium compounds and their use as dyeing auxiliaries - Google Patents

Description

in the

R is an unbranched, unsubstituted or chlorine-substituted C ₈ - stands ₃₀ alkyl C, which is bonded via a secondary carbon atom to the nitrogen atom, represent an optionally substituted Ci - C ₂₀ alkyl or C ₂ -C ₂₀ alkenyl group, a Aralkyl radical or for the rest

CH ₃

-R ₂ -NR Χ ^θ CH ₃

R _{2 represents} an optionally substituted C ₂ - Q ₂ -

Alkylene or -alkenylene radical and X stand for an anion,

characterized in that the technical chlorinated paraffin mixtures obtained by chlorination of 8 to 30 carbon atoms containing straight-chain aliphatic hydrocarbons with a chlorine content of 5 to 30% at 120 to 200 ⁰ C in the presence of acid-binding agents and water are reacted with dimethylamine, the reaction products obtained without separation the tertiary amines obtained from the starting materials are reacted with quaternizing agents and the quaternary ammonium compounds are separated from the starting materials as an aqueous solution.

2. The method according to claim 1, characterized in that the reaction is carried out at 130 to 160 ° C performs.

3. The method according to claims 1 to 2, characterized in that the reaction is carried out in the presence of sodium hydroxide solution.

4. The method according to claims 1 to 3, characterized in that the chlorinated hydrocarbons are those with an average chain length of 15 carbon atoms and a chlorine content of 15 to 30%.

5. The method according to claims 1 to 4, characterized in that the quaternizing agent Benzyl chloride is used.

6. Use of the compounds prepared according to claims 1 to 5 as an aid in Dyeing of fiber materials which can be dyed with cationic dyes with cationic dyes.

the general formula

CH ₃

• I RNR ₁ Χ ^θ

CH ₃

ίο in the

R represents an unbranched Cg-C ₃₀ -alkyl radical, optionally substituted by chlorine, which is bonded to the nitrogen atom via a secondary carbon atom,

is R ₁ for an optionally substituted Ci-C ₂ O-alkyl or C ₂ -C ₂ O-alkenyl radical, an aralkyl radical or for the radical

CH ₃

- R ₂ - ⁸ N- R

Χ ^θ

CH,

The invention relates to a process for the preparation of quaternary ammonium compounds

R _{2 represents} an optionally substituted C ₂ -Q ₂ -Al-

kylene or -alkenylene radical and X stands for an anion,

and the use of the ammonium compounds of the formula I as dyeing auxiliaries when dyeing with cationic dyes, dyeable fiber materials. Aralkyl is preferably benzyl, λ- and /? - Phenylethyl or 1- and 2-naphthylmethyl understood.

As substituents for the radicals mentioned under Ri be for example halogen, such as chlorine or bromine, Ci - Cie-alkoxycarbonyl, carboxylic or sulfonic acid groups or salts thereof, carbamoyl and nitrile and also called Ci - Q-alkyl for the aromatic radicals. Suitable substituents for the radicals R ₂ are, for example, halogen, such as chlorine or bromine or hydroxyl.

Anions of both inorganic and organic acids are suitable as anion X; are preferred Anions of hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, of lower aliphatic see carboxylic acids, e.g. B. formic acid or acetic acid; of aromatic sulfonic acids, such as benzene and Toluenesulfonic acid, and the half-ester of sulfuric acid, such as methylsulfuric acid and ethylsulfuric acid.

There are numerous processes for the preparation of surface-active quaternary ammonium compounds are known in which tertiary amines, at least contain a longer alkyl radical, can be reacted with alkylating agents (cf. K. Lindner »Tenside,

Textilhilfsmittel, Waschrohstoffe "Vol. I, [1964], p. 984). A disadvantage of these methods is that

tertiary amines are used, in general made from expensive natural fat raw materials and must be isolated before quaternizing. It is known from chlorinated aliphatic hydrocarbons by reaction with ammonia or amines to produce long-chain amines (US-PS 23 61 457, DE-AS 1108 236, DE-PS 7 67 087). The production

quaternary ammonium compounds on this basis however, has not found its way into technology because of poor yields and complex manufacturing processes in the form of the multistage reactions caused by the Use of cheap raw materials to compensate for the economic advantage achieved. The difficulty was there in particular, in the fact that they are made as intermediates Amines obtained from chlorinated hydrocarbons are often obtained in only low yields, and their separation of unconverted hydrocarbons, which are always in technically produced chlorinated carbon. Hydrogen are present, a high acid and alkali consumption is required

The invention now relates to a process in which the technical chlorinated paraffins obtained by chlorination of 8 to 30 carbon atoms containing straight-chain aliphatic hydrocarbons with a chlorine content of 5 to 30% at 20 to 200 ^° C. in the presence of acid-binding agents and water are reacted with dimethylamine , the reaction products obtained are reacted with quaternizing agents without separation of the tertiary amines obtained from the starting materials and the quaternary ammonium compounds are separated from the starting materials as an aqueous solution.

