JP3071917B2 - Method for producing nitrogen-containing fatty acid ester and method for producing quaternary ammonium salt containing ester group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 to impart 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 when discharged into a river, causes environmental pollution. On the other hand, a quaternary ammonium salt containing an ester group has biodegradability based on the ester group. As a method for producing a quaternary ammonium salt having this ester group, generally, after reacting a fatty acid derived from tallow with an alkanolamine such as triethanolamine,
A method of quaternizing with a quaternizing agent such as methyl chloride or dimethyl sulfate is employed. For example, JP-A-53-5108
In the publication, fatty acids are quaternized after reaction with alkanolamine without using a catalyst. JP-A-56-18946
In the report, quaternization is carried out after reaction with alkanolamine using p-toluenesulfonic acid with fatty acid as a catalyst.
Further, in JP-A-56-18946, quaternization is carried out after reaction with alkanolamine using tin powder with a fatty acid as a catalyst. However, in these methods, although an esterified product with an alkanolamine can be obtained in a high yield,
The esterified product has the drawback that it is extremely colored and produces an unpleasant odor, and the quaternary ammonium salt derived therefrom also has poor quality.

[0003] Fatty acid lower alkyl esters have the advantage of being cheaper and easier to purify than fatty acids. Therefore, if the fatty acid lower alkyl ester is used for the reaction, it is excellent in color tone and of high quality without unpleasant odor. Can be industrially advantageously obtained. However, the transesterification reaction between a lower alkyl ester of a fatty acid and an alkanolamine has the disadvantage that the reaction rate is slow in a non-catalytic system, and the yield of the esterified product does not increase even when a general alkali catalyst is used. Furthermore, in Japanese Patent Application Laid-Open No. 55-45898, aluminum triisopropoxide is used as a catalyst for this reaction, but the reaction rate of the esterified product is low and is not satisfactory.

[0004]

SUMMARY OF THE INVENTION The present invention provides a method for producing a high-quality esterified product having excellent color tone and no unpleasant odor in a high yield in a reaction between a lower alkyl fatty acid ester and 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 The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by reacting a fatty acid lower alkyl ester with an alkanolamine using a specific solid catalyst, The present inventors have found that a high-yield and high-quality ester can be produced, and have completed the present invention. That is, according to the present invention, carbon number 6
, A lower alkyl ester of a saturated or unsaturated fatty acid and an alkanolamine in the presence of a catalyst in the presence of a catalyst, wherein a solid catalyst containing aluminum and magnesium is used as the catalyst. A manufacturing method is provided. Further, according to the present invention, when performing a transesterification reaction between a lower alkyl ester of a saturated or unsaturated fatty acid having 6 to 22 carbon atoms and an alkanolamine in the presence of a catalyst, a solid zinc compound is used as the catalyst. A method for producing a nitrogen-containing fatty acid ester is provided. Furthermore, according to the present invention, a quaternary ammonium containing an ester group is characterized in that a quaternizing agent is reacted with the nitrogen-containing fatty acid ester obtained by the above method to quaternize the nitrogen atom. A method for producing a salt is provided.

[0006] The fatty acid lower alkyl ester used as a raw material in the present invention is a straight-chain or branched C6-C6 alkyl ester.
22 esters of saturated or unsaturated fatty acids with lower alcohols. 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 acid can be a mono- or polyhydric fatty acid. These fatty acid lower alkyl esters can be used alone or as a mixture of two or more. 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, arachiic acid, behenic acid, dimethyloctanoic acid, butylheptylnonanoic acid, and methylphenic acid. 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, ethyl ester, isopropyl ester, n-propyl ester, isobutyl ester, n-
Butyl ester, t-butyl ester and the like. The unsaturated fatty acid may have a cis or trans stereoisomeric structure, or may be a mixture of both. Particularly, when the ratio of cis / trans is (2)
(5-100) / (0-75).

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

[0008]

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[0009]

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In the above formula, R ¹ , R ³ and R ⁴ are lower alkyl, and usually have 1 to 4 carbon atoms. 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 the like.

