JPH05148198A - Production of nitrogen-containing fatty acid ester and production of ester group-containing quarternary ammonium salt - Google Patents

Abstract

(57) [Summary] [Object] To provide a method for producing a high-quality esterified product having a good color tone and having no unpleasant odor in a high yield in the reaction of a fatty acid lower alkyl ester with an alkanolamine, and to provide the esterified product. It is an object of the present invention to provide a method for producing a high-quality quaternary ammonium salt by using as a raw material. When a saturated or unsaturated fatty acid lower alkyl ester and an alkanolamine are transesterified in the presence of a catalyst, a solid catalyst containing aluminum and magnesium or a solid zinc compound is used as the catalyst. Method for producing nitrogen fatty acid ester. A method for producing a quaternary ammonium salt containing an ester group, which comprises reacting a nitrogen-containing fatty acid ester obtained by the above method with a quaternizing agent to quaternize the nitrogen atom.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a nitrogen-containing fatty acid ester and a method for producing a quaternary ammonium salt containing an ester group.

[0002]

2. Description of the Related Art Conventionally, various softener compositions have been used for imparting flexibility and antistatic properties to clothes after washing. These softener compositions generally contain a di-long chain alkyl di-short chain alkyl quaternary ammonium salt as a main component. This di-long-chain alkyl di-short-chain alkyl quaternary ammonium salt is poor in biodegradability, and therefore, when discharged into a river, causes river pollution. On the other hand, the quaternary ammonium salt containing an ester group has biodegradability based on the ester group. As a method for producing the quaternary ammonium salt having this ester group, generally, after reacting a beef tallow-derived fatty acid with an alkanolamine such as triethanolamine,
A method of quaternizing with a quaternizing agent such as methyl chloride or dimethylsulfate is used. For example, JP-A-53-5108
In the publication, a fatty acid is quaternized after being reacted with an alkanolamine without using a catalyst. JP-A-56-18946
In the report, p-toluenesulfonic acid is used as a catalyst with a fatty acid to react with an alkanolamine for quaternization.
Further, in JP-A-56-18946, tin powder is used with a fatty acid as a catalyst to react with an alkanolamine for quaternization. However, although esterification products with alkanolamines can be obtained in high yield by these methods,
The esterified product had the drawbacks of being markedly colored and producing an unpleasant odor, and the quaternary ammonium salt derived therefrom was also inferior in its quality.

The fatty acid lower alkyl ester has the advantages that it is cheaper to purify than the fatty acid and can be easily carried out. Therefore, if this fatty acid lower alkyl ester is used for the reaction, the color tone is excellent and there is no unpleasant odor. The quaternary ammonium salt of can be industrially advantageously obtained. However, the transesterification reaction of a fatty acid lower alkyl ester with an alkanolamine has a drawback that the reaction rate is slow in a non-catalyst system and the yield of the esterified product does not increase even if a general alkali catalyst is used. Further, in JP-A-55-45898, aluminum triisopropoxide is used as a catalyst for this reaction, but the reaction rate of the esterified product is low, which is not satisfactory.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a high-quality esterified product excellent in color tone and free from unpleasant odor in a high yield in the reaction of a fatty acid lower alkyl ester with an alkanolamine. It is an object of the present invention to provide a method for producing a high-quality quaternary ammonium salt using the esterified product as a raw material.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that by reacting a fatty acid lower alkyl ester with an alkanolamine using a specific solid catalyst, The inventors have found that a high-yield and high-quality esterified product can be produced, and completed the present invention. That is, according to the present invention, when a saturated or unsaturated fatty acid lower alkyl ester and an alkanolamine are transesterified in the presence of a catalyst, a solid catalyst containing aluminum and magnesium is used as the catalyst. A method for producing a nitrogen-containing fatty acid ester is provided. Further, according to the present invention, when a saturated or unsaturated fatty acid lower alkyl ester and an alkanolamine are subjected to a transesterification reaction in the presence of a catalyst, a solid zinc compound is used as the catalyst of a nitrogen-containing fatty acid ester. A manufacturing method is provided. Furthermore, according to the present invention, the nitrogen-containing fatty acid ester obtained by the above-mentioned method is reacted with a quaternizing agent to quaternize the nitrogen atom.
A method for producing a quaternary ammonium salt is provided.

