JP2001172241A - Method for producing aminocarboxylic acid, aminocarboxylic acid and chelating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an aminocarboxylic acid using a simplified production procedure in improved yield while suppressing the formation of by-products and provide an aminocarboxylic acid having excellent chelating action and biodegradability. SOLUTION: The objective method for producing the aminocarboxylic acid expressed by general formula (1) (X is COOM; M groups are H, an alkali metal, an alkaline earth metal or ammonium the same as or different from each other; and R is H or OH) contains a process to add ethylene oxide to a compound expressed by general formula (2) (X and R are each the same defined in the general formula (1)) in an aqueous solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing aminocarboxylic acids, an aminocarboxylic acid, and a chelating agent.

[0002]

2. Description of the Related Art Chelate compounds can block metal ions by forming two or more coordination bonds. Therefore, in order to remove adverse effects due to the presence of metal ions, detergents, fibers, It is used in various fields such as paper pulp, metal surface treatment, and photography, and is currently indispensable to the chemical industry and daily life.

[0003] Chelate compounds are used, for example, in the field of detergents and the like to remove metal ions such as calcium and magnesium in hard water in the preparation of water used. In the fields of fibers and paper pulp, bleaching agents are used. Is used to suppress decomposition by metal ions such as hydrogen peroxide. Representative chelate compounds include, for example, ethylenediaminetetraacetic acid (EDTA) which is inexpensive and has high chelating ability.

[0004] Since these chelate compounds are discarded in household wastewater or industrial waste, there is a concern that they may affect the environment and ecosystem. In recent years, regulations on environmental pollution by chemical substances are becoming stricter, and it is becoming impossible to use chelate compounds that may pollute the environment.

[0005] JP-A-6-59422 discloses a chelate compound represented by the following general formula (4):

[0006]

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A processing composition for a silver halide photographic light-sensitive material containing an aminocarboxylic acid represented by the formula (wherein Y represents COOH) is disclosed. Since the aminocarboxylic acids and the like have a chelating action, this processing composition can perform rapid processing excellent in desilvering properties. Moreover, since it has biodegradability, it is less likely to pollute the environment. Thus, the composition containing aminocarboxylic acids is useful as a chelating agent. On the other hand, the aminocarboxylic acids represented by the general formula (4) have technical room for more effectively enhancing the chelating action and biodegradability in the chemical structure.

The process for producing aminocarboxylic acids is described in US Pat.
roblemy Khimii Komplekson
ov (1985) (dew) p. 108-115. This production method comprises a step of esterifying aminocarboxylic acids to which ethylene oxide has not been added to a dimethyl ester of aminocarboxylic acids by esterification in a methanol / hydrochloric acid solution, a step of adding ethylene oxide to the dimethyl ester of aminocarboxylic acids, and Followed by a step of hydrolysis with sodium hydroxide or the like. However, this production method has a high possibility of producing by-products due to the large number of steps, and has a high production cost. Furthermore, the yield of aminocarboxylic acids as products is extremely low and not practical, and it has been difficult to expect to increase the yield.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and simplifies the production process, reduces the risk of by-products, and further increases the yield of amino acids. An object of the present invention is to provide a method for producing carboxylic acids, and also to provide aminocarboxylic acids having excellent chelating action and biodegradability.

[0010]

The present invention provides a compound represented by the following general formula (1):

[0011]

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(Wherein, X represents COOM. M represents the same or different and represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium group. R represents a hydrogen atom or a hydroxyl group. The method for producing an aminocarboxylic acid represented by the following general formula (2) in an aqueous solution:

[0013]

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(Wherein X and R are the same as described above). This is a method for producing aminocarboxylic acids, which comprises a step of adding ethylene oxide to a compound represented by the formula: The present invention is also a chelating agent comprising an aminocarboxylic acid composition, wherein the aminocarboxylic acid composition has the following general formula (1):

[0015]

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(Wherein X represents COOM. M represents the same or different and represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium group. R represents a hydrogen atom or a hydroxyl group. ) And an aminocarboxylic acid represented by the following general formula (2):

[0017]

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(Wherein X and R are the same as defined above).
The present invention also provides the following general formula (3):

[0019]

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(Wherein X represents COOM; M represents the same or different and represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium group). . The present invention is also a chelating agent containing the above aminocarboxylic acids. less than,
The present invention will be described in detail.

