JP2747792B2 - Method for producing carboxylic acids - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a carboxylic acid having an ether carboxylate structure which is useful as a surfactant.

[0002]

2. Description of the Related Art Conventionally, as a method for synthesizing an ether carboxylate, for example, the following method is known. (JP-A-2-256644) A method for producing a reaction product of a 1,2-alkanediol and a monohaloacetic acid or a salt thereof in the presence of an alkali and, if necessary, water, by carboxymethylation. A method for producing a reaction product of a 1,2-epoxyalkane and a monohaloacetic acid and, if necessary, a salt thereof, in the presence of an alkali and optionally water, by carboxymethylation.

[0003]

However, in the production methods of (1) and (2), the production steps of 1,2-alkanediol and 1,2-epoxyalkane used as raw materials are complicated and the purity is insufficient. There has been a problem that a raw material for obtaining a high-purity ether carboxylate at low cost requires improvement.

[0004]

Means for Solving the Problems The present inventors have intensively studied a method capable of obtaining carboxylic acids with higher purity by using a high-purity raw material obtained by a simpler production method than these raw materials. As a result, the present invention has been achieved.

That is, the present invention is characterized in that a reaction product (A) of a 1-alkene, a monohaloacetic acid and hydrogen peroxide represented by the following general formula (1) is reacted with a base and, if necessary, is subjected to salt exchange. A method for producing a carboxylic acid represented by the following general formula (2): RCHＲCH ₂ (1) (where R is a linear or branched alkyl group having 4 to 34 carbon atoms) .) General Formula RCHCH ₂ OX ₁ (2) | OX ₂ (wherein, R is a linear or branched alkyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —C
H ₂ COOM, and the rest are hydrogen atoms. M is a cation. ) And a reaction product (A) of a 1-alkene, a monohaloacetic acid, and hydrogen peroxide represented by the following general formula (1) with a base, followed by salt exchange, wherein the salt is exchanged. This is a method for producing carboxylic acids represented by the formula: General formula RCH = CH ₂ (1) (wherein, R is a linear or branched alkyl group having 4 to 34 carbon atoms.) General formula RCHCH ₂ OX ₁ (2) | OX ₂ R is a linear or branched alkyl group having 4 to 34 carbon atoms, and at least one of X ₁ and X ₂ is -C
H ₂ COOM, and the rest are hydrogen atoms. M is a cation. )

In the general formula (1), 1-alkene is 1-hexene, 1-octene, 1-nonene, 1-alkene.
Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-eicosene, 1-heicosene, 1-docosene, 1-tricosene, 1-tetracocene, Examples include 7-methyl-1-nonene, 11-methyl-1-heptadecene, 12-methyl-1-eicosene, 15-methyl-1-pentacocene, 17-methyl-1-octacocene, and the like.

The pure content of the 1-alkene is usually 98% by weight.
That is all. This is easily obtained industrially. In addition, the pure content of 1,2-alkanediol and 1,2-epoxyalkane which are raw materials in the conventional method is usually 80 to 85%, respectively.

In the general formulas (1) and (2), the linear or branched alkyl group having 4 to 34 carbon atoms represented by R includes butyl, hexyl, heptyl, octyl, nonyl, Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group,
Octadecyl group, nonadecyl group, eicosyl group, heicosyl group, docosyl group, 2-ethylhexyl group, 2-hexyldecyl group, 2-octylundecyl group, 2-decyltetradecyl group, 2-undecylhexadecyl group and the like. Can be These may be two or more kinds of mixed groups.

In the general formula (2), examples of the cation represented by M include an alkali metal ion, an alkaline earth metal ion, an ammonium cation, a lower alkanolamine cation and a basic amino acid cation. Examples of the alkali metal ion include lithium, potassium, and sodium ions, examples of the alkaline earth metal ion include calcium and magnesium ions, and examples of the lower alkanolamine cation include:
Triethanolamine, diethanolamine, monoethanolamine cations and the like, and basic amino acid cations include lysine and arginine cations. Two or more of these ions may be mixed. Of these, preferred are alkali metal ions, and particularly preferred are potassium and sodium ions.

