JPH10231277A - Production of amide group-containing surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To economically efficiently obtain the subject product excellent in hue even in long-term preservation, by adding an antioxidant and treating the product with it in producing an amide group-containing surfactant by reacting a condensation product with a monohaloalkyl carboxylic acid or its salt. SOLUTION: A higher fatty acid of the formula R<2> COOR<3> (R<2> is an alkyl, etc.; R<3> is H, a 1-3C alkyl, etc.) such as caprylic acid or its ester is reacted with a polyamine such as an alkylene polyamine in the molar ratio of 1:1 to 1:2 to give an amino group-containing derivative of formula I (Z is a 2-4C alkylol), which is reacted with 1-3mol of a monohaloalkyl carboxylic acid of the formula XR<1> COOY (X is a halogen; R<1> is a 1-4C alkylene; Y is an alkali metal) or its salt such as monochloroacetic acid to give an amidoamino acid of formula II. In the reaction, 0.001-5wt.% based on the fatty acid of an antioxidant such as dibutylhydroxytoluene is added to the reaction mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an amide group-containing surfactant. More specifically, the present invention relates to a method for producing an amide group-containing surfactant such as an amide amino acid or betaine which has excellent hue and odor even when stored for a long time and has excellent storage stability.

[0002]

2. Description of the Related Art In recent years,
Surfactants used in detergents, etc. are required to have excellent properties such as biodegradability, safety, and low irritation to the skin, in addition to surface activity. Amide group-containing surfactants such as imidazoline surfactants (also called amide amino acid surfactants) and betaine surfactants are known as surfactants to be filled.

Amide group-containing surfactants such as imidazoline surfactants and betaine surfactants have excellent foaming power,
In addition to detergency, it is characterized by extremely low irritation to the eyes and skin. In recent years, its use as a major component such as a hypoallergenic shampoo has been increasing. One of the qualities required for such an amide group-containing surfactant is hue and odor.

An amide group-containing surfactant can be produced by subjecting a fatty acid or an ester thereof to a polyamine by dehydration condensation, followed by an addition reaction of a monohaloalkylcarboxylic acid or a salt thereof. The fatty acids or esters generally used in such reactions are based on natural raw materials derived from coconut oil or palm kernel oil and contain impurities such as unsaturated components, and can be stored for a long time. Then, oxidation of impurities etc. may occur, and the color tone and odor after storage may deteriorate,
The improvement is desired.

[0005] In order to remove such impurities such as unsaturated components, there is generally a method of saturating the unsaturated components by hydrogenation. However, such a method is complicated in equipment and is economically disadvantageous. It is also impossible to completely saturate.

Accordingly, an object of the present invention is to provide a method for economically and efficiently producing an amide group-containing surfactant which has a good hue and a good odor even when stored for a long period of time.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found a method for producing an amide group-containing surfactant which has solved the above problems, and have completed the present invention. That is,
In the present invention, after a fatty acid or an ester thereof and a polyamine are subjected to a condensation reaction to obtain an amino group-containing fatty acid derivative, a general formula (I) XR ¹ COOY (I) (where X represents a halogen atom and R ¹ Represents a linear or branched alkylene group having 1 to 4 carbon atoms, and Y represents H or an alkali metal.) A monohaloalkylcarboxylic acid or a salt thereof is reacted to produce an amide group-containing surfactant. An object of the present invention is to provide a method for producing an amide group-containing surfactant, which comprises adding an antioxidant.

[0008]

Embodiments of the present invention will be described below in detail. The fatty acid or ester thereof used in the present invention may be a compound represented by the following general formula (II): R ² COOR ³ (II) (wherein R ² is a linear or branched alkyl group, alkenyl group or hydroxyalkyl group having 7 to 23 carbon atoms) Represents a group, R ³
Represents a residue obtained by removing one acyloxy group from H or an alkyl group having 1 to 3 carbon atoms or glyceride. )) Or higher esters thereof. Specifically, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid and coconut oil fatty acids, cottonseed oil fatty acids, corn oil fatty acids, Vegetable or animal oil fatty acids such as tallow fatty acid, babas oil fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, olive oil fatty acid, whale oil fatty acid, and their methyl esters, ethyl esters, glycerides, and mixtures thereof Is exemplified. Among these, R ³
Is preferably H or a higher fatty acid or a lower alkyl ester thereof which is an alkyl group having 1 to 3 carbon atoms, and particularly preferably, R ² is a linear alkyl group having 9 to 17 carbon atoms and R ³
Is H or CH ₃ , or a fatty acid derived from coconut oil or an ester thereof.

