JPH1192443A - Production of amine oxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound having a high conversion ratio (having a low ratio of unconverted amine) and excellent in a hue stability and storage stability by reacting a specific aliphatic tertiary amine with a specific amount of hydrogen peroxide and subsequently treating the reaction product with a specific enzyme. SOLUTION: To (A) an aliphatic tertiary amine of formula I [R<1> is a 8-36C hydrocarbon group; R<2> and R<3> are each a 1-4C alkyl or a 1-4C hydroxylalkyl; (n)=0-11] is added (B) hydrogen peroxide in an amount of 1.1-2 mol, preferably 1.2-1.6 mol, based on 1 mol of the component A in a solvent at 50-80 deg.C over 1-5 hr, and they are made to react with each other for 2-10 hr after the addition. (C) A hydrogen peroxide catabolic enzyme (e.g. catalase) in an amount of preferably 10,000-20,000,000 unit, more preferably 100,000-2,000,000 unit, based on 1 mol of the excess of the component B which has been made to react with the component A is added at 30-80 deg.C to the reaction product of the above reaction, and the mixture is treated for 1-5 hr to obtain the objective compound. The compound can be used as a surfactant for a shampoo, a detergent, a cosmetic or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a process for producing an amine oxide from an aliphatic tertiary amine and hydrogen peroxide, which obtains an amine oxide having a high conversion rate and containing almost no hydrogen peroxide remaining in the reaction mixture. The present invention relates to a production method and a method for producing an amine oxide having excellent color stability.

[0002]

2. Description of the Related Art Aliphatic tertiary amine oxides are excellent in detergency and foaming stability, and have low skin irritation, and are therefore used as surfactants in shampoos and kitchen detergents. In this case, if a large amount of unreacted amine is present, the effect of washing the amine oxide, hue, smell, skin irritation, etc. will be adversely affected. Therefore, a conversion rate of the raw material amine to amine oxide of 99% or more is desired. . However, if a large amount of hydrogen peroxide is used to increase the conversion, unreacted hydrogen peroxide remains, deteriorating performance such as detergency, and increasing skin irritation. For this reason, in order to mix as a household cleaner, the residual amount of hydrogen peroxide is preferably 0.1% or less. Therefore, there is a demand for a product which has a high conversion rate of amine oxide and a small amount of residual hydrogen peroxide. Heretofore, a method has been known in which a tertiary amine is oxidized with hydrogen peroxide in an amount as small as possible (1.0 to 1.1 mole times the theoretical amount) and an additive for promoting oxidation is added to carry out the reaction. Was common.

A typical amine oxide is 30 to 40% by weight.
However, various methods have been proposed to produce amine oxides satisfying the above conditions at this concentration. For example, JP-B-41-14089 discloses a method in which a reaction is carried out in the presence of a chelating agent, diethylenetriaminepentaacetic acid or a salt thereof.
No. 1042 discloses a method in which a reaction is carried out in the presence of sodium pyrophosphate and sodium bicarbonate.
No. 8968 discloses a method of performing a reaction in the presence of a carbonate or bicarbonate and a chelating agent, and Japanese Patent Publication No. 60-55060 discloses a method of performing a reaction in the presence of a polybasic acid such as citric acid or a salt thereof. It has been disclosed.

However, in all of these methods, hydrogen peroxide is reacted from a stoichiometric amount to about 1.1 mole times the starting amine, and in the case of an amine having a large number of carbon atoms in a hydrocarbon group, conversion to amine oxide is carried out. Conversion rate decreases. Also,
When the hydrocarbon group is branched or when an oxyethylene group is added to the hydrocarbon group, the conversion decreases due to steric hindrance. These reaction systems are 30 to 40.
Weight percent aqueous solution and the amount of hydrogen peroxide charged is close to the theoretical amount, especially in the latter part of the reaction, the chance of contact between the raw material amine and hydrogen peroxide decreases, so the reaction rate decreases and the reaction time increases. , Cause coloring of the product. Especially N, N
In the case of aliphatic tertiary amines such as -dihydroxyalkyl-alkylamines, it was difficult to produce amine oxides having good hue stability.

