JPH07138211A - Production of quaternary ammonium salt of alkanolamine ester - Google Patents

Abstract

PURPOSE:To provide a production method for obtaining a quaternary ammonium salt of an alkanolamine ester in high yield in a method consisting of transesterifying a fatty acid lower alkyl ester with an alkanolamine, then quaternizing. CONSTITUTION:A production method for obtaining a quaternary ammonium salt of an alkanolamine ester is characterized by transesterifying a saturated or unsaturated fatty acid lower alkyl ester with an alkanolamine in the presence of an alkali catalyst, treating the prepared transesterification reaction product with an acidic substance to neutralize the alkali catalyst in the transesterification reaction product and then quaternizing the resultant substance in an alcoholic solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a quaternary ammonium salt of an alkanolamine ester which is useful as a raw material for a biodegradable softening agent such as fibers and a hair treatment agent.

[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. The di-long-chain alkyldi-short-chain alkyl quaternary ammonium salt is poor in biodegradability, and therefore, when discharged into a river, causes pollution of the 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, a fatty acid derived from beef tallow is reacted with an alkanolamine such as triethanolamine, and then a quaternary ammonium chloride such as methyl chloride or dimethylsulfate is used. A method of quaternizing with an agent is adopted. For example, in JP-A-53-5108, fatty acids are quaternized after reaction with alkanolamines without using a catalyst. In JP-A-56-18946, p-toluenesulfonic acid is used as a catalyst with a fatty acid as a catalyst to react with an alkanolamine for quaternization. Further, JP-A-56
In Japanese Patent No. 18946, a tin powder is used as a catalyst with a fatty acid to react with an alkanolamine for quaternization. However, although alkanolamine esters, which are reaction products of fatty acids and alkanolamines, can be obtained in high yields by these methods, they have the drawbacks that they are markedly colored and produce an unpleasant odor. The quaternary ammonium salt was similarly inferior in quality.

The fatty acid lower alkyl ester has the advantages that it is cheaper to purify than fatty acid and can be easily produced from fats and oils. Therefore, if this lower alkyl ester is used as a raw material, it has excellent color tone and high quality without unpleasant odor. The fourth
A graded ammonium salt 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. JP-A-5
In Japanese Patent No. 5-45898, aluminum triisopropoxide is used as a catalyst for this transesterification reaction, but the reaction yield of the alkanolamine ester is low, which is not satisfactory. Furthermore, JP-A-63-2
In No. 90853, an inorganic acid, a titanium compound or a zirconium compound is used as a catalyst, but the yield of the alkanolamine ester is also low in these. Therefore, the inventors of the present invention have proposed a production method using a solid catalyst in which a magnesium compound and an alkali metal compound are combined in Japanese Patent Application No. 3-342254, but they are still unsatisfactory. On the other hand, regarding the reaction conditions other than these catalysts, conventionally, there has been adopted a method in which there is no great difference. In particular, a method of removing lower alcohol, water or the like under reduced pressure in order to accelerate the reaction is generally used, and in some cases, as described in JP-A-5-59012, it is inactive during the reaction under reduced pressure. Although some gas is added, basically, lower alcohol has been removed by decompression. There is a drawback that the yield of the esterified product is not increased by either method.

As described above, a high-quality quaternary ammonium salt having a smooth color tone and no unpleasant odor can be obtained by using a fatty acid lower alkyl ester as a raw material. In this case, it is produced by a step of transesterifying a quaternary alkyl ester and an alkanolamine in the presence of an alkaline catalyst, and a step of reacting the transesterification reaction product with a quaternizing agent. The quaternization step can be carried out by using the transesterification reaction product as it is as a reaction raw material and adding a quaternization agent to the reaction to cause a reaction. In this case, the obtained quaternization reaction product is obtained. Has a high viscosity and often causes difficulty in the quaternization reaction operation, and therefore it is a preferred method to dilute with an organic solvent and add a quaternization agent to the diluted solution to perform quaternization. From this point, the inventors of the present invention diluted the transesterification reaction product with an alcohol solvent as a reaction solvent and performed a quaternization reaction in this diluted solution. As a result, the alkanolamine ester as the reaction raw material and the reaction product were formed. As a result, a solvolysis reaction of the quaternary ammonium salt of the alkanolamine ester, which is a product, occurred, and the target quaternary ammonium salt could not be produced in good yield.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a quaternary ammonium salt in a high yield in a method in which a fatty acid lower alkyl ester and an alkanolamine are transesterified and then quaternized. The task is to provide.