The fatty acid lower alkyl ester used as a raw material in the present invention has a linear or branched carbon number of 6 to
22 is an ester of a saturated or unsaturated fatty acid and a lower alcohol. The lower alkyl group (alcohol residue) in the fatty acid lower alkyl ester is preferably an alkyl group having 1 to 4 carbon atoms. Also, the fatty acids can be mono- or polyvalent fatty acids. These fatty acid lower alkyl esters can be used alone or as a mixture of two or more kinds. Specific examples of the fatty acid lower alkyl ester used in the present invention include, for example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, dimethyloctanoic acid, butylheptylnonanoic acid, methylhen. Eicosanoic acid, hexenoic acid, octenoic acid, decenoic acid, dodecenoic acid,
Octadecenoic acid (oleic acid), eicosenoic acid, docosenoic acid (erucic acid), adipic acid, suberic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, octadecamethylenedicarboxylic acid, eicosamethylenedicarboxylic acid, fatty acid derived from tallow , Methyl ester such as fatty acid derived from palm oil, ethyl ester, isopropyl ester, n-propyl ester, isobutyl ester, n-
Examples thereof include butyl ester and t-butyl ester. The unsaturated fatty acid may have a stereoisomeric structure of a cis isomer, a trans isomer, or a mixture of the two, and in particular, the cis isomer / trans isomer ratio is (2
It is preferably 5 to 100) / (0 to 75).

As the alkanolamine used in the present invention, conventionally known ones, for example, those represented by the following general formula are preferably used.

[0008]

[Chemical 1]

[0009]

[Chemical 2]

In the above formula, R ¹ , R ³ and R ⁴ are lower alkyl, and the carbon number thereof is usually 1 to 4. R ² is hydrogen or a methyl group. m is an integer of 1 to 10 and n is an integer of 1 to 3. Specific examples of alkanolamines include, for example, triethanolamine, triisopropanolamine, methyldiethanolamine, methyldiisopropanolamine, ethyldiethanolamine, ethyldiisopropanolamine, propyldiethanolamine, butyldiethanolamine, dimethylethanolamine,
Dimethylisopropanolamine, diethylethanolamine, diethylisopropanolamine, dipropylethanolamine, diisopropylethanolamine,
Dibutylethanolamine, diisobutylethanolamine, di (sec-butyl) ethanolamine, di (t
-Butyl) ethanolamine, 3- (dimethylamino)
-1,2-propanediol, 3- (diethylamino)
-1,2-propanediol, 3- (methylethylamino) -1,2-propanediol, 3- (diisopropylamino) -1,2-propanediol, 3- (dibutylamino) -1,2-propanediol And so on.

The catalyst used in the present invention is a solid catalyst containing aluminum and magnesium or a solid zinc compound. The shape of the catalyst can be any shape such as powder or pellet. In the solid catalyst containing aluminum and magnesium, the aluminum component and the magnesium component may be a simple mixture or may be ionically bonded. Further, the aluminum component and magnesium component present in the solid catalyst can be in various forms such as hydroxide, oxide, fatty acid salt, alkoxide, silicate, and solid solution. Specific examples of the solid catalyst include, for example, alumina / magnesia, a coprecipitate composed of aluminum hydroxide and magnesium hydroxide, a mixture of aluminum hydroxide and magnesium hydroxide, a mixture of aluminum acetate and magnesium acetate, and aluminum methoxy. Mixture of magnesium and magnesium methoxide,
Examples include a mixture of aluminum ethoxide and magnesium ethoxide, synthetic hydrotalcite, a solid solution of alumina and magnesia, a complex oxide of aluminum and magnesium, a magnesium-substituted aluminosilicate, a magnesium silicate containing aluminosilicate, and aluminum magnesium silicate. The atomic ratio (Al / Mg) of aluminum and magnesium in the solid catalyst is 1
It is preferable to define it in the range of / 9 to 8/2. As the solid zinc compound catalyst, a conventionally known solid zinc salt, for example,
Examples thereof include zinc carbonate, zinc borate, fatty acid zinc such as zinc acetate and zinc adipate, and zinc oxide and zinc hydroxide. These can be used alone or in the form of a mixture.

