JP3229683B2 - Method for producing branched fatty acid amide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for easily producing a high-purity branched fatty acid amide from a purified branched fatty acid as a raw material.

[0002]

2. Description of the Related Art Branched fatty acids have excellent melting point depressing properties, lubricity, and compatibility with various solvents due to disorder of the crystal structure resulting from the branching of the hydrophobic group. Have. It is known that various derivatives derived from the compound have similar characteristics.

[0003] However, since branched fatty acids usually contain various impurities derived from the production method, various derivatives derived therefrom are colored or smelled. For example, branched fatty acid amides, which are derivatives of branched fatty acids, are known to be useful as bases, emulsifiers, lubricants and the like for hair or skin cosmetics (Japanese Patent Laid-Open No. 4-211).
640, JP-A-4-69321, JP-A-4-693
No. 20), branched fatty acids and tris (hydroxymethyl)
Reacting with aminomethane to form an oxazoline compound,
The branched fatty acid amide obtained by hydrolyzing it often becomes colored during the reaction or produces a bad smell during storage (Japanese Patent Application Laid-Open No. Hei 4-21640). In order to remove such adverse effects, complicated operations such as column chromatography and crystallization are required, so that much labor and cost are required.

[0004] Therefore, it has been desired to develop a method for simply and inexpensively purifying branched fatty acids and a method for easily producing high-purity branched fatty acid amides on an industrial scale.

[0005]

Means for Solving the Problems The present inventors have made intensive studies in view of the above-mentioned circumstances, and as a result, obtained by subjecting commonly available branched fatty acids to a hydrogenation treatment as a raw material, as a base for cosmetics and the like. The inventors have found that useful high-purity branched fatty acid amides can be easily obtained on an industrial scale, and have completed the present invention.

That is, the present invention firstly provides the following general formula (1)

[0007]

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(Wherein m and n each represent an integer of 0 to 20 and the sum of m and n is 1 to 20), wherein the branched fatty acid is subjected to hydrogenation treatment. It is intended to provide a method for purifying a fatty acid.

In the present invention, secondly, the branched fatty acid (1) obtained by the above hydrogenation treatment is reacted with tris (hydroxymethyl) aminomethane (3) to obtain the following general formula (4)

[0010]

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An oxazoline compound represented by the following formula (2) is obtained by obtaining an oxazoline compound represented by the formula (2), wherein m and n are as defined above, and then hydrolyzing the oxazoline compound (4).

[0012]

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(Wherein, m and n have the same meanings as described above).

M and n in the general formula (2) are each 0
And the sum of m and n is 1 to 20, preferably 10 to 16. Of these, those in which the branched methyl group of the general formula (1) is located near the center of the alkyl main chain are more preferred. Further, those in which m is an integer of 1 to 20 and n is 0 are also preferable.

The branched fatty acids represented by the general formula (1) may be used alone or in a mixture.

A particularly preferred example is isostearic acid. This is obtained, for example, as a by-product during the production of dimer acid from oleic acid, as a by-product during the production of dimer acid from tall oil obtained by decomposing kraft pulp waste liquid with sulfuric acid.

Isostearic acid is usually a mixture in which the number of carbon atoms and the position of the branched methyl group have a constant distribution, and the total number of carbon atoms is 18 (the sum of m and n is 14) is about 75%. Above, those having a total carbon number of 14 as a balance,
16 and 20 and the branched methyl group is distributed near the center of the alkyl main chain (J. Amer. Oil Chem. So
c. 51, 522, 1974; 56, 823.
A, 1979).

In the present invention, the hydrogenation treatment of the branched fatty acid (1) may be carried out by using palladium, nickel, platinum, cobalt or the like.
A conventional hydrogenation catalyst is used in an amount of 5 to 300 with respect to the branched fatty acid (1).
0 ppm is added, the hydrogen pressure is set to normal pressure to 250 kg / cm ² , the temperature is set to 100 to 250 ° C., and the reaction may be performed for 1 to 15 hours. The hydrogenation catalyst, these, carbon, alumina,
What carried 0.5 to 20% on silica, diatomaceous earth, etc. may be used. In addition, as a hydrogenation catalyst, palladium and / or nickel are particularly preferable.