The carboxylic acids represented by the general formula (2)
It can be represented as a mixture of one or more compounds selected from monocarboxymethylated compounds represented by the general formulas (3) and (4) and dicarboxymethylated compounds represented by the general formula (5). . (Each symbol in the formula is the same as in the general formula (2).)

The compounds represented by the general formula (2) and mixtures thereof include those shown in Table 1.

[0012]

[Table 1]

The ratio between the monocarboxymethylated product and the dicarboxymethylated product can be arbitrarily changed depending on the amount of monochloroacetic acid used in the reaction. The preferred weight ratio of the monocarboxymethylated product to the dicarboxymethylated product when used as a raw material for the surfactant is 90:10 to 50:
50.

The monohaloacetic acid includes, for example, monochloroacetic acid and monobromoacetic acid. Among these, monochloroacetic acid is preferred from the viewpoint of cost.

Preferred bases for use in the present invention are caustic alkalis, such as sodium hydroxide and potassium hydroxide. The caustic may be a solid or an aqueous solution. Solid caustic includes flakes, beads and powders. Preferably, it is a bead-like solid caustic from the viewpoint of workability. In the case of flakes, the fluidity at the time of preparation is poor, and in the case of powders, fine powder flies at the time of preparation, causing a problem in safety.

In the present invention, a solvent is used as necessary in any reaction, but it is preferable to use a solvent in order to improve stirring efficiency and cooling efficiency. Examples of the solvent used in the present invention include hydrocarbons such as toluene, xylene, hexane, heptane and cyclohexane, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, dioxolane and dioxane. , Dimethylformamide and the like. Preferred are hydrocarbon solvents, and particularly preferred are toluene, xylene, cyclohexane, hexane and heptane.

In the present invention, in producing the reaction product (A) of the 1-alkene, monohaloacetic acid and hydrogen peroxide represented by the general formula (1), the molar ratio of the 1-alkene to the monohaloacetic acid is usually 1: 1. 0.0: 0.5 to 10, preferably 1.0 to 5.0. The molar ratio of 1-alkene to hydrogen peroxide is usually 1.0: 0.5-3.0, preferably 1.0: 0.0.
9 to 1.5.

In the present invention, in a usual reaction, a reactant (A) represented by the following general formula (3) is obtained as an intermediate. General formula (Wherein, R is a linear or branched alkyl group having 4 to 34 carbon atoms. Y ₁ and Y ₂ are each a hydrogen atom or —OCO
CH ₂ Z. Z is halogen. )

The compounds represented by the general formula (3) and mixtures thereof include those shown in Table 2.

[0020]

[Table 2]

In the present invention, when the molar ratio of monohaloacetic acid is less than 0.5, a large amount of by-products represented by the following general formula (4) is generated, and the purity is reduced. Further, use exceeding 10 has no meaning in terms of cost. <Side reaction> (In the formula, R is a linear or branched alkyl group having 4 to 34 carbon atoms.)

The by-products represented by the general formula (4) include:
Those described in Table 3 are mentioned.

[0023]

[Table 3]

In the present invention, the molar ratio of the alkali used in reacting the reactant (A) with the base is usually 1.0: 1.0 to 4.0, preferably 1.0: 1.0 to monohaloacetic acid.
1.5 to 3.0. If it is less than 1.0, the present carboxylic acids cannot be obtained with high yield. No more than 4.0 inputs are required.

In the present invention, the reaction temperature for producing the reactant (A) is usually 30 to 120 ° C., preferably 50 to 105 ° C. If it is lower than 30 ° C., the reaction becomes extremely slow. When the temperature exceeds 120 ° C., decomposition of hydrogen peroxide precedes, and a safety problem occurs.

In the present invention, when producing the reactant (A), a mineral acid such as sulfuric acid and phosphoric acid, a heteropolyphosphoric acid such as phosphotungstic acid and phosphomolybdic acid, and
Organic phosphoric acids such as -hydroxyethylidene-1,1-diphosphonic acid and aminotrimethylenephosphonic acid, and nitrogen-containing carboxylic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid can be used in combination. When used in combination, the reaction rate can be increased, and the decomposition of hydrogen peroxide by heavy metals such as iron, copper, nickel, chromium, zinc, and lead can be suppressed. The amount of addition is usually 0.1 in the reaction system.
005% to 2.0%, preferably 0.01% to 1.0%. If it is less than 0.005%, the effect is not obtained, and it is not necessary to add 2.0% or more.

