JPS60178846A - Production of mixed quaternary ammonium salt - Google Patents

Abstract

PURPOSE:To produce the titled substance useful as a disinfectant, in a short time, leaving little unreacted material, by reacting a benzyl halide first with an amine composed mainly of a branched-chain alkyl tertiary amine and then with a straight-chain alkyl tertiary amine, in the reaction of an aliphatic tertiary amine with a benzyl halide. CONSTITUTION:The objective compound is produced by reacting an aliphatic tertiary amine with a benzyl halide. In the above process, a tertiary amine composed mainly of a branched-chain alkyl tertiary amine is made to react with excess benzyl halide (benzyl chloride or benzyl brmide), and then a straight-chain alkyl tertiary amine having high reactivity is made to react with the benzyl halide at stoichiometric ratio by adding the tertiary amine in an amount corresponding to the remaining benzyl halide or if the remaining benzyl halide is little, adding necessary amount of the benzyl halide to the system. The above reaction is preferably carried out by using a solvent such as ethanol.

Description

Detailed Description of the Invention The present invention involves reacting an aliphatic tertiary amine with a benzyl halide to produce a mixed solution of a linear alkyl quaternary ammonium salt and a branched alkyl quaternary ammonium salt. It's about how to do it.

Aliphatic quaternary benzyl ammonium salts, especially aliphatic quaternary benzyl ammonium salts
Class benzyl ammonium chloride is useful as a disinfectant. However, the quaternary ammonium salt used for such applications needs to have a low content of unreacted amine. The amount of residual unreacted amine can be reduced by using an excess of benzyl halide relative to the amine. It is also necessary that the amount of benzyl halide is small, and if an excess of benzyl halide is used with respect to the amine, it is necessary to separate and purify the unreacted benzyl halide after reaction route r.

However, when attempting to remove unreacted benzyl halide by distillation after the reaction has ended, since the boiling point of hensyl halides is high (179°C for benzyl chloride and 198°C for benzyl bromide), the ethanol used as the reaction solvent, The isopropanol is distilled off first and becomes a viscous liquid, making it difficult to distill. Ethylene glycol with a high boiling point as a solvent (
(boiling point 197°C), propylene glycol (boiling point 188°C)
When using a dihydric alcohol such as (℃), another problem arises in that the quaternary ammonium salt of the target product is decomposed by being heated at high temperature for a long time during apparatus 1+t: removal distillation of halogenated Henssil. . Therefore, in order to reduce the residual amount of both the unreacted amine and the unreacted benzyl halide, it is necessary to precisely adjust the stoichiometric amounts of 1iEr of the amine and benzyl halide to 11t+.

The amines used for the above purpose are so-called natural amines mainly composed of linear amines obtained using Bor IJr3 as starting materials, and higher alcohols synthesized by the oxo method, which are converted into alkyl chlorides, and then converted into lower dialkyl chlorides. Amination method with amine or JP-A-58-105945
As disclosed in the specification, synthetic amines can be broadly classified into synthetic amines obtained by a method of reacting a long-chain olefin with a lower dialkylamine in the presence of a hydrogen and carbon oxide mixed gas. The synthetic amine is generally a mixed branched and linear alkyl tertiary amine containing 20 to 60% by weight of branched alkyl tertiary amine.

In order to reduce the residual amount of both unreacted amine and unreacted benzyl halide in the reaction product, when linear amine and benzyl halide are reacted in stoichiometric amounts,
The reaction progresses during time t, but when branched and straight chain mixed alkyl tertiary amines are reacted in the same way, the reaction rate of the branched chain alkyl tertiary amine is significantly slower than that of the straight chain alkyl tertiary amine. Reaction rate of linear argyl tertiary amine is 100%
Even if this amount is reached, there is still a large amount of unreacted branched alkyl tertiary amine. In order to increase this reaction rate, it is necessary to use oversprings of benzyl halide, and as a result, it is difficult to reduce the residual amount of benzyl halide.