[0006]

SUMMARY OF THE INVENTION The present inventors have
As a result of intensive studies to solve the above-mentioned problems, as a result, after transesterification reaction of fatty acid lower alkyl ester and alkanolamine, an acidic substance was added to the obtained transesterification reaction product, and then quaternary in an alcohol solvent. Of high quality alkanolamine ester
It was found that a high grade ammonium salt can be produced,
The present invention has been completed. That is, according to the present invention, a saturated or unsaturated fatty acid lower alkyl ester and an alkanolamine are subjected to a transesterification reaction in the presence of an alkaline catalyst, and an acidic substance is added to the obtained transesterification reaction product. A method for producing a quaternary ammonium salt of an alkanolamine ester, which comprises neutralizing an alkaline catalyst in a transesterification reaction product and then performing a quaternization treatment in an alcohol solvent.

As the alkanolamine used in the present invention, conventionally known ones, for example, those represented by the following general formula (1) are preferably used. R ¹ R ² NCH ₂ CH ₂ OH (1) In the above formula, R ¹ and R ² are hydrogen, an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkoxyalkyl group,
It is an aminoalkyl group, an N-substituted aminoalkyl group, an amidoalkyl group or an N-substituted amidoalkyl group, but both are not hydrogen, and at least one of them is a substituent other than hydrogen. In the above substituent, the alkyl group or the alkenyl group may be linear or branched. The alkyl group or alkenyl group usually has 1 to 21 carbon atoms. The alkyl group in the substituted alkyl group may be linear or branched, and the carbon number thereof is usually 1 to 21. In the aminoalkyl group and amidoalkyl group, the amino group (NH ₂ ) can be a substituted amino group substituted with a substituent such as an alkyl group or an alkoxy group.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, dodecyl group and stearyl group. Examples of the alkenyl group include a propanyl group, a hexenyl group, a dodecenyl group, an oleyl group, and an eicosenyl group. As the hydroxyalkyl group, for example, a hydroxymethyl group,
Examples thereof include a hydroxyethyl group, a hydroxybutyl group, a hydroxyoctyl group, a hydroxydodecyl group and a hydroxystearyl group. Examples of the alkoxyalkyl group include a lower alkoxy group-substituted alkyl group such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxyoctyl group, a methoxydodecyl group, an ethoxyoctyl group, and an ethoxydodecyl group.
Examples of the aminoalkyl group include aminomethyl group, aminoethyl group, aminopropyl group, aminobutyl group, aminooctyl group, aminododecyl group, N-methylaminoethyl group, N, N-dimethylaminoethyl group, N-methyl- group. N
-Methoxyaminoethyl group, N, N-dimethoxyaminoethyl group, N, N-diethylaminoethyl group, N-octylaminoethyl group, N-dodecylaminoethyl group, N
-Stearylaminoethyl group, N-methylaminopropyl group, N, N-dimethylaminopropyl group and the like can be mentioned. Examples of the amidoalkyl group include amidoethyl group, amidopropyl group, amidobutyl group, amidooctyl group, amidododecyl group, N-methylamidoethyl group,
N, N-dimethylamidoethyl group, N-methyl-N-methoxyamidoethyl group, N-ethylamidoethyl group, N
-Hexylamidoethyl group, N-octylamidoethyl group, N-dodecylamidoethyl group, N-stearylamidoethyl group and the like can be mentioned.

Specific examples of the alkanolamine preferably used in the present invention include, for example, triethanolamine, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, dimethylethanolamine, diethylethanolamine, dipropylethanolamine, diisopropyl. Examples thereof include ethanolamine, dibutylethanolamine, diisobutylethanolamine, di (sec-butyl) ethanolamine, di (t-butyl) ethanolamine, dodecylethanolamine, N-methyl-N-methoxyethylethanolamine and the like.

As the fatty acid lower alkyl ester used as a raw material in the present invention, conventionally known ones, for example, those represented by the following general formula (2) are preferably used. R ³ COOR ⁴ (2) In the above formula, R ³ is a linear or branched C 1 to C 21 alkyl or alkenyl group, and R ⁴ is a linear or branched C 1 to C 3 Is an alkyl group. This fatty acid lower alkyl ester is particularly a straight or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms and 1 to 3 carbon atoms.
Are preferably esters of lower alcohols with. The fatty acid lower alkyl ester used may be a single type or a mixture of two or more types.

