JP2002179614A - Method for producing organic carboxylic acid quaternary ammonium salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an organic carboxylic acid quaternary ammonium salt substantially free from halogens in high yield in a short time. SOLUTION: This method for producing an organic carboxylic acid quaternary ammonium salt is characterized by comprising the following steps: a quaternary ammonium salt and 1.1-5 molar times, based on the quaternary ammonium salt, of a 1-6C organic carboxylic acid alkali metal salt are agitated in a mixed solution of 5-20 wt.% of water and 1.5-15 wt.times of a 1-6C alcohol followed by distilling off the solvent, and 5-20 wt.times, based on the quaternary ammonium salt, of at least one solvent selected from hydrocarbons, halocarbons, ethers, lower fatty acid esters and ketones is then added to the system followed by agitation and then filtration.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a quaternary ammonium organic carboxylate.

[0002]

BACKGROUND OF THE INVENTION Quaternary ammonium salts are used as cationic surfactants in detergents, textile aids, plastic additives, catalysts and the like. Conventionally, as a method for producing a quaternary ammonium salt, a quaternary ammonium halide can be obtained by reacting a tertiary amine with an alkyl halide. In the case of a quaternary ammonium alkyl sulfate, it can be obtained by reacting a tertiary amine with an alkyl sulfate. On the other hand, as a method for producing a quaternary ammonium organic carboxylate, industrially, an electrolytic method or an ion exchange method using a quaternary ammonium halide as a raw material is used to temporarily convert to a quaternary ammonium hydroxide.
A method of neutralizing with a carboxylic acid is generally known. Also, a method of treating quaternary ammonium acid sulfate described in JP-A-59-116251 with barium hydroxide and a carboxylic acid, or a method containing a tetraalkylammonium halide described in JP-A-61-260045. A method is known in which an aqueous solution is reacted with an organic carboxylic acid or an organic sulfonic acid in a water-immiscible solvent. However, in the method for producing a quaternary ammonium organic carboxylate, a method of once converting a quaternary ammonium halide into a quaternary ammonium hydroxide by an electrolytic method or an ion exchange method, and then neutralizing the quaternary ammonium hydroxide with a carboxylic acid, Kaisho 59
In the method described in JP-A-116251, both the reaction time is long and the reaction goes through a plurality of steps, so that the yield is low and the cost is high. Further, the method described in Japanese Patent Application Laid-Open No. 61-260045 has a problem that halogen cannot be sufficiently removed.

[0003]

In view of the problems described above, there has been a demand for a method for producing a quaternary ammonium organic carboxylate containing almost no halogen in a short time and in a high yield. An object of the present invention is to provide a method for producing a quaternary ammonium organic carboxylate containing almost no halogen in a short time and in a high yield.

[0004]

In order to solve the above-mentioned problems, studies have been made. As a result, after the quaternary ammonium salt and the organic carboxylic acid alkali metal salt are reacted in a specific solvent, the solvent is distilled off, and the hydrocarbon, halogen and the like are removed. One or two or more solvents selected from fluorinated hydrocarbons, ethers, lower fatty acid esters, and ketones are added and stirred, and then filtered. A quaternary ammonium organic carboxylate containing almost no alkali was obtained.

That is, the present invention provides a compound represented by the formula (I) and an alkali metal salt of an organic carboxylic acid having 1 to 6 carbon atoms which is 1.1 to 5 times as much as the compound represented by the formula (I): After stirring in a mixed solution of 5 to 20% by weight of water and 1.5 to 15 times by weight of an alcohol having 1 to 6 carbon atoms, the solvent is distilled off, and a hydrocarbon represented by the formula (I):
Halogenated hydrocarbons, ethers, lower fatty acid esters,
One or two or more solvents selected from ketones 5 to 20
This is a method for producing a quaternary ammonium organic carboxylate, which is characterized in that a weight-fold is added, stirred and filtered.

