JPH10204044A - Production of amino-ethercarboxylic acid or its salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To economically produce the subject high-purity compound, useful as a builder for detergents and excellent in chelating ability in high yield at a low cost by carrying out the oxidizing dehydrogenating reaction of an amino- ether alcohol in the presence of an alkali metallic hydroxide, water and a copper-containing catalyst. SOLUTION: The oxidizing dehydrogenating reaction of an amino-ether alcohol represented by formula I [(m) and (n) are each 0-5] is carried out by using an alkali metallic hydroxide such as NaOH or KOH, water and a copper- containing catalyst, e.g. metallic copper, copper nitrate or a developed Raney copper to remove the produced H. Thereby, an amino-ethercarboxylic acid or its salt represented by formula II (M is H, an alkali metal, etc.) is obtained. The alkali metallic hydroxide is used in an equiv. amount within the range of 0.9-2.0 times based on OH groups in the compound represented by formula I. The water and the catalyst are used in respective amounts of >=50wt.% and 1-50wt.% based on the compound represented by formula I. The produced H is removed so as to usually keep the temperature at 150-260 deg.C and the reactional pressure at 8-30kg/cm<2> G.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an aminoether carboxylic acid or a salt thereof, and more particularly to an aminoether carboxylic acid or a salt thereof useful as a builder for a detergent can be obtained with high purity and high yield. It concerns the manufacturing method.

[0002]

2. Description of the Related Art Builders used in detergents improve the washing effect of surfactants and soaps by capturing calcium ions and magnesium ions in water and softening them. be able to. Conventionally, sodium tripolyphosphate has been mainly used as a builder for detergents. Sodium tripolyphosphate has a very good performance as a builder for detergents, such as chelating performance.However, since it contains phosphorus, the wastewater after washing containing the same is discharged as it is, resulting in eutrophication of rivers and lakes. Cause. For this reason, builders other than sodium tripolyphosphate have been developed.

At present, the use of zeolite, which is a crystalline sodium aluminosilicate of the type 4A, achieves phosphorus-free, and with various devised compositions, a performance comparable to that of conventional phosphorus-containing detergents is obtained. Has been reached.
However, since zeolite is insoluble in water, it is disadvantageous in terms of ion exchange capacity for lowering hardness as compared with a water-soluble chelating agent from the viewpoint of a solid-liquid interface. As a water-soluble chelating agent, organic polycarboxylic acids or salts thereof are already known, but they are insufficient in performance, economy, biodegradability, magnesium in water, and zeolites unsuitable for transition metals. It is only included as an adjuvant.

Under such a background, the general formula (II)

[0005]

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[Wherein, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a basic amino acid group, and a plurality of Ms may be the same or different. m, n: same or different, and represents a number from 0 to 5. Where m
And n do not become 0 at the same time. It has been disclosed that a phosphorus-free chelating agent comprising an aminoether carboxylic acid or a salt thereof having high water solubility and excellent chelating performance is useful as a builder for a detergent (USP 2,316,636). And WO 96/22964).

As a method for producing the aminoethercarboxylic acid represented by the general formula (II) or a salt thereof, two production methods represented by the following reaction formulas (1) and (2) are known.

[0008]

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(In the above series of formulas, m, n and M have the same meanings as above, X represents a leaving group such as a halogen atom or p-toluenesulfonate, and Y represents a protecting group.) The method shown in 1) is a method described in US Pat. No. 2,316,636 and JP-A-7-120894.
lliamson's ether synthesis method, in which the yield is generally low and, for example, when sodium monochloroacetate is used, salt is formed or unreacted sodium monochloroacetate and its decomposition product glycolic acid Since sodium and the like are mixed, the purity of the amino ether carboxylic acid represented by the general formula (II) or a salt thereof is low, and it is difficult to use the amino ether carboxylic acid as a detergent composition as it is.

