JPH083101A - Production of carboxylic acid compound - Google Patents

Abstract

PURPOSE:To easily and in higher purity obtain a carboxylic acid compound having ethercarboxylic acid salt structure useful as surfactant by using a high- purity 1-alkene. CONSTITUTION:This carboxylic acid compound of formula II [at least one or both of X1 and X2 are CH2COOM (M is a cation), and the remaining is H] is obtained by reaction of a base (pref. a caustic alkali) with a reaction product from a 1-alkene of formula I (R is a 4-34C straight chain or branched alkyl), a monohaloacetic acid and hydrogen peroxide followed by, if needed, salt exchange. In this reaction, the molar ratios 1-alkene/monohaloacetic acid and 1-alkene/hydrogen peroxide are 1.0:(0.5-10) [pref. 1.0:(1.0-5.0)] and 1.0:(0.5-3.0) [pref. 1.0:(0.9-1.5)], respectively. The compound of formula II is obtained as a mixture of monocarboxymethylated product and dicarboxymethylated product. When this compound is to be used as a raw material for surfactants, the weight ratio for these two kinds of methylated products is pref. (90:10) to (50:50).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing carboxylic acids having an ether carboxylate structure which are useful as a surfactant.

[0002]

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

[0003]

However, in the production methods of and, since the production process of 1,2-alkanediol or 1,2-epoxyalkane used as a raw material is complicated and the purity is insufficient, There has been a problem that improvement is needed as a raw material for inexpensively obtaining a high-purity ether carboxylate.

[0004]

Means for Solving the Problems The inventors of the present invention diligently studied a method for obtaining a carboxylic acid with a 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 reached.

That is, the present invention is characterized in that the reaction product (A) of 1-alkene represented by the following general formula (1), monohaloacetic acid, and hydrogen peroxide is reacted with a base and, if necessary, salt exchange is carried out. And a method for producing a carboxylic acid represented by the following general formula (2). Formula RCH = CH ₂ (1) (wherein, R is a linear or branched alkyl group having 4 to 34 carbon atoms.) In formula (In the formula, R is a linear or branched alkyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH.
₂ COOM and the rest are hydrogen atoms. M is a cation. )

In the general formula (1), as the 1-alkene, 1-hexene, 1-octene, 1-nonene, 1-
Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-eicocene, 1-heicocene, 1-dococene, 1-tricocene, 1-tetracocene, 7-methyl-1-nonene, 11-methyl-1-heptadecene, 12-methyl-1-eicosene, 15-methyl-1-pentacosene, 17-methyl-1-octacosene and the like can be mentioned.

The pure content of the 1-alkene is usually 98% by weight.
That is all. This product is easily obtained industrially. The pure content of 1,2-alkanediol and 1,2-epoxyalkane, which are the 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 is a butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group,
Examples include 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. To be These may be mixed groups of two or more.

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 alkali metal ions include lithium, potassium and sodium ions, examples of alkaline earth metal ions include calcium and magnesium ions, and examples of lower alkanolamine cations include:
Triethanolamine, diethanolamine and monoethanolamine cations and the like, and basic amino acid cations include lysine and arginine cations and the like. Two or more kinds of these ions may be mixed. Among these, alkali metal ions are preferable, and potassium ions and sodium ions are particularly preferable.

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

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

[0012]

[Table 1]

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

Examples of monohaloacetic acid include monochloroacetic acid and monobromoacetic acid. Of these, preferred is monochloroacetic acid from the viewpoint of cost.

Suitable bases for use in the present invention are caustic alkali such as sodium hydroxide and potassium hydroxide. The caustic may be solid or aqueous. Solid caustic includes flakes, beads and powders. From the standpoint of workability, bead-like solid caustic alkali is preferred. In the case of flakes, the fluidity during charging is poor, and in the case of powder, fine powder flies during charging, causing a safety problem.

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

In the present invention, when the reaction product (A) of 1-alkene represented by the general formula (1), monohaloacetic acid and hydrogen peroxide is produced, the molar ratio of 1-alkene and monohaloacetic acid is usually 1. 0.0: 0.5-10, preferably 1.0-5.0. The molar ratio of 1-alkene to hydrogen peroxide is usually 1.0: 0.5 to 3.0, preferably 1.0: 0.
It is 9 to 1.5.

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

Examples of the compound represented by the general formula (3) and the mixture thereof include those listed 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) are produced and the purity is lowered. Also, use of more than 10 is meaningless in terms of cost. <Side reaction> (In the formula, R is a linear or branched alkyl group having 4 to 34 carbon atoms.)

As the by-product represented by the general formula (4),
Those listed in Table 3 can be mentioned.

[0023]

[Table 3]

In the present invention, the molar ratio of the alkali used in the reaction of the reaction product (A) with the base is usually 1.0: 1.0 to 4.0, preferably 1.0: to monohaloacetic acid.
It is 1.5 to 3.0. If it is 1.0 or less, the present carboxylic acids cannot be obtained in good yield. It is not necessary to input more than 4.0.