The process is advantageously carried out in such a way that the chlorinated hydrocarbon is heated together with an acid-binding agent, dimethylamine and water in a pressure vessel to temperatures of 120 to 200 ^° C., preferably 130 to 160 ^° C., within 2 to 40, preferably 5 to 24 hours, heated, separating the aqueous phase after cooling, and the non-aqueous phase with a quaternizing agent at 80 to 160 ⁰ C, preferably at 100 to 14O ⁰ C, optionally with the addition of water and or or organic solvents reacted If If water was not already added during the quaternization, the product obtained is mixed with water, as a result of which the high-percentage aqueous solution of the quaternary ammonium compound separates smoothly and quickly from the unreacted hydrocarbon. The low-viscosity aqueous solutions obtained in this way can be used in this form for most industrial applications.

Suitable chlorinated, straight-chain aliphatic hydrocarbons are those compounds which are after known processes (cf. Houben-Weyl "Methods of Organic Chemistry", Vol. 5/3 (1962), pp. 565 to 581) by chlorination from 8 to 30, preferably 12 to 22 Paraffins containing carbon atoms, paraffin-hydrocarbon mixtures, hydrocarbons from the Fischer-Tropsch synthesis or from purified petroleum hydrocarbons. the Chlorination products should have a chlorine content of 5 to 30%, which is an average content corresponds to from 0.5 to 3 equivalents of chlorine per mole of hydrocarbon. In general, the chlorinated hydrocarbons are in the form of technical Mixtures with the unchlorinated hydrocarbons are used.

Suitable acid-binding agents are, for example, alkali metal hydroxides, carbonates or bicarbonates, alkaline earth oxides, hydroxides and bicarbonates or called carbonates. They are preferably in at least an equimolar amount to that in the chlorinated Hydrocarbon containing chlorine is used. As acid-binding agents, tertiary amines, such as Triethylamine, pyridine, or the one used Serve dimethylamine. However, sodium or potassium hydroxide is preferably used

The dimethylamine can be injected into the reaction vessel in gaseous form. Advantageously it will However, added to the approaches in the form of its aqueous solutions It is used in amounts of 0.5 to 10, preferably 1 to 4 moles per equivalent of the chlorine bound in the chlorinated hydrocarbon are used

ίο FGr the quaternization can do all the usual, for Quaternization of tertiary amines suitable alkylating agents can be used, for example methyl chloride, methyl iodide, dimethyl sulfate, toluenesulfonic acid methyl ester, dimethyl phosphite, methanephosphonic acid

dimethyl ester, ethyl bromide, ethyl iodide, diethy! sulfate, n-butyl bromide, n-hexyl chloride, dodecyl bromide, dodecyl chloride, tetradecyl chloride, allyl chloride, methallyl chloride, chloroethanol, N.-itrium chloroacetate, methyl chloroacetate, chloroacetamide, propane or butane

sulton, epichlorohydrin, ethylene oxide, propylene oxide, Chloropropane diol, benzyl chloride and substituted benzyl chlorides such as mono-, di- and trichlorobenzyl chloride, Chloromethylnaphthalene, phenoxyethyl chloride, dibromoethane, 1,4-dichlorobutane, 1,6-dichlorohexane, 1,4-dichloro butene-2, Üichlordiäthyläther, 4,4'-dichlorodibutylether, 1,3-dichloropropanol-2, 1,4-bis-chloromethylbenzene and Bis-chloromethyldimethylbenzene.

Preferred alkylating agents are dimethyl sulfate, Methanephosphonic acid dimethyl ester, benzyl chloride, Mono- and dichlorobenzyl chloride, chloroethanol, and sodium chloroacetate, especially benzyl chloride.