The method shown in reaction formula (2) is described in WO96 / 2296.
Although this method is described in No. 4, this method has less impurities such as salt and the like than the method shown in the above reaction formula (1).
Moreover, since it is a catalytic oxidation reaction, it is economically advantageous. However, since the step of desorbing the protecting group Y is included, the steps are complicated, and the load on the production equipment is increased.

Therefore, a method for selectively obtaining the aminoethercarboxylic acid represented by the general formula (II) or a salt thereof in high yield has been desired. Accordingly, an object of the present invention is to provide a method for producing an aminoethercarboxylic acid or a salt thereof represented by the general formula (II) having excellent chelating ability in high purity, high yield, and economically at low cost. Is to do.

[0012]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention provides a compound represented by the general formula (I):

[0013]

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(Wherein, m and n have the same meanings as described above.)
Wherein the amino ether alcohol represented by the general formula (II) is subjected to an oxidative dehydrogenation reaction in the presence of an alkali metal hydroxide, water and a copper-containing catalyst. Or, a method for producing a salt thereof is provided.

[0015]

Embodiments of the present invention will be described below in detail.

Specific examples of the amino ether alcohol represented by the general formula (I) used in the present invention are shown below.

[0017]

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These compounds can be used as one kind or as a mixture of two or more kinds. As the amino ether alcohol represented by the general formula (I), those in which m is a number of 1 to 2 and n is a number of 0 to 2 are preferable.

The amino ether alcohol represented by the general formula (I) can be produced industrially easily and at low cost. For example, it can be produced by a reaction between triethanolamine and ethylene oxide or a reaction between 2- (2-aminoethoxy) ethanol and ethylene oxide.

The alkali metal hydroxide used in the present invention includes sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide and the like. Sodium hydroxide and potassium hydroxide are preferable, and particularly, hydroxide Potassium oxide is preferred because of its high reaction activity. These can be used in the form of flakes, powders, or aqueous solutions, but are preferably used as aqueous solutions because they are easy to handle. The amount of the alkali metal hydroxide used is 0.9 to 2.0 with respect to the hydroxyl group of the amino ether alcohol represented by the general formula (I).
A range of equivalent times is preferred, and a range of 1.0 to 1.5 equivalent times is more preferred.

The reaction of the present invention is performed in the presence of water. By using water, the aminoether alcohol represented by the general formula (I) can react with the alkali metal hydroxide in a uniform state, and the yield is improved. The amount of water used in the present invention is 50% by weight or more, preferably 50 to 50% by weight, based on the amino ether alcohol represented by the general formula (I).
It is in the range of 400% by weight.

The copper-containing catalyst used in the present invention contains copper as an essential component. The raw materials include copper metal, copper nitrate, copper sulfate, copper carbonate, copper oxide, copper chloride, copper hydroxide. , Copper formate, copper acetate and the like can be used. The form of the catalyst is not particularly limited, for example, a catalyst obtained by oxidizing a metal copper surface and reducing it with hydrogen, a developed Raney copper catalyst obtained by developing a Raney copper alloy with an alkaline aqueous solution, or diatomaceous earth, zeolite, silica gel A supported catalyst or the like obtained by supporting on alumina, zirconium oxide, or the like by a coprecipitation method, an impregnation method, or the like, and then reducing with hydrogen can be used. A developed Raney copper catalyst or a copper catalyst supported on zirconium oxide is preferred from the viewpoint of the activity of the reaction and the recovery activity.

The copper-containing catalyst used in the present invention can contain other metals. Examples of these other metals include vanadium, bismuth, tin, antimony, lead, and germanium, and vanadium is particularly preferred. By including at least one selected from these other metals in the copper-containing catalyst, the reaction activity is increased, and a decrease in the recovery activity can be suppressed. The content of these other metals is not particularly limited, but the effect of improving the reaction activity can be seen at 50 ppm to 1% by weight with respect to the copper contained in the catalyst. Even if it is added more, the effect is not increased and it is not economically preferable. In the present invention, the use amount of the copper-containing catalyst is 1 to 50% by weight, preferably 5 to 30% by weight, based on the amino ether alcohol represented by the general formula (I).

