CS239963B1 - Process for preparing quaternary ammonium salts - Google Patents

Abstract

Method for preparing quaternary ammonium salts based on aliphatic alcohol, epichlorohydrin and tertiary aliphatic amine. An aliphatic alcohol with 4 to 22 carbon atoms in the chain is allowed to react with 1.0 to 1.5 equivalents of epichlorohydrin in the presence of fluoroboric acid at a temperature of 90 to 150 °C, after which the resulting intermediate is quaternized undiluted with water at a temperature of 80 to 110 °C with a tertiary amine of the general formula N----- -R2s where 2 3 is an alkyl with 1 to 4 carbon atoms or a hydroxyalkyl with 2 to 4 carbon atoms. Quaternary ammonium compounds, prepared according to our procedure in the form of 20 to 60% aqueous solutions, form water-clear to light yellow, strongly foaming solutions, of unlimited stability.

Description

The invention relates to a novel process for the preparation of quaternary ammonium salts based on aliphatic alcohols, epichlorohydrin and tertiary aliphatic amines.

Quaternary ammonium compounds are ionic, cationically dissociating surfactants and are a very important group of substances. Their hydrophobic part of the molecule is part of a cation, which is practically always ammonium, mostly quaternary, exceptionally different onium ion. They can be represented by the general formula:

^R \ X ^R 3 Bi «1 ^XFI 2 wherein R is a hydrophobic moiety which has to be relatively high molecular weight, with at least 8 carbon atoms in a straight chain. However, this alkyl may also be attached to an aromatic ring or an aralkyl group.

^R 1, 2,3 aryl and Η, x respectively are the hydrophilic moieties, wherein the anion may be of the following nature:

CL®, Br® J ^@, CH ₃ OSO ₃ ^e C ^ OSO.®, CH jCOO®, ΟΗθ.

The use of these compounds is widespread and varied.

The only analogous preparation of quaternary ammonium salts prepared from the reaction of halohydrin compounds with tertiary amines is known from the literature.Wle Japan Kokai 7564 206 (1975), the halohydrin compound is prepared from 520 parts of octanol to which 2 parts of BF- . The reaction mixture was heated at 110 ° C for an additional 1 hour to give 222 parts of the chlorohydrin, which was reacted with 106 parts of triethylamine. The reaction is carried out in aqueous medium under reflux at 85-9 ° C for 15 hours to give the quaternary ammonium salt. Similarly, the amines (CH ₃ N ₂ CH ₂ CH ₂ OH, (C ₂ H ₅ ) ₂ CH ₂ CH ₂ OH, (OHCH ₂ OH ₂ ) ₃ N) react.

-λ '

239 963

Disadvantages of the hitherto known process for the preparation of quaternary ammonium salts of this type are eliminated by the process for the preparation of the quaternary ammonium salts based on aliphatic alcohols according to the invention, which consists in reacting an aliphatic alcohol having 4 to 22 carbon atoms in the chain in the presence of fluoroboric acid 1.5 equivalents, preferably 1.10 to 1.15 equivalents of epichlorohydrin at 90 to 150 ° C, preferably 110 to 130 ° C, after which the resulting intermediate is quaternized with tertiary amine after dilution with water at 80 to 110 ° 0 - R,

and.

wherein R, R xv ₉ , R ₇ denotes alkyl having a carbon number of 1 to 4 or hydroxy 2 to 3 alkyl having 2 to 4 carbon atoms.

The advantages of our process are high, quantitatively yields with maximum ease of production. With an increased molar ratio of 1.15 moles of epichlorohydrin to 1.0 moles of alcohol, all the aliphatic alcohol reacts almost completely to form the mono-, di- and trichlorohydrineter and the reaction mixture does not contain free epichlorohydrin and thus eliminates the difficult separation of unreacted alcohol. Similarly, the quaternization of mono-, di- and trichlorohydrin ethers in our process results in a high yield, practically quantitatively. About 6% of the dimethylaminoethanol used remains unqualified. When using triethylamine, about 15% of the stoichiometric amount of triethylamine employed remains unreacted. We have found empirically that the reactivity of tertiary substituted amines decreases in the order:

^C 2 ^H 5 (CH 3) ₂ NCH ₂ CH ₂ OH

C ₂ H ₅ OH

C ₂ H ₅ OH

C ₂ H ₅ OH

C ₂ H ₅ OH

The quaternary ammonium compounds prepared according to our process in the form of 20 to 50% aqueous solutions are water-to-pale yellow solutions, unlimited in stability.