In a preferred embodiment of the process, a 10 to 25% chlorine-containing, straight-chain hydrocarbon, the middle ket ten length is 15 carbon atoms, in the presence of sodium hydroxide solution or potassium hydroxide solution with 0.5 to 4 times, in particular 1.0 to 2.0 times the molar amount (based on equivalents of chlorine) reacted in an aqueous dimethylamine solution in the pressure vessel. the Reaction is carried out within 2 to 40 hours, preferably from 5 to 24 hours at 140 to 160 ⁰ C. Unreacted dimethylamine is removed, whereupon the precipitating aqueous phase is separated off after cooling. The organic phase is then mixed with the quaternizing agent, optionally together with water, and ^{reacted at 100 to 160 °} C. within 0.5 to 24 hours. After cooling, the aqueous solution of the quaternary ammonium compound separates from not vice versa deposited hydrocarbon. You can direct or can be supplied to the various purposes after the concentration.

The advantage of the method according to the invention over the previously known methods lies in the more economical and environmentally friendly way of working. In the method according to the invention is one with high acid and alkali consumption and high accumulation of saline wastewater related isolation of free amine is not required, which simultaneously creates a Manufacturing step is saved. Another advantage is that when implementing the Chloralkanes with the dimethylamine no solvents or emulsifiers are required. Of that Compounds of the type as they are in the erfindungsge moderate processes can be obtained, emulsion-forming Properties could be expected, it was surprising that the aqueous solutions of the quaternary ammonium compounds smoothly from the

let unreacted hydrocarbons separate.

The quaternary ammonium compounds of the formula (i) prepared by the process according to the invention are surface-active compounds and are suitable for numerous uses, for example as washing, cleaning, textile and dyeing auxiliaries, as emulsifiers, antistatic or plasticizing agents or bactericides. They have excellent solubility and stability in water.

The compounds prepared according to the invention are particularly suitable as an aid in dyeing fiber materials which can be dyed with cationic dyes with cationic dyes. The dyeing of the fiber materials which can be dyed with cationic dyes can be carried out in the customary manner by introducing the dyed material into an aqueous dye liquor heated to about 50 to 60 ° C, which contains the cationic dye, compounds of the formula (I), additions of salts, such as Sodium acetate or sodium sulphate, also containing acids such as acetic acid or formic acid, then the temperature of the dyebath is increased in the course of about 30 minutes to approximately 100 ° C and then the dyebath is kept at this temperature until it is exhausted. Can be the dyed material is also at a temperature of 40 to 100 ° C with a liquor pre-treatment, which the usual salts and acids as well as compounds of formula (I), but does not contain a dye, and only then release the dye and the dyeing at 100 ⁰ Perform C. Finally, it is also possible to introduce the dyed material directly into the dyebath, which is heated to approximately 100 ° C. and which contains compounds of the formula (I).

Dyes of the various classes of compounds come into consideration as cationic dyes, for example Diphenylmethane, triphenylmethane and rhodamine dyes, azo containing onium groups or Anthrpquinone dyes, also thiazine, oxazine, methine and azomethine dyes, such as those for example in Ulimanns Encyclopadie der technischen Chemie, 3rd edition, 1970, supplementary volume, p. 225, are described. Leave the required amounts of the compounds of the formula (I) to be used according to the invention can easily be determined through preliminary tests. In general, amounts of about 0.25 of these compounds up to 2.5%, based on the weight of the dyed material used

As fiber materials dyeable with cationic dyes For example, those made from anionically modified polyesters and polyamides, in particular but those made from polyacrylonitrile or acrylonitrile-containing copolymers are possible.

Suitable copolymers containing acrylonitrile are, for example, copolymers of acrylonitrile with Vinyl chloride, vinylidene chloride, vinyl chloroacetate, vinyl alcohol, acrylic and methacrylic acid, acrylic and methacrylic acid esters, Allyl chloroacetate or basic vinyl compounds such as vinylimidazole, vinylbenzimidazole, Vinylpyridine, vinylmethylpyridine, vinylpyrimidine, provided that the proportion of these co-monomers does not exceed 20 Weight percent is.

For use as auxiliaries for dyeing fiber materials which can be dyed with cationic dyes, those compounds of the formula (I) are preferably suitable in which the radical R is a _{C 1} -C 4 -alkyl radical which is bonded to the nitrogen atom via a secondary carbon atom and which can optionally be partially substituted by unreacted chlorine atoms, the radical Ri stands for a Ci- Ci ₂ -AlkyJrest optionally substituted by a hydroxyl group or in particular for an optionally halogenated benzyl radical, and X- stands for chloride, bromide, methosulfai, or methaüiphosphonate , in particular for the chloride ion.