[0006]

Embedded image

(In the formula, one or two of R ¹ , R ² , R ³ and R ⁴ are a linear or branched alkyl or alkenyl group having 10 to 24 carbon atoms, and the rest is a group having 1 to 3 carbon atoms. An alkyl group or a benzyl group, and X represents a halogen atom.)

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the compound represented by the formula (I) used in the present invention, one or two of R ¹ , R ² , R ³ and R ⁴ are linear or branched having 10 to 24 carbon atoms. And an alkyl or alkenyl group having 1 to 3 carbon atoms.
Is an alkyl group or a benzyl group. Carbon number 10-2
As the linear or branched alkyl group or alkenyl group of 4, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, octadecenyl group, docosyl group, coconut oil alkyl group, tallow alkyl group, hardened tallow alkyl group, Examples include a palm oil alkyl group and a hydrogenated palm oil alkyl group. Examples of the alkyl group or benzyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group,
Examples thereof include an isopropyl group and a benzyl group, preferably a methyl group, an ethyl group or a benzyl group. In the compound represented by the formula (I), X represents a halogen atom, and examples thereof include fluorine, chlorine, bromine, and iodine.

The alkali metal salt of an organic carboxylic acid used in the present invention is an alkali metal salt of an organic carboxylic acid having 1 to 6 carbon atoms, preferably an alkali metal salt of an organic carboxylic acid having 1 to 3 carbon atoms. As the alkali metal salt, a sodium salt or a potassium salt is preferable, and a potassium salt is more preferable.

The alkali metal salt of an organic carboxylic acid has the formula (I)
Is used in an amount of 1.1 to 5 times the amount of the compound represented by the formula (I).
It is 5 to 5 mol times. If the amount of the organic carboxylic acid alkali metal salt is less than 1 mole, the residual halogen content in the product increases. If the amount of the organic carboxylic acid alkali metal salt is more than 5 mole times, the reaction reaches equilibrium. Although it does not change, the yield may decrease due to removal of unreacted alkali metal salts of organic carboxylic acids.

The reaction solvent used in the present invention has the formula (I)
5 to 20% by weight of water and 1 carbon atom
And a mixed solution of 1.5 to 15 times by weight of the alcohol of the formula (I).
Alcohol having 1 to 6 carbon atoms and 1.5 to 10% by weight
It is a mixed solution by weight. When the amount of water is less than 5% by weight, the reaction rate is reduced. When the amount of water is more than 20% by weight, the yield of the product is reduced due to removal of the unreacted alkali metal salt of the organic carboxylic acid.

The alcohol having 1 to 6 carbon atoms used in the present invention is preferably in an amount capable of dissolving the quaternary ammonium organic carboxylate, and is 1.5 to 10 times by weight the compound represented by the formula (I). Is preferred. Examples of the alcohol having 1 to 6 carbon atoms include methanol, ethanol, propanol, isopropanol, butanol, pentanol, and hexanol. Preferably it is an alcohol having 1 to 3 carbon atoms, more preferably an alcohol having 3 carbon atoms. The reaction is carried out by stirring at a temperature at which the compound represented by the formula (I) is dissolved or suspended in the reaction solvent, and the temperature is preferably from 20 to 80 ° C. When the temperature is lower than 20 ° C., the compound represented by the formula (I) is not sufficiently dissolved or suspended in the reaction solvent, and the reaction efficiency is reduced. The temperature is 80 ℃
If it is higher, coloring tends to occur in the quaternary ammonium organic carboxylate, and the quality is reduced.

After completion of the reaction, the solvent is distilled off,
One or more solvents selected from hydrocarbons, halogenated hydrocarbons, ethers, lower fatty acid esters and ketones are added and stirred to remove alkali salts and unreacted alkali metal salts of organic carboxylic acids by filtration. . The recovered reaction solvent can be reused in the process.

