JPH06192194A - Production of branched fatty acid amide - Google Patents

Abstract

PURPOSE:To produce the subject compound useful for cosmetic base materials, etc., without causing dangers such as environmental pollution and fire by reacting a specific branched fatty acid with tris(hydroxymethyl)aminomethane and subsequently hydrolyzing the reactional product in the absence of a solvent in a specific volume of water at a specified temperature. CONSTITUTION:A branched fatty acid of formula I ((m), (n) are integers of 0-20, but (m+n)= 1-20)(preferably isostearic acid) is reacted with tris(hydroxymethyl)aminomethane at 160 deg.C for 6hrs to produce an oxazoline compound of formula II [e.g. 2-heptadecyl-4,4-bis(hydroxymethyl)-2-oxazoline]. The oxazoline compound is mixed with water in an amount of 1-3 time moles, and hydrolyzed in the absence of a solvent at 50-150 deg.C to simply and inexpensively the objective fatty acid [e.g. N-tris(hydroxymethyl)methyl-isostearic acid amide] of formula III useful for cosmetic base materials, emusifiers, lubricants, etc.

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 branched fatty acid amide, and more particularly to a method for producing a branched fatty acid amide useful as a base, emulsifier, lubricant, etc. for hair and / or skin cosmetics.

[0002]

BACKGROUND OF THE INVENTION Several types of branched fatty acid amides have been reported to be useful as bases, emulsifiers, lubricants, etc. for hair and / or skin cosmetics (special features). Kaihei 4-21640, JP-A-4-21640
69321 and JP-A-4-69320).

As a method for producing the above branched fatty acid amide, for example, there is a method in which a branched fatty acid is reacted with tris (hydroxymethyl) aminomethane to obtain an oxazoline compound, and then the compound is hydrolyzed (Japanese Patent Laid-Open Publication No. Hei.
No. 211640).

Regarding the method of hydrolyzing the oxazoline compound, a method of using only water as a solvent (US Pat. No. 2,877,242) and a method of using a mixed solvent of a lower alcohol and water (Japanese Patent Laid-Open No. 4-224548) No. 4,211,640, etc.) are known.

However, the former method has a problem in productivity because it requires a large excess of water, which is about 20 times the weight of the oxazoline compound, whereas the latter method, on the other hand, has a problem.
In addition to the difficulty in productivity, there is a risk of ignition,
Further, when the product is used as it is for hair or skin cosmetics, there is a problem that the emulsifying property is poor and an operation such as topping is required.

Therefore, it has been desired to develop a method for easily and inexpensively producing a branched fatty acid amide useful as a base, emulsifier, lubricant, etc. for hair and / or skin cosmetics.

[0007]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above circumstances, and as a result, by hydrolyzing an oxazoline compound in the presence of a small amount of water in a specific temperature range, gelation can be achieved. Reaction has progressed sufficiently and hair and /
Further, they have found that a branched fatty acid amide suitable for use in skin cosmetics can be obtained simply and inexpensively, and have completed the present invention.

That is, the present invention provides the following general formula (2)

[0009]

[Chemical 4]

(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) By reacting with the following general formula (4)

[0011]

[Chemical 5]

After obtaining an oxazoline compound represented by the formula (wherein m and n are as defined above), the oxazoline compound is hydrolyzed to give the following general formula (1):

[0013]

[Chemical 6]

In the method for producing a branched fatty acid amide represented by the formula (wherein m and n have the same meanings as defined above), the hydrolysis is carried out in the absence of a solvent by 1 with respect to the oxazoline compound (4).
The present invention provides a method for producing a branched fatty acid amide, which comprises adding only a 3 to 3-fold molar amount of water and performing the reaction at a temperature of 50 to 150 ° C.

M and n in the general formula (2) are 0 respectively.
The sum of m and n is 1 to 20, preferably 10 to 16. Among these, those in which the branched methyl group of the general formula (2) is located near the center of the alkyl main chain are more preferable. Further, it is also preferable that m is an integer of 1 to 20 and n is 0. The branched fatty acid represented by the general formula (2) may be a single substance or a mixture thereof.

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, and as a by-product during the production of dimer acid from tall oil obtained by decomposing kraft pulp waste liquid with sulfuric acid. The isostearic acid obtained as the above-mentioned by-product is preferably further hydrogenated or peroxide-treated.