The method for producing a nitrogen-containing fatty acid ester of the present invention is carried out by adding a fatty acid lower alkyl ester and an alkanolamine to a reaction vessel, stirring them, and carrying out a transesterification reaction in the presence of a catalyst. The catalyst is preferably used in powder form. The reaction is carried out under an atmosphere (presence) of an inert gas such as nitrogen gas, and the alcohol (low boiling point) produced as a by-product is distilled off under reduced pressure. The total amount of the catalyst used is usually 0.05 to 2.0% by weight, preferably 0.1 to 1.0% by weight, based on the total amount of the fatty acid lower alkyl ester and the alkanolamine. If the amount of catalyst used is less than 0.05% by weight, the reaction rate will be extremely slow, while if it exceeds 2.0% by weight, the effect will not change, but the catalyst precipitated after completion of the reaction will be filtered. Since the amount of the precipitate is too large when removing it, the yield of the product is reduced, which is not preferable. The reaction temperature is usually 120 to 220 ° C., preferably 15 although it depends on the kind of the raw material.
It is 0 to 200 ° C. If the reaction temperature is lower than 120 ° C., the reaction rate becomes extremely slow, and if it exceeds 220 ° C., a side reaction occurs, causing an unpleasant odor in the obtained esterified product, and the color tone thereof deteriorates. The reaction time is usually about 5 to 15 hours. After completion of the reaction, the esterified product is filtered to remove the catalyst, and then the esterified product is dissolved in an organic solvent according to a conventional method and then quaternized with a quaternizing agent such as methyl chloride or alkylsulfuric acid. A quaternary ammonium salt can be obtained.

[0013]

According to the present invention, it is possible to produce a high-quality nitrogen-containing fatty acid ester having an extremely low unpleasant odor (offensive odor) and a good color tone in a high yield. Therefore, the quaternized product of the nitrogen-containing fatty acid ester obtained in the present invention can be used as a base material for an intermediate raw material, a softening agent for fibers, a fiber treating agent, a hair rinse, etc., without requiring a special purification treatment. It is used to advantage.

[0014]

EXAMPLES Next, the present invention will be specifically described by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. The color tone and odor of the product were evaluated by the following methods. (1) Evaluation of color tone A sample was placed in a Gardner test tube and measured with a Gardner colorimeter in comparison with a standard color. The samples were measured as undiluted solutions at 40 ° C. (2) Evaluation of Odor 10 g of the sample was placed in a 100 ml beaker, left for 1 hour in a hot water bath at 80 ° C., left at room temperature for 30 minutes, and then evaluated for odor. Separately, 0.5 g of beef tallow fatty acid (manufactured by NOF Corporation, trade name "beef tallow fatty acid No. 0") was placed in a 100 ml beaker for comparison and comparison. ⊚: The odor is much weaker than that of the comparative product. ○: The odor is weaker than that of the comparative product. Δ: The odor is the same as that of the comparative control product. X: The odor is stronger than that of the comparative control product.

Example 1 597.0 g of stearic acid methyl ester, 119.2 g of N-methyldiethanolamine and a catalyst were placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube and a by-product alcohol distillation device. Aluminum hydroxide / magnesium hydroxide co-precipitate (2.5 MgO / Al ₂ O ₃
-XH ₂ O) (3.6 g) was charged in a nitrogen gas atmosphere, and the reaction temperature was kept at 180 ° C to gradually increase the degree of vacuum to allow the by-product methyl alcohol to be distilled off and reacted for 13 hours to carry out the transesterification reaction. went. Next, the reaction product was filtered to remove the catalyst, dissolved in 350 ml of isopropyl alcohol, charged into a stainless steel autoclave and replaced under a nitrogen gas atmosphere, and then 101 g of methyl chloride (CH ₃ Cl) was introduced. Then, while maintaining the pressure in the system at 4.5 to 5.0 atm (gauge pressure) at 90 ° C., the reaction is carried out for 8 hours to carry out quaternization to obtain a quaternary ammonium salt which is yellow and has a good odor. It was The results of the reaction are shown in Table 1.

Example 2 593.4 g of a mixture of oleic acid methyl ester and stearic acid methyl ester (weight ratio = 90/10) as fatty acid lower alkyl ester, and synthetic hydrotalcite (Mg ₆ .Al ₂ (OH)) as catalyst ₁₆ CO ₃ · 4H
_The transesterification reaction was performed in the same manner as in Example 1 except that 3.6 g of ₂ O) was used. Next, this reaction product was filtered to remove the catalyst, then dissolved in 350 ml of ethyl alcohol and charged into a four-necked flask to obtain dimethyl sulfate 123.
6 g was added dropwise at 50 ° C over 1 hour, aging and reacting for 3 hours for quaternization, and pale yellow with good odor
A primary ammonium salt was obtained. The reaction results are shown in Table 1.

