DE2723120A1 - Quat. ammonium cpds. used for polyacrylonitrile dyeing auxiliaries - prepd. simply and economically from tert. amine(s) based on di:methylamine and chloroparaffin(s) - Google Patents

Abstract

Quat. ammonium cpds. of formula (I):- RR1N + (cH3)2X - (I) are new. In (I) R is 8-30C straight chain alkyl gp. opt. substd. by Cl and linked to the N by a sec. C atom. R1 is a 1-20C alkyl gp., a 2-20C alkenyl, opt. substd., an aralkyl or a gp. -R2-N + R (CH3)2. X - (II) where R2 is 2-12C alkylene or alkenylene gp. opt. substd. or broken by O, or an aralkylene gp. and X is an anion. (I) are based on tert. amines prepd. from dimethylamine and chloroparaffins obtd. by the chlorinated of straight chain hydrocarbons of 10-30C. (I) are used partic. as auxiliaries in the dyeing of polyesters, polyamides and esp. polyacrylonitrile or acrylonitrile copolymers with cationic dyes. (I) can also be used as surfactants, cleaning agents, detergents, emulsifiers, anti-static agents, plasticisers or bactericides.

Description

Production of quaternary ammonium compounds

The invention relates to a process for the preparation of quaternary ammonium compounds of the general formula in which R represents an unbranched C8-C30-alkyl radical, optionally substituted by chlorine, which is bonded to the nitrogen atom via a secondary carbon atom, R1 represents an optionally substituted C1-C20-alkyl or C2-C2O-alkenyl radical, an aralkyl radical or for the rest R2 stands for an optionally substituted or interrupted by oxygen atoms C2-C12 - alkylene or alkenylene radical or an aralkylene radical and X stands for an anion, and the use of the ammonium compounds of the formula I as dyeing auxiliaries in the dyeing of fiber materials which can be dyed with cationic dyes.

Aralkyl is preferably benzyl, & - and ß-phenylethyl or 1- and 2-naphthylmethyl and, among aralkylene, preferably 1,2-, 1,3- or 1,4-xylylene Understood.

Examples of substituents for the radicals mentioned under R1 are Halogen, such as chlorine or bromine, C1-C18-alkoxycarbonyl, carboxylic or sulfonic acid groups or salts thereof, carbamoyl and nitrile and also for the aromatic radicals Called C1-C6-alkyl. Suitable substituents for the radicals R2 are, for example Halogen, such as chlorine or bromine or hydroxyl and also for the aromatic radicals C1-C4 alkyl.

The anion X is anions of both inorganic and organic acids into consideration; preferred are the anions of hydrochloric acid, hydrobromic acid, Hydriodic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, lower aliphatic carboxylic acids such as formic acid or acetic acid; the aromatic sulfonic acids, such as benzene and toluenesulfonic acid, and the half-ester sulfuric acid, such as methylsulfuric acid and ethylsulfuric acid.

There are numerous methods of making surfactants quaternary ammonium compounds known, in which tertiary amines, the at least contain a longer alkyl radical, can be reacted with an alkylating agent (cf. K.

Lindner "Tenside, Textile Auxiliaries, Washing Raw Materials" Vol. I, (1964), P. 984).

A disadvantage of this process is that it uses tertiary amines which are generally made from expensive natural fat raw materials and must be isolated before quaternizing. It has also already been suggested from chlorinated aliphatic hydrocarbons by reaction with ammonia or Amines long chain amines (US-PS 2,361,457, DT-AS 1 108 236, DT-PS 767 087). The production of quaternary ammonium compounds on this However, the basis has not found its way into technology because of poor yields and complex manufacturing processes in the form of multi-stage reactions through offsetting the economic advantage achieved by using cheap raw materials. The difficulty was in particular that the chlorinated intermediates Amines obtained from hydrocarbons are often obtained in only low yields, and their separation of unreacted hydrocarbons, which are always technically produced chlorinated hydrocarbons are present, a high t ;; illre ^ - and Requires alkali consumption.

