JPH0559033A - Epoxysuccinic acid derivative and its production - Google Patents

Abstract

PURPOSE:To obtain a new epoxysuccinic acid in which a bond between alpha position and beta position of a sulfonated alpha,beta-unsaturated dicarboxylic acid is epoxidized, useful as a starting raw material for detergent, dispersing agent, water treating agent, surfactant, etc. CONSTITUTION:An epoxysuccinic acid derivative expressed by formula I (R is H or 1-4C saturated aliphatic hydrocarbon) or its salt, e.g. sodium sulfoepoxysuccinate. The compound expressed by formula I is obtained by reacting a sulfomaleic anhydride derivative expressed by formula II with hydrogen peroxide in a water solvent in the presence of an inorganic or organic base and epoxidation catalyst (preferably at least one compound of a metal, especially selected from the group consisting of MO, Co, Ti, V and W) at pH 2-8. The objective succinic acid derivative includes a compound constituting a salt between two molecules as shown in formula III (B is divalent inorganic base or organic base).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel epoxysuccinic acid derivative and a process for producing the same, which is useful as a raw material for producing detergents, dispersants, detergents, water treatment agents, surfactants and the like. is there.

[0002]

2. Description of the Related Art A method for producing a sulfonated .alpha.,. Beta.-unsaturated dicarboxylic acid by sulfonating an .alpha.,. Beta.-unsaturated dicarboxylic acid anhydride and then hydrolyzing it is described, for example, in Rec. Tr
av. Chim. , 46 , 473 (1927) and the like. Further, as shown in the following reaction formula, a method for producing an α-hydroxy-β-sulfosuccinate by reacting an alkali metal hydroxide with a sulfonated α, β-unsaturated dicarboxylic acid anhydride, for example, USP3, 912,663.

[0003]

[Chemical 3]

[0004]

DISCLOSURE OF THE INVENTION The present invention aims to provide a novel epoxysuccinic acid derivative in which a sulfonated α, β-unsaturated dicarboxylic acid is epoxidized between the α-position and the β-position, and a method for producing the same. Is.

[0005]

The present invention has the following general formula:
It is an epoxysuccinic acid derivative represented by [I] or a salt thereof.

[0006]

[Chemical 4]

This epoxysuccinic acid derivative is mixed with a sulfomaleic anhydride derivative represented by the following general formula [II] in a pH range of 2 to 8 in the presence of an inorganic base or organic base and an epoxidation catalyst in a water solvent. It can be obtained in good yield by reacting with hydrogen oxide.

[0008]

[Chemical 5]

[0009]

In the epoxysuccinic acid derivative according to the present invention, the substitution period R is hydrogen atom, methyl, ethyl,
Examples thereof include saturated aliphatic hydrocarbons having 1 to 4 carbon atoms such as propyl and butyl. As the salt of the epoxysuccinic acid derivative, lithium, sodium, a salt with an alkali metal such as potassium, magnesium, calcium, strontium, a salt with an alkaline earth metal such as barium, a zinc salt, an inorganic salt such as an ammonium salt, And methylamine, ethylamine, ethanolamine, aniline, dimethylamine,
Examples thereof include salts with organic bases such as pyridine and triethylamine. When the above-mentioned base is, for example, a divalent ion base, a salt is formed between two molecules as shown in the following formula, and such a case is also included in the present invention.