The hydrocarbon is a straight-chain or branched hydrocarbon or a hydrocarbon having a cyclic structure or a benzene ring, and includes pentane, hexane, heptane, octane,
Nonane, decane, isooctane, cyclohexane, benzene, toluene and the like can be mentioned. Examples of the halogenated hydrocarbon include dichloromethane, chloroform and the like.
Examples of the ether include tetrahydrofuran and diethyl ether. Examples of lower fatty acid esters include ethyl acetate and butyl acetate. Ketones include methyl ethyl ketone, acetone and the like. Preference is given to pentane, hexane, heptane, octane, isooctane and toluene. One or more solvents selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, lower fatty acid esters and ketones used in the present invention include:
At the time of filtration, a state in which the quaternary ammonium organic carboxylate is dissolved is preferable. It is preferable to use the above. When the temperature is lower than 20 ° C., the quaternary ammonium organic carboxylate is not sufficiently dissolved, and the yield decreases. The quaternary ammonium organic carboxylate according to the present invention may be in a state of being dissolved in a solvent or in a state of being dried after removing the solvent.

[0015]

According to the method of the present invention, a quaternary ammonium organic carboxylate containing almost no residual halogen can be obtained in a short time in a high yield, which is an industrially extremely significant method.

[0016]

Next, the present invention will be described in more detail by way of examples. The residual halogen content in the obtained quaternary ammonium organic carboxylate was measured by the following method.
In a 300 mL beaker, 10 g of the quaternary ammonium organic carboxylate according to the present invention was weighed, dissolved in 100 mL of isopropyl alcohol, and 10 mL of a 10% by volume aqueous nitric acid solution was added.
After adding L to make the solution acidic, use an automatic titrator (COMMITE-550, manufactured by Hiranuma Sangyo Co., Ltd.) to obtain 0.0
Titration was performed with a 1N silver nitrate standard solution. The residual halogen content was determined by the following equation. Residual halogen content (% by weight) = {(0.01 × halogen molecular weight × A × F) / (S × 1000)} × 100 A: 0.01N silver nitrate standard droplet quantification (mL) F: 0.01N silver nitrate standard Liquid titer S: Sampling amount (g)

Example 1 Di-hardened tallow alkyl dimethyl ammonium chloride 19
2.6 g (0.34 mol), 76.7 g of potassium acetate
(0.78 mol: 2.3 mol times based on the compound represented by the formula (I)), 21.2 g of water (11.0% by weight based on the compound represented by the formula (I)) and 578.0 g of isopropanol (3. With respect to the compound represented by the formula (I).
0 weight times) in a mixed solution of 1% at 55 ° C.
Stirred for hours. After distilling off the water-isopropanol mixed solvent, 2500.0 g of hexane (13.0 times by weight based on the compound represented by the formula (I)) was added, and the mixture was stirred at 50 ° C. The precipitated alkali salt was filtered to obtain 2696.0 g of a hexane solution containing di-hardened tallow alkyldimethylammonium acetate. By distilling off the solvent, the yield was 98.0 based on the starting quaternary ammonium salt.
%, 196.6 g of di-hardened tallow alkyldimethylammonium acetate were obtained. (Residual halogen content: 0.052% by weight)

Example 2 Di-hardened tallow alkyl dimethyl ammonium chloride 14
1.6 g (0.25 mol), sodium acetate 47.6
g (0.58 mol: 2.3 mol times with respect to the compound represented by the formula (I)), 15.6 g of water (11.0% by weight based on the compound represented by the formula (I)) and 425.g of isopropanol. 0 g (3.0 times by weight based on the compound of the formula (I)).
For 1 hour. After distilling off the water-isopropanol mixed solvent, 1840.0 g of hexane (13.0 times by weight based on the compound represented by the formula (I)) was added, and the mixture was stirred at 50 ° C. The precipitated alkali salt was filtered to obtain 1978.0 g of a hexane solution containing di-hardened tallow alkyldimethylammonium acetate. By distilling off the solvent, the yield was 94.0 based on the starting quaternary ammonium salt.
% Of 138.6 g of di-hardened tallow alkyldimethylammonium acetate was obtained. (Residual halogen content: 0.054% by weight)

