JPH06316546A - Production of carboxylic acid compounds - Google Patents

Abstract

PURPOSE:To obtain a carboxylic acid compound for surfactant in a simple process without the need for highly complicated process(es) such as oxidation, by four alternative methods including reaction of a monohaloacetic acid or a salt thereof with an 1,2-alkanediol alcoholate. CONSTITUTION:The carboxylic acid compound of formula II [X1 and X2 are such that at least one of them is CH2COOM (M is H, an alkali metal, ammonium, etc.) and the other may be H] can be obtained by the following four alternative methods: (1) a monohaloacetic acid or a salt thereof is reacted with an 1,2-alkanediol of formula I (R is a 4-34C alkyl or alkenyl) followed by, if desired, converting the reaction product into a free acid or salt thereof; (2) a reaction product from an 1,2-epoxy alkane of formula III and a glycolic alkyl ester of formula IV (Z is an alkyl) is hydrolyzed; (3) the compound of the formula III is reacted with a monohaloacetic acid or, if desired, a salt thereof followed by carboxymethylation of the reaction product in the presence of an alkali and, if desired, water; or (4) an adduct from the compound of the formula III and a monohaloacetic acid, etc., is carboxymethylated.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing carboxylic acids useful as a surfactant.

[0002]

2. Description of the Related Art Sodium poly (oxyethylene) alkyl ether carboxylates and O-substituted glycerates are known as ether carboxylate type surfactants [eg, Chemical Society of Japan, 1385-1].
389, NO. 9 (1980) and JP-A-57-16.
2797].

[0003]

However, the former is a good surfactant in the neutral to weakly alkaline region, but is not necessarily a good surfactant in the weakly acidic and alkaline regions. The latter is complicated and expensive to manufacture.

[0004]

[Means for Solving the Problems] The present inventors
The present invention has been accomplished as a result of extensive studies to find a good method for producing a surfactant in a wide alkaline pH range.
That is, the present invention has the general formula (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms.)
-Alkanediol alcoholate is reacted with monohaloacetic acid or a salt thereof and, if necessary, converted into a free acid or a salt, (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH ₂ COOM, and the other may be a hydrogen atom. M is M. Hydrogen atom, alkali metal, alkaline earth metal,
It is an ammonium, lower alkanolamine cation, lower alkylamine cation or basic amino acid cation. ) A method for producing carboxylic acids, characterized by producing carboxylic acids represented by the formula; (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms.)
-By hydrolyzing a reaction product of an epoxyalkane and a glycolic acid alkyl ester represented by the general formula HOCH ₂ COOZ (4) (wherein Z is an alkyl group having 1 to 4 carbon atoms), the general formula (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH ₂ COOM, and the other may be a hydrogen atom. M is M. Hydrogen atom, alkali metal, alkaline earth metal,
It is an ammonium, lower alkanolamine cation, lower alkylamine cation or basic amino acid cation. ) A method for producing carboxylic acids, characterized by producing carboxylic acids represented by the formula; (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms.)
A compound of the general formula by reacting an epoxy alkane with a monohaloacetic acid and optionally its salt, followed by carboxymethylation in the presence of an alkali and optionally water. (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH ₂ COOM, and the other may be a hydrogen atom. M is M. Hydrogen atom, alkali metal, alkaline earth metal,
It is an ammonium, lower alkanolamine cation, lower alkylamine cation or basic amino acid cation. ) A method for producing carboxylic acids, characterized by producing carboxylic acids represented by the formula; (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms.)
A compound of the general formula by carboxymethylating a reaction product of an epoxy alkane with a monohaloacetic acid and optionally a salt thereof in the presence of an alkali and optionally water. (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH ₂ COOM, and the other may be a hydrogen atom. M is M. Hydrogen atom, alkali metal, alkaline earth metal,
It is an ammonium, lower alkanolamine cation, lower alkylamine cation or basic amino acid cation. ) A carboxylic acid represented by the formula (4) is produced.