In the present invention, the reaction temperature for producing the reaction product (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 reaction product (A), if necessary, a mineral acid such as sulfuric acid or phosphoric acid, a heteropolyphosphoric acid such as phosphotungstic acid or phosphomolybdic acid, 1
An organic phosphoric acid such as -hydroxyethylidene-1,1-diphosphonic acid and aminotrimethylenephosphonic acid, and a nitrogen-containing carboxylic acid 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 added is usually 0.1 in the reaction system.
It is 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 more than 2.0%.

In the present invention, the reaction temperature of the reaction product (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, and when the temperature exceeds 100 ° C, the hydrolysis of monohaloacetic acid precedes, and the yield of the present carboxylic acids decreases.

In the present invention, when the reaction product (A) is reacted with the base, it is preferable to control the water content of the reaction system. The reaction is usually 10% or less, preferably 5% or less. When the water content in the reaction system during the reaction exceeds 10%,
The hydrolysis of monohaloacetic acid to glycolic acid precedes and the yield of the present carboxylic acids decreases.

In the present invention, the method of 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, etc. are not particularly limited.

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

In the present invention, as means for removing the reaction product generated by the side reaction and its carboxymethylated product, M in the general formula (2) is replaced with hydrogen atom and distilled (eg, molecular distillation, thin film distillation, steam distillation, etc.). , And can be purified by a method such as recrystallization, and the content of the by-product represented by the general formula (4) is 0.
It can be 2% or less of the carboxylic acids.

The carboxylic acids produced by the present production method are useful as, for example, skin cleansing agents such as body shampoo and face wash, hair washing agents such as shampoo, and household detergents such as dish washing detergent. Further, taking advantage of the characteristics of the compound of the present invention, cosmetics, pharmaceuticals, pesticides, fibers, machines,
Metal, plastic, rubber, petroleum, paper pulp, leather, cleaning, food, dye, pigment, paint, ink, civil engineering,
Cleaning agents, foaming agents, penetrants in construction, ceramic industry, mining industry, etc.
It can be widely used as an emulsifier, a solubilizer, a dispersant, a lubricant, a lubricant, an antistatic agent and a rust preventive.

[0033]

The present invention will be further described below 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 introduction tube, and a stirrer, 151 g of 1-dodecene (0.90 mol), 383 g of monochloroacetic acid (4.05 mol), 1,
1 g of 1-hydroxyethanediphosphonic acid was charged. Gradually hydrogen peroxide (60%) 5 while keeping the temperature at 85 ° C
3 g (0.94 mol) was reacted dropwise (reaction rate: 98).
%that's all). Then, 213 g of water was charged, and monochloroacetic acid was removed by washing with water, and the molar ratio of monochloroacetic acid was 1-
It was 1.5 mol based on dodecene. Thereafter, 54 g (1.35 mol) of bead-shaped sodium hydroxide was charged in 5 portions over 2 hours. Further aging was carried out for 3 hours. Then, the water content in the system was controlled to 1.0%, and 54 g (1.35 mol) of bead-shaped sodium hydroxide was charged in 5 portions over 2 hours. After completion of the reaction, measurement by liquid chromatography revealed that 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 produced. <Liquid chromatography measurement conditions> ・ Column: Shiseido Capsule Pack C18 SG 1
20A, 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 (0.90 g) of 1-tetradecene was placed in a 4-necked 1 L flask equipped with a reflux condenser, a thermometer, a nitrogen introducing 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 dropped to react (reaction rate: 90%). Then, 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 bead-shaped sodium hydroxide was charged in 5 portions over 2 hours. Further aging was carried out for 3 hours. After that, the water content in the system was controlled to 1.0%, and then 54 g (1.35 mol) of bead-shaped sodium hydroxide was added to 2%.
It took 5 hours to prepare. After the completion of the reaction, the compound No. 24 was 2 when measured by liquid chromatography.
5 g, compound No. 9 is 168 g, compound No. 15 is 58
25 g of the by-product No. 2 was produced.

Example 3 121 g (0.72 mol) of 1-dodecene, 409 g (4.33 mol) of monochloroacetic acid were placed in a 4-necked 1 L flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube and a stirrer. 1 g of ethylenediaminetetraacetic acid was charged. While maintaining the temperature at 85 ° C, gradually hydrogen peroxide (60%) 43 g (0.76)
(Mol) was reacted dropwise (reaction rate: 95%). afterwards,
After charging 284 g of water and removing monochloroacetic acid by washing with water, the molar ratio of monochloroacetic acid is 1 to 1-dodecene.
It was 5 mol. After that, beaded sodium hydroxide 4
3 g (1.08 mol) was charged in 5 portions over 2 hours. Further aging was carried out for 3 hours. After that, the water content in the system was controlled to 1.0%, and then bead-shaped sodium hydroxide 4
3 g (1.08 mol) was charged in 5 portions over 2 hours.
After completion of the reaction, measurement by liquid chromatography revealed that Compound No. 23 was 17 g and Compound No. 7 was 119.
g, compound No. 14 is 48 g, and by-product No. 2 is 18 g
g had been produced.