In the present invention, the reaction temperature between the reactant (A) and the alkali is usually 35 to 100 ° C., preferably 50 to 85 ° C. When the temperature is lower than 35 ° C., the reaction becomes extremely slow. When the temperature exceeds 100 ° C., hydrolysis of monohaloacetic acid precedes and the yield of the present carboxylic acids decreases.

In the present invention, when reacting the reactant (A) with a base, it is preferable to control the amount of water in the reaction system. The reaction is usually performed at 10% or less, preferably 5% or less. When the amount of water in the reaction system during the reaction exceeds 10%,
Hydrolysis of the monohaloacetic acid to glycolic acid precedes and lowers the yield of the carboxylic acids.

In the present invention, the method for introducing the base is not particularly limited, and may be batch or divided. However, a resolution method that allows easy control of the reaction is preferred. The number of divisions, intervals, and the like are not particularly limited.

In the method of the present invention, the by-product generation rate is usually about 10 to 15% by weight lower than the conventional method using a low-purity raw material at the stage after the reaction (before purification).

In the present invention, as a means for removing the reactant produced by the side reaction and the carboxymethylated product thereof, M in the general formula (2) is converted to a hydrogen atom and distilled (for example, molecular distillation, thin film distillation, steam distillation and the like). , Recrystallization and the like, and in each case, the content weight of the by-product represented by the general formula (4) is 0.1%.
It can be up to 2% of the carboxylic acids.

The carboxylic acids produced by the present production method are useful, for example, as body detergents such as body shampoos and facial cleansers, hair detergents such as shampoos, and household detergents such as dishwashing detergents. In addition, taking advantage of the characteristics of the compound of the present invention, cosmetics, pharmaceuticals, pesticides, fibers, machinery,
Metal, plastic, rubber, oil, paper pulp, leather, cleaning, food, dye, pigment, paint, ink, civil engineering,
Cleaning agents, foaming agents, penetrants in construction, ceramics, mining, etc.
It can be widely used as emulsifier, solubilizer, dispersant, leveling agent, lubricant, antistatic agent and rust inhibitor.

[0033]

EXAMPLES Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

Example 1 In a four-necked 1-L flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube, and a stirrer, 151 g (0.90 mol) of 1-dodecene, 383 g (4.05 mol) of monochloroacetic acid, 1,
1 g of 1-hydroxyethanediphosphonic acid was charged. While maintaining the temperature at 85 ° C., gradually hydrogen peroxide (60%) 5
3 g (0.94 mol) was reacted dropwise (reaction rate: 98).
%that's all). Thereafter, 213 g of water was charged, and monochloroacetic acid was removed by washing with water.
1.5 mol with respect to dodecene. Thereafter, 54 g (1.35 mol) of sodium hydroxide in the form of beads was charged in 5 parts over 2 hours. Further aging was performed for 3 hours. Then, after controlling the water content in the system to 1.0%, 54 g (1.35 mol) of sodium hydroxide in the form of beads was charged in 5 parts over 2 hours. After the completion of the reaction, measurement was performed using liquid chromatography. As a result, 23 g of compound No. 23, 159 g of compound No. 7, 57 g of compound No. 14, and 17 g of by-product No. 2 were formed. <Liquid chromatography measurement conditions>-Column: Shiseido Capsule Pack C18 SG 1
20 A, 4.6 mm Φ × 25 cm Column temperature: 40 ° C. Eluent: acetonitrile / water = 53/47 (V /
V), 0.02M phosphoric acid, 0.01M
Sodium dihydrogen phosphate ・ Flow rate: 1.0 ml / min. ・ Sample concentration: 1% ・ Injection volume: 40 μl