The invention now relates to a method in which products, the straight-chain ones containing 8-30 hydrocarbon atoms by chlorination aliphatic hydrocarbons were obtained, at 120-2000C, preferably at 140-1600C, reacted with dimethylamine in the presence of acid-binding agents and the reaction products without isolation of the tertiary amine obtained with quaternizing agents implemented.

The process is advantageously carried out in such a way that the chlorinated hydrocarbon along with an acid binding agent, dimethylamine and water in a pressure vessel at temperatures of 120-200 ° C, preferably 140-160 °, heated within 2-40, preferably 5-24 hours, the aqueous phase after Separates cooling, and the non-aqueous phase with a quaternizing agent 80-160 °, preferably at 100-140 °, optionally with the addition of water and / or organic solvents.

If not already with the quaternization Water added was, the product obtained is mixed with water, whereby the high-proof aqueous solution of the quaternary ammonium compound of unreacted hydrocarbon cuts off smoothly and quickly. The low-viscosity aqueous solutions obtained in this way can be used in this form for most industrial applications.

Suitable as chlorinated, straight-chain aliphatic hydrocarbons punctuate those compounds that are made according to known methods (see Houben-Weyl "methods of organic chemistry "Vol. 5/3 (1962) pp. 565-581) by chlorination of 8-30, paraffins preferably containing 12-22 carbon atoms, paraffin hydrocarbon mixtures, Hydrocarbons from the Fischer-Tropsch synthesis or from purified petroleum hydrocarbons getting produced. The chlorination products should have a chlorine content of 5 - 30 % have, wae on average a content of 0.5 - 3 equivalents of chlorine per Moles of hydrocarbon. In general, these are chlorinated hydrocarbons used in the form of technical mixtures with the unchlorinated hydrocarbons.

Suitable acid-binding agents are, for example, alkali metal hydroxides, carbonates or bicarbonates, alkaline earth oxides, hydroxides, bicarbonates or carbonates. They are preferably used in at least an equimolar amount to the chlorine contained in chlorinated hydrocarbons. Al. acid-binding Means can also be 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 However, it will be advantageous for the batches in the form of an aqueous solution added, Ee is added in amounts of 0.5-10, preferably 1-4 mol, per equivalent of the chlorine bound in the chlorinated hydrocarbon is used for quaternization can use all customary alkylating agents suitable for quaternizing tertiary amines can be used, for example methyl chloride, methyl iodide, dinethyl sulfate, toluenesulfonic acid methyl ester, iimethyl phosphite, methamphosphonic acid dimethyl ester, ithyl bromide, ethyl iodide, diethyl sulfate, n-butyl bromide, n-hexyl chloride, dodecyl bromide, dodecyl chloride, tetradeoylochloride, Allyl chloride, methallyl chloride, chloroethanol, sodium chloroateate, methyl chloroacetate, Chloroacetamide, propane or butanesultone, epichlorohydrin, ethylene oxide, propylene oxide, Chiorpropanediol, 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-dichlorobutene-2, dichlorodiethyl ether, 4,4'-dichlorodibutyl ether, 1,3-dichloropropanol-3, 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 method. becomes a 10 - Straight-chain hydrocarbon containing 25% chlorine, its mean chain length 15 carbon atoms, in the presence of caustic soda or Potassium hydroxide with 0.5 to 4 times, in particular with 1.0 molar amount (based on Equivalents of chlorine) of an aqueous dimethylamine solution in the pressure vessel. the Reaction is done within 2-40 hours, preferably 5-24 hours at 140 - carried out in 1600.

Unreacted dimethylamine is removed, whereupon the precipitating aqueous phase is separated after cooling. The organic phase is then possibly together with water, mixed with the quaternizing agent and at 100 - 1600 implemented within 0.5 - 24 hours. After cooling, the aqueous separates Solution of the quaternary annulus compound of unreacted hydrocarbon away. It can be used for various purposes directly or after concentration will.