Example 3 116.6 g of docosyltrimethylammonium chloride
(0.30 mol), 81.6 g of sodium formate (1.
20 mol: 8.2 g of water (7.0% by weight based on the compound of the formula (I)) and 700.0 g of ethanol (formula (I)) Was suspended or dissolved in a mixed solution (6.0 times by weight with respect to the compound represented by), and the mixture was stirred at 55 ° C for 1 hour. After distilling off the water-ethanol mixed solvent, 932.0 g of toluene
(8.0 times by weight with respect to the compound represented by the formula (I)), and the mixture was stirred at 70 ° C. By filtering the precipitated alkali salt, 1041.0 g of a toluene solution containing behenoyltrimethylammonium formate was obtained. By distilling off the solvent, 109.7 g of behenoyltrimethylammonium formate was obtained in a yield of 92.0% with respect to the starting quaternary ammonium salt. (Residual halogen content: 0.
043% by weight)

Example 4 104.9 g of docosyltrimethylammonium chloride
(0.27 mol), 73.5 g of sodium formate (1.
08 mol: 7.3 g of water (7.0% by weight based on the compound of the formula (I)) and 734.0 g of methanol (the formula (I)). Was suspended or dissolved in a mixed solution (7.0 weight times the compound represented by the formula (1)) and stirred at 55 ° C. for 1 hour. After distilling off the water-methanol mixed solvent, 840.0 g of toluene
(8.0 times by weight with respect to the compound represented by the formula (I)), and the mixture was stirred at 70 ° C. By filtering the precipitated alkali salt, 937.0 g of a toluene solution containing behenoyltrimethylammonium formate was obtained. By distilling off the solvent, 97.3 g of behenoyltrimethylammonium formate was obtained in a yield of 90.7% with respect to the starting quaternary ammonium salt. (Residual halogen content: 0.04
2% by weight)

Example 5 Coconut oil alkyltrimethylammonium chloride 10
1.3 g (0.40 mol), potassium caproate 17
6.2 g (1.60 mol: 3.1 mol times based on the compound represented by the formula (I)) are mixed with 14.2 g of water (14.0% by weight based on the compound represented by the formula (I)) and isopropanol Suspended or dissolved in a mixed solution of 405.0 g (4.0 times by weight based on the compound represented by the formula (I)),
Stirred at 5 ° C for 1 hour. After distilling off the water-isopropanol mixed solvent, 608.0 g of acetone (6.0 times by weight with respect to the compound represented by the formula (I)) is added, and the mixture is stirred at 40 ° C. By filtering the precipitated alkali salt, 724.0 g of an acetone solution containing coconut oil alkyltrimethylammonium caproate was obtained. By distilling off the solvent, the yield based on the starting quaternary ammonium salt was 91.
At 0% 116.8 g of coconut oil alkyltrimethylammonium caproate were obtained. (Residual halogen content: 0.0
47% by weight)

Comparative Example 1 Di-hardened tallow alkyldimethylammonium chloride 11
3.3 g (0.20 mol), 45.1 g of potassium acetate
(0.46 mol: 2.3 mol times based on the compound represented by the formula (I)) in 34.0 g of water (30.0% by weight based on the compound represented by the formula (I)) and 340.0 g of isopropanol (3. With respect to the compound represented by the formula (I).
0 weight times) in a mixed solution of 1% at 55 ° C.
Stirred for hours. After distilling off the water-isopropanol mixed solvent, 1473.0 g of hexane (13.0 times by weight based on the compound represented by the formula (I)) is added, and the mixture is stirred at 50 ° C. By filtering the precipitated alkali salt, 1578.0 g of a hexane solution containing di-hardened tallow alkyldimethylammonium acetate was obtained. By distilling off the solvent, the yield was 89.0 based on the starting quaternary ammonium salt.
% Of di-hardened tallow alkyldimethylammonium acetate was obtained. (Residual halogen content: 0.12% by weight)