In order to increase the reaction rate, US Pat.
No. 432555 and U.S. Pat. No. 3,463,817 propose a method in which the reaction is carried out at a high temperature of 80 ° C. to 115 ° C. in the presence of a chelating agent such as diethylenetriaminepentaacetic acid. However, in this method, although the reaction rate is increased, the product is colored due to the high temperature. Further, when producing amine oxide from a difficult-to-react tertiary amine having a large hydrocarbon group having 18 or more carbon atoms or a highly branched hydrocarbon group, and in order to shorten the reaction time of producing amine oxide, A method is disclosed in which excess hydrogen peroxide is reacted to decompose excess hydrogen peroxide with an alkali such as sodium hydroxide or potassium hydroxide, and then the used alkali is neutralized with a mineral acid or an organic acid ( J. Soc.
t. Chem. Jpn. 28 (1), 57-65 (19
94)). However, in this method, since a large amount of the neutralized salt remains in the product, the product is easily colored by heat, light, or the like, and the hue stability of the product deteriorates. Furthermore, there is a problem in storage stability such that amine oxide is decomposed during storage. As described above, according to the conventional method, it was not possible to obtain an amine oxide which is stable to heat and light and has a high conversion rate.

[0006]

SUMMARY OF THE INVENTION The present invention relates to an aliphatic tertiary compound.
An amine oxide having a high conversion rate containing almost no unreacted aliphatic tertiary amine and excessively used hydrogen peroxide can be easily obtained from the amine, and an amine oxide having good hue stability and storage stability can be obtained. The purpose is to gain.

[0007]

That is, the present invention relates to an aliphatic tertiary amine represented by the formula (I).
A method for producing an amine oxide of the formula (II), characterized by reacting 2 mol of hydrogen peroxide and then adding a hydrogen peroxide decomposing enzyme to the reaction mixture.

[0008]

Embedded image

[0009] (R ¹ is a hydrocarbon group having 8 to 36 carbon atoms, R ²
And R ³ are an alkyl group having 1 to 4 carbon atoms or 1 carbon atom.
4 to 4 hydroxyalkyl groups, n is 0 to 11. )

[0010]

Embedded image

[0011] (R ¹ is a hydrocarbon group having 8 to 36 carbon atoms, R ²
And R ³ are an alkyl group having 1 to 4 carbon atoms or 1 carbon atom.
4 to 4 hydroxyalkyl groups, n is 0 to 11. )

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the aliphatic tertiary amine represented by the formula (I), R ¹ is a linear or branched hydrocarbon group having 8 to 36 carbon atoms, such as octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Tetradecyl group, pentadecyl group, hexadecyl group, isopalmityl group, heptadecyl group, octadecyl group, isostearyl group, nonadecyl group, eicosyl group, docosyl group, tricosyl group, tetracosyl group, hexacosyl group, octacosyl group, triacontyl group, dotriacontyl group, 2 Saturated hydrocarbon groups such as -ethylhexyl group, 2-hexyldecyl group, 2- (3-methylhexyl) -7-methyldecyl group, 2-octyldodecyl group, 2-decyltetradecyl group and 2-undecylpentadecyl group And unsaturated hydrocarbon groups such as octadecenyl group and octadecadienyl group; and mixed hydrocarbon groups such as coconut oil alkyl group, tallow alkyl group and hardened tallow alkyl group, which are mixtures thereof. If the number of carbon atoms is 7 or less, a sufficient surface active effect cannot be obtained, and those having 37 or more carbon atoms are difficult to obtain.

R ¹ (OCH ₂ CH ₂ ) _{n in the} formula (I) is an alkylpolyoxyethylene ether group in which a polyoxyethylene group is bonded to the above-mentioned alcohol having a hydrocarbon group, and n is from 0 to 11. . If n is 12 or more, a sufficient surface active effect cannot be obtained. R ² and R ³ have 1 to 1 carbon atoms
4 is a linear or branched alkyl group or a hydroxyalkyl group, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group; and examples of the hydroxyalkyl group include a hydroxyethyl group, a hydroxypropyl group, and a hydroxyalkyl group. A butyl group.

In the production method of the present invention, usually, a solvent is added to an aliphatic tertiary amine, and the solvent is added to the aliphatic tertiary amine in an amount of 1.1 to 1 per mole of the amine.
After reacting 2 mol of hydrogen peroxide with stirring, hydrogen peroxide decomposing enzyme is added to decompose the remaining hydrogen peroxide to produce a product.

As the hydrogen peroxide, a 20-90% aqueous solution is industrially available and can be used at any concentration.
Preferably, it is about 35%. The amount of hydrogen peroxide used is 1.1 to 2 mol, preferably 1.2 to 1.6 mol, per 1 mol of the aliphatic tertiary amine. If it is less than 1.1 mol, the conversion of amine oxide is low, and if it exceeds 2 mol, it becomes difficult to remove hydrogen peroxide thereafter.