Specific examples of the fatty acid lower alkyl ester used in the present invention include, for example, caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, arachidonic acid, behenic acid, dimethyloctanoic acid, butylheptylnonanoic acid, Methyl heneicosanoic acid, octenoic acid,
Decenoic acid, dodecenoic acid, octadecenoic acid, oleic acid,
Of fatty acids such as linoleic acid, linoleic acid, elaidic acid, eicosenoic acid, erucic acid, docosenoic acid, beef tallow fatty acid, coconut oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid, rapeseed oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, fish oil fatty acid Examples thereof include methyl ester, ethyl ester, isopropyl ester, n-propyl ester and the like. In addition,
The unsaturated fatty acid may be in the cis form or the trans form, or may be a mixture of both.

As the catalyst used in the present invention, an alkaline catalyst which is commonly used as an esterification catalyst is used. In this case, the alkaline catalyst includes not only a catalyst which itself shows alkalinity but also a catalyst which decomposes at a high temperature to be converted into an alkaline substance. Specific examples of the alkaline catalyst include, for example, zinc oxide, zinc hydroxide, zinc acetate, zinc carbonate, zinc oxalate, zinc laurate, zinc oleate, zinc stearate, aluminum oxide, aluminum hydroxide, aluminum acetate, carbonic acid. Aluminum, aluminum oxalate, aluminum laurate, aluminum oleate, aluminum stearate, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, hydrogen carbonate Potassium, lithium carbonate, magnesium carbonate, calcium carbonate, magnesium oxide, calcium oxide, fatty acid sodium, fatty acid potassium, fatty acid lithium, fatty acid magnesium,
In addition to calcium fatty acid, titanium, tin, zinc, silicon,
Examples thereof include metals such as aluminum, alkali metal hydroxides, alkaline earth metal hydroxides, carbonates, oxides and salts of fatty acids. These catalysts are used alone or in the form of a mixture.

In order to produce the alkanolamine ester, the fatty acid lower alkyl ester and the alkanolamine are put in a reaction vessel and stirred to carry out a transesterification reaction in the presence of an alkaline catalyst. The alkaline catalyst is in powder form,
The solution or dispersion is charged into the reactor. The amount of the catalyst used is 0.01 to 1% by weight based on the total amount of the alkanolamine and the fatty acid lower alkyl ester. In particular, it is preferable to use a mixture of an alkali metal hydroxide and an alkaline earth metal oxide, and to use 0.05 to 0.5% by weight of the total amount of the alkanolamine and the fatty acid lower alkyl ester.

The transesterification reaction is preferably carried out by circulating an inert gas such as nitrogen in the system and distilling off by-product alcohol (low boiling point) outside the reaction system. In this case, the amount of the inert gas circulated in the reaction system is 1 to 100 liters / hr, preferably 5 to 50 liters / hr, based on 1 kg of the total amount of the alkanolamine and the fatty acid lower alkyl ester. When an inert gas is used in a ratio lower than this range, the reaction progresses extremely slowly and the yield of the target product is also extremely low. Further, if it is attempted to pass an inert gas in an amount larger than this range, the pressure in the reaction system becomes too high, which is not preferable. The pressure in the reaction system is from normal pressure to slightly increased pressure (0 k
The range of g / cm ² G to ² kg / cm ² G) is preferable. Under reduced pressure, not only oxygen, which causes deterioration of alkanolamine, is easily mixed, but also the reaction proceeds while the lower alcohol locally evaporates in the heating part, so that a side reaction easily occurs. On the other hand, when the inert gas was circulated at normal pressure to slightly pressurized, the lower alcohol was gasified at the interface of the bubbles of the inert gas and moved to the gas phase to cause the reaction to proceed, so that it was overheated. No reaction occurs in the state. Therefore, a product of higher quality can be obtained as compared with the case of performing under reduced pressure. The reaction temperature is set to a temperature higher than the boiling point of the lower alcohol produced by the reaction, preferably about 50 to 150 ° C. Although the specific reaction temperature depends on the type of raw material used, it is usually 80 to
The temperature is 250 ° C, preferably 120 to 200 ° C. 25
When the reaction is carried out at a temperature higher than 0 ° C., a side reaction or a decomposition reaction occurs, an unpleasant odor is produced in the obtained esterified product, and the color tone is deteriorated. The reaction time is usually 6 to 15 hours. As the inert gas, in addition to nitrogen, helium, argon, etc., a gas inert to the reaction such as hydrogen is used.

