JPH06228063A - Production of amines having ester group - Google Patents

Abstract

PURPOSE:To obtain a method for producing high-quality esterified substances excellent in color tone without any unpleasant smell in high yield in a method for reacting a lower alkyl ester of a fatty acid with an alkanolamine. CONSTITUTION:This method for producing amines having ester group is characterized by combining (i) metallic magnesium or a magnesium compound with (ii) an alkaline metal or an alkaline metallic compound in subjecting a lower alkyl ester of a saturated or an unsaturated fatty acid and an alkanolamine to the transeterification in the presence of a catalyst.

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 amines having an ester group, which are raw materials for producing a quaternary ammonium salt having an ester group.

[0002]

2. Description of the Related Art Conventionally, various softening agents 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 thus 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 an amine having an ester group, which is a raw material for producing a quaternary ammonium salt having an ester group, a beef tallow-derived fatty acid is generally reacted with an alkanolamine such as triethanolamine. Done. For example, in JP-A-53-5108, ester amine is obtained from fatty acid by reaction with alkanolamine without using a catalyst. JP-A-56-1894
In JP-A-6, an ester amine is obtained from a fatty acid by reaction with an alkanolamine using p-toluenesulfonic acid as a catalyst. Furthermore, in JP-A-63-23846, an ester amine is obtained from a fatty acid by reaction with an alkanolamine using tin powder as a catalyst. However, in these methods, the esterified product of the alkanolamine is obtained in high yield, and since it is necessary to purify the aliphatic to high purity before use, when considering industrial production,
There is a problem that the product cost becomes high. Further, if the fatty acid is not sufficiently purified, the obtained esterified product is markedly colored with a small amount of impurities, and an unpleasant odor derived from this colored product is also generated.

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 the fatty acid lower alkyl ester is used for the reaction, the color tone is excellent and there is no unpleasant odor. Esterified products of various alkanolamines can be 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. German Patent DE 1,935,499 uses aluminum triisopropoxide as a catalyst for this reaction, but the reaction rate of the esterified product is still low, which is not satisfactory. In JP-A-63-290853, an esterified product is produced from a glyceride and an alkanolamine by using an inorganic acid or a titanium compound or a zirconium compound as a catalyst, but a large amount of glyceride, glycerin, etc. remains in the reaction product. The purity of ester amines is very low. In WO 91/01295, long-chain fatty acid methyl ester (2 mol) is reacted with triethanolamine (1 mol) using sodium methylate as a catalyst to form an ester as a mixture of monoester, diester and triester. The compound is obtained in high yield. However, when an equimolar long-chain fatty acid lower alkyl ester is reacted with the hydroxyl group of alkanolamine, the reaction rate is low even with a sodium-based catalyst, which is not satisfactory.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a method for reacting a fatty acid lower alkyl ester with an alkanolamine to produce a high-quality esterified product having an excellent color tone and having no unpleasant odor in a high yield. The task is to do.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have surprisingly identified a specific transesterification reaction of a fatty acid lower alkyl ester with an alkanolamine. By combining different types of alkali catalysts, it was found that the reactivity was significantly increased compared to when each of the catalysts was used alone, and the color tone of the obtained esterified product was very excellent. The present invention has been completed and the present invention has been completed. That is, according to the present invention, when a transesterification reaction of a saturated or unsaturated fatty acid lower alkyl ester and an alkanolamine in the presence of a catalyst, the catalyst is (i) metal magnesium or a magnesium compound and (ii) an alkali metal Alternatively, there is provided a method for producing amines having an ester group, which is characterized by using an alkali metal compound in combination.

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 2
It is an ester of a saturated or unsaturated fatty acid of 2 and a lower alcohol. In this case, the fatty acid can be a polyhydric fatty acid. The lower alkyl group (alcohol residue) in the fatty acid lower alkyl ester is preferably an alkyl group having 1 to 4 carbon atoms. The fatty acid lower alkyl ester 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, methylheneicosanoic acid, hexenoic acid, octenoic acid, decenoic acid, dodecenoic acid, octadecenoic acid (oleic acid), eicosenoic acid, docosenoic acid (erucic acid), adipic acid, speric acid, azelaic acid, sebacine Acid, decamethylenedicarboxylic acid, octadecamethylenedicarboxylic acid, eicosamethylenedicarboxylic acid, fatty acid derived from beef tallow, fatty acid methyl ester such as palm oil derived fatty acid, ethyl ester, isopropyl ester, n-propyl ester, isobutyl ester, Examples thereof include n-butyl ester and t-butyl ester. The unsaturated fatty acid may have a stereoisomeric structure of cis isomer or trans isomer, or a mixture of the two. However, in particular, the cis isomer / trans isomer has a molar ratio of 25/75 to 100/0. Preferably there is.