As the solvent used for the reaction, water is usually used, but a water-soluble solvent such as methanol, ethanol and isopropanol or a mixed solution thereof can also be used. In the reaction of adding hydrogen peroxide, the reaction temperature is usually 50 ° C. to 80 ° C., and the addition time is 1 to 5 hours.
It is preferable to continue the reaction at the above-mentioned temperature for 2 to 10 hours after completion of the addition.

The hydrogen peroxide decomposing enzyme is generally referred to as catalase or peroxidase. Catalase is extracted from microorganisms such as Penicillium and Micrococcus and other animal livers. And purified products, commercially available products such as Ask Super 25 manufactured by Mitsubishi Gas Chemical Co., Ltd., and microcatalase manufactured by Solvay. Examples of peroxidases include those extracted and purified from wasabi and the like, and oriental yeast. POD manufactured by KK Corporation. Preferably it is catalase.

An appropriate treatment temperature for removing hydrogen peroxide from the hydrogen peroxide decomposing enzyme is 30 ° C. to 80 ° C. 30 ° C
If it is less than 80 ° C., the removal rate of hydrogen peroxide is low. If it exceeds 80 ° C., it causes deactivation of hydrogen peroxide decomposing enzyme, deoxidation reaction of amine oxide, coloring, and the like. The amount of the hydrogen peroxide decomposing enzyme to be added is preferably 10,000 to 2 per 1 mol of the excess hydrogen peroxide reacted with the aliphatic tertiary amine.
0,000,000U, more preferably 100,000U
~ 2,000,000U. U is a unit of enzyme activity, and is 1 μm per minute at 30 ° C. under the optimum conditions of the enzyme.
ol is defined as the amount that converts the substrate. 10,000
If it is less than U, it takes time to decompose hydrogen peroxide, and
If it exceeds 000U, performance such as coloring of amine oxide and storage stability tends to decrease. The treatment with hydrogen peroxide decomposing enzyme is usually performed for 1 to 5 hours.

After the decomposition of hydrogen peroxide, the amount of the hydrogen peroxide decomposing enzyme, even if it remains, is small and does not affect the hue stability or detergency. You don't have to. However, when removing, it can be removed by an ion exchange resin, an adsorbent, an ultrafiltration method or the like. When the solvent used in the reaction is unnecessary, it can be treated with hydrogen peroxide decomposing enzyme and then desolventized under reduced pressure to obtain a high concentration amine oxide.

[0020]

According to the production method of the present invention, it is possible to easily obtain an amine oxide having a high conversion rate containing almost no residual unreacted aliphatic tertiary amine and hydrogen peroxide from the aliphatic tertiary amine, The obtained amine oxide has good hue stability and storage stability. The amine oxide obtained by the production method of the present invention can be used as a surfactant in shampoos, detergents, cosmetics and the like.

[0021]

Next, the present invention will be described with reference to examples and comparative examples. In addition,% means weight%. Example 1 A four-necked reaction flask was charged with 213 g (1 mol) of N, N-dimethyldodecylamine (compound A in Table 1) and 400 g of water, and stirred and maintained at 70 ° C. while 136 g (1%) of a 35% hydrogen peroxide aqueous solution. (4 mol) was added dropwise over 3 hours, and the reaction was continued at the same temperature for 5 hours. Then hydrogen peroxide degrading enzyme (Ask Super 25: Mitsubishi Gas Chemical Co., Ltd.)
(100,000 U) was added, and the mixture was treated at 70 ° C. for 3 hours. The amount of residual hydrogen peroxide, amine oxide conversion and hue stability of this reaction product were measured by the following methods.

Measurement of Residual Hydrogen Peroxide About 1 g of a sample was accurately weighed in a conical flask with a stopper and completely dissolved by adding 10 ml of chloroform. Next, 15 ml of glacial acetic acid was added, the mixture was stoppered, and the mixture was shaken well. The entire flask was shielded from light, 2 ml of a methanol saturated solution of potassium iodide was added, and the mixture was allowed to stand at room temperature in a dark place for 30 minutes. Thereafter, 30 ml of distilled water was added to transfer free iodine to the aqueous layer, and titration was performed with a 0.01 N sodium thiosulfate standard solution until the aqueous layer became colorless. A blank test was performed in parallel, and a calculation was made according to the following equation.