Isostearic acid is usually a mixture having a fixed distribution of carbon numbers and positions of branched methyl groups, and a total carbon number of 18 (the sum of m and n is 14) is about 75%. As described above, the balance having a total carbon number of 14,
And those having a branched methyl group distributed near the center of the alkyl main chain (J. Amer. Oil Chem. So.
c. 51, 522, 1974; 56, 82.
3A, 1979).

The method for producing the branched fatty acid amide (1) of the present invention will be described below. First, tris (hydroxymethyl) aminomethane (3) in an amount of 0.8 to 1.2 mol times that of the branched fatty acid (2) is used in the absence of solvent or in the presence of xylene, mesitylene, cumene, hexane, decane, etc. In a solvent, 100 to 250 ° C, preferably 150 to 2
At a temperature of 00 ° C, while removing the produced water out of the system,
Reaction is carried out for 1 to 24 hours to obtain an oxazoline compound (4). Here, examples of means for removing water to the outside of the system include vacuum dehydration, azeotropic dehydration with a solvent, and dehydration by flowing an inert gas such as N ₂ . These means alone,
You may use 2 or more types together.

In the above reaction, the reaction temperature is 100 ° C.
If it is lower than 250 ° C., the reaction efficiency is slow and the time efficiency is lowered. On the other hand, if it exceeds 250 ° C., a side reaction is likely to occur and the product is often colored.

The oxazoline compound (4) obtained is preferably purified by distillation, preferably molecular distillation or steaming.

Next, the oxazoline compound (4) is hydrolyzed. The hydrolysis reaction is carried out by the oxazoline compound (4)
On the other hand, water is added in an amount of 1 to 3 times, preferably 1.2 to 2 times, and more preferably 1.4 to 1.6 times. If it is less than 1-fold mole, hydrolysis is not substantially completed, and if it is more than 3-fold mole, side reaction such as cleavage of amide bond is likely to occur.

The above hydrolysis reaction can be carried out in a nitrogen atmosphere or an air atmosphere, and is carried out at 50 to 150 ° C., further 60 to 120 ° C., particularly 70 to 100 ° C., preferably 1 to 10 hours. . If it is less than 50 ° C, the hydrolysis reaction does not proceed, while if it exceeds 150 ° C, a side reaction occurs and the product is colored.

The hydrolysis reaction can be carried out only in the presence of a small amount of water as described above, because a branched fatty acid amide forms a lyotropic liquid crystal in the presence of a small amount of water, and thus a gel is formed. However, it is presumed that the hydrolysis reaction can proceed.

Branched fatty acid amide (1) thus obtained
Can be used for various purposes as it is, but can be appropriately subjected to pH adjustment, clay treatment, solvent washing, activated carbon treatment and the like. Further, it can be made into a highly pure product by means of recrystallization, chromatography or the like.

[0025]

Industrial Applicability According to the method for producing a branched aliphatic amide of the present invention, the above compound can be obtained simply and inexpensively without any risk of environmental pollution or ignition by an organic solvent. The branched fatty acid amide obtained by the present invention is extremely useful as a base, emulsifier, lubricant, etc. for hair and / or skin cosmetics.

[0026]

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

Example 1 Production of N-tris (hydroxymethyl) methyl-isostearic acid amide (1-1) (a) 2-heptadecyl-4,4-bis (hydroxymethyl) -2-oxazoline (4-1) Production of isostearic acid (2-1) (manufactured by Emery Co. "Emersul 87" in a reaction vessel having a volume of 1 liter equipped with a thermometer, a reflux condenser, a Dean Stark trap and a stirrer.
5 ") 300 g (1.055 mol) and tris (hydroxymethyl) aminomethane 127.75 g (1.055).
Mole). The temperature was raised with stirring, the reaction was carried out at 160 ° C. for 6 hours, and the calculated amount of water was distilled off to obtain 375 g of the title compound (4-1) (yield 96%). This was a viscous liquid at 140 ° C, but solidified into a wax at room temperature. m. p. 53-58 ° C, gas chromatographic purity; 91.1%.