The polyamine used in the present invention includes an alkylene polyamine, a hydroxyalkyl polyamine, an N-hydroxy lower alkyl alkanolamine and the like. Examples of the alkylene polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine,
Examples of the hydroxyalkylpolyamine include aminoethylethanolamine, aminoethylpropanolamine, aminoethylbutanolamine, N-β-hydroxypropylpropylenediamine, hydroxyethyldiethylenetriamine, and hydroxyethyltriethylenetetramine. And N-hydroxy-lower alkylalkanolamines such as N-β-hydroxyethylethanolamine.

Among these, the compounds represented by the general formula (III) or (IV)
Is preferred. H ₂ NC ₂ H ₄ NHZ (III) (wherein, Z represents an alkylol group having 2 to 4 carbon atoms.)

[0011]

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(Wherein R ⁴ and R ⁵ are the same or different and each represent an alkyl group having 1 to 3 carbon atoms, and a represents a number of 2 to 3.) A diamine represented by the general formula (III) Is aminoethylethanolamine (H ₂ NC ₂ H ₄ NHC ₂ H ₄ OH) as the general formula (IV)
As the diamine represented by, dimethylaminopropylamine is particularly preferred.

In the present invention, first, a fatty acid or an ester thereof is condensed with a polyamine to obtain an amino group-containing fatty acid derivative. Examples of the amino group-containing fatty acid derivative include an imidazoline compound obtained by reacting a fatty acid or an ester thereof with a hydroxyalkyl polyamine or a hydroxyalkyl alkylene polyamine, a fatty acid or an ester thereof, and a reaction of an N-β-hydroxy lower alkyl alkanolamine. Examples include oxazoline compounds, fatty acids or esters thereof, and amidoamines obtained by reacting dialkylaminoalkyleneamines. Preferred are those represented by the general formula (V)

[0014]

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(In the formula, R ² and Z have the same meanings as described above.)
An imidazoline compound represented by the general formula (VI)

[0016]

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(Wherein, R ² , R ⁴ , R ⁵ and a have the same meanings as described above).

In the process of the present invention, the molar ratio of the fatty acid or its ester to the polyamine is usually from 1: 1 to 1: 2, preferably from 1: 1 to 1: 1.5.

Next, an amide group-containing surfactant is obtained by subjecting the amino group-containing fatty acid derivative obtained as described above to an addition reaction with a monohaloalkylcarboxylic acid represented by the general formula (I) or a salt thereof. .

Examples of the monohaloalkylcarboxylic acid represented by the general formula (I) or a salt thereof used in the present invention include monochloroacetic acid, monobromoacetic acid, monochloropropionic acid, monobromopropionic acid, and sodium and potassium salts thereof. However, monochloroacetic acid or a salt thereof is particularly preferred. The amount of the monohaloalkylcarboxylic acid or its salt relative to the amino group-containing fatty acid derivative is 1
The molar ratio is preferably from 1 to 3 times, more preferably from 1 to 1.15 times.

In the present invention, for example, an imidazoline compound represented by the general formula (V) is reacted with a monohaloalkylcarboxylic acid represented by the general formula (I) or a salt thereof to produce a compound represented by the general formula (VII):

[0022]

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(Wherein R ¹ , R ² , Y and Z have the same meanings as described above).
The amidoamine represented by the general formula (VI) is reacted with a monohaloalkylcarboxylic acid represented by the general formula (I) or a salt thereof to form a compound represented by the general formula (VIII):

[0024]

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(Wherein, R ¹ , R ² , R ⁴ , R ⁵ and a have the above-mentioned meanings).

