CS240835B1 - Process for preparing quaternary ammonium salts - Google Patents

Abstract

Method for preparing quaternary ammonium salts based on oxyethylated alkylphenol, epichlorohydrin and tertiary aliphatic amine. Alkylphenol with 4 to 10 carbon atoms in the branch chain, oxyethylated with 2 to 10 moles of ethylene oxide per 1 mole of alkylphenol, 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 is, after dilution with water at a temperature of 80 to 110 °C, quaternized with a tertiary amine of the general formula i, where Ri 2 3 denotes alkyl with a number of carbons of 1 to 4*a’or 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 invention relates to a novel process for the preparation of quaternary ammonium salts based on oxethylated alkylphenols, 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:

where R is a hydrophobic moiety which must be higher molecular, with at least 8 straight-chain carbon atoms. However, this alkyl may also be attached to an aromatic ring or an aralkyl group. ^{r and} i ^to 1,2,3 yl) aryl, or Η X is the hydrophilic portion, wherein the anion may be of the following nature:

Cl °, BR ®, J ®, CH ₃ OSO ₃ ^@ , C ₂ H ₅ OSO ₃ , CH ₃ GOO

The use of these compounds is widespread and varied.

The only analogous transport 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, in acidic conditions, 2 parts of BF ₃ in diethyl ether at 60 to 70 ° C are admixed with 296 parts of epichlorohydrin over 2 hours. The reaction mixture was heated at 110 ° C for an additional 1 hour to give 222 parts of 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 NGH ₂ GH ₂ OH, (G ₂ H ₅ ) ₂ CH ₂ CH ₂ OH, (OHCH ₂ CH ₂ ) ₃ K react.

240 835

Disadvantages of the 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 the oxethylated alkylphenols according to the invention, which consists in in the side chain, oxethylated with 2 to 10 moles of ethylene oxide per mole of alkyl phenol, is 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 90 to 150 ° G, preferably 110-130 ° C, after which the resulting intermediate is quaternized with a tertiary amine of the general formula after dilution with water at 80-110 ° C.

R _n

TO'

AND

RR <

R @ 1 denotes alkyl having a carbon number of 1 to 4 or or a hydroxyl of R @ 1 alkyl having from 2 to 4 carbon atoms.

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 alkylphenols, all oxethylated alkylphenol reacts almost completely to form the mono-, di-, tri-, chlorohydrineter, and the reaction mixture does not contain free epichlorohydrin, thereby avoiding the difficult separation of unreacted oxethylated alkylphenols. Also, the quaternization of mono-, di-, tri-, chlorohydrineter with the result of 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 used remains unreacted. We have found empirically that the reactivity of tertiary substituted amines decreases in the order:

θ2 ^ 5 ^G 2 ^H 5 (ch ₃ ) ₂ nch ₂ ch ₂ oh \ Z ^C 2 ^H 5 / ^N ^ ^C 2 ^H 5 c ₂ h ₅

C ₂ H ₅ OH

C ₂ H ₅ OH

N- C ₂ H ₅ OH C ₂ H ₅ OH

Quaternary ammonium compounds, prepared by ρ <> Λβ of our process in the form of 20 to 50% aqueous solutions, form water-to-pale yellow solutions, unlimitedly stable.

Example 1

240 83S

To a 1.51 sulfonation flask equipped with a dropper, a wall-mounted thermometer, and a KPG stirrer was charged 426 g of octylphenol, oxytized with 5 moles of ethylene oxide. Add 2 g of acetic acid to neutralize residual alkalinity resulting from the alkali catalysed oxethylation of alkylphenol, then sweat 2 g of 40% fluoroboric acid (4 g of fluoroboric acid can also be added without prior addition of acetic acid), then heat to 100 ° C. 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 takes 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 1423 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, light yellow solution. The pH of the acetic acid is adjusted to 6-7 by the addition of 7 g of acetic acid.

2060 g of a clear product are obtained, containing 30% of the active ingredient, which provides clear, highly foaming solutions, with water dilution.

Example 2

In a 1.5 L sulfonation flask equipped with a dropper, a thermometer, a heat sink and a KPG stirrer was charged 308 g of nonylphenol, oxethylated with 2 moles of ethylene oxide. 4 g of fluoroboric acid are added, heating them to 100 ° C, then epichlorohydrin is added at a rate such that the temperature of the reaction mixture is maintained at 110-120 ° C, and dispensing 105 g of eoichlorohydrin, which takes about 1 hour, is added. the reaction mixture is allowed to react at 110 DEG-120 DEG C. for a further 1 hour.

The reaction product obtained is diluted with 1150 g of drinking water, heated to

Q

C, after which 95 g of dimethylaminoethanol was started. After dispensing for about 30 minutes, the temperature of the reaction mixture is maintained at 95-102 ° C for 1.5 hours to give a clear, light yellow solution. The pH is adjusted to 6-7 by the addition of 8 g of acetic acid.

1670 g of a clear product are obtained with a content of 30% of active compound which, when diluted with water, gives a clear, strongly reflecting solution. flows.

- hExample 3 240 835

To a 1.5 L sulfonation flask equipped with a caustic flask, a thermometer, a zon cooler and a KPG stirrer was charged 484 g of nonylphenol, oxidized with 6 moles of ethylene oxide. 4 g of 40% fluoroboric acid are added, heated to 100 ° C, and epichlorohydrin is added dropwise at a rate such that the temperature of the reaction mixture is maintained between 110 and 120 ° C. After dispensing 105 g of epiclorohydrin, which lasts about 1 hour, the reaction product is allowed to react at 110-120 ° C for an additional hour. The reaction product obtained is diluted with 1555 g of common water, heated to 9 DEG C., and then 95 g of dimethylaminoethanol is started. After his overdose, which lasts about about

minutes, the temperature of the reaction mixture is maintained at 95-102 ° C for 1.5 hours to give a clear, light yellow solution. The pH is adjusted to 6-7 by the addition of 7 g of acetic acid.

This yields a clear product containing 30% of the active ingredient which, when diluted with water, provides clear, strongly foaming solutions.

Claims (1)

SUBJECT OF THE INVENTION 240 835 A process for the preparation of quaternary ammonium salts based on oxethylated alkylphenols, characterized in that oxethylated C 4 -C 10 alkylphenol in the branched chain, preferably 8 to 9 side chain carbon atoms, oxethylated with 2 to 10 moles of ethylene oxide per mole of alkylphenols, in the presence of fluoroboric acid, react with 1.0 to 1.5 equivalents, preferably 1.10 to 1.15 equivalents of eoichlorohydrin at a temperature of 90 to 150% _, preferably 110 to 130 ° C, after which the resulting intermediate is diluted with water at a temperature 80 to 110 ° C is quaternized with a tertiary amine of the general formula (I) N - R _o i ² R ₃ wherein R j, R g, R j denote alkyl having a carbon number of 1 to 4 or hydroxyalkyl having 2 to 4 carbon atoms.