Example 2 176 g of 1-tetradecene (0.90 g) was placed in a four-necked 1 L flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a stirrer.
Mol) and 383 g (4.05 mol) of monochloroacetic acid. While maintaining the temperature at 85 ° C., 53 g (0.94 mol) of hydrogen peroxide (60%) was gradually added dropwise to the reaction (reaction rate: 90%). Thereafter, 213 g of water was charged and monochloroacetic acid was removed by washing with water, and the molar ratio of monochloroacetic acid was adjusted to 1.5 mol with respect to 1-dodecene. afterwards,
54 g (1.35 mol) of sodium hydroxide in the form of beads were charged in 5 parts over 2 hours. Further aging was performed for 3 hours. Then, after controlling the water content in the system to 1.0%, 54 g (1.35 mol) of sodium hydroxide in the form of beads was added to 2 parts.
It was charged in five parts over time. After completion of the reaction, Compound No. 24 showed 2 by measurement using liquid chromatography.
5 g, 168 g of compound No. 9 and 58 of compound No. 15
g, and 25 g of By-product No. 2 were produced.

Example 3 In a four-necked 1 L flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer, 121 g (0.72 mol) of 1-dodecene, 409 g (4.33 mol) of monochloroacetic acid, 1 g of ethylenediaminetetraacetic acid was charged. While maintaining the temperature at 85 ° C, 43 g of hydrogen peroxide (60%) (0.76%) was gradually added.
Mol) was reacted dropwise (reaction rate: 95%). afterwards,
284 g of water was charged, and monochloroacetic acid was removed by washing with water. The molar ratio of monochloroacetic acid was 1 to 1-dodecene.
It was 5 mol. Then, beaded sodium hydroxide 4
3 g (1.08 mol) were charged in 5 parts over 2 hours. Further aging was performed for 3 hours. Then, after controlling the water content in the system to 1.0%, sodium hydroxide 4 in the form of beads was added.
3 g (1.08 mol) were charged in 5 portions over 2 hours.
After the completion of the reaction, 17 g of Compound No. 23 and 119 of Compound No. 7 were measured by liquid chromatography.
g, compound No. 14 was 48 g, and by-product No. 2 was 18
g.

Example 4 79 g (0.47 mol) of 1-dodecene and 445 g (4.71 mol) of monochloroacetic acid were placed in a four-necked 1 L flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube and a stirrer. I charged. While maintaining the temperature at 85 ° C., gradually add hydrogen peroxide (6
(0%) 28 g (0.49 mol) was allowed to react dropwise (reaction rate: 90%). Thereafter, 473 g of water was charged, and monochloroacetic acid was removed by washing with water, and the molar ratio of monochloroacetic acid was adjusted to 1.5 mol with respect to 1-dodecene. Thereafter, 28 g (0.70 mol) of sodium hydroxide in the form of beads was charged in 5 parts over 2 hours. Further aging was performed for 3 hours.
Then, after controlling the water content in the system to 1.0%, 28 g (0.70 mol) of sodium hydroxide in the form of beads was charged in 5 parts over 2 hours. After completion of the reaction, measurement using liquid chromatography revealed that 9 g of compound No. 23, 74 g of compound No. 7, 30 g of compound No. 14, and 11 g of by-product No. 2 were formed.

Comparative Example 1 1,4-dodecanediol (purity: 8) was placed in a four-necked 1 L flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube, and a stirrer.
231 g (0.92 mol), 128 g (1.10 mol) of sodium monochloroacetate and 243 g of toluene were charged. While maintaining the temperature at 70 ° C., 44 g (1.10 mol) of an aqueous sodium hydroxide solution in the form of beads was gradually charged in 2 hours. Further aging was performed for 3 hours. During the reaction, the water content in the system was controlled to 2.5%. After completion of the reaction, when measured using liquid chromatography, Compound No.
23, 17 g, Compound No. 7 163 g, Compound No. 14
Was produced, and 46 g of By-product No. 2 was produced.