In the present invention, the addition reaction between the amino group-containing fatty acid derivative and the monohaloalkylcarboxylic acid represented by the general formula (I) or a salt thereof can be carried out by a conventionally known method. For example, when the amino group-containing fatty acid derivative is an imidazoline compound, imidazoline is opened with an aqueous alkali solution, and then a monohaloalkylcarboxylic acid or a salt thereof is reacted. The reaction is preferably maintained at a pH in the range of 8 to 11, and the reaction temperature is preferably in the range of 50 to 90C. The reaction may be carried out under normal pressure or under pressure.

When the amino group-containing fatty acid derivative is the above-mentioned amidoamine, the pH of the amidoamine and the monohaloalkyl carboxylic acid or a salt thereof is kept at 8 to 10 until the betaine formation is completed, and the remaining monohaloalkyl PH 11.5-13 to promote carboxylate hydrolysis
The reaction is preferably carried out in the range of
A range from 50 to 100 ° C is preferred. The reaction may be carried out under normal pressure or under pressure.

In the present invention, when an amide group-containing surfactant is produced by the above reaction, an antioxidant is added to improve the storage stability of hue and odor. The addition of the antioxidant may basically be performed in any step, but the addition of the monohaloalkylcarboxylic acid represented by the general formula (I) or a salt thereof to the amino group-containing fatty acid derivative is performed. It is preferable to add an antioxidant after the step or after the addition reaction.

The antioxidants used in the present invention include:
Sterically hindered phenol compounds such as dibutylhydroxytoluene and butylhydroxyanisole; isoascorbic acid or its alkali metal salt, isopropyl citrate, dl
-Α-tocopherol, nordihydroguaiaretic acid, propyl gallate, and the like, and one or more of these can be used in combination. Among these antioxidants, sterically hindered phenol compounds such as dibutylhydroxytoluene and butylhydroxyanisole are preferable, and dibutylhydroxytoluene is particularly preferable.

In the present invention, the added amount of the antioxidant is
When added during the condensation reaction step between the fatty acid or its ester and the polyamine, the amount is preferably 0.001 to 5% by weight, more preferably 0.01 to 1.0% by weight, based on the fatty acid or its ester. Further, a step of subjecting the amino group-containing fatty acid derivative to the addition reaction of the monohaloalkylcarboxylic acid represented by the general formula (I) or a salt thereof, or when the addition is completed at the end of the addition reaction, 0.001 to 5% by weight, more preferably 0.01 to 1.0% by weight.

[0031]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The percentages are based on weight unless otherwise specified.

Example 1 <Amidation> Coconut fatty acid was placed in a 1-liter five-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a pressure gauge.
207 g (molecular weight: 207) was charged, and the temperature was raised to 180 ° C. while blowing nitrogen gas at 100 cc / Hr from a capillary tube. Thereafter, 102 g of dimethylaminopropylamine (molecular weight: 102) was added dropwise over 3 hours, kept under these conditions for 2 hours, cooled to 50 ° C. after measuring the acid value (AV) to confirm that it was 10 or less. Then, the reaction mixture was taken out.

<Ampholytic> The amidoamine obtained by the above amidation was transferred to a 2-liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and then 740 g of ion-exchanged water was used.
And 116.5 g of sodium monochloroacetate, and heated to 80 ° C. Thereafter, the pH in the system was adjusted to 10 with a 40% aqueous sodium hydroxide solution, followed by a reaction for 5 hours, cooled to 50 ° C., adjusted to pH 7 with 35% HCl, and then 0.2 g of dibutylhydroxytoluene was added. did. This reaction resulted in a reaction mixture containing 30% N-cocoylaminopropyl-N, N-dimethylglycine betaine.

Example 2 <Amidation> Using the same reaction apparatus as in Example 1, coconut oil fatty acid methyl ester was used instead of coconut oil fatty acid for 220.5 minutes.
Amidation was carried out under the same reaction conditions as in Example 1 except that g (molecular weight 220.5, 1 mol) was used.

