JP3338874B2 - Method for producing amines having ester group - Google Patents

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 an amine having an ester group, which is a raw material for producing a quaternary ammonium salt having an ester group.

[0002]

2. Description of the Related Art Conventionally, various softeners have been used for imparting flexibility and antistatic properties to clothes after washing. These softener compositions generally have 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 causes environmental pollution when discharged into a river.

On the other hand, a 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 the quaternary ammonium salt having an ester group, generally, a fatty acid derived from tallow and an alkanolamine such as triethanolamine are reacted. Done. For example, in JP-A-53-5108, an esteramine is obtained from a fatty acid by a reaction with an alkanolamine without using a catalyst. JP-A-56-1894
In Patent Document 6, esteramine is obtained from fatty acid by reaction with alkanolamine using p-toluenesulfonic acid as a catalyst. Further, in JP-A-63-23846, an esteramine is obtained from a fatty acid by reaction with an alkanolamine using tin powder as a catalyst. However, in these methods, esterified products of alkanolamine can be obtained in high yield, and it is necessary to purify and use aliphatics with high purity.
There is a problem that the product cost increases. Further, if the purification of the fatty acid is insufficient, the resulting esterified product is markedly colored with a small amount of impurities, and there is a disadvantage that an unpleasant odor derived from the colored product also occurs.

[0004] Fatty acid lower alkyl esters have the advantage of being more inexpensive 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 free of unpleasant odor. Esterified products of alkanolamines can be 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. German Patent DE 1,935,499 uses aluminum triisopropoxide as a catalyst for this reaction, but the conversion of the esterified product is still low and unsatisfactory. In JP-A-63-290853, an esterified product is produced from 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 or glycerin remains in the reaction product. The purity of the esteramine is very low. In WO 91/01295, a 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]

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

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, surprisingly, a specific transesterification reaction between a lower alkyl ester of a fatty acid and an alkanolamine has been found. By combining various kinds of alkali catalysts, it is found that the reactivity is markedly higher than when each of the catalysts is used alone, and the color tone of the obtained esterified product is extremely excellent. And completed the present invention. That is, according to the present invention, when a lower alkyl ester of a saturated or unsaturated fatty acid and an alkanolamine are subjected to a transesterification reaction in the presence of a catalyst, (i) a metal magnesium or a magnesium compound and (ii) an alkali metal Alternatively, there is provided a method for producing an amine 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 is a straight-chain or branched C6-C2
2 is an ester of a saturated or unsaturated fatty acid 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. Further, the 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, arachinic 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, spearic acid, azelaic acid, sebacin Acid, decamethylene dicarboxylic acid, octadecamethylene dicarboxylic acid, eicosamethylene dicarboxylic acid, fatty acid derived from tallow, fatty acid such as fatty acid derived from palm oil, methyl ester, ethyl ester, isopropyl ester, n-propyl ester, isobutyl ester, Examples include n-butyl ester and t-butyl ester. The unsaturated fatty acid may have a cis or trans stereoisomeric structure, or may be a mixture of both. Particularly, when the molar ratio of cis / trans is 25/75 to 100/0, Preferably, there is.

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

Embedded image General formula (2) R ³ R ⁴ NCH ₂ CH (OH) CH ₂ OH (2) 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, n is an integer of 1 to 3, and s is an integer of 2 to 3. T represents an integer of 0 to 2; w represents an integer of 1 to 3;
+ W = n.

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- (methyl Ethylamino) -1,2-propanediol, 3- (diisopropylamino) -1,2-propanediol, 3-
(Dibutylamino) -1,2-propynediol, N-
Methyl N-ethanol propylene diamine and the like can be 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, and a pellet. Specific examples of preferred magnesium compounds include, for example, magnesium oxide, magnesium hydroxide, besides basic inorganic magnesium compounds such as magnesium carbonate, magnesium methoxide, magnesium ethoxide, magnesium t-butoxide,
Examples 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. Preferred alkali metal compounds include lithium hydroxide, potassium hydroxide, sodium hydroxide, lithium carbonate, potassium carbonate, sodium carbonate, lithium hydrogen carbonate, and carbonate. In addition to basic inorganic alkali metal compounds such as potassium hydrogen and sodium bicarbonate, examples thereof include basic organic alkali metal compounds such as lithium acetate, potassium acetate, sodium acetate, lithium methoxide, potassium methoxide, and sodium methoxide. Can be. The alkali metal compounds can be used alone or in the form of a mixture of two or more.