(B) Preparation of compound (1-1) 150 g of compound (4-1) obtained in (a) in a reaction vessel having a capacity of 300 ml equipped with a thermometer, a reflux condenser and a stirrer.
(0.406 mol) was charged. With stirring at 90 ° C., 11.0 g (0.611 mol) of water was added dropwise over 15 minutes. After reacting at 90 ° C. for 6 hours, the mixture was cooled to room temperature. The reaction liquid at this time was liquid crystal-like and was transparent and uniform. Thus, 161 g of the present compound (1-1) was obtained (yield 100%). Water content: 2.2%, gas chromatography purity: 89.5%.

Example 2 and Comparative Examples 1 to 3 The hydrolysis reaction of the oxazoline compound (4-1) was
N-Tris (hydroxymethyl) methyl-isostearic acid amide (1-1) was obtained in the same manner as in Example 1 except that the solvent shown in Table 1 was used. The data on the yield, purity and appearance are also shown in Table 1.

[0030]

[Table 1]

Example 3 Production of compound (1-1) (a) Purification of isostearic acid (2-1) In a 1 liter autoclave, isostearic acid (2-1) derived from tall oil (“Century manufactured by Union Camp Co.”) was prepared.
1105 ") (hue: G3, iodine value: 7.7) 517 g
(1.69 mol) and 5% Pd / C (50% hydrous product) 1
0.3 g (1% by weight) was charged. The temperature was raised with stirring, and the reaction was carried out at 190 ° C. under a hydrogen pressure of 50 kg / cm ² for 2 hours. After 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 (2-1) having a good hue and a reduced IV (yield 90.5%). b. p. 183-202 ° C / 2-3
mmHg, hue; APHA50, iodine value; 1.8, acid value; 1
85.8, average molecular weight; 302.0.

(B) Preparation of compound (4-1) 250 g of isostearic acid obtained in (a) in a reaction vessel having a capacity of 500 ml equipped with a thermometer, a reflux condenser, a Dean Stark trap, a nitrogen introducing tube and a stirrer ( After charging 0.828 mol, 100.3 g (0.828 mol) of tris (hydroxymethyl) aminomethane (“Tris amino crystal” manufactured by Angus Chemical Co.) was charged with nitrogen substitution. The temperature was raised with stirring at a nitrogen flow rate of 30 to 50 l / hr, the reaction was carried out at 160 ° C. for 6 hours, and 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 chromatographic purity; 9
2.1%. Continue this at 160 ℃, 5mmHg 8
Time steaming was done. The total amount of steam was 1.5 times the weight of the compound (4-1). Thus, 295 g of the purified compound (4-1) was obtained. Gas chromatography purity; 95%.

(C) Production of compound (1-1) 500 ml capacity equipped with thermometer, reflux condenser and stirrer
259 g of the compound (4-1) obtained in (b) in the reaction vessel of
(0.668 mol) was charged, and 18 g of water was added dropwise at 90 ° C. The mixture was refluxed and stirred at 89 to 92 ° C for 6 hours and then cooled to room temperature to obtain 277 g of a liquid crystal compound (1-1).
Hue: APHA200, IV; 1.2, water content: 2.2
%, Gas chromatography purity; 91.3% (vs. solids). This product could be used as it is as a base for cosmetics without being colored or producing an offensive odor even after long-term storage.

Example 4 Production of compound (1-1) (a) Purification of isostearic acid (2-1) In a 1 liter autoclave, isostearic acid (2-1) derived from tall oil (“Century” manufactured by Union Camp Co., Ltd.) was used.
1105 ") (hue: G3, iodine value: 7.7) 517 g
(1.69 mol) and 5% Pd / C (50% hydrous product) 1
0.3 g (1% by weight) was charged. The temperature was raised with stirring, and the reaction was carried out at 190 ° C. under a hydrogen pressure of 50 kg / cm ² for 2 hours. After 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 product was distilled to obtain 468 g of isostearic acid having a good hue and a reduced iodine value (yield 9
0.5%). b. p. 183 ~ 202 ℃ / 2 ~ 3mmH
g, hue; APHA50, iodine value; 1.8, acid value; 18
5.8, average molecular weight; 302.0.