[0023]

(Equation 1)

Measuring Method of Amine Oxide Conversion Rate About 0.5 g of a sample was correctly weighed in a beaker, and 70 ml of ethanol was added thereto and dissolved. The amine value (C) was determined by potentiometric titration. About 0.5 g of a sample is weighed correctly in another beaker, and 70 ml of ethanol and 3 ml of methyl iodide are added and dissolved therein. After heating at 50 ° C. for 15 minutes, an amine value (D) is obtained by potentiometric titration. It was calculated from:

[0025]

(Equation 2)

[0026]

(Equation 3)

Measurement Method of Hue Stability (APHA) The obtained amine oxide was placed in a thermostat at 50 ° C. for 100 m.
1 and sealed and stored in a glass container. Immediately after the production, the hue on the 30th and 60th days was measured according to JIS K-15576.2. The following Examples and Comparative Examples were also measured by the above method.

[0028]

[Table 1]

[0029]

[Table 2]

Example 2 297 g (1 mol) of N, N-dimethyloctadecylamine (compound B in Table 1) and 600 ml of water were placed in a four-necked reaction flask.
g, stirring, and maintaining at 70 ° C., 126 g (1.3 mol) of a 35% aqueous hydrogen peroxide solution was added dropwise over 3 hours.
Thereafter, the reaction was continued at the same temperature for 5 hours. Thereafter, 3 g (150,000 U) of Ask Super 25 was added, and the mixture was treated at 70 ° C. for 3 hours. Table 2 shows the results.

Example 3 A four-necked reaction flask was charged with 381 g (1 mol) of N, N-dimethyl-2-decyltetradecylamine (compound C in Table 1) and 150 g of ethanol, and stirred at 70 ° C. 146 g (1.5 mol) of a 35% aqueous hydrogen peroxide solution was added dropwise over 3 hours, and the reaction was continued at the same temperature for 5 hours. Then 9g of Ask Super 25 (450,00
0U) and treated for 3 hours. Table 2 shows the results.

Example 4 A four-necked reaction flask was charged with 273 g (1 mol) of N, N-dihydroxyethyldodecylamine (compound D in Table 1) and 400 g of water, and stirred at 35 ° C. while maintaining the temperature at 70 ° C.
126 g (1.3 mol) of an aqueous hydrogen peroxide solution was added dropwise over 3 hours, and the reaction was continued at the same temperature for 5 hours. Then add 3g (150,000U) of Ask Super 25 and add 7
The treatment was performed at 0 ° C. for 3 hours. Table 2 shows the results.

Example 5 345 g of N, N-dimethyldodecyltri (oxyethylene) amine (Compound E in Table 1) was placed in a four-necked reaction flask.
(1 mol) and 700 g of water were added, 126 g (1.3 mol) of a 35% aqueous hydrogen peroxide solution was added dropwise over 3 hours while stirring and maintaining the temperature at 70 ° C., and the reaction was continued at the same temperature for 5 hours. Then 3g of Ask Super 25 (150,000
0U) and treated at 70 ° C. for 3 hours. Table 2 shows the results.

Example 6 A four-necked reaction flask was charged with 213 g (1 mol) of N, N-dimethyldodecylamine (compound A in Table 1) and 400 g of water, and stirred and maintained at 70 ° C. while 35% hydrogen peroxide was added. 136 g (1.4 mol) of an aqueous solution was added dropwise over 3 hours, and the reaction was continued at the same temperature for 5 hours. Then, 16 g (800,000 U) of Ask Super 25 was added,
Time treatment was performed. Table 2 shows the results.

Comparative Example 1 Using the starting amine used in Example 1, Japanese Patent Publication No. 41-1
Amine oxide was produced according to the method disclosed in JP-A No. 4089. A four-necked reaction flask was charged with 213 g (1 mol) of N, N-dimethyldodecylamine, 1.3 g of diethylenetriaminepentaacetic acid, and 400 g of water, and stirred to obtain 70 g.
106 g of a 35% aqueous hydrogen peroxide solution (1.
1 mol), and the reaction was continued for 5 hours. Table 2 shows the results.

Comparative Example 2 Using the raw materials used in Example 3, JP-B-60-5506
Amine oxide was produced according to the method described in Japanese Patent Application Publication No. 0 (1990). A four-necked reaction flask was charged with 381 g (1 mol) of N, N-dimethyl-2-decyltetradecylamine, 1.3 g of disodium citrate, and 150 g of ethanol.
106 g of 35% aqueous hydrogen peroxide solution at 3 ° C. for 3 hours
(1.1 mol) was added dropwise, and the reaction was continued for 5 hours.
Table 2 shows the results.