The process for producing amines having an ester group 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. Preferably, the reaction is tracked by high performance liquid chromatography. The reaction is carried out in 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 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. The molar ratio with the alkali metal compound is 1 /
It can be selected in the range of 99 to 99/1. Consumption is
If the amount is less than 0.02% by weight, the reaction rate becomes extremely slow. On the other hand, if the content exceeds 2.0% by weight, the effect is not changed, but the amount of fatty acids produced as by-products increases, which is unfavorable because it adversely affects the odor. The reaction temperature depends on the type of raw materials,
Usually, it is 100-230 degreeC, Preferably it is 150-2.
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, resulting in an unpleasant odor in the obtained esterified product and its color tone is deteriorated. The reaction time is usually
It is about 5 to 15 hours. After completion of the reaction, the esterified product is dissolved in an organic solvent without a solvent or in an organic solvent according to a conventional method, and then quaternized with a normal quaternizing agent, for example, methyl chloride or alkylsulfuric acid. Obtainable.

[0012]

According to the present invention, amines having a high-quality ester group, which have extremely low unpleasant odor (offensive odor), are safe and have good color tone, can be produced in high yield. Also,
This esterified product can be quaternized with a normal quaternizing agent without removing the catalyst by filtration, and the resulting quaternary ammonium salt is safe for the natural environment and requires no special purification treatment. It can be advantageously used as a base for soft compositions, intermediate materials, fiber treatment agents, hair rinses and the like. The amine having an ester group obtained by this transesterification reaction is neutralized with a common inorganic acid or organic acid such as hydrochloric acid or a fatty acid to form a quaternary ammonium salt, whereby a flexible composition or an intermediate raw material is prepared. It can also be advantageously used as a base such as a textile treatment agent and a hair rinse.

[0013]

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 by comparing it with a standard color using a Gardner colorimeter. The sample is 40
Measured in ° C. (2) Evaluation of odor A 10 g sample was taken in a 100 ml beaker, left for 1 hour in a 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 with the following criteria. ：: The odor is very weaker than the comparative product. ：: The odor is weaker than the comparative product. Δ: Odor equivalent to the comparative product. X: The odor is stronger than the comparative product.

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

Example 2 The reaction was carried out in the same manner as in Example 1 except that 4.4 g of magnesium stearate and 0.3 g of lithium hydroxide were used as a catalyst, and a pale yellow ester of alkanolamine having a good odor was used. I got Table 1 shows the reaction results.

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 carried out in the same manner as in Example 1 except that 0.9 g of potassium carbonate was used, to obtain a pale yellow ester of an alkanolamine having good odor as crystals. Table 1 shows the reaction results.

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 carried out in the same manner as in Example 1 except that 0.5 g of methoxide was used to obtain an esterified alkanolamine having a pale yellow color and a good odor. Table 1 shows the reaction results.

Comparative Example 1 A 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 a catalyst.
In this case, the conversion of the raw material fatty acid ester was as low as 70%. Table 1 shows the reaction results.

Comparative Example 2 A 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 a catalyst.
In this case, the conversion of the raw material fatty acid ester was as low as 79%. Table 1 shows the reaction results.

Comparative Example 3 As a catalyst, aluminum triisopropoxide 3.2
A transesterification reaction was carried out in the same manner as in Example 1 except that only g was used. In this case, the conversion of the raw material fatty acid ester was as low as 75%. Table 1 shows the reaction results.

Comparative Example 4 A tallow-derived fatty acid (acid value: 20) was used without using a catalyst.
3.3, iodine value: 86.1) A transesterification reaction was carried out in the same manner as in Example 1 except that 473.8 g 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 poor.
Table 1 shows the reaction results.

[0022]

[Table 1]

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C07C 219/08 C07C 219/08 // C07B 61/00 300 C07B 61/00 300 (56) References JP-A-61-50940 ( JP, A) JP-A-60-233035 (JP, A) JP-A-59-98036 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 213/06 B01J 23/04 B01J 31/02 101 B01J 31/04 C07C 219/06 C07C 219/08 C07B 61/00 300

Claims (5)

(57) [Claims] 1. A transesterification reaction of a lower alkyl ester of a saturated or unsaturated fatty acid with an alkanolamine in the presence of a catalyst, wherein (i) a metal magnesium or a magnesium compound and (ii) an alkali metal or an alkali metal A method for producing an amine having an ester group, which is used in combination with a compound. 2. The method according to claim 1, wherein (i) a metal magnesium 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 the catalyst. 3. The amount of the catalyst to be used is in a range of 0.1 to 0.5 with respect to 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) the metal magnesium or the magnesium compound to (ii) the alkali metal or the alkali metal compound is from 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 according to claim 1, wherein the alkanolamine is represented by the following general formula (1) or (2).
Either way. General formula (1) (Wherein, R ¹ represents a lower alkyl group, R ² represents hydrogen or a methyl group, n represents 1-3, m represents 1-10, s represents an integer of 2-3, t represents 0-2, w Represents 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 lower alkyl groups)