By performing the above-mentioned hydrogenation treatment, the branched fatty acid (1) preferably has an iodine value of 5 or less. And by the above processing, the branched fatty acid (1)
The hue and odor are significantly improved. The branched fatty acid (1) is preferably further purified by distillation, if necessary.

Next, the method for producing the branched fatty acid amide (1) of the present invention will be described. First, tris (hydroxymethyl) aminomethane (3) is used in an amount of 0.8 to 1.2 times mol of the branched fatty acid (1) purified by the hydrogenation treatment.
In an inert solvent such as xylene, mesitylene, cumene, hexane, decane, etc.
The reaction is carried out at a temperature of 50 ° C., preferably 150 to 200 ° C. for 1 to 24 hours while removing generated water out of the system to obtain an oxazoline compound (4). Here, means for removing water out of the system include dehydration under reduced pressure, azeotropic dehydration with a solvent, and dehydration by flowing an inert gas such as N ₂ . These means may be used alone or in combination of two or more.

In the above reaction, the reaction temperature is 100 ° C.
If the temperature is less than 250 ° C., the reaction efficiency is low, so that the time efficiency is reduced. On the other hand, if the temperature exceeds 250 ° C., side reactions are likely to occur and the product is often colored.

The desired branched fatty acid amide (2) is obtained by hydrolyzing the oxazoline compound thus obtained. In the hydrolysis, water is used in an amount of 1 to 3 times, preferably 1.2 to 2 times, more preferably 1.4 to 1.6 times the moles of the oxazoline compound (4) and, if necessary, carbon number. Add lower alcohol of 1 to 6 and add 50 to 1
The reaction is carried out at 50 ° C, preferably 70-100 ° C for 1-30 hours.

The lower alcohol used here is methanol, ethanol, propanol, 2-propanol, isobutanol, sec-butanol, t-butanol.
Butanol, amyl alcohol, t-amyl alcohol, neopentyl alcohol, hexyl alcohol and the like.

When the temperature is lower than 50 ° C., the hydrolysis reaction does not substantially proceed. On the other hand, when the temperature is higher than 150 ° C., a side reaction occurs and the product tends to be colored.

In the above-mentioned hydrolysis reaction, in addition to water and a lower alcohol, an alkaline substance or an acidic substance used for ordinary hydrolysis may coexist.

The thus obtained branched fatty acid amide (2)
Has a hue G ≦ 1 and an iodine value of 1 to 5,
It can be used for various purposes as it is or after removing the solvent.
Further, pH adjustment, clay treatment, solvent washing, activated carbon treatment and the like can be appropriately performed. Further, the product can be further purified by means such as recrystallization and chromatography.

[0027]

According to the present invention, by using a branched fatty acid purified by hydrogenation as a raw material, it is possible to easily obtain a high-purity branched fatty acid amide which is free from coloring and odor and has excellent storage stability. By the method for producing a branched fatty acid amide of the present invention, the compound which is extremely useful as a base, an emulsifier, a lubricant and the like for hair and / or skin cosmetics can be easily obtained on an industrial scale.

[0028]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Purification of Isostearic Acid (1-1) Using Pd / C Catalyst In a 1-liter autoclave, isostearic acid derived from tall oil ("Century 110" manufactured by Union Camp Co., Ltd.)
5 ") (hue; G3, iodine value; 7.7) 517 g (1.
69 mol) and 5% Pd / C (50% water-containing product) (NE Chemcat's “5% Pd carbon powder water-containing product”)
10.3 g (1% by weight) was charged. The temperature was raised while stirring, and the reaction was carried out at 190 ° C. under a hydrogen pressure of 50 kg / cm ² for 2 hours. After the completion of the reaction, the catalyst was removed by pressure filtration using Radiolite Special Flow as a filter aid.
g of a colorless transparent liquid was obtained (hue: APHA60, iodine value: 1.8). This was distilled to obtain 468 g of isostearic acid (1-1) having a better hue and storage stability and a reduced iodine value (yield 90.5%). b.
p. 183 to 202 ° C./2 to 3 mmHg, hue; APHA
50, iodine value; 1.8, acid value; 185.8, average molecular weight: 302.0.