The transesterification reaction product (alkanolamine ester) obtained as described above is prepared by adding an acidic substance thereto to neutralize at least a part of the alkaline catalyst contained in the transesterification reaction product. Quaternization processing is performed. As the acidic substance, any substance can be used as long as it can neutralize an alkaline catalyst and convert it into a neutral or acidic substance, but in general, an inorganic acid, for example, in terms of price, for example, It is preferable to use sulfuric acid, hydrochloric acid, phosphoric acid, or the like. The amount of the acidic substance added is 0.3 amount with respect to the amount required to neutralize at least a part of the alkaline catalyst in the esterification reaction product, usually 1 equivalent of the alkaline catalyst.
It is a ratio of 2 to 2 equivalents, preferably 0.5 to 1.5 equivalents.

The neutralization reaction of the alkaline catalyst in the transesterification reaction product can be carried out by adding an acidic substance to the transesterification reaction product and mixing with stirring. The reaction temperature is room temperature to 150 ° C, preferably 40 to 100 ° C. A reaction time of 0.2 to 2 hours is usually sufficient. Further, the reaction system is preferably an atmosphere of an inert gas such as nitrogen gas. The acidic substance can be added at once or gradually in the form of a concentrate or a solution diluted with a reaction-inert solvent such as water or an organic solvent.
Furthermore, this neutralization reaction can be carried out in either a batch system or a distribution system. The neutralization reaction product thus obtained can be directly subjected to a quaternization treatment, but preferably, the unreacted catalyst or neutralization salt contained in the neutralization reaction product is filtered or centrifuged. Separation by solid-liquid separation means is preferred for quaternization. By removing the unreacted catalyst and the neutralizing salt contained in the neutralization reaction product, a neutralization reaction product having excellent transparency can be obtained.

The neutralization reaction product obtained as described above is
It is reacted with a quaternizing agent according to a conventional method. At this time, the neutralized reaction product is reacted with the quaternizing agent in the form of a mixed solution or suspension with an alcohol solvent. As the alcohol solvent, monohydric alcohols such as methanol, ethanol, propanol, isopropanol and butanol, and polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol and polypropylene glycol are used. As the quaternizing agent, alkyl chloride such as methyl chloride and dialkyl sulfuric acid such as dimethyl sulfuric acid are used.

A reaction example of quaternization with methyl chloride using an alcohol solvent is shown. The weight ratio of alkanolamine ester / alcohol solvent is usually 50/50 to 97 /.
3, preferably 70/30 to 95/5. The reaction temperature is 50 to 130 ° C, preferably 70 to 100 ° C. The reaction pressure is ^{2 to} 10 kg / cm ² G, preferably 3
~ 7 kg / cm ² G. The reaction time is usually 3 to 2
It is 0 hours, preferably 5 to 15 hours. Like this 4
The alkanolamine ester is converted to the fourth
Efficient conversion to primary ammonium salt.

In the quaternization reaction, the transesterification reaction product is subjected to a neutralization reaction treatment and the alkaline catalyst contained therein is neutralized to suppress the expression of the action as an alkaline catalyst. 4 in solvent
In the quaternization treatment, the alkanolamine ester and its quaternary ammonium salt are hardly decomposed by the solvolysis reaction with the alcohol as the reaction solvent, and the alkanolamine ester itself is hardly decomposed. It is possible to obtain a quaternary ammonium salt.
By simply separating the alkaline catalyst from the transesterification reaction product by filtration or the like, it is not possible to prevent the particulate alkaline catalyst or the solution alkaline catalyst from being entrained in the filtrate, and the quaternization reaction. In the above, the solvolysis reaction of the alkanolamine ester and the quaternary ammonium salt thereof occurs, and the desired quaternary ammonium salt cannot be obtained in good yield.

An example of the solvolysis reaction of the above-mentioned alkanolamine ester or its quaternary ammonium salt is as follows. For example, the reaction proceeds as follows.

[0021]

[Chemical 1]

[0022]

[Chemical 2]

In the above formula, R represents an alkyl group or an alkenyl group.