Comparative Example 2 Di-hardened tallow alkyldimethylammonium chloride 17
0.0 g (0.30 mol), potassium acetate 67.7 g
(0.69 mol: 2.3 mol times with respect to the compound represented by the formula (I)) was suspended in a mixed solution of 510.0 g of isopropanol (3.0 times by weight with respect to the compound represented by the formula (I)). It became cloudy or dissolved, and was stirred at 55 ° C. for 1 hour. After distilling off isopropanol, 2210.0 g of hexane (13.0 times by weight of the compound represented by the formula (I)) is added, and the mixture is stirred at 50 ° C. By filtering the precipitated alkali salt, 2365.0 g of a hexane solution containing di-hardened tallow alkyldimethylammonium acetate was obtained.
By distilling off the solvent, 155.8 g of di-hardened tallow alkyldimethylammonium acetate was obtained at a yield of 88.0% based on the starting quaternary ammonium salt. (Residual halogen content: 0.053% by weight)

Comparative Example 3 Coconut oil alkyltrimethylammonium chloride
0 g (0.30 mol), potassium caproate 42.6
g (0.3 mol: 1 mol times based on the compound represented by the formula (I)) was added to 11.4 g of water (15.0% by weight based on the compound represented by the formula (I)) and isopropanol 30
The mixture was suspended or dissolved in a mixed solution of 4.0 g (4.0 weight times the compound represented by the formula (I)), and stirred at 55 ° C. for 1 hour. After distilling off the mixed solvent of water and isopropanol, 456.0 g of acetone (6.0 times by weight with respect to the compound represented by the formula (I)) was added, and the mixture was stirred at 40 ° C. By filtering the precipitated alkali salt, 542.0 g of an acetone solution containing coconut oil alkyltrimethylammonium caproate was obtained. By distilling off the solvent, 88.6% of the starting quaternary ammonium salt was obtained in a yield of 90.3%.
9 g of coconut oil alkyltrimethylammonium caproate were obtained. (Residual halogen content: 0.270% by weight)

COMPARATIVE EXAMPLE 4 392.6 g (4.0 mol: 4 mol times of the compound of the formula (I)) of potassium acetate was added to 1500 g of water.
(264% by weight based on the compound represented by the formula (I)), 566.5 g (1.0 mol) of di-hardened tallow alkyldimethylammonium chloride and 1215 g of methyl isobutyl ketone (to the compound represented by the formula (I)) 2.14 times by weight) and stirred for 80 minutes for 80 minutes.
Heated at ° C. After separation of the phases, 900 g of water were added and the organic phase was washed with vigorous stirring at room temperature for 30 minutes. After washing, the washing solution was separated to obtain 1787 g of a methyl isobutyl ketone solution containing 32.0% by weight of di-hardened tallow alkyldimethylammonium acetate. (The residual halogen content of the obtained solution was 3.4% by weight.) 900 g of water (1) was added to the obtained methyl isobutyl ketone solution.
59% by weight) and the organic phase was washed by stirring at room temperature for 30 minutes. By separating the washing liquid, 1710 g of a methyl isobutyl ketone solution containing 29.0% by weight of di-hardened tallow alkyldimethylammonium acetate was obtained. (The residual halogen content of the obtained solution was 2.1% by weight.) 900 g of water was added to the obtained methyl isobutyl ketone solution.
59% by weight) and the organic phase was washed by stirring at room temperature for 30 minutes. By separating the washing solution, 1646 g of a methyl isobutyl ketone solution containing 26.2% by weight of di-hardened tallow alkyldimethylammonium acetate was obtained. (The residual halogen content of the obtained solution was 1.6% by weight.) 900 g of water was added to the obtained methyl isobutyl ketone solution.
59% by weight) and the organic phase was washed by stirring at room temperature for 30 minutes. By separating the washing liquid, 1577 g of a methyl isobutyl ketone solution containing 23.0% by weight of di-hardened tallow alkyldimethylammonium acetate was obtained. (The residual halogen content of the obtained solution was 1.2% by weight.) 900 g of water was added to the obtained methyl isobutyl ketone solution.
59% by weight) and the organic phase was washed by stirring at room temperature for 30 minutes. By separating the washing liquid, 1521 g of a methyl isobutyl ketone solution containing 20.2% by weight of di-hardened tallow alkyldimethylammonium acetate was obtained. The solvent was removed by distillation under reduced pressure to obtain 306.8 g of di-hardened tallow alkyldimethyl ammonium acetate in a yield of 54.0% based on the raw material quaternary ammonium salt. (Residual halogen content: 1.0% by weight)