As the alkanolamine used in the present invention, conventionally known ones, for example, those represented by the following general formulas (1) and (2) are preferably used. General formula (1)

[Chemical 1] In the general formula ^{(2) R 3 R 4 NCH} 2 CH (OH) CH 2 OH (2) the ^{formula, R 1, R 3, R} 4 is lower alkyl, the number of carbon atoms is a normal 1-4 . R ² is hydrogen or a methyl group. m is an integer of 1 to 10, n is 1 to 3, and s is an integer of 2 to 3. Further, t represents an integer of 0 to 2, w represents an integer of 1 to 3, and t
+ W = n.

Specific examples of the alkanolamine 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- (methyl) Ethylamino) -1,2-bropandiol, 3- (diisopropylamino) -1,2-propanediol, 3-
(Dibutylamino) -1,2-propynediol, N-
Methyl N-ethanol propylene diamine etc. are mentioned.

The present invention is characterized in that (i) metallic magnesium or a magnesium compound and (ii) an alkali metal or an alkali metal compound are used in combination as a catalyst. The shape of the catalyst can be any shape such as an aqueous solution, a powder, or a pellet. Specific examples of preferable magnesium compounds are, for example, magnesium methoxide, magnesium ethoxide, magnesium t-butoxide, in addition to basic inorganic magnesium compounds such as magnesium oxide, magnesium hydroxide and magnesium carbonate.
Examples thereof include basic organic magnesium compounds such as magnesium acetate, magnesium oleate, and magnesium stearate. The magnesium compounds can be used alone or in the form of a mixture. Examples of the alkali metal include metal lithium, metal sodium, and metal potassium, and preferable alkali metal compounds include lithium hydroxide, potassium hydroxide, sodium hydroxide, lithium carbonate, potassium carbonate, sodium carbonate, lithium hydrogen carbonate, and carbonic acid. In addition to basic inorganic alkali metal compounds such as potassium hydrogen and sodium hydrogencarbonate, basic organic alkali metal compounds such as lithium acetate, potassium acetate, sodium acetate, lithium methoxide, potassium methoxide and sodium methoxide are exemplified. You can The alkali metal compound can be used alone or in the form of a mixture of two or more kinds.

The method for producing amines having an ester group according to 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 reaction is preferably traced by high performance liquid chromatography. The reaction is carried out in 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 amount of the catalyst used is usually 0.02 to 2.0% by weight, preferably 0.04 to 1.0% by weight, based on the total amount of the fatty acid lower alkyl ester and the alkanolamine, and the magnesium compound and the alkali metal or The molar ratio with the alkali metal compound is 1 /
It can be selected in the range of 99 to 99/1. The amount used
If it is less than 0.02% by weight, the reaction rate becomes extremely slow. On the other hand, if the amount exceeds 2.0% by weight, the effect does not change, but the amount of fatty acid produced as a by-product increases and the odor is adversely affected. The reaction temperature depends on the type of raw material,
Usually, it is 100 to 230 ° C., preferably 150 to 2
It is 00 ° C. If the reaction temperature is lower than 100 ° C., the reaction rate becomes extremely slow, and if it exceeds 230 ° C., a side reaction occurs, an unpleasant odor is produced in the obtained esterified product, and the color tone is deteriorated. The reaction time is usually
It takes about 5 to 15 hours. After completion of the reaction, this esterified product is dissolved in an organic solvent without solvent according to a conventional method, and then quaternized with a usual quaternizing agent such as methyl chloride or alkyl sulfuric acid to give a quaternary ammonium salt. Obtainable.

[0012]

EFFECTS OF THE INVENTION According to the present invention, it is possible to produce a high-quality amine having an ester group, which has an extremely low unpleasant odor (offensive odor), is safe, and has a good color tone. Also,
This esterified product can be quaternized with a usual quaternizing agent without removing the catalyst by filtration, and the obtained quaternary ammonium salt is safe for the natural environment and does not require any special purification treatment. It can be advantageously used as a base for softening compositions, intermediate raw materials, fiber treatment agents, hair rinses and the like. In addition, the amines having an ester group obtained by this transesterification reaction are neutralized with a usual inorganic acid or organic acid such as hydrochloric acid or fatty acid to form a quaternary ammonium salt, whereby a flexible composition or an intermediate raw material is obtained. It can also be advantageously used as a base such as a fiber lengthening agent and a hair rinse.

[0013]

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 taken in a Gardner test tube and measured by a Gardner colorimeter in comparison with a standard color. The sample is 40 as a stock solution.
It was measured at ° C. (2) Evaluation of Odor 10 g of a 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 fatty acid (manufactured by NOF Corporation, trade name “beef fatty acid No. 0”) was placed in a 100 ml beaker and compared and compared according to the following criteria. A: The odor is much weaker than that of the comparative product. Good: The odor is weaker than that of the comparative product. Δ: The odor is equivalent to that of the comparative control product. X: The odor is stronger than that of the comparative control product.

