CS239964B1 - Process for preparing quaternary ammonium salts - Google Patents

Abstract

Method for preparing quaternary ammonium salts based on oxethylated aliphatic alcohol, epichlorohydrin and tertiary aliphatic amine. An aliphatic alcohol with 4 to 22 carbon atoms in the chain, oxethylated with 2 to 10 moles of ethylene oxide per 1 mole of aliphatic alcohol 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 product, after not diluting with water, is quaternized at a temperature of 80 to 110°C with a tertiary amine of the general formula f1' N------ R, , I 2 where R, 2 j denotes an alkyl with a number of carbons of 1 to 4 and 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 that are indefinitely stable.

Description

The present invention relates to a novel process for the preparation of quaternary ammonium salts based on oxethylated 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:

wherein R is a hydrophobic moiety which must be higher molecular weight, at least 8 to 8 straight-chain carbon atoms. However, this alkyl may also be attached to an aromatic ring or an aralkyl group. ^r 1,2,3, and ¹ ^ ¹ »aryl or H, x 'j _E hydro! nucleophilic portion, the anion may be of the following nature:

ci®, βγ ^θ , j®, ch ₃ axis ₃ ®, c ₂ h ₅ axis ₃ ®, ch ₃ coo °, οη ^θ .

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. According to Japan Kokai 7564 206 (1975), the halohydrin compound is prepared from 520 parts of octanol, to which 296 parts of epichlorohydrin are added in acidic conditions under catalysis of 2 parts of BFn in diethyl ether at 0 to 70 ° C over 2 hours. 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 an aqueous medium at reflux at 85-95 ° C for 15 hours to form the quaternary ammonium salt. Similarly, the amines (CH ₃ ) ₂ NCH ₂ CH ₂ OH, (C 1 H 2 Cl 2 Cl 2 OH, (OHCH ₂ CH ₂ ) 3 N) react.

239 964

Disadvantages of the known process for the preparation of quaternary ammonium salts of this type are overcome by the process for the preparation of the quaternary ammonium salts based on oxethylated aliphatic alcohols according to the invention, which consists in the oxethylated aliphatic alcohol having 4 to 22 carbon atoms of ethylene oxide per mole of aliphatic alcohol, reacted in the presence of fluoroboric acid with 1.0 to 1.5 equivalents, preferably 1.10 to 1.15 equivalents, of epichlorohydrin at a temperature of from 90 to 90

15 ° C, preferably 110 to 130 ° C, whereupon the resulting intermediate is quaternized after dilution with water at 80 to 110 ° C with a tertiary amine of the formula wherein R 1, R ₂ , ^R 3, ^C 8 ^{-C 8} alkyl having a carbon number of 1 to 4 and or (C 2 -C 4) hydroxyalkyl.

The advantage of our process is high, practically quantitative yields with maximum production simplicity. With an increased molar ratio of 1.15 moles of epichlorohydrin to 1.0 moles of oxethylated alcohol, all of the oxethylated aliphatic alcohol reacts almost completely to form the mono-, di-, tri-, chlorohydrineter and the reaction mixture does not contain free epichlorohydrin, eliminating the difficult separation of unreacted oxethylated alcohol. . Also, the fermentation of the mono-, di-, tri- chlorohydrineter produced in our process proceeds with a high yield, practically quantitatively. Only 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 order:

(CH ₃ ) ₂ NCH ₂ CH ₂ OH

/ ^{2 5} k <- c ₂ hrs ₅ ^G 2 ^H 5 ° 2 ^H 5 ° 2 ^H 5

O-H.OH e-5 ./ \

C2H $ 0H

N - C ₂ H ₅ OH c ₂ h ₅ oh

The quaternary ammonium compounds prepared by powdery mildew of our process in the form of 20% to 50% aqueous solutions are water to light yellow solutions, which are unlimitedly stable.

Example 1

- 3239 964

A 1.5 L sulfonation flask equipped with a dropper, thermometer, reflux condenser and KPG stirrer was charged with 400 g of a C12-C15 aliphatic alcohol chain, methylated with 4.5 moles of ethylene oxide per mole of aliphatic alcohol. 2 g of acetic acid are added to neutralize the residual alkalinity resulting from the alkali catalysed oxethylation, then 2 g of 40% fluoroboric acid (possibly also about 5 g of fluoroboric acid without addition of acetic acid) are added and heated to 100 ° C. the epichlorohydrin was added dropwise at a rate such that the temperature of the reaction mixture was maintained at 110-120 ° C. After dispensing 105 g of epichlorohydrin, which lasts about 1 hour, the reaction mixture is allowed to react at 110-120 ° C for a further 1 hour.

The reaction product obtained is diluted with 1,370 g of drinking water, heated to 90 DEG C., and then starting with 95 g of dimethylaminoethanol. After the addition of dimethylaminoethanol, which lasts about 30 minutes, the temperature of the reaction mixture is maintained at 95-102 ° C for 1.5 hours to give a clear, cloudy, light yellow solution. The pH is adjusted to 6 to 7 by adding 6 g of concentrated acetic acid.

There was obtained 1 980 g of a clear product containing 30% of active ingredient, which gave clear, strongly foaming solutions when diluted with water.

Example 2

In a 1.5 L sulfonation flask equipped with a dropper, a thermometer, a KPG reflux condenser, 640 g of mixed aliphatic alcohol having 12 to 15 carbon atoms in the chain, oxethylated with 10 moles of ethylene oxide per mole of aliphatic alcohol, are introduced. 2 g of acetic acid are added to neutralize the residual alkalinity resulting from alkaline oxethylation, followed by addition of acetic acid. 2 g of 40% fluoroboric acid or 5 g of fluoroboric acid without prior addition of acetic acid (pH of the reaction mixture of at least 2 to 3) are heated to 100 ° C, and epichlorohydrin is added dropwise at such a rate that 120 C. After dispensing 105 g of epichlorohydrin, which lasts about 1 hour, the reaction mixture is allowed to react at 110-125% for a further 2 hours.

The reaction product obtained is diluted with 2500 g of DI water, heated to 0 ° C

96 g of dimethylaminoethanol is then started. After the addition of dimethylaminoethanol, which lasts about 30 minutes, the temperature of the reaction mixture is maintained at 95-102 ° C for 2 hours to give a clear, cloudy, light yellow solution. The pH is adjusted to 6 to 7 by adding 9 g 'of concentrated acetic acid.

239 9B4

3,330 g of a product containing 25% of active ingredient are obtained which, when diluted with water, gives clear, strongly foaming solutions.

Claims (1)

SUBJECT OF THE INVENTION 239 964 A process for the preparation of quaternary ammonium salts based on exetylated aliphatic alcohols, characterized in that an oxethylated C 4 -C 22 aliphatic alcohol is methylated with 2 to 10 moles of ethylene oxide per mole of aliphatic alcohol. allow in the presence of fluoroboric acid to react with 1.0 »? 1.5 equivalents, preferably 1.10 to 1.15 equivalents of epichlorohydrin at 90 to 15 ° C, preferably 110 to 130 ° C, after which the resulting intermediate is quaternized with a tertiary amine after dilution with water at 80 to 110 ° C of the general formula N '3 wherein R-p R 8 denotes alkyl having a carbon number of 1 to 4 or hydroxyalkyl having 2 to 4 carbon atoms.