[0024] The reaction temperature in the oxidative dehydrogenation reaction of the present invention is usually 150 to 260 ° C, preferably 180 to 250 ° C, more preferably 180 to 230 ° C. Further, the reaction pressure is preferably lower than this reaction is a dehydrogenation reaction.
Since water is used in the reaction, the generated hydrogen is usually removed so as to keep it at 8 to 30 kg / cm ² G, depending on the amount of water and the reaction temperature.

The type of the reaction in the present invention is a batch type,
Any of the continuous methods can be performed. Examples of a method for removing the catalyst from the mixture after the reaction include a method such as a filtration method, a centrifugation method, and a sedimentation method. The separated catalyst can be reused as it is or after a regeneration treatment.

The general formula (II) obtained by the method of the present invention
The aqueous solution containing an aminoether carboxylic acid or a salt thereof represented by is purified as necessary to obtain a high-quality aminoether carboxylic acid or a salt thereof as a product. It can also be directly incorporated into a detergent or the like without purification.

The aminoethercarboxylic acid represented by the general formula (II) or a salt thereof obtained according to the present invention is useful as a builder of a detergent, and by adding an appropriate amount to a detergent composition, the detergency is improved. And a detergent composition excellent in biodegradability can be obtained. The amount of the amino ether carboxylic acid represented by the general formula (II) or a salt thereof in the detergent composition is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight.
Is more preferred. When the amount is 0.5% by weight or more, the effect of the builder can be sufficiently obtained, and excellent detergency can be obtained. Further, when the content is 40% by weight or less, other components such as a surfactant can be appropriately compounded, and sufficient cleaning performance can be obtained.

[0028]

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

EXAMPLE 1 N- {2- (2-hydroxyethoxy) ethyl} -N, N-diethanolamine was placed in a 1 liter autoclave.
(Hereinafter abbreviated as amino ether alcohol A) 193 g, sodium hydroxide 130 g, water 400 g and developing Raney copper catalyst 1
9.3 g was charged and the inside was replaced with hydrogen gas. The temperature was raised to 220 ° C., and the reaction pressure was maintained at 22 kg / cm ² G. After 8 hours, generation of hydrogen was stopped, and the mixture was stirred for 1 hour and cooled after stirring. The reaction solution was taken out, filtered and analyzed. As a result, 5-amino-3-oxa- represented by the following formula (III):
The yield of pentanoic acid-N, N-diacetate trisodium salt is
It was 85% and the purity in solid content was 81%.

[0030]

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Examples 2-6 According to Example 1, the alkali hydroxide species, catalyst, reaction temperature,
Example 1 except that the pressure and time were changed as shown in Table 1.
The reaction was carried out in the same manner as described above to obtain tri-sodium 5-amino-3-oxa-pentanoate-N, N-diacetate represented by the above formula (III). The yield and purity are shown in Table 1.

[0032]

[Table 1]

Note) * 1: 3.1 mole times added to the raw material amino ether alcohol A * 2: 10% by weight added to the raw material amino ether alcohol A * 3: Conversion of the raw material amino ether alcohol A * 4 : 5-amino-3-oxa-pentanoic acid in solid content
Weight% of trisodium N, N-diacetate * 5: 100 g of zirconium oxide is impregnated with an aqueous solution containing 42 g of copper nitrate, dried, calcined in air at 500 ° C. for 3 hours, and 230 ° C. in hydrogen stream for 6 hours Reduced * 6: A developed Raney copper catalyst containing 75 ppm of vanadium element with respect to copper.

COMPARATIVE EXAMPLE 1 390 g of sodium monochloroacetate, 560 g of water, 68 g of monoethanolamine, and 210 g of sodium carbonate were added to a two-liter four-necked flask and stirred at room temperature for 4 hours. Thereafter, the mixture was heated and stirred at 85 to 95 ° C. for 5 hours.
II) 5-amino-3-oxa-pentanoic acid-
Aqueous solution containing 10% N, N-diacetate trisodium salt 1080
g was obtained. The yield was 36%, and the purity in solid content was 19%.