[0024]

INDUSTRIAL APPLICABILITY According to the present invention, a transesterification reaction product obtained by subjecting a fatty acid lower alkyl ester and an alkanolamine to a transesterification reaction in the presence of an alkaline catalyst is subjected to a neutralization reaction and then a quaternization reaction. By the treatment, it is possible to suppress the solvolysis reaction of the alkanolamine ester or the quaternary ammonium salt of the alkanolamine ester and to obtain the desired quaternary ammonium salt of the alkanolamine ester in good yield. According to the present invention, the alkanolamine ester obtained by the transesterification reaction carried out in the presence of an alkaline catalyst at room temperature to slightly pressure while flowing an inert gas has an extremely low unpleasant odor (offensive odor) and a good hue. is there. Therefore, the quaternary ammonium salt obtained by quaternizing this alkanolamine ester is advantageous as an intermediate raw material, a fabric softening agent, a fiber treating agent, and further as a hair rinse base, etc., without requiring a special purification treatment. Used. The quaternary ammonium salt of the alkanolamine ester obtained by the present invention does not deteriorate the environment because it has excellent biodegradability.

[0025]

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 an APHA tube, and the hue was determined using an APHA colorimetric standard tube. (2) Evaluation of odor Take 10 g of the sample in a 100 ml beaker and
It was left for 1 hour on a hot water bath at 0 ° C. and left for another 30 minutes at room temperature, and then the odor was evaluated. In another 100 ml beaker, 0.5 g of beef fatty acid (made by NOF Corporation, “Beef Fatty Acid 0
No. ”) and compared and contrasted according to the following criteria. ◯: The odor is weaker than that of the comparative product. Δ: The odor is similar to that of the comparative product. ×: The odor is stronger than that of the comparative product.

Example 1 (A-1) (Transesterification Reaction) In a four-necked flask equipped with a stirrer, a thermometer, a gas introduction tube and a by-product alcohol distillation device, 3000 g of oleic acid methyl ester and N-methyl ester were introduced. 600 g of diethanolamine
And 1.8 g of magnesium oxide as a catalyst and 19% by weight
13 g of an aqueous potassium hydroxide solution was charged under a nitrogen atmosphere. The temperature of the reaction system was raised while introducing nitrogen gas at a rate of 108 liters / hr, and the pressure in the system was set to 0.5 to 1.0 atm (gauge pressure) at a reaction temperature of 190 ° C. to produce a by-product. The reaction was carried out for 8 hours while distilling off methanol to obtain a pale yellow alkanolamine ester having a good odor with a yield of 97%. The results of this reaction are shown in Table 1.

(A-2) (Transesterification reaction) In a four-necked flask equipped with the same device as in the transesterification reaction of (A-1), 30 oleic acid methyl ester was added.
12 g, N-methyldiethanolamine (600 g), magnesium oleate (26.4 g) and potassium oleate (14.4 g) as a catalyst were charged, and the reaction was carried out under the same conditions as in the case of (A-1). An alkanolamine ester was obtained. The reaction results are shown in Table 1.

(A-3) (Transesterification reaction) Stearic acid methyl ester 3 was placed in a four-necked flask equipped with the same device as in the case of the transesterification reaction of (A-1).
020 g, 600 g of N-methyldiethanolamine, 1.8 g of magnesium oxide and 13 g of a 19 wt% potassium hydroxide aqueous solution were charged as a catalyst, the reaction was performed under the same conditions as in (A-1), and the reaction product was white and had a good odor. Alkanolamine ester was obtained. The reaction results are shown in Table 1.

(A-4) (Transesterification reaction) Palmitic acid methyl ester 2 was placed in a four-necked flask equipped with the same device as in the transesterification reaction of (A-1).
754 g, 600 g of N-methyldiethanolamine, 1.8 g of magnesium oxide and 13 g of a 19 wt% potassium hydroxide aqueous solution were charged as a catalyst, the reaction was performed under the same conditions as in (A-1), and the reaction product was white and had a good odor. Alkanolamine ester was obtained. The reaction results are shown in Table 1.

(A-5) (Transesterification reaction) The same amount of raw materials was charged in the same reactor as in the transesterification reaction of (A-1), and 300 mm for 2 hours after the initiation of the reaction.
The transesterification reaction was carried out with Hg and then 30 mmHg under reduced pressure for 10 hours to obtain a pale yellow alkanolamine ester having a slight odor. The reaction results are shown in Table 1.

(A-6) (Transesterification reaction) The same amount of raw materials was charged in the same reaction apparatus as in the transesterification reaction of (A-1), and 300 mm for 2 hours after the initiation of the reaction.
Under a reduced pressure of Hg, the pressure was reduced to 30 mmHg while flowing 10 l / hr of nitrogen gas, and the esterification reaction was carried out for 10 hours to obtain a pale yellow alkanolamine ester with a slight odor. The reaction results are shown in Table 1.