(B) Production of compound (4-1) 250 g of isostearic acid obtained in (a) in a reaction vessel having a capacity of 500 ml equipped with a thermometer, a reflux condenser, a Dean Stark trap, a nitrogen introducing tube and a stirrer ( After charging 0.828 mol), the atmosphere was replaced with nitrogen, and 100.3 g (0.828 mol) of tris (hydroxymethyl) aminomethane (“Trisaminocrystal” manufactured by Angus Chemical Co.) was charged. The temperature was raised with stirring at a nitrogen flow rate of 30 to 50 l / hr, the reaction was carried out at 160 ° C. for 6 hours, and the calculated amount of water was distilled off to obtain 314 g of the title compound (4-1) (yield 98 %, Hue; G1). This was a viscous liquid at 140 ° C, but solidified into a wax at room temperature. m.
p. 53-58 ° C., gas chromatographic purity; 9
2.1%. This was subsequently purified by Smith thin film distillation. First, 2.5 ml / mi at 200 ° C and 0.4 mmHg
The top cut was performed with a feed amount of n, and 255 g (yield 85%) obtained as a residue was further added at 270 ° C. and 0.4 mm.
Compound (4-1) 209 purified by distillation after bottom-cutting with Hg at a feed rate of 1.75 ml / min.
g was obtained (yield 82%). Gas chromatographic purity; 99.3%.

(C) Preparation of compound (1-1) 200 g of compound (4-1) obtained in (b) in a reaction vessel of 300 ml capacity equipped with a thermometer, a reflux condenser and a stirrer.
(0.516 mol) was charged. Then water at 90 ° C 2
8 g was dropped. After refluxing and stirring at 90 ° C. for 6 hours, the mixture was cooled to room temperature to obtain 228 g of liquid crystal compound (1-1). Hue; APHA200, iodine value; 1.2, water content;
2.2%, gas chromatographic purity; 95% (vs solids). This product could be used as it is as a cosmetic base without being colored or producing an offensive odor even after long-term storage.

Example 5 Production of compound (1-1) (a) Purification of isostearic acid (2-1) In a 20 l autoclave, isostearic acid (2-1) derived from tall oil (“Century manufactured by Union Camp Co.”) was prepared.
1105 ") (hue; G3, iodine value; 9.7) 10 kg
(32.69 mol) and stabilized Ni (manufactured by JGC Chemical “N-
103 ") 100 g (1% by weight) was charged. Then, the temperature is raised with stirring, and the hydrogen pressure is 50 kg / cm ² at 190 ° C.
And reacted for 10 hours. After completion of the reaction, the catalyst was removed by pressure filtration using Radiolite Special Flow as a filter aid to obtain 9800 g of a colorless transparent liquid (hue; A
PHA200, iodine value; 4.6). This product was distilled to give isostearic acid 90 having a good hue and a reduced iodine value.
00g was obtained (yield 90%). b. p. 192-21
2 ° C / 3 to 7 mmHg, hue: APHA50, iodine value: 3
8, acid value; 180.3, average molecular weight; 311.2.

(B) Production of compound (4-1) In a reaction vessel having a capacity of 5 liters, equipped with a thermometer, a reflux condenser, a Dean Stark trap, a nitrogen introduction tube and a stirrer (a).
After charging 2600 g (8.35 mol) of isostearic acid obtained in 1. above, nitrogen substitution was performed, and tris (hydroxymethyl) was added.
1011.5 g (8.35 mol) of aminomethane (“Tris amino crystal” manufactured by Angus Chemical Co.) was charged. The temperature was raised with stirring at a nitrogen flow rate of 30 to 50 l / hr, 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 99
%). It was a viscous liquid at 140 ° C, but solidified into a wax at room temperature. Hue; APHA150, m.p. p. ; 5
3-58 ° C, gas chromatography purity; 91.1
%. Subsequently, 300 g of this product was purified by Smith thin film distillation. First, 2.5 ml / at 200 ° C and 0.4 mmHg
Top cutting was performed with a feed amount of min to obtain 252 g (yield 84%) as a residue. Furthermore, 270 ° C,
Compound (4-1) purified as a fraction by bottom-cutting at a feed rate of 1.75 ml / min at 0.4 mmHg.
212 g was obtained (84% yield). Hue; G <1, gas chromatographic purity; 99.3%.