Examples 7 to 9 N, N-bis {2- (2-hydroxyethoxy) ethyl} -N-ethanolamine (hereinafter abbreviated as aminoether alcohol B), N- [2 -{2- (2-hydroxyethoxy) ethoxy} ethyl] -N, N-diethanolamine (hereinafter abbreviated as aminoether alcohol C), or 60/20/20 (weight ratio) of aminoether alcohols A, B, and C Using the above mixture, the reaction was carried out in the same manner as in Example 1 except that the reaction temperature, pressure and time were changed as shown in Table 2, to obtain the aminoether carboxylate shown in Table 2. Table 2 shows the yield and purity.

[0036]

[Table 2]

[0037]

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APPLICATION EXAMPLES 1-5 AND COMPARATIVE APPLICATION EXAMPLES 1-2 Powders of a detergent composition were produced by crushing and granulating particles obtained by spray-drying a slurry having the composition shown in Table 3 using a high-speed mixer. . About the obtained detergent composition, the cleaning performance with respect to the artificially contaminated cloth was evaluated by the following method. Table 3 shows the results.

<Method for Evaluating Cleaning Performance> (1) Preparation of Sebum Soil-Contaminated Cloth (Population-Contaminated Cloth) Model sebum soil 2 having the following composition on a 10 cm × 10 cm cotton cloth.
g was evenly applied to prepare a sebum soiled cloth.・ Model sebum dirt composition cottonseed oil 60% cholesterol 10% oleic acid 10% palmitic acid 10% liquid and solid paraffin 10% (2) Preparation of mud soiled cloth (population-clothed cloth) After drying for 4 hours at 120 ° C ± 5 ° C
After drying for 2 hours, disperse about 150 g in 1 liter of perclene, contact a # 2023 cloth with this liquid, brush, remove the dispersion, and remove excess adhered dirt.
A mud stained cloth was made.

(3) Washing conditions and evaluation method 10 cm of the above-prepared washing solution was added to 1 liter of an aqueous cleaning agent solution for evaluation.
Five pieces of cotton sebum stained cloth or mud stained cloth of × 10 cm were put and washed at 100 rpm with a tergotometer. The washing conditions are as follows.・ Washing conditions Washing time 10 minutes Washing agent concentration 0.083% Water hardness 4 ° DH Water temperature 20 ° C Rinsing 5 minutes with tap water Washing power is the self-recording color at 460 nm of the original cloth before and after cleaning. The cleaning rate (%) was determined by the following equation, and the average of the measured values of the five sheets was shown as the cleaning power.

[0041]

(Equation 1)

[0042]

[Table 3]

Note) * 1 LAS: straight-chain alkylbenzene sulfonic acid sodium
(C12-C13 of alkyl group) * 2 AS: Alkyl sodium sulfate (Carbon number of alkyl group
12-14) * 3 Shown in% by weight of solids containing aminoether carboxylate obtained in Examples and Comparative Examples.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 3/00 108 C09K 3/00 108C C11D 3/33 C11D 3/33 // C07B 61/00 300 C07B 61/00 300

Claims (4)

[Claims] 1. A compound of the general formula (I) (Wherein, m and n are the same or different and each represents a number of 0 to 5, provided that m and n are not simultaneously 0). A process for producing an aminoethercarboxylic acid represented by the general formula (II) or a salt thereof, which comprises carrying out an oxidative dehydrogenation reaction in the presence of a catalyst containing water, water and a copper. Embedded image (Wherein, m and n have the same meanings as above, M is a hydrogen atom,
It represents an alkali metal, alkaline earth metal, ammonium or basic amino acid group, and a plurality of M may be the same or different. ) 2. The method according to claim 1, wherein the copper-containing catalyst is a developed Raney copper catalyst or a copper catalyst supported on zirconium oxide. 3. The method according to claim 1, wherein the copper-containing catalyst contains vanadium. 4. The method according to claim 1, wherein the alkali metal hydroxide is potassium hydroxide.