Example 1 239 963

A 1.5 L sulfonation flask equipped with a dropper, thermometer, reflux condenser and KPG stirrer was charged with 133.5 g of an average molecular weight aliphatic alcohol C8 to C18.

130-137. 1 g of an aqueous solution of 40% fluoroboric acid is added, heated to 98 ° C, and epichlorohydrin is added dropwise from the dropper so that the temperature of the reaction mixture is maintained between 110 and 125 ° C.

After dispensing 103.5 g of epichlorohydrin (approximately 1 hour), it is reacted with stirring at 110 ° C for a further 1 hour. After addition of 316 g of water, the reaction product-water mixture is heated to 90 DEG C. and then 94 g of dimethylaminoethanol is dispensed from the dropper over 15 minutes. After stirring at 90-95 ° C for 1 hour, a clear, water-clear, light yellow solution was obtained. The product is adjusted to a pH of 6-7 by adding 3 g of acetic acid with a pH of 9-10 caused by the presence of a small amount of unreacted dimethylaminoethanol.

651 g of a clear product containing 50% of active ingredient are obtained, which gives clear, strongly foaming solutions when diluted with water.

Example 2

To a 1.5 L sulfonation flask equipped with a dropper, thermometer, reflux condenser and KPG stirrer was added 210 g of a mixed aliphatic alcohol C 2 ^to C ^{18 of} an average molecular weight of 204 to 216. Add 1 g of 40% fluoroboric acid, heating The epichlorohydrin is added dropwise at a rate such that the temperature of the reaction mixture is maintained between 110 and 120 ° C. After dispensing 103.5 g of epichlorohydrin, which lasts about 1 hour, the reaction mixture is allowed to react at 110 ° C for a further 1 hour. The reaction intermediate was diluted with 940 g of water, heated to 90 ° C, and dosing of dimethylaminoethanol was started. Dosing of all 94 g of dimethylaminoethanol (about 5% excess) takes about 15 minutes.

After 1 hour of quaternization at a temperature of 90-102 ° C, a clear, cloudy, pale yellow solution is obtained containing 30% of the active ingredient.

The product is adjusted from pH 9-10 to pH 6-7 by addition of 4.5 g concentrated acetic acid.

There are obtained 1353 g of a clear product containing 30% of the active compound which, when diluted with water, gives clear, strongly foaming solutions.

Example 3

To a 1.5 L sulfonation flask equipped with a dropper, thermometer, reflux condenser and KPG stirrer was added 130 g of 2-ethylhexanol and 1 g of 40% fluoroboric acid was added. After heating to 110 ° C

h239 963 was added dropwise with epichiorhydrin at a rate such that the temperature was maintained in the range of 110-120 ° C; 313 g of water are added to the reaction intermediate, heated to 90 ° C, and then dimethylaminoethylfluol is metered in. After the addition of 94 g of dimethylaminoethanol, which takes about 15 minutes, the reaction mixture is allowed to quaternize at 90 to 102 ° C. The pH is adjusted to 6 to 6 by the addition of 3.5 g of concentrated acetic acid

7.

645 g of a clear product containing 50% of the active ingredient are obtained which, when diluted with water, gives clear, strongly foaming solutions.

Claims (1)

Process for the preparation of quaternary ammonium salts based on aliphatic alcohols, characterized in that the aliphatic alcohol having 4 to 22 carbon atoms in the chain is left in the presence of fluoro-acid. roborites are reacted with 1.0 to 1.5 equivalents, preferably 1.10 to 1.15 equivalents of epichlorohydrin at a temperature of 90 to 150 ° C, preferably 110 to 130 ° C, after which the resulting intermediate is diluted with water to at a temperature of 80 DEG to 110 DEG C. it is quaternized with a tertiary amine of the formula (I ⁾ N- ^r 2 ^R 3 wherein, R ₂ , R 3 is alkyl having a carbon number of 1 to 4 or hydroxyalkyl having 2 to 4 carbon atoms.