Comparative Example 3 Using the raw materials used in Example 4, Japanese Patent Publication No. 60-50506
Amine oxide was produced according to the method described in Japanese Patent Application Publication No. 0 (1990). In a four-necked reaction flask, 273 g (1 mol) of N, N-dihydroxyethyldodecylamine, disodium citrate 1.
3 g and 400 g of water were charged, 106 g (1.1 mol) of a 35% aqueous hydrogen peroxide solution was added dropwise at 75 ° C. over 3 hours, and the reaction was continued at the same temperature for 5 hours. Table 2 shows the results.

Comparative Example 4 Using the raw material amine used in Example 5, Japanese Patent Publication No. 411-1
Amine oxide was produced according to the method disclosed in JP-A No. 4089. In a four-necked reaction flask, 345 g (1 mol) of N, N-dimethyldodecyltri (oxyethylene) amine, 1.3 g of diethylenetriaminepentaacetic acid and 700 g of water were placed.
Was charged, 106 g (1.1 mol) of a 35% aqueous hydrogen peroxide solution was added dropwise while maintaining the temperature at 70 ° C., and the reaction was continued at the same temperature for 5 hours. Table 2 shows the results.

Comparative Example 5 Using the starting amine used in Example 1, J. Soc. C
osmet. Chem. Jpn. 28 (1), 57-6
5 (1994) to produce an amine oxide. A four-necked flask is charged with 213 g (1 mol) of N, N-dimethyldodecylamine, and 35
39 g (0.4 mol) of a 2% aqueous hydrogen peroxide solution was added dropwise over 2 hours, and the reaction was further continued for 3 hours. Thereafter, 650 g of water was added, and while maintaining the temperature at 70 ° C., a 35% aqueous hydrogen peroxide solution 6
7 g (0.7 mol) was added dropwise over 2 hours, and the reaction was continued at the same temperature for 5 hours. Next, the temperature was lowered to 50 ° C.
5.0 g of a 5% aqueous sodium hydroxide solution was added. After the reaction at the same temperature for 3 hours, the mixture was neutralized by adding 3.1 ml of 36% hydrochloric acid. Table 2 shows the results.

Comparative Example 6 N, N-dimethyldodecylamine (213 g, 1 mol) and water (400 g) were charged into a four-necked reaction flask, and stirred.
136 g of a 35% aqueous hydrogen peroxide solution (1.
4 mol) was added dropwise over 3 hours, and the reaction was continued at the same temperature for 5 hours. Table 2 shows the results.

From Table 2, it can be seen that when an amine oxide is produced by the method of the present invention, an amine oxide having a small amount of residual hydrogen peroxide and particularly excellent in hue stability can be obtained.
In the method using diethylenetriaminepentaacetic acid (Comparative Example 1 and Comparative Example 4), the amount of residual hydrogen peroxide is about the same or slightly higher, but the hue stability is clearly inferior. In the method using disodium citrate, when a raw material amine having a branched alkyl group is used (Comparative Example 2), the residual hydrogen peroxide and color stability are poor, and the raw material amine having a hydroxyalkyl group is used. In Comparative Example 3, the amount of residual hydrogen peroxide was slightly higher, but the hue stability was clearly inferior. In the method of decomposing excess hydrogen peroxide with sodium hydroxide (Comparative Example 5), the amount of residual hydrogen peroxide is slightly higher, but the hue stability is clearly inferior. It can be seen that the method using no hydrogen peroxide degrading enzyme (Comparative Example 6) is clearly inferior in both residual hydrogen peroxide and hue stability.

Claims (2)

[Claims] 1. After reacting 1.1 to 2 mol of hydrogen peroxide per 1 mol of an aliphatic tertiary amine represented by the following formula (I), hydrogen peroxide decomposing enzyme is added to the reaction mixture. A method for producing an amine oxide, which comprises treating. Embedded image (R ¹ is a hydrocarbon group having 8 to 36 carbon atoms, R ² and R ³ are an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, and n is 0 to 11.) 2. The amount of hydrogen peroxide decomposing enzyme added is 10,000 to 1 mol of excess hydrogen peroxide remaining in the reaction mixture.
The method for producing an amine oxide according to claim 1, wherein the amount is from 0 U to 20,000,000 U.