The method for producing aminocarboxylic acids of the present invention is a method for producing the aminocarboxylic acids represented by the above general formula (1), wherein the compound represented by the above general formula (2) is dissolved in an aqueous solution. A step of adding ethylene oxide. In the general formulas (1) and (2), the alkali metal atom represented by M is not particularly limited, and examples thereof include lithium, sodium, potassium, rubidium, cesium, and francium.
Sodium and potassium are preferred because they are easily available and inexpensive. Further, the alkaline earth metal atom is not particularly limited, for example, beryllium, magnesium,
Calcium, strontium, barium, radium and the like can be mentioned, but magnesium and calcium are preferred from the viewpoint of easy availability and low cost.

The compounds represented by formula (2) may be used alone or in combination of two or more. The compound represented by the general formula (2) is a compound represented by M in the —COOM group.
Is preferably a salt having an alkali metal atom, an alkaline earth metal atom or an ammonium group. More preferably, it is a salt in which M is all sodium.

In the present specification, the step of adding ethylene oxide to the compound represented by the above general formula (2) in an aqueous solution is also referred to as an ethylene oxide addition step. A typical example of the above ethylene oxide addition step is as follows.

[0024]

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In the formula, X and R are the same as described above. The method for producing aminocarboxylic acids of the present invention may include a step of converting the compound represented by the general formula (2) into a salt. The step for converting the compound represented by the general formula (2) into a salt is not particularly limited, and examples thereof include hydroxides and carbonates of alkali metals, hydroxides and carbonates of alkaline earth metals, and ammonium. It is preferable that the step of replacing all the hydrogen ions of the carboxyl group in the compound represented by the general formula (2) using a compound having a cation such as a compound having a group.

In the step of converting the compound represented by the general formula (2) into a salt, the amount of the compound used to replace all the hydrogen ions of the carboxyl group in the compound represented by the general formula (2) Is not particularly limited. For example, it is preferable that the equivalent ratio of the hydrogen ion of the carboxyl group in the compound represented by the general formula (2) to the cation in the compound having the cation be 1 to 3. . More preferably, it is 1-2.

In the above ethylene oxide addition step, the molar ratio of the compound represented by the general formula (2) to the ethylene oxide is not particularly limited. For example, the yield of the aminocarboxylic acid represented by the general formula (1) is controlled. In order to improve the ratio, it is preferable that (the number of moles of ethylene oxide) / (the number of moles of the compound represented by the general formula (2)) be 1.0 to 10. More preferably, 1.0
５5.0.

The reaction method in the ethylene oxide addition step is not particularly limited. For example, it is preferable to replace the reaction system with an inert gas such as nitrogen gas, and to control the reaction of ethylene oxide with ethylene oxide. Is preferably added (dropped) over time. The time for adding (dropping) the ethylene oxide is not particularly limited, and for example, is preferably 0.5 to 6 hours. More preferably, it is 1 to 5 hours.

The reaction medium in the ethylene oxide addition step is not particularly limited as long as it contains water, and includes, for example, water; a mixed medium of water and a water-soluble organic solvent such as alcohol. Among these, it is preferable to use only water. The amount of the reaction medium to be used is not particularly limited. For example, an amount of a homogeneous solution of aspartate, usually 40% of the compound represented by the general formula (2) is used.
It is preferable that the reaction be performed at about the weight%.

The reaction temperature and reaction time in the ethylene oxide addition step are not particularly limited.
The reaction temperature is preferably 15 to 80 ° C., and the reaction time is preferably 0.5 to 5 hours after the addition (dropping) of ethylene oxide is completed. More preferably, the reaction temperature is 2
0 to 60 ° C., and the reaction time is 1 to 4 hours after the addition (dropping) of ethylene oxide is completed.

In the method for producing aminocarboxylic acids of the present invention, in addition to the above-described steps, other cations in the carboxyl group of the aminocarboxylic acids represented by the general formula (1) produced by the above-mentioned ethylene oxide addition step are removed. To the cation or hydrogen ion.