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 an arbitrary shape such as a powder or a 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 the magnesium component present in the solid catalyst can be in various forms such as hydroxide, oxide, fatty acid salt, alkoxide, silicate, solid solution and the like. Specific examples of the solid catalyst include, for example, alumina / magnesia, a coprecipitate 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 methoxide,
Examples thereof include a mixture of aluminum ethoxide and magnesium ethoxide, a synthetic hydrotalcite, a solid solution of alumina and magnesia, a composite oxide of aluminum and magnesium, a magnesium-substituted aluminosilicate, a magnesia-containing aluminosilicate, and aluminum magnesium silicate. The ratio of aluminum and magnesium in the solid catalyst is 1 in atomic ratio (Al / Mg).
It is preferable to define the range of / 9 to 8/2. As the solid zinc compound catalyst, conventionally known solid zinc salts, for example,
In addition to zinc carbonate and zinc borate, zinc fatty acids such as zinc acetate and zinc adipate, as well as zinc oxide and zinc hydroxide can be exemplified. These can be used alone or in the form of a mixture.

The process for producing a nitrogen-containing fatty acid ester according to the present invention is carried out by placing a fatty acid lower alkyl ester and an alkanolamine in a reaction vessel, stirring the mixture, and performing 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 (in the presence) of an inert gas such as nitrogen gas, and while distilling off by-product alcohol (for a low boiling point) 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 lower alkyl fatty acid ester and the alkanolamine. If the amount of the catalyst used is less than 0.05% by weight, the reaction rate becomes extremely slow. On the other hand, if the amount exceeds 2.0% by weight, the effect is not changed. When removing, the amount of the precipitate is too large, and the yield of the product is lowered, which is not preferable. The reaction temperature is usually from 120 to 220 ° C., preferably from 15 to 20 ° C.
0-200 ° 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, resulting in an unpleasant odor in the obtained esterified product and its color tone is also deteriorated. 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 the esterified product is dissolved in an organic solvent according to a conventional method, and then quaternized with a quaternizing agent, for example, methyl chloride or alkyl sulfate. A quaternary ammonium salt can be obtained.

[0013]

According to the present invention, a high-quality nitrogen-containing fatty acid ester having extremely low unpleasant odor (offensive odor) and good color tone can be produced in high yield. Therefore, the quaternized nitrogen-containing fatty acid ester obtained in the present invention can be used as a base material for an intermediate material, a fabric softener, a fiber treatment agent, a hair rinse, etc., without requiring any special purification treatment. It is advantageously used.

[0014]

EXAMPLES Next, the present invention will be described specifically with reference to 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 taken in a Gardner test tube and measured with a Gardner colorimeter in comparison with a standard color. The sample was measured at 40 ° C. in the stock solution. (2) Evaluation of odor 10 g of a sample was placed in a 100 ml beaker, left on a water bath at 80 ° C. for 1 hour, left at room temperature for 30 minutes, and then evaluated for odor. Separately, 0.5 g of tallow fatty acid (trade name “Tallow fatty acid No. 0” manufactured by NOF CORPORATION) was placed in a 100 ml beaker and compared. ◎: Very weak odor than comparative product. …: The odor is weaker than the comparative product. Δ: Odor equivalent to that of the comparative product. ×: Stronger odor than comparative 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 inlet tube and a by-product alcohol distillation apparatus. Aluminum hydroxide / magnesium hydroxide coprecipitate (2.5MgO · Al ₂ O ₃
XH ₂ O) was charged in a nitrogen gas atmosphere, and the reaction temperature was maintained at 180 ° C. while gradually increasing the degree of vacuum to allow a by-product to react for 13 hours while distilling off by-product methyl alcohol to carry out a transesterification reaction. went. Next, the reaction product was filtered to remove the catalyst, dissolved in 350 ml of isopropyl alcohol, charged in a stainless steel autoclave, replaced under a nitrogen gas atmosphere, and then 101 g of methyl chloride (CH ₃ Cl) was introduced. Then, the mixture was reacted at 90 ° C. for 8 hours while maintaining the pressure in the system at 4.5 to 5.0 atm (gauge pressure) to perform quaternization to obtain a quaternary ammonium salt which was yellow and had a good odor. Was. Table 1 shows the reaction results.

