GB1583932A

GB1583932A - Quaternary ammonium compounds

Info

Publication number: GB1583932A
Application number: GB19213/78A
Authority: GB
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1977-05-23
Filing date: 1978-05-12
Publication date: 1981-02-04
Also published as: FR2391991A1; ES470075A1; IT1094777B; JPS53149903A; IT7823628A0; FR2391991B1; BR7803240A

Description

(54) QUATERNARY AMMONIUM COMPOUNDS (71) We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the laws of Federal Republic of Germany, of Leverkusen, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The invention relates to a process for the production of quaternary ammonium compounds of the general formula

in which R represents an unbranched C6-C30-alkyl radical which is optionally substituted by chorine and which is bonded to the nitrogen atom via a secondary carbon atom, R, represents an optionally substituted C1-C20-alkyl or C2-C20-alkenyl radical, an optionally substituted aralkyl radical or the radical

R2 represents a C2-C12-alkylene or alkenylene radical which is optionally substituted or interrupted by oxygen atoms, or an optionally substituted aralkylene radical and X represents an anion, in which a chloroparaffin, which has been obtained by chlorinating a straight chain aliphatic hydrocarbon containing 8 to 30 carbon atoms, is reacted with dimethylamine at 90 to 2000C in the presence of an acid-binding agent and the product is then reacted with a quaternising agent.

Aralkyl is preferably understood as benzyl, a- and p - phenylethyl or 1- and 2 naphthylmethyl and aralkylene is preferably understood as 1,2-, 1,3- or 1,4 xylylene.

Examples which may be mentioned of substituents for the radicals given under R, are hydroxyl, halogen, such as chlorine or bromine, C1-C18-alkoxycarbonyl, carboxylic acid or sulphonic acid groups or salts thereof, carbamoyl and nitrile, and for the aromatic radicals also C1-C6-alkyl.

Preferred suitable radicals R, are the methyl, hydroxyethyl, carboxymethyl, monochlorobenzyl or dichlorobenzyl radical, but in particular the benzyl radical.

Examples of suitable substituents for the radicals R2 are halogen, such as chlorine or bromine, or hydroxyl, and for the aromatic radicals also C1-C4-alkyl.

Possible anions X can be anions of either inorganic or organic acids; preferred anions are those of hydrochloric acid, hydrobromic acid, hydriodic acid, sulphuric acid, nitric acid, phosphoric acid or perchloric acid, of lower aliphatic carboxylic acids, for example formic acid or acetic acid; of aromatic sulphonic acids, such as benzenesulphonic acid and toluenesulphonic acid, and of half-esters of sulphuric acid, such as methylsulphuric acid and ethylsulphuric acid.

The invention also relates to the quaternary ammonium compounds (I) produced by the process of the invention and their use as dyeing auxiliaries in the dyeing of fibre materials which can be dyed with cationic dyestuffs.

The quaternary ammonium compounds (I) are prepared by reacting chloroparaffins, which have been obtained by chlorinating straight-chain aliphatic hydrocarbons containing 8-30 carbon atoms, with dimethylamine at 90--2000C, preferably at 121600C, in the presence of acid-binding agents and then reacting the product with quaternising agents.

The process is advantageously carried out as a one-pot process by heating the chlorinated hydrocarbon together with an acid-binding agent, dimethylamine and water to temperatures from 9O2000C, preferably 120160 , in a pressure vessel in the course of 2-40, preferably 5-24 hours and, after cooling, separating off the aqueous phase and reacting the non-aqueous phase with a quaternising agent at 80160 , preferably at 100140 , water and/or organic solvents optionally being added. If water has not already been added during the quaternisation, water is added to the resulting product, whereby the high-strength aqueous solution of the quaternary ammonium compound is smoothly and rapidly separated off from unreacted hydrocarbon i.e. the starting material for the chlorination. The lowviscosity aqueous solutions thus obtained can be employed in this form for most industrial applications.

Suitable chlorinated, straight-chain aliphatic hydrocarbons are those compounds which are prepared by chlorinating paraffins, mixtures of paraffin hydrocarbons, hydrocarbons from the Fischer-Tropfsch synthesis or purified petroleum hydrocarbons containing 8-30, preferably 12-22, carbon atoms according to known processes (compare Houben-Weyl, "Methoden der organischen Chemie" ("Methods of Organic Chemistry"), Volume 5/3 (1962) page 565-581). The chlorination products should have a chlorine content of 5-3Q7, which corresponds on average to a chlorine content of 0.5-3 equivalents per mol of hydrocarbon. In general, these chlorinated hydrocarbons are employed in the form of industrial mixtures with the non-chlorinated hydrocarbons.