Example 4 79 g (0.47 mol) of 1-dodecene and 445 g (4.71 mol) of monochloroacetic acid were placed in a 4-necked 1 L flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube and a stirrer. I prepared it. Gradually hydrogen peroxide (6
28% (0.49 mol) of 0%) was reacted dropwise (reaction rate: 90%). Then, 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. Then, 28 g (0.70 mol) of sodium hydroxide in the form of beads was charged in 5 portions over 2 hours. Further aging was carried out for 3 hours.
Then, the water content in the system was controlled to 1.0%, and then 28 g (0.70 mol) of bead-shaped sodium hydroxide was charged in 5 portions over 2 hours. After completion of the reaction, measurement by liquid chromatography revealed that compound No. 23 was 9 g, compound No. 7 was 74 g, compound No. 14 was 30 g, and by-product No. 2 was 11 g.

Comparative Example 1 1,2-dodecanediol (purity: 8) was placed in a 4-necked 1 L flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer.
0%) 231 g (0.92 mol), sodium monochloroacetate 128 g (1.10 mol), and toluene 243 g were charged. While maintaining the temperature at 70 ° C., 44 g (1.10 mol) of a bead-shaped aqueous sodium hydroxide solution was gradually charged in 2 hours. Further aging was carried out for 3 hours. During the reaction, the water content in the system was controlled to 2.5%. After completion of the reaction, the compound No. was measured by liquid chromatography.
23 is 17 g, Compound No. 7 is 163 g, Compound No. 14
Was produced in an amount of 60 g, and by-product No. 2 was produced in an amount of 46 g.

Comparative Example 2 71.8 g of monochloroacetic acid, 29.6 g of sodium monochloroacetate and 110.0 g of toluene were charged into a 4-necked 1 L flask equipped with a reflux condenser, 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 carried out for 2 hours. After cooling to 45 ° C., 20.6 g of water and 71.0 g of sodium hydroxide were added portionwise. After the addition was completed, the reaction was carried out at the same temperature for 10 hours. After completion of the reaction, measurement by liquid chromatography revealed that compound No. 23 was 8 g, compound No. 7 was 56 g, compound No. 14 was 20 g, and by-product No. 2 was 20 g.

Comparative Example 3 206 g (1.23 mol) of 1-dodecene and 232 g (2.46 mol) of monochloroacetic acid were placed in a 4-necked 1 L flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube and a stirrer. I prepared it. Gradually hydrogen peroxide (6
72 g (1.27 mol) of 0%) was reacted dropwise (reaction rate: 90%). After that, 95 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
-1.5 mol relative to dodecene. Then, 74 g (1.85 mol) of bead-shaped sodium hydroxide was charged in 5 portions over 2 hours. Further aging was carried out for 3 hours. Thereafter, the water content in the system was controlled to 1.0%, and then 74 g (1.85 mol) of bead-shaped sodium hydroxide was charged in 5 portions over 2 hours. After completion of the reaction, measurement by liquid chromatography revealed that 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 5 137 g of hydrochloric acid (36%) (1.
35 mol) and 427 g of water were added, the Na salt was converted to the acid form, and the produced 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. Compound No. 23 was 4 g and compound N was
160 g of o.1 and 2 and 18 g of compound No. 14 were obtained. <Steam distillation conditions> -Decompression pressure: 100 mmHg-Blowing steam amount: 3 g / min-Distillation temperature Bottom temperature: 230 ° C Tower top temperature: 140 ° C

[0042]

The manufacturing method of the present invention is simple,
Moreover, by using a high-purity 1-alkene, the production process of 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 is solved, this 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 this step, the production rate of by-products can be usually suppressed by about 10 to 15% as compared with the conventional method using a low-purity raw material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Red ▲ Saki ▼ Sayumi 1 11-11, Hitotsubashi-honcho, Higashiyama-ku, Kyoto Sanyo Chemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A reaction product (A) of 1-alkene represented by the following general formula (1), monohaloacetic acid and hydrogen peroxide is reacted with a base, and salt exchange is carried out if necessary. A method for producing a carboxylic acid represented by formula (2). Formula RCH = CH ₂ (1) (wherein, R is a linear or branched alkyl group having 4 to 34 carbon atoms.) In formula (In the formula, R is a linear or branched alkyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH.
₂ COOM and the rest are hydrogen atoms. M is a cation. ) 2. M in the general formula (2) is an alkali metal,
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. 3. The method according to claim 1, wherein the base is caustic.