In the above general formulas (1), (2) and (3), the linear or branched alkyl group having 4 to 34 carbon atoms of R is a butyl group, an octyl group, a decyl group or a dodecyl group, Examples thereof include a tetradecyl group, a hexadecyl group, an octadecyl group, a docosyl group, a 2-ethylhexyl group, a 2-hexyldecyl group, a 2-octylundecyl group, a 2-decyltetradecyl group and a 2-undecylhexadecyl group. Examples of the linear or branched alkenyl group having 4 to 34 carbon atoms include decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group and octadecenyl group. Among R, a linear alkyl group having 8 to 16 carbon atoms is preferable in terms of surface activity, and a decyl group and a dodecyl group are particularly preferable. These may be mixed groups of two or more.

Examples of the alkali metal represented by M in the general formula (1) include sodium, potassium and lithium. Examples of alkaline earth metals include calcium, magnesium and barium. Alkanolamines forming lower alkanolamine cations include mono-, di- and tri-ethanolamines, n- and iso-propanolamines and the like. Examples of the alkylamine forming the lower alkylamine cation include monoethylamine, diethylamine, triethylamine and the like. Examples of the basic amino acid forming the basic amino acid cation include lysine, arginine, ornithine, histidine and the like. Among M, alkali metal and lower alkanolamine cations are preferable, and sodium and triethanolamine cations are particularly preferable. These may be a mixed salt of two or more kinds.

The carboxylic acids represented by the general formula (1) include monocarboxylic acids represented by the following general formula (1 ') and dicarboxylic acids represented by the general formula (1''). [In the formula, one of X ₃ and X ₄ is —CH ₂ COOM, the other is a hydrogen atom, and R and M are the same as those in the general formula (1). ]

Examples of the compound represented by the general formula (1) and the mixture thereof include those listed in Table 1 and Table 2.

[0009]

[Table 1]

[0010]

[Table 2] Table 1 and Table 2 in the Legend _{C 8: n-C 8 H} 17 C 10: n-C 10 H 21 C 12: n-C 12 H 25 C 14: n-C 14 H 29 TEA: HN ( CH ₂ CH ₂ OH) ₃ Na / H: Na / H (50/50)

The carboxylic acids of the present invention are obtained by reacting a monohaloacetic acid or a salt thereof with an alcoholate "general formula (2-1)" of a 1,2-alkanediol "general formula (2)", and optionally a free acid or salt. Can be produced by converting into (I) The reaction formula is shown below. (In the formula, M is an alkali metal, at least one of M ₁ and M ₂ is an alkali metal, and the other may be a hydrogen atom. X
Is monohaloacetic acid or a salt thereof. R, X ₁ and X ₂ are the same as above. )

In order to carry out the method, the general formula (2)
1,2-alkanediol (1,2-dodecanediol, 1,2-tetradecanediol, etc.) is alcoholized (2-1) in the presence of an alkali in a solvent,
Next, monohaloacetic acid or a salt thereof may be added to carry out carboxymethylation.

Examples of the solvent used in the reaction include solvents such as dioxane, diethylene glycol dimethyl ether, hexane, toluene and water, 1,2-alkanediol [general formula (2)], or a mixture of two or more thereof. To be Dioxane, diethylene glycol dimethyl ether and water are preferred. Alcoholate (2
Examples of the alkali that provides -1) include metallic sodium, liquid methylate, NaOH and KOH, and preferably metallic sodium, liquid methylate and NaOH. As monohaloacetic acid or its salt, monochloroacetic acid or its sodium salt is preferable from the viewpoint of cost.

The amount of alkali used to provide the alcoholate (2-1) is usually 0.2 to 6.0 times mol, preferably 0.5 to 3.0 times, the mol of the 1,2-alkanediol. It is a mole. Monohaloacetic acid or a salt thereof may be added usually in an equivalent amount or more with respect to the alcoholate (2-1), preferably 0.9 to 3.0 times by mole.

The temperature of alcoholation and carboxymethylation is usually from 30 ° C to the boiling point of the solvent, preferably from 80 ° C to the boiling point of the solvent. The reaction does not proceed sufficiently at a reaction temperature of less than 30 ° C.

The addition of monohaloacetic acid or a salt thereof may be optional, and may be added to the reaction system all at once or in portions.