Examples which may be mentioned of suitable acid-binding agents are alkali metal hydroxides, carbonates or bicarbonates or alkaline earth metal oxides, hydroxides, bicarbonates or carbonates. They are preferably employed in an amount which is at least equimolar to the chlorine contained in the chlorinated hydrocarbon. Tertiary amines, such as triethylamine or pyridine, or even the dimethylamine employed can also be used as acid-binding agents. However, sodium hydroxide or potassium hydroxide is preferably used.

The dimethylamine can be forced into the reaction vessel in the gaseous state.

However, it is advantageously added to the mixtures in the form of its aqueous solutions. It is employed in amounts of 0.5-10, preferably 1--4, mols per equivalent of the chlorine bonded in the chlorinated hydrocarbon.

All the customary alkylating agents which are suitable tor quaternising tertiary amines can be used for the quaternisation, for example methyl chloride, methyl iodide, dimethyl sulphate, toluenesulphonic acid methyl ester, dimethyl phosphite, methanephosphonic acid dimethyl ester, ethyl bromide, ethyl iodide, diethyl sulphate, n - butyl bromide, n - hexyl chloride, dodecyl bromide, dodecyl chloride, tetradecyl chloride, allyl chloride, methallyl chloride, chloroethanol, sodium chloroacetate, chloroacetic acid methyl ester, chloroacetamide, propaneor butane - sultone, epichlorohydrin, ethylene oxide, propylene oxide, chloropropanediol, benzyl chloride and substituted benzyl chlorides, such as mono-, di- and tri - chlorobenzyl chloride, chloromethylnaphthalene, phenoxyethyl chloride, dibromoethane, 1,4 - dichlorobutane, 1,6 dichlorohexane, 1,4 - dichlorobut - 2 - ene, dichlorodiethyl ether, 4,4' dichlorodibutyl ether, 1,3 - dichloropropan - 2 - ol, 1,4 - bis chloromethylbenzene and bis - chloromethyldimethylbenzene. Preferred alkylating agents are dimethyl sulphate, methanephosphonic acid dimethyl ester, benzyl chloride, mono- and di - chlorobenzyl chloride, chloroethanol and sodium chloroacetate, especially benzyl chloride.

In a preferred embodiment of the process, a straight-chain hydrocarbon which contains 15-30 % of chlorine and has an average chain length of 15 carbon atoms is reacted with 0.5 to 4 times, in particular with 1.0-2.0 times, the molar amount (relative to equivalents of chlorine) of an aqueous dimethylamine solution in the presence of sodium hydroxide solution or potassium hydroxide solution in a pressure vessel. The reaction is carried out in the course of 240 hours, preferably of 5-24 hours, at 140160 . Unreacted dimethylamine is removed, after which the aqueous phase which separates out after cooling is separated off. The quaternising agent is then added to the organic phase, optionally together with water, and the reaction is carried out at 100160 in the course of 0.5-24 hours.

After cooling, the aqueous solution of the quaternary ammonium compound separates out from unreacted hydrocarbon. It can be fed directly, or after concentration, to the various applications.

Numerous processes for the preparation of surface-active quaternary ammonium compounds are known in which tertiary amines which contain at least one relatively long alkyl radical are reacted with alkylating agents (compare K.

Lindner "Tenside, Textilhilfsmittel, Waschrohstoffe" ("Surface-Active Agents, Textile Auxiliaries and Detergent Bases") Volume I, (1964), page 984).

A disadvantage of these processes is that tertiary amines which are generally prepared from expensive naturally occurring crude fats are used. It has also already been proposed to prepare long-chain amines from chlorinated aliphatic hydrocarbons by reaction of ammonia or amines (U.S. Patent Specification 2,361,457, DT-AS (German Published Specification) 1,108,236 and German Patent Specification 767,087). However, the preparation of quaternary ammonium compounds on this basis has not yet been disclosed.

A further advantage is that no solvents or emulsifiers are necessary during the reaction of the chloroalkane with dimethylamine. Since emulsion-forming properties could be expected of the type of compounds such as are obtained in the process according to the invention, it was surprising that the aqueous solutions of the quaternary ammonium compounds could be smoothly separated off from the unreacted hydrocarbons.