Comparative Example 2 71.8 g of monochloroacetic acid, 29.6 g of sodium monochloroacetate, and 110.0 g of toluene were placed in a four-necked 1 L flask equipped with a reflux device, a thermometer, a nitrogen introducing tube, and a stirrer. While maintaining the temperature at 70 ° C., 87.8 g of 1,2-epoxydodecane (purity: 85%) was added dropwise over 3 hours. Further aging was performed 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 charging, the reaction was carried out at the same temperature for 10 hours. After completion of the reaction, measurement was carried out using liquid chromatography, and as a result, 8 g of compound No. 23, 56 g of compound No. 7, 20 g of compound No. 14, and 20 g of by-product No. 2 were produced.

Comparative Example 3 In a four-necked 1 L flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a stirrer, 206 g (1.23 mol) of 1-dodecene and 232 g (2.46 mol) of monochloroacetic acid were placed. I charged. While maintaining the temperature at 85 ° C., gradually add hydrogen peroxide (6
(0%) 72 g (1.27 mol) was reacted dropwise (reaction rate: 90%). Thereafter, 95 g of water was charged, and monochloroacetic acid was removed by washing with water.
-1.5 moles relative to dodecene. Thereafter, 74 g (1.85 mol) of sodium hydroxide in the form of beads was charged in 5 parts over 2 hours. Further aging was performed for 3 hours. Then, after controlling the water content in the system to 1.0%, 74 g (1.85 mol) of sodium hydroxide in the form of beads was charged in 5 parts over 2 hours. After the completion of the reaction, measurement was performed using liquid chromatography. As a result, 25 g of compound No. 23, 168 g of compound No. 7, 60 g of compound No. 14, and 85 g of by-product No. 2 were produced.

Example 5 To the reaction product obtained in Comparative Example 2, 137 g of hydrochloric acid (36%) (1.
35 mol) and 427 g of water were added, the Na salt was changed to the acid form, and the generated NaCL was removed by washing with water. afterwards,
After the toluene was distilled off under reduced pressure, purification was carried out by steam distillation under the following conditions.
160 g of o.1 and 2 and 18 g of compound No. 14 were obtained. <Steam distillation conditions>-Decompression degree: 100 mmHg-Blow-in steam amount: 3 g / min-Distillation temperature Bottom temperature: 230 ° C Tower top temperature: 140 ° C

[0042]

According to the production method of the present invention, the production method is simple,
Moreover, by using a high-purity 1-alkene, the production process of the 1,2-alkanediol or 1,2-epoxyalkane used as a raw material in the conventional production method is complicated, and the purity is low. Since the problem has been solved, the present substance can be produced with high purity and at low cost. That is, in the method of the present invention, after the reaction (before purification)
In the step, the production rate of by-products can be generally suppressed by about 10 to 15% as compared with the conventional method using a raw material having low purity.

Claims (4)

(57) [Claims] 1. A reaction product (A) of a 1-alkene, a monohaloacetic acid and hydrogen peroxide represented by the following general formula (1) is reacted with a base: Method for producing carboxylic acids. General formula RCH = CH ₂ (1) (wherein, R is a linear or branched alkyl group having 4 to 34 carbon atoms.) General formula RCHCH ₂ OX ₁ (2) | OX ₂ R is a linear or branched alkyl group having 4 to 34 carbon atoms, and at least one of X ₁ and X ₂ is -C
H ₂ COOM, and the rest are hydrogen atoms. M is a cation. ) 2. The following general formula, wherein a reaction product (A) of a 1-alkene, a monohaloacetic acid and hydrogen peroxide represented by the following general formula (1) is reacted with a base, and further subjected to salt exchange. A method for producing a carboxylic acid represented by (2). General formula RCH = CH ₂ (1) (wherein, R is a linear or branched alkyl group having 4 to 34 carbon atoms.) General formula RCHCH ₂ OX ₁ (2) | OX ₂ R is a linear or branched alkyl group having 4 to 34 carbon atoms, and at least one of X ₁ and X ₂ is -C
H ₂ COOM, and the rest are hydrogen atoms. M is a cation. ) 3. M in the general formula (2) is an alkali metal,
3. The method according to claim 1, wherein the cation is selected from the group consisting of alkaline earth metals, ammonium cations, lower alkanolamine cations, lower alkylamine cations and basic amino acid cations. 4. The method according to claim 1, wherein said base is caustic.
3. The production method according to any one of 3.