The carboxylic acids of the present invention have the general formula (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms.)
A carboxylic acid or a carboxylic acid by hydrolyzing a reaction product of an epoxyalkane and a glycolic acid alkyl ester represented by the general formula HOCH ₂ COOZ (4) (wherein Z is an alkyl group having 1 to 4 carbon atoms). It can also be produced by converting it to a salt. (II)

The 1,2-epoxyalkane represented by the general formula (3) (1,2-epoxydodecane, 1,2-epoxytetradecane, etc.) and the glycolic acid alkyl ester represented by the general formula (4) (glycol) The reaction with methyl acid, ethyl glycolate, etc.) may be carried out using an alkaline catalyst (sodium hydroxide, potassium hydroxide, triethylamine, etc.) and an acidic catalyst (sulfuric acid, boron trifluoride, etc.) if necessary.

The carboxylic acid of the present invention is obtained by reacting a 1,2-epoxyalkane "general formula (1)" with a monohaloacetic acid and optionally a salt thereof, and then carboxymethylating in the presence of an alkali and optionally water. Can be manufactured by. (III) Further, the carboxylic acid of the present invention is obtained by carboxymethylating a reaction product of a 1,2-epoxyalkane “general formula (1)” with a monohaloacetic acid and optionally a salt thereof in the presence of an alkali and optionally water. It can be manufactured by (IV)

In the above methods (III) and (IV), a solvent can be used if necessary, but it is preferable to use it because the viscosity of the reaction system sharply increases during carboxymethylation. Examples of the solvent to be used include ether solvents such as dioxane and diethylene glycol dimethyl ether, hydrocarbon solvents such as hexane, toluene and xylene, chlorine solvents such as chloroform and dichloroethane, water, 1,2-alkanediol or two of them. The above mixture can be mentioned. Of these, hydrocarbon solvents are preferable, and toluene and xylene are particularly preferable.

Monohaloacetic acid or its salt is preferably monochloroacetic acid or its sodium salt from the viewpoint of cost.

Alkali used in carboxymethylation includes metallic sodium, liquid methylate and NaO.
H, KOH, Na ₂ CO _{3 and the} like are preferable, and N is preferable.
aOH and KOH.

In preparing a reaction product of a 1,2-epoxyalkane, a monohaloacetic acid, and optionally a salt thereof,
The amount of monohaloacetic acid and its salt, if necessary, is 1,
The 2-epoxyalkane is generally 0.2 to 20 times mol, preferably 0.5 to 10 times mol, of the "general formula (1)". The amount of alkali used for carboxymethylation is usually 0.5 to 5 with respect to monohaloacetic acid or a salt thereof.
The molar ratio is 0 times, preferably 0.8 to 2.0 times. In addition, the amount of water used in the case of carboxymethylation is usually 0% by weight to 60% by weight, preferably 10% by weight to 40% by weight, based on the alkali. When it exceeds 60% by weight, hydrolysis of monohaloacetic acid and its salt is promoted and the reaction rate is not increased. An appropriate amount of water will speed up the reaction.

In producing a reaction product of a 1,2-epoxyalkane, a monohaloacetic acid, and optionally a salt thereof,
The weight ratio of monohaloacetic acid and its salt is usually 100: 0 to 4
It is 0:60, preferably 98: 2 to 60:40, and particularly preferably 95: 5 to 70:30. The reaction does not proceed when the proportion of monohaloacetate exceeds 60, but the addition of monohaloacetate prevents the by-production of the dimer of 1,2-epoxyalkane. The reaction temperature is usually 10
C. to 150.degree. C., preferably 30.degree. C. to 100.degree. If the reaction temperature is less than 10 ° C, the reaction does not proceed sufficiently,
A large amount of by-products are generated at a reaction temperature exceeding 150 ° C.

The temperature of carboxymethylation is usually 10 ° C.
To 150 ° C, preferably 30 ° C to 80 ° C.
If the reaction temperature is less than 10 ° C, the reaction does not proceed sufficiently,
Hydrolysis of the monohaloacetate occurs at reaction temperatures above 0 ° C.

In producing a reaction product of a 1,2-epoxyalkane, a monohaloacetic acid, and optionally a salt thereof,
The addition method of 1,2-epoxyalkane and monohaloacetic acid and, if necessary, the salt thereof may be arbitrary, and batch addition and divided addition are possible. It is preferred to add the 1,2-epoxyalkane in portions to the monohaloacetic acid and optionally its salt.