Comparative Example 5 Di-hardened tallow alkyldimethylammonium chloride 11
To 3.3 g (0.2 mol) of isopropanol 517.
3 g (4.57 weight weigh) was added, 20 g (0.2 mol) of concentrated sulfuric acid was dropped under stirring at room temperature, and the mixture was allowed to stand for 5 hours. The precipitated crystals were separated by filtration and washed with isopropanol to obtain di-hardened tallow alkyldimethyl ammonium acid sulfate at a yield of 80.0% with respect to the raw material quaternary ammonium salt.
5 g were obtained. (Residual halogen content: 0.4% by weight) A suspension obtained by adding barium hydroxide octahydrate (0.16 mol) and 9.6 g (0.16 mol) of acetic acid to 147.0 g of water was obtained as described above. Di-hardened tallow alkyldimethylammonium acid sulfate was dissolved in 147.0 g of water, added dropwise with stirring at room temperature, stirred for 6 hours, and the precipitated barium sulfate was filtered off. The resulting filtrate was concentrated under reduced pressure to obtain 73.2 g of di-hardened tallow alkyldimethylammonium acetate in a yield of 62.0% with respect to the starting quaternary ammonium salt. (Residual halogen content: 0.4% by weight)

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

In Examples 1 to 5, quaternary ammonium organic carboxylate containing almost no residual halogen can be obtained in good yield. In Comparative Example 1, since the amount of water used as the reaction solvent was large, the yield was lower than in Examples 1 to 5. In Comparative Example 2, since the reaction solvent did not contain water, the yield was lower than in Examples 1 to 5. In Comparative Example 3, since the amount of the alkali metal salt of the organic carboxylic acid was small, the residual halogen was large as compared with Examples 1 to 5.
In Comparative Example 4, since the reaction with the alkali metal salt of the organic carboxylic acid was carried out with water-methyl isobutyl ketone, the reaction rate and the yield were low. In Comparative Example 5, a quaternary ammonium halide was reacted with sulfuric acid in isopropanol to obtain a quaternary ammonium acid sulfate, and then reacted with an organic carboxylic acid in the presence of barium hydroxide to obtain a quaternary ammonium organic carboxylic acid. This is a method for obtaining salt. Examples 1 to 5
Unlike the above, since the reaction rate is low, the residual halogen content in the quaternary ammonium organic carboxylate increases.

Claims (1)

[Claims] 1. A compound represented by the formula (I) and an alkali metal salt of an organic carboxylic acid having 1 to 6 carbon atoms in an amount of 1.1 to 5 times the amount of the compound represented by the formula (I),
0% by weight and 1.5 to 15 alcohols having 1 to 6 carbon atoms
After stirring in a weight-fold mixed solution, the solvent is distilled off, and one or two selected from hydrocarbons, halogenated hydrocarbons, ethers, lower fatty acid esters and ketones are added to the compound represented by the formula (I). A method for producing a quaternary ammonium organic carboxylate, comprising adding 5 to 20 times by weight of the above solvent, stirring and filtering. Embedded image (In the formula, one or two of R ¹ , R ² , R ³ and R ⁴ are a linear or branched alkyl group or alkenyl group having 10 to 24 carbon atoms, and the rest is an alkyl group having 1 to 3 carbon atoms or A benzyl group and X represents a halogen atom.)