[0010]

[Chemical 6]

Specific examples of the salt of the epoxysuccinic acid derivative include 2-sulfoepoxysuccinic acid dihydrogen 1 sodium, 2-sulfoepoxysuccinic acid dihydrogen 1 potassium 2
-Sulfoepoxy succinic acid dihydrogen 1 ammonium, 2-
Sulfoepoxy succinic acid monosodium hydrogen, 2-sulfoepoxy succinic acid dipotassium hydrogen, 2-sulfoepoxy succinic acid dihydrogen ammonium, 2-sulfoepoxy succinic acid 3 sodium, 2-sulfoepoxy succinic acid 3 potassium, 2-sulfo epoxy succinic acid 3 ammonium, 2-sulfo epoxy succinic acid 2 hydrogen 1/2 calcium, 2-sulfo epoxy succinic acid 2 hydrogen 1/2 magnesium, 2-sulfo epoxy succinic acid 2 hydrogen 1/2 barium, 2- Sulfone Epoxy succinic acid 2 hydrogen 1/2 zinc, 2
-Sulfoepoxy succinic acid 1 hydrogen 1 calcium, 2-sulfo epoxy succinic acid 1 hydrogen 1 magnesium, 2-sulfone epoxy succinic acid 1 hydrogen 1 barium, 2-sulfo epoxy succinic acid 1 hydrogen 1 zinc, 2-sulfo epoxy succinic acid 2 Hydrogen 1 Alinine, 2-Sulfoepoxy succinic acid 2
Hydrogen 1 trimethylamine, 2-sulfoepoxysuccinic acid 2 hydrogen 1 triethylamine, 2-sulfoepoxy succinic acid 2 hydrogen 1 pyridine, 2-sulfoepoxy succinic acid 1 hydrogen 2 aniline, 2-sulfoepoxy succinic acid 1 hydrogen 2 trimethylamine, 2- Sulfoepoxy succinic acid 1 hydrogen 2
Triethylamine, 2-sulfoepoxysuccinic acid 1 hydrogen 2 pyridine, 2-sulfoepoxy succinic acid 3 aniline,
2-sulfoepoxysuccinic acid 3 trimethylamine, 2-
Examples thereof include 2-sulfoepoxysuccinic acid salts such as sulfoepoxysuccinic acid 3 triethylamine and 2-sulfoepoxysuccinic acid 3 pyridine.

The above-mentioned 2-sulfoepoxysuccinic acid derivatives and salts thereof according to the present invention have reaction activity and surface activity derived from sulfonic acid groups and dicarboxylic acid groups and their salts and epoxy groups contained in the molecule. Have, detergent,
Not only is it useful as a raw material for dispersants, detergents, water treatment agents, scale inhibitors, surfactants, etc., but it can also be used as a surfactant or the like by selecting the type of salt.

The above-mentioned 2-sulfoepoxysuccinic acid derivative or a salt thereof is obtained by adding the sulfomaleic anhydride derivative represented by the general formula [II] to an inorganic base or organic base and an epoxidation catalyst in an aqueous solvent. It can be produced in good yield by reacting hydrogen peroxide in the pH range of 2 to 8.

Examples of the inorganic base used here include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as calcium, magnesium and barium, metal hydroxides such as zinc, carbonates and bicarbonates. Salts, ammonia and the like can be mentioned, and preferable examples of the organic base include organic amines such as aniline, trimethylamine, triethylamine and pyridine.

As the epoxidation catalyst, a water-soluble or water-dispersible metal compound containing a metal such as molybdenum, cobalt, titanium, vanadium, or tungsten is used. Among the epoxidation catalysts, sodium tungstate or potassium tungstate is particularly preferable. The preferred addition amount of the epoxidation catalyst is in the range of 0.001 to 1 equivalent based on the raw material compound represented by the general formula [II].

This reaction is carried out in an aqueous solvent, but the pH of the reaction system needs to be set within the range of 2 to 8, more preferably 4 to 6, and the pH is out of this range and in a strongly acidic region or alkaline. In the region, a large amount of a hydroxylated product in which a water molecule is added to the double bond portion of the compound represented by the general formula [II] is by-produced, which not only extremely lowers the yield of the target product but also causes strong acidity below pH 2. On the other hand, for example, sodium tungstate used as an epoxidation catalyst becomes tungstic acid and the catalytic activity is remarkably lowered, and the progress of the epoxidation reaction is remarkably hindered. The temperature of the epoxidation reaction varies depending on the type of the epoxidation catalyst and the reaction pressure, but is usually 0 to 100 ° C, preferably 20 to 90 ° C.
It is carried out in the range of.