The addition of alkali in carboxymethylation may be carried out all at once or in divided portions depending on the degree of heat generation.

The product obtained by the above reaction may be subjected to column chromatography, preparative liquid chromatography or the like to separate unreacted products and by-products to obtain a purified carboxylic acid (salt). To get other salts,
It can be easily obtained by acidifying the obtained salt with a mineral acid such as sulfuric acid and hydrochloric acid, solvent extraction with petroleum ether, diethyl ether, hexane and the like, and then neutralizing with a desired base.

Among the carboxylic acids of the present invention, the monocarboxylic acids of the general formula (1 ′) and the dicarboxylic acids of the general formula (1 ″) have the following properties from the viewpoint of the surfactant.
The former is preferable, but a mixture containing a large proportion of monocarboxylic acids (for example, 20% by weight or more, particularly 50% by weight or more) is also preferable. The products obtained by the methods (I), (III) and (IV) usually consist of a mixture of monocarboxylic acids of the general formula (1 ′) and dicarboxylic acids of the general formula (1 ″). May be isolated, but industrially it is preferable to use the mixture as it is. in this case,
The weight ratio of monocarboxylic acids to dicarboxylic acids is usually 9
/ 1-2 / 8, preferably 8 / 2-5 / 5. (I
With the method I), preferable monocarboxylic acids can be obtained.

[0030]

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

Example 1 50 ml of 1,2-dodecanediol was added to a 1 L four-necked flask.
0 g, dioxane 250 g, and sodium metal 5.7 g were added, the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ° C., 28.8 g of sodium monochloroacetate was gradually added, and after the addition was completed, the mixture was reacted at the same temperature for 3 hours, and the compound No. 7 was obtained (yield: 80%).

Example 2 1,2-tetradecanediol 5 was added to a 1L four-necked flask.
0.0 g, dioxane 250 g, metallic sodium 5.0 g
Was added, the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ° C., 27.8 g of sodium monochloroacetate was gradually added, and after the addition was completed, the mixture was reacted at the same temperature for 3 hours, and the compound No. 9 was obtained (yield: 78%).

Example 3 50% 1,2-dodecanediol was added to a 1 L four-necked flask.
0 g, dioxane 250 g, metallic sodium 11.4 g
Was added, the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ° C., 57.7 g of sodium monochloroacetate was gradually added, and after the addition was completed, the reaction was continued for 3 hours at the same temperature. 14 was obtained (yield: 80%).

Example 4 1,2-tetradecanediol 5 was added to a 1L four-necked flask.
0.0 g, dioxane 250 g, metallic sodium 10.0
g was added, the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ° C., 55.6 g of sodium monochloroacetate was gradually added, and after the addition was completed, the reaction was continued for 3 hours at the same temperature. 15 was obtained (yield: 75%).

Example 5 A 1 L four-necked flask was charged with 110 g of toluene, 71.8 g of monochloroacetic acid and 29.6 g of sodium monochloroacetate, heated to 70 ° C. under a nitrogen stream, and kept at the same temperature for 3 hours for 1,2-epoxy. 74.6 g of dodecane was added dropwise. After completion of the dropping, aging was carried out at the same temperature for 2 hours. After cooling to 45 ° C,
20.6 g of water and 71.0 g of sodium hydroxide were added in portions. After completion of the addition, the reaction was carried out at the same temperature for 10 hours, and the compound NO. 21 was obtained (yield: 90
%)

Example 6 A 1 L four-necked flask was charged with 110 g of toluene, 34.5 g of monochloroacetic acid and 14.2 g of sodium monochloroacetate, heated to 70 ° C. under a nitrogen stream, and kept at the same temperature for 3 hours for 1,2-epoxy. 74.6 g of dodecane was added dropwise. After completion of the dropping, aging was carried out at the same temperature for 2 hours. After cooling to 45 ° C,
Water (8.5 g) and sodium hydroxide (34.1 g) were added in portions. After completion of the addition, the reaction was carried out at the same temperature for 10 hours, and the compound No. 7 was obtained (yield: 83%)