A further advantage of the preferred one-pot process is the more economical procedure and that it pollutes the environment less. In this process it is not necessary to isolate the free tertiary amine, which isolation is associated with a high acid and alkali consumption and the formation of large amounts of salt-containing effluents, and because of this a manufacturing step is simultaneously saved.

The quaternary ammonium compounds of the formula (I) are surface-active compounds and are suitable for numerous applications, for example for use as washing, cleaning, textile and dyeing auxilaries or as emulsifiers, antistatic or softening agents or bactericides. They have an excellent solubility and stability in water.

The compounds (I) are particularly suitable as auxiliaries in the dyeing of fibre materials, which can be dyed with cationic dyestuffs, with cationic dyestuffs. The dyeing of fibre materials which can be dyed with cationic dyestuffs can be carried out in the customary manner by introducing the material to be dyed into an aqueous dye liquors, warmed to about 50--60"C, which contains the cationic dyestuff, compounds of the formula (I), added salts, such as sodium acetate or sodium sulphate, and also acids, such as acetic acid or formic acid, then increasing the temperature of the dyebath to approximately 100"C in the course of about 30 minutes and subsequently keeping the dyebath at this temperature until it is exhausted. It is also possible to pre-treat the material to be dyed with a liquor, at a temperature of 40--100"C, which contains the customary salts and acids as well as compounds of the formula (I), but as yet no dyestuff, and only then to add t'ne dyestuff and carry out the dyeing at 1000C. Finally, it is also possible to immediately introduce the material to be dyed into the dyebath, heated to about 100"C, containing compounds of the formula (I).

Possible cationic dyestuffs are dyestuffs of various classes of compounds, for example diphenylmethane, triphenylmethane and rhodamine dyestuffs, azo or anthraquinone dyestuffs containing onium groups, and furthermore thiazine, oxazine, methine and azomethine dyestuffs, such as are described, for example, in Ullmanns Encyclopadie der technischen Chemie (Ullmann's Encyclopaedia of Industrual Chemistry), 3rd edition, 1970, supplementary volume, page 225.

The required amounts of the compounds of the formula (I) can be easily determined by preliminary experiments. In general, these compounds are used in amounts of about 0.25 to 2.50/,, relative to the weight of material to be dyed which is employed.

Examples of possible fibre materials which can be dyed with cationic dyestuffs are those made of anionically modified polyesters and polyamides, but in particular those made of polyacrylonitrile or copolymers containing acrylonitrile.

Examples of suitable copolymers containing acrylonitrile are copolymers of acrylonitrile with vinyl chloride, vinylidene chloride, vinyl chloroacetate, vinyl alcohol, acrylic acid and methacrylic acid, acrylic acid esters and methacrylic acid esters, allyl chloroacetate or basic vinyl compounds, such as vinylimidazole, vinylbenzimidazole, vinylpyridine, vinylmethylpyridine and vinylpyrimidine, as long as the proportion of these comonomers is not more than 2007o by weight.

Compounds of the formula (I) which are suitable for use as auxiliaries for dyeing fibre materials which can be dyed with cationic dyestuffs are preferably those in which the radical R represents a C,OC20-alkyl radical which is bonded to the nitrogen atom via a secondary carbon atdin and which can be optionally partially substituted by unreacted chlorine atoms, the radical R, represents a C1- C,2-alkyl radical which is optionally substituted by a hydroxyl group, or in particular represents an optionally hologenated benzyl radical and X- represents chloride, bromide, methosulphate or methanephosphonate, in particular the chloride ion.

Example 1 284 parts of a chlorinated Fischer-Tropsch hydrocarbon, which has an average carbon number of 15 and contains about 19% of chlorine bonded via a secondary carbon atom, are mixed with 160 parts of a 40% strength aqueous dimethylamine solution and 145 parts of 45 /O strength sodium hydroxide solution and the mixture is heated to 1500C in an autoclave in the course of 6 hours, whilst stirring. The mixture is stirred at this temperature for 12 hours, a pressure of about 20 atmospheres gauge being set up. After cooling to about 100110 C, excess dimethylamine is removed by venting the autoclave, and after further cooling to 2030 C, the aqueous phase is separated off at the bottom. 270 parts of an oily liquid, the basic nitrogen content of which is 3.64, are obtained as the upper phase. 89 parts of benzyl chloride and 260 parts of water are added to this phase and the mixture is heated to 1200 for 2 hours, whilst stirring. After standing for a short time at about 50 , the unreacted hydrocarbon separates out from the aqueous phase, which contains 256 parts of the compound

The resulting 50% strength aqueous solution can be used in this form, for example as a retarder in the dyeing of polyacrylonitrile fibres. The quaternary ammonium compound can be obtained in the form of a highly viscous liquid by distilling off the water in vacuo. (N: 3.7%, Cl: 11.4%).