The present invention makes it possible to complete the quaternization of such a mixed amine with a hensyl halide in a relatively short time, and to reduce the amount of unreacted amine and unreacted benzyl halide remaining (1). In the method for producing a fat mixed solution, first, a tertiary amine containing a branched chain alkyl tertiary amine as a main component is reacted with an excess amount of benzyl halide, and then a mixture containing substantially branched chain alkyl groups is reacted. This is a method for producing a mixed quaternary ammonium salt, which is characterized by adding a straight chain alkyl tertiary amine and reacting the halogenated benzyl amine.

Among the long-chain alkyl tertiary amines used as raw materials in the present invention, the straight-chain alkyl amine has the general formula (wherein R1 and R2 are each independently a methyl group or an ethyl group, and R3 is a straight chain having 8 to 25 carbon atoms). (It is a chain alkyl group.)
It is an aliphatic tertiary amine represented by
5 is a linear alkyl group, and the total number of carbon atoms in R4 and R5 is 6 to 23. ) is an aliphatic tertiary amine represented by

In the method of the present invention, a tertiary amine whose main component is a branched alkyl tertiary amine is first quaternized with excess lit of benzyl halide, and then a highly reactive straight chain alkyl tertiary amine is converted into a halogenated tertiary amine. Add an amount commensurate with the remaining amount of benzyl chloride, or if the remaining amount of 11J mohalogenated benzyl is smaller than the amount of linear alkyl tertiary amine to be added, add the necessary amount of benzyl halogenide, By reacting a linear alkyl tertiary amine and a halogenated benzyl at jft m 15, it is possible to obtain a mixed alkyl quaternary ammonium salt in a short time with a small amount of unreacted amine and unreacted benzyl halogenide remaining. can.

In the method of the present invention, the reaction between the tertiary amine and the halogenated hensyl is carried out in a monohydric or dihydric lower alcohol solvent such as ethanol, isopropanol, ethylene glycol, or brohylene gelicol, as is known in the art. This can prevent a decrease in the reaction rate due to an increase in the viscosity of the reaction solution. Furthermore, an alkaline agent or water can be added to speed up the reaction rate. As the alkaline agent, sodium pyrolyl acetate, potassium hydroxide, sodium carbonate, sodium bicarbonate, etc. are used.

The reaction temperature can be selected within the range of 40 to 120°C, and the reaction pressure may be at atmospheric pressure, but may be maintained under pressure depending on the type of reaction solvent and reaction temperature.

The tertiary amine as a raw material in the present invention includes, for example, branched and linear mixed alkyl tertiary amines synthesized by the oxo method.
grade amines can be used.

In this case, since the branched chain alkyl tertiary amine and the straight chain alkyl tertiary amine have different boiling points, they are separated by distillation. In this fractional distillation, linear alkyl tertiary amines are allowed to be mixed in an amount of 15 to 30% by weight, or even more in some cases, in the amount of branched alkyl tertiary amines. The amount of branched chain alkyl tertiary amine mixed in the amount of primary amine is preferably 1% by weight or less.

As the benzyl halide, benzyl chloride and benzyl bromide are used.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Reference example (quaternization reaction of linear alkyl tertiary amine) 213.4 g (1.0 mol) of reagent N,N-dimedyldodecylamine distilled to remove impurities and Impropatol 213.4 A glass reaction tank was charged with 5.5 g of water, heated with stirring and maintained at 60°C, and 126.6 g (1.0 mol) of benzyl chloride was added dropwise over 1 hour. After the dropwise addition was completed, the reaction was continued at 60'C for 4 hours.

Collect a portion of the Jy-ratio and add a mixture of n-hexane/methanol/water to extract unreacted amine and unreacted benzyl chloride into the n-hexane phase, and analyze the n-hexane phase by gas chromatography. The unreacted amine and unreacted benzyl chloride concentrations were determined by the method.

The unreacted amine concentration was 0.22% by weight (amine reaction rate 99%).
．． 4 mol%), unreacted benzyl chloride concentration is J1 heavy lit
%Met.

Comparative Example (Quaternization reaction of branched and linear alkyl mixed tertiary amine) 227.4 g of N,N-dimethyl-tridecylamine synthesized from a mixed gas of 1-dodecene, dimethylamine, and hydrogen °-carbon oxide (1.0 mol) linearity 61.4% by weight) and Improper Tool 227.4 g.