[0032]

[Table 1]

(B-1) (Neutralization reaction) A 1-liter four-necked flask equipped with a stirrer, a thermometer, and a N ₂ gas inlet tube was used to produce the transesterification reaction obtained in (A-1) above. 750g of material was charged. After substituting the system with N ₂ gas, the system was heated to 50 to 55 ° C., and then 3.5 g of 43% sulfuric acid (1.0 times equivalent to the catalyst) was added. After stirring at the same temperature for 0.5 hours, 3 g of the filter aid was mixed,
At 55 to 60 ° C., N ₂ pressure filtration was performed using a filter paper to separate the catalyst, and 733 g of a filtrate containing an alkanolamine ester was obtained.

(C-1) (Quaternization reaction) 525 g of the filtrate obtained in (B-1) and ethanol 46
After charging g in an autoclave and replacing the inside of the system with N ₂ gas, 60 g of methyl chloride was introduced, and 3 to 7 k at 90 ° C.
Reaction was carried out at g / cm ² G for 10 hours to obtain a quaternary ammonium salt of an alkanolamine ester.

Example 2 In the neutralization reaction of (B-1) shown in Example 1, 750 g of the transesterification reaction product obtained in (A-2) above.
Was used, and quaternary ammonium salt of alkanolamine ester was obtained in the same manner except that 2.4 g of 43% sulfuric acid (0.7 times equivalent ratio to the catalyst) was used.

Example 3 In the neutralization reaction of (B-1) shown in Example 1, 750 g of the transesterification reaction product obtained in the above (A-4)
Was used, and quaternary ammonium salt of alkanolamine ester was obtained in the same manner except that 4.8 g of 43% sulfuric acid (1.3 times equivalent ratio to the catalyst) was used.

Example 4 In the neutralization reaction of (B-1) shown in Example 1, 35
A quaternary ammonium salt of an alkanolamine ester was obtained in the same manner except that 4.3 g of phosphoric acid (1.5 equivalent ratio based on the catalyst) was used.

Example 5 In the neutralization reaction of (B-1) shown in Example 1, 35
A quaternary ammonium salt of an alkanolamine ester was obtained in the same manner except that 3.2 g of hydrochloric acid (1.0 equivalent ratio to the catalyst) was used.

Example 6 In the neutralization reaction of (B-1) shown in Example 1, 35
% Alkanolamine ester quaternary ammonium salt was similarly used except that 3.2 g of hydrochloric acid (1.0 equivalent ratio to the catalyst) was used and the catalyst was not separated by filtration from the neutralization reaction product. Obtained.

Comparative Example 1 A quaternary ammonium salt of an alkanolamine ester was obtained in the same manner except that the neutralization reaction of (B-1) shown in Example 1 was omitted.

The quaternary ammonium salt of the alkanolamine ester obtained in Examples 1 to 6 and Comparative Example 1 was analyzed, and the alkanolamine ester solvolysis rate (in Table 2, shown as the ester degradation rate). ) Was investigated. The results are shown in Table 2. The solvolysis rate (ester decomposition rate) of the alkanolamine ester was calculated by the following formula. Degradation rate of ester (%) = (A−B) / A × 100 A: Weight of alkanolamine ester before quaternization B: Weight of alkanolamine ester portion in quaternized alkanolamine ester

[0042]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiro Yonejima 1-3-7 Head Office, Sumida-ku, Tokyo Lion Stock Company

Claims (3)

[Claims] 1. A saturated or unsaturated fatty acid lower alkyl ester and an alkanolamine are subjected to a transesterification reaction in the presence of an alkaline catalyst, and an acidic substance is added to the obtained transesterification reaction product to form a transesterification reaction. After neutralizing the alkaline catalyst in the product,
A method for producing a quaternary ammonium salt of an alkanolamine ester, which comprises performing a grading treatment. 2. The acidic substance is at least one selected from sulfuric acid, hydrochloric acid and phosphoric acid, and the amount thereof is 0.3 to 2 times the equivalent ratio with respect to the alkaline catalyst. Method. 3. The alkanolamine is represented by the general formula R ¹ R ² NCH ₂ CH ₂ OH (wherein R ¹ and R ² are hydrogen, an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkoxyalkyl group, an aminoalkyl group, An N-substituted aminoalkyl group, an amidoalkyl group or an N-substituted amidoalkyl group, at least one of which is a substituent other than hydrogen), and the fatty acid lower alkyl ester has the general formula R ³ COOR ⁴ (In the formula, R ³ is an alkyl group or an alkenyl group, and R ⁴
Is a lower alkyl group), and the method according to claim 1 or 2.