Example 2 211 parts of a chlorinated Fischer-Tropsch hydrocarbon with an average chain length of 15 carbon atoms and a content of about 19% of chlorine bonded via a secondary carbon atom are mixed with 150 parts of 50% strength aqueous dimethylamine solution and 108 parts of 45 /" strength sodium hydroxide solution and the mixture is heated to 1450C in an autoclave in the course of 3 hours. It is stirred at 140--1450 for 24 hours, cooled to 100--110" and freed from excess dimethylamine by venting the batch. After further cooling to 2300, 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. 65 parts of benzyl chloride and 298 parts of water are added to this phase and the mixture is heated to 1300 for 2 hours, whilst stirring. After cooling to about 50"C and leaving to stand for a short time, 416 parts of an approximately 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 content of about 15% of chlorine bonded via a secondary carbon atom are reacted with 150 parts of 50 strength aqueous dimethylamine solution and 108 parts of 45 /O strength sodium hydroxide solution as described in Example 2. After separating off 200 parts of the amine-containing oil, 96.5 parts of 3,4 - dichlorobenzyl chloride and 225 parts of water are added to this oil and the mixture is reacted at 1300C in a pressure vessel for 3 hours. After cooling to about 50"C and leaving to stand for a short time, 440 parts of an approximately 50% strength aqueous solution of the compound

separate out at the bottom. 220 parts of a viscous product are obtained from this by distilling off the water in vacuo. (N: 3.1%, Cl: 24.2%).

Example 4 284 parts of a chlorinated, straight-chain hydrocarbon mixture, which has an average chain length of 15 carbon atoms and contains about 20% of chlorine bonded via a secondary carbon atom, are mixed with 400 parts of 50% strength aqueous dimethylamine solution and 148 parts of 45% strength sodium hydroxide solution in an autoclave and the mixture is brought to a temperature of 1500C in the course of 2 hours. It is stirred at this temperature for 6 hours, a pressure of about 22 atmospheres gauge being set up. After cooling to about 100110 C, excess dimethylamine is distilled off into a receiver by venting the autoclave, and after further cooling to 20--300C, the aqueous phase is separated off at the bottom. The upper phase consists of 260 parts of an oily liquid, the basic nitrogen content of which is 3.86. This phase is mixed with 82 parts of sodium chloroacetate and 250 parts of water and the mixture is heated to 12--1300C in an autoclave for 4 hours.

After cooling to 2300C, 500 parts of an approximately 50 /O strength aqueous solution of a compound, which essentially corresponds to the formula

separate out at the bottom. This product can be obtained as a highly viscous liquid by distilling off the water in vacuo. (N: 3.77, Cl: 11.5%).

Example 5 142 parts of a chlorinated paraffin hydrocarbon mixture with an average carbon number of 15 and a content of 20% of chlorine bonded via a secondary carbon atom are mixed with 200 parts of 50% strength dimethylamine solution and 111 parts of 45% strength sodium hydroxide solution in an autoclave. The temperature is brought to 1200C in the course of 1 hour and the mixture is kept at this temperature for 17 hours, a pressure of 13-14 atmospheres gauge being set up.

After cooling to 100110 C, unreacted dimethylamine is let off by venting the autoclave, and after further cooling to 20---300C, the aqueous lower phase is separated off. The upper phase consists of 130 parts of an oily liquid with a basic nitrogen content of 3.8%. 54.5 parts of a N-alkyl chloride, with 6-10 carbon atoms and an average molecular weight of 154, and 95 parts of water are added to this phase and the mixture is stirred at 1600 in an autoclave for 20 hours. After cooling to 20--300C and leaving to stand for a short time, 240 parts of an approximately 60% strength solution of the quaternary ammonium compound, which essentially corresponds to the formula

are obtained as the lower layer.