The advantage of the method according to the invention over the previous known method lies in the more economical and environmentally friendly way of working. The method according to the invention is one with a high acid and alkali expenditure and high production of saline wastewater associated isolation of free amines not required, which saves one manufacturing step at the same time. Another advantage is that in the reaction of the chloroalkane with the Dimethylamine does not require solvents or emulsifiers. Since verb in compounds of the type as obtained in the process according to the invention, emulsifying properties could be expected, it was surprising that the aqueous solutions of the quaternary ammonium compounds differ smoothly from the not allowed to separate converted hydrocarbons.

The quaternary produced by the process according to the invention Ammonium compounds of the formula (1) are surface-active compounds and are suitable for numerous purposes, for example as washing, cleaning, textile and dyeing auxiliaries, as emulsifiers, antistatic or plasticizing agents or bactericide. 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 those which can be dyed with cationic dyes Fiber materials can be carried out in the usual way by the dyed material in an aqueous dye liquor heated to about 50 - 60 OC, which the cationic dye, compounds of the formula (I), additions of salts, such as sodium acetate or sodium sulfate, also containing acids such as acetic acid or formic acid, then the temperature of the dyebath rose to approximately 100 ° C. in the course of 30 minutes and then keep the dye bath at this temperature until it is exhausted is. The dyed material can also be dyed at a temperature of 40 - 100 OC with a liquor pretreat, which the usual salts and acids and compounds of the formula (I), but does not yet contain any dye, only then add the dye and carry out dyeing at 100 ° C. Finally, it is also possible to use the material to be dyed directly into the dyebath heated to approximately 100 ° C, which Contains compounds of formula (I).

As cationic dyes, dyes of the various classes of compounds are carbon into consideration, for example diphenylseth-n-, triphenylmethane and rhodamine dyes, Azo or onium groups Athraquinone dyes, furthermore Thiazine, oxazine, methine and azomethine dyes, such as those in Ullmanns Encyclopedia of Industrial Chemistry, 3. A @ location, 1970, supplementary volume, p. 225 described are.

The required amounts of the compounds to be used according to the invention of formula (I) cannot be determined by preliminary tests. Generally will of the compounds in amounts of approx. 0.25 to 2.5%, based on the weight of the used dyed material, applied.

Fiber materials that can be dyed with cationic dyes are used For example, those made from anionically modified polyesters and polyamides, in particular but those made of polyacrylonitrile or acrylonitrile-containing copolymers, in Question.

Suitable acrylonitrile-containing copolymers are, for example Copolymers of acrylonitrile with vinyl chloride, vinylidene chloride, vinyl chloroacetate, Vinyl alcohol, koryl and methacrylic acid, aoryl and methacrylic acid esters, allyl chloroacetate or basic vinyl compounds such as vinylimidazole, vinylbenzimidazole, vinylpyridine, Vinylmethylpyridine, vinylpyrimidine, provided the proportion of these co-monomers is not is more than 20 percent by weight.

For use as an aid to dyeing with cationic dyes Dyeable fiber materials are preferably compounds of the formula (I), in which the radical R is a C10-C20-alkyl radical, which has a secondary carbon atom is bound to the nitrogen atom and the possibly partially unreacted Chlorine atoms can be substituted, the radical R1 for one optionally by a hydroxyl group substituted C1-C12-alkyl radical or in particular for an optionally halogenated benzyl radical and X stands for chloride, bromide, methosulphate, or methane phosphonate, in particular stands for the chloride ion.