<Ampholytic> The same reaction apparatus as in Example 1 was used except that N-cocoylaminopropyl-N, N-dimethylamine obtained by the above amidation was used.
The same reaction and treatment as described above were performed to obtain a reaction mixture containing 30% of N-cocoylaminopropyl-N, N-dimethylglycine betaine. Example 3 <Amidation> Using the same reactor as in Example 1, 220 g of purified coconut oil (molecular weight 657.5) instead of coconut fatty acid
Amidation was carried out under the same reaction conditions as in Example 1 except that

<Ampholytic> The same reaction apparatus as in Example 1 was used, except that N-cocoylaminopropyl-N, N-dimethylamine obtained by the above amidation was used.
The same reaction and treatment as described above were performed to obtain a reaction mixture containing 30% of N-cocoylaminopropyl-N, N-dimethylglycine betaine. Example 4 <Imidazolinization> In a 5-liter 1-liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a pressure gauge, 207 g of coconut oil fatty acid (molecular weight: 207, 1 mol) was charged, and nitrogen gas was fed into a capillary tube. Blow at 100cc / Hr. Then, 109.2 g of aminoethylethanolamine (molecular weight 104
, 1.05 mol). After the temperature rose to 100 ° C due to heat generation, the reaction pressure was set to 400 mmHg,
The temperature was raised over time. When the reaction temperature reached 200 ° C., the pressure was reduced to 200 mmHg, kept under these conditions for 2 hours, the pressure was further increased to 5 mmHg in 3 hours, and the reaction was terminated. The mixture was removed.
The imidazoline ring content of this reaction mixture was 94% from the measured amine value.

<Amidation amino acid conversion> The reaction mixture obtained by the above imidazoline conversion was transferred to a two-liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and then 18 g of ion-exchanged water and 0.54% of sodium hydroxide were added. g at 80 ℃
And kept for 1 hour. After that, ion-exchanged water 720
g and 116.5 g of sodium monochloroacetate at the same time, and after the temperature is restored to 70 ° C., a 40% aqueous NaOH solution 100
g was charged in 2 hours and aged for 6 hours, then cooled to 50 ° C. and adjusted to pH 7 with 35% HCl. Thereafter, 0.3 g of dibutylhydroxytoluene was added. The obtained compound was a reaction mixture containing 30% of {N-cocoyl-N '-(2-hydroxyethyl) -N'-sodium carboxymethyl} ethylenediamine.

Example 5 <Amidation> The same reaction conditions as in Example 1 were used except that 220 g (molecular weight: 220) of palm kernel oil-distilled distilled fatty acid was used in place of the coconut oil fatty acid using the same reactor as in Example 1. Amidation was carried out.

<Amphoteric> The same reaction apparatus as in Example 1 was used, except that the N-palm kernel oil fatty acid amidopropyl-N, N-dimethylamine obtained by the above amidation was used. Was carried out to obtain a reaction mixture containing 30% of N-palm kernel oil fatty acid amidopropyl-N, N-dimethylglycine betaine.

Example 6 A reaction and treatment were carried out under the same conditions as in Example 1 except that butylhydroxyanisole was used instead of dibutylhydroxytoluene as an antioxidant, and 30% N-cocoylaminopropyl was used. A reaction mixture containing -N, N-dimethylglycine betaine was obtained.

Example 7 A reaction was carried out under the same conditions as in Example 1 except that 0.1 g of an antioxidant, dibutylhydroxytoluene, was charged during the amidation reaction, and 30% of N-cocoylaminopropyl- A reaction mixture containing N, N-dimethylglycine betaine was obtained.

Comparative Examples 1 to 3 In the same manner as in Examples 1 to 3, except that dibutylhydroxytoluene as an antioxidant was not added, 30% of N-cocoylaminopropyl-N, N −
A reaction mixture containing dimethylglycine betaine was obtained.

Comparative Example 4 The procedure of Example 4 was repeated, except that dibutylhydroxytoluene as an antioxidant was not added.
A reaction mixture containing 30% of {N-cocoyl-N '-(2-hydroxyethyl) -N'-sodium carboxymethyl} ethylenediamine was obtained.