Example 6 Yarns made of polyacrylonitrile fibres are introduced, in a liquor ratio of 1:40, into a bath, warmed to 800 C, which contains 0.06 g of a cationic dyestuff of the formula

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

per litre. The bath is heated to 980coin the course of 30 minutes and kept at this temperature for 45 minutes. A uniform blue dyeing is obtained. During the dyeing operation it can be seen that the dyestuff is retarded at the start and only with increasing temperature is slowly, but at the end completely, absorbed onto the fibres.

Example 7 A knitted fabric made of polyacrylonitrile fibres is introduced, in a liquor ratio of 1:15, into a bath at 850C which contains 0.3 g of a dyestuff of the formula

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

The bath is brought to the boil in the course of 30 minutes and kept at the boiling point for 60 minutes. During this time, the dyestuff is slowly and uniformly absorbed onto the fibres. A completely level red dyeing is obtained.

Example 8 Cheeses with a polyacrylic filament yarn are introduced, in a liquor ratio of 1:20, into a bath, warmed to 700C, which contains 0.05 g of a cationic dyestuff as in Example 6 and 9.1 of a dyestuff according to Example 7, 0.25 g of sodium acetate, 0.3 g of glacial acetic acid and 1.6 g of the compound described in Example 5 of the formula

per litre. The bath is heated to 115-1 200C in the course of 75 minutes and dyeing is carried out at this temperature for 75 minutes. Cheeses which are completely uniformly dyed in a violet colour shade are obtained.

Claims

WHAT WE CLAIM IS:

1. A process for the production of a quaternary ammonium compound of the general formula

in which R denotes an unbranched C6 to C30-alkyl radical which is optionally substituted by chlorine and which is bonded to the nitrogen atom via a secondary carbon atom, R1 denotes an optionally substituted C, to C20-alkyl or C2 to C20-alkenyl radical, an optionally substituted aralkyl radical or the radical

R2 denotes a C2 to C,2-alkylene or alkenylene radical which is optionally substituted or interrupted by oxygen atoms, or an optionally substituted aralkylene radical and X denotes an anion, in which a chloroparaffin, which has been obtained by chlorinating a straight chain aliphatic hydrocarbon containing 8 to 30 carbon atoms, is reacted with dimethylamine at 90 to 2000C in the presence of an acid-binding agent and the product is then reacted with a quaternising agent.

2. A process according to Claim 1, in which the chloroparaffin is reacted with dimethylamine at 120 to 1600C.

3. A process according to Claim 1 or 2, in which the reaction with dimethylamine is carried out in the presence of water.

4. A process according to Claim 1 or 2, in which the reaction with dimethylamine is carried out at 120160 in the presence of an alkali metal hydroxide, alkaline earth metal oxide or alkaline earth metal hydroxide as the acidbinding agent.

5. A process according to Claim I or 2, in which the reaction is carried out in the presence of sodium hydroxide solution or potassium hydroxide solution, and dimethylsulphate, methanesulphonic acid dimethylester, chloroethanol, sodium chloroacetate, benzyl chloride, monochlorobenzyl chloride or dichlorobenzyl chloride is used as the quaternising agent.

6. A process according to Claim 1 or 2, in which the chlorinated hydrocarbon which is used has an average chain length of 15 carbon atoms and a chlorine content of 15 to 30%.

7. A process according to Claim 1 or 2, in which benzyl chloride is used as the quaternising agent.

8. A process according to Claim 1, when carried out substantially as described in any one of Examples 1 to 5.

9. A quaternary ammonium compound as defined in Claim 1, when produced by the process of any of Claims 1 to 8.

10. A process for dyeing a fibre material with a cationic dyestuff comprising either introducing the material into an aqueous dyebath warmed to 50 to 600C containing the dyestuff, a compound as claimed in Claim 9, a salt and an acid, increasing the temperature of the dyebath to approximately 1000C in the course of about 30 minutes and subsequent keeping the dyebath at this temperature until it is exhausted, or pretreating the material with a liquor, at a temperature of 40 to 100"C, which liquor contains a salt and an acid and the compound as claimed in Claim 9, and thereafter adding the dyestuff and carrying out the dyeing at 1000C, or introducing the material immediately into a dyebath, heated to about 100"C, containing a compound as claimed in Claim 9.

11. A process according to Claim 10, when carried out substantially as described in any one of Examples 6 to 8.

12. A fibre material when dyed by the process of Claim 10 or 11.