Example 1 284 parts of an chlorinated Fischer-Tropsch hydrocarbon with an average carbon number of 15 and containing about 19% bound chlorine are mixed with 160 parts of a 40% strength aqueous dimethylamine solution and 145 parts of 45% sodium hydroxide solution and placed in an autoclave heated to 180 ° C within 6 hours with stirring. The mixture is stirred at this temperature for 12 hours, a pressure of approx. 20 atmospheres being established. After cooling down to the above. 100-1100 excess dimethylamine is removed by venting the autoclave, and after cooling down further to 20-30 cc, the aqueous phase is separated off at the bottom. 270 parts of an oily liquid with a basic nitrogen content of 3.64% are obtained as the upper phase. This is mixed with 89 parts of benzyl chloride and 260 parts of water and heated to 120 ° for 2 hours with stirring. After standing briefly at about 50 °, the unreacted hydrocarbon separates from the aqueous phase, in the 256 parts of the compound are included. The 50% aqueous solution obtained can in this form, for. B. can be used as a retarder for dyeing polyacrylonitrile fibers.

The quaternary ammonium compound can be removed by distilling off the water in vacuo 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 hydrocarbon with an average chain layer of 15 carbon atoms and a content of oa.

19% chlorine with 150 parts 50 of an aqueous dimethylamine solution and 108 parts 45 of a sodium hydroxide solution and mixed in the autoclave within 3 Heated to 145 cc for hours. The mixture is stirred for 24 hours at 140-145 °, suf 100 - 1100 cooled and by venting the approach of excess dimethylamine freed. After further cooling to 20-300, the lower aqueous phase is separated off. 200 parts of an oily liquid with a basic content are used as the upper phase 3.55% nitrogen is obtained. This is obtained with 65 parts of benzyl chloride and 298 parts water was added and the mixture was heated to 1300 for 2 hours with stirring. After cooling down approx. 50 cc and left to stand for a short time, 416 parts of one separate as the lower phase approx. 50% strength aqueous solution of the compound described in Example 1.

Example s 211 parts of a chlorinated paraffin hydrocarbon with an average chain length of 15 carbon atoms and a content of approx. 15 * chlorine are as described in Example 2 with 150 parts of 50% aqueous Dimethylamine solution and 108 parts of 45% but sodium hydroxide solution implemented.

After separating 200 parts of the amine-containing oil, they become 96.5 parts of 3,4-dichlorobenzyl chloride and 225 parts of water were added and 3 hours implemented at 130 ° C in a pressure vessel. After cooling down to approx.

50 ° C and short standing, 440 parts of one separate at the bottom approx.

50% aqueous solution of the compound away. By distilling off the water in vacuo, 220 parts of a viscous product are obtained therefrom.

(N: 3.1%, Cl: 24.2%) Example 4 284 parts of a chlorinated, straight-chain Hydrocarbon mixture with an average chain length of 15 carbon atoms, and that approx.

Contains 20% combined chlorine, but 400 parts are 50% more aqueous Dimethylarin solution and 148 parts of 45% sodium hydroxide solution mixed in an autoclave and brought to a temperature of 150 ° C within 2 hours. At this The temperature is stirred for 6 hours, a pressure of about 22 atmospheres being established. After cooling to approx. 100-110 ° C, excess is removed by venting the autoclave Dimethylamine is distilled off in a receiver and after further cooling to 20-30 ° C separated the aqueous phase below. The upper phase consists of 260 tsilen one oily liquid, the basic nitrogen content of which is 3.86. These will mixed with 82 parts of sodium chloroacetate and 250 parts of water and placed in an autoclave Heated to 120-130 ° C for 4 hours. After cooling to 20-30 ° C, they separate below 500 parts of an approx.

50% aqueous solution of a compound that essentially has the formula is equivalent to. By distilling off the water in a vacuum, this can be obtained as a highly viscous liquid.