Comparative Example 5 In Example 1, 30% of N-cocoylaminopropyl- was added in the same manner as in Example 1 except that citric acid as a chelating agent was added instead of dibutylhydroxytoluene as an antioxidant. A reaction mixture containing N, N-dimethylglycine betaine was obtained.

Comparative Example 6 In the amphoteric conversion of Example 1, 0.6 g of sodium borohydride (SBH) as a reducing agent was added to a 40% aqueous sodium hydroxide solution instead of adding dibutylhydroxytoluene as an antioxidant. The reaction was carried out under the same conditions as in Example 1 except that the reaction was carried out under the same conditions as in Example 1 except that the reaction was carried out immediately after adjusting the pH of the system to 10 by using a reaction mixture containing 30% N-cocoylaminopropyl-N, N-dimethylglycine betaine. I got

The hue and odor of the reaction mixtures obtained in Examples 1 to 7 and Comparative Examples 1 to 6 immediately after production, and further after storage in a thermostat at 50 ° C. for one month, were evaluated by the following methods. . Table 1 shows the results.

<Hue> Immediately after production and after storage at 50 ° C. for one month, the hue of the reaction mixture was measured with a colorimetric tube. <Odor evaluation method> Immediately after production and after storage at 50 ° C. for one month, 30% of the hue was measured. The reaction mixture containing the amide group-containing surfactant was diluted with ion-exchanged water to a concentration of 10%,
After transferring 30 g to the ml Meyer flask, place it in a 40 ° C constant temperature bath.
After storing for 30 minutes, the stopper was removed and five panelists evaluated according to the following evaluation criteria, and the average score was expressed in the following four grades.

Evaluation criteria 4: No odor 3: Slight odor 2: Relatively strong odor 1: Strong irritating odor Average score of the above evaluation criteria is 4 to 3 ◎ Average score of the above evaluation criteria is Those with less than 3 and 2 or more ○ Those with an average score of less than 2 and 1.5 or more. Those with an average score of less than 1.5 and 1 or more x

[0049]

[Table 1]

Claims (6)

[Claims] Claims: 1. A fatty acid or an ester thereof and a polyamine are subjected to a condensation reaction to obtain an amino group-containing fatty acid derivative.
Formula (I) XR ¹ COOY (I) (wherein, X represents a halogen atom, R ¹ represents a linear or branched alkylene group having 1 to 4 carbon atoms, and Y represents H 2 or an alkali metal. A) producing an amide group-containing surfactant by reacting the monohaloalkylcarboxylic acid or a salt thereof represented by the formula (1) with an antioxidant; 2. The method according to claim 1, wherein the fatty acid or an ester thereof has the general formula (I)
^{I) R 2 COOR 3 (II} ) ( wherein, R ² represents a linear or branched alkyl group, alkenyl group or hydroxyalkyl group having 7 to 23 carbon atoms, R ³
Represents a residue obtained by removing one acyloxy group from H or an alkyl group having 1 to 3 carbon atoms or glyceride. The method according to claim 1, which is a higher fatty acid or an ester thereof represented by the formula: 3. The polyamine is an alkylene polyamine,
The production method according to claim 1 or 2, which is a hydroxyalkyl polyamine or an N-hydroxy lower alkyl alkanolamine. 4. The production method according to claim 1, wherein the monohaloalkylcarboxylic acid represented by the general formula (I) or a salt thereof is monochloroacetic acid or a salt thereof. 5. An antioxidant comprising dibutylhydroxytoluene, butylhydroxyanisole, isoascorbic acid or an alkali metal salt thereof, isopropyl citrate, dl
The production method according to any one of claims 1 to 4, wherein the production method is one or more kinds selected from -α-tocopherol, nordihydroguaiaretic acid, and propyl gallate. 6. The amount of the antioxidant to be added to a fatty acid or an ester thereof or an amino group-containing fatty acid derivative.
The production method according to any one of claims 1 to 5, wherein the content is 0.001 to 5% by weight.