Example 1 497.6 g (1.68 mol) of oleic acid methyl ester and N were placed in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a by-product alcohol distillation device.
In a nitrogen gas atmosphere, 100 g (0.8 mol) of methyldiethanolamine, 0.3 g of magnesium oxide as a catalyst, and 1.05 g of a 40 wt% potassium hydroxide aqueous solution (0.42 g as potassium hydroxide) were charged. Then 1
After raising the reaction temperature to 80 ° C. and distilling off the by-product methyl alcohol, the pressure was reduced to 300 mmHg and reacted for 2 hours. Next, while maintaining the reaction temperature at 180 ° C, 100 m
The transesterification reaction was carried out at mHg for 2 hours and at 20 mmHg for 6 hours to obtain an alkanolamine esterified product having a light yellow color and a good odor. The reaction results are shown in Table 1.

Example 2 The same reaction as in Example 1 was carried out except that 4.4 g of magnesium stearate and 0.3 g of lithium hydroxide were used as the catalyst, and an esterified product of an alkanolamine having a pale yellow color and a good odor was obtained. Got The reaction results are shown in Table 1.

Example 3 500.6 g (1.64 mol) of stearic acid methyl ester and 0.9 g of magnesium ethoxide as a catalyst,
The reaction was performed in the same manner as in Example 1 except that 0.9 g of potassium carbonate was used, to obtain an alkanolamine esterified product in the form of crystals that was pale yellow and had a good odor. The reaction results are shown in Table 1.

Example 4 497.6 g (1.68 mol) of oleic acid methyl ester, 100 G (0.84 mol) of 3- (dimethylamino) -1,2-propanediol and 0.3 g of magnesium acetate as a catalyst, sodium The reaction was performed in the same manner as in Example 1 except that 0.5 g of methoxide was used to obtain an alkanolamine esterified product having a pale yellow color and a good odor. The reaction results are shown in Table 1.

Comparative Example 1 The transesterification reaction was carried out in the same manner as in Example 1 except that only 0.6 g of magnesium oxide was used as the catalyst.
In this case, the reaction rate of the raw material fatty acid ester was as low as 70%. The reaction results are shown in Table 1.

Comparative Example 2 The transesterification reaction was carried out in the same manner as in Example 1 except that only 0.6 g of sodium hydroxide was used as the catalyst.
In this case, the reaction rate of the raw material fatty acid ester was as low as 79%. The reaction results are shown in Table 1.

Comparative Example 3 Aluminum triisopropoxide 3.2 as a catalyst
The transesterification reaction was performed in the same manner as in Example 1 except that only g was used. In this case, the reaction rate of the raw material fatty acid ester was as low as 75%. The reaction results are shown in Table 1.

Comparative Example 4 Fatty acid derived from beef tallow (acid value: 20) was used without using a catalyst.
The transesterification reaction was performed in the same manner as in Example 1 except that 473.8 g of 3.3, iodine value: 86.1) was used. In this case, the reaction rate of the raw material fatty acid ester was as good as 97%, but the color tone was brown and the odor was extremely bad.
The reaction results are shown in Table 1.

[0022]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C07C 213/06 H 7457-4H 219/08 7457-4H // C07B 61/00 300

Claims (5)

[Claims] 1. When performing a transesterification reaction of a saturated or unsaturated fatty acid lower alkyl ester and an alkanolamine in the presence of a catalyst, the catalyst (i) metal magnesium or magnesium compound and (ii) alkali metal or alkali metal A method for producing an amine having an ester group, which comprises using a compound in combination. 2. The method according to claim 1, wherein (i) a magnesium metal or a basic inorganic or organic magnesium compound and (ii) an alkali metal or a basic inorganic or organic alkali metal compound are used in combination as a catalyst. 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, wherein the molar ratio of (i) metal magnesium or magnesium compound to (ii) alkali metal or alkali metal compound is 1/99 to 99/1. 4. The method according to claim 1, wherein the reaction temperature is 100 ° C. to 230 ° C. 5. The alkanolamine is represented by the following general formula (1) or (2).
Either way. General formula (1) (In the formula, R ¹ represents a lower alkyl group, R ² represents hydrogen or a methyl group, n is 1 to 3, m is 1 to 10, s is an integer of 2 to 3, t is 0 to 2, w Is an integer of 1 to 3, and t + w
= N) General formula (2) R ³ R ⁴ NCH ₃ CH (OH) CH ₂ OH (wherein R ³ and R ⁴ represent a lower alkyl group)