Pour 6 g of water into a glass reaction tank, heat it while stirring and keep it at 60°C, and add 39.3 g of allied Henssil l.
(1.1 mol) was added dropwise over 1 hour. 60° after completion of dripping
The reaction was continued for 8 hours at C. The unreacted amine concentration (linear amine - branched chain amine) was 0.5 Fk% (amine reaction rate 98.7 mol%), and the unreacted benzyl chloride concentration was 2.
．． It was 4% by weight.

Table 1 shows the change in the reaction rate between the linear alkyl tertiary amine and the branched alkyl tertiary amine during this period. It can be seen that the reaction rate of branched chain alkyl tertiary amines is extremely slow compared to that of straight chain alkyl tertiary amines.

Example (Fractional quaternization reaction of branched-chain alkyl tertiary amine and straight-chain alkyl tertiary amine) N,N-dimethyl-tridecyl synthesized from 1-dodecene, dimethylamine, and hydrogen/carbon oxide mixed gas The amine was distilled at a pressure of 210 mm Hg using a distillation column with an internal diameter of 4 c1n% and 20 theoretical plates, and the boiling point was 137.
Fraction 1 mainly composed of branched chain amines at 5 to 146.5°C
and fraction 2 consisting essentially of linear amines with a boiling point of 14°C. Fraction 1 consists of 25% by weight of linear amines and 75% by weight of branched amines, and fraction 2 consists of 9% by weight of linear amines.
9.5% by weight and branched amine was 0.5% by weight.

153 g (o, 67 mol) of fraction 1, 153 g of isopropanol, and 3.4 g of water were charged into a glass reaction tank.
Heat with stirring and maintain at 60°C, and add benzyl chloride 18
9.9 g (1.5 mol) were added dropwise over 15 minutes. After the dropwise addition was completed, the reaction was continued at 60°C for 4 hours. The reaction rate of linear amine is 100 mol%, and the reaction rate of branched chain amine is 9
It was 9.7 mol%. The residual concentration of unreacted benzyl chloride was 21.0% by weight.

Next, 188 g (0,83
mol), 188 g of isopropanol, and 3.8 g of water were added, and a second stage reaction was carried out at 60°C for 4 hours. 1st
The unreacted residual concentration of all the amines added in the reactions of stage and second stage was 0.13 times II (amine reaction rate 99.5 mol%), and the residual concentration of unreacted benzyl chloride was less than Jl mass %. .

Table 1 Applicant: Mitsubishi Yuka Co., Ltd. Agent: Patent attorney Katsura Atsuta

Claims (4)

[Claims] (1) In a method for producing a mixed solution of a straight-chain alkyl quaternary ammonium salt and a branched-chain alkyl quaternary ammonium salt by reacting a tertiary amine and a benzyl halide with a fat, first, a branched-chain alkyl quaternary ammonium salt is produced. After reacting a tertiary amine whose main component is a tertiary amine with an excess amount of benzyl halide, a linear alkyl tertiary amine containing substantially no branched chain alkyl group is added to react the benzyl halide. A method for producing a mixed quaternary ammonium salt, the method comprising reacting the mixed quaternary ammonium salt. (2) Straight-chain alkyl tertiary amine has the general formula % (1) However, R1 and R2 are each independently a methyl group or ethyl group, and R3 is a straight-chain alkyl group having 8 to 25 carbon atoms. The method according to claim (1), wherein the aliphatic tertiary amine is an aliphatic tertiary amine represented by: (3) The branched m-alkyl tertiary amine has the general formula (however,
R1 and R2 are each independently a methyl group or an ethyl group, R4 and R5 are each a linear alkyl group, and the total number of carbon atoms in R4 and R5 is 6 to 23. )
The method according to claim (1) or (2), wherein the aliphatic tertiary amine is an aliphatic tertiary amine represented by: (4) Claims (1) to (3) wherein the benzyl halide is benzyl chloride or benzyl bromide.
) The method described in any of the above.