Example 2 Purification of Isostearic Acid (1-1) Using a Stabilized Ni Catalyst In a 20-liter autoclave, tall oil-derived isostearic acid ("Century 110" manufactured by Union Camp Co., Ltd.) was used.
5 ") (hue; G3, iodine value; 9.7) 10 kg (32.
69 mol) and stabilized Ni ("N-10" manufactured by Nikki Chemical Co., Ltd.)
3 ") 100 g (1% by weight) was charged. The temperature was raised while stirring, and the reaction was carried out at 190 ° C. under a hydrogen pressure of 50 kg / cm ² for 10 hours. After completion of the reaction, the catalyst was removed by pressure filtration using Radiolite Special Flow as a filter aid.
800 g of a colorless transparent liquid was obtained (hue; APHA; 20).
0, iodine value; 4.6). This was distilled to obtain 9000 g of isostearic acid (1-1) having good hue and storage stability and reduced iodine value (yield 90%). b.
p. 192 to 212 ° C / 3 to 7 mmHg, hue; APHA
50, iodine value: 3.8, acid value: 180.3, average molecular weight: 311.2.

Example 3 Preparation of N-tris (hydroxymethyl) methyl-isostearic acid amide (2-1) (a) 2-heptadecyl-4,4-bis (hydroxymethyl) -2-oxazoline (4-1) Preparation of 250 g (0.828 mol) of the isostearic acid obtained in Example 1 in a 500-ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark trap, a nitrogen inlet tube, and a stirrer, followed by purging with nitrogen. Then, 100.3 g (0.828 mol) of tris (hydroxymethyl) aminomethane (“Trisaminocrystal” manufactured by Angus Chemical Co., Ltd.) was charged. The temperature was increased while stirring at a nitrogen flow rate of 30 to 50 l / hr, and the reaction was carried out at 160 ° C. for 6 hours. Then, the calculated amount of water was distilled off to obtain 314 g of the title compound (4-1) (yield). 9
8%, hue; G1). This was a viscous liquid at 140 ° C., but solidified into a wax at room temperature. m.
p. 53-58 ° C, gas chromatography purity; 9
2.1%.

(B) Production of compound (2-1) 500 ml capacity equipped with thermometer, reflux condenser and stirrer
259 g of the compound (4-1) obtained in (A)
(0.668 mol) and 36 ml of ethanol.
The temperature was raised while stirring, and 36 g of water was added dropwise at 80 ° C.
The mixture was stirred under reflux at 89 to 92 ° C. for 6 hours, and then cooled to room temperature to obtain 323 g of a liquid crystal compound (2-1). Hue;
APHA200, iodine value; 1.2, water: 8.0%, ethanol: 8.7%, gas chromatography purity: 8
7.5% (vs solids). Even if this thing is stored for a long time,
It could be used as a cosmetic base without coloration or generation of off-flavor.

Example 4 Production of Compound (2-1) (a) Production of Compound (4-1) A 5 liter reaction vessel equipped with a thermometer, a reflux condenser, a Dean-Stark trap, a nitrogen inlet tube, and a stirrer 2600 g (8.35 mol) of isostearic acid obtained in Example 2
Was charged and replaced with nitrogen, and 1011.5 g (8.35 mol) of tris (hydroxymethyl) aminomethane ("Trisaminocrystal" manufactured by Angus Chemical Company) was charged. The temperature was raised while stirring at a nitrogen flow rate of 30 to 50 l / hr, and the reaction was carried out at 160 ° C. for 8 hours, and the calculated amount of water was distilled off to obtain 3289 g of the title compound (4-1) (yield 9).
9%, hue; APHA150). This is 140 ° C
Is a viscous liquid at room temperature, but solidified into a wax at room temperature. m. p. 53-58 ° C, gas chromatography purity; 91.1%.