(C) Preparation of compound (1-1) 200 g of compound (4-1) obtained in (b) in a reaction vessel of 300 ml capacity equipped with a thermometer, a reflux condenser and a stirrer.
(0.518 mol) was charged. Then water at 90 ° C 2
8 g was dropped. After refluxing and stirring at 90 ° C. for 6 hours, the mixture was cooled to room temperature to obtain 228 g of liquid crystal compound (1-1). Hue; APHA150, iodine value; 2.1, water content;
2.2%, gas chromatography purity; 94% (vs. solids). Even if it was stored for a long period of time, it could be used as it was as a cosmetic base without being colored or generating an offensive odor.

Example 6 Production of compound (1-1) (a) Purification of isostearic acid (2-1) A tall container derived from tall oil was placed in a reaction vessel having a volume of 1 liter equipped with a thermometer, a reflux condenser, a dropping funnel and a stirrer. Isostearic acid ("Century 1105" manufactured by Union Camp)
(Hue: G3, iodine value: 7.7) 400.1 g (1.3
(1 mol) and heated to 190 ° C. to obtain DTBPO
8.0 g (ditertiary butyl peroxide) (2.0% by weight of isostearic acid) was added dropwise over 18 minutes. After reacting at 190 ° C. for 2 hours, it was cooled. this house,
388.8 g was distilled under reduced pressure to obtain 350.1 g of isostearic acid having a good hue (yield 90.0%). b.
p. 181 to 194 ° C./0.8 to 2 mmHg, hue; AP
HA70, acid value; 187.5, average molecular weight; 299.
2.

(B) Production of compound (4-1) In a reaction vessel having a capacity of 300 ml equipped with a thermometer, a reflux condenser, a Dean Stark trap, a nitrogen introduction tube and a stirrer, isostearic acid 151. 3 g (0.50
6 mol) and then nitrogen substitution, and 61.3 g (0.506 mol) of tris (hydroxymethyl) aminomethane (“Tris amino crystal” manufactured by Angus Chemical Co.)
Was charged. Then, the temperature was raised with stirring at a nitrogen flow rate of 30 to 50 l / hr, the reaction was carried out at 160 ° C. for 6 hours, and the calculated amount of water was distilled off to obtain 190.6 g of the title compound (4-1).
Was obtained (yield 98%, hue: G1). This one is 14
Although it was a viscous liquid at 0 ° C., it solidified into a wax at room temperature. m. p. 53-58 ° C, gas chromatographic purity; 91.3%. Subsequently, 300 g of this product was purified by Smith thin film distillation. First, 200 ℃, 0.4
Top cutting was performed at a feed rate of 2.5 ml / min at mmHg to obtain 249 g (yield 83%) as a residue. Further, bottom cutting was performed at 270 ° C. and 0.4 mmHg at a feed rate of 1.75 ml / min to obtain 212 g of a purified compound as a fraction (yield 85%). Hue; G <
1, gas chromatographic purity; 99.3%.

(C) Preparation of compound (1-1) 153.8 g of compound (4-1) obtained in (b) in a reaction vessel having a capacity of 300 ml equipped with a thermometer, a reflux condenser and a stirrer.
(0.4 mol) was charged. Then 22g of water at 90 ℃
(1.2 mol) was added dropwise over 15 minutes. After refluxing and stirring at 90 ° C. for 6 hours, the mixture was cooled to room temperature to obtain 175.8 g of liquid crystal compound (1-1). Hue: G = 1, water content: 2.2%, gas chromatography purity: 94.3
% (Vs. solids). It should be noted that this product could be used as it is as a cosmetic base without being colored or producing an offensive odor even after long-term storage.

Claims (1)

[Claims] 1. The following general formula (2): (Wherein m and n each represent an integer of 0 to 20 and the sum of m and n is 1 to 20) and a tris (hydroxymethyl) aminomethane (3) is reacted with the branched fatty acid. Then, the following general formula (4): After obtaining an oxazoline compound represented by the formula (wherein m and n have the same meanings as described above), the oxazoline compound is hydrolyzed to give the following general formula (1): In the method for producing a branched fatty acid amide represented by the formula (wherein m and n have the same meanings as described above), 1 to 3 times the molar amount of water is added to the oxazoline compound (4) in the absence of solvent for the hydrolysis. The method for producing a branched fatty acid amide is carried out at a temperature of 50 to 150 ° C.