example 1

284 parts of a chlorinated Fischer-Tropsch hydrocarbon with an average carbon number of 15 and which contains approx. 19% bound chlorine are mixed with 160 parts of a 40% strength aqueous dimethylamine solution and 145 parts of 45% strength sodium hydroxide solution and placed in an autoclave within 6 Heated to 180 ° C. for hours with stirring. At this temperature, the mixture is stirred for 12 hours, a pressure of approx. 20 bar being established. After cooling to approx. 100 to 110 ° C., excess dimethylamine is removed by venting the autoclave, and after further cooling, it is removed 20 to 30 ° C separated the aqueous phase below. As the upper phase, 270 parts of an oily liquid are obtained, the basic nitrogen content is 3.64% This is mixed with 89 parts Benzylrhlorid and 260 parts of water and heated for 2 hours with stirring to 120 ⁰ C. After standing briefly at approx. 50 ^° C., the unreacted hydrocarbon separates from the aqueous phase, in the 256 parts of the compound

α ^θ

are included. The 50% aqueous solution obtained can in this form, for. B. can be used as a retarder for dyeing polyacrylonitrile fibers. By distilling off the water in vacuo, the quaternary ammonium compound can be obtained in the form of a highly viscous liquid.
(N: 3.7%, Cl: 11.4%)

Example 2

211 parts of a chlorinated Fischer-Tropsch carbon hydrogen with an average chain length of 15 carbon atoms and a chlorine content of approx. 19% are mixed with 150 parts of 50% strength aqueous dimethylamine solution and 108 parts of 45% strength sodium hydroxide solution and placed in an autoclave within 3 Heated to 145 ° C for hours. The mixture is stirred for 24 hours at 140 to 145 ° C, cooled to 100 to 110 ⁰ C and freed by venting the approach of excess dimethylamine. After further cooling to 20.degree. To 30.degree. C., the lower aqueous phase is separated off. 200 parts of an oily liquid with a basic nitrogen content of 3.55% are obtained as the upper phase. This is mixed with 65 parts of benzyl chloride and 298 parts of water and ^{heated to 130 °} C. for 2 hours with stirring. After cooling to approx. 50 ^° C. and briefly standing, 416 parts of an approx. 50% strength aqueous solution of the compound described in Example 1 separate out as the lower phase.

Example 3

211 parts of a chlorinated paraffin hydrocarbon with an average chain length of 15 carbon atoms and a chlorine content of about 15% are reacted as described in Example 2 with 150 parts of 50% strength aqueous dimethylamine solution and 108 parts of 45% sodium hydroxide solution. After 200 parts of the amine-containing oil have been separated off, 96.5 parts of 3,4-dichlorobenzyl chloride and 225 parts of water are added and the mixture is reacted in a pressure vessel at 130 ^° C. for 3 hours. After cooling to about 50 ⁰ C and short standing, below 440 parts separate an about 5O ° / o aqueous solution of the compound

CH ₃

CH ₃

he ³

Example 5

142 parts of a chlorinated paraffinic hydrocarbon with an average carbon number of 15 and a chlorine content of 20% are made with 200 parts

50% aqueous dirnethylamine solution and 111 parts 45% sodium hydroxide solution mixed in an autoclave. The temperature increases to 150 ° C. within 1 hour brought and held at this temperature for 3 hours, a pressure of 22 to 23 bar is established. To cooling to 100 to 110 ° C is unreacted Dimethylamine drained by venting the autoclave, and after further cooling to 20 to 30 ° C the separated aqueous lower phase. The upper phase consists of 130 parts of an oily liquid with a basic nitrogen content of 3.8%. This is made with 54.5 parts of an n-alkyl chloride with 6 to 10 carbon atoms and an average molecular weight of 154 and 95 parts of water and at 160 ° C for 20 hours im Stirred in the autoclave. After cooling to 20 to 30 ° C and briefly standing, are used as an underlayer 240 parts of an approximately 60% solution of the quaternary ammonium compound obtained, which essentially the formula

30th

away. By distilling off the water in a vacuum, this becomes 220 parts * of a viscous product obtain.