Example 7 A 1 L four-necked flask was charged with 110 g of toluene, 32.1 g of monochloroacetic acid and 13.2 g of sodium monochloroacetate, heated to 70 ° C. under a nitrogen stream, and kept at the same temperature for 3 hours for 1,2-epoxy. 80.0 g of tetradecane was added dropwise.
After completion of the dropping, aging was carried out at the same temperature for 2 hours. After cooling to 45 ° C., 10.6 g of water and 31.7 g of sodium hydroxide were added in portions. After the addition was completed, the reaction was carried out at the same temperature for 8 hours, and
The compound NO. 9 was obtained (yield: 85
%)

Example 8 A 1 L four-necked flask was charged with 110 g of toluene, 144.5 g of monochloroacetic acid and 59.3 g of sodium monochloroacetate, heated to 70 ° C. under a nitrogen stream, and kept at the same temperature for 3 hours for 1,2-epoxy. 75.0 g of dodecane was added dropwise. After completion of the dropping, aging was carried out at the same temperature for 2 hours. After cooling to 45 ° C., 41.4 g of water and 142.7 g of sodium hydroxide were added in portions. After completion of the addition, the reaction was carried out at the same temperature for 8 hours, and the compound No. 14 was obtained (yield: 8
5%)

Example 9 A 1 L four-necked flask was charged with 110 g of toluene, 125.4 g of monochloroacetic acid and 51.5 g of sodium monochloroacetate, heated to 70 ° C. under a nitrogen stream, and kept at the same temperature for 3 hours for 1,2-epoxy. 75.0 g of tetradecane was added dropwise. After completion of the dropping, aging was carried out at the same temperature for 2 hours. After cooling to 45 ° C., 36.0 g of water and 123.9 of sodium hydroxide
g was added in portions. After completion of the addition, the reaction was carried out at the same temperature for 8 hours, and the compound No. 15 was obtained (yield: 85%)

[0040]

EFFECTS OF THE INVENTION Unlike the case of O-substituted glycerate, the production method of the present invention does not include a very complicated step such as an oxidation step, and the production method is simple. The carboxylic acids obtained by the method are cosmetics, pharmaceuticals, agricultural chemicals,
Textiles, machines, metals, plastics, rubber, petroleum, paper pulp, leather, cleaning, foods, dyes, pigments, paints, inks, civil engineering, construction, ceramics, mining, etc. It can be widely used as a solubilizer, a dispersant, a smoothing agent, a lubricant, an antistatic agent and an anticorrosive agent.

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Claims (4)

[Claims] 1. A general formula (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms.)
-Alkanediol alcoholate is reacted with monohaloacetic acid or a salt thereof and, if necessary, converted into a free acid or a salt, (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH ₂ COOM, and the other may be a hydrogen atom. M is M. Hydrogen atom, alkali metal, alkaline earth metal,
It is an ammonium, lower alkanolamine cation, lower alkylamine cation or basic amino acid cation. ) A carboxylic acid represented by the formula (3) is produced. 2. The general formula (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms.)
By hydrolyzing a reaction product of an epoxy alkane and a glycolic acid alkyl ester represented by the general formula HOCH ₂ COOZ (4) (wherein Z is an alkyl group having 1 to 4 carbon atoms), (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH ₂ COOM, and the other may be a hydrogen atom. M is M. Hydrogen atom, alkali metal, alkaline earth metal,
It is an ammonium, lower alkanolamine cation, lower alkylamine cation or basic amino acid cation. ) A carboxylic acid represented by the formula (3) is produced. 3. The general formula (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms.)
A compound of the general formula by reacting an epoxy alkane with a monohaloacetic acid and optionally its salt, followed by carboxymethylation in the presence of an alkali and optionally water. (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH ₂ COOM, and the other may be a hydrogen atom. M is M. Hydrogen atom, alkali metal, alkaline earth metal,
It is an ammonium, lower alkanolamine cation, lower alkylamine cation or basic amino acid cation. ) A carboxylic acid represented by the formula (3) is produced. 4. The general formula (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms.)
A compound of the general formula by carboxymethylating a reaction product of an epoxy alkane with a monohaloacetic acid and optionally a salt thereof in the presence of an alkali and optionally water. (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH ₂ COOM, and the other may be a hydrogen atom. M is M. Hydrogen atom, alkali metal, alkaline earth metal,
It is an ammonium, lower alkanolamine cation, lower alkylamine cation or basic amino acid cation. ) A carboxylic acid represented by the formula (3) is produced.