Example 2 As a fatty acid lower alkyl ester, 593.4 g of a mixture of oleic acid methyl ester and stearic acid methyl ester (weight ratio = 90/10) was used, and as a catalyst, synthetic hydrotalcite (Mg ₆ .Al ₂ (OH)) was used. ₁₆ CO ₃ · 4H
_A transesterification reaction was carried out in the same manner as in Example 1 except that 3.6 g of 2O) was used. Next, the reaction product was filtered to remove the catalyst, dissolved in 350 ml of ethyl alcohol, and charged in a four-necked flask.
6 g was added dropwise at 50 ° C. over 1 hour, and the mixture was aged and reacted for further 3 hours to perform quaternization, thereby obtaining a quaternary ammonium salt having a yellow color and a good odor. Table 1 shows the reaction results.

Example 3 541 g of palmitic acid methyl ester was used as a lower alkyl ester of a fatty acid, and aluminum hydroxide was used as a catalyst.
Magnesium hydroxide coprecipitate (Al ₂ O ₃ .MgO solid solution)
A transesterification reaction was carried out in the same manner as in Example 1 except that 3.3 g was used. Next, 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. Table 1 shows the reaction results.

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. I got Table 1 shows the reaction results.

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. Table 1 shows the reaction results.

Example 6 In Example 2, zinc borate (2ZnO ·
Except using _{3B 2 O 3 · 3.5H 2 O} ) 3.6g was experimented in the same manner. The obtained quaternary ammonium salt was yellow and had a good odor. Table 1 shows the reaction results.

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 3.6 aluminum triisopropoxide as catalyst
A transesterification reaction was carried out in the same manner as in Example 2 except that g was used. In this case, the conversion of the raw material fatty acid ester was as low as 79%.

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

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

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

Comparative Example 5 A fatty acid derived from tallow (acid value: 20) was used without using a catalyst.
3.3, iodination: 86.1) An esterification reaction and then 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 of the quaternary ammonium salt is remarkably bad and brown,
And the odor was remarkably bad.

[0027]

[Table 1]

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI C07C 213/06 C07C 213/06 // C07B 61/00 300 C07B 61/00 300 (56) JP, A) JP-A-3-181449 (JP, A) JP-A-1-180861 (JP, A) JP-A-48-91008 (JP, A) JP-A-56-18946 (JP, A) JP-A-51-11706 (JP, A) JP-A-5-310654 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 219/06 B01J 21/10 B01J 23/06 B01J 27 / 232 B01J 31/04 C07C 213/06 C07B 61/00 300

Claims (5)

(57) [Claims] (1) When a transesterification reaction is carried out between a lower alkyl ester of a saturated or unsaturated fatty acid having 6 to 22 carbon atoms and an alkanolamine 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, which is characterized in that: 2. A transesterification reaction between a lower alkyl ester of a saturated or unsaturated fatty acid having 6 to 22 carbon atoms and an alkanolamine in the presence of a catalyst, wherein a solid zinc salt is used as the catalyst. A method for producing a nitrogen fatty acid ester. 3. The amount of the catalyst to be used is in a range of 0.
3. The method according to claim 1, wherein the amount is from 0.5 to 2.0% by weight. 4. An alkanolamine having the general formula: (Wherein, R ¹ represents a lower alkyl group, R ² represents a hydrogen or a methyl group, n represents an integer of 1 to 3, and m represents an integer of 1 to 10) or a general formula: (Wherein R ³ and R ^{4 each} represent a lower alkyl group). 5. An ester group comprising an ester group characterized by reacting a nitrogen-containing fatty acid ester obtained by the method according to claim 1 with a quaternizing agent to quaternize the nitrogen atom. For producing a quaternary ammonium salt.