The method for producing the target compound represented by the general formula [I] will be described below. First, the starting compound represented by the general formula [II] is the following compound [III] produced by a known method from maleic anhydride and sulfuric anhydride.

[0018]

[Chemical 7]

It can be easily obtained by adding dropwise to pure water adjusted to -5 to 50 ° C and stirring for about 5 to 120 minutes. At this time, the compound [III] is at least 30
It is advisable to drop the solution in cold water in a liquid state maintained at a temperature of ℃ or more. When compound [III] is dropped into pure water, the liquid temperature rises due to the reaction heat associated with hydrolysis, and if the temperature rises too much, water is added to the double bond portion of compound [III] to form a hydroxylated product. As a by-product, the reaction system should be cooled during hydrolysis so that the temperature of the reaction system does not exceed 50 ° C. The aqueous solution concentration at this time was
II] to 10-500% by weight of water solvent, more preferably
It is recommended to set it in the range of 150 to 300% by weight. If the concentration is too high, it becomes difficult to stir the reaction system and the temperature control becomes difficult. On the other hand, if the concentration is too low, a large amount of energy is required for the subsequent concentration, which is not practical.

To the thus obtained aqueous solution containing the compound represented by the general formula [II], 1 to 2 equivalents of the above-mentioned inorganic base or organic base is added dropwise to adjust the pH to 2 to 8. During this period, the reaction temperature is maintained at -5 to 50 ° C to prevent the formation of hydroxylated product and ensure an appropriate reaction rate.

To this aqueous solution, 0.001 to 1 equivalent of an epoxidation catalyst is added, and subsequently 1 to 10 equivalents of hydrogen peroxide is added to carry out an epoxidation reaction. At this time, the epoxidation reaction proceeds with the addition of hydrogen peroxide, and the pH of the reaction system
Since it gradually shifts to the acidic side, the aqueous solution of the inorganic base or organic base used for pH adjustment at the initial stage of the reaction is sequentially added to maintain the reaction system in the above-mentioned suitable pH range. Also in this epoxidation reaction step, the temperature of the reaction system gradually rises due to the heat of reaction, so it is desirable to cool it so that the temperature does not become excessively high. The preferred reaction temperature at this time is 0 to 100 ° C, more preferably 20 to 90 ° C.
However, in the early to the first half of the epoxidation reaction, the hydroxylation reaction due to the addition of water to the double bond is likely to occur, so the reaction temperature should be controlled lower, and in the latter half of the epoxidation reaction, It is desired to increase the reaction temperature to increase the reaction yield.

After completion of the reaction, when the reaction solution is poured into an organic solvent such as methanol, ethanol or acetone, the target substance is precipitated. Therefore, if this is purified by a conventional method such as recrystallization method, the target substance of high purity can be obtained. Can be obtained as crystals. Further, when the reaction is completed and then treated with an acid such as hydrogen chloride and then purified, the target substance can be obtained in the form of an organic acid.

[0023]