The method for producing aminocarboxylic acids of the present invention is advantageous in terms of production cost because the production process is simplified. In addition, the possibility that by-products are generated is reduced. Furthermore, according to the ethylene oxide addition step,
In order to react ethylene oxide in an aqueous solution, the reaction can be performed with the molar number of ethylene oxide being excessive relative to the molar number of the compound represented by the general formula (2). Therefore, the synthesizing effect that the production process is simplified and the possibility that by-products are reduced is reduced, so that the aminocarboxylic acids represented by the general formula (1) can be produced with a higher yield. Becomes

The chelating agent of the present invention contains an aminocarboxylic acid composition. The aminocarboxylic acid composition is produced by a production method including a step of adding ethylene oxide to the compound represented by the general formula (2) in an aqueous solution. The method for producing the aminocarboxylic acid composition is the method for producing an aminocarboxylic acid described above,
The method does not include the step of leaving the compound represented by the general formula (2) and isolating the aminocarboxylic acid represented by the general formula (1) as a product. Thereby, the aminocarboxylic acid represented by the general formula (1) and the general formula (2)
And an aminocarboxylic acid composition containing the compound represented by the formula:

The aminocarboxylic acids represented by the general formula (1) and the compound represented by the general formula (2) are characterized in that one of the features of their chemical structures is that a carboxyl group or a substituted carboxyl group has Four and a nitrogen atom are present in one molecule at the same time, and can be a pentadentate or more ligand for a metal ion. Therefore, a good chelating action is exhibited.

The aminocarboxylic acids represented by the general formula (1) and the compound represented by the general formula (2) also
It has excellent chelating activity and high biodegradability. It is not always clear why such high biodegradability is expressed, for example,
(1) In the case of a compound having a tertiary amine structure,
That an atom or an atomic group which is susceptible to biodegradation is bonded to a nitrogen atom constituting the secondary amine, it is considered to be easily degraded. (2) It is considered that a hydroxyl group is likely to be degraded. 3) In the biodegradation of a compound, the reason is considered that if one of the atoms or atomic groups forming the compound undergoes biodegradation, it is considered to be biodegraded in a chain. That is, the aminocarboxylic acid represented by the general formula (1) and the compound represented by the general formula (2) have atoms or atomic groups which are susceptible to biodegradation. It is thought that it will be biodegraded.

A comparison of the biodegradability between the aminocarboxylic acid represented by the general formula (1) and the compound represented by the general formula (2) shows that the aminocarboxylic acid represented by the general formula (1) Is considered to have excellent biodegradability because it has a hydroxyethyl group. Therefore, by adjusting the abundance ratio (molar ratio) between the aminocarboxylic acids represented by the above general formula (1) and the compound represented by the above general formula (2), the fields and requirements used as chelating agents The biodegradability can be adjusted depending on the performance to be performed. Further, when there is a difference in the chelating action, the chelating action can be adjusted.

Adjustment of the abundance ratio (molar ratio) between the aminocarboxylic acid represented by the above general formula (1) and the compound represented by the above general formula (2) in the aminocarboxylic acid composition is performed by adjusting the aminocarboxylic acid. In the production of the acid composition,
The reaction can be carried out by appropriately setting reaction conditions and the like and adjusting the conversion of the compound represented by the general formula (2) to the aminocarboxylic acid represented by the general formula (1).

The abundance ratio (molar ratio) between the aminocarboxylic acid represented by the general formula (1) and the compound represented by the general formula (2) in the aminocarboxylic acid composition is not particularly limited. For example, usually 0.1: 99.9
９９99.9: 0.1. The above abundance ratio is 0.1: 9
If the ratio deviates from 9.9 or 99.9: 0.1, the chelating action and the biodegradability cannot be adjusted.

The above-mentioned abundance ratio is preferably such a ratio that the amount of the aminocarboxylic acid represented by the general formula (1) becomes larger than 0.5: 99.5. When the abundance ratio deviates from 0.5: 99.5 and the amount of the aminocarboxylic acid represented by the general formula (1) becomes too small, the biodegradability decreases and the balance between the biodegradability and the chelating action is obtained. May not be possible.

The above aminocarboxylic acid composition can be suitably used as a chelating agent, and can also be used for other uses requiring chelating action, biodegradability and the like. If necessary, the chelating agent containing the aminocarboxylic acid composition of the present invention may contain a chelating agent other than the above aminocarboxylic acid composition, an additive, or the like.