(N: 3.1%, Cl: 24.2O / o)

Example 4

284 parts of a chlorinated, straight-chain hydrocarbon mixture, the average chain length of which is 15 carbon atoms, and which contains about 20% bound chlorine, are mixed with 400 parts of 50% aqueous dimethylamine solution and 148 parts of 45% sodium hydroxide solution in an autoclave and mixed within 2 hours brought up to a temperature of 150 ° C. The mixture is stirred at this temperature for 6 hours, a pressure of about 22 bar being established. After cooling to about 100 to 110 ° C, excess dimethylamine is distilled off in a template and after further cooling to 20 to 30 ⁰ C, the aqueous phase was separated below the upper phase consists of 260 parts of an oily liquid whose basic by venting the autoclave Nitrogen content is 3.86. These are mixed with 82 parts of sodium chloroacetate and 250 parts of water and in an autoclave for 4 hours at 120 to 130 ⁰ C. After cooling, heated to 20 to 30 ° C below 500 parts separate out of an approximately 50% aqueous solution of a compound from which essentially of the formula

CH ₃

si
C ₁₅ H ₃₁ -N-CH ₂ COONa Cl ^e

CH ₃

CH ₃

CisH ₃ i - N - C6-10H13-21
CH ₃

Cl ⁶

en; ; ·:! U.

Example 6

142 parts of a chlorinated paraffin hydrocarbon with an average carbon number of 15 and a chlorine content of 20% are mixed with 200 parts of 50% strength dimethylamine and 111 parts of 45% strength sodium hydroxide solution in an autoclave. The temperature is ^{brought to 120 °} C. within 1 hour and held at this temperature for 17 hours, a pressure of 13 to 14 bar being established. After cooling to 100 to 110 "C, unreacted dimethylamine is vented by venting the autoclave and contains by further cooling to 20 to 30 ⁰ C, the aqueous lower phase containing sodium chloride, was separated. The upper phase consists of 130 parts of an oily liquid with a basic nitrogen content of 3.8% This is now described with 27.6 parts of 1,6-dichlorohexane and mixed 122 parts of water and from 140 to 145 ° C for 12 hours in autoclave after cooling to 20 to 30 ⁰ C and short. If left to stand, 215 parts of an approximately 60% solution of the quaternary ammonium compound are obtained as the lower layer, which essentially

55 of the formula CH ₃

CH ₃

corresponds to By distilling off the water in a vacuum, this can be obtained as a highly viscous liquid.
(N: 3.77, C1: 11.5%)

C ₁₅ H ₃₁ -N- (CHj) ₆ -NC ₁₅ H ₃ I 2 Cl ^e CH ₃ CH ₃

65 corresponds to 129 parts of a viscous product are obtained from this by distilling off the water. (N: 4.2%, α ^θ : 11.5%).

230242/364

O NH ₂

CH ₂ -NH (CH ₃ J ₂ Cl ^e

0.25 g of sodium acetate, 0.3 g of glacial acetic acid and 0.25 g of the compound of the formula described in Example 1

Example 7

Yarn of polyacrylonitrile fibers are introduced in a liquor ratio of 1:40 in a heated bath at 80 ⁰ C, the g per liter 0.06 a cationic Färb-material of the formula

Cl

10

15th

contains. The bath is heated to 98 ° C in 30 minutes and held at this temperature for 45 minutes. A uniform blue coloration is obtained. During the The dyeing process shows that the dye is retarded at the beginning and only as the temperature rises slowly, but completely pulls on the fiber until the end.

Example 8

A knitted fabric made of polyacrylonitrile fibers is introduced into a bath at 85 ° C in a liquor ratio of 1:15, the 0.3 g of a dye of the formula

20th

C ₂ H ₅ CH ₂ -CH ₂ -N (CHj) ₃

CH ₃ -OSOf

0.25 g of sodium acetate, 0.3 g of glacial acetic acid and 0.3 g of that in example 3 described compound of the formula

CH ₃

• I

Ci ₅ H ₃₁ -N-CH

Cl ^e

those in a flute ratio of 1:20 in one at 70 ° C Brought heated bath, the liter 0.05 g of a cationic dye as in Example 7 and 9.1 one Dye according to Example 8, 0.25 g of sodium acetate, 0.3 g of glacial acetic acid and 1.6 g of that described in Example 5 Compound of formula

35

CH ₃

contains. The bath is brought to a boil in 30 minutes and held at boiling temperature for 60 minutes. During this time, the dye is slowly and evenly absorbed onto the fiber. You get one completely level red coloring.

Example 9
Cross-wound bobbins with a polyacrylic filament yarn are 40

CH ₃

al in -

CH ₃

Cl ^€

contains. Heating the bath in 75 minutes to 115 to 12O ⁰ C and dyed for 75 minutes at this temperature. Completely uniform cheeses colored in a purple hue are obtained.

Claims (1)

1 claims: 1. Process for the preparation of quaternary ammonium compounds of the general formula CH ₃ R-N-R ₁ Χ ^θ CH ₃