(N: 3.77, Cl: 11.5%) Example 5 142 parts of a chlorinated paraffin hydrocarbon with its mean carbon number of 15 and a chlorine content of 20% with 200 parts of 50% strength aqueous dimethylamine solution and 111 parts of 45% strength sodium hydroxide solution mixed in an autoclave. The temperature increases to 150 within 1 hour ° C and kept at this temperature for 3 hours, a pressure of 22 - 23 atm. After cooling down to 100 - 110 ° C, nothing is converted Discharge the dimethylamine by venting the autoclave, and after further cooling at 20-30 ° C., the lower aqueous phase was separated off. The upper phase consists of 130 parts of an oily liquid with a basic nitrogen content of 3tE %. This is made with 54.5 parts of an n-alkyl chloride with 6-10 carbon atoms and an average molecular weight of 154 and 95 parts of water and 1600 Stirred for 20 hours in an autoclave. After cooling to 20-30 OC and leaving to stand for a short time 240 parts of an approx.

60% solution of the quaternary ammonium compound obtained, essentially of the formula is equivalent to.

EXAMPLE 6 Yarns made from polyacrylonitrile fibers are introduced in a liquor ratio of 1:40 into a bath heated to 800.degree. C. containing 0.06 g per liter of a cationic dye of the formula 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 contains. The bath is heated to 980 ° C. in 30 minutes and held at this temperature for 45 minutes. A uniform blue coloration is obtained. During the dyeing process it can be seen that the dye is retarded at the beginning and only slowly pulls onto the fiber as the temperature rises, but until the end it pulls completely.

Example 7 A knitted fabric as polyacrylonitrile fibers is made in a liquor ratio of 1; placed in a bath at 85 ° C containing 0.3 g of a dye of the formula 0.25, sodium acetate, 0.3 g of glacial acetic acid and 0.3 g of the compound of the formula described in Example 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. A completely level red coloration is obtained.

Example 8 Cross-wound bobbins with a polyacrylic filament yarn are placed in a liquor ratio of 1:20 in a bath heated to 700 C, which contains 0.05 g of a cationic dye per liter as in Example 6 and 9.1 of a dye according to Example 7, 0, 25 g of sodium acetate, 0.3 g of glacial acetic acid and 1.6 g of the compound of the formula described in Example 5 contains. The bath is heated to 115-1200 ° C. in 75 minutes and dyed at this temperature for 75 minutes. Completely uniform cheeses colored in a purple hue are obtained.

Claims (1)

Claims. Claim Process for the production of quaternary ammonium compounds. the general formula In which R stands for an unbranched C8-C30-alkyl radical, optionally substituted by chlorine, which is bonded to the nitrogen atom via a secondary carbon atom, for an optionally substituted C1-C20-alkyl or Q 2-C20-alkenyl radical, an aralkyl radical or for the rest R2 stands for an optionally substituted or interrupted by oxygen atoms C2-C12 alkylene or alkenylene radical or an aralkylene radical and X stands for an anion, characterized in that chlorinated paraffins obtained by chlorinating 10-30 carbon atoms, straight-chain aliphatic hydrocarbons , at 120-2000C in the presence of acid-binding agents with dimethylamine and the reaction products obtained reacts without isolation of the tertiary amine obtained with quaternizing agents. Claim 2: Method according to Claim 1, characterized in that the reaction is carried out with dimethylamine in the presence of water. Claim 3: Method according to Claim 1 or 2, characterized in that The reaction is carried out at 130-1600 in the presence of alkali hydroxides, alkaline earth oxides or alkaline earth hydroxides as acid-binding agents. Claim 4 Method according to Claims 1 to 3, characterized in that that the reaction is carried out in the presence of sodium or potassium hydroxide solution and that as quaternizing agent dimethyl sulfate, methanephosphonic acid dimethyl ester, chloroethanol, Sodium chloroacetate, benzyl chloride, monochlorobenzyl chloride or dichlorobenzyl chloride is used. Claim 5s Method according to Claims 1 - 4, characterized in that that solobe as chlorinated hydrocarbons with an average chain length of 15 carbon atoms and a chlorine content of 15 - 30% are used. Claim 6: Method according to Claims 1 to 5, characterized in that that one as Quaternizing agent benzyl chloride used. Claim 7: Use of the prepared according to Claims 1 to 6 Compounds as auxiliaries in the dyeing of cationic dyes Fiber materials with cationic dyes.