Example 3 541 g of palmitic acid methyl ester as a fatty acid lower alkyl ester and aluminum hydroxide as a catalyst.
Magnesium hydroxide coprecipitate (Al ₂ O ₃ · MgO solid solution)
The transesterification reaction was carried out in the same manner as in Example 1 except that 3.3 g was used. Then, this reaction product was subjected to a quaternization reaction in the same manner as in Example 1 to obtain a quaternary ammonium salt which was yellow and had a good odor. The reaction results are shown in Table 1.

Example 4 The reaction was carried out in the same manner as in Example 1 except that a mixture of 1.8 g of aluminum hydroxide and 1.8 g of magnesium hydroxide was used as a catalyst, and a quaternary ammonium salt which was yellow and had a good odor was obtained. Got The reaction results are shown in Table 1.

Example 5 An experiment was conducted in the same manner as in Example 1 except that 3.6 g of zinc carbonate was used as a catalyst. The obtained quaternary ammonium salt was yellow and had a good odor. The reaction results are shown in Table 1.

Example 6 In Example 2, zinc borate (2ZnO.
3B ₂ O ₃ .3.5H ₂ O) was used in the same manner except that 3.6 g was used. The obtained quaternary ammonium salt was yellow and had a good odor. The reaction results are shown in Table 1.

Example 7 An experiment was conducted in the same manner as in Example 3 except that 3.3 g of zinc acetate was used as a catalyst. The obtained quaternary ammonium salt was yellow and had a good odor.

Comparative Example 1 Aluminum triisopropoxide 3.6 as a catalyst
The transesterification reaction was performed in the same manner as in Example 2 except that g was used. In this case, the reaction rate of the raw material fatty acid ester was as low as 79%.

Comparative Example 2 The transesterification reaction was carried out in the same manner as in Example 2 except that 3.6 g of sodium bicarbonate was used as the catalyst. In this case, the reaction rate of the raw material fatty acid ester was as low as 83%.

Comparative Example 3 The transesterification reaction was carried out in the same manner as in Example 2 except that 3.6 g of aluminum hydroxide was used as the catalyst. In this case, the reaction rate of the raw material fatty acid ester was as low as 83%.

Comparative Example 4 The transesterification reaction was carried out in the same manner as in Example 2 except that 3.6 g of magnesium hydroxide was used as the catalyst. In this case, the reaction rate of the raw material fatty acid ester was as low as 83%.

Comparative Example 5 Fatty acid derived from beef tallow (acid value: 20) was used without using a catalyst.
3.3, iodination: 86.1) An esterification reaction and a quaternization reaction were carried out in the same manner as in Example 1 except that 552 g was used. The reaction rate of fatty acids was as good as 97%,
The color tone of the quaternary ammonium salt is remarkably poor and brown,
Also, the odor was extremely bad.

[0027]

[Table 1]

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[Procedure amendment]

[Submission date] February 7, 1992

[Procedure Amendment 1]

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[Claims]

[Chemical 1] (In the formula, R ¹ is a lower alkyl group, R ² is hydrogen or a methyl group, n is 1 to 3, m is an integer of 1 to 10) or the general formula

[Chemical 2] The method according to any one of claims 1 to ³ , wherein R ³ and R ⁴ represent a lower alkyl group.

[Procedure Amendment 2]

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[0002]

2. Description of the Related Art Conventionally, various softener compositions have been used for imparting flexibility and antistatic properties to clothes after washing. These softener compositions generally contain a di-long chain alkyl di-short chain alkyl quaternary ammonium salt as a main component. This di-long-chain alkyl di-short-chain alkyl quaternary ammonium salt is inferior in biodegradability and therefore causes environmental pollution when discharged into a river. On the other hand, the quaternary ammonium salt containing an ester group has biodegradability based on the ester group. As a method for producing the quaternary ammonium salt having this ester group, generally, after reacting a beef tallow-derived fatty acid with an alkanolamine such as triethanolamine,
A method of quaternizing with a quaternizing agent such as methyl chloride or dimethylsulfate is used. For example, JP-A-53-5108
In the publication, a fatty acid is quaternized after being reacted with an alkanolamine without using a catalyst. JP-A-56-18946
In the report, p-toluenesulfonic acid is used as a catalyst with a fatty acid to react with an alkanolamine for quaternization.
Further, in JP-A-56-18946, tin powder is used with a fatty acid as a catalyst to react with an alkanolamine for quaternization. However, although esterification products with alkanolamines can be obtained in high yield by these methods,
The esterified product had the drawbacks of being markedly colored and producing an unpleasant odor, and the quaternary ammonium salt derived therefrom was also inferior in its quality.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