INDUSTRIAL APPLICABILITY The present invention is constituted as described above and can provide a compound containing a sulfonic acid group, an epoxy group and a carboxylic acid group in the molecule and useful as a raw material for a surfactant, a dispersant and the like. is what happened.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. Example 1 A liter-volume flask equipped with a stirrer, a pH meter, a dropping funnel, and a cooling device was charged with 445 ml of pure water and adjusted to 0 ° C. 178 g of maleic acid was gradually added from the dropping funnel. During this time, while cooling the temperature of the aqueous solution so as not to exceed 20 ° C., an aqueous NaOH solution was added dropwise from another dropping funnel to adjust the pH of the reaction system to 4.5. Then, the temperature of this aqueous solution is raised to 60 ° C., and the pH is adjusted with 0.1 N NaOH aqueous solution.
= 4.5, sodium tungstate (3.3 g) was added, the mixture was stirred for 20 minutes, and then 60% hydrogen peroxide solution (56.7 g) was added dropwise over 20 minutes using a dropping funnel. After stirring for 3 hours at the same temperature, the reaction solution was added to 4 liters of methanol in a 5 liter beaker for crystallization,
Further water-methanol solution (water / methanol weight ratio = 50 /
50) was recrystallized twice to obtain 325 g of white crystals (target compound). The yield of white crystals corresponds to 98.0 mol% based on the raw material sulfomaleic anhydride used. The analysis results of the white crystals are as follows. NMR: 1H-NMR (D20) δ 3.9 (s, 1H) ppm (see FIG. 1) 13C-NMR (D20) δ 171.8, 168.1, 72.5, 59.1ppm IR (KBr): 1220 cm ^-1 (epoxy ring symmetry Stretching (see Fig. 2) 940 cm ^-1 (reverse symmetrical stretching of the epoxy ring) 815 cm ^-1 (12μ absorption band of the epoxy ring) Elemental analysis: Empirical formula C ₄ HO ₈ SNa ₃ · 3H ₂ O Calculated value C : 14.47, H: 2.12, S: 9.65, Na: 20.77 Actual value C: 14.46, H: 2.23, S: 9.69, Na: 20.83 From the above analysis results, the obtained white crystals were the target compound, sulfoepoxy amber. It was confirmed to be sodium acid.

Comparative Example 1 In a 1 liter flask equipped with a stirrer, a dropping funnel and a cooling device, 330 g of dioxane was added and adjusted to 0 ° C., and 132 g of powdered cis-epoxysuccinic acid was added thereto.
Was gradually added. Then, while cooling so that the temperature of the solution does not exceed 5 ° C, 80% sulfuric acid was added using a dropping funnel.
g was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 2 hours. After the reaction was completed, the solvent was removed under reduced pressure.
1 g of dark brown crystals were obtained. When the crystals were analyzed by liquid chromatography, they were confirmed to be cis-epoxysuccinic acid, and sulfoepoxysuccinic acid was not produced. As is apparent from this experiment, even if an epoxysuccinic acid is used as a raw material and sulfonated to obtain the objective compound of the present invention, the objective cannot be achieved.

Comparative Example 2 The reaction temperature after the dropwise addition of sulfuric anhydride in Comparative Example 1 was 60 ° C.
When the reaction was carried out in exactly the same manner except that
A tar-like substance was obtained. When this was analyzed by liquid chromatography, it was a mixture of compounds that were difficult to identify, and the presence of sulfoepoxysuccinic acid could not be confirmed. As is clear from the results of Comparative Examples 1 and 2, even if an epoxysuccinic acid is used as a starting material and this is sulfonated with sulfuric anhydride to obtain the object compound of the present invention, the object cannot be achieved.

[Brief description of drawings]

FIG. 1 is an NMR of an epoxysuccinic acid derivative according to the present invention.
It is a chart.

FIG. 2 is an IR chart of an epoxysuccinic acid derivative according to the present invention.

Claims (3)

[Claims] 1. An epoxysuccinic acid derivative or salt thereof represented by the following general formula [I]: [Chemical 1] 2. A sulfomaleic anhydride derivative represented by the following general formula [II] is reacted with hydrogen peroxide in a water solvent in the presence of an inorganic base or an organic base and an epoxidation catalyst in the range of pH 2 to 8. A method for producing an epoxysuccinic acid derivative, comprising obtaining the epoxysuccinic acid derivative according to claim 1 or a salt thereof. [Chemical 2] 3. The method according to claim 2, wherein the epoxidation catalyst is a compound of at least one metal selected from the group consisting of molybdenum, cobalt, titanium, vanadium, and tungsten.