The aminocarboxylic acids represented by the general formula (3) of the present invention are those having the hydroxyl group R in the aminocarboxylic acids represented by the general formula (1), and have an excellent chelating action. In addition, it has excellent biodegradability. It is considered that the reason for having such excellent biodegradability is that it has two hydroxyl groups and thus is easily biodegradable effectively.

The aminocarboxylic acids represented by the general formula (3) of the present invention can be suitably used as a chelating agent, and are also used for other uses requiring a chelating action, biodegradability and the like. Is what you can do. The chelating agent containing an aminocarboxylic acid represented by the general formula (3) of the present invention includes, if necessary, a chelating agent other than the aminocarboxylic acid represented by the general formula (3), an additive, and the like. You may go out. The chelating agent of the present invention,
Excellent in chelating action and biodegradability, detergent,
It can be used in a wide range of fields such as detergent compositions, chemicals for textile industry, chemicals for paper pulp production, chemicals for metal surface treatment, chemicals for photographic development, and the like.

[0043]

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.

Embodiment 1N-hydroxyethyl iminodi
Synthesis of succinic acid tetrasodium salt  Aqueous solution containing 33.7 g of iminodisuccinic acid tetrasodium salt
Charge 84.3 g of the liquid in an autoclave,
After heating to 40 ° C., ethylene oxide
4 g were added over 2 hours. After completion of addition, additional 40 ° C
And stir for 1 hour.
The reaction solution obtained is removed by high-performance liquid chromatography.
Analysis of the target product, N-hydroxy
Contains 3.9 g of thiliminosuccinic acid tetrasodium salt
I was

Embodiment 2N-hydroxyethyl-3-hi
Synthesis of droxyiminodisuccinic acid tetrasodium salt  3-hydroxyethyliminodisuccinic acid tetrasodium salt
78.4 g of an aqueous solution containing 35.3 g in an autoclave
, And sufficiently purged with nitrogen, and heated to 40 ° C.
4.4 g of Tylene oxide were added over 2 hours. Attachment
After completion of the addition, the mixture is further stirred at 40 ° C. for 1 hour to be present in the system.
Ethylene oxide is removed, and the resulting reaction solution is
When analyzed by high performance liquid chromatography,
Certain N-hydroxyethyl-3-hydroxyiminodicos
It contained 4.1 g of succinic acid tetrasodium salt.

[0046]

The method for producing aminocarboxylic acids according to the present invention has the above-mentioned constitution, so that the production process is simplified, the risk of generation of by-products is reduced, and the yield is increased. It can produce acids. The aminocarboxylic acids of the present invention have excellent chelating action and biodegradability, and are useful as chelating agents. The chelating agent of the present invention contains an aminocarboxylic acid composition or an aminocarboxylic acid excellent in chelating action and biodegradability, and is used as a detergent, a detergent composition, a chemical for the textile industry, a chemical for paper pulp production, and a metal. It can be used in a wide range of fields such as surface treatment chemicals and photographic development chemicals.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tomomi Ina 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 2H016 AE07 BK06 BL08 4H003 EB13 FA03 FA07 4H006 AA01 AA02 AA03 AB82 AC41 AC52 BB14 BB47 BB61 BC10 BC19 BE60

Claims (4)

[Claims] 1. The following general formula (1): (Wherein, X represents COOM. M represents the same or different and represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium group. R represents a hydrogen atom or a hydroxyl group). A method for producing an aminocarboxylic acid represented by the following general formula (2) in an aqueous solution: (Wherein X and R are the same as described above), which comprises a step of adding ethylene oxide to the compound represented by the formula (1). 2. A chelating agent comprising an aminocarboxylic acid composition, wherein the aminocarboxylic acid composition has the following general formula (1): (Wherein, X represents COOM. M represents the same or different and represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium group. R represents a hydrogen atom or a hydroxyl group). An aminocarboxylic acid represented by the following general formula (2): (Wherein, X and R are the same as defined above). 3. The following general formula (3): (Wherein, X represents COOM; M represents the same or different and represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an ammonium group). . 4. A chelating agent comprising the aminocarboxylic acid according to claim 3.