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[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that by reacting a fatty acid lower alkyl ester with an alkanolamine using a specific solid catalyst, The inventors have found that a high-yield and high-quality esterified product can be produced, and completed the present invention. That is, according to the present invention, when a saturated or unsaturated fatty acid lower alkyl ester and an alkanolamine are transesterified in the presence of a catalyst, a solid catalyst containing aluminum and magnesium is used as the catalyst. A method for producing a nitrogen-containing fatty acid ester is provided. Further, according to the present invention, when a saturated or unsaturated fatty acid lower alkyl ester and an alkanolamine are subjected to a transesterification reaction in the presence of a catalyst, a solid zinc compound is used as the catalyst, which is a nitrogen-containing fatty acid ester. A method of manufacturing the same is provided. Furthermore, according to the present invention, the nitrogen-containing fatty acid ester obtained by the above-mentioned method is reacted with a quaternizing agent to quaternize the nitrogen atom.
A method for producing a quaternary ammonium salt is provided.

[Procedure amendment 4]

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[Correction method] Change

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Example 1 597.0 g of stearic acid methyl ester, 119.2 g of N-methyldiethanolamine and a catalyst were placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube and a by-product alcohol distillation device. Aluminum hydroxide / magnesium hydroxide co-precipitate (2.5 MgO / Al ₂ O ₃
-XH ₂ O) (3.6 g) was charged in a nitrogen gas atmosphere, and the reaction temperature was kept at 180 ° C to gradually increase the degree of vacuum to allow the by-product methyl alcohol to be distilled off and reacted for 13 hours to carry out the transesterification reaction. went. Next, the reaction product was filtered to remove the catalyst, dissolved in 350 ml of isopropyl alcohol, charged into a stainless steel autoclave and replaced under a nitrogen gas atmosphere, and then 101 g of methyl chloride (CH ₃ Cl) was introduced. Then, while maintaining the pressure in the system at 4.5 to 5.0 atm (gauge pressure) at 90 ° C., the reaction is carried out for 8 hours to carry out quaternization to obtain a quaternary ammonium salt which is yellow and has a good odor. It was The reaction results are shown in Table 1.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

Example 2 593.4 g of a mixture of oleic acid methyl ester and stearic acid methyl ester (weight ratio = 90/10) as fatty acid lower alkyl ester, and synthetic hydrotalcite (Mg ₆ .Al ₂ (OH)) as catalyst ₁₆ CO ₃ · 4H
_The transesterification reaction was performed in the same manner as in Example 1 except that 3.6 g of ₂ O) was used. Next, this reaction product was filtered to remove the catalyst, then dissolved in 350 ml of ethyl alcohol and charged into a four-necked flask to obtain dimethyl sulfate 123.
6 g was added dropwise at 50 ° C. over 1 hour, aging and reacting for 3 hours to carry out quaternization to obtain a quaternary ammonium salt which was yellow and had a good odor. The reaction results are shown in Table 1.

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Claims (5)

[Claims] 1. A nitrogen-containing fatty acid characterized by using a solid catalyst containing aluminum and magnesium as a catalyst when transesterifying a saturated or unsaturated fatty acid lower alkyl ester and an alkanolamine in the presence of a catalyst. Method for producing ester. 2. A method for producing a nitrogen-containing fatty acid ester, characterized in that a solid zinc salt is used as a catalyst in the transesterification reaction of a saturated or unsaturated fatty acid lower alkyl ester and an alkanolamine in the presence of a catalyst. (Number of carbon atoms in the fatty acid C ₆ ~ ₂₂₎ 3. The catalyst is used in an amount of 0. 0, based on the total amount of the fatty acid lower alkyl ester and the alkanolamine.
The method according to claim 1 or 2, which is from 05 to 2.0% by weight. 4. The alkanolamine has the general formula: (In the formula, R ¹ represents a lower alkyl group, R ² represents hydrogen or a methyl group, n represents an integer of 1 to 3, m represents an integer of 1 to 10) or the general formula: The method according to any one of claims 1 to ₃ , wherein R ₃ and R ₄ represent a lower alkyl group. 5. A nitrogen-containing fatty acid ester obtained by the method according to any one of claims 1 to 4 is reacted with a quaternizing agent to quaternize the nitrogen atom, thereby containing an ester group. A method for producing a quaternary ammonium salt.