(B) Production of compound (2-1) 602 g (1.5 g) of the compound (4-1) obtained in (a) was placed in a 1-liter reaction vessel equipped with a thermometer, a reflux condenser and a stirrer.
1 mol) and 82 ml of ethanol. The temperature was raised while stirring, and 81.7 g of water was added dropwise at 80 ° C. 90 ° C
After stirring at reflux for 8 hours, the mixture was cooled to room temperature to obtain 748 g of a liquid crystal compound (2-1). Hue: APHA15
0, iodine value; 2.1, moisture; 7.7%, ethanol;
9.2%, gas chromatography purity; 86.5%
(Vs. solids). This product could be used as a cosmetic base without any coloring or off-flavor even after long-term storage. Furthermore, this one 500
g of ethanol and repeated evaporation, to obtain 442 g of a desolvated product, recrystallized from 4 times the amount of hexane / ethanol (95/5 by weight), washed with hexane and washed with 50 to 6 times.
Drying under reduced pressure at 0 ° C. gave 218.4 g of compound (2-1) (yield: 52%). Hue: APHA200, iodine value;
1,1, Gas chromatography purity; 99.8%. It was a colorless pasty solid at room temperature. Acid value; 0.33, hydroxyl value; 429.0 (theoretical value; 43
4.26).

Comparative Example 1 Preparation of Compound (2-1) (a) Preparation of Compound (4-1) A 500 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark trap, nitrogen inlet tube and stirrer 250 g (0.828 mol) of isostearic acid derived from tall oil (“Century 1105” manufactured by Union Camp Co., Ltd.) (hue: G3, iodine value: 7.7), and then substituted with nitrogen to give tris (hydroxymethyl) amino 100.3 g (0.828 mol) of methane ("Trisaminocrystal" manufactured by Angus Chemical Company) was charged. The temperature was increased while stirring at a nitrogen flow rate of 30 to 50 l / hr,
The reaction was allowed to proceed at 0 ° C. for 6 hours, and the calculated amount of water was distilled off to obtain 308 g of the title compound (4-1) (96% yield, hue;
G4-5). This was a viscous liquid at 140 ° C., but solidified into a wax at room temperature. m. p. ; 53
-58 ° C, gas chromatography purity; 90.1%.

(B) Production of compound (2-1) 259 g of the compound (4-1) obtained in (a) was placed in a 500 ml reactor equipped with a thermometer, reflux condenser and stirrer.
(0.668 mol) and 36 ml of ethanol.
The temperature was raised while stirring, and 36 g of water was added dropwise at 80 ° C.
After refluxing and stirring at 89 to 92 ° C for 6 hours, the mixture was cooled to room temperature to obtain 320 g of a liquid crystal compound (2-1).
Hue: G4, iodine value: 5.7, moisture: 7.7%, ethanol: 8.4%, gas chromatography purity;
0% (vs solids). This product had a poor hue, and further increased the coloration upon storage for a long period of time, and produced an unpleasant odor. Therefore, it was difficult to use it directly as a cosmetic base.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI C07C 53/126 C07C 233/18 233/18 B01J 23/74 321X (58) Investigated field (Int.Cl. ⁷ , DB name) C07C 231 / 10 C07C 51/487 C07C 53/126 C07C 233/18

Claims (3)

(57) [Claims] 1. The following general formula (1) purified by a hydrogenation treatment: (Wherein m and n each represent an integer of 0 to 20, and the sum of m and n is 1 to 20) and tris (hydroxymethyl) aminomethane (3) And reacting with the following general formula (4): (Wherein m and n are as defined above), and then the oxazoline compound (4)
Wherein the following general formula (2) is hydrolyzed: (Wherein, m and n have the same meanings as described above). 2. The method for producing a branched fatty acid amide according to claim 1, wherein palladium and / or nickel is used as a catalyst in the hydrogenation treatment. 3. The method for producing a branched fatty acid amide according to claim 1, wherein the branched fatty acid (1) is purified so as to have an iodine value of 5 or less.